Energy-enhancing structures for energy emitters and collectors

Abstract

An emission enhancement structure having: at least one energy enhancement structure; and an energy converter capable of receiving energy from an energy source, converting the energy, and emitting light from the energy converter having an energy different from the received energy. The energy converter is disposed proximate to the at least one energy enhancement structure so that the emitted light is emitted with a greater intensity than if the converter were remote from the at least one energy enhancement structure. Various uses of energy emitters, energy enhancement structures, and energy collectors in a variety of fields such as color enhancement, and color enhancement structures containing the energy emitters, energy enhancement structures, and energy collectors are also described.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is related to U.S. Provisional Application Serial No. 62 / 955,533, filed December 31, 2019, entitled ENERGY AUGMEN TATION STRUCTURE; ENERGY COLLECTOR CONTAINING THE SAME; AND EMISSION ENHANCEMENTS UTILIZING AT LEAST ONE ENERGY AUGMENTATION STRUCTURE, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. Provisional Application Serial No. 62 / 946,648, filed December 11, 2019, entitled ENERGY AUGMEN TATION STRUCTURE; ENERGY COLLECTOR CONTAINING THE SAME; AND EMISSION ENHANCEMENTS UTILIZING AT LEAST ONE ENERGY AUGMENTATION STRUCTURE, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. Provisional Application Serial No. 62 / 897,677, filed on September 9, 2019, entitled ENERGY AUGMENTATION STRUCTURE; ENERGY COLLECTOR CONTAINING THE SAME; AND EMISSION ENHANCEMENTS UTILIZING AT LEAST ONE ENERGY AUGMENTATION STRUCTURE, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. Provisional Application Serial No. 62 / 855,508, filed on May 31, 2019, entitled ENERGY AUGMENTATION STRUCTURE; ENERGY COLLECTOR CONTAINING THE SAME; AND COLOR ENHANCEMENT UTILIZING AT LEAST ONE ENERGY AUGMENTATION STRUCTURE, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. Provisional Application Serial No. 62 / 813,390, filed on March 4, 2019, entitled COLOR ENHANCE MENT UTILIZING AT LEAST ONE ENERGY AUGMENTATION STRUCTURE, the entire disclosure of which is incorporated herein by reference.This application is related to pending U.S. application serial number 16 / 599,732, filed on October 11, 2019, which claims priority to U.S. provisional application serial number 62 / 745,057, filed on October 12, 2018, the entire contents of each of which are incorporated herein by reference. This application is related to U.S. serial number 13 / 204,355, filed on August 5, 2011, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. provisional patent application 61 / 371,549, filed on August 6, 2010. This application is related to U.S. provisional patent application 61 / 161,328, filed on March 18, 2009, and U.S. provisional patent application 61 / 259,940, filed on November 10, 2009, the entire disclosure of which is incorporated herein by reference. This application is related to U.S. Serial No. 12 / 725,108, the entire disclosure of which is incorporated herein by reference.

[0003] No. 60 / 954,263, filed August 6, 2007, and No. 61 / 030,437, filed February 21, 2008, and U.S. Application Serial No. 12 / 059,484, filed March 31, 2008, the contents of which are hereby incorporated by reference herein. This application is also related to U.S. Application Serial No. 11 / 935,655, filed November 6, 2007; and No. 61 / 042,561, filed April 4, 2008; and No. 61 / 035,559, filed March 11, 2008; and No. 61 / 080,140, ​​filed July 11, 2008, the entire contents of which are hereby incorporated by reference herein. This application is related to U.S. patent application Ser. No. 12 / 401,478, filed March 10, 2009, the entire contents of which are hereby incorporated by reference. This application is related to U.S. patent application Ser. No. 11 / 935,655, filed November 6, 2007, and Ser. No. 12 / 059,484, filed March 31, 2008; U.S. patent application Ser. No. 12 / 389,946, filed February 20, 2009; and U.S. patent application Ser. No. 12 / 417,779, filed April 3, 2009, the entire disclosures of which are hereby incorporated by reference. Background of the Invention Field of the Invention

[0005] The present invention relates to methods, systems and devices for energy enhancement in the presence and absence of energy modulation agents / energy conversion agents and is particularly useful for generating or enhancing photon or electron emission and / or for enhancing light or photon collection. Background Art

[0006] Currently, light (i.e., electromagnetic radiation ranging from radio frequencies through visible wavelengths to X-rays) is used in many industrial, communications, electronic, and pharmaceutical processes. Light in the infrared and visible ranges is typically generated from an electrical energy source, such as by heating a material to very high temperatures at which blackbody emission occurs (as in an incandescent lamp). Light in the visible and ultraviolet ranges is typically generated by heating a gas to an electrical discharge, in which a transition from one electronic state of the gas atoms or molecules occurs simultaneously with the emission of light. There are also semiconductor-based light sources (as in light-emitting diodes and semiconductor lasers), in which electrons / holes in a material recombine to produce light emission.

[0007] Visible light is defined as electromagnetic radiation with a wavelength between 380 nm and 750 nm. Generally speaking, electromagnetic radiation including light is produced by the acceleration and deceleration or change of the motion (vibration) of charged particles, such as parts of molecules (or adjacent atoms) with high thermal energy, or electrons in atoms (or molecules).

[0008] For reference purposes, infrared (IR) radiation is just beyond the red end of the visible range, while ultraviolet (UV) radiation has wavelengths shorter than violet light. The UV portion of the spectrum is divided into three regions: UVA (315–400nm), UVB (280–315nm), and UVC (100–280nm).

[0009] Industrial lamps used in lighting applications cover the visible wavelength range for proper white color perception.Heat sources like heated filaments can be made from different types of conductors including W filaments, halogen protected W filaments, and electrically induced high temperature plasmas (arc lamps).

[0010] The power (energy emitted per second) of a radiation source is often expressed in watts (W), but light may also be expressed in lumens (lm) to account for the eye's varying sensitivity to light of different wavelengths. A related unit is the power of a source per steradian (measured in solid angles) in a given direction, expressed in W / m. 2 (lm / m 2 ) and the radiance (brightness) of the surface in W / m 2 (lm / m 2 or lux) meter's irradiance (illuminance).

[0011] With the development of ultraviolet light sources, ultraviolet radiation is increasingly used for industrial, chemical and pharmaceutical applications. For example, it is known that UV light can sterilize media, and it is known that this light can drive a number of photoactivated chemical processes, such as the cross-linking of polymers in adhesives or coatings. Typically, ultraviolet light sources use gas discharge lamps to generate emitted light in the ultraviolet range. The emitted light is then optically filtered to remove a large number, but not all, of the non-ultraviolet frequencies. Ultraviolet light can also be generated in semiconductor phosphors by exciting these phosphors with high energy sources (e.g., X-ray irradiation).

[0012] With the development of infrared radiation sources, infrared radiation is increasingly being used for communication and signaling purposes. Typically, these sources use either broad-spectrum light sources called glow sticks to produce a broad spectrum of light focused in the infrared range, or lasers to emit very specific infrared wavelengths. For broadband sources, the emitted light is optically filtered to remove many, if not all, non-infrared frequencies.

[0013] It is generally desirable to have devices, materials, and capabilities that can convert light from one frequency range to another. Down-conversion has been a way to convert higher energy light to lower energy, as used in the phosphors mentioned above. Up-conversion has similarly been demonstrated to convert lower energy light to higher energy light. Typically, this process is a multiphoton absorption process, in which two or more photons are used to promote excited electronic states in a host medium, which in turn radiate light at a wavelength having a higher energy than the energy of the incident light that promoted the multiphoton absorption process. Both down-conversion and up-conversion have been studied and documented in the past.

[0014] In fact, researchers have studied the phenomena of photoluminescence and fluorescence, which are the ability of certain solids to emit light when driven or charged by an external energy source. A large number of well-known phosphors and fluorescent materials are triggered by high-energy electrons or photons and emit lower-energy photons. It is known that certain infrared phosphors can convert infrared light into light in the visible range (violet to red).

[0015] The properties of light, such as its radiance, are particularly important in reading or display applications where the human eye must perceive and discern temporary or permanent images formed with visible light, such as those displayed, for example, by road and highway signs. Televisions, computer monitors, displays, and signs use cathode ray tube technology (CRT) technology in which high-energy electrons strike a phosphor that emits visible light. Televisions, computer monitors, displays, and signs have more recently used liquid crystal display or plasma display technology to produce visible images discernible to the human eye.

[0016] In these and other reading or display applications, attempts have been made to develop displays having relatively high contrast images while minimizing the amount of broadband light emitted or reflected by the display that might detract from the contrast of the displayed image.

[0017] In general, the up-conversion and down-conversion discussed above have actually been used in many fields to convert the incident wavelength of light to a different wavelength. In one example, high-energy photons such as X-rays are converted by absorption of the x-ray energy in a phosphor, and the luminescence of the phosphor in the ultraviolet, visible and / or near-infrared spectrum has been used to drive a photosensitive reaction. In other examples, infrared or near-infrared light has been up-converted by absorption of infrared or near-infrared light in a phosphor, and the luminescence of the phosphor in the visible and / or ultraviolet spectrum. In other examples, light in the visible region can be down-converted or up-converted (depending on the selected phosphor) to different bands within the visible wavelength. This shift (energy conversion) can be used for color enhancement and can be used in solar cells to convert a portion of the solar spectrum into another portion that is more conducive to the generation of electricity by a photovoltaic device.

[0018] In many of these previous applications, metal structures have been placed on or near phosphors to produce a plasmon effect, which is essentially an amplification of the local field outside the very near metal structure. The plasmon effect can enhance the coupling of incident light into the phosphor and / or enhance the reactivity of the converted light amount of the adjacent receptor. While plasmons in the metal can propagate along the metal, the transient plasmon decay in the z-direction perpendicular to the metal / dielectric is associated with a 1 / e decay length on the order of half a wavelength (approximately 200 nm for wavelengths in the visible range).

[0019] In some previous applications, photonic bandgap structures have been used. In a photonic bandgap structure, the material composed of a photonic crystal (PhC) is a material with periodic dielectric properties that can prevent certain frequencies or wavelengths of light from propagating in one, two, or any number of directions within the material. In this way, light that is unsuitable or detrimental to a process can be rejected, while light that is more suitable for a process can be confined within the photonic bandgap structure or, better yet, within the photovoltaic converter.

[0020] In the field of solar cells, plasmons, photonic band gaps and the addition of up-conversion and down-conversion are known in the literature. Additionally, anti-reflection coatings and concentrators are well known in the literature.

[0021] The problem with the plasmon effect is that, as mentioned above, the plasmons and the electric field enhancement decay rapidly with distance away from the metallic structure, which means that the effect is only useful for interactions on a small scale.

[0022] The problem with anti-reflective coatings is that although sunlight is not scattered as much as it would be without the coating, the light that is transmitted is still primarily light of a wavelength that is not optimal for electricity generation.

[0023] The problem with concentrators is that, in addition to concentrating light that can be converted to electricity, they also concentrate light that does not produce electricity, which often results in waste heat.

[0024] While photonic bandgap structures can be used to reflect or confine light, they have no efficient way to extract electricity from the wasted light. Summary of the Invention

[0025] In one embodiment, an energy-enhancing structure is provided that is capable of capturing one or more wavelengths of electromagnetic energy and enhancing the one or more wavelengths of electromagnetic energy in at least one property.

[0026] In one embodiment, the energy enhancing structure may be one or more of an electromagnetic resonant body structure, a folded resonant body structure, and a fractal structure having regions of enhanced electromagnetic fields within the structure.

[0027] In another embodiment, an energy collector is provided, comprising: at least one energy enhancing structure; and at least one energy converter, wherein the at least one energy converter is capable of receiving applied electromagnetic energy, converting the applied electromagnetic energy and emitting electromagnetic energy having a wavelength or energy shifted relative to the applied electromagnetic energy from the at least one energy converter, and the energy converter is arranged near the at least one energy enhancing structure so that the emitted electromagnetic energy is emitted with at least one enhanced property compared to a case where the energy converter is away from the at least one energy enhancing structure.

[0028] In one embodiment, the energy converter mentioned above is provided together with an energy enhancement structure, and the energy enhancement structure comprises one or more of the following: an electromagnetic resonant body structure, a folded resonant body structure, and a fractal structure, any of which has a region of enhanced electromagnetic field within the resonant structure.

[0029] In one embodiment, the energy converter mentioned above includes one or more luminescent materials. As described herein, there are uses of the energy enhancement structure and / or energy collector embodiments that enhance bioluminescence, chemiluminescence, photoluminescence, fluorescence, and mechanoluminescence.

[0030] In one embodiment, the one or more luminescent materials include phosphorescent materials, fluorescent materials, electroluminescent materials, chemiluminescent materials, bioluminescent materials, and mechanoluminescent materials used in conjunction with or without the energy-enhancing structures mentioned above. When used in conjunction with the energy-enhancing structures mentioned above, the emitted electromagnetic energy from the luminescent materials is emitted with at least one enhanced property compared to when the energy converter (e.g., the luminescent material) is located away from the at least one energy-enhancing structure.

[0031] In one embodiment, the one or more luminescent materials include phosphorescent materials, fluorescent materials, electroluminescent materials, chemiluminescent materials, bioluminescent materials, and force-induced luminescent materials, used in conjunction with or without the energy-enhancing structures mentioned above, and emitting one of ultraviolet light, visible light, near-infrared light, and infrared light. In this embodiment, UV-emitting electroluminescent materials or force-induced luminescent devices and materials can be used. In this embodiment, UV-emitting bioluminescent materials can be used.

[0032] In one embodiment, a color-enhancing structure is provided, comprising: a) an energy collector including at least one energy-enhancing structure, and b) an energy converter capable of converting light of a second wavelength into light of a third wavelength that is wavelength-shifted relative to the second wavelength, and emitting the light of the third wavelength from the energy converter. In one embodiment, the energy converter is disposed proximate to the at least one energy-enhancing structure such that the wavelength-shifted light is emitted with greater intensity than if the converter were located further away from the at least one energy-enhancing structure.

[0033] In various embodiments, the color-enhancing structure constitutes part of a paint, ink, fabric, filament, road marking, highway marking, motor vehicle, boat, aircraft, reflector, building product, concrete product, epoxy resin product, jewelry product, colored contact lens, candle product, rubber product, plastic product, or other colored surface.

[0034] In another embodiment, a coating is provided that includes a pigment and a color-enhancing structure.

[0035] In another embodiment, an ink is provided that includes a dye and a color-enhancing structure.

[0036] In another embodiment, a display is provided that includes a color filter or color reflecting surface and a color enhancement structure.

[0037] In additional embodiments, uses of the energy enhancing structure and energy collector embodiments are provided in medical treatments, solar cells, adhesives / resins, sterilization, and other end uses.

[0038] In another embodiment, the energy converter mentioned above is arranged together with an energy enhancement structure so that the x-ray induced photoluminescence or fluorescence is brighter than when the energy converter (e.g., x-ray induced photoluminescence or fluorescence material) is far away from the at least one energy enhancement structure.

[0039] In another embodiment, the distributed energy collector mentioned above can deliver light to different locations within a medium within a patient's body.

[0040] In another embodiment, the distributed energy harvester mentioned above can collect light from or deliver light to different locations within a patient's body, including, for example, collecting light from or delivering light to different locations within an organ.

[0041] In another embodiment, UV-emitting luciferases can be used alone or in combination with the energy-enhancing structures mentioned above to generate light in a patient.

[0042] In another embodiment, a distributed energy harvester is provided having separate light collecting components spread together to collect sunlight for conversion to electricity.

[0043] In another embodiment, there is provided the above-mentioned distributed energy collector having separate light collection components that collect sunlight by directing the collected solar flux to photovoltaic, thermoelectric, or thermoemissive cells.

[0044] In another embodiment, a distributed energy collector is provided that is integrated with photovoltaic devices at individual light collecting components within the collector to convert sunlight into electricity at the light collecting components.

[0045] In another embodiment, the distributed energy collector described above is provided, wherein the distributed energy collector has a separate light collection component and / or the energy enhancement structure described above, wherein the energy enhancement structure has a region of enhanced electromagnetic field, so that sunlight heats a thermionic emission cell. When the region of enhanced electromagnetic field is positioned near the thermionic emission cell, the enhanced electromagnetic field enhances thermionic emission.

[0046] In another embodiment, the above-mentioned distributed energy collector can deliver light to different locations within the artificial medium to achieve adhesive curing of the artificial medium.

[0047] In one embodiment, the energy-enhancing structures mentioned above may be used alone to promote thermal curing of the adhesive heated near the region of the intensified electromagnetic field.

[0048] In one embodiment, the energy-enhancing structure mentioned above can be used in conjunction with the energy converter to promote the curing of the adhesive near the region of the enhanced electromagnetic field or outside the energy-enhancing structure by the enhanced emission of the energy converter due to its presence near the region of the enhanced electromagnetic field. In both embodiments, the region of the enhanced electromagnetic field is generated by excitation of the energy-enhancing structure by an infrared laser. In embodiments with an energy converter, x-ray excitation or other high energy sources (electrons, protons, gamma or beta particles) can be used to stimulate the luminescence of the energy converter for photocuring.

[0049] In another embodiment, the distributed energy harvester mentioned above can deliver light to different locations within a medium to sterilize the medium.

[0050] In one embodiment, the energy enhancing structures mentioned above may be used alone to promote localized heating near the region of the intensified electromagnetic field.

[0051] In one embodiment, the energy-enhancing structures described above can be used in conjunction with the energy converter to facilitate sterilization near the region of the enhanced electromagnetic field or outside the energy-enhancing structure by enhanced emission of the energy converter due to its presence near the region of the enhanced electromagnetic field. In both embodiments, excitation of the energy-enhancing structure by an infrared laser creates the region of the enhanced electromagnetic field. In embodiments with an energy converter, x-ray excitation or other high energy sources (electrons, protons, gamma or beta particles) can be used to stimulate luminescence of the energy converter for sterilization.

[0052] In another embodiment, the use of energy-enhancing structures and / or energy-collecting body embodiments to generate characteristic patterns of light emissions from a surface for security applications is provided. In one embodiment, the energy-enhancing structures mentioned above can be used in conjunction with the energy converters to generate patterned emissions of different colors and intensities to be read as characteristic patterns.

[0053] In another embodiment, there is provided the use of an energy enhancing structure and / or energy converter within a plasma (luminescent) capsule to facilitate the generation and maintenance of luminescent plasma state ions.

[0054] In another embodiment, there is provided a use of an energy enhancement structure and / or an energy converter for enhancing electron emission from a surface in the vicinity of the energy enhancement structure.

[0055] In one embodiment, the energy converter mentioned above includes one or more electron-emitting materials. The electron-emitting material can be a photon-generating material that emits electrons in the form of light when exposed to UV light. The electron-emitting material can be a thermal heating material that emits electrons from a heated surface of the emitting material.

[0056] In one embodiment, the energy converter mentioned above comprises a nanoscale field emission tip for the one or more electron emitting materials. When used in conjunction with the energy-enhancing structures mentioned above, the electron flux emitted from the electron emitting material is higher than when the energy converter (e.g., nanoscale field emission tip) is located away from the at least one energy-enhancing structure.

[0057] It is to be understood that both the foregoing general description and the following detailed description of the invention are exemplary and not restrictive of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] A more complete appreciation of the present invention and many of its attendant advantages will be readily obtained as the same will be better understood by reference to the following detailed description considered in conjunction with the accompanying drawings, in which:

[0059] Figure 1 is a schematic diagram showing an energy enhancement body system of the present invention which optionally includes an energy conversion body;

[0060] Figure 2 is a schematic diagram showing a folded resonator of the present invention as an illustrative energy enhancing structure;

[0061] Figure 3 is a diagram illustrating a basic concept underlying one of the energy enhancement structures of the present invention;

[0062] Figure 4 is a schematic diagram showing a staggered antenna configuration as an illustrative energy-enhancing structure of the present invention;

[0063] Figure 5 is a schematic diagram showing the effect of the electrode spacing of the folded resonator of the present invention;

[0064] Figure 6 is the distribution in space a diagram of a pattern of a folded resonator;

[0065] 7A to 7C is a representation of the distribution on a plane or otherwise along the surface of an object. diagrams of several embodiments of patterns for folded resonators;

[0066] Figure 8 is shown distributed on a plane or otherwise along the surface of an object and having a different Figure 1 -D in the orientation a diagram of a pattern of a folded resonator;

[0067] Figure 9 is a diagram showing a light or photon or electron emitting material deposited in the region between the opposing electrodes. a diagram of a pattern of a folded resonator;

[0068] Figure 10 is a diagram showing a patterned deposition of light or photon or electron emitting material in the region between the opposing electrodes a diagram of a pattern of a folded resonator;

[0069] Figure 11 is a diagram showing a patterned deposition of light or photon or electron emitting material in the region between the opposing electrodes a diagram of a pattern of a folded resonator;

[0070] Figure 12 A fractal pattern showing a metal trace having an electrical path for looping to connect to an opposing electrode. a diagram of a pattern of a folded resonator;

[0071] Figure 13 is a diagram showing a fractal antenna section in which the straight side of the metal pad has a locally enhanced electric field;

[0072] Figure 14 It shows Figure 13 A diagram of a repeating pattern of fractal antenna segments;

[0073] Figure 15 is a diagram showing a pattern of a bow-tie fractal antenna segment;

[0074] Figure 16 is a diagram showing a pair of three-dimensional fractal structures having an intensified electric field therebetween;

[0075] Figure 17 is a diagram showing a pattern of paired three-dimensional fractal structures;

[0076] Figure 181 is a diagram showing a ¾ wavelength resonator antenna having a distal end projecting outward while maintaining parallelism;

[0077] Figure 19 is a diagram showing packaging configurations of three different 3 / 4 wavelength resonators maintained on a plane without overlapping distal ends;

[0078] Figure 20 is a diagram showing another packaging configuration of three different 3 / 4 wavelength resonators maintained in a flat surface with overlapping distal ends;

[0079] Figure 21 is a diagram showing yet another packaging configuration of a ¾ wavelength resonator having an axial symmetry that is off-plane (or away from) the plane;

[0080] Figure 22 is a diagram showing a multi-layer packaging configuration in parallel planes for the folded 3 / 4 wavelength resonator shown;

[0081] Figure 23 It shows the Figure 22 FIG. 1 is a diagram of a multi-layer packaging configuration in which the distal end of the ¾ wavelength resonator protrudes outward and is in parallel planes;

[0082] Figure 24A are diagrams illustrating different in-plane packaging configurations;

[0083] Figure 24B is a diagram showing another different in-plane packaging configuration;

[0084] Figure 25A is a schematic diagram illustrating a distributed point light collector / emitter of the present invention;

[0085] Figure 25B yes Figure 25A Schematic diagram of a cross section of a collector / emitter;

[0086] Figure 26 is a schematic diagram showing the structures of various converters of the present invention;

[0087] Figure 27 is a schematic diagram of plasmon resonance as the thickness of the shell changes;

[0088] Figure 28A is a schematic diagram showing other different converter structures of the present invention;

[0089] Figure 28B is another schematic diagram showing other different converter structures of the present invention;

[0090] Figure 28Cis a schematic diagram showing various plasmon active converter structures of the present invention;

[0091] Figure 28D is a schematic diagram of a photosensitive molecule of the present invention connected to a plasmonically active upconverter structure;

[0092] Figure 29 is a diagram showing a mechanoluminescent emitter of the present invention;

[0093] Figure 30 is a diagram showing a composite piezoelectric / electroluminescent emitter of the present invention;

[0094] Figure 31 It shows Figure 30 A diagram showing the distribution of the composite emitter over the entire light emitting surface;

[0095] Figure 32 It shows Figure 30 a map of the distribution of composite emitters within a target area of ​​light emission;

[0096] Figure 33 is a schematic diagram of a reflective resonator of the present invention;

[0097] Figure 34 is a schematic diagram of an LED white light source with variable color temperature control;

[0098] Figure 35 is a schematic diagram of an electroluminescent light source;

[0099] Figure 36 is a schematic diagram of an electroluminescent light source of the present invention;

[0100] Figure 37 is a schematic diagram of a compression layer substrate configuration according to one embodiment of the present invention;

[0101] Figure 38 is formed in Figure 37 Schematic diagram of a coating on a compression layer substrate configuration;

[0102] Figure 39 is a schematic diagram of the micro-transfer printing technology of the present invention;

[0103] Figure 40 yes Figure 6 G is an overall diagram of the micro-transfer printing process;

[0104] Figure 41 is a schematic diagram of a micro-transferred antenna on a pre-coated compressively stressed glass substrate;

[0105] Figure 42 is a schematic diagram showing a multilayer structure of the present invention, wherein the antenna (resonator) of the present invention is embedded in the multilayer structure;

[0106] Figure 43 is a schematic diagram illustrating the formation of discrete micro-color enhancers of the present invention;

[0107] Figure 44 is a schematic diagram of the geometry of a retroreflective coating using the color-enhancing structure of the present invention;

[0108] Figure 45 is a schematic diagram illustrating the function of the amplifying / resonating body antenna of the present invention in a coating;

[0109] Figure 46 is a schematic diagram of a top coating layer including a color-enhancing structure of the present invention on a coating surface;

[0110] Figure 47 is a schematic diagram of an electronic ink display using the color enhancement structure of the present invention;

[0111] Figure 48 is another schematic diagram of an electronic ink display using the color enhancement structure of the present invention;

[0112] Figure 49 is another schematic diagram of an electronic ink display using the color enhancement structure of the present invention;

[0113] Figure 50 is another schematic diagram of an electronic ink display using the color enhancement structure of the present invention;

[0114] Figure 51 is a schematic diagram of an IR light activated display using the color enhancement structure of the present invention;

[0115] Figure 52 is another schematic diagram of an IR light activated display using the color enhancement structure of the present invention;

[0116] Figure 53 is another schematic diagram of an IR light activated display using the color enhancement structure of the present invention;

[0117] Figure 54 is a schematic diagram of an LCD light-activated display having a color filter having the color enhancement structure of the present invention. DETAILED DESCRIPTION

[0118] Reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to corresponding elements.

[0119] As mentioned above, energy converters such as up-conversion materials and down-conversion materials have actually been used in many fields to convert the incident wavelength of light into different wavelengths. Metal structures have been placed on or near phosphors to produce plasmon effects, which are essentially amplifications of the local fields to the outside of very adjacent metal structures. In some applications, photonic bandgap structures have been used in solar cell applications to prevent the light of certain frequencies or wavelengths from propagating in one, two, or any number of directions within the material. Additionally, anti-reflection coatings and concentrators are well known in the literature.

[0120] The inventors have recognized that the shortcomings of these structures can be addressed by using the energy enhancement structures described herein, used alone or in combination with energy converters.

[0121] A. Energy Enhancement Structure

[0122] In the present invention, the term "energy enhancement" means achieving some change in at least one property of one or more wavelengths of electromagnetic energy, including but not limited to: intensity, power, associated electric field, associated magnetic field, amplitude, photon flux, magnetic flux, phase, coherence, propagation direction, etc. The structure that performs energy enhancement can be referred to as an "energy enhancement structure" or "energy enhancement body". These terms are used interchangeably herein. Preferably, the energy enhancement structure is a non-plasmonic structure (a structure that does not exhibit plasmonic properties).

[0123] The energy enhancer may take any desired form, so long as the energy enhancer is capable of performing the necessary function of enhancing energy applied thereto, thereby causing a change in at least one property of electromagnetic energy of one or more wavelengths as described above. Examples of such energy enhancers include, but are not limited to, at least one non-plasmonic member selected from the group consisting of a resonator, a fractal antenna, a grid pattern, an antenna, a cavity, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure, to name a few.

[0124] In one embodiment, Figure 1 As shown schematically, an energy enhancement body 10 is provided that is capable of receiving or capturing electromagnetic energy representing one or more wavelengths of incident energy waves 12. As a result of receiving or capturing the incident energy waves 12, the energy enhancement body 10 is capable of enhancing the received or captured energy wave flux 12 of the one or more wavelengths in at least one property. Figure 1 As shown, in one embodiment, the energy enhancement body 10 then outputs at least one energy wave 14 having an enhanced property, wherein the enhanced energy wave 14 is incident on a target 20. Details of the enhancement are described below.

[0125] In another embodiment, the output (enhanced) energy wave 14 (i.e., output electromagnetic energy of one or more wavelengths) can be incident on an energy converter 16 (such as the up-conversion material and down-conversion material mentioned above). The energy converter 16 can output photons or electrons 18, which can be directed to a target 20. In these embodiments, the target 20 can receive either the photons or electrons 18 or the output enhanced energy wave 14 simultaneously or separately.

[0126] In one embodiment, the energy enhancement body 10 may be one or more of: an electromagnetic resonant body structure, a folded resonant body structure, and a fractal structure having regions of enhanced electromagnetic fields within these structures.

[0127] the following Figure 2 FIG. 2 is a diagram showing a folded resonator structure 22 according to the present invention.

[0128] The resonator in one embodiment of the present invention is a 3 / 4λ bent metal structure, such as Figure 2 As shown, the metal structure has a "folded" structure formed for the opposing electrodes, which generate a strong electric field between them. The following table lists exemplary characteristics of the "folded structure" antenna:

[0129] Table 1

[0130]

[0131] Calculations for the theoretical 3 / 4λ and a slightly oversized antenna to account for all the bend corners involved in making the antenna may result in such a structure having a size between the theoretical 0.75*λ and an oversized upper limit of 0.78*λ.

[0132] While the resonator shown in most of the figures can be characterized as having a rectangular loop connecting opposing antenna segments or electrodes, the present invention is not limited thereto. Other "loop" shapes can be used, as long as the opposing electrodes are parallel and coplanar with each other, wherein the loop forms an electrical path with a length of 1 / 2λ, while the opposing electrodes each have a length of 1 / 8λ, thereby producing a 3 / 4λ resonator.

[0133] Figure 3 This is a diagram showing the basic concept of one of the energy enhancement structures of the present invention. Figure 3 Depicted in FIG is a sine wave representing, for example, a transient waveform of a light wave (incident energy flux 12). The diagram shows the wavelength 3 / 4 length, and how to construct in one embodiment The resonator, wherein the open ends of the resonator are "folded" together to form in this embodiment Fold the resonator 22. Figure 3 As shown, the folded ends form a region of intensified, amplified electric field indicated by the horizontally oriented arrows between the opposing open ends. (or its harmonics When light (e.g., from a source like a CMOS sensor) is incident on the folded antenna structure, a portion of the light couples into the structure, creating an amplified electric field. Because light from the sun continuously enters with different rotated polarizations, subsequent light waves continue to "pump" the electric field in the resonant structure until some "loss" mechanism limits the field's strength. For resonators made of low-loss materials, a high Q factor is achieved, which in this case can mean that the electric field strength between the opposing electrodes can be, for example, 100 to 1000 times the peak amplitude of the electric field vector of the incident waveform.

[0134] In another embodiment, the resonant antenna may have the following Figure 4 Here, The structures are opposite and interlocked, and there is no "folded" structure. Figure 4 In the diagram in , the horizontal stub is 1 / 4 as long, the vertically extending connectors are 1 / 4 as long, and the vertical spacing between the horizontal stubs and the staggered extensions varies between Configuration 1 and Configuration 2 as shown. In one embodiment of the present invention, the energy converter, light or electron emitting material, or color emitting or color converting material (i.e., emissive material 24) is as shown. Figure 4 As shown, they are placed inside or around areas of enhanced electric fields.

[0135] Figure 5 It shows that different electrodes with different distances between the opposing electrodes and thus different electric field strengths can be produced. Folded resonator. In this way, the folded resonator of the present invention can be adjusted so that the strength of the electric field between the opposing electrodes does not exceed the dielectric strength of any material between them. Exceeding the dielectric strength of any material between them may cause damage to the material because strong currents (e.g., micro-arcing) will flow during any time the dielectric strength is exceeded, thereby damaging the material. As shown here, the opposing sides do not need to have a length of exactly 1 / 8λ.

[0136] In one embodiment of the present invention, an energy converter, luminescent or electron-emitting material, or color-emitting or color-converting material (i.e., emissive material) 24 is placed within or around the enhanced electric field region near / between the opposing electrodes. In one embodiment of the present invention, the color-emitting or color-converting material itself can absorb colored light, such as blue light, and emit lower-energy, down-converted red light. In this case, a red phosphor can be the color-emitting or color-converting material.

[0137] Although In one embodiment, the folded resonator can be designed to The resonator is preferably designed to resonate from light at a different frequency than the blue light absorbed by the red phosphor. In one embodiment, to achieve color enhancement of an object under sunlight, Folded resonators can be designed to be powered by infrared light from the solar spectrum (e.g. ) is driven to generate an intensified electric field, and the red phosphor disposed in the intensified electric field region will have brighter red light emission than in the absence of the intensified electric field.

[0138] Figure 6 is the distribution in space Figure 2 shows the pattern of the folded resonator 22. As will be discussed in more detail later, there is a distribution There are many ways to fold the resonator. The present invention is not limited to Figure 6 The regular uniform spacing and size of the resonators shown. There is no requirement that the distribution be regular, uniformly spaced, uniformly sized, or uniformly oriented. Resonators of varying sizes, spacing, and orientations can provide better utilization of the full spectrum of the sun or any other light source incident on the object.

[0139] Figure 7A is a representation of the distribution on a plane or otherwise along the surface of an object. Figure 22 is a diagram of a pattern of folded resonators 22. In one embodiment, such a pattern can be formed by a lithographic or embossing process onto a planar surface such as a glass plate, or onto a curved sheet type product. In one embodiment, the glass plate itself can be a phosphor plate, or can have sections of different phosphor materials deposited in a pattern that will align / match with corresponding positions of opposing electrodes on each resonator. In one embodiment, the sheet product can be a laminate type product applied to, for example, a nominally white object. Upon solar irradiation, the infrared portion of the solar spectrum (which nominally only heats the surface) will produce intensified electric field regions. In these regions, down-conversion phosphors that convert deep blue and ultraviolet light to visible light will convert the deep blue and ultraviolet light of the solar spectrum to visible light, and the intensified electric field will be strengthened into more powerful visible light emission.

[0140] In one embodiment, the energy enhancer may be Figure 7B The perforations in one embodiment are in an intensified electric field region so that phosphor or other energy conversion material or device can be disposed in the perforations.

[0141] In one embodiment (concerning color enhancement), the sheet product can be a laminated type product applied to, for example, a nominally green object. Upon solar irradiation, the infrared portion of the solar spectrum (which nominally heats only the surface) generates regions of enhanced electric fields. In these regions, down-conversion phosphors that convert blue, deep blue, and ultraviolet light to green convert the blue, deep blue, and ultraviolet light of the solar spectrum to green light, and the enhanced electric fields intensify into a more powerful green emission.

[0142] In one embodiment, the sheet product can be a laminated type product applied to, for example, a nominally red object. Upon solar irradiation, the infrared portion of the solar spectrum (which nominally only heats the surface) generates regions of intensified electric fields. In these regions, down-conversion phosphors that convert green, blue, deep blue, and ultraviolet light to red convert the green, blue, deep blue, and ultraviolet light of the solar spectrum to red light, and the intensified electric field intensifies into a more powerful red emission.

[0143] In one embodiment, Figure 7C As shown, the energy enhancers can be provided on a sheet and then divided into different small pieces that can be easily added and mixed into the medium to be treated.

[0144] Figure 8 is shown distributed on a plane or otherwise along the surface of an object and having an orientation different from that in FIG. 7 Figure 2 shows the pattern of the folded resonator 22. By having different orientations, the electric field may not be aligned in a way that helps drive the The rotated polarization of the folded resonator will cause its electric field to align in a way that helps drive the resonator in a different orientation and thus a better alignment. Therefore, if a sheet type product is used, multiple layers of differently oriented The folded resonators are stacked together.

[0145] Figure 9 is a diagram showing an energy converter, luminescent or electron emitting material, or color emitting or color converter material (ie, emissive material 24) deposited in the region between the opposing electrodes. Figure 2 is a diagram of a pattern of a folded resonator 22. Here, although shown in a plan view, the color conversion or reinforcement material deposited in the region between the opposing electrodes may be deposited so that the color conversion or reinforcement material has a The upper surface of the folded resonator is raised above the metal trace. In this embodiment, the raised section intercepts the fringe fields of the intensified electric field between the opposing electrodes.

[0146] Figure 10 is a diagram showing an energy converter, luminescent or electron emitting material, or color emitting or color converter material (ie, emissive material 24) deposited in the region between the opposing electrodes. Figure 2 shows a pattern of folded resonator 22. Here, as before, the color conversion or reinforcement material deposited in the region between the opposing electrodes may be deposited such that the color conversion or reinforcement material has a The upper surface of the folded resonator is raised above the metal trace. In this embodiment, the raised section intercepts the fringe fields of the intensified electric field between the opposing electrodes. In this embodiment, the raised section extends around the corners, where geometrically the corners further intensify the electric field.

[0147] Figure 11 is a diagram showing an energy converter, luminescent or electron emitting material, or color emitting or color converter material (ie, emissive material 24) deposited in the region between the opposing electrodes. Figure 2 shows a pattern of folded resonator 22. Here, as before, the color conversion or reinforcement material deposited in the region between the opposing electrodes may be deposited such that the color conversion or reinforcement material has a The upper surface of the folded resonator is raised above the metal trace. In this embodiment, the raised section intercepts the fringe fields of the intensified electric field between the opposing electrodes. In this embodiment, the raised section extends around the corner, where geometrically, the corner further intensifies the electric field and extends around the end of the opposing electrode.

[0148] exist Figure 9 、 Figure 10 and Figure 11In the embodiments shown, an energy converter, or luminescent or electron emitting material, or color emitting or color converter material (i.e., emissive material 24) is disposed on one or more energy enhancing structures (i.e., folded resonator). Therefore, the energy enhancement structure is preferably in an enhanced electric field region. In particular, in the presence of a current flow that conductively couples the energy converter to an energy enhancement structure, the enhanced electric field can represent an enhanced energy region. In later embodiments, conductively coupling the energy converter to an energy enhancement structure has multiple advantages. Therefore, arranging the energy converter, or the color conversion or reinforcement material near one or more energy enhancement structures can have a physical conductive connection between the energy converter and at least one energy enhancement structure. Alternatively, the coupling can be more of a radiation or capacitive coupling of the electric field from the resonant structure to an energy converter, or a color conversion or reinforcement material that is arranged inside the energy enhancement structure, outside the energy enhancement structure, in a layer with the energy enhancement structure, or in a layer above or below the energy enhancement structure.

[0149] As used herein, "in proximity" refers to the placement of one thing within, outside, adjacent to, or adjacent to the structure of another thing, and can include placement of one thing above or below another thing in any three-dimensional direction. Thus, in one embodiment of the present invention, the color-converting or enhancing material is disposed in proximity to the energy-enhancing structure.

[0150] Figure 12 is a fractal pattern showing a metal trace having an electrical path for looping to connect to a counter electrode. Figure 3 shows the pattern of the folded resonator 30. The fractal pattern of the electrical path with this pattern means that the metal traces can The characteristic supports various wavelength resonances due to the diversity of possible loop paths available, as the width of each segment of the conductive path can vary in width, permitting electrical paths of different physical lengths around the loop.

[0151] Figure 13 A diagram of another fractal antenna segment 32 is shown, where the straight sides of the metal spacers have locally enhanced electric field regions 24. Here, in one embodiment, the fractal antenna segment is designed to resonate in the infrared range, where the enhanced electric field regions 34 (e.g., toward the straight sides of the metal spacers as shown) are where blue and red phosphors (or other emissive materials 24) may be deposited so that their emission is enhanced by the enhanced electric fields in those regions 34.

[0152] Figure 14 It shows Figure 13FIG. 1 is a diagram of a repeating pattern (array) of fractal antenna segments 32 .

[0153] Figure 15 is a diagram showing a pattern (array) of bow-tie fractal antenna segments, thereby providing Figure 14 An alternative embodiment of a fractal antenna segment.

[0154] In one embodiment of the present invention, the resonant structure may comprise a three-dimensional fractal pattern. It is known in the art to fabricate three-dimensional fractal structures by nanoscale anisotropic etching of silicon, such as described by Brian Wang in Nanoscale Etching of Three-Dimensional Fractal Structures, June 22, 2013, Journal of Micromechanics and Microengineering (available at www.nextbigfuture.com / 2013 / 06 / nanoscale-etching-of-3d-fractal.html), many applications of which include three-dimensional fractal antennas and structures for filters, the entire contents of which are incorporated herein by reference. In one embodiment of the present invention, metal is deposited on a siliceous three-dimensional fractal structure to form a multidimensional light collector.

[0155] Figure 16 3D fractal structures are shown with a pair of three-dimensional fractal structures having an enhanced electric field region 34 between the pairs. The paired three-dimensional fractal structures are color-enhancing structures according to one embodiment of the present invention. In one embodiment of the present invention, these pyramidal structures are metallized by metallizing opposing faces, forming a first loop conductor around the other side of the first pyramid, then connecting across the region between the pair, and then forming a second loop around the sides of the second pyramid based on the metallized opposing faces of the second pyramid to simulate (as viewed from above) Figure 3 shown Folded resonator.

[0156] In one embodiment, the converter (emitter) material 24 will be located adjacent to different sections of the pyramidal structure, and preferably between the pair of opposing faces where the enhanced electric field (indicated by the arrows) exists. With respect to the three-dimensional aspect of the invention, the red, yellow, green, and blue converters (or other designated emitters) can be located at different levels within this enhanced electric field region.

[0157] Figure 17 It shows Figure 16 Figure 1 shows a pattern (array) of paired three-dimensional fractal structures.

[0158] exist Figures 12 to 17In the embodiments shown, an energy converter, or luminescent or electron emitting material, or color emitting or color converter material (i.e., emissive material 24) is disposed on one or more energy enhancing structures (i.e., folded resonator). Therefore, the energy enhancement structure is preferably in an enhanced electric field region. In particular, in the presence of a current flow that conductively couples the energy converter to an energy enhancement structure, the enhanced electric field can represent an enhanced energy region. In later embodiments, conductively coupling the energy converter to an energy enhancement structure has multiple advantages. Therefore, arranging the energy converter, or the luminescent or electron emitting material, or the color emitting or color converter material near one or more energy enhancement structures can have a physical conductive connection between the energy converter and at least one energy enhancement structure. Alternatively, the coupling can be more of a radiation coupling of the electric field from the resonant structure to the energy converter, or the color conversion or reinforcing material arranged inside the energy enhancement structure, outside the energy enhancement structure, in a layer with the energy enhancement structure, or in a layer above or below the energy enhancement structure.

[0159] The energy enhancement structures are not limited to those shown above. Other variations are possible. In addition, in one embodiment of the present invention, The folded resonator does not need to have Figure 3 As shown, the "folded section" is folded inward. Alternatively, as Figure 18 As shown, the present invention The resonator may have a folded section that folds outward, wherein the enhanced electric field region is outside the "loop" of the resonator. The distal end of the antenna protrudes outward while maintaining parallelism. Specifically, Figure 8 yes Schematic diagram of external electrode type folded resonator 22. This external opposing electrode pair design follows Figures 5 to 11 General configuration, scaling aspects, converter material placement, etc. shown, but with inner fold sections replaced by outer electrode pairs.

[0160] In one embodiment of the present invention, The external electrode type folded resonators 22 provide the ability to be packaged in a concentric arrangement with gradually increasing or decreasing resonator size. These resonators are maintained in a flat surface without overlapping distal ends. Figure 19 Multiple concentric Schematic diagram of the external electrode type folded resonator 22. Each of the external electrode type folded resonators 22 has a different electrical length, so the multiple concentric The external electrode-type resonators are "tuned" to different wavelengths associated with the respective electrical lengths. Three different frequencies are thus focused between the distal ends of the antenna.

[0161] In another embodiment, Figure 20 Multiple concentric electrodes with overlapping electrodes Schematic diagram of an external electrode type folded resonator 22. In one embodiment, the overlap provides a Figure 19 More concentrated / enhanced field areas in a non-overlapping arrangement.

[0162] The present invention is not limited to Figure 19 or Figure 20 The planar concentric packaging arrangement shown. Figure 20 The three different 3 / 4 wavelength resonators in the antenna are maintained in a plane with overlapping distal ends. The antennas are inductively coupled. In one embodiment, the present invention utilizes an off-plane configuration with axial symmetry, wherein the antennas are in an axially rotated, multi-frequency, interwoven 3 / 4 wave resonator structure. Figure 21 is a schematic diagram of an axially rotated, multi-frequency, interwoven 3 / 4 wave resonator 22 showing (in this example) three different sized resonators arranged about / along a common axis but axially rotated for multi-frequency resonance. In one embodiment, in this configuration, the resulting electric field is concentrated without one electrode segment disrupting the electric field of another electrode segment.

[0163] In another embodiment, an energy collector is provided, comprising: at least one energy enhancing structure; and at least one energy converter, wherein the at least one energy converter is capable of receiving applied electromagnetic energy, converting the applied electromagnetic energy and emitting electromagnetic energy having a wavelength or energy shifted relative to the applied electromagnetic energy from the at least one energy converter, and the energy converter is arranged near the at least one energy enhancing structure so that the emitted electromagnetic energy is emitted with at least one enhanced property compared to a case where the energy converter is away from the at least one energy enhancing structure.

[0164] In one embodiment, the present invention may use different layers to The resonator is set on it, regardless of whether the resonator is Internal folded resonator or External electrode type resonator. Figure 22 and Figure 23 Such packaging is shown in FIG for a configuration in which the distal ends are folded inwards or protruded outwards, respectively, and lie in parallel planes.

[0165] In the present invention Figure 20 Shown as having multiple concentric In the embodiment of the external electrode type resonator 22, the antenna is inductively decoupled. This configuration allows the electric field from three different frequencies to be focused on a longer path. This configuration can be used to create a mirror configuration to extend the Figure 24A The length of the focused electric field is shown.

[0166] The resonator configuration in this case is mirrored with another set of antennas (folded resonator 22) to produce a longer path (doubled) of the focused electric field. Figure 24B As shown, the resonant body antenna configuration can be positioned in more creative ways to enhance the electric field focused around the target.

[0167] The configuration in FIG25 allows the target to be surrounded within the plane of the resonant structure / antenna for heating and focusing energy around the target. This prevents heat dissipation in silicon where thermal conductivity is high. The silicon substrate in this example can be single crystal, polycrystalline, or amorphous.

[0168] In one embodiment of the present invention, "energy-enhancing structures" refer to structures in which spatial regions of an energy collector comprise converter materials (or other luminescent or electron-emitting materials) exposed to energy that stimulates emission of light at a different energy (wavelength) from the converter materials exposed to said energy, while being in a spatial region / volume (e.g., between, around, or near a folded structure or external electrode pair) where there is an artificially induced higher electric field and / or higher energy density. These artificial regions can be created, for example, by using structures including, but not limited to, multi-faceted collector devices, resonators, fractal antennas, and grid (or electrode) patterns.

[0169] By placing a luminescent or electron-emitting material in the vicinity of the energy-enhancing structure of the present invention, whether the energy-enhancing structure is in the enhanced electric field region or otherwise outside the enhanced electric field region, the energy-enhancing structure of the present invention is able to generate light, which can be used in various applications, particularly for photostimulation of biological, chemical and physical reactions, such as, for example, photoactivation of photoreactive drugs, photoactivation of photosensitive materials such as adhesives or lithographic photoresists, or direct interaction with biological and chemical agents in the environment of the enhancement structure, as in sterilization.

[0170] In one embodiment, the light-emitting or electron-emitting material mentioned above is provided together with an energy enhancement structure, which includes one or more of the following: an electromagnetic resonant body structure, a folded resonant body structure, and a fractal resonant structure, any of which has a region of enhanced electromagnetic field within the resonant structure.

[0171] In one embodiment, the energy converter, or luminescent or electron emitting material mentioned above comprises one or more luminescent materials. As described herein, there is use of energy enhancement structure and / or energy collector embodiments that enhance bioluminescence, chemiluminescence, photoluminescence, fluorescence, force-induced luminescence and / or electron emission.

[0172] In one embodiment, for one or more luminescent materials, the energy converters or luminescent materials mentioned above include phosphorescent materials, fluorescent materials, electroluminescent materials, chemiluminescent materials, bioluminescent materials, and mechanoluminescent materials used with or without the energy-enhancing structures mentioned above. When used in conjunction with the energy-enhancing structures mentioned above, the emitted electromagnetic energy from the luminescent material is emitted with at least one enhanced property compared to when the energy converter (e.g., luminescent material) is away from the at least one energy-enhancing structure.

[0173] In one embodiment, the bioluminescent material is a UV-emitting bioluminescent material, such as catalytic luciferase and photoprotein.

[0174] In one embodiment, the energy converter or luminescent material mentioned above includes phosphorescent materials, fluorescent materials, electroluminescent materials, chemiluminescent materials, bioluminescent materials, and force-induced luminescent materials used in conjunction with or without the energy-enhancing structure mentioned above, and emitting one of ultraviolet light, visible light, near-infrared light, and infrared light. In this embodiment, UV-emitting electroluminescent materials or force-induced luminescent devices and materials can be used. In this embodiment, UV-emitting bioluminescent materials can be used.

[0175] In some embodiments, the metal pattern forms a folded resonant body with opposing electrodes, the electric field is oriented between the opposing electrodes, and the converter is positioned between the opposing electrodes, or within the fringe electric field of the opposing electrodes, or otherwise positioned near the opposing electrodes. In one example, the folded resonant body is Folded resonator. In one example, the metal pattern includes at least one of the following: Au, Ag, Cu, Al, or a transparent metal oxide. In another example, the metal pattern may be formed of a refractory metal such as Ti, W, and Mo.

[0176] In some embodiments, the metal pattern mentioned above includes an outer electrode pair structure having opposing electrodes, the electric field is oriented between the opposing electrodes, and the converter is positioned between the opposing electrodes, or positioned within the fringe electric field of the opposing electrodes, or otherwise positioned near the opposing electrodes. In one example, the resonator is The external electrode pair resonator. In one example, the metal pattern includes at least one of the following: Au, Ag, Cu, Al, or a transparent metal oxide. In another example, the metal pattern can be formed of a refractory metal such as Ti, W, and Mo.

[0177] In some embodiments, multiple resonators and multiple converters are positioned at multiple locations throughout the light collector. In one example, the multiple converters are positioned to convert light that is internally scattered within the light collector.

[0178] In some embodiments of the energy-enhancing structure, the first-level metal pattern (or second-level metal pattern) comprises a metal core clad with a high-K dielectric, followed by a cladding layer of a low-K dielectric. In some embodiments of the energy-enhancing structure, the first-level metal pattern (or second-level metal pattern) mentioned above comprises a radial conductor pattern. In some embodiments of the energy-enhancing structure, the first-level metal pattern (or second-level metal pattern) mentioned above comprises a fractal pattern. In one example, the fractal pattern is embedded within the dielectric material.

[0179] In some embodiments of the energy enhancement structure, the first level metal pattern (or the second level metal pattern) mentioned above comprises a three-dimensional fractal structure.

[0180] In some embodiments of the energy enhancement structure, a panel is provided, the panel having a first layer metal pattern and a second layer metal pattern, and optionally a plurality of converters formed in or on the metal patterns. In some embodiments of the enhancement structure, a sheet is provided, the sheet having a first layer metal pattern and a second layer metal pattern, and optionally a plurality of converters formed in or on the metal patterns.

[0181] In some embodiments of the energy enhancement structure, the above-mentioned first level metal patterns (or second level metal patterns) have different sizes and / or orientations relative to each other or relative to the second level metal patterns.

[0182] In another embodiment, the energy enhancing body can collect or distribute light.

[0183] Figure 25A Schematic diagram of the distributed point light collector / emitter of the present invention, showing the distribution of branches that can collect light from the distribution point 710 or conversely distribute light from the central source 766 to the distribution point 710. Figure 25BA section of a collector / emitter is shown in , which shows the core metal, optional light converter material, high K dielectric, and low K dielectric. In this arrangement, as shown, the light is confined and there are no losses other than scattering into the collector / emitter at the ends.

[0184] B. Energy Converter

[0185] In various embodiments of the present invention, energy converters may be used with or without the energy enhancers described above. In some embodiments, the converters are used to upconvert light, such as converting light from the IR state to visible electromagnetic radiation, and to downconvert light, such as converting light from the UV range to visible electromagnetic radiation. In various embodiments, the present invention upconverts energy, preferably light in the visible spectrum. The present invention contemplates various applications in which upconversion and downconversion materials are included with or without energy enhancers to enhance electromagnetic energy emission, preferably light or photon emission. When an energy enhancer is present, the energy enhancer may be separate from or attached to the energy converter. In certain embodiments, the energy converter may be formed on the surface of the energy converter by chemical vapor deposition ("CVD") or physical vapor deposition ("PVD") processes or other nanoscale "printing" methods. Such embodiments may be particularly useful in methods for treating human or animal patients, where "imprinting" such energy enhancers on the surface of the energy converter ensures proximity between the energy enhancer and the energy converter to maximize interaction with the applied energy. Alternatively, the energy-enhancing agent can be formed on the surface of an inert, non-energy-converting particle, such as one formed of silicon dioxide or one coated with a biologically and / or chemically inert coating (e.g., diamond, diamond-like carbon, or a similar inert material). Such an energy-enhancing agent can then be co-administered with the energy-converting agent to a human or animal patient.

[0186] Suitable energy modulation agents or energy converters (the two terms are used interchangeably herein) of the present invention include, but are not limited to, biocompatible fluorescent metal nanoparticles, fluorescent dye molecules, gold nanoparticles, water-soluble quantum dots encapsulated by polyamidoamine dendrimers, luciferase (bioluminescence), biocompatible phosphorescent molecules, combined electromagnetic energy capture molecules, and lanthanide chelates capable of strong luminescence.

[0187] Alternatively, energy modulation agent or energy converter can emit the energy in the form suitable for absorbing at target site or receptor.For example, the initial energy source can be acoustic energy, and an energy converter may be able to receive acoustic energy and emit the photon energy (for example, ultrasonic luminescent molecule) that will be received by another energy converter that can receive photon energy.Other examples include receiving the energy at x-ray wavelength and emitting the energy converter at UV wavelength, preferably at UV-A wavelength.A plurality of such energy converters can be used to form a cascade to transfer energy from the initial energy source via a series of energy converters.

[0188] Resonant Energy Transfer (RET) is an energy transfer mechanism between two molecules with overlapping emission and absorption bands. Electromagnetic emitters are able to convert the incoming wavelength to a longer wavelength. For example, UV-B energy absorbed by a first molecule can be transferred to a UV-A emitting molecule in close proximity to the UV-B absorbing molecule through dipole-dipole interactions. Alternatively, materials that absorb shorter wavelengths can be selected to provide RET for a non-emissive molecule that has an absorption band that overlaps with the emission band of the transfer molecule. Alternatively, phosphorescence, chemiluminescence, or bioluminescence can be used to transfer energy to a target site or receptor, such as a photoactivatable agent.

[0189] In other embodiments, biocompatible emitting sources such as fluorescent metal nanoparticles or fluorescent dye molecules are selected as energy converters emitting in the UV-A band. In another embodiment, the energy converter comprising a UV-A emitting source can be gold nanoparticles comprising, for example, clusters of 5 gold atoms.

[0190] In another embodiment, an energy converter comprising a UV emitting or luminescent luciferase is selected as an emission source. Luciferase can be combined with ATP or another molecule and then oxidized with additional molecules to stimulate light emission at a desired wavelength. Alternatively, a phosphorescent emission source can be used as an energy converter. One advantage of a phosphorescent emission source is that the phosphorescent emitting molecule or other source can be electrically activated or photoactivated before being inserted into a tumor or directly into the area of ​​the tumor by systemic administration. Phosphorescent materials can have longer relaxation times than fluorescent materials because the relaxation of triplet states is subject to forbidden energy state transitions, thereby storing energy in excited triplet states, and only a limited number of quantum mechanical energy transfer processes can be used to return to lower energy states. There is a delay or extension in energy emission ranging from a fraction of a second to several hours. In addition, the energy emitted during phosphorescent relaxation is otherwise no different from fluorescence, and the wavelength range can be selected by selecting a specific phosphor.

[0191] In one embodiment, the energy converter of the present invention may include a persistent afterglow phosphor material that emits light in the visible to near-ultraviolet and ultraviolet range. In one embodiment, a strontium aluminate salt doped with Eu is used as an energy converter, wherein deep UV light or x-rays or electron beams "charge" the photoluminescence, so that these phosphors can be charged, for example, outside the patient and then injected into a target or diseased area that will emit UV photons. In another embodiment, a strontium magnesium aluminate salt is used as an energy converter, wherein deep UV light or x-rays or electron beams "charge" the photoluminescence, so that these phosphors can be charged, for example, outside the patient and then injected into a target or diseased area that will emit UV photons. U.S. Patent Application Publication No. 20070221883 (the entire contents of which are incorporated herein by reference) specifically describes a strontium magnesium aluminate salt activated by gadolinium, which has an excitation maximum at about 172 nm and emits as a narrow-band UV emission at about 310 nm. The '883 publication also describes other energy converters that can be used in the present invention, whereby a method for Sr(Al,Mg) 12 O 19 : The emission spectrum of the Gd phosphor between 300nm and 320nm, and the two 312nm lines of the emitting phosphor YMgB5O 10 :Gd, Ce and YMgB5O 10 : Gd, Ce, Pr. WO2016200349 (the entire contents of which are incorporated herein by reference) describes a persistent yellow-green light-emitting phosphorescent pigment in a strontium aluminate salt (SrAl2O4) system, which can be used as an energy converter in the present invention. WO2016200348 (the entire contents of which are incorporated herein by reference) describes a persistent blue-green light-emitting phosphorescent pigment in a strontium aluminate salt (Sr4Al14O25) system, which can be used as an energy converter in the present invention. “Recent advances in ultraviolet persistent phosphors,” Optical Materials X 2 (2019) by Xiong et al. (the entire contents of which are incorporated herein by reference) describes a variety of ultraviolet afterglow phosphors that can be used as energy converters in the present invention. The following table provides a list of such afterglow phosphors:

[0192]

[0193] In one embodiment, the CaAl2O4:CeO4 catalyst described by Xiong et al. can be used. 3+ A phosphor having an emission peak at 400 nm and a duration of more than 10 hours, wherein the phosphor can be charged by x-ray irradiation outside the patient and then injected into the diseased area to provide internally generated UV light.

[0194] In one embodiment, the afterglow phosphors mentioned can be activated in vitro and introduced into the patient's body along with psoralen (or other photoactivatable drug) by exchange of body fluids, or, for example, by supplying the afterglow phosphor and photoactivatable drug into the patient's bloodstream.

[0195] In one embodiment, the mentioned afterglow phosphors can be activated in vivo by injecting the phosphor into the diseased area followed by exposure to x-rays.

[0196] In another embodiment, a combined electromagnetic energy capture molecule is designed, such as the combined light capture molecule disclosed in J.Am.Chem.Soc.2005,127,9760-9768, the entire contents of which are incorporated herein by reference. By combining a group of fluorescent molecules in a molecular structure, a resonant energy transfer cascade can be used to capture broadband electromagnetic radiation, resulting in the emission of narrowband fluorescent energy. In another embodiment, the Stokes shift of an emission source or a series of emission sources arranged in a cascade is selected to convert shorter wavelength energy such as X-rays into longer wavelength fluorescent emissions such as optical or UV-A emissions.

[0197] In one embodiment, a lanthanide chelate capable of strong luminescence is used as the energy converter. In another embodiment, a biocompatible endogenous fluorophore emitter is selected as the energy converter.

[0198] In one embodiment, the energy converter of the present invention can include visible light and UV light emitting bioluminescent materials. In one embodiment, bioluminescent materials such as coelenterate type luciferin analogs can be used, including amide monoanions known to emit at 480nm and oxyluciferin known to emit at 395nm.

[0199] Among various materials, luminescent nanoparticles have caused more and more technical and industrial concerns. In the context of the present invention, nanoparticles refer to particles less than one micron in size. Although the specification of the present invention has described the specific examples using nanoparticles, in many embodiments, the present invention is not limited to particles less than one micron in size. However, in many embodiments, less than one micron, and especially less than the size range of 100nm can produce particularly interesting properties, such as emission lifetime luminescence quenching, quantum luminescence efficiency and concentration quenching, and such as diffusion, penetration and dispersion in media where larger particles cannot migrate.

[0200] In various embodiments, the present invention can use various down conversion materials (or the mixture of down conversion materials) to strengthen light or photon emission with or without energy enhancer.These down conversion materials can comprise quantum dot, semiconductor material, the alloy of semiconductor material, scintillating material and phosphor material, the material that shows X-ray excited luminescence (XEOL), organic solid, metal complex, inorganic solid, crystal, rare earth material (lanthanide), polymer, scintillator, phosphor material etc. and the material that shows exciton property.Therefore, the down conversion material that is used to strengthen light or photon emission can be by the energy conversion of one in ultraviolet light, x-ray and high energy particle into visible light.The down conversion material that is used to strengthen light or photon emission can be by energy from higher energy visible light conversion to lower energy visible light.

[0201] In one embodiment of the present invention, a quantum dot mixture can be used with or without an energy enhancer for multiple nanoparticles. Quantum dots are typically nanometer-sized particles whose energy state in the material of the quantum dot depends on the size of the quantum dot. For example, quantum dots are known to be semiconductors whose conductive properties are closely related to the size and shape of the individual crystals. Generally speaking, the smaller the size of the crystal, the larger the band gap, and the greater the energy difference between the highest valence band and the lowest conduction band. Therefore, more energy is required to excite the quantum dot, and at the same time, more energy is released when the crystal returns to its resting state. In fluorescent dye applications, this is equivalent to emitting higher frequency light after exciting the quantum dot as the crystal size becomes smaller, which results in a color shift from red to blue in the emitted light. Quantum dots represent a way to convert ultraviolet light in the spectrum to a target wavelength or energy emission. Quantum dots represent a way to convert blue light in the spectrum to a target wavelength or energy emission.

[0202] As described in U.S. Patent No. 6,744,960 (incorporated by reference in its entirety), quantum dots of different sizes produce different color emissions. In their research and applicable to the present invention, quantum dots can comprise various materials, including semiconductors such as zinc selenide (ZnSe), cadmium selenide (CdSe), cadmium sulfide (CdS), indium arsenide (InAs), and indium phosphide (InP). Another material that can be appropriately employed is titanium dioxide (TiO2). The size of the particles (i.e., quantum dots 18) can range from about 2 to 10 nm. Because the size of these particles is so small, quantum physics determines many of the electrical and optical properties of quantum dots. One such result of applying quantum mechanics to quantum dots 18 is that quantum dots absorb a broad spectrum of optical wavelengths and re-emit radiation with a wavelength longer than the wavelength of the absorbed light. The wavelength of the emitted light is determined by the size of the quantum dots. For example, a CdSe quantum dot with a diameter of 5.0 nm emits radiation with a narrow spectral distribution centered at about 625 nm, while a quantum dot 18 comprising a CdSe having a size of 2.2 nm emits light having a central wavelength of about 500 nm. Semiconductor quantum dots comprising CdSe, InP, and InAs can emit radiation with a central wavelength ranging from 400 nm to about 1.5 μm. Titanium dioxide TiO2 also emits within this range. The line width of the emission of these semiconductor materials, i.e., the full width at half maximum (FWHM), can range from about 20 to 30 nm. In order to produce this narrowband emission, the quantum dots only need to absorb light having a wavelength shorter than the wavelength of the light emitted by the quantum dots. For example, for a CdSe quantum dot with a diameter of 5.0 nm, light having a wavelength shorter than about 625 nm is absorbed to produce emission at about 625 nm, while for a 2.2 nm quantum dot comprising CdSe, light having a wavelength less than about 500 nm is absorbed and re-emitted at about 500 nm. In practice, however, the excitation or pump radiation is at least about 50 nanometers shorter than the emitted radiation.

[0203] Specifically, in one embodiment of the present invention, a quantum dot mixture (QDM) coating can be deposited using standard precipitation techniques using CVD and / or sol-gel techniques. The QDM coating can be made of a silicate structure that does not attenuate UV output. Within the silicate family, silicon dioxide (SiO2) is suitable because it maximizes UV transmission through the coating. The coating can also include a second layer of biocompatible glass. Such biocompatible glass and glass-ceramic compositions can contain calcium, lanthanides or yttrium, silicon, phosphorus, and oxygen. Other biocompatible materials and technologies are described in the following patents, which are incorporated herein in their entirety: U.S. Patent Nos. 5,034,353; 4,786,617; 3,981,736; 3,922,155; 4,120,730; and U.S. Patent Application Nos. 2008 / 0057096; 2006 / 0275368; and 2010 / 0023101.

[0204] In addition, the down conversion materials described herein of the present invention can be coated with an insulating material, such as silicon dioxide, which will reduce the possibility of any chemical interaction between the luminescent particles and the medium in which these particles are included. These and other conversion materials described herein can be used with or without energy enhancers. One of the main limiting factors for biocompatible applications of inorganic nanoparticles is their toxicity. In general, all semiconductor nanoparticles are more or less toxic. For biocompatible applications, nanoparticles with as low toxicity as possible are desired, otherwise the nanoparticles must be kept separate from the medium. Pure TiO2, ZnO and Fe2O3 are biocompatible. CdTe and CdSe are toxic, while ZnS, CaS, BaS, SrS and Y2O3 have less toxicity. In addition, the toxicity of the nanoparticles may come from their inorganic stabilizers, such as TGA, or from dopants, such as Eu 2+ Cr 3+ or Nd 3+ Other suitable down-conversion materials that may appear to be the most biocompatible are zinc sulfide, ZnS:Mn 2+ , iron oxide, titanium oxide, zinc oxide, zinc oxide containing a small amount of Al2O3, and AgI nanoclusters encapsulated in zeolites. For non-medical applications where toxicity may not be a critical issue, the following materials (and those listed elsewhere) are considered suitable: lanthanum and gadolinium oxyhalides activated with thulium, Er-doped 3+ BaTiO3 nanoparticles, doped with Yb 3+ CsMnCl3 and RbMnCl3, BaFBr:Eu 2+ Nanoparticles, cesium iodide, bismuth germanate, cadmium tungstate, and CsBr doped with divalent Eu.

[0205] In various embodiments of the present invention, the following light-emitting polymers are also suitable as conversion materials with or without energy enhancers: poly(p-phenylene vinylene), poly(p-phenylene ethylene), poly(p-phenylene), poly(thiophene), poly(pyridine vinylene), poly(pyrrole), poly(acetylene), poly(vinylcarbazole), poly(fluorene), etc., as well as their copolymers and / or derivatives.

[0206] In various embodiments of the present invention, the following materials can be used in a manner similar to that detailed in U.S. Patent No. 7,090,355 with or without an energy enhancer, the entire contents of which are incorporated herein by reference. For down conversion, the following materials can be used. Inorganic or ceramic phosphors or nanoparticles, including but not limited to: metal oxides, metal halides, metal chalcogenides (e.g., metal sulfides) or mixtures thereof, such as metal oxygen halides, metal oxygen chalcogenides. Laser dyes and organic small molecules, and fluorescent organic polymers. Semiconductor nanoparticles, such as II-VI or III-V compound semiconductors, such as fluorescent quantum dots. Metal organic molecules, including at least one metal center, such as rare earth elements (e.g., Eu, Tb, Ce, Er, Tm, Pr, Ho) and transition metal elements, such as Cr, Mn, Zn, Ir, Ru, V, and main group elements, such as B, Al, Ga, etc. The metal element is chemically bonded to the organic group to prevent fluorescence quenching in the matrix or solvent. Phosphors that can be used include those from the garnet series: (Y m A 1-m )3(Al n B 1-n )5O 12 , doped with Ce; where 0≦m, n≦1, where A includes other rare earth elements, and B includes B and Ga. Furthermore, phosphors containing metal silicates, metal borates, metal phosphates, and metal aluminates can be used. Furthermore, nanoparticle phosphors containing common rare earth elements (e.g., Eu, Tb, Ce, Dy, Er, Pr, and Tm) and transition elements or main group elements (e.g., Mn, Cr, Ti, Ag, Cu, Zn, Bi, Pb, Sn, and Tl) as fluorescent activators can be used. Materials such as tungstates containing Ca, Zn, Cd, etc., metal vanadates, and ZnO can be used.

[0207] Commercial laser dye materials available from several laser dye suppliers, including Lambda Physik and Exciton, can also be used with or without an energy enhancer. A partial list of preferred laser dye classes includes: pyrromethene, coumarin, rhodamine, fluorescein, other aromatic hydrocarbons and their derivatives, etc. In addition, there are many polymers containing unsaturated carbon-carbon bonds that are also used as fluorescent materials and have many optical and fluorescent applications. For example, MEH-PPV, PPV, etc. have been used in optoelectronic devices, such as polymer light emitting diodes (PLEDs). Such fluorescent polymers can be used directly as the fluorescent layer of transparent 2-D display screens with or without an energy enhancer.

[0208] As mentioned above, semiconductor nanoparticles (for example, quantum dots) can be used with or without energy enhancers. The term "semiconductor nanoparticles" refers to an inorganic grain with a diameter between 1nm and 1000nm, preferably between 2nm and 50nm in this area. Semiconductor nanoparticles can emit electromagnetic radiation (that is, semiconductor nanoparticles are luminous) after excitation. Nanoparticles can be homogeneous nanocrystals, or include multiple shells. For example, nanoparticles can include the "core" of one or more first semiconductor materials, and can be surrounded by the "shell" of a second semiconductor material. The core and / or shell can be semiconductor materials, including but not limited to those of the following groups: II-VI (ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, etc.) and III-V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, etc.) and IV (Ge, Si, etc.) materials, as well as alloys or mixtures thereof.

[0209] Fluorescent metallo-organic molecules containing rare earth or transition element cations can be used in down-conversion materials with or without energy enhancers. Such molecules include a metal center of a rare earth element (including Eu, Tb, Er, Tm, and Ce) protected by an organic chelate group. The metal center can also include transition elements such as Zn, Mn, Cr, and Ir, as well as main-group elements such as B, Al, and Ga. Such metallo-organic molecules can be readily dissolved in liquids or transparent solid matrix media. Some examples of such fluorescent metallo-organic molecules include: 1. Tris(dibenzoylmethane)mono(phenanthroline)europium(III); 2. Tris(8-hydroxyquinolinolato)erbium; 3. Tris(1-phenyl-3-methyl-4-(2,2-dimethylpropane-1-yl)pyrazol-5-one)terbium(III); 4. Bis(2-methyl-8-hydroxyquinolinolato)zinc; and 5. Diphenylborane-8-hydroxyquinoline.

[0210] The specific examples of the down-conversion material for red light emission include those materials and europium complex discussed above, such as those described in Japanese Patent Publication (Kokai) No. 2003-26969, and the europium complex is constructed so that a beta-diketone ligand is coordinated to europium, thereby forming a europium complex that can emit red fluorescence. Other specific examples of rare earth element complexes include complexes comprising the following: lanthanum (Ln), europium (Eu), terbium (Tb) and gadolinium (Gd) and combinations thereof. Europium (Eu) complex can emit red fluorescence when the ultraviolet irradiation is 365nm to 410nm with a wavelength range. Terbium (Tb) can emit green fluorescence when the ultraviolet irradiation is 365nm with a wavelength.

[0211] In other down-conversion embodiments, the down-conversion material that emits red light may include europium, the luminescent particles that emit green light may include terbium, and the luminescent particles that emit blue or yellow light may include cerium (and / or thulium). In an up-conversion embodiment, the up-conversion material that emits red light may include praseodymium, the luminescent particles that emit green light may include erbium, and the luminescent particles that emit blue light may include thulium. In an embodiment, the conversion material may be a luminescent particle composed of fluorescent molecules that emit different colors (e.g., red, green, and blue), or light of different wavelengths or energies. In an embodiment, the conversion material may be a luminescent particle made of a pure organic dye or a metal organic dye with or without an energy enhancer.

[0212] In addition to combinations of rare earth complexes such as a europium complex and a terbium complex, it is also possible to use a europium complex in combination with a non-complex green-light-emitting fluorescent substance, or a terbium complex in combination with a non-complex red-light-emitting fluorescent substance.

[0213] Other down converter materials (which may be used with or without an energy enhancer) include, for example, ZnS, PbS, SbS3, MoS2, PbTe, PbSe, BeO, MgO, Li2CO3, Ca(OH)2, MoO3, SiO2, Al2O3, TeO2, SnO2, KBr, KCl, and NaCl. As mentioned above, these materials may include dopants to adjust the emission properties. Examples of suitable doped (or alloyed) glass systems include: Y2O3:Gd, Y2O3:Dy, Y2O3:Tb, Y2O3:Ho, Y2O3:Er, Y2O3:Tm, Gd2O3:Eu, Y2O2S:Pr, Y2O2S:Sm, Y2O2S:Eu, Y2O2S:Tb, Y2O2S:Ho, Y2O2S:Er, Y2O2S:Dy, Y2O2S:Tm, ZnS:Ag:Cl (blue), ZnS:Cu:Al (green), Y2O2S:Eu (red), Y2O3:Eu (red), YVO4:Eu (red), and Zn2SiO4:Mn (green).

[0214] More specifically with respect to down-converter materials suitable for the present invention, U.S. Patent No. 4,705,952 (the contents of which are hereby incorporated by reference herein) describes a phosphor triggered by infrared light that stores energy in the form of visible light of a first wavelength and releases energy in the form of visible light of a second wavelength when triggered by infrared light. The phosphor in U.S. Patent No. 4,705,952 is a composition of alkaline earth metal sulfides, rare earth dopants, and fusible salts. The phosphor in U.S. Patent No. 4,705,952 is more specifically a phosphor made of: strontium sulfide, barium sulfide, and mixtures thereof; including dopants from the rare earth group and europium oxide, and mixtures thereof; and including fusible salts of: fluorides, chlorides, bromides, and iodides of lithium, sodium, potassium, cesium, magnesium, calcium, strontium, and barium, and mixtures thereof. The materials described in U.S. Patent No. 4,705,952 can be used in various embodiments of the present invention with or without energy enhancers. In one example, an infrared-triggered phosphor would be used in conjunction with a folded resonator, and reception of a microwave or IR signal would locally heat and trigger emission. (This application may be particularly well-suited for color enhancement and / or security applications.)

[0215] In other embodiments of the present invention, the down-converter material (or mixture of down-converter materials) (which may be used with or without an energy enhancer) may include Y2O3:Li. Sun et al., “Luminescent properties of Li+doped nanosized Y2O3:Eu,” Solid State Comm. 119 (2001) 393-396 (incorporated herein by reference in its entirety) describe such materials. Hou et al., “Luminescent properties nano-sized Y2O3:Eu fabricated by co-precipitation method,” Journal of Alloys and Compounds, Vol. 494, No. 1-2, April 2, 2010, pp. 382-385 (incorporated herein by reference in its entirety) describe nano-sized yttrium oxide (Y2O3) powder that has been successfully synthesized by a co-precipitation method. The powder is well crystallized, and the grains are approximately spherical, with good dispersibility. Eu 3+ The quenching concentration of Li+ ions is 9 mol%, which is much higher than that of micro-scale powders. The incorporation of Li+ ions greatly improves the luminescence intensity. 0.87 Eu 0.09 Li 0.04 The highest emission intensity was observed under )2O3), and the fluorescence intensity increased by up to 79%. Yi et al. "Improved cathodoluminescent characteristics of Y2O3:Eu 3+ thin films by Li-doping," Appl. Phys. A 87, 667–671 (2007) (incorporated herein by reference in its entirety) describes Y2O3:Eu 3+ and Li-doped Y2O3:Eu 3+ Cathodoluminescence spectra of both films and methods of making these materials.

[0216] Specific down-conversion materials can also include at least one or more of the following: Y2O3, Y2O3:Gd, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, YbF3 doped with Na, ZnS, ZnSe, MgS, CaS, Zn2SiO4:Mn, LaOBr:Tm and lead alkali silicates of compositions comprising SiO2, B2O3, Na2O, K2O, PbO, MgO or Ag, and combinations or alloys or layers thereof. In addition, the down-conversion material can be a sulfur-containing phosphor, which can, for example, assist in rubber vulcanization or other photoactivation processes. An example of such a sulfur-containing phosphor is: (Sr,Ca)Ga2S4. Other examples of the phosphor particles include thiogallate matrix materials selected from the group consisting of SrGa2S4, CaGa2S4, BaGa2S4, MgGa2S4 and solid solutions thereof. As described in US6153123A, the particle size of such phosphors can be controlled to be in the range of 25nm to 300 microns. The down-conversion material may include a dopant including at least one of Er, Eu, Yb, Tm, Nd, Mn, Sb, Tb, Ce, Y, U, Pr, La, Gd and other rare earth species or combinations thereof. The dopant may be included in a concentration of 0.01% to 50% by molar concentration. Sometimes, it is preferred to have a combination of dopants rather than just one, as is the case in silicate matrices containing Mn and Sb.

[0217] In other embodiments, the present invention can use a variety of up-conversion materials (or mixtures of up-converters) with or without energy enhancers to enhance light of a specific wavelength or energy emitted from a certain material or surface. These up-conversion materials can include similar materials as discussed above with respect to down-conversion, but are typically included in the matrix crystal in a doped or impurity state that provides an up-conversion pumping mechanism. Thus, up-conversion materials for enhancing wavelength or energy emission can convert energy from one of near-infrared, infrared, and microwave radiation. Up-conversion materials for enhancing color emission can convert energy from lower energy visible light to higher energy visible light.

[0218] In one example, nanoparticles of lanthanide oxide doped particles can be excited with near-infrared light, such as lasers at 980 nm and 808 nm, to produce visible light in different parts of the red, green, and blue spectrum (different wavelengths or energies), depending on the selected dopant trivalent rare earth ion or ions, their concentrations, and the matrix lattice.

[0219] The lanthanide-doped oxides suitable for the present invention differ from more conventional multi-photon upconversion processes, where absorption of, for example, two photons is required in a simultaneous event to drive an electron from a valence state directly into a high-level conduction band state, where relaxation across the band gap of the material produces fluorescence. Here, co-doping creates multiple states in the band gap of NaYF4, such that Yb 3+ Ions have a potential to be pumped by single photon events. 2 F 5 / 2 energy state, and other single photon absorption events can be gathered from this to even higher states. Once in this excited state, it is possible to transition to a higher energy radiative state, from which the light emission will be in a comparative 2 F 5 / 2 In other words, the incident light in the Yb 3+ Ionic 2 F 5 / 2 The energy state is to absorb 980nm light, thereby allowing the establishment of a certain aggregate for transition to a higher energy state, such as 4 F 7 / 2 The state of the foundation of the energy state. Here, it starts from 4 F 7 / 2 Transitions in energy states produce visible emission.

[0220] U.S. Patent No. 7,008,559 (incorporated herein by reference in its entirety) describes the up-conversion properties of ZnS, wherein excitation at 767 nm produces emission in the visible range. The materials described in U.S. Patent No. 7,008,559 (including ZnS, and doped with Er) 3+ BaTiO3 nanoparticles and Yb-doped 3+ CsMnCl3) with or without energy enhancers is suitable in various embodiments of the present invention.

[0221] In addition, materials specified for upconversion materials in the present invention (with or without energy enhancement) include CdTe, CdSe, ZnO, CdS, Y2O3, MgS, CaS, SrS and BaS. Such upconversion materials can be any semiconductor, and more specifically, but not limited to, sulfide, telluride, selenide and oxide semiconductors and their nanoparticles, such as ZnO. 1-x Mn x S y 、Zn 1-x Mn x Se y 、Zn 1-x Mn x Te y 、Cd 1-x MnSy , Cd 1-x , Mn x , Se y , Cd 1-x , Mn x , Te y , Pb 1-x , Mn x , S y , Pb 1- x , Mn x , Se y , Pb 1-x , Mn x , Te y , Mg 1-x , MnS y , Ca 1-x , Mn x , S y , Ba 1-x , Mn x y, S y and Sr 1-x etc. (where 0 < x ≤ 1 and 0 < y ≤ 1). The complexes of the semiconductors described above are also expected to be useful in the present invention - for example (M 1-z N z ) 1-x , Mn x A 1-y B y (M = Zn, Cd, Pb, Ca, Ba, Sr, Mg; N = Zn, Cd, Pb, Ca, Ba, Sr, Mg; A = S, Se, Te, O; B = S, Se, Te, O; 0 < x ≤ 1, 0 < y ≤ 1, 0 < z ≤ 1). Two examples of such complexes are Zn 0.4 Cd[[ID=跟65]] 0.4 , Mn[[ID=跟67]] 0.2 , S and Zn 0.9 , Mn 0..1 [[ID=跟72]], S 0.8 , Se 0.2 . Additional conversion materials include insulating and non-conductive materials such as BaF2, BaFBr, and BaTiO3, to name just a few exemplary compounds. Semiconductors suitable for co-doping with transition ions and rare earth ions in the present invention include sulfide, telluride, selenide, and oxide semiconductors and their nanoparticles such as ZnS; Mn; Er; ZnSe; Mn, Er; MgS; Mn, Er; CaS; Mn, Er; ZnS; Mn, Yb; ZnSe; Mn, Yb; MgS; Mn, Yb; CaS; Mn, Yb, etc., and their complexes: (M[[ID=跟77]] 1-z [[ID=跟78]]N[[ID=跟79]] z [[ID=跟80]])[[ID=跟81]] 1-x [[ID=跟82]] (Mn[[ID=跟83]] q [[ID=跟84]]R[[ID=跟85]] 1-q [[ID=跟86]])x A 1-y B y (M=Zn, Cd, Pb, Ca, Ba, Sr, Mg; N=Zn, Cd, Pb, Ca, Ba, Sr, Mg; A=S, Se, Te, O; B=S,...0 <z < 1, o < 1).

[0222] Some nanoparticles, such as ZnS:Tb 3+ 、Er 3+ ; ZnS:Tb 3+ ;Y2O3:Tb 3+ ;Y2O3:Tb 3+ 、Er3 + ; ZnS:Mn 2+ ; ZnS:Mn, Er 3+ In the art are known for both down-conversion luminescence and up-conversion luminescence, and will be suitable for the present invention with or without an energy enhancer. In an up-conversion embodiment, the luminescent particle emitting red light may include praseodymium, the luminescent particle emitting green light may include erbium, and the luminescent particle emitting blue light may include thulium.

[0223] ​In general, the upconversion process typically requires doping a dielectric crystal (of any size > 0.1 nm) with one or more rare earth dopants such as Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd, and other rare earth species or combinations thereof, comprising at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2, wherein the incident radiation is at a longer wavelength than the emitted radiation from the crystal. The wavelength emitted is entirely dependent on the selected dopant ion(s), and their association and relative concentration in the host crystal. For the example of upconversion in a Y2O3 matrix crystal, to achieve blue emission (approximately 450–480 nm), one can synthesize [Y2O3; Yb(3%), Tm(0.2%)], where the percentages of Yb and Tm doped in the crystal are those achieved relative to 100% Y atoms. Similarly, typical green upconversion materials are [Y2O3; Yb(5%), Ho(1%)] and [Y2O3; Yb(2%), Er(1%)], and typical red upconversion materials are [Y2O3; Yb(10%), Er(1%)] and [Y2O3; Yb(5%), Eu(1%)]. The concentrations of the dopants relative to each other and the crystal matrix must be adjusted for each combination, and there are multiple ways to achieve multiple wavelengths or energies of emission from even the same dopant.

[0224] In the doping of Tm 3+ Upconversion of red light at a wavelength of approximately 650 nm in a fluorozirconate glass can be used in the present invention to generate blue light. In this system, the blue light consists of two emission bands; one at 450 nm attributed to the 1D2→3H4 transition and the other at 475 nm attributed to the 1G4→3H6 transition. Others have observed that the emission intensity of both bands varies quadratically with excitation power. For Tm 3+ For glasses with a concentration of 0.2 mol % and above, cross-relaxation processes occur, which reduces the upconversion efficiency.

[0225] Already in LuPO4:Yb 3+ 、Tm 3+ and YbPO4:Er 3+ Nanocrystals have been observed to emit visible light upon excitation with near-infrared (NIR) light in optically clear colloidal solutions in chloroform. Others have shown that excitation at 975 nm can produce visible emission in the blue, green, or red spectral regions.

[0226] Tellurium and germanium oxides (tellurites and germanates) are also suitable upconverters. For example, these glasses can be doped with Tm, Yb, Ho, Er, Pr.

[0227] Yb-doped 3+ BaZrO3 is also suitable for up-conversion. 3+ and / or Tm 3+ Doping is also suitable for tuning the emission wavelength.

[0228] In another embodiment, Nd prepared by the Morss method 3+ :Cs2NaGdCl6 and Nd 3+ 、Yb 3+ Cs2NaGdCl6 polycrystalline powder samples have been reported to be upconverters and are suitable for the present invention. These materials have shown that upconversion emissions close to 538nm (green), 603nm (orange) and 675nm (red) have been observed under 785nm irradiation, and the upconversion emissions have been assigned to 4G7 / 2→4I9 / 2, (4G7 / 2→4I11 / 2; 4G5 / 2→4I9 / 2) and (4G7 / 2→4I13 / 2; 4G5 / 2→4I11 / 2) respectively.

[0229] In another embodiment, Nd-based 3+ and Ho 3+ Co-doped ZrF4 fluoride glass has been reported to be an upconverter and is suitable for the present invention. In the upconversion luminescence of ZrF4 fluoride glass, it can be seen that the green emission is extremely strong, while the blue and red emission intensities are very weak.

[0230] In another embodiment, the co-doped Tm 3+ / Yb 3+ TeO2-Ga2O3-R2O (R = Li, Na, K) glasses have been reported to be upconverters and are suitable for the present invention. These materials exhibit strong blue upconversion emission centered at 476 nm under 977 nm excitation, accompanied by weak red emission at 650 nm.

[0231] In another embodiment, [Ru(dmb)]3] 2+(dmb = 4,4 - dimethyl - 2,2’ - bipyridine) The metal - to - ligand charge - transfer (MLCT) transition that occurs in the presence of anthracene or 9,10 - diphenylanthracene has been reported to be an up - converter and is suitable for the present invention. The up - converted singlet fluorescence has been reported to be caused by triplet - triplet annihilation at low excitation powers. In particular, 9,10 - diphenylanthracene (DPA) (substituted anthracene) shows higher up - conversion efficiency. In these experiments, workers using this material system speculated that DPA increased the singlet fluorescence quantum yield ( = 0.95) relative to anthracene ( = 0.27). This effect brought about an approximate 24.4 ± 6.1 enhancement of green - to - blue up - conversion, thus permitting the process to be directly visualized at low excitation powers, for example, by a commercial green laser pen ( <5 mW peak power).

[0232] In certain embodiments, additional energy converters include, but are not limited to (listed without preference or utility ranking):

[0233] CaF2, ZnF2, KMgF3, ZnGa2O4, ZnAl2O4, Zn2SiO4, Zn2GeO4, Ca5(PO4)3F, Sr5(PO4)3F, CaSiO3, MgSiO3, ZnS, MgGa2O4, LaAl 11 O 18 、Zn2SiO4, Ca5(PO4)3F, Mg4Ta2O9, CaF2, LiAl5O8, LiAlO2, CaPO3, AlF3, and LuPO4:Pr 3+ . Examples also include alkaline earth chalcogenide phosphors, which are illustrated in turn by the following non - inclusive list: MgS:Eu 3+ 、CaS:Mn 2+ 、CaS:Cu, CaS:Sb, CaS:Ce 3+ 、CaS:Eu 2+ 、CaS:Eu 2 + Ce 3+ 、CaS:Sm 3+ 、CaS:Pb 2+ 、CaO:Mn 2+ 、CaO:Pb 2+ .

[0234] Additional examples include ZnS - type phosphors, covering various derivatives: ZnS:Cu,Al(Cl), ZnS:Cl(Al), ZnS:Cu,I(Cl), ZnS:Cu, ZnS:Cu,In.

[0235] Also included are IIIb-Vb compound phosphors, which include elements from Group IIIb and Group Vb of the periodic table. These semiconductors include BN, BP, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb, and these materials may include donors and acceptors that work together to trigger a light-emitting diode. These donors include, but are not limited to, Li, Sn, Si, Li, Te, Se, S, and O, and acceptors include, but are not limited to, C, Be, Mg, Zn, Cd, Si, and Ge. Also included are primary GaP light-emitting diodes, including, but not limited to, GaP:Zn,O, GaP:NN, GaP:N, and GaP, which emit red, yellow, green, and pure green, respectively.

[0236] The material may also include materials such as GaAs with the following composition variations: In 1-y (Ga 1- x Al x ) y P.

[0237] Also included is silicon carbide (SiC), which has commercial relevance as a light-emitting platform in blue light-emitting diodes. These include the polytypes 3C-SiC, 6H-SiC, 4H-SiC, which have donors such as N and Al, and acceptors such as Ga and B.

[0238] Additional examples include multi-band luminescent materials, including but not limited to the following compositions: (Sr,Ca,Ba)5(PO4)3Cl:Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ 、CeMgAl 11 O 19 :Ce 3+ :Tb 3+ 、LaPO4:Ce 3+ :Tb 3+ 、GdMgB5O 10 :Ce3:Tb 3+ 、Y2O3:Eu 3+ 、(Ba,Ca,Mg)5(PO4)3Cl:Eu 2+ , 2SrO 0.84 P2O50.16B2O3:Eu 2+ 、Sr4Al 14 O 25 :Eu 2+ .

[0239] Also included are materials commonly used in fluorescent high-pressure mercury discharge lamps. These materials can be excited with X-rays and are exemplified by the following family names: Phosphates (Sr,M)(PO4)2:Sn 2+ , Mg or Zn activator, germanate 4MgO.GeO2:Mn 4+ 、4(MgO,MgF2)GeO2:Mn 4+ , yttrium salt Y2O3:Eu 3+ , vanadate YVO4:Eu 3+ 、Y(P,V)O4:Eu 3+ 、Y(P,V)O4:In + , halogenated silicate Sr2Si3O 82 SrCl2:Eu 2+ 、Aluminate (Ba,Mg)2Al 16 O 24 :Eu 2+ 、(Ba,Mg)2Al 16 O 24 :Eu 2+ 、Mn 2+ 、Y2O3Al2O3:Tb 3+ .

[0240] Another grouping using matrix compounds includes halophosphate phosphors, phosphate phosphors, silicate phosphors, aluminate phosphors, borate phosphors, tungstate phosphors, and other chemical components in phosphors. Halophosphates include but are not limited to: 3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ 、3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ / Mn 2+ 、Sr 10 (PO4)6Cl2:Eu 2+ 、(Sr,Ca) 10 (PO4)6Cl2:Eu 2+ 、(Sr,Ca) 10 (PO4)6.nB2O3:Eu 3+ 、(Sr,Ca,Mg) 10 (PO4)6Cl2:Eu 2+ Phosphate phosphors include but are not limited to: Sr2P2O7:Sn 2+ 、(Sr,Mg)3(PO4)2:Sn 2+ 、Ca3(PO4)2.Sn 2+ 、Ca3(PO4)2:Tl + 、(Ca,Zn)3(PO4)2:Tl + 、Sr2P2O7:Eu2+ 、SrMgP2O7:Eu 2+ 、Sr3(PO4)2:Eu 2+ 、LaPO4:Ce 3 + 、Tb 3+ 、La2O3.0.2SiO2.0.9P2O5:Ce 3+ .Tb 3+ 、BaO.TiO2.P2O5. Silicate phosphor Zn2SiO4:Mn 2+ 、CaSiO3:Pb 2+ / Mn 2+ 、(Ba,Sr,Mg).3Si2O7:Pb 2+ 、BaSi2O5:Pb 2+ 、Sr2Si3O8·2SrCl2:Eu 2+ 、Ba3MgSi2O8:Eu 2+ 、(Sr,Ba)Al2Si2O8:Eu 2+ .

[0241] Aluminate phosphors include but are not limited to: LiAlO2:Fe 3+ 、BaAl8O 13 :Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、Sr4Al 14 O 25 :Eu 2+ 、CeMgAl 11 O 19 :Ce 3+ / Tb 3+ .

[0242] Borate phosphors include: Cd2B2O5:Mn 2+ 、SrB4O7F:Eu 2+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ 、GdMgB5O 10 :Ce 3 + / Mn 3+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ / Mn 2+.

[0243] Tungstate phosphors include but are not limited to: CaWO4, (Ca, Pb) WO4, MgWO4. Other phosphors Y2O3:Eu 3+ 、Y(V,P)O4:Eu 2+ 、YVO4:Dy 3+ 、MgGa2O4:Mn 2+ 、6MgO.As2O5:Mn 2+ 、3.5MgO.0.5MgF2.GeO2:Mn 4+ .

[0244] Activators of various doped phosphors include but are not limited to: Tl + , Pb 2+ 、Ce 3+ 、Eu 2+ WO4 2- 、Sn 2+ 、Sb 3+ 、Mn 2+ 、Tb 3+ 、Eu 3+ 、Mn 4+ 、Fe 3+ . Luminescence center Tl + Used with chemical compositions such as: (Ca,Zn)3(PO4)2:Tl + 、Ca3(PO4)2:Tl + . Luminescence center Mn 2+ Used with chemical compositions such as: MgGa2O4:Mn 2 + 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、Zn2SiO4:Mn 2+ 、3Ca3(PO4)2.Ca(F,Cl)2:Sb 2+ / Mn 2+ 、CaSiO3:Pb 2+ / Mn 2+ 、Cd2B2O5:Mn 2+ 、CdB2O5:Mn 2+ 、GdMgB5O 10 :Ce 3+ / Mn 2+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ / Mn 2+The luminescent center Sn2+ is used with chemical compositions such as: Sr2P2O7:Sn 2+ 、(Sr,Mg)3(PO4)2:Sn 2+ Luminescent center Eu 2+ Used with chemistries such as: SrB4O7F:Eu 2+ 、(Sr,Ba)Al2Si2O8:Eu 2+ 、Sr3(PO4)2:Eu 2+ 、Sr2P2O7:Eu 2+ 、Ba3MgSi2O8:Eu 2+ 、Sr 10 (PO4)6Cl2:Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、(Sr,Ca) 10 (PO4)6Cl2:Eu 2+ . Luminescence center Pb 2+ Used with chemical compositions such as: (Ba,Mg,Zn)3Si2O7:Pb 2+ 、BaSi2O5:Pb 2+ 、(Ba,Sr)3Si2O7:Pb 2+ .

[0245] Luminescence center Sb 2+ Used with chemical compositions such as: 3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ 、3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ / Mn 2+ .

[0246] Luminescence center Tb 3+ Used with chemical compositions such as: CeMgAl 11 O 19 :Ce 3+ / Tb 3+ 、LaPO4:Ce 3+ / Tb 3+ 、Y2SiO5:Ce 3+ / Tb 3+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ Luminescent center Eu 3+ Used with chemical compositions such as: Y2O3:Eu 3+、Y(V,P)O4:Eu 3+ . Luminescence center Dy 3+ Used with chemical compositions such as: YVO4:Dy 3+ . Luminescent center Fe 3+ For use with chemistries such as: LiAlO2:Fe 3+ . Luminescence center Mn 4+ Used with chemical compositions such as: 6MgO.As2O5:Mn 4+ 、3.5MgO0.5MgF2.GeO2:Mn 4+ . Luminescence center Ce 3+ Used with chemical compositions such as: Ca2MgSi2O7:Ce 3+ and Y2SiO5:Ce 3+ . Luminescence center WO4 2- Used with chemical components such as: CaWO4, (Ca, Pb) WO4, MgWO4. Luminescent center TiO4 4- Used with chemical compositions such as: BaO.TiO2.P2O5.

[0247] Additional phosphor chemistries of interest using X-ray excitation include, but are not limited to, the k-edges of these phosphors. Low energy excitation can lead to strong luminescence in materials with low k-edges. Some of these chemistries and their corresponding k-edges are listed below:

[0248]

[0249]

[0250] These materials can be used alone or in combination of two or more. Various compositions can be prepared to obtain a desired output wavelength or wavelength spectrum.

[0251] In the present invention, the phosphor selection may be selected so that under irradiation with x-rays or other high energy sources, the light emitted from the phosphor may have exemplary properties including, for example:

[0252] Emitting in the wavelength range of 190-250nm;

[0253] Emitting in the wavelength range of 330-340nm;

[0254] Mechanoluminescent materials (organic and inorganic):

[0255] In another embodiment of the present invention, a mechanoluminescent material may be used as an energy converter, and optionally may be used in conjunction with the energy enhancing structures described above.

[0256] Mechanoluminescent materials convert ultrasonic or mechanical energy (such as vibrations naturally present in an object such as a motor, or vibrations driven by a transducer) into visible light. Here, for example, the mechanoluminescent material would be placed near (e.g., between, around, or within) the folded structure or the external electrode pair.

[0257] In one embodiment, the electromagnetic wave energy enhancer captures electromagnetic energy of one or more wavelengths and enhances the electromagnetic energy of one or more wavelengths in terms of at least one property (such as the electric field intensity near the mechanoluminescent material), while the mechanoluminescent material can be regarded as an energy converter that converts ultrasonic or mechanical energy into electromagnetic radiation (i.e., emits light).

[0258] In one embodiment of the invention, an increased electric field in the folded structure or external electrode pair increases the luminescence of the mechanoluminescent material. The energy for establishing the electric field in the folded structure or external electrode pair is provided separately from the mechanical energy driving the mechanoluminescence.

[0259] Various mechanoluminescent materials suitable for the present invention include, with or without energy enhancers, ZnS:Mn 2+ 、SrAl2O4:Eu 2+ 、ZnS:Cu、SrAMgSi2O7:Eu 2+ (A=Ca, Sr, Ba), KCl, KI, KBr, NaF, NaCl, LiF, RbCl, RbBr, RbI, MgO, SrAl2O4, CaAl2O4, Sr 1-x Ba x Al2O4 (x=0, 0.1, 0.2, 0.4), Sr 0.9 Ca 0.1 Al2O4、Zn2Ge 0.9 Si 0.1 O4, MgGa2O4, ZnGa2O4, ZnAl2O4, ZnS, ZnTe, (ZnS) 1-x (MnTe) x (x<1 / 4), CaZnOS, BaZnOS, Ca2MgSi2O7, Sr2MgSi2O7, Ba2MgSi2O7, SrCaMgSi2O7, SrBaMgSi2O7, Sr n MgSi2O 5+n (1≤n≤2), Ca2Al2SiO7, Sr2Al2SiO7, CaYAl3O7, CaAl2Si2O8, Ca 1-x Sr x Al2Si2O8(x<0.8), SrMg2(PO4)2, Ba1-x Ca x TiO3(0.25 <x<0.8)、Ba 1-x Ca x TiO3, LiNbO3, Sr2SnO4, (Ca,Sr,Ba)2SnO4, Sr3Sn2O7, Sr3(Sn,Si)2O7, Sr3(Sn,Ge)2O7 , Ca3Ti2O7, CaNb2O6, Ca2Nb2O7, Ca3Nb2O8, BaSi2O2N2, SrSi2O2N2, CaZr(PO4)2, ZrO2.

[0260] In one embodiment, co-doped europium-holmium strontium aluminate can be used alone or in combination with an energy enhancer as a mechanoluminescent material (i.e., an energy converter). Co-doped europium-holmium strontium aluminate and other mechanoluminescent materials convert sonic energy or acoustic energy into photon emission, and the materials may or may not be placed near the energy enhancer.

[0261] Yanim Jia, in “Novel Mechano-Luminescent Sensors Based on Piezoelectric / Electroluminescent Composites,” Sensors (Basel). 2011; 11(4): 3962–396 (incorporated by reference in its entirety), describes a mechanoluminescent composite material made of a piezoelectric material and an electroluminescent material. In this composite device, when stress is applied to the piezoelectric layer, charges are induced on both the top and bottom surfaces of the piezoelectric layer due to the piezoelectric effect. These induced charges generate light output from the electroluminescent layer due to the electroluminescent effect.

[0262] Here, in one embodiment of the present invention with or without an energy enhancer, such a composite material made of a piezoelectric material and an electroluminescent material (hereinafter referred to as a "composite mesoluminescent emitter") provides a structure that emits light when stimulated with mechanical or vibrational energy, such as from an acoustic or ultrasonic transducer.

[0263] Electroluminescent and phosphorescent materials (organic and inorganic): In various embodiments, the present invention may utilize organic fluorescent molecules or inorganic particles capable of fluorescence and phosphorescence having crystalline, polycrystalline, or amorphous microstructures for use in converters (optionally including the energy-enhancing structures described above).

[0264] A list of inorganic molecules that can be used in the electroluminescent and phosphorescent materials described below, with or without energy enhancers, includes, but is not limited to, the following inorganic electroluminescent phosphor materials:

[0265] SrS:Ce 3+

[0266] CaGa2S4:Ce 3+

[0267] SrS:Cu +

[0268] CaS:Pb 2+

[0269] BaAl2S4:Eu 2+

[0270] ZnS:Tb 3+

[0271] ZnMgS:Mn 2+

[0272] SrGa2S4:Eu 2+

[0273] CaAl2S4:Eu 2+

[0274] BaAl2S4:Eu 2+

[0275] ZnS:Mn 2+

[0276] MgGa2O4:Eu 3+

[0277] (Ca,Sr)Y2S4:Eu 2+

[0278] BaAl2S4:Eu 2+

[0279] Organic molecules that can emit phosphorescence under the influence of an electric field are also of interest in this application. As examples, organic fluorescent compounds with high quantum yields include:

[0280] Naphthalene,

[0281] Pyrene,

[0282] Perylene,

[0283] Anthracene,

[0284] Philippines,

[0285] p-terphenyl,

[0286] Tetraphenyl,

[0287] trans-stilbene,

[0288] Tetraphenylbutadiene,

[0289] Distyrylbenzene,

[0290] 2,5-diphenyloxazole,

[0291] 4-Methyl-7-diethylaminocoumarin,

[0292] 2-phenyl-5-(4-biphenyl)-1,3,4-oxadiazole,

[0293] 3-phenylcarbonylstyryl,

[0294] 1,3,5-Triphenyl-2-pyrazoline,

[0295] 1,8-Naphthoylene-1',2'-benzimidazole,

[0296] 4-Amino-N-phenyl-naphthalimide.

[0297] The inorganic fluorescent and phosphorescent materials detailed herein are numerous and various examples are given as examples and not by way of limitation and may be used with or without energy enhancers. In addition, these materials may be doped with specific ions (activators or combinations of activators) that occupy sites in the lattice structure in the case of crystalline or polycrystalline materials and may occupy network-forming sites or bridging and / or non-bridging sites in amorphous materials. These compounds may include (not listed in order of preference or utility) the following examples of materials:

[0298] CaF2, ZnF2, KMgF3, ZnGa2O4, ZnAl2O4, Zn2SiO4, Zn2GeO4, Ca5(PO4)3F, Sr5(PO4)3F, CaSiO3, MgSiO3, ZnS, MgGa2O4, LaAl 11 O 18 , Zn2SiO4, Ca5(PO4)3F, Mg4Ta2O9, CaF2, LiAl5O8, LiAlO2, CaPO3, AlF3.

[0299] Also included are alkaline earth chalcogenide phosphors, which in turn are exemplified by the following non-inclusive list:

[0300] MgS:Eu 3+ 、CaS:Mn 2+ 、CaS:Cu、CaS:Sb、CaS:Ce 3+ 、CaS:Eu 2+ 、CaS:Eu 2+ Ce 3+ 、CaS:Sm 3+ 、CaS:Pb 2+ 、CaO:Mn2+ 、CaO:Pb 2+ .

[0301] Examples include ZnS type phosphors, including various derivatives:

[0302] ZnS:Cu,Al(Cl), ZnS:Cl(Al), ZnS:Cu,I(Cl), ZnS:Cu, ZnS:Cu,In.

[0303] IIIb-Vb compound phosphors, comprising elements from Groups IIIb and Vb of the periodic table, are suitable converter materials. These semiconductors include BN, BP, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb. These materials also have donors and acceptors that work together to create a light-emitting diode. Donors include Li, Sn, Si, Li, Te, Se, S, and O, while acceptors include C, Be, Mg, Zn, Cd, Si, and Ge. As an example, GaP light-emitting diodes include GaP:Zn,O, GaP:NN, GaP:N, and GaP, which emit red, yellow, green, and pure green, respectively.

[0304] Composite materials also include materials such as GaAs with compositional variations of the following kind: In1-y(Ga1-xAlx)yP (to provide a simple example).

[0305] Silicon carbide (SiC) is commercially relevant as a light-emitting platform in blue light-emitting diodes. These include the polytypes 3C-SiC, 6H-SiC, and 4H-SiC, which have donors such as N and Al, and acceptors such as Ga and B.

[0306] Multi-band luminescent materials suitable for converter materials include, for example, the following components:

[0307] (Sr,Ca,Ba)5(PO4)3Cl:Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ 、CeMgAl 11 O 19 :Ce 3+ :Tb 3+ 、LaPO4:Ce 3+ :Tb 3+ 、GdMgB5O 10 :Ce 3+ :Tb 3+ 、Y2O3:Eu 3+ 、(Ba,Ca,Mg)5(PO4)3Cl:Eu2+ , 2SrO 0.84 P2O5·0.16B2O3:Eu 2 + 、Sr4Al 14 O 25 :Eu 2+ .

[0308] Other materials suitable for converter materials include those used for fluorescent high-pressure mercury discharge lamps, which can be excited with X-rays and are exemplified by the following family names:

[0309] Phosphate (Sr,M)(PO4)2:Sn 2+ , Mg or Zn activator, germanate 4MgO.GeO2:Mn 4+ 、4(MgO,MgF2)GeO2:Mn 4+ , yttrium salt Y2O3:Eu 3+ , vanadate YVO4:Eu 3+ 、Y(P,V)O4:Eu 3+ 、Y(P,V)O4:In + , halogenated silicate Sr2Si3O8·2SrCl2:Eu 2+ 、Aluminate (Ba,Mg)2Al 16 O 24 :Eu 2+ 、(Ba,Mg)2Al 16 O 24 :Eu 2+ 、Mn 2+ 、Y2O3Al2O3:Tb 3+ .

[0310] Another material grouping that utilizes a matrix compound suitable for converter materials includes halophosphate phosphors, phosphate phosphors, silicate phosphors, aluminate phosphors, borate phosphors, tungstate phosphors, and chemical components found in other phosphors.

[0311] Illustrative halophosphates include:

[0312] 3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ 、3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ / Mn 2+ 、Sr 10 (PO4)6Cl2:Eu 2+ 、(Sr,Ca) 10 (PO4)6Cl2:Eu 2+ 、(Sr,Ca) 10(PO4)6.nB2O3:Eu 3+ 、(Sr,Ca,Mg) 10 (PO4)6Cl2:Eu 2+ As an example, the phosphate phosphor includes: Sr2P2O7:Sn 2+ 、(Sr,Mg)3(PO4)2:Sn 2+ 、Ca3(PO4)2.Sn 2+ 、Ca3(PO4)2:Tl + 、(Ca,Zn)3(PO4)2:Tl + 、Sr2P2O7:Eu 2+ 、SrMgP2O7:Eu 2+ 、Sr3(PO4)2:Eu 2+ 、LaPO4:Ce 3+ 、Tb 3+ 、La2O3·0.2SiO2·0.9P2O5:Ce 3+ .Tb 3+ 、BaO.TiO2·P2O5. Silicate phosphor Zn2SiO4:Mn 2+ 、CaSiO3:Pb 2+ / Mn 2 + 、(Ba,Sr,Mg).3Si2O7:Pb 2+ 、BaSi2O5:Pb 2+ 、Sr2Si3O8·2SrCl2:Eu 2+ 、Ba3MgSi2O8:Eu 2+ 、(Sr,Ba)Al2Si2O8:Eu 2+ .

[0313] Aluminate phosphors include:

[0314] LiAlO2:Fe 3+ 、BaAl8O 13 :Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、Sr4Al 14 O 25 :Eu 2+ 、CeMgAl 11 O 19 :Ce 3+ / Tb 3+ .

[0315] Borate phosphors include:

[0316] Cd2B2O5:Mn 2+ 、SrB4O7F:Eu 2+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ 、GdMgB5O 10 :Ce 3+ / Mn 3+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ / Mn 2+ .

[0317] Tungstate phosphors include:

[0318] CaWO4, (Ca, Pb)WO4, MgWO4. Other phosphors Y2O3:Eu 3+ 、Y(V,P)O4:Eu 2+ 、YVO4:Dy 3+ 、MgGa2O4:Mn 2+ 、6MgO.As2O5:Mn 2+ 、3.5MgO.0.5MgF2·GeO2:Mn 4+ .

[0319] Relevant activators for various doped phosphors include the following list:

[0320] Tl + , Pb 2+ 、Ce 3+ 、Eu 2+ WO4 2- 、Sn 2+ 、Sb 3+ 、Mn 2+ 、Tb 3+ 、Eu 3+ 、Mn 4+ 、Fe 3+ .

[0321] In various embodiments, the luminescent center Tl+ can be used with chemical components such as:

[0322] (Ca,Zn)3(PO4)2:Tl + 、Ca3(PO4)2:Tl + .

[0323] Similarly, the luminescent center Mn2+ can be used with chemical components such as:

[0324] MgGa2O4:Mn 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、Zn2SiO4:Mn 2+ 、3Ca3(PO4)2·Ca(F,Cl)2:Sb 2+ / Mn 2+ 、CaSiO3:Pb 2+ / Mn 2+ 、Cd2B2O5:Mn 2+ 、CdB2O5:Mn 2+ 、GdMgB5O 10 :Ce 3+ / Mn 2+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ / Mn 2+ .

[0325] In addition, the luminescence center Sn 2+ Can be used with chemical ingredients such as:

[0326] Sr2P2O7:Sn 2+ 、(Sr,Mg)3(PO4)2:Sn 2+ .

[0327] Luminescent center Eu 2+ Can also be used with chemical ingredients such as:

[0328] SrB4O7F:Eu 2+ 、(Sr,Ba)Al2Si2O8:Eu 2+ 、Sr3(PO4)2:Eu 2+ 、Sr2P2O7:Eu 2+ 、Ba3MgSi2O8:Eu 2 + 、Sr 10 (PO4)6Cl2:Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、(Sr,Ca) 10 (PO4)6Cl2:Eu 2+ .

[0329] Luminescence center Pb 2+Can be used with chemical ingredients such as:

[0330] (Ba,Mg,Zn)3Si2O7:Pb 2+ 、BaSi2O5:Pb 2+ 、(Ba,Sr)3Si2O7:Pb 2+ .

[0331] Luminescence center Sb 2+ Can be used with chemical ingredients such as:

[0332] 3Ca3(PO4)2·Ca(F,Cl)2:Sb 3+ 、3Ca3(PO4)2·Ca(F,Cl)2:Sb 3+ / Mn 2+ .

[0333] The luminescent center Tb3+ can be used with chemical components such as:

[0334] CeMgAl 11 O 19 :Ce 3+ / Tb 3+ 、LaPO4:Ce 3+ / Tb 3+ 、Y2SiO5:Ce 3+ / Tb 3+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ .

[0335] Luminescent center Eu 3+ Can be used with chemical ingredients such as:

[0336] Y2O3:Eu 3+ 、Y(V,P)O4:Eu 3+ .

[0337] Luminescence center Dy 3+ Can be used with chemical ingredients such as:

[0338] YVO4:Dy 3+ .

[0339] Luminescent center Fe 3+ Can be used with chemical ingredients such as:

[0340] LiAlO2:Fe 3+ .

[0341] Luminescence center Mn 4+Can be used with chemical ingredients such as:

[0342] 6MgO.As2O5:Mn 4+ 、3.5MgO.0.5MgF2·GeO2:Mn 4+ .

[0343] Luminescence center Ce 3+ Can be used with chemical ingredients such as:

[0344] Ca2MgSi2O7:Ce 3+ and Y2SiO5:Ce 3+ .

[0345] Luminescent center WO4 2- Can be used with chemical ingredients such as:

[0346] CaWO4, (Ca,Pb)WO4, MgWO4.

[0347] Luminescent center TiO4 4- Can be used with chemical ingredients such as:

[0348] BaO·TiO2·P2O5.

[0349] In various embodiments of the present invention, phosphor chemistries utilized in x-ray excitation can be used with or without energy enhancers. Of particular interest are the k-edges of these phosphors. Low energy excitation can result in intense luminescence from materials with low k-edges. Some of these chemistries and their corresponding k-edges include the following:

[0350] BaFCl:Eu 2+ 37.38keV

[0351] BaSO4:Eu 2+ 37.38keV

[0352] CaWO4 69.48keV

[0353] Gd2O2S:Tb 3+ 50.22keV

[0354] LaOBr:Tb 3+ 38.92keV

[0355] LaOBr:Tm 3+ 38.92keV

[0356] La2O2S:Tb 3+ 38.92keV

[0357] Y2O2S:Tb 3+ 17.04keV

[0358] YTaO4 67.42keV

[0359] YTaO4:Nb 67.42keV

[0360] ZnS:Ag 9.66keV

[0361] (Zn,Cd)S:Ag 9.66 / 26.7keV

[0362] In one embodiment of the present invention, light from these materials (e.g., by excitation with high energy particles, including x-rays, gamma rays, protons, and electrons) can be modulated by including these materials in the vicinity of (including within) the color-enhancing structures described herein. For example, in medical treatments where x-rays excite phosphors to photostimulate a response in a patient, there may be applied infrared radiation to drive the resonance of the energy-enhancing structures described herein while irradiating with high energy particles, where the x-ray phosphors will have enhanced light emission in the presence of an enhanced electric field. In another example, in medical or scientific instrumentation, there may be applied electric fields to enhance emission from these x-ray phosphors while irradiating with high energy particles.

[0363] Electroluminescent materials: Various materials used for electroluminescence in the present invention with or without energy enhancers may include but are not limited to:

[0364] 4,4′,4″-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA)

[0365] N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)

[0366] 4,4′,4″-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA)

[0367] N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)

[0368] Tris-(8-hydroxyquinolinolato)aluminum

[0369] 2,4,6-Tris(2-pyridyl)-s-triazine (TPT)

[0370]

[0371] 2,2′,2"-(1,3,5-phenylene)-tris(1-phenyl-1-H-benzimidazole)Alq

[0372]

[0373] 2,2′,2"-(1,3,5-phenylene)-tris(1-phenyl-1-H-benzimidazole)TPBI

[0374]

[0375] 2,9-Dimethyl-4,7-diphenyl-1,10-o-phenanthroline BCP 2,9-Dimethyl-4,7-diphenyl-1,10-o-phenanthroline BCP

[0376]

[0377] Plasmon-enhanced structures: Figure 26 is a schematic diagram illustrating an upconverter or downconverter material (ie, photosensitive material) for use in the color enhancement / enhancement structures referred to herein, with or without an energy enhancer, according to one embodiment of the present invention. Figure 26 A plurality of structural configurations for placing a dielectric core upconverter or downconverter material (which has nanoscale dimensions) in close proximity to a metal housing are shown. Incident light at wavelength λ1 interacts with the upconverting dielectric core. The interaction of light λ1 with the dielectric core produces secondary emission at frequency λ2, which has a shorter wavelength than λ1 and therefore has a higher energy than λ1. While the exact physical mechanism of upconversion may depend on the specific upconversion materials and processes used in a particular application, the following explanation is provided for the purposes of discussion and illustration.

[0378] exist Figure 26 In the context of λ1, three separate processes are well understood for upconversion processes involving trivalent rare earth ions when the wavelength λ1 interacts with the dielectric material core.

[0379] The three processes are:

[0380] 1) Excited-state absorption, whereby two photons are absorbed sequentially by the same ion to excite and aggregate one or more states;

[0381] 2) Energy transfer upconversion, which is the transfer of excitation from one ion to another ion that is already in an excited state; and

[0382] 3) Multiphoton cooperative processes, in which two neighboring ions in an excited state jointly emit from a virtual state.

[0383] Regardless of which of these processes occurs between the selected ion or ions and the matrix lattice, the end result is the emission of photons from the matrix lattice with energy greater than the excitation energy to perform an upconversion or downconversion process.

[0384] Therefore, the specific ions that are activated (whether they are dopant ions or matrix ions of the lattice such as in neodymium oxide) will be selected based on the matrix material being processed so that the dopant ions or matrix ions in the dielectric core provide ionic states that can be pumped by the NIR source to produce the resulting emission λ2.

[0385] Therefore, in one embodiment, the present invention provides an up-conversion or down-conversion material, which is configured to produce radiation with a second wavelength λ2 having higher or lower energy than the first wavelength λ1 when exposed to radiation with a first wavelength λ1. The system may include a metal structure (e.g., a metal shell covering a portion of the nanoparticles) disposed relative to the nanoparticles. The system may include a receptor disposed in a medium close to the nanoparticles. The receptor itself may fluoresce after being activated by the second wavelength λ2, thereby generating visible light. In one embodiment of the present invention, the physical properties of the metal structure (such as those described above and below in the accompanying drawings) are set to a certain value, wherein the surface plasmon resonance in the metal structure resonates at a certain frequency, and the frequency provides spectral overlap with the first wavelength λ1 or the second wavelength λ2. This system with a metal structure disposed relative to the up-conversion or down-conversion nanoparticles becomes a converter for the color enhancement / enhancement structure mentioned herein.

[0386] In the context of the present invention, the term "physical properties" of a metal shell or core may relate to any property of the metal itself, or of the size or shape of the shell or core, that may affect the surface plasmon resonant frequency. Such physical properties may include, but are not limited to, electrical conductivity, radial dimensions, chemical composition, or crystalline state of the metal shell or core.

[0387] In various embodiments, the metallic structure can be a metallic shell that encapsulates at least a portion of the nanoparticles in the metallic shell, wherein the electrical conductivity, radial dimensions, or crystalline state of the metallic shell causes the surface plasmon resonance in the metallic structure to resonate at a frequency that provides spectral overlap with the first wavelength λ1 or the second wavelength λ2. In various embodiments, the metallic structure can be a multilayer metallic shell that encapsulates at least a portion of the nanoparticles in the metallic shell, wherein the electrical conductivity, radial dimensions, or crystalline state of the metallic shell causes the surface plasmon resonance in the metallic structure to resonate at the first wavelength λ1 and the second wavelength λ2. This capability permits amplification of radiation at λ1 and λ2.

[0388] In various embodiments, the metal structure can be a metal particle present in one or more multiple structures. These multiple structures can have various shapes, including, for example, spherical, ellipsoidal, rod-shaped, cube, triangle, pyramidal, columnar, crescent, tetrahedral, star-shaped or its combination, arranged adjacent to the nanoparticle, wherein the electrical conductivity, size (for example, lateral dimension or thickness) or crystalline state of the metal structure make the surface plasmon resonance in the metal particle or the rod resonate with a certain frequency, and the frequency provides a spectrum overlap with the first wavelength λ 1 or the second wavelength λ 2. Such shapes are described in the accompanying drawings of the present invention and in the drawings in U.S. Serial No. 12 / 401,478, which is incorporated by reference in its entirety. Shape selection may affect the frequency of surface plasmon resonance. It is known that plasmon bands can change with the shape (for example, oblate and oblate ellipsoids) of the nanoparticle. The paper "Spectralbounds on plasmon resonances for Ag and Au prolate and oblate nanospheroids," Vol. 2, 029501 (September 26, 2008), in the Journal of Nanophotonics (incorporated by reference in its entirety), shows the shift of plasmon resonances of prolate and oblate ellipsoids in the formation of Ag and in the formation of Au. In one embodiment of the invention, as the aspect ratio of the metal structure of the invention increases, the prolate ellipsoid resonances are red-shifted relative to the sphere, with no lower limit (under the assumption of the Drude dispersion model). On the other hand, the oblate resonances are "blue-shifted" as the ellipsoid becomes increasingly flattened, but only up to a limit.

[0389] In various embodiments, the metal structure disposed relative to the up-converting or down-converting nanoparticle can be a metal structure disposed within the nanoparticle, wherein the conductivity or dimensions (e.g., lateral dimensions or thickness) of the metal structure cause the surface plasmon resonance in the metal structure to resonate at a frequency that provides spectral overlap with the first wavelength λ 1 or the second wavelength λ 2 . In various embodiments, the metal structure can be a multilayer metal structure disposed within the nanoparticle, wherein the conductivity or dimensions (e.g., lateral dimensions or thickness) of the metal structure cause the surface plasmon resonance in the metal structure to resonate at the first wavelength λ 1 and the second wavelength λ 2 . This capability again permits amplification of radiation at λ 1 and λ 2 .

[0390] In another embodiment, the invention provides nanoparticle structures comprising a dielectric core below 1000 nm and a metallic structure arranged relative to the nanoparticles. The dielectric core comprises at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2. In certain embodiments, such nanoparticle structures can exhibit surface plasmon resonance in the metallic structure to enhance up-conversion of light from a first wavelength λ1 to a second wavelength λ2.

[0391] As described above, the shell (or other structure) is specifically designed to have a layer thickness (or, for example, a lateral dimension) to enhance the photon upconversion process through plasmon enhancement. The thickness (or other physical property) of the shell is "tuned" to a thickness suitable for the absorption process by having a certain dimension at which the plasmons (i.e., electron oscillations) in the shell resonate at a frequency that provides spectral overlap with the absorption band being directed. Thus, if upconversion is to be stimulated by 980 nm NIR light, the thickness of the shell is "tuned" to a thickness at which the plasmon resonance resonates at a frequency that is also 980 nm (or around it, as plasmon resonances are generally broad at these wavelengths).

[0392] Plasmon resonant shells can be made from a variety of transition metals, including but not limited to gold, silver, platinum, palladium, nickel, ruthenium, rhenium, copper, and cobalt, or combinations or alloys or layers thereof. Such plasmon resonant shells can also be made from combinations of metals and non-metals. When formed from gold nanoshells, the recommended thickness for resonance with 980 nm light is approximately 3.5 nm surrounding an 80 nm upconversion core, as predicted by extended Mie theory calculations. (See Jain et al. , Nanolett. 2007, 7(9), 2854, the entire contents of which are incorporated herein by reference.) Figure 27 from Jain et al. and illustrates the ability of the present invention to "tune" the metal housing to have spectral overlap with the excitation and / or emission radiation wavelengths.

[0393] In one embodiment of the present invention, the metal structure provided with respect to the up-conversion or down-conversion nanoparticles may be an alloy, such as, for example, an Au:Ag alloy. The alloy content may be set to adjust the frequency of the surface plasmon resonance. In one embodiment of the present invention, the metal structure may be an alloy, such as, for example, a Pt:Ag alloy. The alloy content may be set to adjust the frequency of the surface plasmon resonance. In one embodiment of the present invention, the metal structure may be an alloy, such as, for example, a Pt:Au alloy. The alloy content may be set to adjust the frequency of the surface plasmon resonance.

[0394] In one embodiment of the present invention, the converter nanoparticles may be an alloy of two or more materials. In this embodiment, the alloy may have a composition between the two or more materials, and the composition is set to a composition value at which excitation of the alloy at a first wavelength λ1 produces emission at a second wavelength λ2. In one embodiment of the present invention, the nanoparticles may be an alloy of zinc sulfide and zinc selenide. In one embodiment of the present invention, the nanoparticles may be an alloy of zinc sulfide and cadmium sulfide.

[0395] In one embodiment of the present invention, the zinc sulfide and zinc selenide nanoparticle alloy may have an alloy content configured to provide a predetermined surface plasmon resonance. In one embodiment of the present invention, the zinc sulfide and cadmium sulfide nanoparticle alloy may have an alloy content configured to provide a predetermined surface plasmon resonance.

[0396] Some techniques for producing nanoparticles and nanoparticle alloys suitable for the present invention are described in the following documents, all of which are incorporated herein in their entirety: U.S. Patent Nos. 7,645,318; 7,615,169; 7,468,146; 7,501,092; U.S. Patent Application Publication Nos. 2009 / 0315446; 2008 / 0277270; 2008 / 0277267; 2008 / 0277268; and WO 2009 / 133138.

[0397] In one embodiment of the present invention, the thickness of the metal shell disposed relative to the upconverting or downconverting nanoparticles is set based on the absorption frequency (or in some cases, the emission frequency) of the specific dopant ions in the dielectric core to improve the overall efficiency of the upconverted light emission process. Thus, the thickness of the shell can be viewed as a tool to enhance the absorption of λ1 in one case and the emission of λ2 in another, or in other cases as an enhancing feature that jointly enhances the overall net process.

[0398] Additionally, plasmon-phonon coupling can be used to lower the resonant frequency by tuning the band to a certain degree off-resonance. This may be used to optimize the resonant energy transfer process to achieve the goal of shifting the output color to a desired color for a coating, colored, or display surface. In one example, Figure 27 An example of plasmon resonance shift as a function of shell thickness is shown.

[0399] Here, in one embodiment of the present invention, the ability to generate stimulated emission at a target wavelength, color, or energy is complemented by the ability to design nanoparticles with designed absorption bands. Such absorbing materials can, for example, further be used to enhance the monochromaticity of light observed from a coating, ink, dye, or other reflective surface treated with the color-enhancing composition of the present invention.

[0400] The details of preparing this nanoparticle system are included in U.S. Serial No. 12 / 725,108, the entire contents of which are incorporated herein by reference. The absorption spectrum of Y2O3 alone (lower trace) is completely featureless, showing absorption near 200 nm due to tri-arginine and a gentle slope associated with scattering, as well as absorption of the Y2O3 nanoparticles extending into the visible portion of the spectrum. On the other hand, gold-coated Y2O3 (upper trace) exhibits a strong absorption band at 546 nm, a characteristic of the plasmon resonance band caused by the gold shell surrounding the Y2O3 core. The red shift of the plasmon absorption to 546 nm is consistent with the presence of a gold shell surrounding the dielectric core.

[0401] In one embodiment of the present invention, as described above, the converter material for the upconverter dielectric core can include a variety of dielectric materials. In various embodiments of the present invention, the upconverter dielectric core more specifically includes an oxide material doped with lanthanides. Lanthanides include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and ytterbium (Lu). Other suitable dielectric core materials include non-lanthanides, such as yttrium (Y) and scandium (Sc). Therefore, suitable dielectric core materials include Y2O3, Y2O2S, NaYF4, NaYbF4, Na-doped YbF3, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, or SiO2. These dielectric cores can be doped with Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd, and other rare earth species or combinations thereof.

[0402] Lanthanides usually exist as trivalent cations, in which case their electron configuration is (Xe)4f n , where n is 1(Ce 3+ ) to 14(Lu 3+ ). Transitions within the f cluster determine many of the photophysical properties of lanthanide ions, such as persistent luminescence and steep absorption and emission lines. The f electrons are protected from external perturbations by populated 5s and 5p orbitals, resulting in line-shaped spectra. The LaPorte-forbidden nature of ff electron transitions leads to long excited-state lifetimes, ranging from microseconds to milliseconds.

[0403] Therefore, the example of doping material among the present invention comprises oxide, such as yttrium oxide and neodymium oxide and aluminum oxide, and sodium yttrium fluoride and nanocrystal perovskite and garnet, such as yttrium aluminum garnet (YAG) and yttrium aluminum perovskite (YAP).In these materials, some but not all in these materials need doping to promote up-conversion efficiency.In various embodiments of the present invention, matrix nanocrystal is doped with trivalent rare earth lanthanide ions from those lanthanide series elements given above.

[0404] More specifically, in various embodiments of the present invention, these dopant pairs are introduced in order to create more energy states that can be reached in the matrix crystal. The activation and pumping of these energy states strictly follow the principles discussed above. In the present invention, the doping concentration can range from about 0.2% to 20% in terms of ions entering the matrix lattice or in terms of weight % or mol % variation. The efficiency of the upconversion process of specific wavebands in these materials can be adjusted by the doping percentage to induce and enhance the target emission. Lanthanide-doped upconverters can use (but are not limited to) the following molar percentages of dopant compositions: 5% Er, 10% Yb, 0.2% Tm+3% Yb and 1% Er+10% Yb.

[0405] The size of the nanocrystals also has an impact on the efficiency of the upconversion process, as larger nanocrystals will have more sites for dopant ions to be accommodated in the matrix lattice, thereby enabling more emission to be produced from the same doped matrix than would be the case with smaller nanocrystals. While the dopant percentages listed above are not strictly fixed, these numbers provide a basic guide to typical percentages that one would use to obtain the specific dielectric core materials of the present invention.

[0406] Furthermore, in one embodiment of the present invention, some of these base crystals (e.g., neodymium oxide) may not require specific doping to promote upconversion, as has been seen in one case of Nd2O3 producing emissions at 372 nm, 402 nm, and 468 nm at an excitation wavelength of 587 nm. See Que, W et al., Journal of Applied Physics 2001, Vol. 90, p. 4865, the entire contents of which are incorporated herein by reference. In one embodiment of the present invention, neodymium oxide is doped with Yb 3+ By using lower energy Yb 3+ Activator makes Nd 3+ Ion sensitization to enhance upconversion.

[0407] In one embodiment of the invention, the dielectric core is coated with, for example, a metal shell to strengthen electron-phonon coupling and thereby improve up-conversion or down-conversion efficiency as discussed above. In another embodiment of the invention, the shell can include a SiO2- and / or TiO2-coating, and in one embodiment, this coating is coated on doped Y2O3 up-conversion nanoparticles, thereby improving up-conversion efficiency relative to uncoated nanocrystals in some cases. In another embodiment of the invention, the shell can include a SiO2- and / or TiO2-coating, and in one embodiment, this coating is coated on doped Y2O3 down-conversion nanoparticles, thereby improving down-conversion efficiency relative to uncoated nanocrystals in some cases. In addition, in one embodiment of the invention, the coating can be a polymer. In one embodiment, this coating is provided on a NaYF4:Ln / NaYF4 dielectric core. Such coatings can improve up-conversion efficiency relative to uncoated up-converters.

[0408] In another embodiment of the present invention, the phonon modes of undoped matrix lattice (e.g., Y2O3) nanocrystals are tuned, for example, by shells of Au, Ag, Pt, and Pd of varying thickness. In various embodiments of the present invention, the upconverter dielectric core and shell system includes Y2O3:Ln with a NaYF4 shell, Y2O3:Ln with an Au(Ag,Pt) shell, NaYF4:Ln with a Y2O3 shell, and NaYF4:Ln with an Au(Ag,Pt) shell as upconverter nanocrystals. In this system, the core diameter and the outer / inner diameter of the metal-coated shell can be set to a size that is expected to be tuned for plasmon mode overlap.

[0409] In other embodiments as discussed below, the metal coating or the metal structure that are provided with respect to up-conversion or down-conversion nanoparticles can be present in dielectric inside, and the relative position of metal structure and dielectric structure can strengthen plasmon resonance.These structures with metal structure inside can be referred to as metal core up-converter or metal core down-converter. The metal core technology for energy conversion is useful because this technology utilizes the metal nanoparticles with improved surface morphology compared to the shell coating on the core dielectric. The metal or metal alloy in the inner core metal energy converter can be selected to tune its plasmon activity.These structures with metal structure outside can be referred to as core up-converter or core down-converter.

[0410] In various embodiments of the present invention, the upconverter or downconverter dielectric core can be coated with a thiol-terminated silane to provide a SiO2 coating around the core with a reactivity similar to Y2O3. In one embodiment of the present invention, the method described above is used to synthesize the following core-shell nanoparticles: Y2O3:Ln with a NaYF4 shell, Y2O3:Ln with an Au(Ag,Pt) shell, NaYF4:Ln with a Y2O3 shell, NaYF4:Ln with an Au(Ag,Pt) shell, wherein the core and shell diameters vary between 2 and 20 nm. In these material systems, the adjusted ratio of the core-shell diameters can permit plasmon-phonon resonances that should amplify the absorption and / or upconversion emission of NIR light. In these material systems, control of the core and shell diameters is a factor that determines size-dependent effects and subsequent tuning of the plasmon-phonon resonances.

[0411] In one embodiment of the present invention, the upconverter dielectric core can be a hybrid core-shell material, including, for example, semiconductor-type Y2O3 and NaYF4 cores doped with various Ln series metals, which have been shown to have greater upconversion efficiency. These doped Y2O3 and NaYF4 cores will have a shell of Au (Ag, Pt, Pd) or an undoped Y2O3 and NaYF4 matrix, which has the potential to enhance or tune the phonon modes required for energy transfer during the upconversion process. Solubility can be improved, for example, by adding thiolated organics (Au shell), organic chain triethanolsilane (Y2O3 shell), and trioctylphosphine-oleic acid amine (NaYF4 shell). All core-shell nanoparticles can be further dissolved into a colloidal suspension with the addition of tri-arginine peptide, polyethylene glycol, and polyethyleneimine surfactants.

[0412] Figure 28ASome of the various embodiments of converter structures that can be designed according to the present invention are shown: (a) a structure comprising upconverter (UC) molecules bound to metal (gold) nanoparticles; (b) a structure comprising UC-containing nanoparticles covered with metal nanoparticles; (c) metal nanoparticles covered with UC-containing nanocaps; (d) UC-containing nanoparticles covered with metal nanocaps; (e) metal nanoparticles covered with UC nanoshells; (f) UC-containing nanoparticles covered with metal nanoshells; and (g) UC-containing nanoparticles covered with metal nanoshells having a protective coating.

[0413] The configuration (in Figure 28A UC materials) would be suitable for enhancement of down conversion materials such as quantum dots or phosphors described herein. In addition, in one embodiment of the present invention, dielectric spacers (e.g., silicates as discussed below) may be used with Figure 6 Ab structure is used together to make the particle type metal structure separate. In another embodiment of the present invention, the dielectric spacer can be used with Figure 28A Used together with the structure of to separate metal layers, whether these layers are partial metal layers or continuous metal layers. Figure 28B Schematic diagram in .

[0414] In various embodiments of the present invention, the multilayer metal nanoshells discussed in this application have the potential to electromagnetically enhance two spectral regions. Thus, the metal structures of the present invention can be used in up-conversion mode to enhance both excitation at wavelength λ1 and emission at wavelength λ2. This feature can also be used in down-conversion to primarily enhance emission at wavelength λ2 and potentially enhance excitation at wavelength λ1.

[0415] In various embodiments of the present invention, such metallic structures include conductive materials made of, for example, metals, or doped glasses, or doped semiconductors. These conductive materials may be in the form of pure or nearly pure elemental metals, alloys of such elemental metals, or layers of conductive materials (regardless of continuity). The conductive materials may (as described above) include non-metallic materials as minor components, the amount of which does not render the composite material insulating.

[0416] Similarly, in various embodiments of the present invention, the up-conversion or down-conversion material may include at least one of a dielectric, a glass, or a semiconductor. The up-conversion or down-conversion material may include an alloy of two or more dielectric materials, an alloy of two or more glasses, or an alloy of two or more semiconductors.

[0417] therefore, Figure 28AThis represents an embodiment in which the dielectric core of the present invention is supplemented with a shell. The shell can include a metal layer of a specified thickness. The metal layer can include materials such as nickel, gold, iron, silver, palladium, platinum and copper, and combinations thereof. The metal layer can also be made of a combination of metals and non-metals. The shell serves as a plasmon shell, wherein surface plasmons can be formed in the metal between the dielectric core and the external environment acting as an external dielectric. The shell (as shown) may not be a complete shell. Partial metal shells or metal shells of different thicknesses are also acceptable in the present invention.

[0418] As discussed below, in another embodiment of the present invention, the metal housing serves as a scattering center for UV light, wherein the UV light will be scattered from the paint or coating (the light, even if absorbed in the paint or coating, will minimally contribute to local heating of the paint or coating material).

[0419] Figure 28C Several further embodiments of plasmonically active nanostructures with upconversion (UC) materials that can be designed are shown: (a) metal nanoparticles; (b) UC nanoparticle cores covered with metal nanocaps; (c) spherical metal nanoshells covering UC ellipsoidal cores; (d) oblate metal nanoshells covering UC ellipsoidal cores; (e) metal nanoparticle cores covered with UC nanoshells; (f) metal nanoshells with protective coatings; (g) multilayer metal nanoshells covering UC ellipsoidal cores; (h) multiple nanoparticle structures; (i) metal nanotubes and nanotriangles / nanoprisms; and (j) metal cylinders.

[0420] Figure 28D Still other embodiments of plasmonically active nanostructures with upconversion materials and attached photoactive (PA) molecules are shown. For example, in the case of psoralen (as the PA molecule), the length of the linker between the PA molecule and the UC material or metal surface is tailored so that it is long enough to allow the PA molecule to be active (attached to DNA) and short enough to allow efficient excitation of the PA molecule by the UC excitation light. Figure 28D Shown are (a) PA molecules bound to UC nanoparticles; (b) nanoparticles containing UC materials covered with metal nanoparticles; (c) metal nanoparticles covered with UC material nanocaps; (d) nanoparticles containing UC materials covered with metal nanocaps; (e) metal nanoparticles covered with UC material nanoshells; (f) nanoparticles containing UC materials covered with metal nanoshells; and (g) nanoparticles containing UC materials covered with metal nanoshells having a protective coating.

[0421] In the case of up-converter and down-converter structures of the present invention, the plasmon effect is favourable. The plasmon effect can increase the local intensity of received light or the local intensity of the emitted light from up-converter and / or down-converter structures of the present invention. The plasmon effect can occur in the entire electromagnetic region, provided that suitable nanostructures, nanometer-scale dimensions, metal types have been used. The plasmon effect is feasible in a wide range of electromagnetic spectra, ranging from gamma rays and X-rays to ultraviolet, visible light, infrared, microwaves and radio frequency energy. However, for practical reasons, visible light and NIR light are used for metal structures such as silver and gold nanoparticles, because the plasmon resonances of silver and gold occur in the visible and NIR regions respectively.

[0422] In various embodiments, nanoparticles of yttrium oxide doped with neodymium and ytterbium, yttrium oxide doped with europium and ytterbium, and any combination of neodymium oxide nanocrystals doped with rare earth trivalent ions can be used. The dual-doping components of yttrium oxide, neodymium and ytterbium, and also dual-doping with europium and ytterbium, are novel for the yttrium oxide matrix lattice, but such dual-doping systems have been shown to work in other matrix lattices such as YAG.

[0423] It has been shown that these doubly doped lanthanide glasses can be effectively upconverted on bulk materials and can thus provide novel upconverter structures at the nanoscale. These yttrium oxide nanostructures of the present invention provide a number of advantages. Small-scale synthetic methods for producing nanoscale yttrium oxide are easier to control and implement in yttrium oxide than in YAG. The matrix structure of yttrium oxide scintillates by downconversion. Combinations of these dopants in yttrium oxide can, for example, provide yttrium oxide nanocrystals with predetermined emission colors to achieve the color shift of the present invention.

[0424] In one embodiment of the present invention, dual dopants allow for excitation of either ion in the host glass. For example, excitation with 980 nm light excites ytterbium ions, where energy transfer from one excited state of the ytterbium ion to the other dopant provides a mechanism for upconversion emission of light in the visible and NIR spectral regions.

[0425] Up-conversion phosphors similar in chemical composition to the down-conversion fluorescent materials discussed above can be used. The up-conversion phosphors can include laser dyes, such as small organic molecules that can be excited by absorbing at least two infrared photons, accompanied by the emission of visible light. The up-conversion phosphors can include fluorescent polymers, such as polymers of the class that can be excited by absorbing at least two infrared photons, accompanied by the emission of visible light. The up-conversion phosphors can include inorganic or ceramic particles, or nanoparticles, including conventional up-conversion phosphors (e.g., metal fluorides, metal oxides) that can be excited by absorbing at least two infrared photons, accompanied by the emission of visible light. The up-conversion phosphors can include semiconductor particles, including nanoparticles, such as group II-VI or group III-V compound semiconductors, such as quantum dots, which are described in detail above in the "down-conversion" semiconductors.

[0426] Fluorescent upconversion inorganic phosphors may include, but are not limited to, metal oxides, metal halides, metal chalcogenides (e.g., sulfides), or mixtures thereof, such as metal oxyhalides, metal oxychalcogenides. Fluorescent upconversion inorganic phosphors are usually doped with rare earth elements (e.g., Yb 3+ 、Er 3+ 、Tm 3+ ). Some matrix examples include, but are not limited to: NaYF4, YF3, BaYF5, LaF3, La2MoO8, LaNbO4, LnO2S; where Ln is a rare earth element such as Y, La, Gd).

[0427] These converters (as well as other energy converters described herein that receive energy and produce light or electron emission) may optionally include any of the energy-enhancing structures described above.

[0428] In various embodiments of the present invention, the energy converter can be used in conjunction with the energy enhancers described above for color enhancement. In some embodiments, the converter is used to up-convert light, e.g., convert light from an IR state to visible electromagnetic radiation, and to down-convert light, e.g., convert light from the UV range to visible electromagnetic radiation. In various embodiments, the present invention up-converts energy, preferably up-converts light in the visible spectrum. The present invention contemplates various applications including up-conversion materials and down-conversion materials to enhance the color of an object being displayed, with or without an energy enhancer. These applications may include coatings on signs, walls, cars, buildings, ships, and aircraft. These applications may include display monitors, computer monitors, phone displays, watch dials, instrument dials, to name just a few.

[0429] Among various materials, luminescent nanoparticles have caused more and more technical and industrial concerns. In the context of the present invention, nanoparticles refer to particles less than one micron in size. Although the specification of the present invention has described the specific examples using nanoparticles, in many embodiments, the present invention is not limited to particles less than one micron in size. However, in many embodiments, less than one micron, and especially less than the size range of 100nm can produce particularly interesting properties, such as emission lifetime luminescence quenching, quantum luminescence efficiency and concentration quenching, and such as diffusion, penetration and dispersion in media where larger particles cannot migrate.

[0430] In various embodiments, the present invention can use various down-conversion materials (or the mixture of down-conversion materials) to strengthen the light of the specific color that the observer can observe when there is or does not have energy enhancer.These down-conversion materials can comprise quantum dot, semiconductor material, the alloy of semiconductor material, scintillating material and phosphor material, the material that demonstrates X-ray excited luminescence (XEOL), organic solid, metal complex, inorganic solid, crystal, rare earth material (lanthanide), polymer, scintillator, phosphor material etc. and the material that demonstrates exciton property.Therefore, the down-conversion material that is used to strengthen color emission can be by the energy conversion of one in ultraviolet light, x-ray and high-energy particle into visible light. The down-conversion material that is used to strengthen color emission can be by energy conversion of one in ultraviolet light, x-ray and high-energy particle into low-energy visible light when there is or does not have energy enhancer.

[0431] In one embodiment of the present invention, a mixture of quantum dots can be used for color enhancement with or without an energy enhancer. Quantum dots are typically nanometer-sized particles whose energy state in the material of the quantum dots depends on the size of the quantum dots. For example, quantum dots are known to be semiconductors whose conductive properties are closely related to the size and shape of the individual crystals. Generally speaking, the smaller the size of the crystal, the larger the band gap, and the greater the energy difference between the highest valence band and the lowest conduction band. Therefore, more energy is required to excite the quantum dots, and at the same time, more energy is released when the crystal returns to its resting state. In fluorescent dye applications, this is equivalent to emitting higher frequency light after exciting the quantum dots when the crystal size becomes smaller, which can cause a color shift from red to blue in the emitted light. Quantum dots represent a way to convert ultraviolet light in the spectrum into a target color emission, such as green light emission. Quantum dots represent a way to convert blue light in the spectrum into a target color emission, such as green light emission.

[0432] As described in U.S. Patent No. 6,744,960 (incorporated by reference in its entirety), quantum dots of different sizes produce different color emissions. In their research and applicable to the present invention, quantum dots can comprise various materials, including semiconductors such as zinc selenide (ZnSe), cadmium selenide (CdSe), cadmium sulfide (CdS), indium arsenide (InAs), and indium phosphide (InP). Another material that can be appropriately employed is titanium dioxide (TiO2). The size of the particles (i.e., quantum dots 18) can range from about 2 to 10 nm. Because the size of these particles is so small, quantum physics determines many of the electrical and optical properties of quantum dots. One such result of applying quantum mechanics to quantum dots 18 is that quantum dots absorb a broad spectrum of optical wavelengths and re-emit radiation with a wavelength longer than the wavelength of the absorbed light. The wavelength of the emitted light is determined by the size of the quantum dots. For example, a CdSe quantum dot with a diameter of 5.0 nm emits radiation with a narrow spectral distribution centered at about 625 nm, while a quantum dot 18 comprising a CdSe having a size of 2.2 nm emits light having a central wavelength of about 500 nm. Semiconductor quantum dots comprising CdSe, InP, and InAs can emit radiation with a central wavelength ranging from 400 nm to about 1.5 μm. Titanium dioxide TiO2 also emits within this range. The line width of the emission of these semiconductor materials, i.e., the full width at half maximum (FWHM), can range from about 20 to 30 nm. In order to produce this narrowband emission, the quantum dots only need to absorb light having a wavelength shorter than the wavelength of the light emitted by the quantum dots. For example, for a CdSe quantum dot with a diameter of 5.0 nm, light having a wavelength shorter than about 625 nm is absorbed to produce emission at about 625 nm, while for a 2.2 nm quantum dot comprising CdSe, light having a wavelength less than about 500 nm is absorbed and re-emitted at about 500 nm. In practice, however, the excitation or pump radiation is at least about 50 nanometers shorter than the emitted radiation.

[0433] Specifically, in one embodiment of the present invention, a quantum dot mixture (QDM) coating can be deposited using CVD and / or sol-gel techniques using standard precipitation techniques, which can be used with or without an energy enhancer. The QDM coating can be made of a silicate structure that does not attenuate UV output. Within the silicate family, silicon dioxide (SiO2) is suitable because it maximizes UV transmission through the coating. The coating can also include a second layer of biocompatible glass. Such biocompatible glass and glass-ceramic compositions can contain calcium, lanthanides or yttrium, silicon, phosphorus, and oxygen. Other biocompatible materials and technologies are described in the following patents, which are incorporated herein in their entirety: U.S. Patent Nos. 5,034,353; 4,786,617; 3,981,736; 3,922,155; 4,120,730; and U.S. Patent Application Nos. 2008 / 0057096; 2006 / 0275368; and 2010 / 0023101.

[0434] In addition, the down conversion materials described herein of the present invention can be coated with an insulating material, such as silicon dioxide, which will reduce the possibility of any chemical interaction between the luminescent particles and the medium in which these particles are included. These and other conversion materials herein can be used with or without energy enhancers. One of the main limiting factors for biocompatible applications of inorganic nanoparticles is their toxicity. In general, all semiconductor nanoparticles are more or less toxic. For biocompatible applications, nanoparticles with as low toxicity as possible are desired, otherwise the nanoparticles must be kept separate from the medium. Pure TiO2, ZnO and Fe2O3 are biocompatible. CdTe and CdSe are toxic, while ZnS, CaS, BaS, SrS and Y2O3 have less toxicity. In addition, the toxicity of the nanoparticles may come from their inorganic stabilizers, such as TGA, or from dopants, such as Eu 2+ Cr 3+ or Nd 3+ Other suitable down-conversion materials that may appear to be the most biocompatible are zinc sulfide, ZnS:Mn 2+ , iron oxide, titanium oxide, zinc oxide, zinc oxide containing a small amount of Al2O3, and AgI nanoclusters encapsulated in zeolites. For non-medical applications where toxicity may not be a critical issue, the following materials (and those listed elsewhere) are considered suitable: lanthanum and gadolinium oxyhalides activated with thulium, Er-doped 3+ BaTiO3 nanoparticles, doped with Yb 3+ CsMnCl3 and RbMnCl3, BaFBr:Eu 2+ Nanoparticles, cesium iodide, bismuth germanate, cadmium tungstate, and CsBr doped with divalent Eu.

[0435] In various embodiments of the present invention, the following light-emitting polymers are also suitable as conversion materials with or without energy enhancers: poly(p-phenylene vinylene), poly(p-phenylene ethylene), poly(p-phenylene), poly(thiophene), poly(pyridine vinylene), poly(pyrrole), poly(acetylene), poly(vinylcarbazole), poly(fluorene), etc., as well as their copolymers and / or derivatives.

[0436] In various embodiments of the present invention, the following materials can be used in a manner similar to that detailed in U.S. Patent No. 7,090,355, the entire contents of which are incorporated herein by reference. For down conversion, the following materials can be used with or without energy enhancers. Inorganic or ceramic phosphors or nanoparticles, including but not limited to: metal oxides, metal halides, metal chalcogenides (e.g., metal sulfides) or mixtures thereof, such as metal oxygen halides, metal oxygen chalcogenides. Laser dyes and organic small molecules, and fluorescent organic polymers. Semiconductor nanoparticles, such as II-VI or III-V compound semiconductors, such as fluorescent quantum dots. Metal organic molecules, including at least one metal center, such as rare earth elements (e.g., Eu, Tb, Ce, Er, Tm, Pr, Ho) and transition metal elements, such as Cr, Mn, Zn, Ir, Ru, V, and main group elements, such as B, Al, Ga, etc. The metal element is chemically bonded to the organic group to prevent quenching of fluorescence in the matrix or solvent. Phosphors that can be used include those from the garnet series: (Y m A 1-m )3(Al n B 1-n )5O 12 , doped with Ce; where 0 ≤ m, n ≤ 1, where A includes other rare earth elements, and B includes B and Ga. Furthermore, phosphors containing metal silicates, metal borates, metal phosphates, and metal aluminates can be used. Furthermore, nanoparticle phosphors containing common rare earth elements (e.g., Eu, Tb, Ce, Dy, Er, Pr, Tm) and transition or main group elements (e.g., Mn, Cr, Ti, Ag, Cu, Zn, Bi, Pb, Sn, Ti) as fluorescence activators can be used. Materials such as tungstates containing Ca, Zn, Cd, metal vanadates, and ZnO can be used with or without energy enhancers.

[0437] Commercial laser dye materials available from several laser dye suppliers, including Lambda Physik and Exciton, can also be used with or without energy enhancers. A partial list of preferred laser dye classes includes: pyrromethene, coumarin, rhodamine, fluorescein, other aromatic hydrocarbons and their derivatives, etc. In addition, there are many polymers containing unsaturated carbon-carbon bonds that are also used as fluorescent materials and have many optical and fluorescent applications. For example, MEH-PPV, PPV, etc. have been used in optoelectronic devices, such as polymer light emitting diodes (PLEDs). Such fluorescent polymers can be directly used as the fluorescent layer of transparent 2-D display screens.

[0438] As mentioned above, semiconductor nanoparticles (for example, quantum dots) can be used with or without energy enhancers. The term "semiconductor nanoparticles" refers to an inorganic grain with a diameter between 1nm and 1000nm, preferably between 2nm and 50nm in this area. Semiconductor nanoparticles can emit electromagnetic radiation (that is, semiconductor nanoparticles are luminous) after excitation. Nanoparticles can be homogeneous nanocrystals, or include multiple shells. For example, nanoparticles can include the "core" of one or more first semiconductor materials, and can be surrounded by the "shell" of a second semiconductor material. The core and / or shell can be semiconductor materials, including but not limited to those of the following groups: II-VI (ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, etc.) and III-V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, etc.) and IV (Ge, Si, etc.) materials, as well as alloys or mixtures thereof.

[0439] Fluorescent metallo-organic molecules containing rare earth or transition element cations can be used in down-conversion materials with or without energy enhancers. Such molecules include a metal center of a rare earth element (including Eu, Tb, Er, Tm, and Ce) protected by an organic chelate group. The metal center can also include transition elements such as Zn, Mn, Cr, and Ir, as well as main-group elements such as B, Al, and Ga. Such metallo-organic molecules can be readily dissolved in liquids or transparent solid matrix media. Some examples of such fluorescent metallo-organic molecules include: 1. Tris(dibenzoylmethane)mono(phenanthroline)europium(III); 2. Tris(8-hydroxyquinolinolato)erbium; 3. Tris(1-phenyl-3-methyl-4-(2,2-dimethylpropane-1-yl)pyrazol-5-one)terbium(III); 4. Bis(2-methyl-8-hydroxyquinolinolato)zinc; and 5. Diphenylborane-8-hydroxyquinoline.

[0440] The specific examples of the down-conversion material for red light emission include those materials and europium complex discussed above, such as those described in Japanese Patent Publication (Kokai) No. 2003-26969, and the europium complex is constructed so that a beta-diketone ligand is coordinated to europium, thereby forming a europium complex that can emit red fluorescence. Other specific examples of rare earth element complexes include complexes comprising the following: lanthanum (Ln), europium (Eu), terbium (Tb) and gadolinium (Gd) and combinations thereof. Europium (Eu) complex can emit red fluorescence when the ultraviolet irradiation is 365nm to 410nm with a wavelength range. Terbium (Tb) can emit green fluorescence when the ultraviolet irradiation is 365nm with a wavelength.

[0441] In other down-conversion embodiments with or without an energy enhancer, the down-conversion material emitting red light may include europium, the luminescent particles emitting green light may include terbium, and the luminescent particles emitting blue light or yellow light may include cerium (and / or thulium). In an up-conversion embodiment, the up-conversion material emitting red light may include praseodymium, the luminescent particles emitting green light may include erbium, and the luminescent particles emitting blue light may include thulium. In an embodiment, the conversion material may be a luminescent particle composed of fluorescent molecules emitting different colors (e.g., red, green, and blue). In an embodiment, the conversion material may be a luminescent particle made of a pure organic dye or a metal organic dye with or without an energy enhancer.

[0442] In addition to combinations of rare earth complexes such as a europium complex and a terbium complex, it is also possible to use a europium complex in combination with a non-complex green-light-emitting fluorescent substance, or a terbium complex in combination with a non-complex red-light-emitting fluorescent substance.

[0443] Other down converter materials, with or without energy enhancers, include, for example, ZnS, PbS, SbS3, MoS2, PbTe, PbSe, BeO, MgO, Li2CO3, Ca(OH)2, MoO3, SiO2, Al2O3, TeO2, SnO2, KBr, KCl, and NaCl. As mentioned above, these materials may include dopants to adjust the emission properties. Examples of suitable doped (or alloyed) glass systems include: Y2O3:Gd, Y2O3:Dy, Y2O3:Tb, Y2O3:Ho, Y2O3:Er, Y2O3:Tm, Gd2O3:Eu, Y2O2S:Pr, Y2O2S:Sm, Y2O2S:Eu, Y2O2S:Tb, Y2O2S:Ho, Y2O2S:Er, Y2O2S:Dy, Y2O2S:Tm, ZnS:Ag:Cl (blue), ZnS:Cu:Al (green), Y2O2S:Eu (red), Y2O3:Eu (red), YVO4:Eu (red), and Zn2SiO4:Mn (green).

[0444] More specifically with respect to down-converter materials suitable for the present invention with or without energy enhancers, U.S. Patent No. 4,705,952 (the contents of which are hereby incorporated herein by reference) describes a phosphor triggered by infrared light that stores energy in the form of visible light of a first wavelength and releases energy in the form of visible light of a second wavelength when triggered by infrared light. The phosphor in U.S. Patent No. 4,705,952 is a composition of alkaline earth metal sulfides, rare earth dopants, and fusible salts. The phosphor in U.S. Patent No. 4,705,952 is more specifically a phosphor made of: strontium sulfide, barium sulfide, and mixtures thereof; including dopants from the rare earth group and europium oxide, and mixtures thereof; and including fusible salts of: fluorides, chlorides, bromides, and iodides of lithium, sodium, potassium, cesium, magnesium, calcium, strontium, and barium, and mixtures thereof. The materials described in US Patent No. 4,705,952 may be used in various embodiments of the present invention with or without energy enhancers.

[0445] In other embodiments of the present invention, the down-converter material (or mixture of down-converter materials) may include Y2O3:Li. Sun et al., “Luminescent properties of Li+doped nanosized Y2O3:Eu,” Solid State Comm. 119 (2001) 393-396 (incorporated herein by reference in its entirety) describe such materials. Hou et al., “Luminescent properties nano-sized Y2O3:Eu fabricated by co-precipitation method,” Journal of Alloys and Compounds, Vol. 494, No. 1-2, April 2, 2010, pp. 382-385 (incorporated herein by reference in its entirety) describe nano-sized yttrium oxide (Y2O3) powder that has been successfully synthesized by a co-precipitation method. The powder is well crystallized, and the grains are approximately spherical with good dispersibility. Eu 3+ The quenching concentration of Li+ ions is 9 mol%, which is much higher than that of micro-scale powders. The incorporation of Li+ ions greatly improves the luminescence intensity. 0.87 Eu 0.09 Li 0.04 )2O3) was observed to have the highest emission intensity, and the fluorescence intensity increased by up to 79%. Yi et al. "Improved cathodoluminescent characteristics of Y2O3:Eu 3+ thin films by Li-doping," Appl. Phys. A 87, 667–671 (2007) (incorporated herein by reference in its entirety) describes Y2O3:Eu 3+ and Li-doped Y2O3:Eu 3+ Cathodoluminescence spectra of both films and methods of making these materials.

[0446] In other embodiments, the present invention can use a variety of up-conversion materials (or mixtures of up-converters) with or without energy enhancers to enhance light of a specific color that can be observed from a reflective material or surface. These up-conversion materials can include similar materials as discussed above with respect to down-conversion, but are typically included in the matrix crystal in a doped or impurity state that provides an up-conversion pumping mechanism. Thus, up-conversion materials for enhancing color emission can convert energy from one of near-infrared, infrared, and microwave radiation. Up-conversion materials for enhancing color emission can convert energy from lower energy visible light to higher energy visible light.

[0447] Upconversion materials, with or without energy enhancers, can be used in various ways to enhance visible light emission by converting infrared light from the solar spectrum (as in sunlight exposure) or the blackbody spectrum (as in incandescent lamps). In one example, nanoparticles doped with lanthanide oxides can be excited with near-infrared light, such as lasers at 980 nm and 808 nm, to produce visible light in different parts of the red, green, and blue spectrum, depending on the selected dopant(s), trivalent rare earth ions, their concentrations, and the matrix lattice.

[0448] The lanthanide-doped oxides suitable for the present invention differ from more conventional multi-photon upconversion processes, where absorption of, for example, two photons is required in a simultaneous event to drive an electron from a valence state directly into a high-level conduction band state, where relaxation across the band gap of the material produces fluorescence. Here, co-doping creates multiple states in the band gap of NaYF4, such that Yb 3+ Ions have a potential to be pumped by single photon events. 2 F 5 / 2 energy state, and other single photon absorption events can be gathered from this to even higher states. Once in this excited state, it is possible to transition to a higher energy radiative state, from which the light emission will be in a comparative 2 F 5 / 2 In other words, the incident light in the Yb 3+ Ionic 2 F 5 / 2 The energy state is to absorb 980nm light, thereby allowing the establishment of a certain aggregate for transition to a higher energy state, such as 4 F 7 / 2 The state of the foundation of the energy state. Here, it starts from 4 F 7 / 2 Transitions in energy states produce visible emission.

[0449] U.S. Patent No. 7,008,559, the entire content of which is incorporated herein by reference, describes the upconversion properties of ZnS, where excitation at 767 nm produces emission in the visible range. The materials described in U.S. Patent No. 7,008,559 (including ZnS, as well as BaTiO3 nanoparticles doped with Er 3+ and CsMnCl3 doped with Yb 3+ ) are suitable in various embodiments of the present invention with or without an energy enhancer.

[0450] In addition, the materials designated for upconversion materials in the present invention include CdTe, CdSe, ZnO, CdS, Y2O3, MgS, CaS, SrS, and BaS with or without an energy enhancer. Such upconversion materials can be any semiconductor, and more specifically, but not limited to, sulfide, telluride, selenide, and oxide semiconductors and their nanoparticles, such as Zn 1-x Mn x S y , Zn 1-x Mn x Se y , Zn 1-x Mn x Te y , Cd 1-x MnS y , Cd 1-x Mn x Se y , Cd 1-x Mn x Te y , Pb 1-x Mn x S y , Pb 1- x Mn x Se y , Pb 1-x Mn x Te y , Mg 1-x MnS y , Ca 1-x Mn x S y , Ba 1-x Mn x S y and Sr 1-x etc. (where 0 < x ≦ 1, and 0 < y ≦ 1). Complexes of the semiconductors described above are also expected to be useful in the present invention - for example (M 1-z N z ) 1-x Mn x A1-y B y (M = Zn, Cd, Pb, Ca, Ba, Sr, Mg; N = Zn, Cd, Pb, Ca, Ba, Sr, Mg; A = S, Se, Te, O; B = S, Se, Te, O; 0 < x ≤ 1, 0 < y ≤ 1, 0 < z ≤ 1). Two examples of such complexes are Zn 0.4 Cd 0.4 Mn 0.2 S and Zn 0.9 Mn 0..1 S 0.8 Se 0.2 . Additional conversion materials include insulating and non-conductive materials such as BaF2, BaFBr, and BaTiO3, to name just a few exemplary compounds. Semiconductors co-doped with transition ions and rare earth ions suitable for the present invention include sulfide, telluride, selenide, and oxide semiconductors and their nanoparticles such as ZnS; Mn; Er; ZnSe; Mn, Er; MgS; Mn, Er; CaS; Mn, Er; ZnS; Mn, Yb; ZnSe; Mn, Yb; MgS; Mn, Yb; CaS; Mn, Yb, etc., and their complexes: (M 1-z N<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In general, the upconversion process typically requires doping a dielectric crystal (of any size > 0.1 nm) with one or more rare earth dopants such as Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd, and other rare earth species or combinations thereof, comprising at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2, wherein the incident radiation is at a longer wavelength than the emitted radiation from the crystal. The wavelength emitted is entirely dependent on the selected dopant ion(s), and their association and relative concentration in the host crystal. For the example of upconversion in a Y2O3-based crystal, to achieve blue emission (approximately 450–480 nm), one can synthesize [Y2O3; Yb(3%), Tm(0.2%)], where the percentages of Yb and Tm doped in the crystal are those achieved relative to 100% Y atoms. Similarly, typical green upconversion materials are [Y2O3; Yb(5%), Ho(1%)] and [Y2O3; Yb(2%), Er(1%)], and typical red upconversion materials are [Y2O3; Yb(10%), Er(1%)] and [Y2O3; Yb(5%), Eu(1%)]. The concentrations of the dopants relative to each other and the crystal matrix must be adjusted for each combination, and there are multiple ways to achieve multiple colors from even the same dopant, with or without an energy enhancer.

[0453] In the doping of Tm 3+ Upconversion of red light at a wavelength of approximately 650 nm in a fluorozirconate glass can be used in the present invention to generate blue light. In this system, the blue light consists of two emission bands; one at 450 nm attributed to the 1D2→3H4 transition and the other at 475 nm attributed to the 1G4→3H6 transition. Others have observed that the emission intensity of both bands varies quadratically with excitation power. For Tm 3+ For glasses with a concentration of 0.2 mol % and above, cross-relaxation processes occur, which reduces the upconversion efficiency.

[0454] Already containing LuPO4:Yb 3+ 、Tm 3+ and YbPO4:Er 3+ Visible emission has been observed in optically clear colloidal solutions of nanocrystals in chloroform following excitation with near-infrared (NIR) light. Others have shown that excitation at 975 nm can produce visible luminescence in the blue, green, or red spectral regions.

[0455] Tellurium and germanium oxides (tellurites and germanates) are also suitable upconverters. For example, these glasses can be doped with Tm, Yb, Ho, Er, Pr.

[0456] Yb-doped 3+ BaZrO3 is also suitable for up-conversion. 3+ and / or Tm 3+ Doping is also suitable for tuning the emission wavelength.

[0457] In another embodiment, Nd prepared by the Morss method 3+ :Cs2NaGdCl6 and Nd 3+ 、Yb 3+ Cs2NaGdCl6 polycrystalline powder samples have been reported to be upconverters and are suitable for the present invention. These materials have shown that upconversion emissions close to 538nm (green), 603nm (orange) and 675nm (red) have been observed under 785nm irradiation, and the upconversion emissions have been assigned to 4G7 / 2→4I9 / 2, (4G7 / 2→4I11 / 2; 4G5 / 2→4I9 / 2) and (4G7 / 2→4I13 / 2; 4G5 / 2→4I11 / 2) respectively.

[0458] In another embodiment, Nd-based 3+ and Ho 3+ Co-doped ZrF4 fluoride glass has been reported to be an upconverter and is suitable for the present invention. In the upconversion luminescence of ZrF4 fluoride glass, it can be seen that the green emission is extremely strong, while the blue and red emission intensities are very weak.

[0459] In another embodiment, the co-doped Tm 3+ / Yb 3+ TeO2-Ga2O3-R2O (R = Li, Na, K) glasses have been reported to be upconverters and are suitable for the present invention. These materials exhibit strong blue upconversion emission centered at 476 nm under 977 nm excitation, accompanied by weak red emission at 650 nm.

[0460] In another embodiment, [Ru(dmb)3] 2+The metal-to-ligand charge transfer (MLCT) transition in (dmb = 4,4'-dimethyl-2,2'-bipyridine) in the presence of anthracene or 9,10-biphenylanthracene has been reported to be an upconverter and is suitable for the present invention. Upconversion is an upconverter and is suitable for the present invention. It has been reported that the upconverted singlet fluorescence is caused by triplet-triplet annihilation at low excitation power. In particular, 9,10-biphenylanthracene (DPA) (substituted anthracene) showed a higher upconversion efficiency. In these experiments, the workers using this material system hypothesized that DPA increased the singlet fluorescence quantum yield (=0.95) relative to anthracene (=0.27)7. This effect resulted in an enhancement of the green to blue light upconversion by approximately 24.4±6.1, allowing the process to be carried out at low excitation power, for example by a commercial green laser pointer (λ ex =532nm, <5mW peak power) for direct visualization.

[0461] Structures with energy-enhancing structures described herein for color enhancement are denoted as color-enhancing / energy-enhancing structures or energy-enhancing / enhancing structures.

[0462] By placing an energy converter or color conversion or enhancement material in the vicinity of the energy enhancement structure of the present invention, regardless of whether the energy enhancement structure is in the enhanced electric field region or otherwise outside the enhanced electric field region, the color enhancement / energy enhancement structure or energy enhancement / enhancement structure of the present invention can generate light, which can be used for various applications, in particular for photostimulation of biological, chemical and physical reactions, such as photoactivation of photoreactive drugs, photoactivation of photosensitive materials such as adhesives or lithographic photoresists, or direct interaction with biological and chemical agents in the environment of the enhancement structure as in sterilization.

[0463] Thus, in one embodiment of the present invention, the color-enhancing structures described herein can receive polychromatic light from various sources, such as sunlight, incandescent light bulbs, fluorescent tubes, and LED light sources, each having a different wavelength or wavelength band. For these wavelengths or different wavelength bands, the resonator is "matched" or "tuned" to those wavelengths so that a strong electric field is established, particularly between the outer electrode pair, or between the folded resonator electrode pair (if used). In these strong electric field regions, a color converter (up-converting and / or down-converting phosphor) can be disposed that absorbs light from one of the different wavelengths or wavelength bands and emits light from another wavelength or different wavelength band. In one embodiment, the strong electric field increases the intensity of the emitted light from the phosphor. In addition, unlike the plasmons mentioned above where the electric field enhancement is limited to the region within 100 to 200 nm of the metal, the resonator establishes an increased electric field within the volume of the external electrode pair, or the folded resonator electrode pair (if used), so that the phosphor material near and within the external electrode pair (or folded resonator electrode pair) exhibits greater intensity than when the converter is far away from the resonator.

[0464] In view of the foregoing, the present invention generally relates to methods and systems for color enhancement using color enhancement structures, the color enhancement structures having: a) an energy collector, the energy collector including at least one energy enhancement structure, and b) an energy converter, the energy converter capable of converting electromagnetic energy of a second wavelength / quanta into light of a third wavelength having a wavelength / energy shifted relative to the second wavelength / quanta of electromagnetic energy, and emitting the light of the third wavelength from the energy converter. In one embodiment, the energy converter is positioned proximate to the at least one energy enhancement structure such that the wavelength-shifted light is emitted with a greater intensity than if the converter were remote from the at least one energy enhancement structure. For ease of understanding, the term "wavelength" will be used to describe the electromagnetic energy entering the energy converter, but in some embodiments, the electromagnetic energy may be better described based on its energy level or intensity.

[0465] By placing an energy converter or color conversion or enhancement material near the energy enhancement structure of the present invention, regardless of whether the energy enhancement structure is in the enhanced electric field area or otherwise outside the enhanced electric field area, the color enhancement / enhancement structure or energy enhancement / enhancement structure of the present invention can enhance the conversion of one form of energy to another form of energy, as the conversion of one or more wavelengths of light to other wavelengths of light, or as the conversion of one or more wavelengths of light to electrical energy, or as the conversion of one or more wavelengths of light to heat.

[0466] The conversion of one or more wavelengths of light to other wavelengths can be used for color shifting and color enhancement applications. The conversion of one or more wavelengths of light to electrical energy can be used to capture solar energy using, for example, photovoltaic cells. The conversion of one or more wavelengths of light to heat can also be used to capture solar energy using, for example, thermoelectric cells or other thermoelectric energy devices, such as thermoelectric generators.

[0467] In some embodiments of the color enhancement / energy enhancement structure, the color enhancement structure includes a multidimensional light collector, the multidimensional light collector including a first level metal pattern and a second level metal pattern, the second level metal pattern being offset relative to the first level metal pattern in at least one of a lateral or axial direction. At least one of the metal patterns optionally includes a first resonator sized to resonate with a first wavelength of light. The first resonator can be one of a folded structure or an external electrode pair structure as described above. The color enhancement structure has a converter capable of converting light of a second wavelength into light of a third wavelength having a wavelength shifted relative to the second wavelength of light, and emitting the third wavelength of light from the converter. The converter is arranged together with the first resonator so that the wavelength-shifted light is emitted with a greater intensity than if the converter were spaced away from the first resonator.

[0468] In some embodiments, the energy converter is disposed proximate to the at least one energy-enhancing structure to conductively couple the energy converter to the at least one energy-enhancing structure.

[0469] For example, in some embodiments, an energy converter is disposed proximate to at least one energy-enhancing structure and includes a physical conductive connection between the energy converter and the at least one energy-enhancing structure.

[0470] In some embodiments of the color enhancement / energy enhancement structure, the energy converter comprises a down converter that converts ultraviolet light or blue light into red light, yellow light, or green light. In some embodiments of the color enhancement / enhancement structure, the energy converter comprises an up converter that converts infrared light or red light into yellow light, green light, or blue light.

[0471] In some embodiments of the color enhancement / energy enhancement structure, the metal pattern mentioned above constitutes a folded resonant body with opposing electrodes, the electric field is oriented between the opposing electrodes, and the converter is positioned between the opposing electrodes, or positioned within the fringe electric field of the opposing electrodes, or otherwise positioned near the opposing electrodes. In one example, the folded resonant body is Folded resonator. In one example, the metal pattern includes at least one of the following: Au, Ag, Cu, Al, or a transparent metal oxide. In another example, the metal pattern may be formed of a refractory metal such as Ti, W, and Mo.

[0472] In some embodiments of the color enhancement / energy enhancement structure, the metal pattern mentioned above constitutes an external electrode pair structure having opposing electrodes, the electric field is oriented between the opposing electrodes, and the converter is positioned between the opposing electrodes, or positioned within the fringe electric field of the opposing electrodes, or otherwise positioned near the opposing electrodes. In one example, the resonator is The external electrode pair resonator. In one example, the metal pattern includes at least one of the following: Au, Ag, Cu, Al, or a transparent metal oxide. In another example, the metal pattern can be formed of a refractory metal such as Ti, W, and Mo.

[0473] In some embodiments of the color enhancement / energy enhancement structure, color enhancement structure, there is an anti-reflective film disposed on at least one of the metal patterns or on the converter.

[0474] In some embodiments of the color-enhancing / energy-enhancing structure, the first resonator mentioned above includes a plurality of resonators, the converter mentioned above includes a plurality of converters, and the plurality of converters are disposed at a plurality of locations throughout the light collector. In one example, the plurality of converters are positioned to convert light scattered internally within the light collector.

[0475] In some embodiments of the color enhancement / energy enhancement structure, the aforementioned first-level metal pattern (or second-level metal pattern) comprises a metal core clad with a high-K dielectric, followed by a cladding layer of a low-K dielectric. In some embodiments of the color enhancement / energy enhancement structure, the aforementioned first-level metal pattern (or second-level metal pattern) comprises a radial conductor pattern. In some embodiments of the color enhancement / energy enhancement structure, the aforementioned first-level metal pattern (or second-level metal pattern) comprises a fractal pattern. In one example, the fractal pattern is embedded within the dielectric material.

[0476] In some embodiments of the color-enhanced / energy-enhanced structure, the first-level metal pattern (or the second-level metal pattern) mentioned above comprises a three-dimensional fractal structure.

[0477] In some embodiments of color enhancement / energy enhancement structures, a light collector comprises a transparent panel having a first layer metal pattern and a second layer metal pattern, and optionally a plurality of converters formed in the metal pattern. In some embodiments of color enhancement / enhancement structures, a light collector comprises a transparent sheet having a first layer metal pattern and a second layer metal pattern, and optionally a plurality of converters formed in the metal pattern.

[0478] In some embodiments of the color enhancement / energy enhancement structure, the above-mentioned first level metal patterns (or second level metal patterns) have different sizes and / or orientations relative to each other or relative to the second level metal patterns.

[0479] In fact, Figure 29 Schematic diagram of a reflective resonator including a mechanoluminescent material according to the present invention. In this example, the mechanoluminescent material is placed between a folded resonator structure, but the mechanoluminescent material can also be placed between an external electrode pair of the resonator structure. Therefore, in one embodiment, the electromagnetic wave energy enhancement body captures electromagnetic energy of one or more wavelengths and enhances the electromagnetic energy of one or more wavelengths in terms of at least one property (such as the electric field strength near the mechanoluminescent material). At the same time, the mechanoluminescent material can be regarded as an energy converter that converts ultrasonic or mechanical energy into electromagnetic radiation (i.e., emits light).

[0480] In one embodiment of the invention, an increased electric field in the folded structure or external electrode pair increases the luminescence of the mechanoluminescent material. The energy for establishing the electric field in the folded structure or external electrode pair is provided separately from the mechanical energy driving the mechanoluminescence.

[0481] For example, Figure 29 The reflective resonator can be placed adjacent to the exhaust pipe of an engine or other waste heat dissipation machine. In one embodiment, Figure 29 The reflective resonator may be mounted on a stainless steel arm connected to the heat pipe. The stainless steel will couple mechanical vibrations to the reflective resonator while thermally isolating the reflective resonator from the exhaust pipe, allowing even inorganic myoluminescent materials to be used.

[0482] When the engine begins to exhibit higher levels of vibration, or vibrations at different frequencies, the intensity of the emitted light changes, providing a visible light signature that the engine or machine is under stress due to electrical load or wear or mechanical failure.

[0483] In one embodiment of the present invention, Figure 29 The reflective structure shown does not need to include a resonator and its resonant elements. In one embodiment of the present invention, Figure 29 The reflective structure shown can be placed directly on a machine operating at relatively low temperatures, around 100°C. In this embodiment, the reflective structure does not need to include a resonant body and its resonant elements. However, if a resonant body and its resonant elements are present, a laser, such as a 656nm laser, can "probe" the resonant body and enhance the mesoluminescence "on demand." This allows for early detection of mechanical problems during development.

[0484] Various mechanoluminescent materials suitable for the present invention include: ZnS:Mn 2+ 、SrAl2O4:Eu 2+ 、ZnS:Cu、SrAMgSi2O7:Eu 2+ (A=Ca, Sr, Ba), KCl, KI, KBr, NaF, NaCl, LiF, RbCl, RbBr, RbI, MgO, SrAl2O4, CaAl2O4, Sr 1-x Ba x Al2O4 (x=0, 0.1, 0.2, 0.4), Sr 0.9 Ca 0.1 Al2O4、Zn2Ge 0.9 Si 0.1 O4, MgGa2O4, ZnGa2O4, ZnAl2O4, ZnS, ZnTe, (ZnS) 1-x (MnTe) x (x<1 / 4), CaZnOS, BaZnOS, Ca2MgSi2O7, Sr2MgSi2O7, Ba2MgSi2O7, SrCaMgSi2O7, SrBaMgSi2O7, Sr n MgSi2O 5+n (1≤n≤2), Ca2Al2SiO7, Sr2Al2SiO7, CaYAl3O7, CaAl2Si2O8, Ca 1-x Sr x Al2Si2O8(x<0.8), SrMg2(PO4)2, Ba 1-x Ca x TiO3(0.25 <x<0.8)、Ba 1-x Ca x TiO3, LiNbO3, Sr2SnO4, (Ca,Sr,Ba)2SnO4, Sr3Sn2O7, Sr3(Sn,Si)2O7, Sr3(Sn,Ge)2O7 , Ca3Ti2O7, CaNb2O6, Ca2Nb2O7, Ca3Nb2O8, BaSi2O2N2, SrSi2O2N2, CaZr(PO4)2, ZrO2.

[0485] Yanim Jia, in “Novel Mechano-Luminescent Sensors Based on Piezoelectric / Electroluminescent Composites,” Sensors (Basel). 2011; 11(4): 3962–396 (incorporated by reference in its entirety), describes a mechanoluminescent composite material made of a piezoelectric material and an electroluminescent material. In this composite device, when stress is applied to the piezoelectric layer, charges are induced on both the top and bottom surfaces of the piezoelectric layer due to the piezoelectric effect. These induced charges generate light output from the electroluminescent layer due to the electroluminescent effect.

[0486] Here, in one embodiment of the present invention, such composite materials made of piezoelectric materials and electroluminescent materials (hereinafter referred to as "composite myoluminescent emitters") provide structures that emit light when stimulated with mechanical or vibrational energy, such as from an acoustic or ultrasonic transducer. Details of various electroluminescent materials that can be used in composite myoluminescent emitters are provided in the following sections, where the electroluminescent materials are individually placed near opposing resonator electrodes.

[0487] Figure 30 Schematic diagram of a composite myoluminescent emitter composed of a piezoelectric material and an electroluminescent material. In one embodiment, the composite myoluminescent emitter can be Figure 29 Mechanoluminescent light emitters in.

[0488] In another embodiment, a composite mesoluminescent emitter can be used without the need for any resonant body structure. Figure 31 is a schematic diagram showing composite mechanoluminescent emitters distributed across a region of interest for light generation therefrom. Figure 31 It is shown that these composite mesoluminescent emitters can be stimulated / activated using an ultrasonic transducer.

[0489] In color enhancement applications, applying ultrasonic energy can alter the color emission from a surface. Such applications can be used in security systems, where an article would contain a pattern of composite mesoluminescent emitters. This pattern is not noticeable until it is activated by ultrasonic or acoustic energy, at which point light of a predetermined wavelength is emitted. The emitted light can be visible or infrared, depending on the type of detector used to detect the emitted light.

[0490] In the relevant applications of these composite mesoluminescent emitters, Figure 32Schematic diagram illustrating a composite myoluminescent emitter distributed within a medium of interest for generating light therefrom or therefrom. In the present invention, the light can be activated and deactivated, and the intensity of the light can be varied, by the on / off state of an ultrasonic transducer. There are no power leads extending into the medium of interest. There is no space occupied by batteries or control elements to turn the power on and off. The composite myoluminescent emitter can be miniaturized. The composite myoluminescent emitter can be aggregated in a container. In some embodiments, the container may not be fully enclosed, thereby permitting the container to be tilted to reposition the composite myoluminescent emitter within the container.

[0491] Electroluminescent and phosphorescent materials (organic and inorganic): In various embodiments, the present invention may use organic fluorescent molecules or inorganic particles with crystalline, polycrystalline or amorphous microstructures capable of emitting fluorescence and phosphorescence for converters (optionally including the energy enhancement structure described above) with or without energy enhancement bodies.

[0492] The list of inorganic molecules that can be used in resonant structures to enhance color emission includes, but is not limited to, the following inorganic electroluminescent phosphor materials:

[0493] SrS:Ce 3+

[0494] CaGa2S4:Ce 3+

[0495] SrS:Cu +

[0496] CaS:Pb 2+

[0497] BaAl2S4:Eu 2+

[0498] ZnS:Tb 3+

[0499] ZnMgS:Mn 2+

[0500] SrGa2S4:Eu 2+

[0501] CaAl2S4:Eu 2+

[0502] BaAl2S4:Eu 2+

[0503] ZnS:Mn 2+

[0504] MgGa2O4:Eu 3+

[0505] (Ca,Sr)Y2S4:Eu 2+

[0506] BaAl2S4:Eu 2+

[0507] Organic molecules that can emit phosphorescence under the influence of an electric field are also of interest in this application. As examples, organic fluorescent compounds with high quantum yields include:

[0508] Naphthalene,

[0509] Pyrene,

[0510] Perylene,

[0511] Anthracene,

[0512] Philippines,

[0513] p-terphenyl,

[0514] Tetraphenyl,

[0515] trans-stilbene,

[0516] Tetraphenylbutadiene,

[0517] Distyrylbenzene,

[0518] 2,5-diphenyloxazole,

[0519] 4-Methyl-7-diethylaminocoumarin,

[0520] 2-phenyl-5-(4-biphenyl)-1,3,4-oxadiazole,

[0521] 3-phenylcarbonylstyryl,

[0522] 1,3,5-Triphenyl-2-pyrazoline,

[0523] 1,8-Naphthoylene-1',2'-benzimidazole,

[0524] 4-Amino-N-phenyl-naphthalimide.

[0525] The inorganic fluorescent and phosphorescent materials described in detail herein are numerous and various examples are given by way of example and not limitation. In addition, these materials may be doped with specific ions (activators or combinations of activators) that occupy sites in the lattice structure in the case of crystalline or polycrystalline materials and may occupy network-forming sites or bridging and / or non-bridging sites in amorphous materials. These compounds may include (not ranked in order of preference or utility) the following examples of materials:

[0526] CaF2, ZnF2, KMgF3, ZnGa2O4, ZnAl2O4, Zn2SiO4, Zn2GeO4, Ca5(PO4)3F, Sr5(PO4)3F, CaSiO3, MgSiO3, ZnS, MgGa2O4, LaAl 11 O 18 , Zn2SiO4, Ca5(PO4)3F, Mg4Ta2O9, CaF2, LiAl5O8, LiAlO2, CaPO3, AlF3.

[0527] Also included are alkaline earth chalcogenide phosphors, which in turn are exemplified by the following non-inclusive list:

[0528] MgS:Eu 3+ 、CaS:Mn 2+ 、CaS:Cu、CaS:Sb、CaS:Ce 3+ 、CaS:Eu 2+ 、CaS:Eu 2+ Ce 3+ 、CaS:Sm 3+ 、CaS:Pb 2+ 、CaO:Mn 2+ 、CaO:Pb 2+ .

[0529] Examples include ZnS type phosphors, including various derivatives:

[0530] ZnS:Cu,Al(Cl), ZnS:Cl(Al), ZnS:Cu,I(Cl), ZnS:Cu, ZnS:Cu,In.

[0531] IIIb-Vb compound phosphors, comprising elements from Groups IIIb and Vb of the periodic table, are suitable converter materials. These semiconductors include BN, BP, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb. These materials also have donors and acceptors that work together to create a light-emitting diode. Donors include Li, Sn, Si, Li, Te, Se, S, and O, while acceptors include C, Be, Mg, Zn, Cd, Si, and Ge. As an example, GaP light-emitting diodes include GaP:Zn,O, GaP:NN, GaP:N, and GaP, which emit red, yellow, green, and pure green, respectively.

[0532] Composite materials also include materials such as GaAs with compositional variations of the following kind: In1-y(Ga1-xAlx)yP (to provide a simple example).

[0533] Silicon carbide (SiC) is commercially relevant as a light-emitting platform in blue light-emitting diodes. These include the polytypes 3C-SiC, 6H-SiC, and 4H-SiC, which have donors such as N and Al, and acceptors such as Ga and B.

[0534] Multi-band luminescent materials suitable for converter materials include, for example, the following components:

[0535] (Sr,Ca,Ba)5(PO4)3Cl:Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ 、CeMgAl 11 O 19 :Ce 3+ :Tb 3+ 、LaPO4:Ce 3+ :Tb 3+ 、GdMgB5O 10 :Ce 3+ :Tb 3+ 、Y2O3:Eu 3+ 、(Ba,Ca,Mg)5(PO4)3Cl:Eu 2+ , 2SrO 0.84 P2O5·0.16B2O3:Eu 2 + 、Sr4Al 14 O 25 :Eu 2+ .

[0536] Other materials suitable for converter materials include those used for fluorescent high-pressure mercury discharge lamps, which can be excited with X-rays and are exemplified by the following family names:

[0537] Phosphate (Sr,M)(PO4)2:Sn 2+ , Mg or Zn activator, germanate 4MgO.GeO2:Mn 4+ 、4(MgO,MgF2)GeO2:Mn 4+ , yttrium salt Y2O3:Eu 3+ , vanadate YVO4:Eu 3+ 、Y(P,V)O4:Eu 3+ 、Y(P,V)O4:In + , halogenated silicate Sr2Si3O8·2SrCl2:Eu 2+ 、Aluminate (Ba,Mg)2Al 16 O 24 :Eu 2+ 、(Ba,Mg)2Al16 O 24 :Eu 2+ 、Mn 2+ 、Y2O3Al2O3:Tb 3+ .

[0538] Another material grouping that utilizes a matrix compound suitable for converter materials includes halophosphate phosphors, phosphate phosphors, silicate phosphors, aluminate phosphors, borate phosphors, tungstate phosphors, and chemical components found in other phosphors.

[0539] Illustrative halophosphates include:

[0540] 3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ 、3Ca3(PO4)2.Ca(F,Cl)2:Sb 3+ / Mn 2+ 、Sr 10 (PO4)6Cl2:Eu 2+ 、(Sr,Ca) 10 (PO4)6Cl2:Eu 2+ 、(Sr,Ca) 10 (PO4)6.nB2O3:Eu 3+ 、(Sr,Ca,Mg) 10 (PO4)6Cl2:Eu 2+ As an example, the phosphate phosphor includes: Sr2P2O7:Sn 2+ 、(Sr,Mg)3(PO4)2:Sn 2+ 、Ca3(PO4)2.Sn 2+ 、Ca3(PO4)2:Tl + 、(Ca,Zn)3(PO4)2:Tl + 、Sr2P2O7:Eu 2+ 、SrMgP2O7:Eu 2+ 、Sr3(PO4)2:Eu 2+ 、LaPO4:Ce 3+ 、Tb 3+ 、La2O3·0.2SiO2·0.9P2O5:Ce 3+ .Tb 3+ 、BaO.TiO2·P2O5. Silicate phosphor Zn2SiO4:Mn 2+ 、CaSiO3:Pb 2+ / Mn 2 + 、(Ba,Sr,Mg).3Si2O7:Pb 2+ 、BaSi2O5:Pb2+ 、Sr2Si3O8·2SrCl2:Eu 2+ 、Ba3MgSi2O8:Eu 2+ 、(Sr,Ba)Al2Si2O8:Eu 2+ .

[0541] Aluminate phosphors include:

[0542] LiAlO2:Fe 3+ 、BaAl8O 13 :Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、Sr4Al 14 O 25 :Eu 2+ 、CeMgAl 11 O 19 :Ce 3+ / Tb 3+ .

[0543] Borate phosphors include:

[0544] Cd2B2O5:Mn 2+ 、SrB4O7F:Eu 2+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ 、GdMgB5O 10 :Ce 3+ / Mn 3+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ / Mn 2+ .

[0545] Tungstate phosphors include:

[0546] CaWO4, (Ca, Pb)WO4, MgWO4. Other phosphors Y2O3:Eu 3+ 、Y(V,P)O4:Eu 2+ 、YVO4:Dy 3+ 、MgGa2O4:Mn 2+ 、6MgO.As2O5:Mn 2+ 、3.5MgO.0.5MgF2·GeO2:Mn 4+ .

[0547] Relevant activators for various doped phosphors include the following list:

[0548] Tl + , Pb 2+ 、Ce 3+ 、Eu 2+ WO4 2- 、Sn 2+ 、Sb 3+ 、Mn 2+ 、Tb 3+ 、Eu 3+ 、Mn 4+ 、Fe 3+ .

[0549] In various embodiments, the luminescent center Tl+ can be used with chemical components such as:

[0550] (Ca,Zn)3(PO4)2:Tl + 、Ca3(PO4)2:Tl + .

[0551] Similarly, the luminescent center Mn2+ can be used with chemical components such as:

[0552] MgGa2O4:Mn 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、Zn2SiO4:Mn 2+ 、3Ca3(PO4)2·Ca(F,Cl)2:Sb 2+ / Mn 2+ 、CaSiO3:Pb 2+ / Mn 2+ 、Cd2B2O5:Mn 2+ 、CdB2O5:Mn 2+ 、GdMgB5O 10 :Ce 3+ / Mn 2+ 、GdMgB5O 10 :Ce 3+ / Tb 3+ / Mn 2+ .

[0553] In addition, the luminescence center Sn 2+ Can be used with chemical ingredients such as:

[0554] Sr2P2O7:Sn 2+ 、(Sr,Mg)3(PO4)2:Sn 2+ .

[0555] Luminescent center Eu 2+ Can also be used with chemical ingredients such as:

[0556] SrB4O7F:Eu 2+ 、(Sr,Ba)Al2Si2O8:Eu 2+ 、Sr3(PO4)2:Eu 2+ 、Sr2P2O7:Eu 2+ 、Ba3MgSi2O8:Eu 2 + 、Sr 10 (PO4)6Cl2:Eu 2+ 、BaMg2Al 16 O 27 :Eu 2+ / Mn 2+ 、(Sr,Ca) 10 (PO4)6Cl2:Eu 2+ .

[0557] Luminescence center Pb 2+ Can be used with chemical ingredients such as:

[0558] (Ba,Mg,Zn)3Si2O7:Pb 2+ 、BaSi2O5:Pb 2+ 、(Ba,Sr)3Si2O7:Pb 2+ .

[0559] Luminescence center Sb 2+ Can be used with chemical ingredients such as:

[0560] 3Ca3(PO4)2·Ca(F,Cl)2:Sb 3+ 、3Ca3(PO4)2·Ca(F,Cl)2:Sb 3+ / Mn 2+ .

[0561] The luminescent center Tb3+ can be used with chemical components such as:

[0562] CeMgAl 11 O 19 :Ce 3+ / Tb 3+ 、LaPO4:Ce 3+ / Tb 3+ 、Y2SiO5:Ce 3+ / Tb 3+ 、GdMgB5O 10 :Ce3+ / Tb 3+ .

[0563] Luminescent center Eu 3+ Can be used with chemical ingredients such as:

[0564] Y2O3:Eu 3+ 、Y(V,P)O4:Eu 3+ .

[0565] Luminescence center Dy 3+ Can be used with chemical ingredients such as:

[0566] YVO4:Dy 3+ .

[0567] Luminescent center Fe 3+ Can be used with chemical ingredients such as:

[0568] LiAlO2:Fe 3+ .

[0569] Luminescence center Mn 4+ Can be used with chemical ingredients such as:

[0570] 6MgO.As2O5:Mn 4+ 、3.5MgO.0.5MgF2·GeO2:Mn 4+ .

[0571] Luminescence center Ce 3+ Can be used with chemical ingredients such as:

[0572] Ca2MgSi2O7:Ce 3+ and Y2SiO5:Ce 3+ .

[0573] Luminescent center WO4 2- Can be used with chemical ingredients such as:

[0574] CaWO4, (Ca,Pb)WO4, MgWO4.

[0575] Luminescent center TiO4 4- Can be used with chemical ingredients such as:

[0576] BaO.TiO2·P2O5.

[0577] In various embodiments of the present invention, phosphor chemistries that utilize X-ray excitation can be used. Of particular interest are the k-edges of these phosphors. Low energy excitation can result in strong luminescence from materials with low k-edges. Some of these chemistries and their corresponding k-edges include the following:

[0578]

[0579]

[0580] In one embodiment of the present invention, light from these materials (e.g., by excitation with high energy particles, including x-rays, gamma rays, protons, and electrons) can be modulated by including these materials in the vicinity of (including within) the color-enhancing structures described herein. For example, in medical treatments where x-rays excite phosphors to photostimulate a response in a patient, there may be applied infrared radiation to drive the resonance of the color-enhancing / energy-enhancing structures described herein while irradiating with high energy particles, where the x-ray phosphors will have enhanced emission in the presence of an enhanced electric field. In another example, in medical or scientific instrumentation, there may be applied electric fields to enhance emission from these x-ray phosphors while irradiating with high energy particles.

[0581] C. Color Enhancement Structure

[0582] The present invention provides methods, systems, and devices for enhancing the effectiveness and / or efficiency of light emission from a medium using phosphorescent, fluorescent, and scintillating materials, or other energy conversion materials and devices described herein, with and without the energy enhancement structures described above. Utilizing energy enhancement structures, the present invention can generate localized regions with strong electric fields to enhance or accelerate light, or photon, or electron emission from materials proximate to these localized regions.

[0583] Phosphorescent Devices: Now that a wide variety of converter materials have been described that can be used for color enhancement in the present invention, Figure 33 is a schematic diagram of a reflective resonator of the present invention, wherein a converter material (such as phosphor and other luminescent materials described above) is used Inside the folded resonator, the folded resonator has metal traces made of transparent indium tin oxide on one side and a reflective metal such as Au, Ag, Al, or Cu on the other side. Alternatively, the resonator can have an external electrode pair structure (instead of the folded structure shown), and the converter material will reside within the electrode pair.

[0584] Figure 34Schematic diagram of an LED white light source with variable color temperature control. This structure closely follows the content described in US Patent Application Publication No. 2007 / 0215890 (the entire content of which is incorporated herein by reference).

[0585] As indicated above, in this embodiment, a conventional blue LED is attached to a base using solder bumps or other means. The base has metal contact pads on its surface to which the LED is electrically connected. The contact pads lead to other conductors formed on the periphery or underside of the base for connection to a power source such as a current source. Here, in one embodiment of the present color enhancement invention, the base is electrically connected to an electric field applicator. The electric field applicator can be a simple grid element as shown, which establishes a different controllable voltage at each of the levels shown so that the electric field inside the red phosphor plate and the green phosphor plate can be adjusted. By increasing or decreasing the electric field inside the red phosphor plate or the electric field inside the green phosphor plate, the intensity of the red and green light can be adjusted as needed and continuously (if necessary).

[0586] Here, in one embodiment of the present color enhancement invention, the base is not electrically connected to the electric field applicator, and the electric field applicator can be a folded resonator, such as the one described above. Folded resonator, or it can be a structure with external electrode pairs Resonator. Here, especially for high-power LED operation that generates waste heat, Folded resonator or The wavelength of the external electrode to the resonator may be approximately 5-10 microns, especially for high-power LED operation which generates waste heat.

[0587] As in the '890 publication, the LED can be formed using AlInGaN material and preferably emits blue light with a peak wavelength of about 460-470 nm to match the spectral distribution of conventional blue filters in LCDs. Other emission wavelengths (also contemplated for blue) may also be suitable, such as 440-480 nm. The top surface of the blue LED can be of any size, with a typical size being equal to or less than 1 mm. 2 .

[0588] Placed over the LEDs are a red phosphor plate and a green phosphor plate. The size of each plate can match the size of the LED, or can be slightly larger or smaller, depending on the emission pattern of the LED, tolerances, and the characteristics of the phosphor plates. The plates can extend beyond the LED surface by as much as 25%. In one embodiment, the plates are smaller than the LEDs (e.g., at most 50% smaller than the LEDs) to produce a larger blue component in the white light, or to allow the green and red phosphor plates to be placed side by side. In thin LEDs, there will be insignificant side emission. Any side emission will mix with the white light in the backlight box.

[0589] As in the '890 publication, the thickness of each phosphor plate can be between 50-300 microns, depending on the type of phosphor used, the type of blue LED used (e.g., higher power LEDs may require thicker plates), the density of the phosphor, and other factors that will be understood by those skilled in the art.

[0590] Electroluminescent device: Figure 35 Schematic diagram of an electroluminescent light source. A typical modern electroluminescent (EL) device has two co-layered organic materials. The EL device consists of a transparent indium tin oxide (ITO) anode, a hole transport layer (HTL) and an electron transport layer (ETL), and a metal cathode made of an alloy metal, and numerous embodiments are possible. The electron current (charge carrier flow) provides electrons to the emissive layer. The holes generated and flow (charge carriers) in the emissive layer can recombine with the electrons in the emissive layer and output light.

[0591] Figure 36 Schematic diagram of an electroluminescent light source having an electroluminescent medium in a folded resonant electrode according to the present invention.

[0592] Various materials for the coating in the emissive layer of the present invention may include, but are not limited to:

[0593] 4,4′,4″-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA)

[0594] N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)

[0595] 4,4′,4″-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA) N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) Tris-(8-hydroxyquinolinolato)aluminum

[0596] 2,4,6-Tris(2-pyridyl)-s-triazine (TPT)

[0597]

[0598] 2,2′,2"-(1,3,5-phenylene)-tris(1-phenyl-1-H-benzimidazole)Alq

[0599]

[0600] 2,2′,2"-(1,3,5-phenylene)-tris(1-phenyl-1-H-benzimidazole)TPBI

[0601]

[0602] 2,9-Dimethyl-4,7-diphenyl-1,10-o-phenanthroline BCP 2,9-Dimethyl-4,7-diphenyl-1,10-o-phenanthroline BCP

[0603]

[0604] In another embodiment, an optically transparent anode, such as indium tin oxide (ITO), is used. The converter material is placed in the capacitive portion of the curved antenna, which exposes the organic layers consisting of a hole transport layer (HTL) and an electron transport layer (ETL), as well as the metal cathode. In this example, the electromagnetic energy coupled to the antenna can operate from RF and microwave regimes to IR and UV regimes.

[0605] exist Figure 3-2 In embodiments, the energy converter or color conversion or enhancement material is disposed on the energy enhancement structure (ie, The energy-enhancing structure is therefore preferably located in the enhanced electric field region between the folded opposing electrodes. In one embodiment of the present invention, the enhanced electric field is an enhanced energy region because there is a conductive coupling of the energy converter (electroluminescent material) to an energy-enhancing structure ( folded resonant body).

[0606] Plasmon enhancement structure for color enhancement device:

[0607] The color enhancement device mentioned above can utilize the plasmon enhancement structure mentioned above. As mentioned above, Figure 26 is a schematic diagram illustrating an upconverter or downconverter material (ie, photosensitive material) for use in the color enhancement / enhancement structures referred to herein, with or without an energy enhancer, according to one embodiment of the present invention. Figure 26A plurality of structural configurations for placing a dielectric core upconverter or downconverter material (which has nanoscale dimensions) in close proximity to a metal housing are shown. Incident light at wavelength λ1 interacts with the upconverting dielectric core. The interaction of light λ1 with the dielectric core produces secondary emission at frequency λ2, which has a shorter wavelength than λ1 and therefore has a higher energy than λ1. While the exact physical mechanism of upconversion may depend on the specific upconversion materials and processes used in a particular application, the following explanation is provided for the purposes of discussion and illustration.

[0608] exist Figure 26 In the context of λ1, three separate processes are well understood for upconversion processes involving trivalent rare earth ions when the wavelength λ1 interacts with the dielectric material core.

[0609] The three processes are:

[0610] 1) Excited-state absorption, whereby two photons are absorbed sequentially by the same ion to excite and aggregate one or more states;

[0611] 2) Energy transfer upconversion, which is the transfer of excitation from one ion to another ion that is already in an excited state; and

[0612] 3) Multiphoton cooperative processes, in which two neighboring ions in an excited state jointly emit from a virtual state.

[0613] Regardless of which of these processes occurs between the selected ion or ions and the matrix lattice, the end result is the emission of photons from the matrix lattice with energy greater than the excitation energy to perform an upconversion or downconversion process.

[0614] Therefore, the specific ions that are activated (whether they are dopant ions or matrix ions of the lattice such as in neodymium oxide) will be selected based on the matrix material being processed so that the dopant ions or matrix ions in the dielectric core provide ionic states that can be pumped by the NIR source to produce the resulting emission λ2.

[0615] Therefore, in one embodiment, the present invention provides an up-conversion or down-conversion material, which is configured to produce radiation with a second wavelength λ2 having higher or lower energy than the first wavelength λ1 when exposed to radiation with a first wavelength λ1. The system may include a metal structure (e.g., a metal shell covering a portion of the nanoparticles) disposed relative to the nanoparticles. The system may include a receptor disposed in a medium close to the nanoparticles. The receptor itself may fluoresce after being activated by the second wavelength λ2, thereby generating visible light. In one embodiment of the present invention, the physical properties of the metal structure (such as those described above and below in the accompanying drawings) are set to a certain value, wherein the surface plasmon resonance in the metal structure resonates at a certain frequency, and the frequency provides spectral overlap with the first wavelength λ1 or the second wavelength λ2. This system with a metal structure disposed relative to the up-conversion or down-conversion nanoparticles becomes a converter for the color enhancement / enhancement structure mentioned herein.

[0616] In the context of the present invention, the term "physical properties" of a metal shell or core may relate to any property of the metal itself, or of the size or shape of the shell or core, that may affect the surface plasmon resonant frequency. Such physical properties may include, but are not limited to, electrical conductivity, radial dimensions, chemical composition, or crystalline state of the metal shell or core.

[0617] In various embodiments, the metallic structure can be a metallic shell that encapsulates at least a portion of the nanoparticles in the metallic shell, wherein the electrical conductivity, radial dimensions, or crystalline state of the metallic shell causes the surface plasmon resonance in the metallic structure to resonate at a frequency that provides spectral overlap with the first wavelength λ1 or the second wavelength λ2. In various embodiments, the metallic structure can be a multilayer metallic shell that encapsulates at least a portion of the nanoparticles in the metallic shell, wherein the electrical conductivity, radial dimensions, or crystalline state of the metallic shell causes the surface plasmon resonance in the metallic structure to resonate at the first wavelength λ1 and the second wavelength λ2. This capability permits amplification of radiation at λ1 and λ2.

[0618] In various embodiments, the metal structure can be a metal particle present in one or more multiple structures. These multiple structures can have various shapes, including, for example, spherical, ellipsoidal, rod-shaped, cube, triangle, pyramidal, columnar, crescent, tetrahedral, star-shaped or its combination, arranged adjacent to the nanoparticle, wherein the electrical conductivity, size (for example, lateral dimension or thickness) or crystalline state of the metal structure make the surface plasmon resonance in the metal particle or the rod resonate with a certain frequency, and the frequency provides a spectrum overlap with the first wavelength λ 1 or the second wavelength λ 2. Such shapes are described in the accompanying drawings of the present invention and in the drawings in U.S. Serial No. 12 / 401,478, which is incorporated by reference in its entirety. Shape selection may affect the frequency of surface plasmon resonance. It is known that plasmon bands can change with the shape (for example, oblate and oblate ellipsoids) of the nanoparticle. The paper "Spectralbounds on plasmon resonances for Ag and Au prolate and oblate nanospheroids," Vol. 2, 029501 (September 26, 2008), in the Journal of Nanophotonics (incorporated by reference in its entirety), shows the shift of plasmon resonances of prolate and oblate ellipsoids in the formation of Ag and in the formation of Au. In one embodiment of the invention, as the aspect ratio of the metal structure of the invention increases, the prolate ellipsoid resonances are red-shifted relative to the sphere, with no lower limit (under the assumption of the Drude dispersion model). On the other hand, the oblate resonances are "blue-shifted" as the ellipsoid becomes increasingly flattened, but only up to a limit.

[0619] In various embodiments, the metal structure disposed relative to the up-converting or down-converting nanoparticle can be a metal structure disposed within the nanoparticle, wherein the conductivity or dimensions (e.g., lateral dimensions or thickness) of the metal structure cause the surface plasmon resonance in the metal structure to resonate at a frequency that provides spectral overlap with the first wavelength λ1 or the second wavelength λ2. In various embodiments, the metal structure can be a multilayer metal structure disposed within the nanoparticle, wherein the conductivity or dimensions (e.g., lateral dimensions or thickness) of the metal structure cause the surface plasmon resonance in the metal structure to resonate at the first wavelength λ1 and the second wavelength λ2. This capability again permits amplification of radiation at λ1 and λ2.

[0620] In another embodiment, the invention provides nanoparticle structures comprising a dielectric core below 1000 nm and a metallic structure arranged relative to the nanoparticles. The dielectric core comprises at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2. In certain embodiments, such nanoparticle structures can exhibit surface plasmon resonance in the metallic structure to enhance up-conversion of light from a first wavelength λ1 to a second wavelength λ2.

[0621] As described above, the shell (or other structure) is specifically designed to have a layer thickness (or, for example, a lateral dimension) to enhance the photon upconversion process through plasmon enhancement. The thickness (or other physical property) of the shell is "tuned" to a thickness suitable for the absorption process by having a certain dimension at which the plasmons (i.e., electron oscillations) in the shell resonate at a frequency that provides spectral overlap with the absorption band being directed. Thus, if upconversion is to be stimulated by 980 nm NIR light, the thickness of the shell is "tuned" to a thickness at which the plasmon resonance resonates at a frequency that is also 980 nm (or around it, as plasmon resonances are generally broad at these wavelengths).

[0622] Plasmon resonant shells can be made from a variety of transition metals, including but not limited to gold, silver, platinum, palladium, nickel, ruthenium, rhenium, copper, and cobalt, or combinations or alloys or layers thereof. Such plasmon resonant shells can also be made from combinations of metals and non-metals. When formed from gold nanoshells, the recommended thickness for resonance with 980 nm light is approximately 3.5 nm surrounding an 80 nm upconversion core, as predicted by extended Mie theory calculations. (See Jain et al. , Nanolett. 2007, 7(9), 2854, the entire contents of which are incorporated herein by reference.) Figure 27 from Jain et al. and illustrates the ability of the present invention to "tune" the metal housing to have spectral overlap with the excitation and / or emission radiation wavelengths.

[0623] In one embodiment of the present invention, the metal structure provided with respect to the up-conversion or down-conversion nanoparticles may be an alloy, such as, for example, an Au:Ag alloy. The alloy content may be set to adjust the frequency of the surface plasmon resonance. In one embodiment of the present invention, the metal structure may be an alloy, such as, for example, a Pt:Ag alloy. The alloy content may be set to adjust the frequency of the surface plasmon resonance. In one embodiment of the present invention, the metal structure may be an alloy, such as, for example, a Pt:Au alloy. The alloy content may be set to adjust the frequency of the surface plasmon resonance.

[0624] In one embodiment of the present invention, the converter nanoparticles may be an alloy of two or more materials. In this embodiment, the alloy may have a composition between the two or more materials, and the composition is set to a composition value at which excitation of the alloy at a first wavelength λ1 produces emission at a second wavelength λ2. In one embodiment of the present invention, the nanoparticles may be an alloy of zinc sulfide and zinc selenide. In one embodiment of the present invention, the nanoparticles may be an alloy of zinc sulfide and cadmium sulfide.

[0625] In one embodiment of the present invention, the zinc sulfide and zinc selenide nanoparticle alloy may have an alloy content configured to provide a predetermined surface plasmon resonance. In one embodiment of the present invention, the zinc sulfide and cadmium sulfide nanoparticle alloy may have an alloy content configured to provide a predetermined surface plasmon resonance.

[0626] Some techniques for producing nanoparticles and nanoparticle alloys suitable for the present invention are described in the following documents, all of which are incorporated herein in their entirety: U.S. Patent Nos. 7,645,318; 7,615,169; 7,468,146; 7,501,092; U.S. Patent Application Publication Nos. 2009 / 0315446; 2008 / 0277270; 2008 / 0277267; 2008 / 0277268; and WO 2009 / 133138.

[0627] In one embodiment of the present invention, the thickness of the metal shell disposed relative to the upconverting or downconverting nanoparticles is set based on the absorption frequency (or in some cases, the emission frequency) of the specific dopant ions in the dielectric core to improve the overall efficiency of the upconverted light emission process. Thus, the thickness of the shell can be viewed as a tool to enhance the absorption of λ1 in one case and the emission of λ2 in another, or in other cases as an enhancing feature that jointly enhances the overall net process.

[0628] Additionally, plasmon-phonon coupling can be used to lower the resonant frequency by tuning the band to a certain degree off-resonance. This may be used to optimize the resonant energy transfer process to achieve the goal of shifting the output color to a desired color for a coating, colored, or display surface. In one example, Figure 27 An example of plasmon resonance shift as a function of shell thickness is shown.

[0629] Here, in one embodiment of the present invention, the ability to generate stimulated emission at a target wavelength, color, or energy is complemented by the ability to design nanoparticles with designed absorption bands. Such absorbing materials can, for example, further be used to enhance the monochromaticity of light observed from a coating, ink, dye, or other reflective surface treated with the color-enhancing composition of the present invention.

[0630] The details of preparing this nanoparticle system are included in U.S. Serial No. 12 / 725,108, the entire contents of which are incorporated herein by reference. The absorption spectrum of Y2O3 alone (lower trace) is completely featureless, showing absorption near 200 nm due to tri-arginine and a gentle slope associated with scattering, as well as absorption of the Y2O3 nanoparticles extending into the visible portion of the spectrum. On the other hand, gold-coated Y2O3 (upper trace) exhibits a strong absorption band at 546 nm, a characteristic of the plasmon resonance band caused by the gold shell surrounding the Y2O3 core. The red shift of the plasmon absorption to 546 nm is consistent with the presence of a gold shell surrounding the dielectric core.

[0631] In one embodiment of the present invention, as described above, the converter material for the upconverter dielectric core can include a variety of dielectric materials. In various embodiments of the present invention, the upconverter dielectric core more specifically includes an oxide material doped with lanthanides. Lanthanides include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and ytterbium (Lu). Other suitable dielectric core materials include non-lanthanides, such as yttrium (Y) and scandium (Sc). Therefore, suitable dielectric core materials include Y2O3, Y2O2S, NaYF4, NaYbF4, Na-doped YbF3, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, or SiO2. These dielectric cores can be doped with Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd, and other rare earth species or combinations thereof.

[0632] Lanthanides usually exist as trivalent cations, in which case their electron configuration is (Xe)4f n , where n is 1(Ce 3+ ) to 14(Lu 3+ ). Transitions within the f cluster determine many of the photophysical properties of lanthanide ions, such as persistent luminescence and steep absorption and emission lines. The f electrons are protected from external perturbations by populated 5s and 5p orbitals, resulting in line-shaped spectra. The LaPorte-forbidden nature of ff electron transitions leads to long excited-state lifetimes, ranging from microseconds to milliseconds.

[0633] Therefore, the example of doping material among the present invention comprises oxide, such as yttrium oxide and neodymium oxide and aluminum oxide, and sodium yttrium fluoride and nanocrystal perovskite and garnet, such as yttrium aluminum garnet (YAG) and yttrium aluminum perovskite (YAP).In these materials, some but not all in these materials need doping to promote up-conversion efficiency.In various embodiments of the present invention, matrix nanocrystal is doped with trivalent rare earth lanthanide ions from those lanthanide series elements given above.

[0634] More specifically, in various embodiments of the present invention, these dopant pairs are introduced in order to create more energy states that can be reached in the matrix crystal. The activation and pumping of these energy states strictly follow the principles discussed above. In the present invention, the doping concentration can range from about 0.2% to 20% in terms of ions entering the matrix lattice or in terms of weight % or mol % variation. The efficiency of the upconversion process of specific wavebands in these materials can be adjusted by the doping percentage to induce and enhance the target emission. Lanthanide-doped upconverters can use (but are not limited to) the following molar percentages of dopant compositions: 5% Er, 10% Yb, 0.2% Tm+3% Yb and 1% Er+10% Yb.

[0635] The size of the nanocrystals also has an impact on the efficiency of the upconversion process, as larger nanocrystals will have more sites for dopant ions to be accommodated in the matrix lattice, thereby enabling more emission to be produced from the same doped matrix than would be the case with smaller nanocrystals. While the dopant percentages listed above are not strictly fixed, these numbers provide a basic guide to typical percentages that one would use to obtain the specific dielectric core materials of the present invention.

[0636] Furthermore, in one embodiment of the present invention, some of these base crystals (e.g., neodymium oxide) may not require specific doping to promote upconversion, as has been seen in one case of Nd2O3 producing emissions at 372 nm, 402 nm, and 468 nm at an excitation wavelength of 587 nm. See Que, W et al., Journal of Applied Physics 2001, Vol. 90, p. 4865, the entire contents of which are incorporated herein by reference. In one embodiment of the present invention, neodymium oxide is doped with Yb 3+ By using lower energy Yb 3+ Activator makes Nd 3+ Ion sensitization to enhance upconversion.

[0637] In one embodiment of the invention, the dielectric core is coated with, for example, a metal shell to strengthen electron-phonon coupling and thereby improve up-conversion or down-conversion efficiency as discussed above. In another embodiment of the invention, the shell can include a SiO2- and / or TiO2-coating, and in one embodiment, this coating is coated on doped Y2O3 up-conversion nanoparticles, thereby improving up-conversion efficiency relative to uncoated nanocrystals in some cases. In another embodiment of the invention, the shell can include a SiO2- and / or TiO2-coating, and in one embodiment, this coating is coated on doped Y2O3 down-conversion nanoparticles, thereby improving down-conversion efficiency relative to uncoated nanocrystals in some cases. In addition, in one embodiment of the invention, the coating can be a polymer. In one embodiment, this coating is provided on a NaYF4:Ln / NaYF4 dielectric core. Such coatings can improve up-conversion efficiency relative to uncoated up-converters.

[0638] In another embodiment of the present invention, the phonon modes of undoped matrix lattice (e.g., Y2O3) nanocrystals are tuned, for example, by shells of Au, Ag, Pt, and Pd of varying thickness. In various embodiments of the present invention, the upconverter dielectric core and shell system includes Y2O3:Ln with a NaYF4 shell, Y2O3:Ln with an Au(Ag,Pt) shell, NaYF4:Ln with a Y2O3 shell, and NaYF4:Ln with an Au(Ag,Pt) shell as upconverter nanocrystals. In this system, the core diameter and the outer / inner diameter of the metal-coated shell can be set to a size that is expected to be tuned for plasmon mode overlap.

[0639] In other embodiments as discussed below, the metal coating or the metal structure that are provided with respect to up-conversion or down-conversion nanoparticles can be present in dielectric inside, and the relative position of metal structure and dielectric structure can strengthen plasmon resonance.These structures with metal structure inside can be referred to as metal core up-converter or metal core down-converter. The metal core technology for energy conversion is useful because this technology utilizes the metal nanoparticles with improved surface morphology compared to the shell coating on the core dielectric. The metal or metal alloy in the inner core metal energy converter can be selected to tune its plasmon activity.These structures with metal structure outside can be referred to as core up-converter or core down-converter.

[0640] In various embodiments of the present invention, the upconverter or downconverter dielectric core can be coated with a thiol-terminated silane to provide a SiO2 coating around the core with a reactivity similar to Y2O3. In one embodiment of the present invention, the method described above is used to synthesize the following core-shell nanoparticles: Y2O3:Ln with a NaYF4 shell, Y2O3:Ln with an Au(Ag,Pt) shell, NaYF4:Ln with a Y2O3 shell, NaYF4:Ln with an Au(Ag,Pt) shell, wherein the core and shell diameters vary between 2 and 20 nm. In these material systems, the adjusted ratio of the core-shell diameters can permit plasmon-phonon resonances that should amplify the absorption and / or upconversion emission of NIR light. In these material systems, control of the core and shell diameters is a factor that determines size-dependent effects and subsequent tuning of the plasmon-phonon resonances.

[0641] In one embodiment of the present invention, the upconverter dielectric core can be a hybrid core-shell material, including, for example, semiconductor-type Y2O3 and NaYF4 cores doped with various Ln series metals, which have been shown to have greater upconversion efficiency. These doped Y2O3 and NaYF4 cores will have a shell of Au (Ag, Pt, Pd) or an undoped Y2O3 and NaYF4 matrix, which has the potential to enhance or tune the phonon modes required for energy transfer during the upconversion process. Solubility can be improved, for example, by adding thiolated organics (Au shell), organic chain triethanolsilane (Y2O3 shell), and trioctylphosphine-oleic acid amine (NaYF4 shell). All core-shell nanoparticles can be further dissolved into a colloidal suspension with the addition of tri-arginine peptide, polyethylene glycol, and polyethyleneimine surfactants.

[0642] Figure 28ASome of the various embodiments of converter structures that can be designed according to the present invention are shown: (a) a structure comprising upconverter (UC) molecules bound to metal (gold) nanoparticles; (b) a structure comprising UC-containing nanoparticles covered with metal nanoparticles; (c) metal nanoparticles covered with UC-containing nanocaps; (d) UC-containing nanoparticles covered with metal nanocaps; (e) metal nanoparticles covered with UC nanoshells; (f) UC-containing nanoparticles covered with metal nanoshells; and (g) UC-containing nanoparticles covered with metal nanoshells having a protective coating.

[0643] The configuration (in Figure 28A UC materials) would be suitable for enhancement of down conversion materials such as quantum dots or phosphors described herein. In addition, in one embodiment of the present invention, dielectric spacers (e.g., silicates as discussed below) may be used with Figure 6 Ab structure is used together to make the particle type metal structure separate. In another embodiment of the present invention, the dielectric spacer can be used with Figure 28A Used together with the structure of to separate metal layers, whether these layers are partial metal layers or continuous metal layers. Figure 28B Schematic diagram in .

[0644] In various embodiments of the present invention, the multilayer metal nanoshells discussed in this application have the potential to electromagnetically enhance two spectral regions. Thus, the metal structures of the present invention can be used in up-conversion mode to enhance both excitation at wavelength λ1 and emission at wavelength λ2. This feature can also be used in down-conversion to primarily enhance emission at wavelength λ2 and potentially enhance excitation at wavelength λ1.

[0645] In various embodiments of the present invention, such metallic structures include conductive materials made of, for example, metals, or doped glasses, or doped semiconductors. These conductive materials may be in the form of pure or nearly pure elemental metals, alloys of such elemental metals, or layers of conductive materials (regardless of continuity). The conductive materials may (as described above) include non-metallic materials as minor components, the amount of which does not render the composite material insulating.

[0646] Similarly, in various embodiments of the present invention, the up-conversion or down-conversion material may include at least one of a dielectric, a glass, or a semiconductor. The up-conversion or down-conversion material may include an alloy of two or more dielectric materials, an alloy of two or more glasses, or an alloy of two or more semiconductors.

[0647] therefore, Figure 28AThis represents an embodiment in which the dielectric core of the present invention is supplemented with a shell. The shell can include a metal layer of a specified thickness. The metal layer can include materials such as nickel, gold, iron, silver, palladium, platinum and copper, and combinations thereof. The metal layer can also be made of a combination of metals and non-metals. The shell serves as a plasmon shell, wherein surface plasmons can be formed in the metal between the dielectric core and the external environment acting as an external dielectric. The shell (as shown) may not be a complete shell. Partial metal shells or metal shells of different thicknesses are also acceptable in the present invention.

[0648] As discussed below, in another embodiment of the present invention, the metal housing serves as a scattering center for UV light, wherein the UV light will be scattered from the paint or coating (the light, even if absorbed in the paint or coating, will minimally contribute to local heating of the paint or coating material).

[0649] Figure 28C Several further embodiments of plasmonically active nanostructures with upconversion (UC) materials that can be designed are shown: (a) metal nanoparticles; (b) UC nanoparticle cores covered with metal nanocaps; (c) spherical metal nanoshells covering UC ellipsoidal cores; (d) oblate metal nanoshells covering UC ellipsoidal cores; (e) metal nanoparticle cores covered with UC nanoshells; (f) metal nanoshells with protective coatings; (g) multilayer metal nanoshells covering UC ellipsoidal cores; (h) multiple nanoparticle structures; (i) metal nanotubes and nanotriangles / nanoprisms; and (j) metal cylinders.

[0650] Figure 28D Still other embodiments of plasmonically active nanostructures with upconversion materials and attached photoactive (PA) molecules are shown. For example, in the case of psoralen (as the PA molecule), the length of the linker between the PA molecule and the UC material or metal surface is tailored so that it is long enough to allow the PA molecule to be active (attached to DNA) and short enough to allow efficient excitation of the PA molecule by the UC excitation light. Figure 28D Shown are (a) PA molecules bound to UC nanoparticles; (b) nanoparticles containing UC materials covered with metal nanoparticles; (c) metal nanoparticles covered with UC material nanocaps; (d) nanoparticles containing UC materials covered with metal nanocaps; (e) metal nanoparticles covered with UC material nanoshells; (f) nanoparticles containing UC materials covered with metal nanoshells; and (g) nanoparticles containing UC materials covered with metal nanoshells having a protective coating.

[0651] In the case of up-converter and down-converter structures of the present invention, the plasmon effect is favourable. The plasmon effect can increase the local intensity of received light or the local intensity of the emitted light from up-converter and / or down-converter structures of the present invention. The plasmon effect can occur in the entire electromagnetic region, provided that suitable nanostructures, nanometer-scale dimensions, metal types have been used. The plasmon effect is feasible in a wide range of electromagnetic spectra, ranging from gamma rays and X-rays to ultraviolet, visible light, infrared, microwaves and radio frequency energy. However, for practical reasons, visible light and NIR light are used for metal structures such as silver and gold nanoparticles, because the plasmon resonances of silver and gold occur in the visible and NIR regions respectively.

[0652] In various embodiments, nanoparticles of yttrium oxide doped with neodymium and ytterbium, yttrium oxide doped with europium and ytterbium, and any combination of neodymium oxide nanocrystals doped with rare earth trivalent ions can be used. The dual-doping components of yttrium oxide, neodymium and ytterbium, and also dual-doping with europium and ytterbium, are novel for the yttrium oxide matrix lattice, but such dual-doping systems have been shown to work in other matrix lattices such as YAG.

[0653] It has been shown that these doubly doped lanthanide glasses can be effectively upconverted on bulk materials and can thus provide novel upconverter structures at the nanoscale. These yttrium oxide nanostructures of the present invention provide a number of advantages. Small-scale synthetic methods for producing nanoscale yttrium oxide are easier to control and implement in yttrium oxide than in YAG. The matrix structure of yttrium oxide scintillates by downconversion. Combinations of these dopants in yttrium oxide can, for example, provide yttrium oxide nanocrystals with predetermined emission colors to achieve the color shift of the present invention.

[0654] In one embodiment of the present invention, dual dopants allow for excitation of either ion in the host glass. For example, excitation with 980 nm light excites ytterbium ions, where energy transfer from one excited state of the ytterbium ion to the other dopant provides a mechanism for upconversion emission of light in the visible and NIR spectral regions.

[0655] Up-conversion phosphors similar in chemical composition to the down-conversion fluorescent materials discussed above can be used. The up-conversion phosphors can include laser dyes, such as small organic molecules that can be excited by absorbing at least two infrared photons, accompanied by the emission of visible light. The up-conversion phosphors can include fluorescent polymers, such as polymers of the class that can be excited by absorbing at least two infrared photons, accompanied by the emission of visible light. The up-conversion phosphors can include inorganic or ceramic particles, or nanoparticles, including conventional up-conversion phosphors (e.g., metal fluorides, metal oxides) that can be excited by absorbing at least two infrared photons, accompanied by the emission of visible light. The up-conversion phosphors can include semiconductor particles, including nanoparticles, such as group II-VI or group III-V compound semiconductors, such as quantum dots, which are described in detail above in the "down-conversion" semiconductors.

[0656] Fluorescent upconversion inorganic phosphors may include, but are not limited to, metal oxides, metal halides, metal chalcogenides (e.g., sulfides), or mixtures thereof, such as metal oxyhalides, metal oxychalcogenides. Fluorescent upconversion inorganic phosphors are usually doped with rare earth elements (e.g., Yb 3+ 、Er 3+ 、Tm 3+ ). Some matrix examples include, but are not limited to: NaYF4, YF3, BaYF5, LaF3, La2MoO8, LaNbO4, LnO2S; where Ln is a rare earth element such as Y, La, Gd).

[0657] According to the present invention, these up-conversion and down-conversion materials are mixtures of color emitters that are configured to emit visible light at a first wavelength λ1 in response to absorbing light or energy across wavelength bands within and outside the visible spectrum when exposed to a light source. The visible light emission is enhanced relative to the amount of light emitted by reflection of the first wavelength λ1 alone.

[0658] The color emitter particles can have a diameter of less than about 1000 nanometers. The luminescent particles (up- or down-converting) can include a metal structure disposed relative to the particle. A physical property of the metal structure can be set to a value where a surface plasmon resonance in the metal structure resonates at a frequency that provides spectral overlap with the first wavelength λ1. The physical property of the metal structure can be set to a value where a surface plasmon resonance in the metal structure resonates at a frequency that provides enhanced emission at the first wavelength λ1.

[0659] Other Applications of Color Enhancement / Enhancing Structures: As described in detail below, the mixture of color emitters and the aforementioned color enhancing structures (optionally including the aforementioned energy enhancers) can be used in displays. The mixture of color emitters and the aforementioned color enhancing structures can be a color emitting pixel display element. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a color filter. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a color filter for a display. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a colored surface. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a colored reflective surface. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a colored reflective surface in a pixel of a display. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a white light emitting pixel display element. The mixture of color emitters can be a component of a coating. The mixture of color emitters and the aforementioned color enhancing structures can be a component of glass beads disposed in a retroreflective coating. The mixture of color emitters and the aforementioned color enhancing structures can be a component of a binder layer that secures the glass beads in the retroreflective coating to the base coating. The mixture of color emitters can be a component of an ink.

[0660] The mixture of color emitters and the color enhancement structure mentioned above may be at least one of red, blue, and green emitters configured to produce red, blue, and green light emissions from an upconversion process. The mixture of color emitters and the color enhancement structure mentioned above may be at least one of red, blue, and green emitters configured to produce red, blue, and green light emissions from a downconversion process. The mixture of color emitters and the color enhancement structure mentioned above may be at least one of red, blue, and green emitters configured to produce red, blue, and green light emissions from a mixture of an upconverter and a downconverter.

[0661] The mixture of color emitters included with the aforementioned color-enhancing structure can be a fluorescent emitter comprising at least one of europium, terbium, cerium, and erbium, or a combination thereof. The mixture of color emitters and the aforementioned color-enhancing structure can include a first material configured to emit a first visible color in response to absorption of ultraviolet light, and a second material configured to emit a second visible color in response to absorption of infrared light, wherein the second visible color is different from the first visible color. The mixture of color emitters and the aforementioned color-enhancing structure can include a third material configured to emit a third visible color in response to absorption of ultraviolet light, wherein the third visible color is different from the first and second visible colors. The first, second, and third visible colors can be primary colors or mixtures of primary colors. Alternatively or additionally, the mixture of color emitters and the aforementioned color-enhancing structure can include a third material configured to emit a third visible color in response to absorption of infrared light. The third visible color can be different from the first and second visible colors.

[0662] The mixture of color emitters and the aforementioned color-enhancing structure may include a first material configured to emit a first visible color in response to absorbing ultraviolet light; and a second material configured to emit a second visible color in response to absorbing infrared light. The second visible color may be substantially the same color as the first visible color. The mixture of color emitters and the aforementioned color-enhancing structure may include a third material configured to emit a third visible color in response to absorbing ultraviolet light. The third visible color may be different from the first and second visible colors. Alternatively or in addition, the mixture of color emitters and the aforementioned color-enhancing structure may include a third material configured to emit a third visible color in response to absorbing infrared light. The third visible color may be different from the first and second visible colors. The first, second, and third visible colors may be primary colors or mixtures of primary colors.

[0663] The mixture of color emitters and the color enhancement structure mentioned above can include a metal structure disposed relative to the nanoparticle emitter. The metal structure can be a metal shell comprising at least one of a spherical shell, an oblate shell, a crescent shell, or a multilayer shell. The metal structure can be at least one of Au, Ag, Cu, Ni, Pt, Pd, Co, Ru, Rh, Al, Ga, or a combination, alloy, or layer thereof. The nanoparticle emitter can be at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2, or an alloy or layer thereof. The nanoparticle emitter may include a dopant comprising at least one of Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd, and other rare earth species or combinations thereof. The dopant may have a concentration of 0.01% to 50% by mole.

[0664] The color emitter may be a down converter comprising at least one of: Y2O3; ZnS; ZnSe; MgS; CaS; Mn, Er ZnSe; Mn, Er MgS; Mn, Er CaS; Mn, Er ZnS; Mn, Yb ZnSe; Mn, YbMgS; Mn, Yb CaS; Mn, Yb ZnS:Tb 3+ 、Er 3+ ; ZnS:Tb 3+ ;Y2O3:Tb 3+ ;Y2O3:Tb 3+ 、Er3 + ; ZnS:Mn 2+ ; ZnS:Mn, Er 3+, a lead alkali silicate comprising SiO2, B2O3, Na2O, K2O, PbO, MgO, or Ag; and combinations, alloys, or layers thereof. The color emitter may be a dielectric upconverter comprising at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2, or alloys or layers thereof. The dielectric upconverter may have a particle size ranging from at least one of 2-1000 nm, 2-100 nm, 2-50 nm, 2-20 nm, or 2-10 nm. The dielectric upconverter may include a dopant comprising at least one of Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd, and other rare earth species or combinations thereof. The dopant may have a molar concentration of 0.01% to 50%. A metallic structure may be disposed relative to the dielectric upconverter, and the metallic structure may include at least one of Au, Ag, Cu, Ni, Pt, Pd, Co, Ru, Rh, Al, Ga, or alloys or layers thereof. The dielectric upconverter may be configured to exhibit visible emission upon interaction with NIR light.

[0665] Methods of applying antennae to microparticles used as pigments and dyes for color enhancement: In various embodiments, the present invention provides color enhancement of various paint pigments and dyes. The following describes the preparation of these "micro color enhancement enhancement devices."

[0666] In one embodiment, a glass substrate serves as the carrier in this case.The glass substrate can be made of various compositions including soda lime silicate, borosilicate and sodium aluminosilicate.

[0667] In this embodiment, a glass substrate is exposed to a molten form of the potassium salt KNb3 to exchange sodium in the glass for potassium in the molten bath. During this ion exchange, the outermost layer enters a state of compression because potassium ions outnumber sodium ions. The compression layer is characterized by the penetration depth and concentration of potassium. In the case of sodium aluminosilicates with a high gamma ratio Γ greater than 1, a glass medium is provided in which the penetration depth of potassium is shallow and the concentration is high. The gamma ratio Γ in this case refers to the ratio of the number of moles of Al2O3 to NaO2 in the glass chemistry. As a result, a thin, highly compressed potassium-rich layer forms under tension on top of the sodium-rich glass layer. Figure 37 is a schematic diagram of a compression layer substrate configuration according to one embodiment of the present invention.

[0668] The glass substrate is then coated with a slurry containing a coating pigment or dye dissolved in or mixed with a solvent (as appropriate). The slurry can be applied using various techniques, including but not limited to spin coating, drawbars, Mayer bars, screen printing, or simply printing using an inkjet printer equipped to handle solvents. The substrate is dried at low temperature to remove the solvent. The "coated" layer is now ready to receive the antenna.

[0669] Figure 38 is formed in Figure 37 Schematic diagram of a coating on a compressive layer substrate configuration. At this stage, the glass substrate may have a coating of paint pigment or dye, or a phosphor layer applied as a coating. The coating may include any of the converters described herein. In this example, the compressive layer may have a thickness of approximately 5 microns. Coatings containing pigments, dyes, phosphors, or other converters may have a thickness in the range of 3 microns.

[0670] The antenna (or resonator) structure is fabricated on a different substrate, preferably a silicon wafer coated with a thin glass chemical. The wafer on which the antenna is created undergoes various photo-definable lithographic steps, such as chemical reactions, etching, and metallization, to arrange the antenna structure of interest. Once the antenna is prepared, a laser can be used to drill through the glass layer attached to the silicon wafer. Laser drilling can be performed in columns and rows to highlight each antenna structure.

[0671] like Figure 39 As shown in the process, the antenna structure is now ready to be transferred using, for example, micro-transfer printing. A source wafer is provided with the antenna pattern of interest. Patterned imprinting creates a number of antennas, which are then transferred to a target substrate (in this case, a coated glass substrate coated with a pigment).

[0672] This process is known as a process that can be used to transfer small features, such as small nano- and micron-scale features, from a source to a target substrate. The source substrate can be a wafer that already has various devices finely formed on it, including integrated circuits, LEDs, or in this case, antennas. The target wafer can be a variety of other substrates, including plastics, glass, ceramics, and paper. Figure 40 This is a general diagram of the process.

[0673] In one embodiment of the invention, the antenna structure is transferred from a Si wafer containing a lithographically defined antenna to a glass substrate that has been pre-coated with a pigment or dye or a phosphor or other converter. Figure 41 Schematic diagram of a microtransferred antenna on a pre-coated compressively stressed glass substrate.

[0674] Once the antenna is placed on the glass substrate, an optional coating is applied to the glass layer. Preferably, this optional coating is similar to the previously applied coating of paint pigment, dye, or phosphor. As shown in the schematic, the glass substrate has a multilayer structure in which the antenna (resonator) of the present invention is embedded in the pigment or organic dye. Figure 42 is a schematic diagram showing a multilayer structure of the present invention in which the antenna (resonator) of the present invention is embedded.

[0675] To facilitate the release of the antenna embedded in the paint pigment, a diamond scratcher is used to score the entire compressive layer, bridging it to the tension zone. Once this is achieved, the glass instantly shatters into small pieces. If released from the glass dome, the glass would shatter into countless small pieces and projectiles.

[0676] Figure 43 is a schematic diagram illustrating the formation of discrete micro color energy enhancers of the present invention.Once the glass is crushed, the resulting pieces have a glass portion on top of which resides a coating with an embedded antenna.

[0677] Stainless steel, aluminum, and copper are some examples of materials that do not necessarily require a protective layer of coating, painting, staining, or sealing. Coated surfaces almost always have a specific color chosen to enhance the attractiveness of the object.

[0678] As in http: / / www.howeverythingworks.org / supplements / paint.pdf As described herein, the pigment particles in a paint determine the paint's opacity, or color. Pure white paint has pigments that don't absorb light but instead scatter it in random directions. White pigment particles are clear and have a relatively high refractive index. The pigment particles are embedded in a polymer layer. As light attempts to pass through the paint, a portion of the light is reflected at each boundary between the polymer and the pigment, and almost no light reaches the back of the layer. Because the pigment particles in a paint are typically rough and randomly oriented, they scatter light in all directions, making the paint appear white. This high reflectivity gives the paint its hiding power—the paint's ability to prevent light from reaching the material beneath it and then returning to the paint's surface.

[0679] Paints with pigments that have an extremely high refractive index are best at hiding the surface they cover. Light absorbed by the pigment affects the paint. For example, a pigment that absorbs blue light will give the paint a yellow hue. The reflected light has the color characteristics of the unabsorbed color of the spectrum. In other words, coloring pigments impart their color to a paint by selectively absorbing certain parts of the spectrum of light that strikes it.

[0680] U.S. Patent No. 4,283,320 (incorporated herein by reference in its entirety) describes an opaque latex paint having a small particle size, film-forming latex binder combined with a trace amount of opaque pigment, and a large amount of non-film-forming polymer particles (plastic pigment) to provide a semi-gloss latex paint composition having an excellent hard enamel surface and desirable film integrity properties. The plastic pigment particles in U.S. Patent No. 4,283,320 are between about 0.1 and 0.5 microns and contain 0.2% to 2% of a comonomer containing a carboxylic acid group. The semi-gloss plastic pigment latex paint of U.S. Patent No. 4,283,320 is mixed at a pigment volume content (PVC) of between about 30% and 45%, which is much higher than conventional high-quality enamel latex paints. In one embodiment of the present invention, the color-enhancing mixture described herein is applied to the latex paint of U.S. Patent No. 4,283,320 or to the surface of the paint of U.S. Patent No. 4,283,320.

[0681] U.S. Patent No. 5,134,186 (incorporated herein by reference in its entirety) describes a coating having a film former and a polymer composition. The polymer composition comprises from about 30 to about 50 weight percent of a substantially non-self-polymerizable monomer and from about 50 to about 70 weight percent of a copolymerizable monomer having a water-soluble homopolymer. In one embodiment of the present invention, the color-enhancing mixture described herein is applied to a latex coating of U.S. Patent No. 5,134,186 or to a surface of a coating of U.S. Patent No. 5,134,186.

[0682] U.S. Patent No. 4,789,694 (incorporated herein by reference in its entirety) describes a coating composition having a non-cationic functional emulsion polymer mixture suitable for co-reaction with glycoluril to provide a cured thermosetting coating film at room temperature. Curing is performed by copolymerizing ethylenically unsaturated monomers (including functional monomers, but excluding amine monomers) in an aqueous polymerization medium, followed by ion exchange of the resulting reactive emulsion polymer. The glycoluril can be treated by the ion exchange step alone or in combination with the reactive emulsion polymer. In one embodiment of the present invention, the color-enhancing mixture described herein is applied to a latex paint of U.S. Patent No. 4,789,694 or to a surface of a coating of U.S. Patent No. 4,789,694.

[0683] U.S. Patent No. 4,613,633 (incorporated herein by reference in its entirety) describes copolymer latexes having heterogeneous polymer particles particularly suitable for paper coating, and paper coating compositions containing such latexes that provide coated paper with improved suitability for blister packaging and printing. In one embodiment of the present invention, the color-enhancing mixture described herein is applied to or onto the surface of a latex coating of U.S. Patent No. 4,613,633.

[0684] U.S. Patent No. 7,682,435 (the entire contents of which are incorporated herein by reference) describes an oil-based pigment ink composition comprising at least a pigment, a polymer compound, and an organic solvent, wherein as the organic solvent, the ink composition comprises 20% to 90% by weight of butyl methoxyacetate, based on the ink composition as a whole; and particularly describes the above oil-based pigment ink composition, which comprises, as other organic solvents, 1% to 50% by weight of a nitrogen-containing and / or oxygen-containing heterocyclic compound, and / or 1% to 50% by weight of a (poly)alkylene glycol derivative, based on the ink composition as a whole; and particularly describes the above oil-based pigment ink composition, wherein the ink composition has a flash point of 61° C. or higher, a viscosity of 2.0 to 6.5 cp at 25° C., and a surface tension of 20 to 40 mN / m at 25° C. In one embodiment of the present invention, the color intensifying mixture described herein is applied to the oil-based pigment ink of US Patent No. 7,682,435 or to the surface of the coating of US Patent No. 7,682,435.

[0685] U.S. Patent Application Publication No. 20090088500 (the entire contents of which are incorporated herein by reference) describes an oil-based ink composition comprising a colorant, an organic solvent, and a polymer compound, and optionally an alkylamine ethylene oxide derivative as a pH adjuster, wherein when ions in the ink composition are transferred to water, the pH of the aqueous phase is 5.5 to 10. This oil-based ink composition prevents corrosion of the nozzle plate and improves storage stability, thereby ensuring printer reliability, such as inkjet stability, even after long-term storage, and can withstand outdoor service environments. In one embodiment of the present invention, the color-enhancing mixture described herein is applied to the oil-based ink composition of U.S. Patent Application Publication No. 20090088500.

[0686] In general, the color-intensifying mixtures described herein and the color-intensifying / enhancing structures mentioned above are suitable for use with other coatings or inks to intensify the color perceived by an observer.

[0687] The human eye is not an instrument that measures the exact wavelength of light. Instead, it discerns three distinct ranges of wavelengths. Within the retina of the human eye, there are specialized cells that detect only specific wavelengths of light. Some of these cells detect red light, others detect green light, and still others detect blue light. These three types of color-sensitive cells are called cones. Cones are most abundant in the fovea, an area of ​​high visual acuity near the center of the retina. Retinal cells are more light-sensitive than cones but cannot distinguish between colors. Rods perceive light and dark. It might seem that these three types of color sensors would limit us to seeing three colors. However, when two or more color sensors are stimulated simultaneously, a wide range of colors can be perceived. Each sensor tells the brain how much light it is seeing, and the brain interprets the combined responses as a specific color.

[0688] Generally speaking, visible light of a particular wavelength stimulates all three types of cone cells to some degree. However, the cells do not react equally to every wavelength of light. When exposed to 680nm (680 nanometers) light, cone cells specialized for red light react much more strongly than those specialized for green or blue light. Due to this strong reaction of the red sensors, the light appears red. Yellow light at 580nm is between red and green. Both red-sensitive cones and green-sensitive cones react moderately when exposed to yellow light. The brain interprets this balanced reaction as yellow light.

[0689] However, the same reaction can be elicited from your retina by exposing it to a mixture of equal amounts of pure red and pure green light. Again, both the red-sensitive and green-sensitive cones react moderately, and this appears to the brain as yellow light, even though no pure yellow light at 580 nm reaches your retina. Similarly, a mixture of pure red, green, and blue light allows a person to see nearly any color. The only challenge lies in selecting the pure red, green, and blue wavelengths. This is the technology used by televisions. It produces relatively pure red, green, and blue light with phosphorescent dots, "tricking" the eye into seeing any color in the entire visible spectrum.

[0690] So, in red paint, the paint absorbs light that stimulates your eye's green or blue sensors. All that's left is reflected light that stimulates the red sensor, so the eye perceives the paint as red. Most paint pigments are based on specific molecules that absorb light within a specific range of wavelengths. Many metal compounds, including those of copper, chromium, iron, antimony, nickel, and lead, absorb specific wavelengths of light and appear vibrant colors. If one starts with white light and removes varying amounts of its three primary colors, one can create paint of any color. If you remove all light, the paint appears black. Yellow pigment absorbs some blue light, and cyan pigment absorbs some red light. What's left is mostly green light. The more of each primary pigment you add to the paint, the more thoroughly the paint absorbs its color of light, and the darker the paint becomes.

[0691] Ink is similar to paint, except that it contains dissolved dyes rather than solid pigment particles. Ink does not contain any reflective white pigment. The ink itself is often transparent yet pigmented. Ink relies on the underlying paper to reflect light. Paper is primarily composed of cellulose, a transparent natural polymer. Because this cellulose is finely divided within the paper, it reflects light at every surface, giving the paper a white appearance. During manufacturing, white paint pigments are often applied to the paper to make it even whiter.

[0692] In one aspect of the present invention, the absorption of light in a coating, which typically results in only heating of the coating, is changed to a dynamic whereby the absorbed light (which would normally be lost in absorption) is replaced with the emission of light of the desired coating color. Thus, particularly in the case of coatings or inks that include the aforementioned color-enhancing structures, the brightness of the coating or ink or coating is enhanced, which is superior to what would normally be lost in absorption. Furthermore, the "color shift" of light bands in the ultraviolet or infrared, which normally do not contribute to visible light, to the perceived light reflected to the eye provides an additional source of color enhancement.

[0693] Conventionally, in the production of fluorescent inks, fluorescent pigments are used to replace organic or inorganic color pigments that exhibit absorption in the visible light region and are used in ordinary printing inks. In order to identify the fluorescent image formed on the image printed product, ultraviolet light is used as excitation light to irradiate the image printed product. When the image printed product is irradiated with ultraviolet light, the ultraviolet light is absorbed by the fluorescent substance of the fluorescent image, thereby causing the emission of fluorescence in the visible light region. This fluorescence is discerned by visual observation or using a camera and represents a limited demonstration of the concept utilized but extended by the present invention. Here, in one aspect of the present invention, a mixture of down-conversion particles tuned to specific excitation and emission is used to replace fixed fluorescent particles and is used in conjunction with the color enhancement structure mentioned above. Here, in one aspect of the present invention, a mixture of down-conversion particles tuned to specific excitation and emission is used to replace or supplement the mixture of down-conversion particles and is used in conjunction with the color enhancement structure mentioned above.

[0694] As described in U.S. Patent No. 6,744,960 (the entire contents of which are incorporated herein by reference) and as used in the present invention, the pump radiation can include natural light, i.e., sunlight, or artificial light, such as light from a UV or blue light emitting diode (LED) or fluorescent lamp. The light incident on the fluorescent structure need only include radiation having a wavelength within the absorption spectrum of the quantum dots. Since the absorption spectrum of the quantum dots includes wavelengths shorter than the emission wavelength of the quantum dots, the pump radiation includes wavelengths shorter than the emission wavelength. For example, sunlight can be used to pump a fluorescent structure 10 having a layer of quantum dots comprising CdSe particles having a diameter of 5.0 nm, which emit at an optical wavelength of 625 nm, because the sun radiates light over a broad spectrum, including light with wavelengths at least 50 nm shorter than 625 nm. Alternatively, such a fluorescent structure can be pumped with one or more light emitting diodes (LEDs) providing light at, for example, 550 nm. Incandescent lamps as well as ultraviolet light sources such as UV LEDs will also be able to excite the layer of quantum dots.

[0695] The fluorescent structures described in U.S. Patent No. 6,744,960 and suitable for use in the present invention can be employed in a variety of applications requiring bright, narrow-band illumination. For example, light sources for colored illumination can be used in the construction of signs, in the creation of art or architectural designs, and in areas of vibrant color, including outlines, trim, and borders on products including, but not limited to, furniture, automobiles, appliances, electronics, clothing, or any other object where vibrant colors can be used for aesthetic or functional purposes. These fluorescent structures can advantageously produce intense, colored illumination during daytime exposure to sunlight. Because quantum dots do not degrade due to exposure to UV rays, such as those produced by the sun, the structures have a long lifespan and can be incorporated into architectural features, such as borders that highlight the roof of a building during daylight hours.

[0696] However, unlike in U.S. Patent No. 6,744,960, in the present invention, the fluorescence is supplemented by IR light stimulation of the up-converting particles from a natural or artificial source and an even brighter structure is produced. In addition, the mixture of down-converters and the color-enhancing / enhancing structures mentioned above allow a wider spectrum of "out-of-band" color regions from natural or artificial radiation sources to be used and tuned to, for example, a specific color emission or primary color mixture emission.

[0697] In another embodiment of the present invention, a light-emitting composition is provided, comprising: a first color emitter configured to emit visible light of a target color in response to absorbing energy in a first wavelength band when exposed to an energy source; and a second color emitter configured to emit visible light that deviates from the target color in response to absorbing energy in the first wavelength band when exposed to the energy source. In particular, when the color enhancement / enhancement structure mentioned above is included in the composition, the intensity of light at the target color that can be observed is enhanced relative to reflected white light that would not be emitted from the first and second color emitters. Furthermore, by shifting the emission around the target color, the resulting color appears to the human eye to have a richer color. The offset can be 5, 10, 15, 20, 25, and 30 nm or greater. The offset can be positive or negative relative to the target color. More specifically, the color purity or chromaticity can be altered by the offset defined above.

[0698] In another embodiment, the offset value can produce a saturation quality that causes the target color to appear different under different lighting conditions. For example, a room painted to a specific target color using a mixture of different color emitters can appear different at night (under artificial lighting conditions) than during the day. The offset can be 50, 100, 150, 200, 250, and 300 nm or greater. The offset can be a positive or negative offset relative to the target color.

[0699] Furthermore, a target color can be varied from its original color by adding white pigment to make a lighter version or by adding black pigment to make a darker version.

[0700] Table 2 included below includes the recognized wavelength intervals for the major visible color bands.

[0701] Table 2

[0702] color Wavelength interval red About 700–635 nm orange color About 635-590nm yellow About 590-560nm green About 560-490nm blue About 490-450nm Purple About 450-400nm

[0703] One particular area of ​​application for the color-shifting particle mixture is its use as a coating on glass beads used in retroreflective paints. FIG7 shows a schematic diagram of the retroreflective paint geometry. The glass beads act as optical elements that direct incident light along a reflective path back to the viewer (almost aligned with the incident light, if not completely). Instead of diffuse scattering, the light is directed back and appears brighter than "normal." In the present invention, the color-shifting particle mixture and the color-enhancing / reinforcing structures mentioned above can be applied to the paint binder, or as Figure 44 Shown as a color converter layer on glass beads, light (not having the color of the painted surface) will be converted to that color of the painted surface (or a certain combination of primary color emissions simulating the color of the painted surface), thereby enabling additional light enhancement.

[0704] In conventional retroreflective road paint applications, there are two categories of retroreflective beads: IGB-I and IGB-II. IGB-I is used to mix with the paint before stripping it from the road. As the paint layer wears away, the beads are exposed, thereby enhancing the visibility of the road marking. IGB-II is used to drip onto the newly stripped paint surface on the road to provide immediate enhanced visibility for nighttime drivers. Table 3 (below) http: / / www.indoglassbeads.com / road- marking-glass-beading.htm Reproduced from) provides the generally accepted specifications for these materials.

[0705] Table 3

[0706] Chemical and physical properties

[0707] Basic Materials SiO2 69% to 71% shape spherical color transparent Specific gravity g / cm3 2.5 Hardness (Mohs) 6.0 Refractive index 1.5-1.55

[0708]

[0709]

[0710] U.S. Patent No. 5,650,213 (incorporated herein by reference in its entirety) describes a retroreflective composition having a non-volatile matrix material, a volatile component, and a plurality of retroreflective microspheres, wherein the ratio of the volume of the matrix material to the volume of the retroreflective microspheres is in the range of 75% to 185%. The retroreflective microspheres in U.S. Patent No. 5,650,213 have a diameter of 20 to 200 microns, are composed of glass, and have a refractive index in the range of 1.7 to 2.5. In one embodiment of the present invention, these and other retroreflective compositions include the color enhancement mixture of the present invention (optionally including the color enhancement / reinforcement structure mentioned above) coated thereon or in the coating composition itself.

[0711] Thus, in the present invention, glass beads in, for example, a blue paint would have down-converters and up-converters in the color converter layer and include the aforementioned color-enhancing / reinforcement structures on the glass beads, so that white light (such as white light from the headlights on a car) would convert more of its UV and IR light to blue light, thereby generating more blue light to reflect from the blue paint surface. Alternatively, for a green paint surface, white light would convert more of its UV and IR light to green, thereby generating more green light to reflect from the glass beads in the paint surface.

[0712] In one embodiment of the invention, retroreflection bounces light around a 3D reflective surface to send it back in the direction of the source. The micro color enhancers of the invention (having a resonator / antenna structure) are added to glass beads to form, in one embodiment, a coating additive such as for coating highway pavement. Figure 45 Schematic diagram showing the effect of the amplifying / resonating body antenna of the present invention in a coating.

[0713] In addition to use in traffic signs and other coating applications, these retroreflective / resonator structures are also suitable for many applications that use light to scan objects and "read" the reflected light, as well as bar code applications.

[0714] Figure 46A schematic diagram of a paint surface with a color-shifting layer configured as a topcoat is shown. Similar to the previously described, a blue paint having the color-enhancing / reinforcement structure described above would have down-converters and / or up-converters in the color converter layer applied to the topcoat, such that white light (e.g., such as from a car's headlights) would convert more of its UV and IR light into blue light, thereby generating more blue light to reflect from the blue paint surface. Alternatively, for a green paint surface, white light would convert more of its UV and IR light into green light, thereby generating more green light to reflect from the glass beads in the paint surface.

[0715] In another embodiment, the colors in the visible part of the spectrum will also be color-shifted. A blue paint having the color-enhancing / enhancing structure mentioned above will have down-converters and / or up-converters in the color converter layer applied at the top coat, so that white light (such as white light from the headlights on a car) will convert more of its deep blue and red and green light to blue light, thereby generating more blue light to reflect from the blue paint surface. Alternatively, for a green paint surface, white light will convert more of its blue and red light to green light, thereby generating more green light to reflect from the glass beads in the paint surface.

[0716] In other words, using the color-shifting particles of the present invention in the color converter layer and the color-enhancing / enhancing structures mentioned above, the red paint or ink has color-shifting particles that down-convert light in the spectrum with energy higher than red (e.g., blue light) and / or up-convert light in the spectrum with energy lower than red (e.g., near-IR light and IR light). Similarly, the green paint or ink has color-shifting particles that down-convert light in the spectrum with energy higher than green (e.g., blue light) and / or up-convert light in the spectrum with energy lower than green (e.g., red light, near-IR light, and IR light). Similarly, the blue paint or ink has color-shifting particles that down-convert light in the spectrum with energy higher than blue (e.g., UV light) and / or up-convert light in the spectrum with energy lower than blue (e.g., green light, red light, near-IR light, and IR light).

[0717] cosmetic: Cosmetics are substances used to enhance the appearance or odor of the human body. These include, but are not limited to, skin creams, lotions, powders, perfumes, lipsticks, nail polish, eye and face makeup, perms, tinted contact lenses, hair color, hair sprays and gels, deodorants, baby products, bath oils, bubble baths, bath salts, butters, and many other types of products. A subset of cosmetics is called "color cosmetics," which primarily refers to coloring products intended to alter the wearer's appearance. Many manufacturers distinguish between decorative cosmetics and skincare cosmetics.

[0718] In one aspect of the invention, the color mixtures described above with the color-enhancing / enhancing structures mentioned above are included in cosmetics intended to change the appearance of the user. In one aspect of the invention, the color mixtures described above are included in cosmetics intended to protect the body from harmful UV aging effects.

[0719] Thus, products suitable for incorporating the color mixtures described above with the aforementioned color-enhancing / enhancing structures include, but are not limited to, lipstick, lip gloss, lip liner, lip plumper, lip balm, lip conditioner, lip primer, and lip booster. These products also include foundations (typically liquid, cream, or powder) for smoothing the face and covering spots or uneven skin tones. These products can also include powders for giving a matte finish, as well as for covering minor flaws or blemishes. These products can also include lip balm, rouge, or blush, cheek colorants for bringing out color on the cheeks and making cheekbones appear more defined. These products can also include bronzers, which add a touch of color to the skin by adding a gold or bronze hue. These products can also include mascara (available in natural colors such as brown and black, but also in bolder colors such as blue, pink, or purple) for darkening, lengthening, and thickening eyelashes. These products may also include eyeliners, eye shadows, eye shimmer and glitter eyeliners, and different colored pencils for coloring and emphasizing the eyelids, eyebrow pencils, eyebrow gels, eyebrow waxes, gels and powders for coloring and defining eyebrows. These products may also include nail polish for coloring the fingers and toes. These products may also include concealers and makeup for covering any imperfections of the skin.

[0720] Also included in the general category of cosmetics are skin care products. These include creams and lotions that moisturize the face and body, sunscreens that protect the skin from harmful UV radiation, and care products that repair or conceal skin imperfections (acne, wrinkles, dark circles, etc.). Cosmetics can be liquids or cream emulsions; powders, both pressed and loose; dispersions; and anhydrous creams or sticks.

[0721] In this application area, the color mixture of the present invention having the aforementioned color-enhancing / enhancing structure can not only provide color shifting capabilities (as detailed above), but also reduce the damage caused by UV light to skin or hair exposed to UV light. In this way, the cosmetic product can additionally or optionally provide a protective coating having a mixture of light-scattering and luminescent particles, wherein the mixture is configured to convert a first portion of the UV light into visible light when exposed to UV light, emit a portion of the visible light from the mixture, and reflect a second portion of the UV light from the mixture so that the second portion of the UV light is not absorbed by the skin or hair.

[0722] By way of example, but not limitation to the details described below, due to the refractive index difference between air and the protective coating, UV light from the sun incident on the protective coating may have 50% or more of the UV light reflected. The portion of the UV light that enters the inner layer of the protective coating is converted to visible light. The remaining...

Claims

1. An energy emitter, comprising: at least one energy-enhancing structure, wherein the energy-enhancing structure is at least one non-plasmonic structure selected from the group consisting of: a folded resonator, a fractal antenna, a grid pattern, an antenna, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure; and An energy converter, which is capable of receiving energy from an energy source, converting the energy and emitting light with energy higher or lower than the received energy from the energy converter, and the energy converter is arranged near the at least one energy enhancement structure so that the emitted light is emitted with a greater intensity than the case where the energy converter is far away from the at least one energy enhancement structure or the case where the energy enhancement structure does not exist.

2. The energy emitter of claim 1, wherein the at least one energy enhancing structure comprises a structure wherein a locally enhanced electric field exists in a portion of the structure when the structure receives electromagnetic energy.

3. The energy emitter of claim 2, wherein the at least one energy enhancing structure comprises at least one resonant body dimensioned to resonate with the applied electromagnetic energy.

4. The energy emitter of claim 3, wherein the resonant body comprises a folded resonant body.

5. The energy emitter of claim 4, wherein the folded resonator comprises an electrical conductor configured in a fractal pattern.

6. The energy emitter of claim 4, wherein the folded resonator comprises a 3 / 4 wavelength resonator having opposite ends folded inwardly from a center of the folded resonator with a gap between the opposite ends.

7. An energy emitter as claimed in claim 6, wherein the locally enhanced electric field exists near the opposed ends.

8. The energy emitter of claim 4, wherein the folded resonator comprises a 3 / 4 wavelength resonator having opposite ends folded outward from a center of the folded resonator with a gap between the opposite ends.

9. The energy emitter of claim 8, wherein the locally enhanced electric field exists near the opposed ends.

10. The energy emitter of claim 3, wherein the resonant body comprises a fractal pattern.

11. The energy emitter of claim 10, wherein the fractal pattern comprises a three-dimensional fractal pattern.

12. The energy emitter of claim 3, wherein the at least one resonant body comprises a plurality of resonant bodies.

13. The energy emitter of claim 12, wherein the resonator is disposed on a sheet.

14. An energy emitter as claimed in claim 13, wherein the sheet comprises a sheet for placement within a medium to be treated.

15. The energy emitter of claim 13, wherein the sheet material comprises a flexible sheet material for placement within a medium to be treated.

16. The energy emitter of claim 13, wherein the sheet material comprises a rigid sheet material for placement within a medium to be treated.

17. The energy emitter of claim 13, wherein the plurality of resonators comprises an array of the resonators disposed on a sheet.

18. The energy emitter of claim 12, wherein each of the resonant bodies comprises a freestanding resonant body.

19. The energy emitter of claim 18, wherein the freestanding resonator is disposed within a medium to be treated.

20. The energy emitter of claim 1, wherein the at least one energy enhancement structure comprises a first level metal pattern and a second level metal pattern, the second level metal pattern being offset relative to the first level metal pattern in at least one of a lateral or axial direction.

21. The energy emitter of claim 20, wherein at least one of the metal patterns comprises a first resonant body dimensioned to resonate with applied electromagnetic energy.

22. The energy emitter of claim 21, wherein The at least one of the metal patterns comprises a folded resonator having opposing electrodes, the electric field being oriented between the opposing electrodes, and The energy converter is positioned between the opposing electrodes or within the fringe electric field of the opposing electrodes.

23. The energy emitter of claim 22, wherein the opposing electrodes are oriented outside the folded resonator and parallel to each other.

24. The energy emitter of claim 22, wherein the opposing electrodes are oriented inside the folded resonator and are parallel to each other.

25. The energy emitter of claim 22, wherein the folded resonant body comprises Folded resonator.

26. The energy emitter of claim 20, wherein said at least one of said metal patterns comprises a plurality of said folded resonators, said folded resonators being concentrically arranged and optionally coplanar with each other, such that an outer opposing electrode of each folded resonator does not spatially overlap with an outer opposing electrode of another folded resonator of said plurality of folded resonators.

27. The energy emitter of claim 20, wherein said at least one of said metal patterns comprises a plurality of said folded resonators, said folded resonators being arranged concentrically and optionally coplanar with each other, such that said outer counter-electrode of each folded resonator spatially overlaps with an outer counter-electrode of one or more of said other folded resonators of said plurality of folded resonators.

28. The energy emitter of claim 1, further comprising an anti-reflection film disposed on the at least one energy enhancement structure or the energy conversion body.

29. The energy emitter of claim 1, wherein the at least one energy enhancement structure is disposed adjacent to a down conversion material comprising the energy converter.

30. The energy emitter of claim 1, wherein the at least one energy enhancing structure is disposed adjacent to an upconversion material comprising the energy converter.

31. The energy emitter of claim 1, wherein said at least one energy enhancing structure is disposed adjacent a phosphor comprising said energy converter.

32. The energy emitter of claim 1, wherein said at least one energy enhancing structure is disposed adjacent a piezoelectric device comprising said energy converter.

33. The energy emitter of claim 32, wherein the piezoelectric device is configured to receive sonic or acoustic energy and to emit at least one of ultraviolet light or visible light in response to absorbing the sonic or acoustic energy.

34. The energy emitter of claim 1, wherein the at least one energy enhancement structure is disposed adjacent to a mechanoluminescent device that constitutes the energy conversion body.

35. The energy emitter of claim 34, wherein the mechanoluminescent device is configured to receive sonic energy or acoustic energy and to emit at least one of ultraviolet light or visible light in response to absorbing the sonic energy or acoustic energy.

36. The energy emitter of claim 1, wherein said at least one energy enhancement structure is disposed within a plasma capsule device constituting said energy conversion body.

37. The energy emitter of claim 36, wherein the plasma capsule device is configured to receive radio frequency or microwave energy and to emit at least one of ultraviolet light or visible light in response to absorbing the radio frequency or microwave energy.

38. The energy emitter of claim 1, wherein said at least one energy enhancing structure is disposed adjacent to an x-ray stimulated phosphor comprising said energy conversion body.

39. The energy emitter of claim 38, wherein the x-ray stimulated phosphor emits one of ultraviolet light or visible light in response to absorbing x-rays.

40. The energy emitter of claim 39, wherein the x-ray stimulated phosphor emits said one of ultraviolet light or visible light for a period of at least 1 minute after x-ray stimulation.

41. The energy emitter of claim 39, wherein the x-ray stimulated phosphor emits said one of ultraviolet light or visible light for a period of at least 10 minutes after x-ray stimulation.

42. The energy emitter of claim 39, wherein the x-ray stimulated phosphor emits said one of ultraviolet light or visible light for a period of at least 60 minutes after x-ray stimulation.

43. The energy emitter of claim 38, wherein the x-ray stimulation phosphor emits lower energy x-rays in response to absorbing higher energy x-rays.

44. The energy emitter of claim 1, wherein the energy received from the energy source is selected from one or more of: acoustic waves, sonic waves, radio waves, microwaves, far infrared, near infrared, visible light, UV, x-rays, gamma rays, electron beams, and proton beams.

45. The energy emitter of claim 1, wherein the energy conversion body is disposed proximate to the at least one energy enhancement structure comprises conductive coupling of the energy conversion body to the at least one energy enhancement structure.

46. ​​The energy emitter of claim 45, wherein the conductive coupling comprises a physical conductive connection between the energy converter and the at least one energy enhancement structure.

47. The energy emitter of claim 1, wherein the energy converter comprises one or both of: (i) a down converter that converts ultraviolet light or blue light into red, yellow, or green light, or (ii) an up converter that converts infrared light or red light into yellow, green, or blue light.

48. An energy emitter as claimed in claim 1, wherein said at least one energy enhancing structure constitutes a plurality of energy collectors.

49. An energy emitter as claimed in claim 48, wherein the energy converter is positioned to convert energy scattered internally within the energy collector.

50. The energy emitter of claim 48, wherein the energy collector comprises a metal core clad with a high-K dielectric, and a subsequent cladding layer of a low-K dielectric.

51. The energy emitter of claim 48, wherein the energy collector comprises a radial collector pattern.

52. The energy emitter of claim 7, wherein the energy collector comprises a fractal pattern.

53. The energy emitter of claim 52, wherein the fractal pattern is embedded within a dielectric material.

54. The energy emitter of claim 1, wherein said at least one energy-enhancing structure forms an integral part of at least one of: a paint, an ink, a fabric, a filament, a road sign, a highway marking, a motor vehicle, a watercraft, an aircraft, a reflector, a building product, a concrete product, an epoxy product, a jewelry product, a colored contact lens, a candle product, a rubber product, a plastic product, a colored surface, a solar cell, a plasma capsule, an x-ray detector, or a sterilizer.

55. The energy emitter of claim 1, wherein the energy converter forms a component of at least one of: a paint, an ink, a fabric, a filament, a road sign, a highway marking, a motor vehicle, a boat, an aircraft, a reflector, a building product, a concrete product, an epoxy product, a jewelry product, a colored contact lens, a candle product, a rubber product, a plastic product, a colored surface, a solar cell, a plasma capsule, an x-ray detector, or a sterilizer.

56. An energy emitter as claimed in claim 1, wherein said energy converter forms an integral part of a coloured reflective surface.

57. An energy emitter as claimed in claim 1, wherein the energy converter forms an integral part of a colored reflective surface in a pixel of a display.

58. The energy emitter of claim 1, wherein the energy converter forms an integral part of a white light emitting pixel display element.

59. The energy emitter of claim 1, wherein the energy converter forms an integral part disposed within a retroreflective coating.

60. The energy emitter of claim 1, wherein the energy converter forms a component of ink.

61. The energy emitter of claim 1, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green emission from an upconversion process.

62. The energy emitter of claim 3, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from an upconversion process.

63. The energy emitter of claim 1, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green emission from a down conversion process.

64. The energy emitter of claim 3, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from a down conversion process.

65. The energy emitter of claim 1, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green emission from a mixture of upconverters and downconverters.

66. The energy emitter of claim 3, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green emission from a plurality of mixtures of upconverters and downconverters.

67. The energy emitter of claim 1, wherein the energy converter comprises a mixture of fluorescent emitters comprising at least one of europium, terbium, cerium, and erbium or a combination thereof.

68. The energy emitter of claim 3, wherein the energy converter comprises a plurality of mixtures of fluorescent emitters, the fluorescent emitters comprising at least one of europium, terbium, cerium and erbium or a combination thereof.

69. The energy emitter of claim 1, wherein the energy converter comprises: a first material configured to emit a first visible color in response to absorbing ultraviolet light; as well as A second material is configured to emit a second visible color in response to absorbing infrared light, wherein the second visible color is different from the first visible color.

70. The energy emitter of claim 69, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the ultraviolet light, wherein the third visible color is different from the first visible color and the second visible color.

71. The energy emitter of claim 70, wherein the first visible color, the second visible color, and the third visible color are primary colors.

72. The energy emitter of claim 69, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the infrared light, wherein the third visible color is different from the first visible color and the second visible color.

73. The energy emitter of claim 1, wherein the energy converter comprises: a first material configured to emit a first visible color in response to absorbing ultraviolet light; as well as A second material is configured to emit a second visible color in response to absorbing infrared light, wherein the second visible color is substantially the same color as the first visible color.

74. The energy emitter of claim 73, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the ultraviolet light, wherein the third visible color is different from the first visible color and the second visible color.

75. The energy emitter of claim 73, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the infrared light, wherein the third visible color is different from the first visible color and the second visible color.

76. The energy emitter of claim 75, wherein the first visible color, the second visible color, and the third visible color are at least two of the primary colors.

77. An energy emitter as claimed in claim 3, wherein said energy converter forms an integral part of a colored reflective surface.

78. An energy emitter as claimed in claim 3, wherein the energy converter forms an integral part of a colored reflective surface in a pixel of a display.

79. The energy emitter of claim 3, wherein the energy converter forms an integral part of a white light emitting pixel display element.

80. The energy emitter of claim 3, wherein the energy converter forms an integral part disposed within a retroreflective paint.

81. An energy emitter as claimed in claim 3, wherein the energy converter constitutes an ink component.

82. The energy emitter of claim 3, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from an upconversion process.

83. The energy emitter of claim 20, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from an upconversion process.

84. The energy emitter of claim 3, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from a down conversion process.

85. The energy emitter of claim 20, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from a down conversion process.

86. The energy emitter of claim 3, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green emission from a mixture of upconverters and downconverters.

87. The energy emitter of claim 20, wherein the energy converter constitutes at least one of a red, blue, and green emitter configured to produce red, blue, and green light emissions from a plurality of mixtures of up-converters and down-converters.

88. The energy emitter of claim 3, wherein the energy converter comprises a mixture of fluorescent emitters comprising at least one of europium, terbium, cerium, and erbium or a combination thereof.

89. The energy emitter of claim 20, wherein the energy converter comprises a plurality of mixtures of fluorescent emitters, the fluorescent emitters comprising at least one of europium, terbium, cerium, and erbium or a combination thereof.

90. The energy emitter of claim 3, wherein the energy converter comprises: a first material configured to emit a first visible color in response to absorbing ultraviolet light; as well as A second material is configured to emit a second visible color in response to absorbing infrared light, wherein the second visible color is different from the first visible color.

91. The energy emitter of claim 90, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the ultraviolet light, wherein the third visible color is different from the first visible color and the second visible color.

92. The energy emitter of claim 91, wherein the first visible color, the second visible color, and the third visible color are primary colors.

93. The energy emitter of claim 90, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the infrared light, wherein the third visible color is different from the first visible color and the second visible color.

94. The energy emitter of claim 3, wherein the energy converter comprises: a first material configured to emit a first visible color in response to absorbing ultraviolet light; as well as A second material is configured to emit a second visible color in response to absorbing infrared light, wherein the second visible color is substantially the same color as the first visible color.

95. The energy emitter of claim 94, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the ultraviolet light, wherein the third visible color is different from the first visible color and the second visible color.

96. The energy emitter of claim 94, wherein the energy converter further comprises a third material configured to emit a third visible color in response to absorbing the infrared light, wherein the third visible color is different from the first visible color and the second visible color.

97. The energy emitter of claim 96, wherein the first visible color, the second visible color, and the third visible color are at least two of the primary colors.

98. The energy emitter of claim 1, wherein the energy converter comprises at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2 or alloys or layers thereof.

99. The energy emitter of claim 98, wherein the energy converter further comprises a dopant, the dopant comprising at least one of Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd and other rare earth species or combinations thereof.

100. The energy emitter of claim 99, wherein the dopant is included in a concentration of 0.01% to 50% by mole.

101. An energy emitter as described in claim 1, wherein the energy converter comprises a down converter, the down converter comprising at least one of the following: Y2O3; ZnS; ZnSe; MgS; CaS; Mn, Er ZnSe; Mn, Er MgS; Mn, ErCaS; Mn, Er ZnS; Mn, Yb ZnSe; Mn, Yb MgS; Mn, Yb CaS; Mn, Yb ZnS:Tb 3+ , Er 3+ ; ZnS:Tb 3+ ;Y2O3:Tb 3+ ;Y2O3:Tb 3+ 、Er3 + ; ZnS:Mn 2+ ; ZnS:Mn,Er 3+ .

102. The energy emitter of claim 1, wherein the energy converter comprises an upconverter comprising at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2 or alloys or layers thereof.

103. The energy emitter of claim 1, wherein the energy converter comprises an upconverter, the upconverter comprising at least one of: doping with Tm 3+ Fluorozirconate glass; LuPO4:Yb 3+ 、Tm 3+ and YbPO4:Er 3+ Nanocrystals; tellurium and germanium oxides; tellurium and germanium oxides doped with at least one of Tm, Yb, Ho, Er or Pr; Yb doped 3+ BaZrO3; Nd 3+ :Cs2NaGdCl6、Nd 3+ , Yb 3+ :Cs2NaGdCl6; based on Nd 3+ and Ho 3+ Co-doped ZrF4 fluoride glass; Co-doped Tm 3+ / Yb 3+ TeO2-Ga2O3-R2O (R = Li, Na, K) glass; and metal to ligand charge transfer (MLCT) transition materials; and [Ru(dmb)3] 2+ (dmb = 4,4'-dimethyl-2,2'-bipyridine) MLCT transition material.

104. A coating, comprising: pigment; as well as The energy emitter as claimed in claim 1.

105. An ink, comprising: dye; as well as The energy emitter as claimed in claim 1.

106. A light display, the light display comprising: at least one of a color filter or a color reflecting surface; An energy emitter as claimed in claim 1 included in said color filter or as part of said color reflecting surface.

107. A protective coating for reducing damage from UV light to an object exposed to UV light radiation, the protective coating comprising: A mixture of light scattering particles and the energy emitter as claimed in claim 1; and The mixture is configured such that upon exposure to UV light, converting a first portion of the UV light into visible light, emitting a portion of the visible light from the mixture, and A second portion of the UV light is reflected from the mixture such that the second portion of the UV light is not absorbed by the object.

108. A luminescent composition, comprising: a first color emitter configured to emit visible light of a first target color when exposed to an energy source having an energy above or below the visible spectrum; a second color emitter configured to emit visible light of a second target color when exposed to the energy source; and The energy emitter as claimed in claim 1.

109. A cosmetic, comprising: A color emitter, the color emitter comprising, a first color emitter configured to emit visible light of a first target color in response to absorbing energy across a first wavelength band when exposed to an energy source; a second color emitter configured to emit visible light of a second target color in response to absorbing energy across a second wavelength band when exposed to the energy source; as well as The energy emitter as claimed in claim 1.

110. The cosmetic of claim 109, wherein the cosmetic is a skin cream.

111. The cosmetic of claim 109, wherein the cosmetic is mascara.

112. The cosmetic of claim 109, wherein the cosmetic is at least one member selected from the group consisting of a shampoo, a conditioner, a hair gel, a hair styling compound, a hair spray, and a hair lotion.

113. The cosmetic of claim 109, wherein the cosmetic is a lip balm.

114. The cosmetic of claim 109, wherein the cosmetic is rouge.

115. A method for enhancing visible light emission from a surface, the method comprising: providing at least one color enhancement structure on said surface, wherein said color enhancement structure comprises at least one energy emitter as claimed in claim 1; exposing the surface and the at least one color-enhancing structure to applied energy from an energy source; and The visible light is emitted by converting a portion of the applied energy into visible light of at least one target color.

116. A method for enhancing visible light emission from a coating, the method comprising: providing at least one color enhancement structure in the coating or near the surface of the coating, wherein the color enhancement structure comprises at least one energy emitter as claimed in claim 1; exposing the coating or a surface of the coating and the at least one color-enhancing structure to applied energy from an energy source; and The visible light is emitted by converting a portion of the applied energy into the visible light of at least one target color.

117. A method for enhancing visible light emission from an ink, the method comprising: providing at least one color enhancement structure in the ink, wherein the color enhancement structure comprises at least one energy emitter as claimed in claim 1; exposing the ink and the at least one color-enhancing structure to applied energy from an energy source; and The visible light is emitted by converting a portion of the applied energy into the visible light of at least one target color.

118. A method for enhancing visible light emission from a display, the method comprising: providing at least one color enhancement structure on a color filter or color reflecting surface of the display, wherein the color enhancement structure comprises at least one energy emitter as claimed in claim 1; exposing the color filter or color reflecting surface and the at least one color enhancing structure to applied energy from an energy source; and The visible light is emitted by converting a portion of the applied energy into the visible light of at least one target color.

119. An energy or color enhancement device, the energy or color enhancement device comprising: An energy collector comprising at least one energy enhancing structure, wherein the energy enhancing structure is at least one non-plasmonic structure selected from the group consisting of: a folded resonator, a fractal antenna, a grid pattern, an antenna, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure; and an energy converter capable of receiving applied electromagnetic energy, converting the applied electromagnetic energy and emitting from the energy converter an emission energy of a wavelength having a wavelength / energy shifted relative to the applied electromagnetic energy, and the energy converter is disposed in the vicinity of the energy enhancement structure, Wherein the energy-enhancing structure is configured to provide an electric field between opposing elements of the structure.

120. An energy or color enhancement device, the energy or color enhancement device comprising: An energy collector comprising at least one energy enhancing structure, wherein the energy enhancing structure is at least one non-plasmonic structure selected from the group consisting of: a folded resonator, a fractal antenna, a grid pattern, an antenna, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure; and an energy converter capable of receiving applied electromagnetic energy, converting the applied electromagnetic energy and emitting from the energy converter an emission energy of a wavelength having a wavelength / energy shifted relative to the applied electromagnetic energy, and the energy converter is disposed in the vicinity of the energy enhancement structure, The energy collector collects energy from the branch antennas.

121. The apparatus of claim 120, wherein each array element of the branch antenna comprises a metal core and a dielectric cladding.

122. An energy or color enhancement device, the energy or color enhancement device comprising: An energy collector comprising at least one energy enhancing structure, wherein the energy enhancing structure is at least one non-plasmonic structure selected from the group consisting of: a folded resonator, a fractal antenna, a grid pattern, an antenna, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure; and An energy converter, comprising a mechanoluminescent emitter, which is capable of receiving at least one of acoustic energy, vibration energy and ultrasonic energy, converting the received energy and emitting light of a certain wavelength from the energy converter.

123. The device of claim 122, wherein the mesoluminescent emitter comprises a piezoelectric material coupled to an electroluminescent material to form a composite emitter.

124. An energy enhancement structure capable of capturing one or more wavelengths of electromagnetic energy and enhancing the one or more wavelengths of electromagnetic energy in at least one property, wherein: The energy-enhancing structure is at least one non-plasmonic structure selected from the group consisting of a folded resonator, a fractal antenna, a grid pattern, an antenna, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure.

125. The energy enhancement structure of claim 124 comprising a folded resonant body having opposing electrodes, the electric field being oriented between the opposing electrodes.

126. The energy enhancement structure of claim 125, wherein the opposing electrodes are oriented outside of the folded resonator and parallel to each other.

127. The energy enhancement structure of claim 125, wherein the opposing electrodes are oriented inside the folded resonator and are parallel to each other.

128. The energy enhancing structure of claim 125, wherein the folded resonant body comprises Folded resonator.

129. An energy enhancement structure as described in claim 125, wherein the folded resonator is a plurality of said folded resonators, and the folded resonators are arranged concentrically and optionally coplanar with each other, so that the external opposing electrodes of each folded resonator do not spatially overlap with the external opposing electrodes of other folded resonators in the plurality of folded resonators.

130. An energy enhancement structure as described in claim 125, wherein the folded resonator is a plurality of said folded resonators, which are arranged concentrically and optionally coplanar with each other, so that the external opposing electrodes of each folded resonator spatially overlap with the external opposing electrodes of one or more of the other folded resonators in the plurality of folded resonators.

131. An energy collector, comprising: At least one energy enhancement structure, wherein the energy enhancement structure is at least one non-plasmonic structure selected from the group consisting of: a folded resonator, a fractal antenna, a grid pattern, an antenna, an etalon, a nanoparticle, a microparticle, a nanostructure, and a microstructure; and at least one energy converter, the at least one energy converter capable of receiving applied electromagnetic energy, converting the applied electromagnetic energy and emitting electromagnetic energy from the at least one energy converter having a wavelength or energy shifted relative to the applied electromagnetic energy, and the energy converter is disposed in proximity to the at least one energy enhancement structure such that the emitted electromagnetic energy is emitted with at least one enhanced property compared to a condition where the energy converter is remote from the at least one energy enhancement structure.

132. The energy collector of claim 131, wherein the at least one energy converter is at least one member selected from the group consisting of a phosphor, a luminescent phosphor, an electroluminescent particle, an upconverter, a downconverter, and a scintillator.

133. The energy collector of claim 131, wherein positioning the energy converter proximate the at least one energy enhancement structure comprises conductively coupling the at least one energy converter to the at least one energy enhancement structure.

134. An energy collector as described in claim 133, wherein conductively coupling includes placing the at least one energy converter in proximity to the at least one energy enhancement structure, physically located within the at least one energy enhancement structure, or located within the generated electric field of the at least one energy enhancement structure.

135. The energy collector of claim 133, wherein conductively coupling comprises a physical conductive connection between the at least one energy converter and the at least one energy enhancement structure.

136. An energy collector as described in claim 131, wherein the applied electromagnetic energy is selected from radio waves, microwaves, far infrared, near infrared, visible light, UV, x-rays, gamma rays, electron beams and proton beams.

137. The energy collector of claim 131, wherein the at least one energy enhancing structure comprises a first resonant body dimensioned to resonate with the applied electromagnetic energy, the first resonant body optionally comprising a fractal pattern.

138. An energy collector as described in claim 131, wherein the energy enhancement structure comprises a folded resonator having opposing electrodes, and the electric field is directed between the opposing electrodes.

139. The energy collector of claim 136, wherein the opposing electrodes are oriented outside of the folded resonator and are parallel to each other.

140. The energy collector of claim 136, wherein the opposing electrodes are oriented inside the folded resonator and are parallel to each other.

141. The energy collector of claim 138, wherein the folded resonator comprises Folded resonator.

142. An energy collector as described in claim 138, wherein the folded resonator is a plurality of the folded resonators, which are concentrically arranged and optionally coplanar with each other, so that the external opposing electrodes of each folded resonator do not spatially overlap with the external opposing electrodes of other folded resonators in the plurality of folded resonators.

143. An energy collector as described in claim 138, wherein the folded resonator is a plurality of the folded resonators, which are concentrically arranged and optionally coplanar with each other, so that the external opposing electrodes of each folded resonator spatially overlap with the external opposing electrodes of one or more of the other folded resonators in the plurality of folded resonators.

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