Color enhancing optical light propagators, optical films, color enhancing films, and film assemblies, articles containing the same, and methods for preparing the same

Abstract

An optical light propagator is provided, having a core formed of a high-κ dielectric material capable of transmitting wavelengths in the UV-visible range, and an outer coating on the core wherein the outer coating is formed of a low- κ dielectric material; wherein the outer coating has a plurality of porosities along the optical light propagator, wherein each of the plurality of porosities transits from an outer surface of the outer coating to an outer surface of the core at an interface between the outer coating and the core, such that wavelengths transmitted through the core of the optical light propagator are emitted through each of the plurality of porosities along the optical light propagator, and fibers, sheets, yarns, and articles made therefrom.

Description

ATTORNEY DOCKET: 018607-156990 TITLE OF THE INVENTION COLOR ENHANCING OPTICAL LIGHT PROPAGATORS, OPTICAL FILMS, COLOR ENHANCING FILMS, AND FILM ASSEMBLIES, ARTICLES CONTAINING THE SAME, AND METHODS FOR PREPARING THE SAME CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is related to, AND CLAIMS PRIORITY TO, U.S. Provisional Application Serial No.63 / 514,432, filed July 19, 2023, pending, the entire contents of which are incorporated herein by reference. This application is also related to, and claims priority to, U.S. Provisional Application Serial No.63 / 609,928, filed December 14, 2023, pending, the entire contents of which are incorporated herein by reference. BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

[0002] The present invention relates to a “leaky” optical light propagator, in the form of a fiber, a sheet / film, or a waveguide, color enhancing optical films and film assemblies, articles prepared from the same, and methods for preparing the same, providing enhanced color effects to the articles. DESCRIPTION OF THE RELATED ART

[0003] In various commercial products, there is a desire to provide vivid colors, color effects, iridescence, opalescence, and other visual options. However, for the most part, up until now, the colors available have been relatively limited to those than can be produced by fabric dyes, certain nanoparticles embedded in or on a fiber, surface effects, etc.

[0004] The field of optical waveguides is a fairly developed field and used for many different purposes, such as data transmission, light transmission, etc. The typical light waveguide is designed to provide the maximum transmission of light from the source end to the output end of the waveguide, with minimal leakage being the goal. Optical waveguides can certainly provide transmission of desired light to a specific location. However, such light transmission would not be distributed across a surface of an article.

[0005] Accordingly, there is a need for providing a way to transmit light of a desired wavelength using optical light propagators or waveguides, such that the light can be delivered either directly or modified to a broader surface to provide various light and color effects and enhancements to the surface of an article. SUMMARY OF THE INVENTION

[0006] Another object of the present invention is to provide a leaky optical light propagator in the form of a fiber, a sheet, a film, or a waveguide that permits the exhibit of selected wavelengths / colors along the surface of the optical light propagator, and articles made therefrom.

[0007] A further object of the invention is to provide articles prepared from the leaky optical light propagator of the invention, whereby the articles can exhibit enhanced color effects on their surface by virtue of the light being leaked and / or modified by the optical light propagator of the invention.

[0008] Another object of the present invention is to provide articles that combine the use of the leaky optical light propagator of the invention with the color enhancing film / assembly of the invention to provide articles having unique color enhanced decorative or informative aspects or components.

[0009] These and other objects and advantages of the invention, either alone or in combinations thereof, may be satisfied by an optical light propagator comprising: a core formed of a high-κ dielectric material capable of transmitting wavelengths in the UV-visible range, and

[0010] an outer coating on the core wherein the outer coating is formed of a low- κ dielectric material;

[0011] wherein the outer coating has a plurality of porosities along the optical light propagator, wherein each of the plurality of porosities transits from an outer surface of the outer coating to an outer surface of the core at an interface between the outer coating and the core, such that wavelengths transmitted through the core of the optical light propagator are emitted through each of the plurality of porosities along the optical light propagator. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

[0013] FIG.1 provides a schematic of a typical optical fiber.

[0014] FIG.2 provides a schematic of an embodiment of the optical light propagator of the invention in the form of an optical fiber.

[0015] FIG.3 provides a schematic of another embodiment of the optical light propagator of the invention in the form of an optical fiber.

[0016] FIG.4 provides a schematic of another embodiment of the optical light propagator of the invention in the form of an optical sheet or film.

[0017] FIG.5 provides a schematic of an embodiment of a method for preparing an optical fiber of the invention.

[0018] FIG.6 provides a schematic of an embodiment of a method for preparing a yarn of the present invention containing the inventive optical fiber.

[0019] FIG.7 provides a representation of a cross section of an embodiment of the optical fiber of the invention.

[0020] FIG.8 provides a representation of a cross section of an embodiment of a yarn of the present invention containing the inventive optical fiber.

[0021] FIG.9 provides a representation of applying an external light source to an embodiment of yarn of the present invention containing the inventive optical fiber.

[0022] FIG.10 provides a representation of a sole (100) of an athletic shoe containing a distributed light source (110) and battery (120), used for activating a yarn of the present invention when the yarn is used to make the shoe upper.

[0023] FIG.11 provides a depiction of a coating applicator apparatus (200) that can be used in embodiments of the present invention to prepare a coating on the leaky light propagator / optical fiber of various embodiments of the present invention.

[0024] FIG.12 provides a depiction of a series of coating applicator apparatus (200) and (300) for providing multiple coating types onto a leaky light propagator / optical fiber of various embodiments of the present invention.

[0025] FIG.13A provides a depiction of one embodiment of the present invention where the end of the inventive fiber (410) is placed in close proximity to an LED source (420) that is mounted on a flexible circuit (430) that supplies the necessary power, with the end of theinventive fiber (410), LED source (420), and flexible circuit (430) being embedded in an optically clear encapsulant (440).

[0026] FIG.13B provides a depiction of an embodiment of the present invention where multiple inventive fibers are part of the inventive fabric (411), where the inventive fabric (411) is placed in close proximity to the LED source (420) mounted on the flex circuit (430), and the end of the inventive fabric (411), LED source (420) and flex circuit (430) are embedded in an optically clear encapsulant (440) such that the ends of the inventive fibers contained in the inventive fabric are contained within the encapsulant.

[0027] FIG.13C provides a perspective depiction of an embodiment of the inventive fabric (411), LED source (420) (in this case an LED strip), and optically clear encapsulant (440) (the flex circuit is not shown) which can be used, for example, in clothing and tapestry articles.

[0028] FIG.14 illustrates an embodiment of the present invention showing a knit upper fabric containing a fiber of the present invention, prepared for making an athletic shoe.

[0029] FIG.15 illustrates an embodiment of the present invention knit upper fabric in construction of an athletic shoe, providing a heel view of an athletic shoe.

[0030] FIG.16 illustrates an embodiment of the present invention in which the knit fabric comprising the fibers of the present invention is used in the foxing material on the heel of the shoe. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] In the context of the present invention, the term “photoactivatable” refers to components that when exposed to light of a certain wavelength will emit or scatter light.

[0032] One embodiment of the present invention provides an optical light propagator comprising: a core formed of a high-κ dielectric material capable of transmitting wavelengths in the UV-visible range, and an outer coating on the core wherein the outer coating is formed of a low- κ dielectric material; wherein the outer coating has a plurality of porosities along the optical light propagator, wherein each of the plurality of porosities transits from an outer surface of the outer coating to an outer surface of the core at an interface between the outer coating and the core, such that wavelengths transmitted through the core of the optical light propagator are emitted through each of the plurality of porosities along the optical light propagator.

[0033] In certain embodiments, the optical light propagator of the invention is configured as an optical fiber. FIG.1 shows a representation of the construction of a typical optical fiber. The optical fiber has a core, a cladding around the core, and optionally a jacket on the outer surface of the cladding. The core has a diameter “D-core” and a refractive index of ncore. The cladding layer has a diameter of “D-clad” and a refractive index of ncladding.

[0034] The light waveguiding works in fibers by the following principle: When light propagates in a material of higher refractive index and is incident on an interface at a shallow angle, it will be internally reflected by the interface if the material on the other side of the interface has a lower refractive index. This then keeps the light in the material of higher refractive index. If the material on the other side of the interface has a higher refractive index, then the light will leak through the interface. Typically, the refractive index of the core is greater than the refractive index of the cladding layer (or ncore> ncladding). Therefore, the light in the core of the fiber which has a higher refractive index can be trapped in the core (waveguided) by using a lower index cladding.

[0035] Typical optical fiber core diameters range from 4 to 8 microns for single mode fibers, from 50 to 100 microns for multimode fibers used in communication, and from 200 to 1000 microns for large core fibers used in power transmission. In the present invention, the optical fiber embodiments would preferably be multimode fibers.

[0036] Typical cladding diameters can be around 80 microns for single mode fibers; and, between 125 – 140 microns for telecommunication fibers. Multimode fibers are preferred for the present invention.

[0037] The optical fibers (core and cladding) can be made of any desired material having the necessary refractive indexes. In preferred embodiments, the optical fibers are formed of silica glass with small amounts of impurities added to the core to adjust the index of refraction. The adjustment can be gradual (graded index fiber) or can be discontinuous (step index fiber). In especially designed fibers, several different cladding layers can be used. In certain embodiments, the optical fibers can be made of all plastic. These plastic fibers are typically lower quality than glass fibers with higher attenuation coefficients. The jacket material can also be made of plastic, preferably made from a thin polymer coating. In the present invention the jacket is not necessary for the optical functionality but could be useful as an encapsulant that protects the inventive fiber from wear and tear, so long as the jacket permits transmission of the desired frequencies of light.

[0038] In optical fibers, the light propagates inside the core. Some portion of the light travels in the cladding layer. This is called the evanescent wave and it corresponds to thepenetration of the core wave as it reflects at the interface with the clad. Dopants are preferred in the core. There could be options in which dopants are put in the clad, but the source intensity will be lower in the core than in the clad.

[0039] In certain embodiments, it is the field profile of the propagating mode (as determined by the index structure of the fiber and light frequency) that would define how much of the light actually is available within the clad (evanescent field). Addition of dopants directly to the core of the fiber is done routinely for a variety of applications, including telecom and for different wavelength shifting modes (the dopants including rare-earth and quantum dot materials QDs). Depending upon the materials involved, introduction of dopants into the core can be done at the preform level from which glass fibers are drawn. Plastic fibers could also be used to introduce such color-producing agents (ionic, particulate etc.). In the present invention, the fiber structure can be used for excitation delivery, via evanescent field or via even a direct break in the core-clad structure, into a color modulating coating (or multilayer) added to the initial fiber structure. The introduction of changes in fiber geometry (core / clad diameter ratio) and / or index structure (core / clad index contrast) that can be used locally modify (or pattern) the magnitude of the excitation light leakage into the color coating (i.e. via defect introduction, manufactured changes in core / clad ratio, bending etc.) In that way, a single, fiber structure (that would be tailored for a given application) can be coated with an array of different coating types. These coatings can be used to further tune the excitation leakage (depending upon the index relative to the fiber clad) and the resulting color (depending upon dopant species and multilayer structure, if included).

[0040] Furthermore, there is a difference between UV and visible sources. For UV, two cladding layers could be used,a thin one to contain the UV and a thicker one for the visible colors created, then we can scratch the outer thicker clad and leak the colors only and keep the UV inside the thin inner clad.

[0041] In embodiments of the optical fiber of the present invention, however, the refractive index of the cladding layer is varied at different areas of the cladding layer to be higher than the refractive index in the core, resulting in leakage of the light out of the core through the cladding layer along the length of the fiber.

[0042] In certain embodiments of the present invention, either the cladding layer or an additional conformal coating on the outer surface of the cladding layer is provided with one or more energy modulation agents distributed throughout, wherein the one or more energy modulation agents are configured in order to absorb the light being leaked from the core andconvert it to a desired wavelength of colored visible or UV light, depending on the effect desired from the optical fiber of the invention.

[0043] FIG.2 shows a representation of an embodiment of an optical fiber of the present invention wherein the core has leakage areas created on its outer surface either in an outer covering / inner cladding layer via various techniques, or created directly in the core layer itself. The cladding layer in this embodiment has embedded and distributed throughout the one or more energy modulation agents (or light modulating agents), and optionally a jacket layer as desired. If a jacket layer is present, it is preferred that it be transparent and capable of transmitting the wavelengths emitted by the one or more energy modulation agents embedded in the cladding layer as shown.

[0044] In a further embodiment of the invention, as shown in FIG.3, it is the core that contains the one or more energy modulation agents, along with having the leakage areas along its length. The cladding layer 1 (and optional jacket or cladding layer 2) can be formed of materials with adjusted refractive indexes to further enhance / alter the wavelength of emissions from the one or more energy modulation agents to produce various optical effects.

[0045] The one or more energy modulation agents can be upconverting or downconverting energy modulation agents. In the context of the present invention, the term “upconverting” is intended to mean conversion of an electromagnetic energy of lower energy (higher or longer wavelength) to an electromagnetic energy of higher energy (lower or shorter wavelength), such as conversion of infrared (IR) to visible light. In the context of the present invention, the term “downconverting” is intended to mean conversion of an electromagnetic energy of higher energy (lower or shorter wavelength) to an electromagnetic energy of lower energy (higher or longer wavelength), such as conversion of ultraviolet (UV) to visible light. Suitable energy modulation agents for use in the present invention are described in more detail below.

[0046] In other embodiments of the present invention, the optical light propagator is a thin film light propagator in the form of a sheet or film. FIG.4 is a schematic representing an embodiment of the thin film light propagator in the form of a sheet or film. In this type of embodiment, the light propagator is designed as a slab (sheet or film) instead of a cylinder (fiber) and the waveguiding effect is controlled in only one dimension by stacking a core layer (40) sandwiched between upper and lower cladding (outer coating) layers (45).

[0047] Any type of energy modulation agent can be used in the light propagators of the present invention, with numerous examples provided below. In certain preferred embodiments, the one or more energy modulation agents are selected to be at least onemember selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

[0048] Types of Energy Modulation Agents (or Energy Converters)

[0049] The energy converters used in the present invention can be any material that absorbs an applied radiation and emits a defined emission wavelength or wavelength spectrum. The energy converters preferably emit wavelengths or wavelength spectra in the UV, visible / color, and / or IR wavelengths. The applied energy can range from IR up through x- rays, depending on the energy converter used and the end use chosen.

[0050] In various embodiments of the invention, energy converters can be used with or without the energy augmentation structures described in U.S. Published Application 2022 / 0275914, incorporated herein by reference in its entirety. In some embodiments, the converters are for up conversion of light e.g., from the IR regime into visible electromagnetic radiation and for down conversion of light e.g., from the UV range into visible electromagnetic radiation. The invention in various embodiments up converts energy, preferably light in the visible spectrum. The invention encompasses a variety of applications where the up and down conversion materials with or without the energy augmentation structures are included to enhance electromagnetic energy emission, preferably light or photon emission. When an energy augmentation structure is present, it may be separate from or connected to the energy converter. In certain embodiments, the energy converter can have the energy augmentation structure formed on its surface through chemical vapor deposition (“CVD”) or physical vapor deposition (“PVD”) processes or other nanoscale “printing” methods. Alternatively, the energy augmentation structure can be formed on a surface of an inert non-energy converting particle, formed, for example, from silica or formed from a non- energy converting particle coated with a biologically and / or chemically inert coating (such as, for example, diamond, diamond-like carbon, or similar inert materials). Such an energy augmentation structure can then be used with a similarly coated energy converter for uses requiring biologically or chemically inert conditions.

[0051] Suitable energy modulation agents or energy converters (the two terms are used interchangeably herein) of the invention include, but are not limited to, a biocompatible fluorescing metal nanoparticle, fluorescing dye molecule, gold nanoparticle, a quantum dot encapsulated by a variety of methods practiced in the field, such as polyamidoamine in various forms, a luciferase (bioluminescence), a biocompatible phosphorescent molecule, acombined electromagnetic energy harvester molecule, and a lanthanide chelate capable of intense luminescence.

[0052] Resonance Energy Transfer (RET) is an energy transfer mechanism between two molecules having overlapping emission and absorption bands. Electromagnetic emitters are capable of converting an arriving wavelength to a longer wavelength. For example, UV-B energy absorbed by a first molecule may be transferred by a dipole-dipole interaction to a UV-A-emitting molecule in close proximity to the UV-B-absorbing molecule. Alternatively, a material absorbing a shorter wavelength may be chosen to provide RET to a non-emitting molecule that has an overlapping absorption band with the transferring molecule's emission band. Alternatively, phosphorescence, chemiluminescence, or bioluminescence may be used to convert an applied energy to an emitted energy of desired wavelength.

[0053] In one embodiment, the energy converters of the invention can include persistent after-glow phosphor materials emitting light in the visible to near ultraviolet and ultraviolet range. In one embodiment, Eu-doped strontium aluminate is used as an energy converter in which deep UV light “charges” the photoluminescence. In another embodiment, gadolinium strontium magnesium aluminate is used as an energy converter in which deep UV light “charges” the photoluminescence. U.S. Pat. Appl. Publ. No.20070221883 (the entire contents of which are incorporated herein by reference) describes specifically gadolinium- activated strontium magnesium aluminate having an excitation maximum at about 172 nm, and which emits in a narrow-band UV emission at about 310 nm. The ‘883 publication also describes other useful energy converters for this invention, making note of emission spectra between 300 nm and 320 nm for a Sr(Al,Mg)12O19:Gd phosphor and two 312 nm line emitting phosphors, YMgB5O10:Gd, Ce and YMgB5O10:Gd, Ce, Pr. WO2016200349 (the entire contents of which are incorporated herein by reference) describes long lasting yellowish-green emitting phosphorescent pigments in the strontium aluminate (SrAl2O4) system, which could serve as energy converters in the present invention. WO 2016200348 (the entire contents of which are incorporated herein by reference) describes long lasting bluish-green emitting phosphorescent pigments in the strontium aluminate (Sr4Al14O25) system, which could serve as energy converters in the present invention. Xiong et al in “Recent advances in ultraviolet persistent phosphors,” Optical Materials X 2 (2019) (the entire contents of which are incorporated herein by reference) describes a number of ultraviolet persistent phosphors that could as energy converters in the present invention. The table below provides a listing of such persistent phosphors:

[0054]

[0055] In one embodiment, the phosphor described by Xiong et al as CaAl2O4:Ce3+having an emission peak of 400 nm and a persistent time of more than 10 h could be used.

[0056] In one embodiment, a lanthanide chelate capable of intense luminescence is used as an energy converter. In another embodiment, a biocompatible, endogenous fluorophore emitter is selected as an energy converter.

[0057] Among various materials, luminescent nanoparticles have attracted increasing technological and industrial interest. In the context of the invention, nanoparticle refers to a particle having a size less than one micron. While the description of the invention describes specific examples using nanoparticles, the invention in many embodiments is not limited to particles having a size less than one micron. However, in many of the embodiments, the size range of less than one micron, and especially less than 100 nm produces properties of special interest such as for example emission lifetime luminescence quenching, luminescent quantum efficiency, and concentration quenching and such as for example diffusion, penetration, and dispersion into mediums where larger size particles would not migrate.

[0058] This invention in various embodiments can use a wide variety of down conversion materials (or mixtures of down conversion materials) with or without the energy augmentation structures to enhance light or photon emission. These down conversion materials can include quantum dots, semiconductor materials, alloys of semiconductor materials, scintillation and phosphor materials, materials that exhibit X-ray excited luminescence (XEOL), organic solids, metal complexes, inorganic solids, crystals, rare earth materials (lanthanides), polymers, scintillators, phosphor materials, etc., and materials that exhibit excitonic properties. Accordingly, the down conversion materials to enhance light or photon emission can convert energy from one of ultraviolet light, x-rays, and high energyparticles to visible light, although down conversion of ultraviolet light or blue light may have more commercial application for the color enhancements described below. The down conversion materials to enhance light or photon emission can convert energy from higher energy visible light to lower energy visible light.

[0059] In one embodiment of the invention, a quantum dot mixture with or without the energy augmentation structures can be used for the multiple nanoparticles. Quantum dots are in general nanometer size particles whose energy states in the material of the quantum dot are dependent on the size of the quantum dot. For example, quantum dots are known to be semiconductors whose conducting characteristics are closely related to the size and shape of the individual crystal. Generally, the smaller the size of the crystal, the larger the band gap, the greater the difference in energy between the highest valence band and the lowest conduction band becomes. Therefore, more energy is needed to excite the dot, and concurrently, more energy is released when the crystal returns to its resting state. In fluorescent dye applications, this equates to higher frequencies of light emitted after excitation of the dot as the crystal size grows smaller, resulting in a color shift from red to blue in the light emitted. Quantum dots represent one way to down convert ultraviolet light of the spectrum to a targeted wavelength or energy emission. Quantum dots represent one way to down convert blue light of a spectrum to a targeted wavelength or energy emission.

[0060] As described in U.S. Pat. No.6,744,960 (the entire contents of which are incorporated by reference), different size quantum dots produce different color emissions. In that work and applicable to this 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 may suitably be employed is titanium dioxide (TiO2). The size of the particle, i.e., the quantum dot, may range from about 2 to 10 nm. Since the size of these particles is so small, quantum physics governs many of the electrical and optical properties of the quantum dot. One such result of the application of quantum mechanics to the quantum dot is that quantum dots absorb a broad spectrum of optical wavelengths and re-emit radiation having a wavelength that is longer than the wavelength of the absorbed light. The wavelength of the emitted light is governed by the size of the quantum dot. For example, CdSe quantum dots 5.0 nm in diameter emit radiation having a narrow spectral distribution centered about 625 nm while quantum dots including CdSe 2.2 nm in size emit light having a center wavelength of about 500 nm. Semiconductor quantum dots comprising CdSe, InP, and InAs, can emit radiation having center wavelengths in the range between 400 nm to about 1.5 μm. Titaniumdioxide TiO2 also emits in this range. The linewidth of the emission, i.e., full-width half- maximum (FWHM), for these semiconductor materials may range from about 20 to 30 nm. To produce this narrowband emission, quantum dots simply need to absorb light having wavelengths shorter than the wavelength of the light emitted by the dots. For example, for 5.0 nm diameter CdSe quantum dots light having wavelengths shorter than about 625 nm is absorbed to produce emission at about 625 nm while for 2.2 nm quantum dots comprising CdSe light having wavelengths smaller 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.

[0061] Specifically, in one embodiment of the invention, a quantum dot mixture (QDM) coating can be deposited using CVD and or sol-gel techniques using standard precipitation techniques. The QDM coating can be made of a silicate structure that does not diminish UV output. Within the silicate family, silica (SiO2) is suitable since it maximizes UV transmission through the coating. The coating can further include a second layer of an inert or a biocompatible glass. Such bio-compatible glass and glass ceramic compositions can contain calcium, a lanthanide or yttrium, silicon, phosphorus and oxygen. Other biocompatible materials and techniques are described in the following patents which are incorporated herein in their entirety: U.S. Pat. Nos.5,034,353; 4,786,617; 3,981,736; 3,922,155; 4,120,730; and U.S. Pat. Appl. Nos.2008 / 0057096; 2006 / 0275368; and 2010 / 0023101.

[0062] Further, the down conversion materials for the invention described here can be coated with insulator materials such as for example silica which will reduce the likelihood of any chemical interaction between the luminescent particles and the medium the particles are included therein. These and the other conversion materials described here can be used with or without energy augmentation structures. The following materials (as well as those listed elsewhere) are also considered suitable: lanthanum and gadolinium oxyhalides activated with thulium; Er3+doped BaTiO3nanoparticles, Yb3+doped CsMnCl3and RbMnCl3, BaFBr:Eu2+nanoparticles, Cesium Iodine, Bismuth Germanate, Cadmium Tungstate, and CsBr doped with divalent Eu.

[0063] In various embodiments of the invention, the following luminescent polymers with or without energy augmentation structures are also suitable as conversion materials: poly(phenylene ethynylene), poly(phenylene vinylene), poly(p-phenylene), poly(thiophene), poly(pyridyl vinylene), poly(pyrrole), poly(acetylene), poly(vinyl carbazole), poly(fluorenes), and the like, as well as copolymers and / or derivatives thereof.

[0064] In various embodiments of the invention, the following materials, with or without energy augmentation structures, can be used similar to that detailed in U.S. Pat. No. 7,090,355, the entire contents of which are incorporated herein by reference. For down- conversion, the following materials can be used. Inorganic or ceramic phosphors or nano- particles, including but not limited to metal oxides, metal halides, metal chalcogenides (e.g. metal sulfides), or their hybrids, such as metal oxo-halides, metal oxo-chalcogenides. Laser dyes and small organic molecules, and fluorescent organic polymers. Semiconductor nano- particles, such as II–VI or III–V compound semiconductors, e.g. fluorescent quantum dots. Organometallic molecules including at least a metal center such as rare earth elements (e.g. Eu, Tb, Ce, Er, Tm, Pr, Ho) and transitional metal elements such as Cr, Mn, Zn, Ir, Ru, V, and main group elements such as B, Al, Ga, etc. The metal elements are chemically bonded to organic groups to prevent the quenching of the fluorescence from the hosts or solvents. Phosphors can be used including the Garnet series of phosphors: (Y m A 1-m ) 3 (Al n B 1-n ) 5 O 12 , doped with Ce; where 0≦m, n≦1, where A includes other rare earth elements, B includes B, Ga. In addition, phosphors containing metal silicates, metal borates, metal phosphates, and metal aluminates hosts can be used. In addition, nano-particulates phosphors containing common rare earth elements (e.g. Eu, Tb, Ce, Dy, Er, Pr, and Tm) and transitional or main group elements (e.g. Mn, Cr, Ti, Ag, Cu, Zn, Bi, Pb, Sn, and Tl) as the fluorescent activators, can be used. Materials such as Ca, Zn, Cd in tungstates, metal vanadates, ZnO, etc. can be used.

[0065] Commercial laser dye materials obtained from several laser dye vendors, including Lambda Physik, and Exciton, etc. can also be used with or without energy augmentation structures. A partial list of the 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, which also serve as fluorescent materials and find many optical and fluorescent applications. For example, MEH-PPV, PPV, etc. have been used in opto-electronic devices, such as polymer light emitting diodes (PLED). Such fluorescent polymers can be used directly as the fluorescent layer of the transparent 2-D display screen with and without energy augmentation structures.

[0066] As noted above, semiconductor nanoparticles (e.g., quantum dots) can be used with or without energy augmentation structures. The terms “semiconductor nanoparticles,” in the art refers to an inorganic crystallite between 1 nm and 1000 nm in diameter, preferably between 2 nm to 50 nm. A semiconductor nano-particle is capable of emittingelectromagnetic radiation upon excitation (i.e., the semiconductor nano-particle is luminescent). The nanoparticle can be either a homogeneous nano-crystal, or comprises of multiple shells. For example, the nanoparticle can include a “core” of one or more first semiconductor materials, and may be surrounded by a “shell” of a second semiconductor material. The core and / or the shell can be a semiconductor material including, but not limited to, those of the group II–VI (ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, PbS, PbSe, PbTe, and the like) and III–V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, and the like) and IV (Ge, Si, and the like) materials, and an alloy or a mixture thereof.

[0067] Fluorescent organometallic molecules containing rare earth or transitional element cations can be used for down conversion materials, with or without energy augmentation structures. Such molecules include a metal center of rare earth elements including Eu, Tb, Er, Tm, Ce protected with organic chelating groups. The metal center may also include transitional elements such as Zn, Mn, Cr, Ir, etc. and main group elements such as B, Al, Ga. Such organometallic molecules can readily dissolve in liquid or transparent solid host media. Some examples of such fluorescent organometallic molecules include: 1. Tris(dibenzoylmethane)mono(phenanthroline)europium(III); 2. Tris(8- hydroxyquinoline)erbium; 3. Tris(1-phenyl-3-methyl-4-(2,2-dimethylpropan-1-oyl)pyrazolin -5-one)terbium(III); 4. Bis(2-methyl-8-hydroxyquinolato)zinc; 5. Diphenylborane-8- hydroxyquinolate.

[0068] Specific examples of down-conversion materials for red emission include those discussed above and europium complexes such as those described in JP Laid-open Patent Publication (Kokai) No.2003-26969, constructed such that β-diketone ligand is coordinated to europium forming an europium complex capable of emitting red fluorescence. Other specific examples of the rare earth element complexes include complexes include lanthanum (Ln), europium (Eu), terbium (Tb), and gadolinium (Gd) and combinations thereof. An europium (Eu) complex is capable of emitting red fluorescence when irradiated with ultraviolet rays having a wavelength ranging from 365 nm to 410 nm. Terbium (Tb) is capable of emitting green fluorescence when irradiated with ultraviolet rays having a wavelength of 365 nm.

[0069] In other down-conversion embodiments, the down conversion light emitting materials which emit red light may include europium, light emitting materials which emit green light may include Terbium, and light emitting materials which emit blue or yellow light may include cerium (and / or thulium). In up-conversion embodiments, up conversionmaterials which emit red light may include praseodymium, light emitting materials which emit green light may include erbium, and light emitting materials which emit blue light may include thulium. In various embodiments, the conversion materials can be light emitting particles made of fluorescent molecules that emit different colors (e.g. red, green, and blue), or different wavelengths or energies of light. In embodiments, the conversion materials can be light emitting particles made of pure organic or organo-metallic dyes with or without energy augmentation structures.

[0070] In addition to the combinations of rare earth complexes, such as a combination of a europium complex and a terbium complex, it is also possible employ a combination of a europium complex and a green-emitting fluorescent substance which is not a complex, or a combination of a terbium complex and a red-emitting fluorescent substance which is not a complex.

[0071] Other down converter materials (which can be used with or without energy augmentation structures) include for example ZnS, PbS, SbS3, MoS2, PbTe, PbSe, BeO, MgO. Li2CO3, Ca(OH)2, MoO3, SiO2, Al2O3, TeO2, SnO2, KBr, KCl, and NaCl. These materials can include dopants to tailor the emission properties, as noted above. Examples of doped (or alloyed) glass systems suitable for the 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).

[0072] With regard more specifically to down converter materials suitable for the invention, U.S. Pat. No.4,705,952 (the contents of which are hereby incorporated herein by reference) describes an infrared-triggered phosphor that stores energy in the form of visible light of a first wavelength and released energy in the form of visible light of a second wavelength when triggered by infrared light. The phosphors in U.S. Pat. No.4,705,952 were compositions of alkaline earth metal sulfides, rare earth dopants, and fusible salts. The phosphors in U.S. Pat. No.4,705,952 were more specifically phosphors made from strontium sulfide, barium sulfide and mixtures thereof; including a dopant from the rare earth series and europium oxide, and mixtures thereof; and including a fusible salt 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. Pat. No.4,705,952 are useful in various embodiments of the invention with or without energy augmentation structures. In one example, the infrared-triggered phosphors would be used in conjunction with the conversionenhancement structures, and the receipt of a microwave or IR signal would locally heat and trigger emission.

[0073] In other embodiments of the invention, the down converter materials (or mixtures of down converters materials (which can be used with or without energy augmentation structures) can include Y2O3: Li. Sun et al “Luminescent properties of Li+ doped nanosized Y2O3:Eu,” Solid State Comm.119 (2001) 393-396 (the entire contents of which are incorporated herein by reference) describe such materials. Hou et al “Luminescent properties nano-sized Y2O3:Eu fabricated by co-precipitation method,” Journal of Alloys and Compounds, vol.494, issue 1-2, 2 April 2010, pages 382-385 (the entire contents of which are incorporated herein by reference) describe that nano-sized yttria (Y2O3) powders have been successfully synthesized by a co-precipitation method. The powders were well crystallized, and the grains were almost spherical with good dispersibility. The quenching concentration of Eu3+ions is 9 mol% which is much higher than micro-scaled powders. The incorporation of Li+ ions greatly improved the luminescence intensity. The highest emission intensity was observed with 4 mol% Li+ doped Y2O3:Eu powder ((Y0.87Eu0.09Li0.04)2O3) and the fluorescence intensity was increased by as much as 79%. Yi et al “Improved cathodoluminescent characteristics of Y2O3:Eu3+thin films by Li-doping,” Appl. Phys. A 87, 667–671 (2007) (the entire contents of which are incorporated herein by reference) describe cathodoluminescent spectra for both Y2O3:Eu3+and Li-doped Y2O3:Eu3+films and methods for making these materials.

[0074] Specific downconverting materials may also include at least one or more of Y2O3, Y2O3:Gd, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, ZnS, ZnSe, MgS, CaS, Zn2SiO4:Mn, LaOBr:Tm and alkali lead silicate including compositions of SiO2, B2O3, Na2O, K2O, PbO, MgO, or Ag, and combinations or alloys or layers thereof. Furthermore, the down-converting materials can be sulfur containing phosphors, which can help for example in the rubber vulcanization or other photoactivated processes. An example of such a sulfur containing phosphor is: (Sr,Ca)Ga2S4. Other examples wherein said phosphor particles comprise a thiogallate host material selected from the group consisting of SrGa2S4, CaGa2S4 BaGa2S4, MgGa2S4 and solid solutions thereof. The particle size of such phosphor can be controlled from 25 nm to 300 microns in size as described in US6153123A. The downconverting materials can 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 a combination thereof. The dopant can be included at a concentration of 0.01%-50% by mol concentration. At times it is preferable to have acombination of dopants rather than one dopant such is the case for a Mn and Sb in silicate matrices.

[0075] The invention in other embodiments can use a wide variety of up conversion materials (or mixtures of up converters), with or without the energy augmentation structures to enhance a particular wavelength or energy of light emitted from a material or surface. These up conversion materials can include similar materials as discussed above with regard to down conversion but typically included doped or impurity states in a host crystal that provide a mechanism for up conversion pumping. Accordingly, the up conversion materials to enhance wavelength or energy emission can convert energy from one of near infrared, infrared, and microwave irradiation. Certain of the upconversion materials can convert energy from lower energy visible light to higher energy visible light.

[0076] In one example, a nanoparticle of a lanthanide doped oxide can be excited with near infrared light such as laser light at 980 nm and 808 nm to produce visible light in different parts of the red, green, blue spectrum (different wavelengths or energies) depending on the dopant trivalent rare earth ion(s) chosen, their concentration, and the host lattice.

[0077] The lanthanide doped oxides suitable for this invention differ from more traditional multi-photon up conversion processes where the absorption of, for example, two photons is needed in a simultaneous event to promote an electron from a valence state directly into an upper level conduction band state where relaxation across the band gap of the material produces fluorescence. Here, the co-doping produces states in the band gap of the NaYF4 such that the Yb3+ion has an energy state at2F5 / 2pumpable by a single photon event and from which other single photon absorption events can populate even higher states. Once in this exited state, transitions to higher energy radiative states are possible, from which light emission will be at a higher energy than that of the incident light pumping the2F5 / 2 energy state. In other words, the energy state at2F5 / 2of the Yb3+ion is the state that absorbs 980 nm light permitting a population build up serving as the basis for the transitions to the higher energy states such as the4F7 / 2energy state. Here, transitions from the4F7 / 2energy state produce visible emissions.

[0078] U.S. Pat. No.7,008,559 (the entire contents of which are incorporated herein by reference) describes the upconversion performance of ZnS where excitation at 767 nm produces emission in the visible range. The materials described in U.S. Pat. No.7,008,559 (including the ZnS as well as Er3+doped BaTiO3 nanoparticles and Yb3+doped CsMnCl3) are suitable in various embodiments of the invention, with or without the energy augmentation structures.

[0079] Further, materials specified for up conversion materials in the invention (with or without energy augmentation) include CdTe, CdSe, ZnO, CdS, Y2O3, MgS, CaS, SrS and BaS. Such up conversion materials may be any semiconductor and more specifically, but not by way of limitation, sulfide, telluride, selenide, and oxide semiconductors and their nanoparticles, such as Zn1-xMnxSy, Zn1-xMnxSey, Zn1-xMnxTey, Cd1-xMnSy, Cd1-xMnxSey, Cd1-xMnxTey, Pb1-xMnxSy, Pb1-xMnxSey, Pb1-xMnxTey, Mg1-xMnSy, Ca1-xMnxSy, Ba1-xMnxSyand Sr1-x, etc. (wherein, 0<x≦1, and 0<y≦1). Complex compounds of the above-described semiconductors are also contemplated for use in the invention--e.g. (M1-zNz)1-xMnxA1-yBy (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 complex compounds are Zn0.4Cd0.4Mn0.2S and Zn0.9Mn0..1S0.8Se0.2. Additional conversion materials include insulating and nonconducting materials such as BaF2, BaFBr, and BaTiO3, to name but a few exemplary compounds. Transition and rare earth ion co-doped semiconductors suitable for the 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 complex compounds: (M1-zNz)1-x(MnqR1-q)xA1-yBy (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<q<1).

[0080] Some nanoparticles such as ZnS:Tb3+, Er3+; ZnS:Tb3+; Y2O3:Tb3+; Y2O3:Tb3+, Er3+; ZnS:Mn2+; ZnS:Mn,Er3+are known in the art to function for both down-conversion luminescence and upconversion luminescence and would be suitable for the invention with or without energy augmentation structures. In up-conversion embodiments, light emitting particles which emit red light may include praseodymium, light emitting particles which emit green light may include erbium, and light emitting particles which emit blue light may include thulium.

[0081] In general, the upconversion process generally requires one of more rare-earth dopants, such as Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd and other rare-earth species or a combination thereof, doped into a dielectric crystal (of any size >0.1nm), including at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2, where incident radiation is at longer wavelength than emissive radiation from the crystal. The wavelength emitted in based entirely on the dopant ion(s) chosen and their associated and relative concentration in the host crystal. For the example of upconversion in a Y2O3 host crystal, to achieve a blue emission(~450 – 480 nm) one could synthesize [Y2O3; Yb (3%), Tm (0.2%)], where the Yb and Tm are the percentages doped in the crystal relative to the Y atoms being 100%. Likewise, 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 dopants relative to each other and the crystal matrix must be tuned for every combination, and there are multiple ways to achieve multiple wavelength or energy emissions from even the same dopants.

[0082] Up-conversion of red light with a wavelength of about 650 nm in Tm3+doped flourozirconate glasses can be used in the invention to produce blue light. In this system, the blue light consists of two emission bands; one at 450 nm which is ascribed to the 1D2→3H4 transition, the others at 475 nm is ascribed to the 1G4→3H6 transition. The emission intensities of both bands have been observed by others to vary quadratically with the excitation power. For glasses with a Tm3+concentration of 0.2 mol% and greater, cross- relaxation processes occur which decrease the up-conversion efficiency.

[0083] The emission of visible light upon excitation in the near-infrared (NIR) has been observed in optically clear colloidal solutions of LuPO4:Yb3+, Tm3+, and YbPO4:Er3+nanocrystals in chloroform. Excitation at 975 nm has been shown by others to produce visible emission in the blue, green, or red spectral regions.

[0084] Tellurium and germanium oxides (tellurites and germanates) are also suitable upconverters. These glasses can be doped with Tm, Yb, Ho, Er, Pr, for example.

[0085] Yb3+doped BaZrO3is also suitable for upconversion. Er3+and / or Tm3+doping are also suitable for tailoring the emission wavelengths.

[0086] In another embodiment, Nd3+:Cs2NaGdCl6and Nd3+, Yb3+:Cs2NaGdCl6polycrystalline powder samples prepared by Morss method have been reported to be up converters and are suitable for the present invention. These materials, under 785 nm irradiation, have shown upconversion emissions near 538 nm (Green), 603 nm (Orange), and 675 nm (Red) were observed and assigned to 4G7 / 2→4I9 / 2, (4G7 / 2→4I11 / 2; 4G5 / 2→4I9 / 2), and (4G7 / 2→4I13 / 2; 4G5 / 2→4I11 / 2), respectively.

[0087] In another embodiment, Nd3+and Ho3+co-doped -based ZrF4fluoride glasses under 800 nm excitation have been reported to be up converters and are suitable for the present invention. Among the up-conversion luminescences for the ZrF4fluoride glasses, the green emission was seen to be extremely strong and the blue and red emission intensities were very weak.

[0088] In another embodiment, Tm3+ / Yb3+-codoped TeO2-Ga2O3-R2O (R=Li, Na, K) glasses have been reported to be up converters and are suitable for the present invention. These materials, under excitation at 977 nm, showed intense blue upconversion emission centered at 476 nm along with a weak red emission at 650 nm.

[0089] In another embodiment, metal-to-ligand charge transfer (MLCT) transition in [Ru(dmb)3]2+(dmb = 4,4 -dimethyl-2,2 -bipyridine) in the presence of anthracene or 9,10- diphenylanthracene have been reported to be up converters and are suitable for the present invention. Upconverted singlet fluorescence resulting from triplet–triplet annihilation at low excitation power has been reported. In particular 9,10-diphenylanthracene (DPA) (substituted for anthracene) showed higher efficiencies for upconversion. In these experiments, workers with this material system assumed that DPA's increased singlet fluorescence quantum yield ( = 0.95) relative to anthracene ( = 0.27). This work lead to an approximate 24.4 ± 6.1 enhancement of green-to-blue light upconversion permitting direct visualization of the process at low excitation power, for example by a commercial green laser pointer (ex= 532 nm, <5 mW peak power).

[0090] In certain embodiments, further energy converters include, but are not limited to, (not ranked by order of preference or utility):

[0091] CaF2, ZnF2, KMgF3, ZnGa2O4, ZnAl2O4, Zn2SiO4, Zn2GeO4, Ca5(PO4)3F, Sr5(PO4)3F, CaSiO3, MgSiO3, ZnS, MgGa2O4, LaAl11O18, Zn2SiO4, Ca5(PO4)3F, Mg4Ta2O9, CaF2, LiAl5O8, LiAlO2, CaPO3, AlF3, and LuPO4:Pr3+. Examples further include the alkali earth chalcogenide phosphors which are in turn exemplified by the following non-inclusive list: MgS:Eu3+, CaS:Mn2+, CaS:Cu, CaS:Sb, CaS:Ce3+, CaS:Eu2+, CaS:Eu2+Ce3+, CaS:Sm3+, CaS:Pb2+, CaO:Mn2+, CaO:Pb2+.

[0092] Further examples include the ZnS type phosphors that encompass various derivatives: ZnS:Cu,Al(Cl), ZnS:Cl(Al), ZnS:Cu,I(Cl), ZnS:Cu, ZnS:Cu,In.

[0093] Also included are the compound IIIb-Vb phosphors which include the group IIIb and Vb elements of the periodic table. These semiconductors include BN, BP, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb and these materials may include donors and acceptors that work together to induce light emission diodes. These donors include, but are not limited to, Li, Sn, Si, Li, Te, Se, S, O and acceptors include, but are not limited to, C, Be, Mg, Zn, Cd, Si, Ge. Further included are the major GaP light emitting diodes which include, but are not limited to, GaP:Zn,O, GaP:NN, Gap:N and GaP, which emit colors Red, Yellow, Green and Pure Green respectively.

[0094] The materials can further include such materials as GaAs with compositional variation of the following sort: In1-y(Ga1-xAlx)yP.

[0095] Also included is silicon carbide SiC, which has commercial relevancy as a luminescent platform in blue light emitting diodes. These include the polytypes 3C-SiC, 6H- SiC, 4H-SiC with donors such as N and Al and acceptors such as Ga and B.

[0096] Further examples include multiband luminescent materials include, but not limited to, the following compositions (Sr, Ca, Ba)5(PO4)3Cl:Eu2+, BaMg2Al16O27:Eu2+, CeMgAl11O19:Ce3+:Tb3+, LaPO4:Ce3+:Tb3+, GdMgB5O10:Ce3:Tb3+, Y2O3:Eu3+, (Ba,Ca,Mg)5(PO4)3Cl:Eu2+, 2SrO0.84P2O50.16B2O3:Eu2+, Sr4Al14O25:Eu2+.

[0097] Materials typically used for fluorescent high pressure mercury discharge lamps are also included. These can be excited with X-Ray and are exemplified by way of family designation as follows: Phosphates (Sr, M)(PO4)2:Sn2+, Mg or Zn activator, Germanate 4MgO.GeO2:Mn4+, 4(MgO, MgF2)GeO2:Mn4+, Yttrate Y2O3:Eu3+, Vanadate YVO4:Eu3+, Y(P,V)O4:Eu3+, Y(P,V)O4:In+, Halo-Silicate Sr2Si3O82SrCl2:Eu2+, Aluminate (Ba,Mg)2Al16O24:Eu2+, (Ba, Mg)2Al16O24:Eu2+,Mn2+, Y2O3Al2O3:Tb3+.

[0098] Another grouping by host compound includes chemical compositions in the halophosphates phosphors, phosphate phosphors, silicate phosphors, aluminate phosphors, borate phosphors, tungstate phosphors, and other phosphors. The halophosphates include, but are not limited to: 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+, 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+ / Mn2+, Sr10(PO4)6Cl2:Eu2+, (Sr,Ca)10(PO4)6Cl2:Eu2+, (Sr,Ca)10(PO4)6.nB2O3:Eu3+, (Sr, Ca,Mg)10(PO4)6Cl2:Eu2+. The phosphate phosphors include, but are not limited to: Sr2P2O7:Sn2+, (Sr,Mg)3(PO4)2:Sn2+, Ca3(PO4)2.Sn2+, Ca3(PO4)2:Tl+, (Ca,Zn)3(PO4)2:Tl+,CaSiO3:Pb2+ / Mn2+, (Ba, Sr, Mg).3Si2O7:Pb2+, BaSi2O5:Pb2+, Sr2Si3O8.2SrCl2:Eu2+, Ba3MgSi2O8:Eu2+, (Sr,Ba)Al2Si2O8:Eu2+.

[0099] The aluminate phosphors include, but are not limited to: LiAlO2:Fe3+, BaAl8O13:Eu2+, BaMg2Al16O27:Eu2+, BaMg2Al16O27:Eu2+ / Mn2+, Sr4Al14O25:Eu2+, CeMgAl11O19:Ce3+ / Tb3+.

[0100] The borate phosphors include: Cd2B2O5:Mn2+, SrB4O7F:Eu2+, GdMgB5O10:Ce3+ / Tb3+, GdMgB5O10:Ce3+ / Mn3+, GdMgB5O10:Ce3+ / Tb3+ / Mn2+.

[0101] The tungstate phosphors include, but are not limited to: CaWO4, (Ca,Pb)WO4, MgWO4. Other phosphors Y2O3:Eu3+, Y(V,P)O4:Eu2+, YVO4:Dy3+, MgGa2O4:Mn2+, 6MgO.As2O5:Mn2+, 3.5MgO.0.5MgF2.GeO2:Mn4+.

[0102] The activators to the various doped phosphors include, but are not limited to: Tl+, Pb2+, Ce3+, Eu2+, WO42-, Sn2+, Sb3+, Mn2+, Tb3+, Eu3+, Mn4+, Fe3+. The luminescence center Tl+is used with a chemical composition such as: (Ca,Zn)3(PO4)2:Tl+, Ca3(PO4)2:Tl+. The luminescence center Mn2+is used with chemical compositions such as MgGa2O4:Mn2+, BaMg2Al16O27:Eu2+ / Mn2+, Zn2SiO4:Mn2+, 3Ca3(PO4)2.Ca(F,Cl)2:Sb2+ / Mn2+, CaSiO3:Pb2+ / Mn2+, Cd2B2O5:Mn2+, CdB2O5:Mn2+, GdMgB5O10:Ce3+ / Mn2+, GdMgB5O10:Ce3+ / Tb3+ / Mn2+. The luminescence center Sn2+ is used with chemical compositions such as: Sr2P2O7:Sn2+, (Sr,Mg)3(PO4)2:Sn2+. The luminescence center Eu2+is used with chemical compositions such as: SrB4O7F:Eu2+, (Sr,Ba)Al2Si2O8:Eu2+, Sr3(PO4)2:Eu2+, Sr2P2O7:Eu2+, Ba3MgSi2O8:Eu2+, Sr10(PO4)6Cl2:Eu2+, BaMg2Al16O27:Eu2+ / Mn2+, (Sr,Ca)10(PO4)6Cl2:Eu2+. The luminescence center Pb2+is used with chemical compositions such as: (Ba,Mg,Zn)3Si2O7:Pb2+, BaSi2O5:Pb2+, (Ba,Sr)3Si2O7:Pb2+.

[0103] The luminescence center Sb2+is used with chemical compositions such as: 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+, 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+ / Mn2+.

[0104] The luminescence center Tb3+is used with chemical compositions such as: CeMgAl11O19:Ce3+ / Tb3+, LaPO4:Ce3+ / Tb3+, Y2SiO5:Ce3+ / Tb3+, GdMgB5O10:Ce3+ / Tb3+. The luminescence center Eu3+is used with chemical compositions such as: Y2O3:Eu3+, Y(V,P)O4:Eu3+. The luminescence center Dy3+is used with chemical compositions such as: YVO4:Dy3+. The luminescence center Fe3+is used with chemical compositions such as: LiAlO2:Fe3+. The luminescence center Mn4+is used with chemical compositions such as: 6MgO.As2O5:Mn4+, 3.5MgO0.5MgF2.GeO2:Mn4+. The luminescence center Ce3+is used with chemical compositions such as: Ca2MgSi2O7:Ce3+and Y2SiO5:Ce3+. The luminescence center WO42-is used with chemical compositions such as: CaWO4, (Ca,Pb)WO4, MgWO4. The luminescence center TiO44-is used with chemical compositions such as: BaO.TiO2.P2O5.

[0105] These materials can be used alone or in combinations of two or more. A variety of compositions can be prepared to obtain the desired output wavelength or spectrum of wavelengths.

[0106] In the present invention, the phosphor selection could be chosen such that under x- ray or other high energy source irradiation, the light emitted from the phosphors could, for example, have exemplary characteristics including:

[0107] Emissions in 190 -250 nm wavelength range;

[0108] Emissions in the 330-340 nm wavelength range.

[0109] Electroluminescent and phosphorescent materials (organic and inorganic): The present invention in various embodiments can utilize organic fluorescent molecules or inorganic particles capable or fluorescence and phosphorescence having crystalline, polycrystalline or amorphous micro-structures for the converters (optionally including the energy augmentation structures described above).

[0110] The list of inorganic molecules that can be used with or without energy augmentation structures for the electroluminescence and phosphorescent materials described below include but is not limited to the following inorganic electroluminescent phosphor materials:

[0111] SrS:Ce3+

[0112] CaGa2S4:Ce3+

[0113] SrS:Cu+

[0114] CaS:Pb2+

[0115] BaAl2S4:Eu2+

[0116] ZnS:Tb3+

[0117] ZnMgS:Mn2+

[0118] SrGa2S4:Eu2+

[0119] CaAl2S4:Eu2+

[0120] BaAl2S4:Eu2+

[0121] ZnS:Mn2+

[0122] MgGa2O4:Eu3+

[0123] (Ca, Sr)Y2S4:Eu2+

[0124] BaAl2S4:Eu2+

[0125] Organic molecules that can phosphoresce under the influence of an electric field are also of interest in the present application. The organic fluorescent compounds with high quantum yield include by way of illustration:

[0126] Naphthalene,

[0127] Pyrene,

[0128] Perylene,

[0129] Anthracene,

[0130] Phenanthrene,

[0131] p-Terphenyl,

[0132] p-Quartphenyl,

[0133] Trans-stilbene,

[0134] Tetraphenylbutadiene,

[0135] Distyrylbenzene,

[0136] 2,5-Diphenyloxazole,

[0137] 4-Methyl-7-diethylaminocoumarin,

[0138] 2-Phenyl-5-(4-biphenyl)-1,3,4-oxadiazole,

[0139] 3-Phenylcarbostyryl,

[0140] 1,3,5-Triphenyl-2-pyrazoline,

[0141] 1,8-Naphthoylene -1’, 2’-bezimidazole,

[0142] 4-Amino-N-phenyl-naphthalimide.

[0143] The inorganic fluorescent and phosphorescent materials detailed here are numerous, and various examples are given by way of illustration rather than limitation and can be used with or without energy augmentation structures. Furthermore, these materials can be doped with specific ions (activators or a combination of activators) that occupy a site in the lattice structure in the case of crystalline or polycrystalline materials and could occupy a network forming site or a bridging and / or non-bridging site in amorphous materials. These compounds could include (not ranked by order of preference or utility) the following material examples:

[0144] CaF2, ZnF2, KMgF3, ZnGa2O4, ZnAl2O4, Zn2SiO4, Zn2GeO4, Ca5(PO4)3F, Sr5(PO4)3F, CaSiO3, MgSiO3, ZnS, MgGa2O4, LaAl11O18, Zn2SiO4, Ca5(PO4)3F, Mg4Ta2O9, CaF2, LiAl5O8, LiAlO2, CaPO3, AlF3.

[0145]

[0146] Further included are alkali earth chalcogenide phosphors which are in turn exemplified by the following non-inclusive list:

[0147] MgS:Eu3+, CaS:Mn2+, CaS:Cu, CaS:Sb, CaS:Ce3+, CaS:Eu2+, CaS: Eu2+Ce3+, CaS: Sm3+, CaS:Pb2+, CaO:Mn2+, CaO:Pb2+.

[0148] The examples include the ZnS type phosphors that encompass various derivatives:

[0149] ZnS:Cu,Al(Cl), ZnS:Cl(Al), ZnS:Cu,I(Cl), ZnS:Cu, ZnS:Cu,In.

[0150] Compound IIIb-Vb phosphors which include the group IIIb and Vb elements of the periodic table are suitable for converter materials. These semiconductors include BN, BP,BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb and these materials have donors and acceptors that work in together to induce light emission diodes. The donors include Li, Sn, Si, Li, Te, Se, S, O, and acceptors include C, Be, Mg, Zn, Cd, Si, Ge. As an example, GaP light emitting diodes include GaP:Zn, O, GaP:NN, Gap:N and GaP which emit colors Red, Yellow, Green and Pure Green respectively.

[0151] The compounded materials further include such materials as GaAs with compositional variation of the following sort: In1-y(Ga1-xAlx)yP (provides a simple example).

[0152] Silicon Carbide SiC as a luminescent platform has commercial relevancy if the blue light emitting diodes. These include the polytypes 3C-SiC, 6H-SiC, 4H-SiC with donors such as N and Al and acceptors such as Ga and B.

[0153] Multiband luminescent materials suitable for converter materials include for example the following compositions:

[0154] (Sr, Ca, Ba)5(PO4)3Cl:Eu2+, BaMg2Al16O27:Eu2+, CeMgAl11O19:Ce3+:Tb3+, LaPO4:Ce3+:Tb3+, GdMgB5O10:Ce3+:Tb3+, Y2O3:Eu3+, (Ba,Ca,Mg)5(PO4)3Cl:Eu2+, 2SrO0.84P2O5.0.16B2O3:Eu2+, Sr4Al14O25:Eu2+.

[0155] Other materials suitable for converter materials include those materials used for fluorescent high pressure mercury discharge lamps can be excited with X-Ray and are exemplified by way of family designation as follows:

[0156] Phosphates (Sr, M)(PO4)2:Sn2+, Mg or Zn activator, Germanate 4MgO.GeO2:Mn4+, 4(MgO, MgF2)GeO2:Mn4+, Yttrate Y2O3:Eu3+, Vanadate YVO4:Eu3+, Y(P,V)O4:Eu3+, Y(P,V)O4:In+, Halo-Silicate Sr2Si3O8.2SrCl2:Eu2+, Aluminate (Ba,Mg)2Al16O24:Eu2+, (Ba, Mg)2Al16O24:Eu2+,Mn2+, Y2O3Al2O3:Tb3+.

[0157] Another grouping of materials suitable for converter materials by host compound include chemical compositions in the Halophosphates phosphors, Phosphate phosphors, Silicate phosphors, Aluminate phosphors, Borate phosphors, Tungstate phosphors, and other phosphors.

[0158] The halophosphates include by way of illustration:

[0159] 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+, 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+ / Mn2+, Sr10(PO4)6Cl2:Eu2+, (Sr,Ca)10(PO4)6Cl2:Eu2+, (Sr,Ca)10(PO4)6.nB2O3:Eu3+, (Sr, Ca,Mg)10(PO4)6Cl2:Eu2+. The phosphate phosphors include by way of illustration Sr2P2O7:Sn2+, (Sr,Mg)3(PO4)2:Sn2+, Ca3(PO4)2.Sn2+, Ca3(PO4)2:Tl+, (Ca,Zn)3(PO4)2:Tl+, Sr2P2O7:Eu2+, SrMgP2O7:Eu2+, Sr3(PO4)2:Eu2+, LaPO4:Ce3+, Tb3+, La2O3.0.2SiO2.0.9P2O5:Ce3+.Tb3+, BaO.TiO2.P2O5. Thesilicate phosphors Zn2SiO4:Mn2+, CaSiO3:Pb2+ / Mn2+, (Ba, Sr, Mg).3Si2O7:Pb2+, BaSi2O5:Pb2+, Sr2Si3O8.2SrCl2:Eu2+, Ba3MgSi2O8:Eu2+, (Sr,Ba)Al2Si2O8:Eu2+.

[0160] The aluminate phosphors include:

[0161] LiAlO2:Fe3+, BaAl8O13:Eu2+, BaMg2Al16O27:Eu2+, BaMg2Al16O27:Eu2+ / Mn2+, Sr4Al14O25:Eu2+, CeMgAl11O19:Ce3+ / Tb3+.

[0162] The borate phosphors include:

[0163] Cd2B2O5:Mn2+, SrB4O7F:Eu2+, GdMgB5O10:Ce3+ / Tb3+, GdMgB5O10:Ce3+ / Mn3+, GdMgB5O10:Ce3+ / Tb3+ / Mn2+.

[0164] The tungstate phosphors include:

[0165] CaWO4, (Ca,Pb)WO4, MgWO4. Other phosphors Y2O3:Eu3+, Y(V,P)O4:Eu2+, YVO4:Dy3+, MgGa2O4:Mn2+, 6MgO.As2O5:Mn2+, 3.5MgO.0.5MgF2.GeO2:Mn4+.

[0166] Activators of relevance to the various doped phosphors include the following list:

[0167] Tl+, Pb2+, Ce3+, Eu2+, WO42-, Sn2+, Sb3+, Mn2+, Tb3+, Eu3+, Mn4+, Fe3+.

[0168] In various embodiments, the luminescence center Tl+ can be used with a chemical composition such as:

[0169] (Ca,Zn)3(PO4)2:Tl+, Ca3(PO4)2:Tl+.

[0170] Similarly, the luminescence center Mn2+ can be used with chemical compositions such as

[0171] MgGa2O4:Mn2+, BaMg2Al16O27:Eu2+ / Mn2+, Zn2SiO4:Mn2+, 3Ca3(PO4)2.Ca(F,Cl)2:Sb2+ / Mn2+, CaSiO3:Pb2+ / Mn2+, Cd2B2O5:Mn2+, CdB2O5:Mn2+, GdMgB5O10:Ce3+ / Mn2+, GdMgB5O10:Ce3+ / Tb3+ / Mn2+.

[0172] Further, the luminescence center Sn2+can be used with chemical compositions such as:

[0173] Sr2P2O7:Sn2+, (Sr,Mg)3(PO4)2:Sn2+.

[0174] The luminescence center Eu2+can also be used with chemical compositions such as:

[0175] SrB4O7F:Eu2+, (Sr,Ba)Al2Si2O8:Eu2+, Sr3(PO4)2:Eu2+, Sr2P2O7:Eu2+, Ba3MgSi2O8:Eu2+, Sr10(PO4)6Cl2:Eu2+, BaMg2Al16O27:Eu2+ / Mn2+, (Sr,Ca)10(PO4)6Cl2:Eu2+.

[0176] The luminescence center Pb2+can be used with chemical compositions such as:

[0177] (Ba,Mg,Zn)3Si2O7:Pb2+, BaSi2O5:Pb2+, (Ba,Sr)3Si2O7:Pb2+.

[0178] The luminescence center Sb2+can be used with chemical compositions such as:

[0179] 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+, 3Ca3(PO4)2.Ca(F,Cl)2:Sb3+ / Mn2+.

[0180] The luminescence center Tb3+ can be used with chemical compositions such as:

[0181] CeMgAl11O19:Ce3+ / Tb3+, LaPO4:Ce3+ / Tb3+, Y2SiO5:Ce3+ / Tb3+, GdMgB5O10:Ce3+ / Tb3+.

[0182] The luminescence center Eu3+can be used with chemical compositions such as:

[0183] Y2O3:Eu3+, Y(V,P)O4:Eu3+.

[0184] The luminescence center Dy3+can be used with chemical compositions such as:

[0185] YVO4:Dy3+.

[0186] The luminescence center Fe3+can be used with chemical compositions such as:

[0187] LiAlO2:Fe3+.

[0188] The luminescence center Mn4+can be used with chemical compositions such as:

[0189] 6MgO.As2O5:Mn4+, 3.5MgO.0.5MgF2.GeO2:Mn4+.

[0190] The luminescence center Ce3+can be used with chemical compositions such as:

[0191] Ca2MgSi2O7:Ce3+and Y2SiO5:Ce3+.

[0192] The luminescence center WO42-can be used with chemical compositions such as:

[0193] CaWO4, (Ca,Pb)WO4, MgWO4.

[0194] The luminescence center TiO44-can be used with chemical compositions such as:

[0195] BaO.TiO2.P2O5.

[0196] In various embodiments of this invention, the phosphor chemistry utilized in x-ray excitations can be used with or without energy augmentation structures. Of particular interest is the k-edge of these phosphors. Low energy excitation can lead to intense luminescence in materials with low k-edge. Some of these chemistries and the corresponding k-edge are included as follows:

[0197] BaFCl:Eu2+37.38 keV

[0198] BaSO4:Eu2+37.38 keV

[0199] CaWO469.48 keV

[0200] Gd2O2S:Tb3+50.22 keV

[0201] LaOBr:Tb3+38.92 keV

[0202] LaOBr:Tm3+38.92 keV

[0203] La2O2S:Tb3+38.92 keV

[0204] Y2O2S:Tb3+17.04 keV

[0205] YTaO4 67.42 keV

[0206] YTaO4:Nb 67.42 keV

[0207] ZnS:Ag 9.66 keV

[0208] (Zn,Cd)S:Ag 9.66 / 26.7 keV

[0209] Electro Luminescent Materials: Various materials used for the electro- luminescence in the present invention with or without energy augmentation structures can include but are not limited to:

[0210] 4,4′,4′′-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA)

[0211] N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)

[0212] 4,4′,4′′-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA)

[0213] N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)

[0214] Tris-(8-hydroxyquinoline)aluminum

[0215] 2,4,6-Tris(2-pyridyl)-s-triazine (TPT)yl-

[0223] Here, in one embodiment of the invention, the capability to produce stimulated emission at a targeted wavelength or color or energy is complemented by the ability to design nanoparticles that have designed absorption bands. Such absorption materials could for example further serve to improve the monochromaticity of light observed from a paint, ink, dye, or otherwise reflecting surface treated with the color enhancing compositions of the invention.

[0224] Details of the preparation of 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 Y2O3alone (lower trace) is fairly featureless, showing absorption due to the tri-arginine near 200 nm and a gentle slope associated with scattering and absorption by the Y2O3nanoparticles extending into the visible portion of the spectrum. The gold-coated Y2O3 (upper trace), on the other hand, exhibit a strong absorption band at 546 nm, which is characteristic of the plasmonics resonance band due to the gold shell around the Y2O3 cores. The red-shifting of the plasmon absorption to 546 nm is consistent with the presence of a gold shell around a dielectric core.

[0225] In one embodiment of the invention, the converter materials for the upconverter dielectric core can include a wide variety of dielectric materials, as described above. In various embodiments of the invention, the upconverter dielectric core includes more specifically lanthanide doped oxide materials. 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 lutetium (Lu). Other suitable dielectric core materials include non-lanthanide elements such as yttrium (Y) and scandium (Sc). Hence. 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 a combination thereof.

[0226] Lanthanides usually exist as trivalent cations, in which case their electronic configuration is (Xe) 4fn, with n varying from 1 (Ce3+) to 14 (Lu3+). The transitions within the f-manifold are responsible for many of the photo-physical properties of the lanthanide ions, such as long-lived luminescence and sharp absorption and emission lines. The f- electrons are shielded from external perturbations by filled 5s and 5p orbitals, thus giving riseto line-like spectra. The f-f electronic transitions are LaPorte forbidden, leading to long excited state lifetimes, in the micro- to millisecond range.

[0227] Accordingly, examples of doped materials in the invention include oxides such as yttrium oxide and neodymium oxide and aluminum oxide as well as sodium yttrium fluoride and nanocrystalline perovskites and garnets such as yttrium aluminum garnet (YAG) and yttrium aluminum perovskite (YAP). Of these materials, doping is required for some, but not all of these materials, for promoting upconversion efficiencies. In various embodiments of the invention, the host nanocrystals are doped with trivalent rare earth lanthanide ions from those lanthanide series elements given above.

[0228] More specifically, in various embodiments of the invention, pairs of these dopants are introduced in order to make accessible more energy states in the host crystal. The activation and pumping of these energy states follows closely the principles discussed above. Doping concentrations in the invention can range from 0.2% to 20% roughly per ion into the host lattice or in a weight or mol% variation. The efficiency of the upconversion processes of specific bands in these materials can be modulated by the percentages doped to induce and enhance targeted emissions. Lanthanide doped upconverters while not limited to, can use the following mol percent dopant compositions: 5% Er, 10% Yb, 0.2% Tm + 3% Yb, and 1% Er + 10% Yb.

[0229] The size of the nanocrystal will also have an effect on the efficiency of the upconversion process, as a larger nanocrystal will have more sites for dopant ions to be accommodated into the host lattice, therefore enabling more emissions from the same doped host than if the nanocrystal were smaller. While the dopant percentages listed above are not rigidly fixed, these numbers provide a rudimentary teaching of the typical percentages one would use in obtaining a particular dielectric core material of the invention.

[0230] Moreover, some of these host crystals (e.g., neodymium oxide) in one embodiment of the invention may require no specific doping to facilitate upconversion, which has been seen in one instance in Nd2O3with an excitation wavelength of 587 nm producing emissions at 372 nm, 402 nm, and 468 nm. See Que, W et al. Journal of Applied Physics 2001, vol 90, pg.4865, the entire contents of which are incorporated herein by reference. Doping neodymium oxide with Yb3+, in one embodiment of the invention, would enhance upconversion through sensitizing the Nd3+ions with a lower energy Yb3+activator.

[0231] In various embodiments of the invention, the upconverter or down converter dielectric core can be coated with thiol-terminated silanes to provide a coating of SiO2 about the core of similar reactivity to Y2O3. In one embodiment of the invention, the above-described methodology is used to synthesize core-shell nanoparticles of Y2O3:Ln with NaYF4 shells, Y2O3:Ln with Au(Ag,Pt) shells, NaYF4:Ln with Y2O3shells, NaYF4:Ln with Au(Ag,Pt) shells where core and shell diameters varying from 2 to 20 nm. In these material systems, the tuned ratio of core-to-shell diameter may permit a plasmon-phonon resonance which should amplify absorption of NIR light and / or upconverted emission. In these material systems, control of the core and shell diameters is one factor determining the size dependent effect and subsequent tuning of plasmon-phonon resonance.

[0232] In one embodiment of the invention, the upconverter dielectric core can be mixed core-shell materials including for example semiconducting Y2O3 and NaYF4 cores doped with various Ln series metals, which have been shown to possess large upconverting efficiencies. These doped Y2O3 and NaYF4 cores will have shells of Au(Ag,Pt, Pd) or undoped Y2O3and NaYF4matrices which have the potential to enhance or tune the phonon modes needed for energy transfer in the upconversion process. Solubility can be enhanced, for example, by addition of thiolated organics (Au shell), organic chain triethanolsilane (Y2O3 shell), and trioctylphosphine-oleic amine (NaYF4 shell). All core-shell nanoparticles may further be solubilized into a colloidal suspension with the addition of triarginine peptide, polyethylene glycol, and polyethyleneimine surfactants.

[0233] Similarly, in various embodiments of the invention, the up or down converting materials can include at least one of a dielectric, a glass, or a semiconductor. The up or down converting materials can include an alloy of two or more dielectric materials, an alloy of two or more glasses, or an alloy of two or more semiconductors.

[0234] In various embodiments, nanoparticles of neodymium and ytterbium doped yttrium oxide, europium and ytterbium doped yttrium oxide, and any combination of rare earth trivalent ions doped into a neodymium oxide nanocrystal can be used. The dual doped yttrium oxide of composition neodymium and ytterbium and also the dual doped europium and ytterbium are new for the yttrium oxide host lattice, although such dual doped systems have been shown to work in other host lattices such as YAG.

[0235] These dual doped lanthanide glasses have been shown to upconvert efficiently on bulk materials, and thereby can provide new upconverter structures at the nano-scale. There are advantages offered by these yttrium oxide nanostructures of the invention. The small scale synthetic methodology for creating nanoscale yttrium oxide is easier to control and produce in yttrium oxide than in YAG. The host structure of yttrium oxide scintillates by down conversion. These combinations of dopants in yttrium oxide for example can providepredetermined emission colors for the yttrium oxide nanocrystal for the color shifting of the invention.

[0236] In one embodiment of the invention, a dual dopant permits excitation of either ion in the host glass. For instance, excitation by 980 nm light excites an ytterbium ion, where through transfer of energy from one excited state of the ytterbium ion to another dopant provides a mechanism for upconversion emission of light in the visible and NIR spectral regions.

[0237] As noted above, semiconductor nanoparticles (e.g., quantum dots) can be used with or without the energy augmentation structures. The terms “semiconductor nanoparticles,” in the art refers to an inorganic crystallite between 1 nm and 1000 nm in diameter, preferably between 2 nm to 50 nm. A semiconductor nano-particle is capable of emitting electromagnetic radiation upon excitation (i.e., the semiconductor nano-particle is luminescent). The nanoparticle can be either a homogeneous nano-crystal, or comprises of multiple shells. For example, the nanoparticle can include a “core” of one or more first semiconductor materials, and may be surrounded by a “shell” of a second semiconductor material. The core and / or the shell can be a semiconductor material including, but not limited to, those of the group II–VI (ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, and the like) and III–V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, and the like) and IV (Ge, Si, and the like) materials, and an alloy or a mixture thereof.

[0238] Fluorescent organometallic molecules containing rare earth or transitional element cations can be used for down conversion materials with or without the energy augmentation structures. Such molecules include a metal center of rare earth elements including Eu, Tb, Er, Tm, Ce protected with organic chelating groups. The metal center may also include transitional elements such as Zn, Mn, Cr, Ir, etc. and main group elements such as B, Al, Ga. Such organometallic molecules can readily dissolve in liquid or transparent solid host media. Some examples of such fluorescent organometallic molecules include: 1. Tris(dibenzoylmethane)mono(phenanthroline)europium(III); 2. Tris(8- hydroxyquinoline)erbium; 3. Tris(1-phenyl-3-methyl-4-(2,2-dimethylpropan-1-oyl)pyrazolin -5-one)terbium(III); 4. Bis(2-methyl-8-hydroxyquinolato)zinc; 5. Diphenylborane-8- hydroxyquinolate.

[0239] Specific examples of down-conversion materials for red emission include those discussed above and europium complexes such as those described in JP Laid-open Patent Publication (Kokai) No.2003-26969, constructed such that β-diketone ligand is coordinatedto europium forming an europium complex capable of emitting red fluorescence. Other specific examples of the rare earth element complexes include complexes include lanthanum (Ln), europium (Eu), terbium (Tb), and gadolinium (Gd) and combinations thereof. A europium (Eu) complex is capable of emitting red fluorescence when irradiated with ultraviolet rays having a wavelength ranging from 365 nm to 410 nm. Terbium (Tb) is capable of emitting green fluorescence when irradiated with ultraviolet rays having a wavelength of 365 nm.

[0240] In other down-conversion embodiments with or without the energy augmentation structures, the down conversion materials which emit red light may include europium, light emitting particles which emit green light may include Terbium, and light emitting particles which emit blue or yellow light may include cerium (and / or thulium). In up-conversion embodiments, up conversion materials which emit red light may include praseodymium, light emitting particles which emit green light may include erbium, and light emitting particles which emit blue light may include thulium. In embodiments, the conversion materials can be light emitting particles made of fluorescent molecules that emit different colors (e.g. red, green, and blue). In embodiments, the conversion materials can be light emitting particles made of pure organic or organo-metallic dyes with or without the energy augmentation structures.

[0241] In addition to the combinations of rare earth complexes, such as a combination of a europium complex and a terbium complex, it is also possible employ a combination of a europium complex and a green-emitting fluorescent substance which is not a complex, or a combination of a terbium complex and a red-emitting fluorescent substance which is not a complex.

[0242] Other down converter materials with or without the energy augmentation structures include for example ZnS, PbS, SbS3, MoS2, PbTe, PbSe, BeO, MgO. Li2CO3, Ca(OH)2, MoO3, SiO2, Al2O3, TeO2, SnO2, KBr, KCl, and NaCl. These materials can include dopants to tailor the emission properties, as noted above. Examples of doped (or alloyed) glass systems suitable for the 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).

[0243] With regard more specifically to down converter materials suitable for the invention with or without the energy augmentation structures, U.S. Pat. No.4,705,952 (the contents of which are hereby incorporated herein by reference) describes an infrared-triggered phosphorthat stores energy in the form of visible light of a first wavelength and released energy in the form of visible light of a second wavelength when triggered by infrared light. The phosphors in U.S. Pat. No.4,705,952 were compositions of alkaline earth metal sulfides, rare earth dopants, and fusible salts. The phosphors in U.S. Pat. No.4,705,952 were more specifically phosphors made from strontium sulfide, barium sulfide and mixtures thereof; including a dopant from the rare earth series and europium oxide, and mixtures thereof; and including a fusible salt 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. Pat. No.4,705,952 are useful in various embodiments of the invention with or without the energy augmentation structures.

[0244] In other embodiments of the invention, the down converter materials (or mixtures of down converters materials can include Y2O3: Li. Sun et al “Luminescent properties of Li+ doped nanosized Y2O3:Eu,” Solid State Comm.119 (2001) 393-396 (the entire contents of which are incorporated herein by reference) describe such materials. Hou et al “Luminescent properties nano-sized Y2O3:Eu fabricated by co-precipitation method,” Journal of Alloys and Compounds, vol.494, issue 1-2, 2 April 2010, pages 382-385 (the entire contents of which are incorporated herein by reference) describe that nano-sized yttria (Y2O3) powders have been successfully synthesized by a co-precipitation method. The powders were well crystallized, and the grains were almost spherical with good dispersibility. The quenching concentration of Eu3+ions is 9 mol% which is much higher than micro-scaled powders. The incorporation of Li+ ions greatly improved the luminescence intensity. The highest emission intensity was observed with 4 mol% Li+ doped Y2O3:Eu powder ((Y0.87Eu0.09Li0.04)2O3) and the fluorescence intensity was increased by as much as 79%. Yi et al “Improved cathodoluminescent characteristics of Y2O3:Eu3+thin films by Li-doping,” Appl. Phys. A 87, 667–671 (2007) (the entire contents of which are incorporated herein by reference) describe cathodoluminescent spectra for both Y2O3:Eu3+and Li-doped Y2O3:Eu3+films and methods for making these materials.

[0245] The invention in other embodiments can use a wide variety of up conversion materials (or mixtures of up converters) with or without the energy augmentation structures to enhance a particular color of light observable from reflective material or surface. These up conversion materials can include similar materials as discussed above with regard to down conversion but typically included doped or impurity states in a host crystal that provide a mechanism for up conversion pumping. Accordingly, the up conversion materials to enhance color emission can convert energy from one of near infrared, infrared, and microwaveirradiation. The upconversion materials to enhance color emission can convert energy from lower energy visible light to higher energy visible light.

[0246] Upconversion materials with or without the energy augmentation structures can be used in various ways to enhance visible light emission by way of conversion of infrared light from a solar spectrum (as in daylight exposure) or a black body spectrum (as in an incandescent lamp). In one example, a nanoparticle of a lanthanide doped oxide can be excited with near infrared light such as laser light at 980 nm and 808 nm to produce visible light in different parts of the red, green, blue spectrum depending on the dopant trivalent rare earth ion(s) chosen, their concentration, and the host lattice.

[0247] The lanthanide doped oxides suitable for this invention differ from more traditional multi-photon up conversion processes where the absorption of, for example, two photons is needed in a simultaneous event to promote an electron from a valence state directly into an upper level conduction band state where relaxation across the band gap of the material produces fluorescence. Here, the co-doping produces states in the band gap of the NaYF4 such that the Yb3+ion has an energy state at2F5 / 2 pumpable by a single photon event and from which other single photon absorption events can populate even higher states. Once in this exited state, transitions to higher energy radiative states are possible, from which light emission will be at a higher energy than that of the incident light pumping the2F5 / 2 energy state. In other words, the energy state at2F5 / 2of the Yb3+ion is the state that absorbs 980 nm light permitting a population build up serving as the basis for the transitions to the higher energy states such as the4F7 / 2energy state. Here, transitions from the4F7 / 2energy state produce visible emissions.

[0248] U.S. Pat. No.7,008,559 (the entire contents of which are incorporated herein by reference) describes the upconversion performance of ZnS where excitation at 767 nm produces emission in the visible range. The materials described in U.S. Pat. No.7,008,559 (including the ZnS as well as Er3+doped BaTiO3 nanoparticles and Yb3+doped CsMnCl3) are suitable in various embodiments of the invention with or without the energy augmentation structures.

[0249] Further, materials specified for up conversion materials in the invention with or without the energy augmentation structures include CdTe, CdSe, ZnO, CdS, Y2O3, MgS, CaS, SrS and BaS. Such up conversion materials may be any semiconductor and more specifically, but not by way of limitation, sulfide, telluride, selenide, and oxide semiconductors and their nanoparticles, such as Zn1-xMnxSy, Zn1-xMnxSey, Zn1-xMnxTey, Cd1-xMnSy, Cd1-xMnxSey, Cd1-xMnxTey, Pb1-xMnxSy, Pb1-xMnxSey, Pb1-xMnxTey, Mg1-xMnSy, Ca1-xMnxSy, Ba1-xMnxSy and Sr1-x, etc. (wherein, 0<x≦1, and 0<y≦1). Complex compounds of the above-described semiconductors are also contemplated for use in the invention--e.g. (M1-zNz)1-xMnxA1-yBy(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 complex compounds are Zn0.4Cd0.4Mn0.2S and Zn0.9Mn0..1S0.8Se0.2. Additional conversion materials include insulating and nonconducting materials such as BaF2, BaFBr, and BaTiO3, to name but a few exemplary compounds. Transition and rare earth ion co-doped semiconductors suitable for the 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 complex compounds: (M1-zNz)1-x(MnqR1-q)xA1-yBy (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<q<1).

[0250] Some nanoparticles such as ZnS:Tb3+, Er3+; ZnS:Tb3+; Y2O3:Tb3+; Y2O3:Tb3+, Er3+; ZnS:Mn2+; ZnS:Mn,Er3+are known in the art to function for both down-conversion luminescence and upconversion luminescence and would be suitable for the invention with or without the energy augmentation structures. In up-conversion embodiments, light emitting particles which emit red light may include praseodymium, light emitting particles which emit green light may include erbium, and light emitting particles which emit blue light may include thulium.

[0251] In general, the upconversion process generally requires one of more rare-earth dopants, such as Er, Eu, Yb, Tm, Nd, Tb, Ce, Y, U, Pr, La, Gd and other rare-earth species or a combination thereof, doped into a dielectric crystal (of any size >0.1nm), including at least one of Y2O3, Y2O2S, NaYF4, NaYbF4, YAG, YAP, Nd2O3, LaF3, LaCl3, La2O3, TiO2, LuPO4, YVO4, YbF3, YF3, Na-doped YbF3, or SiO2, where incident radiation is at longer wavelength than emissive radiation from the crystal. The wavelength emitted in based entirely on the dopant ion(s) chosen and their associated and relative concentration in the host crystal. For the example of upconversion in a Y2O3host crystal, to achieve a blue emission (~450 – 480 nm) one could synthesize [Y2O3; Yb (3%), Tm (0.2%)], where the Yb and Tm are the percentages doped in the crystal relative to the Y atoms being 100%. Likewise, 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 dopants relative to each other and the crystal matrix must betuned for every combination, and there are multiple ways to achieve multiple colors from even the same dopants with or without the energy augmentation structures.

[0252] Up-conversion of red light with a wavelength of about 650 nm in Tm3+doped flourozirconate glasses can be used in the invention to produce blue light. In this system, the blue light consists of two emission bands; one at 450 nm which is ascribed to the 1D2→3H4 transition, the others at 475 nm is ascribed to the 1G4→3H6 transition. The emission intensities of both bands have been observed by others to vary quadratically with the excitation power. For glasses with a Tm3+concentration of 0.2 mol% and greater, cross- relaxation processes occur which decrease the up-conversion efficiency.

[0253] The emission of visible light upon excitation in the near-infrared (NIR) has been observed in optically clear colloidal solutions of LuPO4:Yb3+, Tm3+, and YbPO4:Er3+nanocrystals in chloroform. Excitation at 975 nm has been shown by others to produce visible luminescence in the blue, green, or red spectral regions.

[0254] Tellurium and germanium oxides (tellurites and germinates) are also suitable upconverters. These glasses can be doped with Tm, Yb, Ho, Er, Pr, for example.

[0255] Yb3+doped BaZrO3 is also suitable for upconversion. Er3+and / or Tm3+doping are also suitable for tailoring the emission wavelengths.

[0256] In another embodiment, Nd3+:Cs2NaGdCl6 and Nd3+, Yb3+:Cs2NaGdCl6 polycrystalline powder samples prepared by Morss method have been reported to be up converters and are suitable for the present invention. These materials, under 785 nm irradiation, have shown upconversion emissions near 538 nm (Green), 603 nm (Orange), and 675 nm (Red) were observed and assigned to 4G7 / 2→4I9 / 2, (4G7 / 2→4I11 / 2; 4G5 / 2→4I9 / 2), and (4G7 / 2→4I13 / 2; 4G5 / 2→4I11 / 2), respectively.

[0257] In another embodiment, Nd3+and Ho3+co-doped -based ZrF4 fluoride glasses under 800 nm excitation have been reported to be up converters and are suitable for the present invention. Among the up-conversion luminescences for the ZrF4 fluoride glasses, the green emission was seen to be extremely strong and the blue and red emission intensities were very weak.

[0258] In another embodiment, Tm3+ / Yb3+-codoped TeO2-Ga2O3-R2O (R=Li, Na, K) glasses have been reported to be up converters and are suitable for the present invention. These materials, under excitation at 977 nm, showed intense blue upconversion emission centered at 476 nm along with a weak red emission at 650 nm.

[0259] In another embodiment, metal-to-ligand charge transfer (MLCT) transition in [Ru(dmb)3]2+(dmb = 4,4 -dimethyl-2,2 -bipyridine) in the presence of anthracene or 9,10-diphenylanthracene have been reported converters and are suitable for the present invention. Upconverted to be up converters and are suitable for the present invention. Upconverted singlet fluorescence resulting from triplet–triplet annihilation at low excitation power has been reported. In particular 9,10-diphenylanthracene (DPA) (substituted for anthracene) showed higher efficiencies for upconversion. In these experiments, workers with this material system assumed that DPA's increased singlet fluorescence quantum yield ( = 0.95) relative to anthracene ( = 0.27)7. This work lead to an approximate 24.4 ± 6.1 enhancement of green-to-blue light upconversion permitting direct visualization of the process at low excitation power, for example by a commercial green laser pointer (ex= 532 nm, <5 mW peak power).

[0260] TABLE 1 shows a list of other suitable phosphors:

[0261] In one embodiment of the invention, besides the YTaO4, noted above, other energy converters can include phosphors were obtained from the following sources. “Ruby Red” obtained from Voltarc, Masonlite & Kulka, Orange, Conn., and referred to as “Neo Ruby”; “Flamingo Red” obtained from EGL Lighting. Berkeley Heights, N.J, and referred to as “Flamingo”; “Green” obtained from EGL Lighting, Berkeley Heights, N.J. and referred to as “Tropic Green”; “Orange” obtained from Voltarc, Masonlite & Kulka. Orange, Conn, and referred to as “Majestic Orange”; “Yellow” obtained from Voltarc. Masonlite & Kulka, Orange. Conn., and referred to as “Clear Bright Yellow.” The “BP” phosphors are shown in detail below in TABLE 2:

[0262]

[0263] The “BP” phosphors are available from PhosphorTech Corporation of Kennesaw, Ga., from BASF Corporation, or from Phosphor Technology Ltd, Norton Park, Norton Road Stevenage, Herts, SG12BB, England.

[0264] Other useful energy converters include semiconductor materials including for example TiO2, ZnO, and Fe2O3which are biocompatible, and CdTe and CdSe which would preferably be encapsulated because of their expected toxicity. Other useful energy converters include ZnS, CaS, BaS, SrS and Y2O3which are less toxic. Other suitable energy converters which would seem the most biocompatible are zinc sulfide, ZnS:Mn2+, ferric oxide, titanium oxide, zinc oxide, zinc oxide containing small amounts of Al2O3and AgI nanoclusters encapsulated in zeolite. For non-medical applications, where toxicity may not be as critical a concern, the following materials (as well as those listed elsewhere) are considered suitable: lanthanum and gadolinium oxyhalides activated with thulium; Er3+doped BaTiO3 nanoparticles. Yb3+doped CsMnCl3and RbMnCl3. BaFBr:Eu2+nanoparticles, cesium iodide, bismuth germanate, cadmium tungstate, and CsBr doped with divalent Eu.

[0265] In various embodiments of the invention, the following luminescent polymers are also suitable as energy converters: poly(phenylene ethynylene), poly(phenylene vinylene), poly(p-phenylene), poly(thiophene), poly(pyridyl vinylene), poly(pyrrole), poly(acetylene),poly(vinyl carbazole), poly(fluorenes), and the like, as well as copolymers and / or derivatives thereof.

[0266] As a non-limiting list, the following are also suitable energy converters: Y2O3 ZnS; ZnSe;MgS; CaS; Mn, Er ZnSe; Mn, Er MgS; Mn, Er CaS; Mn, Er ZnS; Mn, Yb ZnSe; Mn, Yb MgS; Mn, Yb CaS; Mn, Yb ZnS:Tb3+, Er3+; ZnS:Tb3+; Y2O3:Tb3+; Y2O3:Tb3+, Er3+; ZnS:Mn2+; ZnS:Mn,Er3+; CaWO4, YaTO4, YaTO4:Nb, BaSO4:Eu, La2O2S:Tb, BaSi2O5:Pb, NaI(Tl), CsI(Tl), CsI(Na), CsI(pure), CsF, KI(Tl), LiI(Eu), BaF2, CaF, CaF2(Eu), ZnS(Ag), CaWO4, CdWO4, YAG(Ce) (Y3Al5O12(Ce)), BGO bismuth germanate, GSO gadolinium oxyorthosilicate, LSO lutetium oxyorthosilicate. LaCl3(Ce). LaBr3(Ce). LaPO4; Ce, Tb (doped). Zn2SiO4:Mn with Mn doped between 0.05-10%, and YTaO4.

[0267] TABLE 3

[0268] In one embodiment, phosphors used in the invention as energy converters can include phosphor particles, ionic doped phosphor particles, single crystal or poly-crystalline powders, single crystal or poly-crystalline monoliths, scintillator particles, a metallic shellencapsulating at least a fraction of a surface of the phosphors, a semiconductor shell encapsulating at least a fraction of a surface of the phosphors, and an insulator shell encapsulating at least a fraction of a surface of the phosphors, and phosphors of a distributed particle size.

[0269] In one embodiment, the upconverter structures of the invention are complexed with the X-ray down converting particles or other energy converters permitting for example X-ray irradiation to also assist in this process. In one embodiment, the X-ray down converting particles or other energy converters or metallic structures described herein permit X-ray irradiation to be used alone or in combination with the up converting particles.

[0270] In one embodiment, the color enhancing / energy augmentation structures noted above are integrally included with the up converting or down converting particles. In one embodiment, the color enhancing / energy augmentation structures noted above are attached as a sheet or cover over or under the up converting or down converting particles. In one embodiment, the color enhancing / energy augmentation structures noted above are attached as a sheet the up converting or down converting materials deposited in a vicinity of the intensified electric fields.

[0271] In another embodiment, noted above, the color enhancing / energy augmentation structures could include mechano-luminescent structures, and application of ultrasonic energy to the mechano-luminescent structures would change the color emission from a surface. Such applications could be used in security systems where an item would contain a pattern of the composite mechano-luminescent emitters. The pattern would not be apparent until it was activated with ultrasonic or acoustic energy upon which time light of a predetermined wavelength would be emitted. The light emitted might be visible or infrared light depending on the type of detector used to detect the emitted light.

[0272] Energy converters suitable for use in the present invention have been described in the following: US Published Application No.2008 / 0248001; US Published Application No. 2009 / 0104212; US Published Application No.2009 / 0294692; US Published Application No. 2010 / 0003316; US Published Application No.2010 / 0016783; US Published Application No. 2010 / 0261263; US Published Application No.2010 / 0266621; US Published Application No. 2011 / 0021970; US Published Application No.2011 / 0117202; US Published Application No. 2011 / 0126889; US Published Application No.2011 / 0129537; US Published Application No. 2011 / 0263920; US Published Application No.2012 / 0064134; US Published Application No. 2012 / 0089180; US Published Application No.2013 / 0102054; US Published Application No. 2013 / 0129757; US Published Application No.2013 / 0131429; US Published Application No.2013 / 0156905; US Published Application No.2013 / 0171060; US Published Application No. 2013 / 0240758; US Published Application No.2014 / 0134307; US Published Application No. 2014 / 0163303; US Published Application No.2014 / 0166202; US Published Application No. 2014 / 0222117; US Published Application No.2014 / 0242035; US Published Application No. 2014 / 0243934; US Published Application No.2014 / 0272030; US Published Application No. 2014 / 0323946; US Published Application No.2014 / 0341845; US Published Application No. 2014 / 0343479; US Published Application No.2015 / 0182934; US Published Application No. 2015 / 0202294; US Published Application No.2015 / 0246521; US Published Application No. 2015 / 0251016; US Published Application No.2015 / 0265706; US Published Application No. 2015 / 0283392; US Published Application No.2015 / 0290614; US Published Application No. 2016 / 0005503; US Published Application No.2016 / 0067524; US Published Application No. 2016 / 0159065; US Published Application No.2016 / 0243235; US Published Application No. 2016 / 0263393; US Published Application No.2016 / 0325111; US Published Application No. 2016 / 0331731; US Published Application No.2016 / 0354467; US Published Application No. 2016 / 0362534; US Published Application No.2017 / 0027197; US Published Application No. 2017 / 0043178; US Published Application No.2017 / 0050046; US Published Application No. 2017 / 0096585; US Published Application No.2017 / 0113061; US Published Application No. 2017 / 0121472; US Published Application No.2017 / 0154866; US Published Application No. 2017 / 0157418; US Published Application No.2017 / 0162537; US Published Application No. 2017 / 0173350; US Published Application No.2017 / 0186720; US Published Application No. 2017 / 0190166; US Published Application No.2017 / 0196977; US Published Application No. 2017 / 0239489; US Published Application No.2017 / 0239637; US Published Application No. 2017 / 0240717; US Published Application No.2017 / 0258908; US Published Application No. 2017 / 0319868; US Published Application No.2017 / 0319869; US Published Application No. 2018 / 0036408; US Published Application No.2018 / 0154171; US Published Application No. 2018 / 0154178; US Published Application No.2018 / 0169433; US Published Application No. 2018 / 0170028; US Published Application No.2018 / 0269174; US Published Application No. 2018 / 0271121; US Published Application No.2018 / 0304225; US Published Application No. 2018 / 0311355; US Published Application No.2018 / 0317307; US Published Application No. 2018 / 0344850; US Published Application No.2018 / 0358327; US Published Application No. 2019 / 0016869; US Published Application No.2019 / 0022221; US Published Application No. 2019 / 0100680; US Published Application No.2019 / 0134419; US Published Application No. 2019 / 0134595; US Published Application No.2019 / 0134596; US Published Application No. 2019 / 0157234; US Published Application No.2019 / 0168015; US Published Application No.2019 / 0184190; US Published Application No.2019 / 308030; US Published Application No. 2019 / 0336605; US Published Application No.2019 / 0336785; US Published Application No. 2019 / 0336786; US Published Application No.2019 / 0341364; U.S. Application Serial No. 16 / 074,707, filed 8 / 1 / 2018; U.S. Application Serial No.16 / 516,463, filed 7 / 19 / 2019; U.S. Application Serial No.16 / 554,831, filed 8 / 29 / 2019 U.S. Application Serial No.16 / 599,732, filed 10 / 11 / 2019; U.S. Application Serial No.16 / 674,435, filed 11 / 5 / 2019; and U.S. Application Serial No.16 / 728,803, filed 12 / 27 / 2019; the relevant portions of each of which are hereby incorporated by reference in their entireties.

[0273] ACTIVE / PASSIVE SYSTEMS

[0274] In various embodiments of the present invention, the production of enhanced visible colors can be obtained in fibers and / or films and / or other objects where color enhancement is desirable. Applications for color enhancement include but are not limited to inclusion by a variety of methods of the above-noted conversion materials and coatings into color enhancement systems that can be classified for the purpose of illustration, not limitation, into four different systems.

[0275] 1. Active systems relying on direct exposure of the color-generating materials or architectures with UV sources or other energy sources for down conversion or optionally up conversion.

[0276] 2. Active systems relying on direct exposure of the color-generating materials or architectures with visible light sources (ambient or artificial).

[0277] 3. Passive systems corresponding to those color-generating materials or architectures exposed to ambient light sources that include UV spectral components.

[0278] 4. Passive systems corresponding to those color-generating materials or architectures exposed to ambient light sources including visible light spectral components.

[0279] The table below shows certain embodiments within each of these four systems:

[0280] In all these systems, selected colors are enhanced by all the optical phenomena available for producing color, and excitation light and the light colors generated are delivered to desired design places using either fiber optic light propagators and or optical thin film sheet light propagators. Depending on the embodiment of the invention, the fibers and sheet light propagators (or waveguides) of the invention can deliver an excitation energy, the converted energy, or both.

[0281] 1. Active systems with UV sources.

[0282] The sources of color in this system are preferably quantum dots (produced and capped individually and separated in solution as practiced in the art), phosphors (coated individually and separated in solution as practiced in the art), and / or semiconductor dyes produced as practiced in the art, and as discussed below. These sources can be mixed and embedded into specialized glass (or plastic) fibers and into specialized light propagator films. In certain embodiments, a UV source provides the source of excitation light to produce color from these materials using a process of fluorescence, also called phosphorescence as practiced in the art.

[0283] Semiconductor dyes that can be used in embodiments of the present invention can be made from inorganic materials or organic chemistries.

[0284] Quantum dots (QDs) or nanocrystals is a class of inorganic nanomaterials that exhibit semiconductor-like behavior and have unique properties aided by their small size. These materials (discussed above) are often used in various applications, including electronics, biology, and photonics. QDs are typically compound semiconductor materials such as cadmium selenide (CdSe), cadmium sulfide (CdS), lead sulfide (PbS), or indium phosphide (InP). Core-shell structures are common, where the semiconductor core issurrounded by a shell of a different semiconductor material to enhance stability and optical properties.

[0285] QDs have unique properties that arise from quantum confinement effects. When the size of a semiconductor particle becomes comparable to or smaller than the exciton Bohr radius, quantum effects become significant. Various materials have distinct exciton Bohr radii. For example, InP is a III–V semiconductor with a bulk bandgap energy of 1.35 eV and an exciton Bohr radius of the order of 10 nm, therefore allowing for the synthesis of materials with emission wavelengths covering the entire visible range, from blue (λ = 480 nm) to near IR (λ = 750 nm). The Bohr radius of the exciton is 5.8 nm for CdS and the quantum confinement occurs when the size of the crystallite is around 5–6 nm and below. ZnS QD radius is 2.47 nm which is less than its exciton Bohr radius (2.5 nm), representing strong quantum confinement. The Bohr radii for CdSe, PbS, and PbSe semiconductors are 5.6, 18, and 46 nm respectively.

[0286] The optical and electronic properties of quantum dots are size-dependent. As the size of the particles changes, the bandgap changes inversely, resulting in a shift in the absorption and emission spectra. Larger size quantum dots create a decrease in energy band gap and emit large wavelength photons (red-shift). Small quantum dot sizes have an increase in energy band gap and emit short wavelength light (blue shift). This size-tunability is advantageous for a variety of applications. The emission wavelength can be precisely controlled by adjusting the size of the nanoparticles. Quantum dots are employed in display technologies such as QLED (Quantum Dot Light Emitting Diode) displays, to enhance color quality and efficiency. Additionally, quantum dots are used in sensors for detecting various analytes due to their sensitivity.

[0287] Semiconductor dyes exhibit strong fluorescence or photoluminescence, making them useful in biological imaging, display technologies, and sensing applications.

[0288] For example, in biological imaging, semiconductor dyes are used as fluorescent probes due to their bright and tunable emission. Semiconductor nanoparticles can also be used in solar cells / photovoltaics to improve absorption and enhance energy conversion efficiency.

[0289] Surface Functionalization: Semiconductor dyes can be functionalized with different surface coatings to improve stability, solubility, and biocompatibility for specific applications. Some compound semiconductor chemistries may not be environmentally friendly.

[0290] One approach to the potentially hazardous chemistries of semiconductor dyes is by encapsulation. One encapsulation method that is effective is through the application of a diamond-like carbon coating on the semiconductor dye particle surface. This method does not compromise the color output but provides a useful way to take full advantage of chemistries that are not environmentally friendly or nano particles that present a health hazard.

[0291] Organic semiconductor dyes are a class of materials that combine the properties of semiconductors with the versatility and chemical diversity of organic compounds. These materials find applications in various electronic devices, including organic light-emitting diodes (OLEDs), organic solar cells, organic field-effect transistors (OFETs), and sensors. Organic semiconductor dyes are most often composed of carbon-based molecules that contain conjugated pi-electron systems. This conjugation allows for the delocalization of electrons, giving rise to semiconducting properties.

[0292] Of particular interest in the case of the present invention are the optical and electronic properties. Organic semiconductor dyes exhibit absorption and emission in the visible and near-infrared regions. An excitation from a ground state to an excited state is followed by a decay to the ground state accompanied by light emission. To some degree, the bandgap and energy levels can be modified through molecular structure conformational changes and chemical doping. The most famous application is the OLED.

[0293] Organic semiconductor dyes are widely used in OLEDs for display and lighting applications. Organic semiconductor dyes emit light when an electric current is applied, and their color can be controlled by selecting specific dye molecules. In one embodiment of the present invention, organic semiconductor dyes can be used as an excitation light source for subsequent down conversion or up conversion. In organic solar cells the dyes are employed in organic photovoltaic devices, where they absorb sunlight and generate electric current through the photovoltaic effect. Organic semiconductor dyes are also used in organic field- effect transistors (OFETs), which can be integrated in flexible circuits. Lastly, organic semiconductor dyes are used in sensors for detecting various analytes, taking advantage of changes in electrical or optical properties upon interaction with the target.

[0294] The advantage of organic semiconductor dyes is that organic chemistry offers a rich diversity of molecules leading to a wide range of structural possibilities. This repertoire of choices allows for design molecules with specificity for certain properties and applications.

[0295] Charge Transport: Charge carriers (electrons and holes) can move through organic semiconductor materials, making them suitable for applications where electronic conductivityis crucial. Organic semiconductor materials can be doped to modify their electrical properties, enhancing conductivity and enabling better device performance. Organic semiconductors are often considered more environmentally friendly than their inorganic counterparts, reducing concerns about toxicity. There are numerous organic semiconductor dyes used in various electronic applications. Organic semiconductor dyes can be polymers or single molecules. Examples of polymeric semiconductors that can be used in the present invention for example for the above-noted excitation light source include, but are not limited to, Poly(3-hexylthiophene) (P3HT), Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and polyfluorene. Examples of semiconductor molecules that can be used in the present invention include, but are not limited to, pentacene, tetracene, anthracene, and fullerenes (C60 and C70). Examples of oligomeric semiconductors that can be useful in the present invention include, but are not limited to, tetrathiafulvalene (TTF), perylene diimide (PDI), and thiophene-based oligomers. Examples of conjugated polymers that can be used in the present invention include, but are not limited to, polythiophene, polyfluorene, polyphenylenevinylene(PPV), and poly(9,9-dioctylfluorene-co-bithiophene)(F8T2). Some examples of fluorescent organometallic molecules that may be used in the present invention include, but are not limited to, tris(dibenzoylmethane)mono(phenanthroline)europium(III); tris(8-hydroxyquinoline)erbium; tris(1-phenyl-3-methyl-4-(2,2-dimethylpropan-1- oyl)pyrazolin-5-one)terbium(III); bis(2-methyl-8-hydroxyquinolato)zinc; and diphenylborane-8-hydroxyquinolate.

[0296] Fluorescent organic dyes are compounds that emit light (fluoresce) when exposed to wavelengths of light exciting their bandgap. These dyes find widespread use in various applications, including fluorescence microscopy, biological imaging, sensors, and optoelectronics. Examples of fluorescent organic dyes that can be used in the present invention are provided below.

[0297] Fluorescein is a widely used green fluorescent dye. It is commonly used in biological research and medical diagnostics. Rhodamine dyes emit red to pink fluorescence. They are used in biological imaging and fluorescence microscopy. Cyanine dyes come in various forms Cy3, Cy5 and Cy7, and cover a range of colors from green to N-IR and are used in biology and bioimaging. BODIPY (boron dipyrromethene) dyes exhibit strong and tunable fluorescence. They find applications in imaging, sensors. Texas Red is a red fluorescent dye commonly used in biochemistry and molecular biology applications. Alexa Fluor dyes, developed by Invitrogen, cover a broad range of colors and are widely used in fluorescence microscopy and flow cytometry. Fluorophores commonly used for DNA / RNAstaining can also be used, including, but not limited to, DAPI (4',6-diamidino-2-phenylindole) and SYBR Green. Azo dyes and GFP (Green fluorescent protein) can also be used in embodiments of the present invention. Acridine Orange is a fluorescent dye used for staining DNA and RNA in microscopy. Indocyanine Green (ICG) is a near-infrared dye used in medical imaging, especially in fluorescence-guided surgery.

[0298] These examples represent a fraction of the many fluorescent organic dyes available, which can be used in various embodiments of the present invention. The choice of a fluorescent dye depends on factors such as the desired emission wavelength, brightness, chemical stability, and compatibility with the experimental system, and is well within the capabilities of one of ordinary skill.

[0299] The relative fluorescence intensities of aromatic hydrocarbons in the crystalline state are as follows: naphthalene (9), anthracene (38), phenanthrene (44), chrysene (44), pyrene (71), triphenylene (38), perylene (47), acenaphthene (4), fluorene (53), biphenyl (12), p- terphenyl (41), o-diphenylbenzene (5), m-diphenylbenzene (12) and p-quaterphenyl (100).

[0300] For certain embodiments of the present invention, it is also possible to tune the emission wavelengths of organic semiconductors and fluorescent molecules through chemical modifications. For instance, the incorporation of alkyl substituents into the benzene molecule displaces the absorption of fluorescence toward longer wavelengths – this is how tuning can be accomplished in this case.

[0301] Incorporation into the aromatic ring of a substituent which enlarges the system of conjugated double bonds (a vinyl or phenyl group) brings about the bathochromic shift of the absorption spectrum (a hyperchromic effect) and an increase in quantum yield. For example, from biphenyl to p-vinylbiphenyl, the quantum yield in heptane increases from 0.18 to 0.61. Another example includes the fact that substituents containing an atom with lone-pair electrons exert a similar effect on the position of the absorption bands. The incorporation of an electron-donor group together with an electron acceptor displaces the fluorescence maximum toward longer wavelengths and increases the quantum yield. Intense fluorescence is observed when the electron-donor and acceptor substituents are at the end of the conjugation chain and in the case with terephthalates (2-6) containing hydroxy or amino groups in the benzene nucleus.

[0302] In certain embodiments of the present invention, these types of modifications can be used with fluorescent semiconducting dyes and their chemical derivatives in order to yield a boost in florescence intensity or a shift in peak emissions. More specifically, in certain embodiments, the intense fluorescence of anthracene and its derivatives are preferred for thepresent application. Single crystals of anthracene have been known to make efficient plastic scintillators. The standard optical absorption and emission data of anthracene is available in the PhotochemCAD package, version 2.1a (Du 1998, Dixon 2005).

[0303] Certain embodiments of the present invention can also use a wide variety of the major classes of organic luminescent materials including, but not limited to:

[0304] Aromatic hydrocarbons and their substituent products; compounds with arylethylene and arylacetylene groups; 1,2-diarylethylenes; diarylpolyenes; diaryl-substituted 1,4- divinylbenzenes; stilbenes; 1,4-distyrylbenzenes; 1,2-distyrylbenzenes; 1,3-distyrylbenzenes; triaryl-substituted-1,3,5-trivinylbenzenes; arylacetylenes; compounds with an exocyclic C=N group; five-membered heterocyclic compounds (such as furan, thiophene, pyrrole and derivatives); aryl-substituted oxazoles; 1,3,4-oxidiazoles; 1,3,4-thiadiazoles; aryl-substituted 2-pyrrazolines and pyrazoles; benzazoles; anthrone derivatives; quinones; derivatives of aromatic acids; coumarin and carbostyryls; derivatives of 5-oxazolone; indigoids and thioindigoids; naphthalic acid derivatives; derivatives of naphthalic anhydride and naphthylamide; derivatives of 1,8-naphthoylene-1’, 2’-benzimidazole; and derivatives of 4- carboxynaphthalic anhydride.

[0305] More specifically, the color output is of relevance. The compounds leading to specific emissions materials that yield violet, blue, cyan, green, yellow, orange and red. Examples of such compounds that yield the following peaks under excitations from a 365nm source include, but are not limited to, anthracene with emissions at 400 nm and 425 nm, 9,10- diphenylanthracene with emissions at 440 nm, 1,5-diphenyl-3-styryl-2-pyrazoline with emissions at 475 nm, 2-(2-hydroxyphenyl)benzoxazole with emissions at 500nm, uranine with emissions at 540 nm, rhodamine B with emissions at 600 nm, 4-(4- dimethylaminobenzylidene)-2-phenyl-5-oxazolone with emissions at 610 nm, and N- salicylidene-4-dimethylaminoaniline with emissions at 610 nm.

[0306] An additional important aspect of certain embodiments of the present invention is the ability to mix both dyes and pigments, in order to provide a fiber of a specific color having a coating loaded with a pigment of that specific color. For example, the coating on a fiber that would glow orange under UV excitation will have both a luminophore as well as an orange pigment that yields an orange color in daylight. The orange pigment would have a low-level concentration as to not block the fluorescence under UV light. Similarly, a violet pigment can be added to a violet luminophore, a blue pigment can be added to a blue luminophore, a green pigment can be added to a green luminophore, a yellow pigment can be added to a yellow luminophore, an orange pigment can be added to an orange luminophore,and a red pigment can be added to a red luminophore. In this way the fabric design (in a shoe for example) would maintain the same color patterns with or without the UV light. Of course, with the UV light turned on, the visible colors would be augmented to yield more brilliance and pleasing visual effects.

[0307] On the other hand, it is possible to use energy converters in white powder form (in the case of phosphors) and without adding a pigment. Once the UV light turns on, the article utilizing the novel fiber would exhibit / emit a distinct color other than white.

[0308] It is also possible to add the brilliance of daylight-fluorescent (DF) paints and coatings by adding organic luminophores. The brightness of ordinary paints coating a given physical article is determined by the light reflected from the surface of the article. In the case of DF paints part of the absorbed light triggers luminescence which adds to the reflected light which intensifies the observed colors. The UV light from sunlight is sufficiently powerful to trigger the luminescence of DF paints.

[0309] DF pigments can be combined with different binders and organic vehicles to form thick films and inks. The most widely used DF pigments are based on carbamide and melamine-formaldehyde resins modified with mono or polyhydric alcohols as well as arylsulfamides.

[0310] Dyes and pigments are commonly used as coloring agents. There are several differences between them. They are both contrasted here for the sake of clarification. Typically, dyes are soluble and pigments are insoluble and are suspended in a medium or binder. Also, there is commonly a difference in particle size of dyes and pigments which affects the way they behave with respect to mix rheology. Pigments are usually resistant against fading, and dyes are often prone to fading over time especially in UV rich conditions. So, pigments are typically considered to have better longevity compared to dyes. In dyes, functional groups bond between dye and the substrate or resin, while this is not normally the case for pigments. Dyes are typically organic, and pigments are typically inorganic (but not always).

[0311] Glass and / or plastic fibers can carry both the stimulating UV light and the resulting specified color in waveguide fashion along the length of the fiber. The optical fibers can be any desired material having the requisite transmissivity and refractive index, In preferred embodiments, glass fibers are used because plastic may not adequately transmit the UV stimulating light. Along the length of the fibers, interruptions are caused to emit the light from the fiber at selected places or to leak the created color from the dopants to the outside. This can be done by causing refractive index variations and physical (geometrical) variationsin the fiber to allow the light to escape from its waveguiding mode. Examples include adding an extra cladding material layer that has a higher index of refraction than the cladding layer, thus allowing light to escape the fiber, creating refractive index variations in the core that send light into cladding modes, or cause interference of selected colors in either the core or the cladding layers, and causing geometrical or physical imperfections, such as by scratching the surface of the fibers, via abrasion, chemical etching or other methods, creating defect structures and or porosity in the core or cladding or added layers, bending the fibers in tight corners or designing lumpy fibers with variations in diameter along the length. Bending the fibers in tight corners can be performed by twisting a fiber bundle to cause leaky corners. In this case the pitch is controlled using the number of turns used for twisting. The lumpy fibers can be obtained by changing the rate at which the fiber is pulled. FIG.5 provides a schematic representation showing one embodiment of a method for producing the optical fibers of the invention, in which a preform of glass of desired refractive index is fed into a furnace to render it malleable, followed by pulling the glass into a monofilament fiber. A laser micrometer or other detection device can be used to monitor the pull rate in the glass fiber formation, thus permitting alterations of the pull rate to be made in real time or according to a preset program in order to generate the “lumpy” fiber having different thicknesses along its length. The faster rate results in a thinner fiber section and the slower rate results in a thicker section. The variation of thickness results in light leaking from the optical fiber. The fiber once formed is then passed through a coating mechanism such as a coating dip or cup, containing energy modulation agents in a polymer solution for coating on the surface of the glass fiber, followed by curing the polymer and collecting the formed fiber on a spool.

[0312] The optical fibers can be used as single filaments, a bundle of filaments, or in any desired configuration. In certain embodiments, the fibers can be arranged side to side to form a ribbon configuration containing a plurality of fibers, having one end bundled for attachment to one or more radiation sources. In this way, a single radiation source can provide the radiation / light being transmitted via a plurality of optical fibers forming the ribbon.

[0313] Other methods can include varying the core to cladding ratio along the length of the fiber and introducing distributed defects. The variations and defects can be produced periodically or non-periodically as per the design of the application.

[0314] Using UV light sources as in this approach allows obtaining any desired color in the visible range of light from blue to red.

[0315] In various of these embodiments, once can also use a plurality of stacked alternating layers of active and passive materials in which the stimulating source light activates the active materials such as quantum dots, dyes, phosphors, etc. as described above.

[0316] 2. Active systems with visible light sources

[0317] Similar sources of color can be used in this approach with visible light sources. The production of color in this embodiment is by the process of luminescence, whereby light of a given color impacts the color source material, and it emits a bright light of a different color at a different wavelength (typically longer wavelength or lower energy). Since the stimulating light source is in the visible range, plastic fibers can be used. The same variations in refractive index and geometrical or physical variations as listed in (1) can be used to send the light out of the fiber or waveguiding film. In plastic fibers, geometrical variations are easier to obtain.

[0318] In this approach, it is also possible to use the light source at the desired color without a doping or energy modulation agent material. Then the leaky designs listed above in (1) are possible to emit the desired light directly from the waveguiding systems without needing to convert it. This opens the possibility of the most cost effective design to be weaved into a yarn.

[0319] 3 and 4: Passive systems

[0320] In passive systems, there is no stimulation source so the processes relies on ambient light as in wavelength shifting and iridescence. In wavelength shifting, the same energy modulation agents as listed in (1) can be used, except that ambient light is the only light incident on the fibers or film light propagators. Here, color enhancement comes from collecting light with wavelength shorter than the characteristic emission wavelength of the energy modulation agent and then the energy modulation agent wavelength shifts the light to its characteristic emission wavelength, to thus enhance the emitted color.

[0321] In certain passive systems, a multilayer cladding can be used to enhance iridescence. In essence, this approach is similar to the above except that iridescence becomes a primary source of the color enhancement, and the colors enhanced are in the yellow orange, red region of the optical spectrum. In iridescence, the ambient light is reflected differently (for example at different angles) for different colors. When many surfaces reflect the same color in the same direction, the color appears enhanced. This is done as described in (1) by variations in refractive index and variations in the geometry and physical makeup of the fiber or light propagator film. The variations can be periodic or non-periodic or random as desired by theapplication. In this type of enhancement, as in opal gems, the enhanced color changes with the angle of observation.

[0322] Below, a brief listing of potential modifications to the multilayer assemblies described earlier is provided. The primary focus in the options described below addresses the introduction or replacement of optical functions associated with different layers to influence the management of both ambient light as well as light produced via active (UV- excited) emission. The following embodiments of the present invention assume the use of a light propagator based, UV-delivery layer or other light propagators providing non- UV sources of excitation for activating up-conversion phosphors. Many of these embodiments, however, are also compatible with a direct (non-light propagator based) UV-delivery approach.

[0323] The optical fiber embodiments of the present invention can be used as the optical fiber alone, or can be combined with other natural or synthetic fibers to form a textile yarn. FIG.6 provides a representation of a potential process for preparing a yarn from the optical fiber embodiments of the present invention, combining the optical fiber with filaments of a synthetic fiber formed from polymer. In the figure, polymer chips are melted by the heater, and pumped through a spinneret to form filaments, which are then combined with the optical fiber of the invention, passed over a series of draw bars and / or rollers, to provide a yarn which is wound onto spools as needed. FIG.7 shows a cross section view of one embodiment of optical fiber of the present invention having a core with a cladding layer (outer coating) which contains one or more energy modulation agents distributed therein. FIG.8 shows that same cross sectional view of the optical fiber once combined with other fibers to form one embodiment of a yarn of the present invention.

[0324] Certain embodiments of the present invention provide for a textile yarn, where the textile yarn is a composite yarn and wherein the optical fiber is a filament and the one or more natural or synthetic fibers may be staple fibers having a limited length for example between 60 and 150 nm. In these embodiments, the staple fibers are entangled and combined with the optical fiber filament to provide the composite yarn.

[0325] In other embodiments of the present invention textile yarn, both the optical fiber and the one or more natural or synthetic fibers are filaments (as depicted in FIG.6). In those embodiments, the filaments of the optical fiber and one or more natural or synthetic fibers can be run parallel without entanglement, or can be entangled or twisted during forming of the yarn.

[0326] In the textile yarn embodiments of the present invention, any natural or synthetic fibers can be used. Preferably, the one or more natural or synthetic fibers are selected from the group consisting of wool, cotton, silk, alpaca, mohair, cellulosic fibers, polyesters, nylons, rayons, polyvinyl chloride fibers, elastomer fibers, aramids, polyolefins, acrylics, liquid crystal polymer fibers, carbon fibers, fiberglass, and metal fibers.

[0327] Once formed, the optical fiber, textile yarn, or optical light propagator sheet can be used to form an article having enhanced color characteristics. For the optical fiber or textile yarn embodiments, the article is preferably a member selected from the group consisting of shoes, shirts, pants, socks, jackets, sweaters, undergarments, bed linens, window coverings, and floor coverings. In certain embodiments, the article is shoes, preferably athletic shoes. In certain embodiments, the textile yarn or a fabric made therefrom, is used to form at least a part of an upper of the athletic shoes. FIG.9 provides a representation of applying an external light source to an embodiment of yarn of the present invention containing the inventive optical fiber.

[0328] In embodiments, where the textile yarn or fabric is used to form an upper of an athletic shoe, as depicted in FIG.10, the light effects can be achieved by embedding a distributed light source (110) along one or both sides of the shoe sole portion (100), and providing a battery source (120) embedded within the shoe sole portion (100) to power the light source (110). The light thus emitted, is then channeled through the optical fiber forming the textile yarn and contained in the fabric forming the uppers, to provide interesting light and color effects to the shoe upper during wear.

[0329] In certain embodiments, where the optical light propagator of the present invention is configured as a sheet or film, the sheet or film can be formed into articles of any desired shape or size. In preferred embodiments, the article thus formed is a tabletop or countertop, a cabinet face, drawer front, or cabinet door. The sheet or film can be formed into any desired article particularly having a flat surface, and provide interesting color and light effects to the surface. Such an article would also need a light source and power source such as a battery to power the light source.

[0330] In preparing optical fiber embodiments of the present invention, the fibers are preferably formed via the drawing of fibers from a molten glass composition (for glass based fibers) or from a molten polymer composition (for polymer fibers), in each case being a composition comprising one or more energy converters as described above. In each case, it is important to control the thermal budget of the molten glass or molten polymer composition in order to ensure that it does not exceed the melting temperature of the one or more energyconverters. The typical energy converters used in embodiments of the present invention are stable at relative high temperatures, with melting temperatures often ranging from about 1500 ^C (for zinc silicates for example) to about 2100 ^C (for yttrium tantalates, for example). This a bigger concern when the optical fibers of embodiments of the present invention are made from glass due to the significantly higher melting temperature of glass compared to polymers used to form optical fibers. It is important to avoid surpassing the melting temperature of the energy converters, since doing so will risk denaturing the luminescence and / or phosphorescence properties of the energy converter being used.

[0331] The temperature at which a fiber is drawn depends on the type of fiber being produced and the manufacturing process used. Fiber drawing is a technique used to create fibers of various glass chemistries.

[0332] In general, the fiber drawing process involves melting the raw material (e.g., glass or polymer) and then drawing it into thin fibers through a series of dies or nozzles. The temperature required for fiber drawing varies depending on the material composition and their properties.

[0333] For example, in the production of optical fibers, which are used in telecommunications and data transmission, the temperature can be quite high, typically in the range of 1,800°C for glass optical fibers. With respect to embodiments of the present invention, a lower melting point glass composition is preferred for the reasons noted above.

[0334] The melting point of silica based glass can be reduced, for example, by the addition of Na2O (a few mole % between 5 to 6 moles %) to reduce its melting point to between 1300 ^C and 1400 ^C without significantly sacrificing the UV transparency of the glass produced. The melting point of silica can be similarly reduced by the addition of a combination of CaO and Na2O. Phase diagrams and melting points associated with a continuum of glass compositions well known in the art (see for example, Journal of the European Ceramic Society, Volume 42, Issue 5, May 2022, Pages 2449-2463, for a phase diagram for the addition of CaO and Na2O to silica glass compositions and the corresponding effect on melting temperatures of the silica glass compositions formed).

[0335] Within the context of the present invention, the glass used to form the optical fibers of certain embodiments of the present invention needs to be capable of transmitting UV radiation (i.e. a UV transmissive glass) with minimal attenuation. Glasses that are capable of transmitting UV radiation (UV transmissive glasses) typically contain specific materials thatallow UV light to pass through with minimal attenuation. Some common glass compositions that are known for their UV transmittance properties include: - Fused Silica (Fused Quartz): Fused silica is composed of pure silicon dioxide (SiO2) and is highly transparent to UV light across a wide range of wavelengths, including UVA, UVB, and UVC. It is one of the most commonly used materials in UV optics and ultraviolet applications due to its excellent UV transmittance. - Borosilicate Glass: Borosilicate glasses, like Pyrex, also exhibit good UV transmittance, particularly in the UVA and UVB regions. These glasses contain a significant amount of silica, along with boron oxide and other additives, which contribute to their UV transmission properties. - Lithium Fluoride (LiF) and Magnesium Fluoride (MgF2) Glass: While not traditional glasses in the sense of silica-based compositions, these fluoride crystals are highly transparent to UV light and are used in certain UV optics and spectroscopy applications.

[0336] These UV-transmitting glasses conventionally find applications in various fields, including UV spectroscopy, photolithography, germicidal lamps, UV curing, and scientific research that involves UV light. It is important to note that UV transmittance can vary depending on the glass thickness, impurities, and manufacturing processes, so it is essential to select the appropriate glass type based on the specific UV wavelength range and application requirements.

[0337] The melting point of window glass depends on its specific composition. Window glass is typically made from soda-lime glass, which is the most common type of glass used for windows and glassware. Soda-lime glass is composed mainly of silica (sand), soda ash, and lime.

[0338] The approximate melting point of soda-lime glass is around 1,500°C to 1,600°C (2,732 °F to 2,912 °F). However, it's important to note that the melting process for glass is not as simple as heating it to its melting point. Glassmaking involves a complex manufacturing process that includes heating the raw materials to a high temperature until they become a molten glass mixture. The molten glass is then carefully shaped, cooled, and annealed to create the final glass product.

[0339] There are other types of glass with different compositions used for specific applications that may have different melting points. For example, borosilicate glass (e.g., Pyrex) has a higher melting point, typically around 1,650 °C. This type of glass is known forits resistance to thermal shock and is used in laboratory glassware and certain specialized applications.

[0340] In summary, the melting point of window glass is around 1,500 °C to 1,600 °C (2,732°F to 2,912°F) for soda-lime glass, but there are other types of glass with different compositions and melting points used for various applications.

[0341] Borosilicate glasses from the Pyrex family have good enough UV transmission which typically extends down to wavelengths around 290-300 nanometers (nm) and sometimes even shorter and could be a good candidate for the present invention, depending on choice of energy converter used.

[0342] The lower melt temperature glass compositions, as well polymer fiber compositions, tend to limit UV transmission, with transmission becoming attenuated as the distance of transmission increases. In the case of embodiments of the present invention optical fibers, the best glass compositions are those that balance lower melt temperature and good UV transmission in order to pass light from the UV excitation source through a leaky fiber at a predetermined distance. Similarly, the best polymer compositions are the ones that transmit UV energy without excessive attenuation nor bleaching over time for the intended applications.

[0343] Additionally, many of the glass compositions discussed herein can be produced by a low temperature solution precipitation method, commonly called ‘sol-gel’ as practiced in the art. The sol-gel method produces a porous matrix at temperatures of 300 to 600 ^C. the porosity is of such a small scale that only Rayleigh scattering is observed. The porosity can be decreased and the Rayleigh scattering eliminated by a higher temperature treatment between 650 and 1,000 ^C.

[0344] For example, the distance of propagation can range from a matter of inches to 100 feet or more, depending on the end use contemplated. In the case of shoes, the distance of propagation can be limited, for example, to less than 20 inches. In making of clothing articles, the propagation distance is projected to be up to 10 ft. In certain embodiments, such as the making of floor coverings such as carpets, the propagation distance could be in the range of up to 100ft or more.

[0345] For both safety reasons and efficacy reasons, the UV excitation light from the leaky fibers of embodiments of the present invention should be completely absorbed by the one or more energy converters to generate visible light of the desired wavelengths. If, however, the UV energy from the UV excitation light is not completely absorbed by the energy converters,then it is preferably to have provisions in place to have a coating that transmits the visible light from the energy converters and arrests any UV light that was not otherwise absorbed or dissipated. For this reason, in certain embodiments of the present invention, the optical fibers have an external coating having UV attenuation, but high visible transmission.

[0346] While both glass and polymer UV attenuating chemistries are known in the art, organic coatings are preferred.

[0347] UV attenuation, also known as UV absorption, in glass refers to the ability of the glass material to absorb ultraviolet (UV) radiation and prevent it from passing through. Glass can be designed to have different levels of UV attenuation depending on its intended use and application.

[0348] Ordinary soda-lime glass, which is commonly used in windows and glassware, does provide some level of UV attenuation, particularly in the shorter UVB (280-315 nm) and UVC (100-280 nm) wavelengths. However, it is not very effective in blocking UVA (315- 400 nm) radiation, which is the longest wavelength in the UV spectrum. So, even cost- effective soda-lime glass compositions could be used in the present invention for UV sources that are in the UV-A.

[0349] To enhance UV attenuation in glass, especially for applications where protection from harmful UV radiation is essential, certain compounds or coatings can be incorporated into the glass composition. These specialized glasses are often referred to as "UV-filtering" or "UV-absorbing" glasses.

[0350] Some common methods to achieve higher UV attenuation in glass include: - Addition of Metal Oxides: Certain metal oxides, such as titanium dioxide or zinc oxide, can be added to the glass composition. These metal oxides absorb UV radiation, providing better UV attenuation properties to the glass. - Laminated Glass: Laminated glass consists of two or more glass layers with an interlayer of UV-absorbing material, such as polyvinyl butyral (PVB). The interlayer helps block a significant portion of harmful UV radiation. - Coatings: Applying specialized UV-absorbing coatings on the glass surface can improve its UV attenuation properties. These coatings selectively block specific UV wavelengths while allowing visible light to pass through.

[0351] UV attenuation in glass is an important consideration in various applications, such as: - Protecting artwork, artifacts, and sensitive materials in museums from UV damage.- Reducing UV exposure in buildings to protect occupants and furnishings from fading and potential health risks. - Manufacturing UV-filtering lenses for eyewear, which protect the eyes from harmful UV radiation.

[0352] When UV protection is critical, using additional measures such as UV-blocking films, coatings, or protective clothing can also be implemented.

[0353] Unlike glass fibers, synthetic polymer fibers, like those used in textiles and clothing, are drawn at lower temperatures. The temperature for drawing polymer fibers can range from around 200 °C to 300 °C (392 °F to 572 °F), depending on the specific type of polymer being used.

[0354] Polymer synthetic fibers are composed of long chains of polymers, which are large molecules made up of repeating units called monomers. The specific composition of a polymer synthetic fiber depends on the type of polymer used in its production. Some common types of polymer synthetic fibers and their compositions are as follows: - Polyethylene (PE) Fiber: Polyethylene fibers are made from ethylene monomers. Polyethylene fibers are known for their high strength and are used in applications such as ropes and high-performance textiles. - Polypropylene (PP) Fiber: Polypropylene fibers are made from propylene monomers. Polypropylene fibers are lightweight and have good resistance to moisture, making them suitable for applications like carpets and outdoor textiles. - Polyester Fiber: Polyester fibers are made from the polymerization of terephthalic acid and ethylene glycol. Polyester fibers are widely used in clothing, home textiles, and various industrial applications due to their durability and wrinkle resistance. - Nylon (Polyamide) Fiber: Nylon fibers are made from the polymerization of various diamines and dicarboxylic acids. Nylon fibers are known for their strength and elasticity, making them suitable for applications such as apparel, carpets, and parachutes. - Acrylic Fiber: Acrylic fibers are made from acrylonitrile monomers. Acrylic fibers are often used as a substitute for wool in various textiles and garments.

[0355] These are just a few examples of the many types of polymer synthetic fibers available. Each type of fiber has its own unique properties and characteristics, making them suitable for different applications in industries ranging from textiles to engineering and beyond.

[0356] Polymer optical fibers of various types, including those noted above, can be commercially obtained from a variety of sources, including, but not limited to, Mitsubishi Rayon, Mitsubishi Chemical Corporation, Asahi Kasei Corporation, Toray Industries, Inc., Versatile Link (a Broadcom Limited company), CeramOptec GmbH, POFLink Optic Technology Co., Ltd, OFS Fitel, LLC, and NANOLINK Materials Co. Ltd. for example.

[0357] In the case of using such polymer fibers in the present invention, there are no concerns about the thermal exposure exceeding the temperature limit of the energy converters. However, the same concern about UV leaking from the fiber is present, as it was in the case of glass fibers. Accordingly, a polymer coating that stops UV and transmits visible light is preferred whether the leaky light propagator / optical fiber of the present invention is made of glass or polymer.

[0358] There are a variety of processes that can be used to coat an optical fiber (whether of glass or polymer). The processes can be used to place the above-described conformal coatings containing one or more energy converters onto the leaky optical light propagators, or can be used to apply an organic coating that blocks UV and transmits visible light from the leaky optical light propagators. Referring to the formation of a conformal coating as noted above, having dispersed throughout the coating one or more energy modulation agents. These coatings can be applied to the surface of the glass or polymer fiber via a solution coating procedure or the solution precipitation ‘sol-gel’ method mentioned above. In such a process, an organic vehicle is prepared by dissolving a polymer resin in a suitable solvent. Suitable polymers include, but are not limited to, various (meth)acrylate based polymers such as polymethylmethacrylate or poly(isobutyl)methacrylate. The polymer is dissolved in a suitable solvent such as acetone or isopropyl alcohol, for example, in a preferred polymer:solvent weight ratio of from 10:90 to 50:50, more preferably from 15:85 to 25:75, most preferably 20:80. To this mixture, one or more energy converting particles are added which will absorb any UV radiation and emit visible light of the desired color, to enhance the visible light radiation already being transmitted from the leaky optical fiber / light propagator, or as the primary source of the visible light generation. The one or more energy converting particles are added to the polymer / solvent vehicle mixture in any desired loading, preferably in an amount from 5 to 50% by weight, more preferably from 5 to 20% by weight, still more preferably from 10-15% by weight, most preferably at 12% by weight, based on total weight of polymer / solvent / energy converter coating composition. The mixture is then thoroughly mixed until uniform, and transferred to an applicator apparatus.

[0359] A similar process can be used to prepare embodiments of the present invention having a coating applied in order to block emission of any UV while having high transmissibility of the visible light emitting from the leaky light propagator itself and / or the conformal coating. In certain embodiments where the UV light is being converted by energy converters embedded in the leaky light propagator fiber itself, this UV blocking / visible transmitting coating can be applied directly to the cladding layer or even the optical light propagator fiber itself. In other embodiments, where the leaky light propagator emits UV light which is converted to visible light by energy converters contained in a conformal coating on the leaky light propagator / fiber, the UV blocking / visible transmitting coating is applied on top of the conformal coating.

[0360] A suitable applicator apparatus and coating method for coating a leaky light propagator / fiber according to embodiments of the present invention is represented in Figure 11, wherein the optical fiber (210) is inserted into the applicator apparatus (200) via applicator closure (110). The optical fiber (210) then travels through the applicator closure (250), through the mixture (220) of organic vehicle (polymer plus solvent) and energy converters, passing out of the applicator apparatus (200) via nozzle (230). The resulting coated fiber (215) can then be used as is. It is noted that this apparatus can be used to apply the conformal coating to the leaky light propagator fiber, or alternatively, can be used to apply a UV blocking / light transmitting coating directly onto the leaky light propagator fiber (in which case the coating mixture (220) would not necessarily contain the one or more energy converters, but could if desired).

[0361] Alternatively, as depicted in Figure 12, a series of applicator apparatus can be used to apply multiple coatings in sequence. For example, the process depicted in Figure 11 is shown in the top portion of Figure 12, producing a coated fiber (215) having one or more energy converters contained in the applied coating. The resulting coated fiber (215) can then be passed through a dryer station (260) and treated by passing through a further applicator apparatus (300) via applicator closure (350) and through a mixture (320) of an organic vehicle containing a UV absorbing polymer having high transmission in the visible wavelength range, passing out of the second applicator apparatus (300) via nozzle (330) to provide the coated fiber (315) having both the coating containing the one or more energy modulation agents (conformal coating) and the UV absorbing / high visible transmissive coating.

[0362] In the present invention, various inventive elements are used to modulate color either actively using a light source or passively using sunlight. The present invention can be applied to clothing articles, shoes or tapestries.

[0363] In the case of active color modulation embodiments of the present invention, the invention comprises coupling at least one inventive fiber to a light source preferably emitting UV; and, using the inventive fiber as a peripheral part and / or an integral part of the article. Figure 13A shows one embodiment of the present invention where the end of the inventive fiber (410) is placed in close proximity to an LED source (420) that is mounted on a flexible circuit (430) that supplies the necessary power. The LED (420) and the end of the inventive fiber (410) are preferably embedded in an optically clear encapsulant (440). Figure 13B shows an embodiment of the present invention where multiple inventive fibers are part of the inventive fabric (411), where the inventive fabric (411) is placed in close proximity to the LED source (420) mounted on the flex circuit (430), and the end of the inventive fabric (411), LED source (420) and flex circuit (430) are embedded in an optically clear encapsulant (440) such that the ends of the inventive fibers contained in the inventive fabric are contained within the encapsulant. The resulting inventive fabric can be used to make various apparel articles and consumer goods.

[0364] When the present invention is embodied in a fabric, Figure 13C shows a perspective depiction of the inventive fabric (411), LED source (420) (in this case an LED strip), and optically clear encapsulant (440) (the flex circuit is not shown) which can be used, for example, in clothing and tapestry articles.

[0365] The inventive fiber and / or fabric can be used to make a variety of apparel items, including, but not limited to, shoes, shirts, socks, pants, jackets, sweaters, etc. In the case of shoes, a preferred use is in the preparation of an athletic shoe. In certain embodiments, the present invention fabric can be used as the upper fabric (the Knit Upper or the knit fabric) of the athletic shoe. Figure 14 illustrates one example of a knit upper fabric prepared for making an athletic shoe, showing the knit upper fabric (510), having a flexible LED strip (520) located on each side of the knit upper fabric (510), with the flexible LED strip (520) and end of the knit upper fabric (510) on both sides being encapsulated with an optically clear encapsulant (540).

[0366] Figure 15 illustrates an embodiment of the present invention showing a heel view of an athletic shoe where the knit upper fabric 510 used in construction of an athletic shoe. In Figure 15, the knit upper fabric (510) is either stitched or bonded to an insole (550). In general, the knit upper (510) is bonded to the insole (550). The optically transparentencapsulant (540) would preferably be located in the outer surface of the insole (550). The EVA rubber of the midsole / outsoles (560) has provisions for a groove (570) where the optically transparent encapsulant (540) is nested. The midsole (560) can optionally have an outsole (580) which does not interfere with the elements of the inventive fabric.

[0367] The inventive fiber and / or fabric of the present invention can also be used in other areas of clothing articles, such as in the production of logos on articles of clothing, in parts of clothing such as cuffs or seams, etc to add special lighting / color effects. In the area of shoes, and particularly athletic shoes, the fiber and / or fabric of embodiments of the present invention can be used in the foxing material (typically used for placing logos or other identifying marks on the athletic shoes). Figure 16 illustrates an embodiment of the present invention in which the knit fabric comprising the fibers of the present invention is used in the foxing material on the heel of the shoe. In the figure, the fabric (600) forming the shoe itself can be any fabric, including a fabric of the present invention if desired. In the figure, the fabric (600) is a conventional fabric used in forming athletic shoe knit uppers. The knit upper fabric (600) is either stitched or bonded to an insole (650). In general, the knit upper (600) is bonded to the insole (650). The optically transparent encapsulant (640) would preferably be located in the outer surface of the insole (650). The EVA rubber of the midsole / outsoles (660) has provisions for a groove (670) where the optically transparent encapsulant (640) is nested. The midsole (660) can optionally have an outsole (680) which does not interfere with the elements of the inventive fabric. In this case the inventive fabric (610) is only used in the foxing area of the shoe, with the LED source (not shown) and the optically transparent encapsulant (640) being located in the groove (670) within the midsole / outsoles (660) just below the foxing area and insole (650). Similarly, the inventive fabric could be used in the company logo or any other part of the shoe that can accentuate its look and aesthetic presentation.

[0368] In another embodiment, the inventive fiber is used to make logos (or other patterned indicia). The color enhanced logos can be self-contained (or stand-alone logos) with a small battery on board and an adhesive backing to adhere to a consumer good article. The self- contained logo with battery on board can be held in place in any desired manner, including using magnets on each side of a clothing article, stitching the self-contained logo in place, attaching the self-contained logo using a hook and loop attachment (such as Velcro), or using double sided tape to attach the self-contained logo, for example.

[0369] The following are exemplary embodiments of the present invention:

[0370] Embodiment 1. An optical light propagator comprising:a core formed of a high-κ dielectric material capable of transmitting wavelengths in the UV-visible range, and an outer coating on the core wherein the outer coating is formed of a low- κ dielectric material; wherein the outer coating has a plurality of porosities along the optical light propagator, wherein each of the plurality of porosities transits from an outer surface of the outer coating to an outer surface of the core at an interface between the outer coating and the core, such that wavelengths transmitted through the core of the optical light propagator are emitted through each of the plurality of porosities along the optical light propagator.

[0371] Embodiment 2. The optical light propagator of Embodiment 1, wherein the optical light propagator is configured as an optical fiber or an optical guide or an optical waveguide or an optical medium.

[0372] Embodiment 3. The optical light propagator of Embodiment 1, wherein the optical light propagator is configured as a sheet or film such that the core is a sheet of film having the outer coating in sheet or film form placed on at least one side of the core.

[0373] Embodiment 4. The optical light propagator of any one of Embodiments 1-3, wherein the outer coating is further coated by a conformal coating having dispersed throughout one or more energy modulation agents.

[0374] Embodiment 5. The optical light propagator of any one of Embodiments 1-4, wherein the optical light propagator is further coated, on the outer coating or on the conformal coating, if present, with a UV blocking / visible light transmitting coating.

[0375] Embodiment 6. The optical light propagator of Embodiment 4, wherein the one or more energy modulation agents are configured to absorb the wavelengths emitted through the plurality of porosities along the length of the optical fiber, and emit an emitted energy of a desired visible wavelength range.

[0376] Embodiment 7. The optical light propagator of one of Embodiments 4 or 6, wherein the one or more energy modulation agents is at least one member selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

[0377] Embodiment 8. The optical light propagator of any one of Embodiments 1-7, wherein the high-κ dielectric material forming the core is a glass.

[0378] Embodiment 9. The optical light propagator of any one of Embodiments 1-7, wherein the high-κ dielectric material forming the core is a polymer.

[0379] Embodiment 10. A textile yarn, comprising:the optical light propagator of any one of Embodiments 1-2 or 4-9, wherein the optical light propagator is configured as an optical fiber, and one or more natural or synthetic fibers.

[0380] Embodiment 11. The textile yarn of Embodiment 10, wherein the optical fiber and the one or more natural or synthetic fibers are twisted together to form the yarn.

[0381] Embodiment 12. The textile yarn of one of Embodiments 10 or 11, wherein the textile yarn is a composite yarn wherein the optical fiber is a filament and the one or more natural or synthetic fibers are staple fibers.

[0382] Embodiment 13. The textile yarn of one of Embodiments 10 or 11, wherein both the optical fiber and the one or more natural or synthetic fibers are filaments.

[0383] Embodiment 14. The textile yarn of Embodiment 13, wherein the optical fiber and the one or more natural or synthetic fibers are entangled to form the textile yarn.

[0384] Embodiment 15. The textile yarn of any one of Embodiments 10-14, wherein the one or more natural or synthetic fibers are selected from the group consisting of wool, cotton, silk, alpaca, mohair, cellulosic fibers, polyesters, nylons, rayons, polyvinyl chloride fibers, elastomer fibers, aramids, polyolefins, acrylics, liquid crystal polymer fibers, carbon fibers, fiberglass, and metal fibers.

[0385] Embodiment 16. A fabric prepared from the textile yarn of any one of Embodiments 10-15.

[0386] Embodiment 17. An article comprising the fabric of Embodiment 16.

[0387] Embodiment 18. An article prepared using the textile yarn of any one of Embodiments 10-15.

[0388] Embodiment 19. The article of one of Embodiments 17 or 18, wherein the article is a member selected from the group consisting of shoes, shirts, pants, socks, jackets, sweaters, undergarments, bed linens, window coverings, and floor coverings.

[0389] Embodiment 20. The article of Embodiment 19, wherein the article is shoes.

[0390] Embodiment 21. The article of Embodiment 20, wherein the shoes are athletic shoes.

[0391] Embodiment 22. The article of Embodiment 21, wherein the fabric or textile yarn forms at least a part of an upper of the athletic shoes.

[0392] Embodiment 23. The article of claim 21, wherein the fabric or textile yarn forms at least a part of a foxing material of the athletic shoes.

[0393] Embodiment 24. The article of one of Embodiments 22 or 23, wherein the athletic shoes further comprise a sole having therein a powered light source configured to provide thewavelengths in the UV-visible range that are transmitted through the core of the optical fiber contained in the textile yarn or fabric.

[0394] Embodiment 25. The article of any one of Embodiments 17-24, wherein the textile yarn contained therein is present in a predetermined pattern.

[0395] Embodiment 26. The optical light propagator of Embodiment 3, wherein the outer coating sheet or film is placed on both sides of the core sheet or film.

[0396] Embodiment 27. The optical light propagator of one of Embodiments 3 or 26, wherein the outer coating sheet or film is further coated by a conformal coating sheet or film having dispersed throughout one or more energy modulation agents.

[0397] Embodiment 28. The optical light propagator of Embodiment 27, wherein the one or more energy modulation agents are configured to absorb the wavelengths emitted through the plurality of porosities along the length of the optical fiber, and emit an emitted energy of a desired visible wavelength range.

[0398] Embodiment 29. The optical light propagator of any one of claim 26-28, wherein the optical light propagator is further coated, on the outer coating or on the conformal coating, if present, with a UV blocking / visible light transmitting coating.

[0399] Embodiment 30. The optical light propagator of any one of Embodiments 27-29, wherein the one or more energy modulation agents is at least one member selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

[0400] Embodiment 31. The optical light propagator of any one of Embodiments 1-9 or 26-30, wherein the core further comprises one or more energy modulation agents distributed throughout the core.

[0401] Embodiment 32. The optical light propagator of Embodiment 26, wherein the one or more energy modulation agents distributed throughout the core are configured to absorb the wavelengths transmitted along the length of the optical fiber, and emit an emitted energy of a desired visible wavelength range through the plurality of porosities.

[0402] Embodiment 33. The optical light propagator of one of Embodiments 31 or 32, wherein the one or more energy modulation agents distributed throughout the core is at least one member selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

[0403] Embodiment 34. An article formed from the optical light propagator of any one of Embodiments 3 or 26-31.

[0404] Embodiment 35. The article of Embodiment 34, wherein the article is a tabletop or countertop.

[0405] Embodiment 36. The article of Embodiment 34, wherein the article is a cabinet face, drawer front, or cabinet door.

[0406] Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims

CLAIMS:

1. An optical waveguide comprising: a core formed of a high-κ dielectric material capable of transmitting wavelengths in the UV-visible range, and an outer coating on the core wherein the outer coating is formed of a low- κ dielectric material; wherein the outer coating has a plurality of porosities along the optical waveguide, wherein each of the plurality of porosities transits from an outer surface of the outer coating to an outer surface of the core at an interface between the outer coating and the core, such that wavelengths transmitted through the core of the optical waveguide are emitted through each of the plurality of porosities along the optical waveguide.

2. The optical waveguide of claim 1, wherein the optical waveguide is configured as an optical fiber.

3. The optical waveguide of claim 1, wherein the optical waveguide is configured as a sheet or film such that the core is a sheet of film having the outer coating in sheet or film form placed on at least one side of the core.

4. The optical waveguide of any one of claims 1-3, wherein the outer coating is further coated by a conformal coating having dispersed throughout one or more energy modulation agents.

5. The optical waveguide of any one of claim 1-4, wherein the optical waveguide is further coated, on the outer coating or on the conformal coating, if present, with a UV blocking / visible light transmitting coating.

6. The optical waveguide of claim 4, wherein the one or more energy modulation agents are configured to absorb the wavelengths emitted through the plurality of porosities along the length of the optical fiber, and emit an emitted energy of a desired visible wavelength range.

7. The optical waveguide of one of claims 4 or 6, wherein the one or more energy modulation agents is at least one member selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

8. The optical waveguide of any one of claims 1-7, wherein the high-κ dielectric material forming the core is a glass.

9. The optical waveguide of any one of claims 1-7, wherein the high-κ dielectric material forming the core is a polymer.

10. A textile yarn, comprising: the optical waveguide of any one of claims 1-2 or 4-9, wherein the optical waveguide is configured as an optical fiber, and one or more natural or synthetic fibers.

11. The textile yarn of claim 10, wherein the optical fiber and the one or more natural or synthetic fibers are twisted together to form the yarn.

12. The textile yarn of one of claims 10 or 11, wherein the textile yarn is a composite yarn wherein the optical fiber is a filament and the one or more natural or synthetic fibers are staple fibers.

13. The textile yarn of one of claims 10 or 11, wherein both the optical fiber and the one or more natural or synthetic fibers are filaments.

14. The textile yarn of claim 13, wherein the optical fiber and the one or more natural or synthetic fibers are entangled to form the textile yarn.

15. The textile yarn of any one of claims 10-14, wherein the one or more natural or synthetic fibers are selected from the group consisting of wool, cotton, silk, alpaca, mohair, cellulosic fibers, polyesters, nylons, rayons, polyvinyl chloride fibers, elastomer fibers, aramids, polyolefins, acrylics, liquid crystal polymer fibers, carbon fibers, fiberglass, and metal fibers.

16. A fabric prepared from the textile yarn of any one of claims 10-15.

17. An article comprising the fabric of claim 16.

18. An article prepared using the textile yarn of any one of claims 10-15.

19. The article of one of claims 17 or 18, wherein the article is a member selected from the group consisting of shoes, shirts, pants, socks, jackets, sweaters, undergarments, bed linens, window coverings, and floor coverings.

20. The article of claim 19, wherein the article is shoes.

21. The article of claim 20, wherein the shoes are athletic shoes.

22. The article of claim 21, wherein the fabric or textile yarn forms at least a part of an upper of the athletic shoes.

23. The article of claim 21, wherein the fabric or textile yarn forms at least a part of a foxing material of the athletic shoes.

24. The article of one of claims 22 or 23, wherein the athletic shoes further comprise a sole having therein a powered light source configured to provide the wavelengths in the UV-visible range that are transmitted through the core of the optical fiber contained in the textile yarn or fabric.

25. The article of any one of claims 17-24, wherein the textile yarn contained therein is present in a predetermined pattern.

26. The optical waveguide of claim 3, wherein the outer coating sheet or film is placed on both sides of the core sheet or film.

27. The optical waveguide of one of claims 3 or 26, wherein the outer coating sheet or film is further coated by a conformal coating sheet or film having dispersed throughout one or more energy modulation agents.

28. The optical waveguide of claim 27, wherein the one or more energy modulation agents are configured to absorb the wavelengths emitted through the plurality of porosities along the length of the optical fiber, and emit an emitted energy of a desired visible wavelength range.

29. The optical waveguide of any one of claim 26-28, wherein the optical waveguide is further coated, on the outer coating or on the conformal coating, if present, with a UV blocking / visible light transmitting coating.

30. The optical waveguide of any one of claims 27-29 , wherein the one or more energy modulation agents is at least one member selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

31. The optical waveguide of any one of claims 1-9 or 26-30, wherein the core further comprises one or more energy modulation agents distributed throughout the core.

32. The optical waveguide of claim 31, wherein the one or more energy modulation agents distributed throughout the core are configured to absorb the wavelengths transmitted along the length of the optical fiber, and emit an emitted energy of a desired visible wavelength range through the plurality of porosities.

33. The optical waveguide of one of claims 31 or 32, wherein the one or more energy modulation agents distributed throughout the core is at least one member selected from the group consisting of phosphors, quantum dots, and organometallic dyes.

34. An article formed from the optical waveguide of any one of claims 3 or 26-31.

35. The article of claim 34, wherein the article is a tabletop or countertop.

36. The article of claim 34, wherein the article is a cabinet face, drawer front, or cabinet door.

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