System and method for depositing phosphor-containing inks

Abstract

Phosphor materials and devices containing such phosphor materials are disclosed. An ink composition according to the present disclosure comprises a phosphor material comprising a Mn < 4 + > doped phosphor of the following Formula 1: Ax [MFy]: Mn < 4 + > (I), and at least one rare earth containing garnet phosphor, the at least one rare earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, where the at least one rare earth-containing garnet phosphor has a D50 particle size of from about 0.5 microns to about 15 microns, where A is Li, Na, K, Rb, Cs, or a combination thereof; m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to International Patent Application PCT / US2023 / 020927, filed May 4, 2023, concerning “Systems and Met Houses for Depositing Phosphor Contining Ink”, which claims priority to U.S. Provisional Patent Application Serial No. 63 / 453,396, filed March 20, 2023, concerning “Phosphor Converted Microglass Arrangement with Reflexive Layer for A Transparent Distributed Architecture”, and U.S. Provisional Patent Application Serial No. 63 / 498,414, filed April 26, 2023, concerning “Phosphor Ink Printed Color Filter Parts”, which are incorporated herein by reference in their entirety. Background Technology

[0003] The subject matter described in this article generally relates to inks containing phosphor materials deposited for lighting and display applications.

[0004] Narrow-band emitting phosphor materials have enabled high color quality in LED-based lighting and displays. Next-generation displays can incorporate effective areas of 10,000 μm. 2 Or even smaller mini-LEDs and micro-LEDs, which are capable of producing light visible to the human eye at very low drive currents. Mini-LEDs are LEDs with a size of approximately 100 μm to 0.7 mm. For micro-LEDs, the display can be self-emissive or include miniaturized backlighting devices that form an array of individual LEDs less than 100 μm in size.

[0005] New methods are needed to apply phosphor materials to miniaturized μm-scale LED devices to fully realize the potential of mini-LED and micro-LED technologies. Coating and printing processes, such as inkjet printing, spin coating, or slot die coating of phosphor materials, are being developed to fabricate LEDs including small-sized LEDs.

[0006] Inkjet-printable inks have been prepared using quantum dots. Quantum dot materials possess nanoparticle size and a strong absorption coefficient. However, quantum dots are limited by their low quantum efficiency (QE) and poor thermal stability, which severely restricts their practical applications.

[0007] Phosphors offer improved properties compared to quantum dot materials. Phosphors used with small-sized LEDs must have correspondingly small sizes. Printing and coating compositions require stable dispersions, but phosphor materials tend to precipitate or separate with common organic solvents, which is undesirable for subsequent coating and printing processes. Furthermore, smaller-particle-size phosphor materials often agglomerate when mixed with common solvents, making them unsuitable for ink compositions or formulations. Summary of the Invention

[0008] In one embodiment, an ink composition is provided. The ink composition comprises a phosphor material, said phosphor material being composed of Mn of Formula 1. 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers.

[0009] A x [MF y ]:Mn 4+ I

[0010] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0011] In another embodiment, an apparatus is disclosed comprising an LED light source optically coupled and / or radiatively connected to a phosphor composition comprising a phosphor material. The phosphor material is composed of Mn from the following formula 1. 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers.

[0012] A x [MF y ]:Mn 4+ I

[0013] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0014] In yet another embodiment, a light-emitting array is disclosed. The light-emitting array includes a plurality of mini-LEDs or micro-LEDs disposed on a substrate, at least one of the mini-LEDs or at least one of the micro-LEDs being encapsulated within a dike structure or well structure. The dike structure or well structure is configured to contain a phosphor composition deposited within it. At least a portion of the substrate contained within each of the dike structures or well structures is coated with a reflective material. The phosphor composition comprises Mn from the following formula 1. 4+ Phosphor materials composed of doped phosphors, wherein Mn 4+ The D50 particle size of the doped phosphor is approximately 0.5 micrometers to approximately 15 micrometers.

[0015] A x [MF y ]:Mn 4+ I

[0016] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0017] In yet another embodiment, a transparent display is disclosed. The transparent display includes a mini-LED array or micro-LED array disposed on a substrate, at least one mini-LED in the mini-LED array or at least one micro-LED in the micro-LED array being encapsulated within a dike structure or well structure. The dike structure or well structure is configured to contain a phosphor composition deposited within the dike structure or well structure. At least a portion of the substrate contained within each of the dike structures or well structures is coated with a reflective material. The phosphor composition comprises Mn from the following formula 1. 4+ Phosphor materials composed of doped phosphors, wherein Mn 4+ The D50 particle size of the doped phosphor is approximately 0.5 micrometers to approximately 15 micrometers.

[0018] A x [MF y ]:Mn 4+ I

[0019] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF yThe absolute value of the charge of the ion; and y is 5, 6 or 7, wherein the transparent display has at least 60% transparency.

[0020] In yet another embodiment, a vehicle taillight is disclosed. The taillight includes a plurality of LED light sources arranged in a row, the plurality of LED light sources being optically coupled and / or radiatively connected to a composition comprising a phosphor material, the phosphor material being composed of Mn from Formula 1. 4+ The composition consists of doped phosphors, wherein the D50 particle size of the phosphor material is approximately 0.5 micrometers to approximately 15 micrometers.

[0021] A x [MF y ]:Mn 4+ I

[0022] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0023] In yet another embodiment, a vehicle taillight is disclosed. The taillight includes a plurality of LED light sources optically coupled and / or radiatively connected to a composition comprising a phosphor material, the phosphor material being composed of Mn from Formula 1. 4+ The composition consists of doped phosphors, with the phosphor material coated on glass, reflective surfaces, or flexible surfaces, wherein Mn... 4+ The D50 particle size of the doped phosphor is from approximately 0.5 micrometers to approximately 15 micrometers.

[0024] A x [MF y ]:Mn 4+ I

[0025] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0026] In yet another embodiment, a membrane is provided. The membrane comprises a phosphor material, said phosphor material being composed of Mn from Formula 1. 4+The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers.

[0027] A x [MF y ]:Mn 4+ I

[0028] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0029] In another embodiment, an apparatus is disclosed comprising an LED light source optically coupled and / or radiatively connected to a film comprising a phosphor material. The phosphor material is composed of Mn from the following formula 1. 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers.

[0030] A x [MF y ]:Mn 4+ I

[0031] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7. Attached Figure Description

[0032] These and other features, aspects, and advantages of this disclosure will be better understood after reading the following detailed description with reference to the accompanying drawings, in which similar symbols denote similar parts throughout the drawings.

[0033] Figure 1A This is a schematic cross-sectional view of an apparatus according to one embodiment of the present disclosure.

[0034] Figure 1B This is a schematic cross-sectional view of an apparatus according to an exemplary embodiment.

[0035] Figure 1C This is a schematic cross-sectional view of an apparatus according to an exemplary embodiment.

[0036] Figure 1D This is a schematic cross-sectional view of an apparatus according to an exemplary embodiment.

[0037] Figure 1E This is a schematic cross-sectional view of an apparatus according to an exemplary embodiment.

[0038] Figure 2 This is a schematic cross-sectional view of a lighting device according to one embodiment of the present disclosure.

[0039] Figure 3 This is a schematic cross-sectional view of a lighting device according to another embodiment of this disclosure.

[0040] Figure 4 This is a cross-sectional side perspective view of a lighting device according to one embodiment of the present disclosure.

[0041] Figure 5A This is a schematic perspective view of a surface mount device (SMD) according to one embodiment of the present disclosure.

[0042] Figure 5B This is a schematic cross-sectional view of an SMD according to an exemplary embodiment.

[0043] Figure 5C This is a schematic cross-sectional view of an apparatus according to an exemplary embodiment.

[0044] Figure 6 This is a schematic diagram of a contact stencil printing system according to an embodiment of the present disclosure.

[0045] Figure 7 This is a schematic diagram of a template printing system according to an embodiment of this disclosure.

[0046] Figures 8A to 8D This is a schematic diagram of the layout of printing wells according to the embodiments of this disclosure.

[0047] Figure 9 This is a schematic diagram of the dike layout according to the implementation scheme of this disclosure.

[0048] Figure 10 Is using Figure 6 The contact stencil printing system deposits the composition onto the substrate.

[0049] Figure 11 Is using Figure 7 The pattern-removing stencil printing system deposits the composition onto the substrate.

[0050] Figures 12A to 12DThis includes illustrations showing the aspect ratio of a pattern of a printed ink composition deposited using a template to print according to embodiments of the present disclosure.

[0051] Figure 13A and Figure 13B The image shows a pattern of a printing ink composition deposited via a template, and Figure 13B It is the photoluminescence intensity diagram of the pattern.

[0052] Figure 14A and Figure 14B This is a schematic diagram of a high-precision pickup and placement system according to an embodiment of this disclosure.

[0053] Figure 15 It is a dip coating system according to an embodiment of this disclosure.

[0054] Figure 16A and Figure 16B These are, respectively, top and side views of example red, green, and blue (RGB) pixels according to an embodiment of this disclosure.

[0055] Figure 17 This is an illustration comparing the red light emission of the filter portion of a red subpixel filled with KSF phosphor at depths of 8 μm and 16 μm, according to an embodiment of this disclosure.

[0056] Figure 18 The photoluminescence mapping of the blank substrate is shown.

[0057] Figure 19 The photoluminescence mapping of the red subpixel filled with KSF is shown.

[0058] Figure 20 A graph showing the percentage of external quantum efficiency (EQE) is displayed.

[0059] Figure 21 This is a schematic diagram of a hybrid conductive mesh according to an embodiment of the present disclosure.

[0060] Figure 22 This is a chromaticity diagram of the color points of an example LED array.

[0061] Unless otherwise indicated, the accompanying drawings provided herein are intended to illustrate the features of embodiments of this disclosure. These features are considered applicable to a wide variety of systems that include one or more embodiments of this disclosure. Therefore, the drawings are not intended to include all conventional features known to those skilled in the art as necessary for practicing the embodiments disclosed herein. Detailed Implementation

[0062] In the following specification and claims, many terms will be referenced, and these terms shall be defined to have the following meanings.

[0063] Unless the context clearly specifies otherwise, the singular forms “a,” “an,” and “the” include plural referents. As used herein, unless the context clearly specifies otherwise, the term “or” does not imply exclusivity but rather the presence of at least one of the cited components, and includes the possibility of combinations of the cited components.

[0064] As used herein and throughout the specification and claims, approximate language may be applied to modify any quantitative representation that allows for permissible variation without causing a change in its associated essential function. Therefore, values ​​modified by one or more terms such as “about,” “substantially,” and “approximately” are not limited to the specified precise values. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. Here and throughout the specification and claims, unless otherwise indicated by context or language, scope limitations may be combined and / or interchanged; such scopes are identified and include all subscopes contained herein.

[0065] "Optional" or "optionally" means that the event or situation described below may or may not occur, or the material identified below may or may not exist, and the description includes the case where the event or situation occurs or the material exists, and the case where the event or situation does not occur or the material does not exist.

[0066] The square brackets in the formula indicate that at least one of the elements is present in the phosphor material, and any combination of two or more of the elements may be present. For example, the formula [Ca,Sr,Ba]3MgSi2O8:Eu 2+ ,Mn 2+ It covers at least one of Ca, Sr, or Ba, or any combination of two or more of Ca, Sr, or Ba. Examples include Ca3MgSi2O8:Eu. 2+ .Mn 2+ Sr3MgSi2O8:Eu 2+ .Mn 2+ ; or Ba3MgSi2O8:Eu 2+ .Mn 2+ The formula following the colon ":" indicates that the phosphor material is doped with an activator. The formula following the colon ":" and showing more than one activator separated by commas indicates that the phosphor material is doped with any one or two activators. For example, the formula [Ca,Sr,Ba]3MgSi2O8:Eu 2+ ,Mn 2+ Covering [Ca,Sr,Ba]3Mg Si2O8:Eu 2+ [Ca,Sr,Ba]3MgSi2O8:Mn2+ Or [Ca,Sr,Ba]3MgSi2O8:Eu 2+ and Mn 2+ .

[0067] In one aspect, an ink composition is provided. The ink composition comprises: a phosphor material, said phosphor material comprising Mn of Formula 1. 4+ Doped phosphor: and at least one binder material or solvent, wherein Mn 4+ The D50 particle size of the doped phosphor is from about 0.5 micrometers to about 15 micrometers, and the viscosity of the ink composition is from greater than 2000 cP to about 30,000 cP.

[0068] A x [MF y ]:Mn 4+ I

[0069] Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

[0070] Ink compositions can be customized for specific printing applications. For example, ink compositions can be customized for any of the following printing applications: inkjet printing, flexographic printing, microdispensing printing, screen printing, direct writing printing, aerosol jet printing, gravure printing, etc. Additionally or alternatively, ink compositions can be customized for extrusion. For example, low-viscosity ink compositions can be customized for inkjet printing, flexographic printing, and / or microdispensing printing; medium-viscosity inks can be customized for screen printing, direct writing printing, aerosol jet printing, gravure printing, flexographic printing, and / or microdispensing printing; and high-viscosity inks can be customized for high-viscosity screen printing, direct writing printing, and / or extrusion.

[0071] The ink composition contains phosphor material. The type, quantity, and size of the phosphor are determined by the optical application (specifically, color point and optical density).

[0072] The phosphor material may be present in the ink composition in an amount of about 5% by weight to about 70% by weight. In another embodiment, the phosphor material may be present in an amount of about 30% by weight to about 60% by weight. In yet another embodiment, the phosphor material may be present in an amount of about 10% by weight to about 50% by weight. The percentage by weight of the phosphor material is based on the total weight of the ink composition.

[0073] Mn in Formula I 4+Doped phosphors are complex fluoride materials or coordination compounds containing at least one coordination center surrounded by fluoride ions acting as ligands, and subject to charge compensation via counterions as needed. For example, in K₂SiF₆:Mn 4+ In this configuration, the coordination center is Si and the counterion is K. The activator ion (Mn) 4+ It also acts as a coordination center, thereby replacing a portion of the host lattice center (e.g., Si). The host lattice (including the antiion) can further alter the excitation and emission properties of the activator ions.

[0074] In specific embodiments, the coordination center of the phosphor (i.e., M in Formula I) is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. More specifically, the coordination center may be Si, Ge, Ti, or a combination thereof. The counterion or A in Formula I may be Li, Na, K, Rb, Cs, or a combination thereof, more particularly K or Na. Examples of phosphors of Formula I include K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ K2[GeF6]Mn 4+ Rb2[TiF6]Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4 + K3[BiF6]K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ K3[TaF7]:Mn 4+ In the specific implementation scheme, the phosphor of formula I is K2SiF6:Mn 4+ (PFS) or Na2[SiF6]:Mn 4+ (NSF).

[0075] Mn 4+The amount of activator Mn incorporated into a phosphor (referred to as Mn%) improves color conversion. Increasing the Mn% doping level improves color conversion by increasing the intensity of red light emission, maximizing the absorption of excited blue light, and reducing the amount of unconverted blue light or blue light bleed-through from blue-emitting LEDs.

[0076] In one implementation, red light emits Mn 4+ The Mn loading or Mn% of the doped phosphor is at least 1 wt%. In another embodiment, the Mn loading of the red emitting phosphor is at least 1.5 wt%. In another embodiment, the Mn loading of the red emitting phosphor is at least 2 wt%. In another embodiment, the Mn% of the red emitting phosphor is at least 3 wt%. In another embodiment, the Mn% is greater than 3.0 wt%. In another embodiment, the Mn content in the red emitting phosphor is from about 1 wt% to about 4 wt%. In another embodiment, the Mn% of the red emitting phosphor is from about 2 wt% to about 5 wt%.

[0077] In one implementation, Mn 4+ Doped phosphors can be manganese-doped potassium fluorosilicates, such as K₂SiF₆:Mn₂. 4+ (PFS). The PFS exhibits narrow-band emission with multiple peaks and an average full width at half maximum (FWHM) of less than 4 nm. In another embodiment, the red-emitting phosphor may be Na2SiF6:Mn. 4+ (NFS).

[0078] In one implementation, Mn can be 4+ The doped phosphor undergoes further processing, such as annealing, washing, calcination, or any combination of these processes. Mn 4+ Post-processing techniques for doped phosphors are described in U.S. Patent Nos. 8,906,724, 8,252,613, 9,698,314, U.S. Publication No. 2016 / 0244663, U.S. Publication No. 2018 / 0163126, and U.S. Publication No. 2020 / 0369956, the entire contents of each of these patent publications being incorporated herein by reference. In one embodiment, Mn may be... 4+ The phosphors are annealed, treated with multiple washing processes, and then calcined.

[0079] To improve reliability, Mn in Equation I... 4+The doped phosphor may be at least partially coated with a surface coating to enhance the stability of the phosphor particles and resist agglomeration and increase the zeta potential of the particles by modifying the surface of the particles. In one embodiment, the surface coating may be a metal fluoride, silicon dioxide, or an organic coating. In one embodiment, based on Mn... 4+ The red-emitting phosphor of the phosphor-activated composite fluoride material is at least partially coated with a metal fluoride, which increases the positive Zeta potential and reduces agglomeration. In one embodiment, the metal fluoride coating comprises MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AlF3, or combinations thereof. In another embodiment, the amount of the metal fluoride coating is from about 0.1 wt% to about 10 wt%. In another embodiment, the metal fluoride coating is present in an amount from about 0.1 wt% to about 5 wt%. In another embodiment, the amount of the metal fluoride coating is from about 0.3 wt% to about 3 wt%. Based on Mn 4+ The activated composite fluoride material is prepared by coating a metal fluoride red-emitting phosphor as described in WO 2018 / 093832, U.S. Publication No. 2018 / 0163126 and U.S. Publication No. 2020 / 0369956, the entire contents of each of which are incorporated herein by reference.

[0080] The phosphor material may include an additional phosphor, such as yttrium aluminum garnet phosphor (YAG). The powder ratio (e.g., YAG:PFS) can be adjusted to achieve the desired color point. The phosphor material may include an additional phosphor, such as a rare earth garnet phosphor. Rare earth elements include: Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In one embodiment, the rare earth garnet phosphor is yttrium aluminum garnet phosphor (YAG). The ratio of the rare earth garnet phosphor to Mn can be adjusted. 4+ The ratio of phosphor doped with different amounts is used to achieve the desired color point. In some embodiments, the phosphor material includes rare-earth garnet phosphors (e.g., YAG) and Mn. 4+ Doped phosphors (e.g., PFS). In other embodiments, the phosphor material comprises a high percentage of rare-earth garnet phosphors. In some embodiments, the rare-earth garnet phosphors may be present in the phosphor material in an amount from about 80% to about 100% by weight. Additionally, Mn... 4+ The doped phosphor can be present in the phosphor material in an amount from about 20% by weight to about 0.1% by weight. In some embodiments, rare earth garnet phosphor can be present in the phosphor material in an amount from about 90% by weight to about 100% by weight. Additionally, Mn... 4+The doped phosphor can be present in the phosphor material in an amount from about 10% by weight to about 0.1% by weight. In some embodiments, rare earth garnet phosphor can be present in the phosphor material in an amount from about 95% by weight to about 100% by weight. Additionally, Mn... 4+ The doped phosphor may be present in the phosphor material in an amount from about 5% by weight to about 0.1% by weight. The percentage by weight of the phosphor material is based on the total weight of the phosphor material. In some embodiments, the rare-earth garnet phosphor comprises YAG and Mn. 4+ Doped phosphors include PFS.

[0081] The ink composition comprises at least one binder material or at least one solvent. In some embodiments, the ink composition comprises both a binder material and a solvent.

[0082] The ink composition may include a binder material to further optimize the ink properties. A wide variety of binder and resin systems with different chemical properties and viscosities can be used.

[0083] In one embodiment, the adhesive matrix comprises a crosslinked polymer. In another embodiment, the adhesive material comprises a curable material, such as a photocurable or UV-curable material, or a thermocurable or thermosetting adhesive material, or a combination thereof. Thermocurable or thermosetting adhesive materials polymerize or crosslink to form a cured resin adhesive matrix. Exemplary thermosetting and UV adhesive materials include epoxy resins, acrylates, methacrylates, vinyl esters, and siloxane families. Examples of suitable commercial resin systems include, but are not limited to: Pixelligent UVG curable ink base, optical adhesive (Norland 68T), and Pixelligent PixJet SFZ-1 with 40 wt% ZrO2 in an acrylic formulation.

[0084] In one embodiment, the adhesive material may be present in an amount of up to about 75% by weight. In another embodiment, the adhesive may be present in an amount of up to about 70% by weight. In another embodiment, the adhesive may be present in an amount of about 5% by weight to about 75% by weight. In another embodiment, the adhesive is present in an amount of about 10% by weight to about 70% by weight. In another embodiment, the amount of adhesive present is about 20% by weight to about 50% by weight. The weight percentages are based on the total weight of the ink composition.

[0085] In another embodiment, the ink composition comprises a first polymerization initiator and a second polymerization initiator for a two-step curing process, wherein during the first curing step, a photo-initiated polymerization process is initiated by radiation at a wavelength less than 400 nm (UV curing). The first polymerization initiator has a higher decomposition rate than the second polymerization initiator. The second curing process does not involve UV radiation, wherein the second polymerization initiator has a higher decomposition rate than the first polymerization initiator. The concentration of the post-curing phosphor is increased by 5%, preferably 10%, and the volume reduction (shrinkage) of the printed material is <20%, preferably <15%. The total printed volume shrinkage does not exceed 20% by volume. The ink composition may contain a solvent. The amount, polarity, and vapor pressure of the solvent can contribute to obtaining a stable ink that meets the viscosity, wettability, and optical density standards of the ink composition. The solvent is present in an amount that can effectively dissolve the phosphor material and any binder material and adjust the ink composition to the desired viscosity. In one embodiment, the solvent is present in an amount from about 5% by weight to about 95% by weight. In another embodiment, the solvent is present in an amount from about 10% by weight to about 75% by weight. In yet another embodiment, the solvent is present in an amount from about 20% by weight to about 50% by weight. The solvent weight percentage is based on the weight of the ink composition.

[0086] A variety of solvent systems proven effective in the printing industry can be used to formulate phosphor particles into inks. A suitable solvent has a boiling point and polarity that matches the desired printing application and does not adversely interact with the binder materials or phosphors used.

[0087] Solvents can be polar or nonpolar. Examples of solvents include, but are not limited to: acetone, ethylene glycol ethers (such as diethylene glycol methyl ether), propylene methacrylates (such as propylene glycol dimethacrylate), cyclic aromatic solvents (such as toluene, xylene, and anisole), aliphatic solvents (such as hexane and tetradecane), alcohols (such as ethanol, isopropanol, and octanol), glycols (such as ethylene glycol and propylene glycol), terpineol, acetates (such as butyl acetate, propylene glycol methyl ether acetate (PGMEA)), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), diethylene glycol methyl ether (DGME), and ethyl 2-(2-butoxyethoxy)acetate (BEA).

[0088] Cosolvents and solvent mixtures can also be used to improve fluid dynamics, printing processes, and film-forming properties. Solvent mixtures can consist of any two or more of the solvents listed above, or they can consist of one of the solvents with a small amount of a common organic solvent added.

[0089] The ink composition comprises a phosphor material having a D50 particle size ranging from about 0.5 to about 15 micrometers. For the preparation of the ink composition, for printing, and for film formation, the particle size needs to be small. In another embodiment, the D50 particle size of the phosphor material ranges from about 0.5 micrometers to about 10 micrometers. In another embodiment, the D50 particle size of the phosphor material ranges from about 0.5 micrometers to about 5 micrometers. In some embodiments, as discussed above, the ink composition comprises a rare-earth garnet phosphor (e.g., YAG) and a Mn4+ doped phosphor (e.g., PFS). In some embodiments, the D50 particle size of the rare-earth garnet phosphor ranges from about 0.5 to about 15 micrometers. In another embodiment, the D50 particle size of the rare-earth garnet phosphor ranges from about 0.5 micrometers to about 10 micrometers. In another embodiment, the D50 particle size of the rare-earth garnet phosphor ranges from about 0.5 micrometers to about 5 micrometers.

[0090] D50 (also represented as D) 50 D90 is defined as the median granularity of the volume distribution. 90 D10 is a particle size larger than 90% of the particles in the volume distribution. 10 The particle size distribution is larger than the 10% of particles in the distribution. The particle size of phosphors can be easily measured by laser diffraction or optical microscopy, and commercially available software can generate particle size distributions and spans. The span is a measure of the width of the particle size distribution curve for particulate materials or powders, and is defined by the following formula:

[0091]

[0092] Where D 90 D 10 and D 50 As defined above. For phosphor particles, the range of particle size distribution is not necessarily limited and can be ≤1.0 in some embodiments.

[0093] The viscosity of the ink composition is from about 10 cP to about 30,000 cP. In another embodiment, the viscosity is from about 1,000 cP to about 30,000 cP.

[0094] In some embodiments, the ink composition is a low-viscosity ink composition. The low-viscosity ink composition comprises a viscosity ranging from about 10 cP to about 1000 cP. In another embodiment, the viscosity of the low-viscosity ink composition is in the range of about 10 cP to less than 1000 cP. Particles can easily precipitate from the low-viscosity ink composition, therefore it is desirable to include phosphor materials with very small particle sizes. The low-viscosity ink composition can be used in printing applications such as banked structures or well structures.

[0095] In one embodiment, the ink composition is a medium viscosity ink composition. A medium viscosity ink composition includes a viscosity ranging from about 1,000 cP to about 10,000 cP. In another embodiment, the viscosity is in the range of greater than 1,000 cP to less than 10,000 cP.

[0096] In one embodiment, the ink composition is a high-viscosity ink composition. The high-viscosity ink composition includes a viscosity ranging from about 10,000 cP to about 30,000 cP. In another embodiment, the viscosity is in the range of greater than 10,000 cP to about 30,000 cP.

[0097] The viscosity range is the initial viscosity range of the ink composition.

[0098] Additional additives can be added to the ink composition to further adjust the ink or film properties, such as adhesion or cohesion, light scattering, evaporation rate, stability, shelf life, etc.

[0099] In one embodiment, the ink composition comprises a scattering aid, such as ZrO2 nanoparticles. Examples of scattering particles include, but are not limited to: titanium dioxide, aluminum oxide (Al2O3), zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF), aluminum fluoride (AlF3), or combinations thereof. In other embodiments, additional additives improve film quality, such as pentaerythritol tetra(3-mercaptopropionate) (BB PTh) from Bruno Bock.

[0100] The additive can be added to the ink composition in an amount of about 5% to about 20% by weight, based on the weight of the ink composition.

[0101] External heating can be used to improve the flowability of ink compositions, but it should be noted that prolonged exposure to temperatures above 65°C may lead to premature curing.

[0102] The ink company uses solvent-based mixing and removal methods for preparation.

[0103] The phosphor is mixed with a solvent or binder material until the phosphor is dispersed in the solvent and the solvent is partially removed. In some embodiments, the solvent is optional. Typically, the base ink, additives, and a small amount of solvent are mixed together, and then the phosphor material is added in 2-4 increments, mixing between additions. Additional solvent may be required to achieve the desired viscosity for good dispersion and coating.

[0104] When more than one phosphor (such as YAG) is present, the second phosphor can be added first, followed by Mn in increments of approximately 2g. 4+ Phosphor. In one embodiment, the solution is vortexed between each powder addition. For example, the solution may be vortexed for 1 minute after each sample. In another embodiment, the mixture may be hornsonicated.

[0105] Once the particles are properly dispersed and homogenized, the solvent is partially removed. This process allows for the incorporation of large quantities of particles and enables the end user to control the viscosity by how much solvent remains in the final formulation.

[0106] In one embodiment, the suspension is subjected to rotary evaporation until the desired amount of solvent is removed.

[0107] The ink solution can be cured after it has been applied to the printing technique described herein. The ink solution can also be applied to a substrate or formed into a film. In one embodiment, the ink composition is subjected to a suitable temperature for thermal curing or to a suitable radiation wavelength for UV curing, such as less than 400 nm.

[0108] In one embodiment, the ink composition is applied using a two-step curing process involving UV and thermal curing. The system contains both photosensitive and thermosensitive groups. The first curing process utilizes UV curing to softly cure the material in place. The wavelength used for polymerization initiation is less than 400 nm (classified as UV curing). The second curing step is thermal curing, which uses heat to initiate the remaining polymerization reaction. The second curing step acts as an adhesion or through-cure mechanism. In the film, the second step can reduce the volume of the deposited film through shrinkage.

[0109] The advantage of a two-step curing method for film curing is that it allows for adjustment of the degree of shrinkage of the deposited film and the shrinkage point during the process. The concentration of PFS can be adjusted by changing the film densification mechanism, depending on the content of each polymerization initiator. UV-curing systems rely on UV radiation contacting every surface, and one cannot assume curing in shaded or deeper areas. Thermal curing alone is typically slow, and therefore, "sinking" or separation / peeling can occur in the deposited ink. It is conceivable to use UV curing for "soft curing," followed by thermal curing for "thorough curing" of the shape or film.

[0110] A two-step curing method can also be used to form one feature on top of another cured feature by UV curing, followed by thermal curing to further "bond" the two layers together.

[0111] Phosphor materials may include one or more other luminescent materials. Additional luminescent materials, such as blue, yellow, red, orange, or other colored phosphors, may be used in phosphor materials to customize the white light produced and generate a specific spectral power distribution.

[0112] Suitable phosphors for use in phosphor materials include, but are not limited to: ((Sr 1-z [Ca,Ba,Mg,Zn] z ) 1-(x+w) [Li,Na,K,Rb] w Ce x )3(Al 1-y Si y )O 4+y+3(x-w) F 1-y-3(x-w) (0 <x≤0.10,0≤y≤0.5,0≤z≤0.5,0≤w≤x);[Ca,Ce]3Sc2Si3O 12 (CaSiG); [Sr,Ca,Ba]3Al 1-x Si x O 4+x F 1-x :Ce 3+ (SASOF));[Ba,Sr,Ca]5(PO4)3[Cl,F,Br,OH]:Eu 2+ ,Mn 2+ [Ba,Sr,Ca]BPO5:Eu 2+ ,Mn 2+ [Sr,Ca] 10 (PO4)6*vB2O3:Eu 2+ (where 0) <v≤1);Sr2Si3O8*2SrCl2:Eu 2+ [Ca,Sr,Ba]3MgSi2O8:Eu 2+ ,Mn 2+; BaAl8O 13 :Eu 2+ ; 2SrO*0.84P2O5*0.16B2O3:Eu 2+ ; [Ba,Sr,Ca]MgAl 10 O 17 :Eu 2+ ,Mn 2+ ; [Ba,Sr,Ca]Al2O4:Eu 2+ ; [Y,Gd,Lu,Sc,La]BO3:Ce 3+ ,Tb 3+ ; ZnS:Cu + ,Cl - ; ZnS:Cu + ,Al 3+ ; ZnS:Ag + ,Cl - ; ZnS:Ag + ,Al 3+ ; [Ba,Sr,Ca]2Si 1-n O 4-2n :Eu 2+ (where 0 ≤ n ≤ 0.2); [Ba,Sr,Ca]2[Mg,Zn]Si(2)O7:Eu 2+ ; [Sr,Ca,Ba][Al,Ga,In]2S4:Eu 2+ ; [Y,Gd,Tb,La,Sm,Pr,Lu]3[Al,Ga] 5-a O 12-3 / 2a :Ce 3+ (where 0 ≤ a ≤ 0.5); [Ca,Sr]8[Mg,Zn](SiO4)4Cl2:Eu 2+ ,Mn 2+ ; Na2Gd2B2O7:Ce 3+ ,Tb 3+ ; [Sr,Ca,Ba,Mg,Zn]2P2O7:Eu 2+ ,Mn 2+ ; [Gd,Y,Lu,La]2O3:Eu 3+ ,Bi 3+ ; [Gd,Y,Lu,La]2O2S:Eu 3+ ,Bi 3+ ; [Gd,Y,Lu,La]VO4:Eu 3+ ,Bi 3+ ; [Ca,Sr,Mg]S:Eu 2+ ,Ce 3+ ; SrY2S4:Eu 2+ ; CaLa2S4:Ce 3+; [Ba, Sr, Ca]MgP2O7:Eu 2+ , Mn 2+ ; [Y, Lu]2WO6:Eu 3+ , Mo 6+ ; [Ba, Sr, Ca] b Si g N m :Eu 2+ (where 2b + 4g = 3m); Ca3(SiO4)Cl2:Eu 2+ ; [Lu, Sc, Y, Tb] 2-u-v Ce v Ca 1+ u Li w Mg 2-w P w [Si, Ge] 3-w O 12-u / 2 (where 0.5 ≤ u ≤ 1, 0 < v ≤ 0.1 and 0 ≤ w ≤ 0.2); [Y, Lu, Gd] 2-m [Y, Lu, Gd]Ca m Si4N 6+m C 1-m :Ce 3+ (where 0 ≤ m ≤ 0.5); [Lu, Ca, Li, Mg, Y], α - SiAlON, doped with Eu 2+ and / or Ce 3+ ; Sr(LiAl3N4):Eu 2+ , [Ca, Sr, Ba]SiO2N2:Eu 2+ , Ce 3+ ; β - SiAlON:Eu 2+ ; 3.5MgO*0.5MgF2*GeO2:Mn 4+ ; Ca 1-c-f Ce c Eu f Al 1+c Si 1-c N3 (where 0 ≤ c ≤ 0.2, 0 ≤ f ≤ 0.2); Ca 1-h-r Ce h Eu r Al 1-h (Mg, Zn) h SiN3 (where 0 ≤ h ≤ 0.2, 0 ≤ r ≤ 0.2); Ca 1-2s-t Ce s [Li, Na] s Eu t AlSiN3 (where 0 ≤ s ≤ 0.2, 0 ≤ t ≤ 0.2, s + t > 0); [Sr, Ca]AlSiN3:Eu2+ Ce 3+ and Li2CaSiO4:Eu 2+ .

[0113] In a specific implementation scheme, the additional phosphor includes: [Y,Gd,Lu,Tb]3[Al,Ga]5O 12 :Ce 3+ β-SiAlON:Eu 2+ [Sr,Ca,Ba][Ga,Al]2S4:Eu 2+ [Li,Ca]α-SiAlON:E u 2+ [Ba,Sr,Ca]2Si5N8:Eu 2+ [Ca,Sr]AlSiN3:Eu 2+ [Ba,Sr,Ca]LiAl3N4:Eu 2+ [Sr,Ca,Mg]S:Eu 2+ and [Ba,Sr,Ca]2Si2O4:Eu 2+ .

[0114] The phosphor material may include at least one green-emitting phosphor. The green-emitting phosphor may include any suitable green-emitting phosphor, including uranium phosphors. In one embodiment, the green-emitting uranium phosphor includes, but is not limited to: Ba3(PO4)2(UO2)2P2O7, Ba3(PO4)2(UO2)2V2O7, γγ-Ba2UO2(PO4)2, BaMgUO2(PO4)2, BaZnUO2(PO4)2, Na2UO2P2O7, K2UO2P2O7, Rb2UO2P2O7, Cs2UO2P2O7, and K4UO2(PO4). 2、 K4UO2(VO4)2 or NaUO2P3O9, as described in U.S. Patent No. 11,254,864 and incorporated herein by reference.

[0115] Other suitable additional luminescent materials for use in ink compositions may include electroluminescent polymers such as polyfluorene, preferably poly(9,9-dioctylfluorene) and its copolymers, such as poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole); and polystyrene and its derivatives. Furthermore, the luminescent layer may include blue, yellow, orange, green, or red phosphorescent dyes or metal complexes, quantum dot materials, or combinations thereof. Materials suitable for use as phosphorescent dyes include, but are not limited to: tris(1-phenylisoquinoline)iridium(III) (red dye), tris(2-phenylpyridine)iridium (green dye), and bis(2-(4,6-difluorophenyl)pyridine-N,C2)iridium(III) (blue dye). Fluorescent and phosphorescent metal complexes commercially available from ADS (American Dyes Source, Inc.) may also be used. ADS green dyes include ADS060GE, ADS061GE, ADS063GE, ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

[0116] Exemplary QD materials include, but are not limited to: group II-IV compound semiconductors, such as CdS, CdSe, CdS / ZnS, CdSe / ZnS, or CdSe / CdS / ZnS; group II-VI semiconductors, such as CdTe, ZnSe, ZnTe, ZnS, HgTe, HgS, HgSe, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, HgST e, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; III-V or IV-VI compound semiconductors, such as GaN, GaP, GaNP, GaNAs, GaPAs, GaAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, AlN, AlNP, AlNAs, AlP, AlPAs, AlAs, InN, InNP, InP, InNAs, InPAs, InAS, InAlNP, InAlNAs, InAlPAs, PbS / ZnS or PbSe / ZnS; Group IV, such as Si, Ge, SiC and SiGe; Chalcopyrite-type compounds, including but not limited to CuInS2, CuInSe2, CuGaS2, CuGaSe2, AgInS2, AgInSe2, AgGaS2, AgGaSe2 or perovskite QD, having the formula ABX3, wherein A is cesium, methylammonium or formamidinium, B is lead or tin and C is chloride, bromide or iodide. Quantum dot materials may include core-shell nanostructures with an Ag-In-Ga-S (AIGS) core and an Ag-Ga-S (AGS) shell.

[0117] In one embodiment, the perovskite quantum dots may be CsPbX3, where X is Cl, Br, I, or a combination thereof. The average size of the QD material may range from about 2 nm to about 20 nm. The surface of the QD particles may be further modified with ligands (such as amine ligands, phosphine ligands, phospholipids, and polyvinylpyridine). In one aspect, the red phosphor may be a quantum dot material.

[0118] All semiconductor quantum dots may also have a suitable shell or coating for passivation and / or environmental protection. The QD material may be a core / shell QD, comprising a core, at least one shell coated on the core, and an outer coating comprising one or more ligands (preferably organic polymer ligands). Exemplary materials for preparing core-shell QDs include, but are not limited to: Si, Ge, Sn, Se, Te, B, C (including diamond), P, Co, Au, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdS e, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, MnS, MnSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si3N4, Ge3N4, Al2O3, [Al,Ga,In]2[S,Se,Te]3, and suitable combinations of two or more of these materials. Exemplary core-shell luminescent nanocrystals include, but are not limited to: CdSe / ZnS, CdSe / CdS, CdSe / CdS / ZnS, CdSeZn / CdS / ZnS, CdSeZn / ZnS, InP / ZnS, PbSe / PbS, PbSe / PbS, CdTe / CdS, and CdTe / ZnS.

[0119] The ratios of individual phosphors and other luminescent materials in an ink composition can be varied according to the desired light output characteristics. The relative proportions of individual phosphors and other luminescent materials in various ink compositions can be adjusted so that when their emissions are combined and used in a device (e.g., a lighting device), visible light with predetermined x and y values ​​is present on the CIE chromaticity diagram.

[0120] In one embodiment, one or more films can be prepared from an ink composition. The one or more films can be deposited on a substrate, such as a glass substrate and / or a flexible substrate. For example, one or more films can be deposited on a substrate comprising a polymeric material, such as polyethylene terephthalate (PET). In some embodiments, one or more films further include a plastic layer disposed over the ink composition. The plastic layer may comprise a polymer, such as PET. Additionally or alternatively, one or more films further include a dichroic filter disposed on a first side or a second side of the substrate, wherein the second side of the substrate is the side of the substrate on which the ink composition is deposited, and the first side of the substrate is opposite to the second side. Additionally or alternatively, one or more films further include a reflective layer disposed on the first side or a second side of the substrate, wherein the second side of the substrate is the side of the substrate on which the ink composition is deposited, and the first side of the substrate is opposite to the second side. One or more films can be deposited on LEDs (such as mini-LEDs or micro-LEDs) such as by coating, using a doctor's blade, or by printing. In one embodiment, the film is prepared by coating the ink composition onto the substrate with a doctor's blade. The solvent can then be removed, and the film can be cured, for example, by UV light or thermal curing. In one embodiment, the film is prepared by partially curing an ink composition, such as by UV light or thermal curing (e.g., using UV light or heat to remove a portion of the solvent). The film is then deposited on an LED (e.g., a mini LED, a micro LED, etc.) and then fully cured, for example, by UV light or thermal curing (e.g., using UV light or heat to remove the remaining solvent). By partially curing, depositing on the LED, and then fully curing, the film adheres better to the LED.

[0121] Additional processes for preparing phosphor compositions that can be used with the systems and methods described herein are described in PCT application No. PCT / US2023 / 020966, filed May 4, 2023, entitled “RED-EMITTING PHO SPHORS HAVING SMALL PARTICLE SIZE, PROCESSES FOR PREPARING AND DEVICES THEREOF”, which is incorporated herein by reference in its entirety.

[0122] In one embodiment, the lighting device includes the device. In another embodiment, the backlight device includes the device. In another embodiment, the display includes the device. In another embodiment, the device is a self-emissive display and does not include a liquid crystal display (LCD). In one embodiment, the display is a micro-LED display, such as a phosphor-converted micro-LED display.

[0123] The apparatus according to this disclosure includes an LED light source that is radiatively connected to and / or optically coupled to a phosphor composition. Figures 1A to 1E An apparatus 10 according to various embodiments of the present disclosure is shown. Reference Figure 1A The device 10 includes an LED light source 12 and a phosphor composition 14. The LED light source 12 may be a UV-emitting or blue-emitting LED. In some embodiments, the LED light source 12 produces blue light with a wavelength range of about 380 nm to about 460 nm. In the device 10, the phosphor composition 14 is radiatively coupled and / or optically coupled to the LED light source 12. Radiative connection or coupling or optical coupling means that radiation from the LED light source 12 can excite the phosphor composition 14, and the phosphor composition 14 can emit light in response to the excitation of radiation. The phosphor composition 14 may be disposed on a portion or part of the LED light source 12, or located at a distance from the LED light source 12. In some embodiments, the device may be a backlight unit for display applications. In other embodiments, the LED light source 12 is a micro-LED, and the device is used for a self-emissive display. Figure 1B An exemplary embodiment is shown in which the phosphor composition 14 is disposed on an LED light source 12. The LED light source 12 is disposed on a reflective layer 16. The reflective layer 16 reflects light from the LED light source 12 toward the LED light source and the phosphor composition 14. The reflective layer 16 may be any material suitable for reflecting light. In one embodiment, the reflective layer 16 may be a metallic layer, such as aluminum, silver, a silver alloy, or an aluminum alloy. Figure 1C An exemplary embodiment is shown in which the phosphor composition 14 is disposed on the LED light source 12. An encapsulating material layer or barrier layer 18 is disposed on the phosphor composition 14. The encapsulating material layer or barrier layer 18 may be a low-temperature glass, or a polymer or resin known in the art, such as epoxy resin, silicone resin, epoxy-silicone resin, acrylate, or a combination thereof. The encapsulating material layer or barrier layer 18 should be transparent to allow light to pass through these elements. Figure 1D An exemplary embodiment of an LED light source 14 is shown, depicted as an array of LED light sources 12. In some embodiments, the LED light source 12 is a miniature LED or a micro LED. Figure 1E An exemplary embodiment is shown in which the phosphor composition 14 is located away from the LED light source 12 (which is depicted as an array of LED light sources 12).

[0124] The general discussion of the example LED light sources discussed in this article refers to light sources based on inorganic LEDs. Many white LEDs are based on GaInN chips that emit blue or UV light. In addition to inorganic LED light sources, the term LED light source is also intended to encompass all LED light sources, such as semiconductor laser diodes (LDs), organic light-emitting diodes (OLEDs), or hybrids of LEDs and LDs. LED light sources can be miniature LEDs or micro-LEDs, which can be used in self-emissive displays. Furthermore, it should be understood that, unless otherwise indicated, an LED light source can be replaced, supplemented, or enhanced by another radiation source, and any reference to semiconductors, semiconductor LEDs, or LED chips refers only to any suitable radiation source, including but not limited to LDs and OLEDs.

[0125] The phosphor composition 14 can be present in any form, such as powder, glass, or composite material (e.g., phosphor-polymer composite or phosphor-glass composite). Furthermore, the phosphor composition 14 can be used as a layer, sheet, film, strip, dispersed microparticle, or combination thereof. In some embodiments, the phosphor composition 14 comprises a uranium-based phosphor material in glass form. In some embodiments of these embodiments, the device 10 may comprise the phosphor composition 14 in the form of a phosphor wheel (not shown). The phosphor wheel may comprise a phosphor composition embedded in glass. A phosphor wheel and related device are described in WO 2017 / 196779.

[0126] The phosphor composition is optically coupled or radiatively connected to an LED light source. In one embodiment, a white light composite can be obtained by fusing red and green phosphor materials with an LED light source, such as a blue or UV LED.

[0127] Figure 2 A lighting device or luminaire 20 according to some embodiments is shown. In one embodiment, the lighting device 20 may be a backlight device. The lighting device 20 includes an LED chip 22 and leads 24 electrically attached to the LED chip 22. The leads 24 may include thin wires supported by a thicker lead frame 26, or the leads 24 may include self-supporting electrodes and the lead frame may be omitted. The leads 24 supply current to the LED chip 22, and thus cause it to emit radiation.

[0128] A phosphor composition layer 30 is disposed on the surface of the LED chip 22. The phosphor layer 30 can be disposed by any suitable method, such as using a paste or ink composition prepared by mixing a phosphor composition with a binder material or solvent (as discussed above). In one such method, a silicone slurry in which phosphor composition particles are randomly suspended or uniformly dispersed is placed around the LED chip 22. This method merely exemplifies the possible positions of the phosphor layer 30 and the LED chip 22. The phosphor layer 30 can be coated onto the light-emitting surface of the LED chip 22 by applying the slurry over it and drying the slurry, or directly onto the light-emitting surface. Light emitted by the LED chip 22 mixes with light emitted by the phosphor composition to produce the desired emission.

[0129] Continue to refer to Figure 3 The LED chip 22 may be encapsulated within a housing 28. The housing 28 may be formed of, for example, glass or plastic. The LED chip 22 may be encapsulated by an encapsulation material 32. The encapsulation material 32 may be a low-temperature glass, or a polymer or resin known in the art, such as epoxy, silicone, epoxy-silicone, acrylate, or combinations thereof. In an alternative embodiment, the lighting device 20 may include only the encapsulation material 32, without the housing 28. Both the housing 28 and the encapsulation material 32 should be transparent to allow light to pass through these elements.

[0130] In such Figure 3 In some embodiments shown, the phosphor composition 33 is dispersed within the encapsulation material 32, rather than as... Figure 4 The phosphor composition 33 is formed directly on the LED chip 22. It may be dispersed within a portion of the encapsulation material 32 or throughout the entire volume of the encapsulation material 32. Blue or UV light emitted by the LED chip 22 mixes with light emitted by the phosphor composition 33, and the mixed light is transmitted from the lighting device 20.

[0131] In yet another embodiment, the phosphor composition layer 34 is coated onto the surface of the housing 28, instead of as... Figure 4 As shown, a phosphor layer 34 is formed on the LED chip 22. As shown, the phosphor layer 34 is coated on the inner surface 29 of the housing 28, but if desired, the phosphor layer 34 can also be coated on the outer surface of the housing 28. The phosphor layer 34 can be coated on the entire surface of the housing 28, or only on the top portion of the inner surface 29 of the housing 28. The UV / blue light emitted by the LED chip 22 mixes with the light emitted by the phosphor layer 34, and the mixed light is transmitted. Of course, the phosphor composition can be located at any two or all three locations (e.g., ...). Figures 4 to 6(as shown) or any other suitable location, such as separate from, away from, or integrated into the LED chip 22. In one embodiment, the phosphor layer 34 may be a film and located away from the LED chip 22. In another embodiment, the phosphor layer 34 may be a film and disposed on the LED chip 22. In some embodiments, the phosphor layer 34 may be applied to the LED chip 22 as an ink composition. In some embodiments, the phosphor layer 34 may be applied to the LED chip 22 as an ink composition and dried to form a film on the LED chip 22. In some embodiments, the phosphor composition may be a single layer or multiple layers. In some embodiments, the film is a multilayer structure, wherein each layer in the multilayer structure includes at least one phosphor or quantum dot material. In another embodiment, the device structure includes a phosphor composition layer on the LED chip and a remote layer comprising quantum dot material. In another embodiment, the device structure includes a phosphor composition layer on the LED chip and a remote layer comprising both quantum dot material and phosphor material. In another embodiment, the device structure includes a phosphor composition layer on the LED chip and a film comprising quantum dot material located away from the LED chip. In another embodiment, the device structure includes a phosphor composition layer on an LED chip and a film comprising quantum dot material and phosphor material located away from the LED chip.

[0132] In Figure 1 to Figure 4 In any of the above-described structures, the lighting device 20 may further include a plurality of scattering particles (not shown) embedded in the encapsulation material 32. The scattering particles may include, for example, alumina, silicon dioxide, zirconium oxide, or titanium dioxide. The scattering particles effectively scatter the directional light emitted from the LED chip 22, preferably with negligible absorption.

[0133] In one embodiment, lighting device 20 (shown in) Figure 3 and Figure 4 (The image shows) a backlight device. In another embodiment, the backlight device includes a backlight unit 10. Some embodiments include a surface mount device (SMD) type light-emitting diode 50 (shown in...) for backlight applications. Figure 5A , Figure 5B and Figure 5C (Chinese). Reference Figure 5A The SMD is a "side-emitting type" and has a light-emitting window 52 on the protruding portion of the light guide member 54. The SMD package includes an LED chip 56 as defined above and a phosphor composition 58 as described herein. Figure 5B The phosphor composition 58 is shown disposed on the LED chip 56, while Figure 5C The phosphor composition 58 is shown disposed away from the LED chip 56. Figure 5Band Figure 5C The diagram also shows an LED chip 56 and a light guide member 54 disposed on a reflective layer 59. The reflective layer 59 reflects light from the LED chip 56 and the light guide member 54 toward the phosphor composition 58. The reflective layer 59 can be any material suitable for reflecting light. In one embodiment, the reflective layer 59 can be a metallic layer, such as silver, aluminum, an aluminum alloy, or a silver alloy. In another embodiment, the device can be a direct-light display.

[0134] By using the phosphor compositions described herein, devices can be provided to generate white light for display applications, such as LCD backlight units, wherein the devices have a high color gamut and high luminosity. Alternatively, devices can be provided to generate white light for general illumination, wherein the devices have high luminosity and high CRI values ​​over a wide range of color temperatures of interest (e.g., 2000K to 10,000K).

[0135] The devices disclosed herein include lighting and display apparatuses for general lighting and display applications. Examples of display apparatuses include liquid crystal display (LCD) backlight units, televisions, computer monitors, automotive displays, laptop computers, notebook computers, mobile phones, smartphones, tablet computers, and other handheld devices. In the case where the display is a backlight unit, a phosphor composition may be incorporated into a film, sheet, or strip radiatively coupled and / or optically coupled to an LED light source, as described in U.S. Patent Application Publication No. 2017 / 0254943. The film, sheet, or strip may be any film, sheet, or strip described herein. Examples of other apparatuses include chromatic lamps, plasma screens, xenon lamps, UV-excited marking systems, automotive headlights, automotive taillights, cinema projectors, laser pumping devices, and point sensors. In one embodiment, the apparatus may be a fast-response display excluding an LCD. A fast-response display may be a self-emissive display comprising micro-LEDs of phosphor conversion (PC). In some embodiments, the apparatus is a substantially transparent, fully transparent, and / or translucent display. For example, the apparatus may include an automotive windshield. In some implementations, the device includes a head-up display (e.g., any transparent display that presents data without requiring the user to look away from their normal viewing angle). Head-up displays can include automotive head-up displays, aircraft head-up displays, military vehicle head-up displays, augmented reality (AR) head-up displays, and / or virtual reality (VR) head-up displays. This list of applications is intended to be exemplary only and not exhaustive.

[0136] In some embodiments, the phosphor composition is disposed remotely from the LED. The phosphor composition disposed at a distance may include a film comprising the phosphor composition. In some embodiments, a single film comprising the phosphor composition may be disposed over multiple LEDs (e.g., small-sized LEDs, such as arrays or rows of mini-LEDs or micro-LEDs). In other embodiments, a separate film comprising the phosphor composition may be disposed over each of the multiple LEDs. Alternatively or additionally, the phosphor composition may be coated onto one or more LEDs. For example, in some embodiments, the phosphor composition may be coated onto one or more LEDs and disposed thereat a distance.

[0137] In some embodiments, the membrane comprises phosphors having micron or submicron particle sizes. In other embodiments, the membrane comprises nanoscale particles. In one embodiment, the membrane comprises Mn 4+ The doped phosphor has a D50 particle size of less than 20 μm, less than 10 μm, particularly less than 5 μm, and more particularly nanoscale. In another embodiment, the D50 particle size can be from about 1 micrometer to about 20 micrometers. In another embodiment, the D50 particle size is from about 1 micrometer to about 15 micrometers. In another embodiment, the D50 particle size is from about 1 micrometer to about 10 micrometers. In another embodiment, the D50 particle size is from about 1 micrometer to about 5 micrometers. In another embodiment, the D50 particle size is from about 1 micrometer to about 3 micrometers. In another embodiment, the D50 particle size is from about 50 nm to about 1000 nm. In another embodiment, the D50 particle size is from about 100 nm to about 1000 nm. In another embodiment, the D50 particle size is from about 200 nm to about 1000 nm. In another embodiment, the D50 particle size is from about 250 nm to about 1000 nm. In another embodiment, the D50 particle size is from about 500 nm to about 1000 nm. In another embodiment, the D50 particle size is from about 750 nm to about 1000 nm. In another embodiment, the D50 particle size is from about 50 nm to about 10 micrometers. In another embodiment, the D50 particle size is from about 200 nm to about 5 micrometers. In another embodiment, the D50 particle size is from about 250 nm to about 5 micrometers. In another embodiment, the D50 particle size is from about 500 nm to about 5 micrometers. In another embodiment, the D50 particle size is from about 750 nm to about 5 micrometers. In another embodiment, the D50 particle size is from about 750 nm to about 3 micrometers.

[0138] In some embodiments, one or more LEDs (e.g., an LED array or LED bar) are disposed on a reflective surface. The reflective surface causes light from the LED light source to be reflected toward the LED and phosphor composition. The reflective surface can be any material suitable for reflecting light. In one embodiment, the reflective surface can be a metallic layer, such as aluminum, silver, a silver alloy, or an aluminum alloy. For example, the reflective surface can contain TiO2, ZrO2, ZnO2, BaSO4, or any combination thereof. In some embodiments, one or more LEDs (e.g., an LED array or LED bar) are disposed on a glass substrate. In some embodiments, one or more LEDs (e.g., an LED array or LED bar) are disposed on a flexible surface. The flexible surface may contain a polymer material.

[0139] Figure 6 This is a schematic diagram of a contact stencil printing system 100 according to one embodiment of the present disclosure. The contact stencil printing system 100 can be used to deposit a composition such as phosphor ink onto a target substrate including multiple light-emitting elements (including but not limited to LEDs, mini LEDs, OLEDs, or micro LEDs).

[0140] The contact stencil printing system 100 may include a substrate 102, a substrate support 104, a stencil 106, a stencil frame clamp 108, and an alignment adjuster 112. The stencil 106 may be fabricated on a flexible 2-mil, 3-mil, and 5-mil polyimide substrate. These thicknesses are provided by way of example only, and various other thicknesses may be used. In some embodiments, the stencil 106 is made of… or It is made from a polyimide substrate.

[0141] Template 106 includes one or more openings. The one or more openings may include various shapes (e.g., circular, rectangular, square, or any other shape) with width and / or length dimensions as small as 25 μm. The one or more openings may be formed via a laser cutting tool and may include various patterns, lengths, widths, and orientations. For example, the configuration of the one or more openings may take into account parameters of the composition being deposited, including but not limited to the composition's viscosity, wettability, solvent type, quantity, epoxy / emulsion type, and / or PFS to YAG ratio.

[0142] The template 106 can be held in place by a plurality of template frame clamps 108. The template 106 is placed above a substrate 102, which is supported by a plurality of supports 104. The substrate 102 and the supports 104 can be located on an adjustable surface 110. The adjustable surface 110 can be adjusted vertically via an alignment adjuster 112. More specifically, the alignment adjuster can be configured to adjust the position of the substrate 102 relative to the template 106 such that the template 106 contacts the substrate 102.

[0143] In some embodiments, composition transfer using the stencil printing system 100 occurs because the doctor blade 120 moves across the stencil 106 and simultaneously presses the stencil 106 downward, thereby bringing the stencil 106 into contact with the substrate 102. Printing speed (e.g., the squeezing motion on the stencil) is important because slow printing results in more and / or wider material transfer due to the longer contact time between the stencil and the substrate, while faster printing speeds result in more controlled material transfer due to the short-term interaction between the substrate and the stencil.

[0144] Figure 7 This is a schematic diagram of a stencil printing system 150 according to one embodiment of the present disclosure. The stencil printing system 200 can be used to deposit compositions such as phosphor inks onto target substrates (such as LEDs, mini-LEDs, OLEDs, or micro-LEDs). The stencil 106 can be fabricated on flexible 2-mil, 3-mil, and 5-mil polyimide substrates. These thicknesses are provided by way of example only, and various other thicknesses can be used. In some embodiments, the stencil 106 is made of… or It is made from a polyimide substrate.

[0145] Template 106 includes one or more openings. The one or more openings may include various shapes (e.g., circular, rectangular, square, or any other shape) with width and / or length dimensions as small as 25 μm. The one or more openings may be formed via a laser cutting tool and may include various patterns, lengths, widths, and orientations. The configuration of the one or more openings may take into account parameters of the composition being deposited, including but not limited to the composition's viscosity, wettability, solvent type, quantity, epoxy / emulsion type, and / or PFS to YAG ratio.

[0146] Similar to the contact stencil printing system 100, the strip stencil printing system 150 may include a substrate 102, a substrate support 104, a stencil 106, stencil frame clamps 108, and an alignment adjuster 112. The stencil 106 can be held in place by a plurality of stencil frame clamps 108. The stencil 106 is placed above the substrate 102, which is supported by a plurality of supports 104. The substrate 102 and the supports 104 may be located on an adjustable surface 110. The adjustable surface 110 can be adjusted vertically via the alignment adjuster 112. More specifically, the alignment adjuster may be configured to adjust the position of the substrate 102 relative to the stencil 106 such that the stencil 106 contacts the substrate 102. Printing speed (e.g., the squeezing motion on the stencil) is important because slow printing results in more and / or wider material transfer because the stencil remains in contact with the substrate for a longer period, while faster printing speeds result in more controlled material transfer because of the short-term interaction between the substrate and the stencil.

[0147] However, the printing system 150 also includes one or more release elements or spacers 130. The spacers 130 are located between the substrate 102 and the stencil 106, thereby separating the substrate 102 and the stencil 106 by a certain distance. Generally, the farther the spacers 130 are from the substrate 102, the smaller the difference in contact angle between the stencil opening and the substrate 102, thus achieving better printing uniformity over a large printing area. The composition transfer occurring using the stencil printing system 150 also occurs because the doctor blade 120 moves past the stencil 106 and simultaneously presses the stencil 106 downwards, thereby bringing the stencil 106 into contact with the substrate 102.

[0148] In exemplary embodiments, the template 106 is stretched uniformly over the substrate 102. In some embodiments, the template 106 is cut shorter than the stretch limit of the template frame. Cutting the template 106 shorter than the stretch limit of the template frame helps eliminate bumps that may lead to uneven printing. For example, in some embodiments, the template 106 is stretched to the upper limit of the template frame clamp 108. This may result in the template 106 being stretched uniformly over the entire template area without any bumps, which can lead to uneven printing. In some embodiments, an adhesive, such as tape, is applied to one or more edges of the template 106, causing the template 102 to be stretched further, thereby eliminating any residual bumps and / or undulations in the template. In some embodiments, the adhesive includes polyamide tape.

[0149] In some implementations, calibration is performed prior to composition transfer. More specifically, spacer 130 can cause a mismatch between the stencil opening and the target printing point. Calibration ensures proper alignment between the stencil opening and the target printing point.

[0150] In some implementations, multiple passes can be used to create ink height and / or increase the aspect ratio over the target printing area. The aspect ratio of a geometry is the ratio of its dimensions along its different dimensions. For example, the aspect ratio of a rectangle is the ratio of its long side to its short side (e.g., the width to height ratio when the rectangle is oriented in a "landscape" format). While the spacers 130 of the strip stencil printing system 150 provide controlled and precise ink transfer, non-stencil printing (e.g., printing using the contact stencil printing system 100) enables large-volume ink transfer. In some implementations, performing non-stencil printing (e.g., printing using the contact stencil printing system 100) after strip printing (e.g., using the strip stencil printing system 150) can be used to create material height and / or increase the aspect ratio over the target printing area. Strip printing can transfer a controlled amount of ink to form an ink base, while non-stencil printing can transfer more material onto the ink base. Using the same material base provides better wettability for subsequent printing runs, resulting in better ink transfer and higher print height.

[0151] Figures 8A to 8C This is a schematic diagram of the dike arrangement 200 according to the implementation scheme of this disclosure. More specifically, Figures 8A to 8C A dike arrangement 200 is illustrated at different stages of the dispensing or printing process. Printing and transferring high aspect ratio conversion layers on small feature light-emitting elements (e.g., mini-LEDs and / or micro-LEDs) assembled on a common substrate surface is challenging. Compared to current printing and / or dispensing techniques, the dike arrangement 200 enables the realization of high aspect ratio conversion layers on small feature light-emitting elements in a more efficient and cost-effective manner. For example, in some embodiments, an aspect ratio of at least 0.1 (i.e., 1:10) can be achieved. In another embodiment, the aspect ratio is from about 0.1 to about 10. In another embodiment, the aspect ratio is from about 0.1 to 5. In another embodiment, the aspect ratio is from about 0.5 to 5. In yet another embodiment, the aspect ratio is from about 0.1 to 3, more particularly from 0.1 to 1 and from 0.1 to 0.5.

[0152] exist Figure 8A In this embodiment, multiple light-emitting elements 202 (e.g., LEDs, mini LEDs, and / or micro LEDs) operating with a desired color point (e.g., white light) are disposed on a substrate 210. Figure 8B In this configuration, one or more walls 204 are disposed around each of the plurality of light-emitting elements 202. In some embodiments, each light-emitting element 202 is surrounded by one or more walls 204. For example, each light-emitting element 202 is surrounded by a plurality of walls 204, said walls being square, rectangular, elliptical, circular, or other shapes, thereby forming a dike structure around each light-emitting element 202. Figures 8A to 8D In the illustrated embodiment, each light-emitting element 202 is surrounded by four walls 204 formed on the planar structure 210, which forms a dike structure 206. In other embodiments (such as...) Figure 9 In the illustrated embodiment, wall 204 is formed within layer 244 located on top of planar substrate 210, thereby forming well structure 246. Therefore, the dike arrangement 200 may include each light-emitting element 202 surrounded by dike structure 206 or well structure 246.

[0153] In some embodiments, each dike structure 206 or well structure 246 is filled with an ink composition. The dike structure 206 or well structure 246 prevents the ink composition from spreading, thereby enabling the formation of a thicker film. For example, in some embodiments, the dike structure 206 or well structure 246 enables the formation of films with a thickness of up to about 100 micrometers. In contrast, films formed on light-emitting elements are typically only about 10 micrometers high.

[0154] In some implementations, each dike structure 206 and / or well structure 246 is transmitted via printing (e.g., using...). Figure 6 Contact stencil printing system 100 or Figure 7 The template printing system 150 is filled with an ink composition. In these embodiments, relatively low viscosity inks can be used, which are generally easier to print and have fewer bubbles. Generally, lower viscosity inks result in thinner films, but the dike structure 206 and / or well structure 246 allow for the formation of films up to 100 micrometers thick using relatively low viscosity inks. In other words, the dike structure 206 and / or well structure 246 enable the use of lower viscosity inks with certain advantages (e.g., fewer bubbles) while still allowing for the formation of thick films. In some embodiments, template printing is desirable because it provides control over the printing speed and, with appropriate aperture sizes, allows for the transfer of an appropriate amount of material at the desired location to fill the well structure without any material spilling into the next pixel / filter. Furthermore, in some embodiments including well structures, a relatively thin stencil thickness can be used to assist micrometer-level alignment for better transparency. Additionally, for transparent display applications, the well structure 246 can achieve higher transparency by minimizing the amount of ink composition that diffuses when deposited on the light-emitting element 202.

[0155] The transparent display according to this disclosure may include an array of light-emitting elements (e.g., mini-LEDs or micro-LEDs) disposed on a substrate, each light-emitting element being surrounded by a dike structure 206 in which an ink composition is deposited. The ink composition may be any ink composition described herein, or any ink composition described in PCT application No. PCT / US2023 / 020966, filed May 4, 2023, entitled “RED-EMITTING PHOSPHORSHAVING SMALL PARTICLE SIZE, PROCESSES FOR PREPARING AND DEVICES THEREOF,” which is incorporated herein by reference in its entirety. For example, the ink composition may contain Mn 4+ Doped phosphors (e.g., PFS) and / or rare earth garnet phosphors (e.g., YAG). If the ink composition contains Mn 4+ By doping with phosphors and rare-earth garnet phosphors, the powder ratio (e.g., YAG:PFS) can be adjusted to achieve the desired color point. Rare earth elements include: Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In one embodiment, the rare-earth garnet phosphor is yttrium aluminum garnet phosphor (YAG). In some embodiments, the ink composition contains a high percentage of rare-earth garnet phosphors. In some embodiments, the ink composition contains greater than or equal to 90% by weight of rare-earth garnet phosphors and less than or equal to 10% by weight of Mn. 4+ Doped phosphors. In some embodiments, the ink composition contains greater than or equal to 95% rare earth garnet phosphors and less than or equal to 5% Mn. 4+ Doped phosphors. In some embodiments, the ink composition contains greater than or equal to 99% rare earth garnet phosphors and less than or equal to 1% Mn. 4+ Doped phosphors. In some embodiments, the rare-earth garnet phosphor comprises YAG and Mn. 4+ Doped phosphors include PFS.

[0156] In some embodiments, the substrate comprises a transparent or translucent material. In other embodiments, the substrate comprises a glass substrate. In some embodiments, the transparent display according to this disclosure may be at least 50% transparent, and in some cases at least 60% transparent, and in some cases at least 70% transparent. In some embodiments, the transparent display comprises an array of light-emitting elements laminated in or encapsulated by or otherwise covered by a glass material. In some embodiments, one or more walls 204 of one or more dike structures 206 are composed of a transparent or translucent material.

[0157] In some embodiments, one or more walls 204 are composed of or coated with a reflective material. Additionally or alternatively, a portion of the substrate within each of one or more dike structures 206 is coated with a reflective material. The reflective material may be configured to reflect back all or some of the visible wavelengths incident upon it. In some embodiments, the reflective material may include TiO2, ZrO2, BaSO4, or any combination thereof. The reflective material coated onto portions of the substrate within one or more walls 204 and / or dike structures 206 can increase the brightness of the light-emitting element 202 by minimizing light reflected back toward the light-emitting element 202. In some embodiments, a first portion of the substrate 210 covered by the reflective material has a higher reflectivity than a second portion of the substrate 210 not covered by the reflective material.

[0158] exist Figure 8C In this structure, the dike structure or alternative well structure is filled with an optically active material 230. The optically active material may include downconversion materials, such as phosphors. In some embodiments, the dike structure or alternative well structure is filled by a dispensing and / or printing method. For example, in some embodiments, using… Figure 6 Contact stencil printing system 100 or Figure 7 A stencil printing system 150 is used to fill dike or well structures. A stencil printing system 200 achieves material transfer with high reproducibility and uniformity in a cost-effective manner. In other embodiments, wells are filled via dispensing or printing methods known in the art.

[0159] Figure 10 The composition is deposited on the substrate 300 using a contact stencil printing system 100, and Figure 11 The composition is deposited onto the substrate 400 using a template-free printing system 150. Figure 10 and Figure 11 In both systems, a 3-mil stencil is used, featuring 120μm square openings spaced 450μm apart. Compared to the contact stencil printing system 100, the strip stencil printing system 150 achieves a greater transfer of composition to the surface of the substrate 102. More specifically, the distance introduced by the spacer 130 between the substrate 102 and the stencil 106 facilitates the removal of the stencil openings after the composition has been transferred, resulting in a defined composition transfer. This may result in a high aspect ratio (height to width) of the substrate. A high aspect ratio is desirable because a relatively high height is required to convert blue light emitted from blue light sources (such as OLEDs, LEDs, mini-LEDs, or micro-LEDs) or potential UV light sources into red light.

[0160] Figures 12A to 12DThis includes illustrations showing the aspect ratio of a pattern of printing ink composition deposited using a template. More specifically, Figure 12A This is a three-dimensional illustration 500, showing the height 506 and depth 506 of each of the deposited ink compositions along the width 504 of the substrate. Similarly, Figures 12B to 12D Figures 510, 520, and 530 are shown, illustrating the height 512 of each of the deposited ink compositions along the width 514 of the substrate. (As can be seen from...) Figures 12A to 12D Extracted from [the data], relatively high aspect ratios can be achieved in a reproducible manner using template printing. Figures 12A to 12D In the example shown, an aspect ratio of 0.1 is achieved. In another embodiment, the aspect ratio is from about 0.1 to about 10. In another embodiment, the aspect ratio is from about 0.1 to 5. In another embodiment, the aspect ratio is from about 0.5 to 5. In another embodiment, the aspect ratio is from about 0.1 to 3, more particularly from 0.1 to 1 and from 0.1 to 0.5.

[0161] Figure 13A The image shows a pattern 600 of a printed ink composition deposited using a 2-mil stencil via a stripper stencil. Figure 13B Figure 610 shows the photoluminescence intensity of pattern 600 under light excitation at 457 nm and emission intensity at 630 nm. (See figure 610.) Figure 13A and Figure 13B As clearly shown, stencil printing deposits the ink composition only in the intended location without causing any spillage.

[0162] Figure 14A and Figure 14B This is a schematic diagram of a high-precision pickup and placement system 700 according to an embodiment of this disclosure. More specifically, Figure 14A and Figure 14B The pick and place arrangement 700 is shown at different stages of the high-precision and high-resolution pick and place process. Figure 14A and Figure 14B The process shown can be used for both assembled LED panels and individual LEDs before assembly.

[0163] exist Figure 14A In the middle, the light-emitting element 702 is disposed on the substrate. Figure 14A The emitting surface 704 for preparing each light-emitting element 702 is shown. More specifically, each emitting surface 704 is coated with an optical adhesive 730. Figure 14A In the illustrated embodiment, the optical adhesive 730 is applied to the emitting surface 704 by spraying using a spray nozzle 706. However, the optical adhesive 730 may also be applied to the emitting surface 704 by dispensing or other methods known in the art.

[0164] In some embodiments, a film comprising a phosphor composition may be disposed on a small-sized LED (such as a mini LED or micro LED). In some embodiments, a single film comprising a phosphor composition may be disposed on multiple LEDs (e.g., an array or row of small-sized LEDs, such as mini LEDs or micro LEDs). In other embodiments, a separate film comprising a phosphor composition may be disposed on each of the multiple LEDs.

[0165] Figure 14B The deposition of an optically active film 730 (e.g., a film containing a phosphor material) onto each emitting surface 704 coated with an optical adhesive 730 is illustrated. The size and shape of the optically active film 730 can be designed for the emitting surface 704. For example, prior to assembly, a large area of ​​the optically active film can be cut into small pieces via a laser of a sharp roll cutter or other methods known in the art. Figure 14B In the illustrated embodiment, the optically active film 730 is applied to the emitting surface 704 coated with an optical adhesive 730 via a high-precision pick-and-place tool 740. In some embodiments, the pick-and-place tool 740 includes a nozzle configured to pick up the optically active film 730 and place it onto the emitting surface 704. The optical adhesive 730 secures the optically active film 730 to the emitting surface 704. In some embodiments, the optically active film 730 is cured using hot air, UV light, and / or any other method known in the art. The optically active film 730 enables the light-emitting element 702 to operate with a desired color point (e.g., white light).

[0166] Figure 15 This is a dip coating system 900 according to an embodiment of the present disclosure. Similar to the high-precision pick-and-place system 700, the dip coating system 900 uses a high-precision pick-and-place tool 940. However, the dip coating system 900 uses the pick-and-place tool 940 to pick up each light-emitting element 902 and immerse each light-emitting element 902 into an ink composition 950. In some embodiments, the pick-and-place tool 940 includes a nozzle configured to pick up the light-emitting element 902 and immerse the light-emitting surface of the light-emitting element 902 into the ink composition bath 950. Immersion time, surface wettability, and bath temperature will determine the volumetric transfer. The ink composition 950 may contain a phosphor material. In some embodiments, the ink composition 950 contains PFS phosphors and / or KFS phosphors. Additionally or alternatively, the ink composition 950 contains an optical adhesive. The ink composition 950 may include any ink composition described herein.

[0167] After the target immersion time, a pick-and-place tool 940 removes the light-emitting element 902 from the ink composition bath 950. The resulting coating 906 on the light-emitting element 902 is then cured. In some embodiments, hot air and / or UV light are used to cure the coating 906. Alternatively or alternatively, any method known in the art can be used to cure the ink composition. This process (e.g., immersing the light-emitting element 902 in the ink composition bath 950 and curing the resulting coating 906) is repeated until the desired conversion layer is achieved. The cured coating on the light-emitting element 902 enables the light-emitting element 902 to operate with a desired color point (e.g., white light). More specifically, LEDs (e.g., mini LEDs, micro LEDs, etc.) with the desired color point can be customized as components that can be assembled onto any desired panel on an electronic assembly line, resulting in a relatively fast, efficient, and cost-effective process.

[0168] Figure 16A This is a top view of an example red, green, and blue (RGB) pixel 1000, which includes a blue sub-pixel 1010, a green sub-pixel 1020, and a red sub-pixel 1030. Figure 16B This is a side view of an example RGB pixel layout 1000. Each subpixel may include a well containing multiple walls. An ink composition containing a blue emitting phosphor may be deposited in the blue subpixel 1010, an ink composition containing a green emitting phosphor may be deposited in the green subpixel 1020, and an ink composition containing a red emitting phosphor may be deposited in the red subpixel 1030. The ink compositions deposited into the blue subpixel 1010, green subpixel 1020, and red subpixel 1030 may be cured into color filter portions 1014, 1024, and 1034, respectively. Thus, the blue subpixel 1010 is configured to emit blue light 1016, the green subpixel 1020 is configured to emit green light 1026, and the red subpixel 1030 is configured to emit red light 1036. In some embodiments, each subpixel 1010, 1020, and 1030 includes color filter materials 1014, 1024, and 1034, respectively. In some embodiments, stencil printing is used to deposit the ink composition. Stencil printing can be performed via a contact stencil printing system 100 (see [link]). Figure 6 ) or template printing system 150 (see Figure 7 This can be performed using hot air, UV light, and / or any other method known in the art to cure the ink composition.

[0169] In some embodiments, the ink composition may include a refractive index of about 0.1 to about 3. In other embodiments, the ink composition may include a refractive index of about 1 to about 1.6. In other embodiments, the ink composition may include a refractive index of about 1.50. In other embodiments, the ink composition may include a refractive index of about 1.51. Ink compositions including relatively high refractive indices increase the effective path length of the excitation light 1040 (e.g., blue light) to achieve additional absorption.

[0170] In some embodiments, as noted above, a scattering agent is added to the sub-pixel. In some embodiments, the scattering agent may include a refractive index of about 0.1 to about 3. In other embodiments, the scattering agent may include a refractive index of about 1 to about 1.6. In other embodiments, the scattering agent may include a refractive index of about 1.50. In other embodiments, the scattering agent may include a refractive index of about 1.51. Including a scattering agent with a relatively high refractive index increases the effective path length of the excitation light 1040 (e.g., blue light) to achieve additional absorption.

[0171] In some embodiments, a sub-pixel may be partially filled with a first ink composition and partially filled with a second ink composition. The second ink composition may be located in a portion of the pixel or sub-pixel through which the excitation light enters (e.g., Figure 16B Near the side portion 1002). Excitation light 1040 can enter the pixel and encounter the second ink composition, then the first ink composition. A two-pass printing method can be used to fill the sub-pixel. Printing can be performed via a contact stencil printing system 100 (see...). Figure 6 ) or template printing system 150 (see Figure 7The ink composition can be cured using hot air, UV light, and / or any other method known in the art. The first and second ink compositions may include different refractive indices. For example, in some embodiments, the second ink composition includes a relatively low refractive index, while the first ink composition includes a relatively high refractive index. For example, in some embodiments, the first ink composition includes a higher refractive index than the second ink composition. This causes the excitation light to first encounter the second ink composition, resulting in low reflection, and then encounter the first ink composition, which increases the effective excitation light path achieved once coupled to the color filter section. In another embodiment, the second ink composition includes a refractive index of about 0.1 to about 2. In another embodiment, the second ink composition includes a refractive index of about 0.1 to about 1.6. In another embodiment, the second ink composition includes a refractive index of about 0.1 to about 1.51. In some embodiments, the first ink composition includes a refractive index greater than about 1. In another embodiment, the first ink composition includes a refractive index greater than about 1.3. In another embodiment, the first ink composition includes a refractive index greater than about 1.50. In another embodiment, the first ink composition comprises a refractive index greater than about 1.51.

[0172] In some embodiments, in addition to the first and second ink compositions, the sub-pixel may also include a third ink composition. In such embodiments, the second ink composition may have a relatively low refractive index, the first ink composition may have a relatively high refractive index, and the third ink composition may have a relatively high refractive index. In such embodiments, each of the first and third ink compositions may have a higher refractive index than the second ink composition. In another embodiment, the second ink composition comprises a refractive index of about 0.1 to about 2. In another embodiment, the second ink composition comprises a refractive index of about 0.1 to about 1.6. In another embodiment, the second ink composition comprises a refractive index of about 0.1 to about 1.51. In some embodiments, the first ink composition comprises a refractive index greater than about 1. In another embodiment, the first ink composition comprises a refractive index greater than about 1.3. In another embodiment, the first ink composition comprises a refractive index greater than about 1.50. In another embodiment, the first ink composition comprises a refractive index greater than about 1.51. In some embodiments, the third ink composition comprises a refractive index greater than about 1. In another embodiment, the third ink composition comprises a refractive index greater than about 1.3. In another embodiment, the third ink composition comprises a refractive index greater than about 1.50. In another embodiment, the third ink composition comprises a refractive index greater than about 1.51.

[0173] In some embodiments, at least one film (not shown) is disposed on the side of one or more sub-pixels 1010, 1020, 1030, or on the pixel 1000 through which excitation light enters (e.g., side 1002). The at least one film may be configured to modify optical properties. For example, at least one filter may comprise a film that transmits blue light and reflects red and / or green light, thereby increasing brightness by increasing the amount of blue light entering sub-pixels 1010, 1020, and 1030 and passing through blue sub-pixel 1010, being converted to green light by green sub-pixel 1020, and being converted to red light by red sub-pixel 1030. In some embodiments, at least one filter comprises a dichroic filter. Additionally or alternatively, at least one film is configured to protect the ink composition from at least one of oxygen or moisture.

[0174] In some implementations, quantum dot color filters (QDCFs) are utilized. QDCFs can improve the color quality, viewing angle, and energy efficiency of a display. By using a blue light source (such as OLED, LED, mini-LED, or micro-LED) or a UV light source and replacing the traditional color filter with a QDCF material, at least a portion of the blue light is converted to a higher wavelength range, such as red and / or green light.

[0175] In some embodiments, RGB pixels 1000 are part of a display device that includes a backlight unit (BLU) configured to emit blue light 1040. In such embodiments, the QDCF may include a scattering agent in the blue sub-pixel 1010 and quantum dots in the red sub-pixel 1030 and green sub-pixel 1020 to achieve a wide color gamut. In addition to the quantum dots in the red sub-pixel 1030 and green sub-pixel 1020, at least one binder that absorbs blue light, at least one scattering agent, and / or additional color filter materials may be added to minimize blue light leakage through the sub-pixels (which would result in a reduced color gamut).

[0176] The nanoscale size, high absorption cross-section, and surface termination between quantum dots and ligands of quantum dots have enabled the commercialization of display architectures containing quantum dot cells (QDCFs). However, the use of QDCFs has some drawbacks, such as self-absorption loss. Furthermore, quantum dots in QDCF-containing displays typically require encapsulation to prevent degradation due to moisture and / or oxygen. Encapsulation can introduce parallax issues. Additionally, the necessary coating, shelling, printing, and / or curing processes can reduce the quantum efficiency of the quantum dots in the QDCF portion. In some cases, the net effect is a reduction in external quantum efficiency due to significant overlap between quantum dot absorption and emission in high-load inks. Previously, it was considered that typical phosphors were unsuitable for color filter applications due to their large particle size, and that if synthesized to submicron levels, the quantum efficiency and absorption would be too low, while excessive agglomeration would prevent printing into subpixels. The embodiments disclosed herein address these problems of current QDCFs.

[0177] In some embodiments according to this disclosure, stencil printing is used to fill the red subpixel 1030 with an ink composition. In some embodiments, the ink composition comprises a KSF phosphor (K2SiF6:Mn) having a small particle size and a high manganese content. Compared to quantum dot color filter solutions, KSF phosphor (K2SiF6:Mn) has a narrower emission intensity, does not have self-absorption problems in thick films, and does not reduce quantum efficiency when cured into the color filter portion. In another embodiment, the D50 particle size of the KSF phosphor is from about 0.1 μm to about 15 μm and contains at least 2.0 wt% Mn content. In another embodiment, the D50 particle size of the KSF phosphor is from about 0.1 μm to about 8 μm and contains at least 2.0 wt% Mn content. In another embodiment, the D50 particle size of the KSF phosphor is from about 0.1 μm to about 4 μm and contains 2.0 wt% to 4.0 wt% Mn content. In other embodiments, the ink composition comprises NSF phosphor (Na2SiF6) having a small particle size and high manganese content. Stencil printing can be performed via a contact stencil printing system 100 (see...). Figure 6 ) or template printing system 150 (see Figure 7 This can be performed using hot air, UV light, and / or any other method known in the art to cure the ink composition.

[0178] In some embodiments, as described above, stencil printing is used to coat the red sub-pixel 1030 with an ink composition containing KSF phosphors. The ink composition may also contain a surface agent (such as MgF2) to achieve a well-dispersed KSF ink with good printability, which absorbs most of the excitation light (e.g., blue or UV light) and has a quantum efficiency greater than 80%. This ink composition does not exhibit self-absorption, has good reliability, and does not require encapsulation. Furthermore, typical KSF inks require a 30% to 70% load to absorb most of the excitation light in a well with a depth of 8–16 μm. In another embodiment, the green sub-pixel 1020 is coated with a green emitting material, and a scattering agent or blue emitting material is added to the blue sub-pixel 1010. Such embodiments achieve functional display when excited by blue emitting LED or OLED light or UV light.

[0179] Additionally, in some embodiments, one or more walls of a subpixel are coated with a reflective (e.g., white) surface. For example, in some embodiments, one or more walls of the red subpixel 1030 are coated with a reflective (e.g., white) surface.

[0180] In some embodiments, the subpixels of RGB pixel 1000 include a depth of 6-20 μm. In other embodiments, the subpixels of RGB pixel 1000 include a depth of 14-20 μm. The inventors have found that increasing the well depth from 8 μm to 16 μm increases the red light emission 1036 achieved by red subpixel 1030 by more than 30% compared to red subpixels with a well depth of 8 μm.

[0181] Figure 17 Illustration 1100 compares the red light emission of the color filter portion of red subpixels filled with KSF phosphors at depths of 8 μm and 16 μm. Figure 17 In this context, the ink refractive index and viscosity differ between the color filter sections, which will be described in more detail below. Figure 17 In the figure, part 1-9 of x-axis 1102 corresponds to a well depth of 8 μm, while part 10-14 of x-axis 1104 corresponds to a well depth of 16 μm.

[0182] Red light emission was tested using a first method 1108 using an Edinburgh spectrometer and a second method 1110 using a QE tester. In the first method 1108, the coated color filter portion was excited by a xenon lamp at 450 nm excitation selected via a monochromator. A series of gratings and mirrors produced a spot size of approximately 2 cm, which excited the 60 x 60 mm coated color filter portion. Most of the blue light illuminating the red subpixel was transmitted into the cured subpixel and attenuated as the KSF phosphor ink absorbed the light, such that the color filter material needed to absorb less than 20% of the incident blue light after passing through the cured KSF phosphor ink. The KSF phosphor ink converted the absorbed blue photons into red photons via downconversion, and the emitted red photons passed through the color filter material and exited from the back side of the color filter portion. These emitted red photons then passed through a second monochromator and were detected by a photomultiplier tube (PMT) detector. Then, the colored portions of the KSF phosphor print are compared with each other based on the overall red light emission intensity.

[0183] The second method 1110 utilizes a QE tester and involves a blue-emitting LED with a reflective ring. A KSF phosphor-coated color filter portion is located at the top of the ring within a closed integrating sphere, and the emitted red light intensity is coupled out of the integrating sphere via an optical fiber coupled to a charge-coupled device (CCD) array detector. The integrated red light emission intensity of each portion can then be compared and normalized to the portion with the highest integrated emission intensity. The correlation between the first method 1108 and the second method 1110 is 95.6%, thus providing confidence in the measurement results.

[0184] Figure 17 The color filter section 14 is printed with an ink composition having a refractive index greater than 1.57 and a viscosity of approximately 5000 cPs. Profilometry was used to determine that the wells in the color filter section 14 were completely filled. Figure 17 As clearly shown, portion 14 produced the maximum brightness. A color filter portion printed with 3-5 micrometer NSF phosphor was also fabricated and measured, achieving up to 90% brightness relative to color filter portion 14.

[0185] Example

[0186] Example 1

[0187] Sample OS042022:

[0188] Weigh 2.2167g SFZ-1 + 0.4545g BB PTh + 0.8589g DGME into a 15ml (4 daphnes) amber vial. Vortex the mixture for 15-20 seconds. Add the first increment of PFS (1.0007g) and vortex the mixture for 20-30 seconds. Add the second increment of PFS (1.0008g) and vortex the mixture again, followed by a 3-5 minute sonication bath. Add the third increment of PFS (1.0065g), followed by vortexing and sonication bath. After the final addition of PFS (0.9956g) and subsequent mixing and sonication, the slurry is too dry, and 1.1579g DGME is added, followed by mixing and sonication bath. The slurry was still very thick, and an additional 0.2476 g of DGME was added, followed by vortex mixing and bath sonication. Then, the slurry was subjected to pulsed sonication (1 second on, 2 seconds off) using an angular ultrasonic device for a total of 20 seconds of effective sonication. The slurry became hot but remained very thick. An additional 0.1102 g of DGME was added, followed by vortex mixing and bath sonication again. The slurry was again subjected to pulsed sonication (1 second on, 2 seconds off) using an angular ultrasonic device for a total of 20 seconds of effective sonication. The slurry was then rolled overnight, and the next day, it was subjected to pulsed sonication (1 second on, 2 seconds off) using an angular ultrasonic device for a total of 20 seconds of effective sonication. The slurry was then placed in a vacuum dryer for 15 minutes to degas before coating.

[0189] Doctor blade coating on glass substrate

[0190] Ink was applied to a 1” x 1” Corning glass substrate with a thickness of 1.1 mm using an Erichsen Coatmaster 510 coater equipped with a vacuum stage. To obtain a final film thickness of 10–30 μm, a coater with a gap of 1–3 mils was used at a speed of 10 mm / s.

[0191] Glass substrates coated with a wet film were placed on a heating plate at 110°C to remove the solvent, and then they were UV cured for 2 minutes.

[0192] Table 1

[0193]

[0194]

[0195] Sample OS041522:

[0196] Weigh 2.218g SFZ-1 + 0.4562g BB PTh + 0.5515g DGME into a 15ml (4 daphnes) amber vial. Vortex the mixture for 15-20 seconds. Add the first increment of PFS (1.0004g) and vortex the mixture for 20-30 seconds. Add the second increment of PFS (1.0072g) and vortex the mixture again, followed by a 3-5 minute sonic bath. Add the third increment of PFS (1.0122g), then vortex and sonicate for 3-5 minutes. After the final addition of PFS (0.9768g), subsequent mixing, and a 3-5 minute sonic bath, the slurry is too thick; add 0.2562g DGME, then mix and sonicate again. The slurry was still very thick, and an additional 0.2097 g of DGME was added, followed by vortex mixing and 3-5 minutes of bath sonication. Then, the slurry was subjected to pulsed sonication (1 second on, 2 seconds off) with an angle ultrasonic transducer for a total of 1 minute of effective sonication. The slurry became hot and thinned. The slurry was then tumbled overnight, and the next day, it was subjected to pulsed sonication (1 second on, 2 seconds off) with an angle ultrasonic transducer for a total of 1 minute of effective sonication and became hot. The slurry was then placed in a vacuum dryer for 15 minutes to degas before coating.

[0197] Doctor blade coating on glass substrate

[0198] Ink was applied to a 1” x 1” Corning glass substrate with a thickness of 1.1 mm using an Erichsen Coatmaster 510 coater equipped with a vacuum stage. To obtain a final film thickness of 10–30 μm, a coater with a gap of 1–3 mils was used at a speed of 10 mm / s.

[0199] Glass substrates coated with a wet film were placed on a heating plate at 110°C to remove the solvent, and then they were UV cured for 2 minutes.

[0200] Table 2

[0201] Membrane ID Gap (mil) Film thickness (μm) OS041522-0.5 mil-A 0.5 3 OS041522-0.5 mil-B 0.5 7 OS041522-0.5 mil-C 0.5 5 OS041522-1 Mil-A 1 9 OS041522-1 Mil-B 1 13 OS041522-1 Mil-C 1 12 OS041522-1 Mil-D 1 15 OS041522-1 Mil-E 1 14 OS041522-1.5 Mil-A 1.5 18 OS041522-1.5 Mil-B 1.5 22 OS041522-1.5 Mil-C 1.5 14 OS041522-1.5 Mil-D 1.5 16

[0202] Sample OS031422:

[0203] Weigh 3.6793g SFZ-1 + 0.602g BB PTh + 1.0089g DGME into a 15ml (4 daphnes) amber vial. Vortex the mixture for 15-20 seconds. Add 6.3621g PFS (total) in three portions. After each portion is added, vortex the mixture for 20-30 seconds, followed by a 3-5 minute bath sonication. Then, pulse sonicate the slurry with an angle sonicator for 3 minutes (1 second on, 2 seconds off), for a total of 1 minute of effective sonication. Finally, place the slurry in a vacuum desiccant for 10 minutes to degas it before coating.

[0204] Doctor blade coating on glass substrate

[0205] Ink was applied to a 1” x 1” Corning glass substrate with a thickness of 1.1 mm using an Erichsen Coatmaster 510 coater equipped with a vacuum stage. To obtain a final film thickness of 10–30 μm, a coater with a gap of 1–3 mils was used at a speed of 10 mm / s.

[0206] Glass substrates coated with a wet film were placed on a heating plate at 110°C to remove the solvent, and then they were UV cured for 2 minutes.

[0207] Table 3

[0208]

[0209] Sample OS031122:

[0210] Weigh 4.2766g SFZ-1 + 0.2354g BB PTh + 1.0381g DGME into a 15ml (4 daphnes) amber vial. Vortex the mixture for 15-20 seconds. Add the first increment of PFS (2.7311g) and vortex the mixture for 20-30 seconds. Add the second increment of PFS (2.3979g) and vortex the mixture again. The slurry is too dry. Add 1.066g DGME and vortex the mixture for 20-30 seconds. Add the third increment of PFS (2.2586g) and vortex. The slurry is too thick, so add 0.4086g DGME and mix again. The slurry is still too thick, so add an additional 0.2176g DGME and vortex. Next, the slurry was pulsed ultrasonically treated with an angular ultrasonic transducer for 3 minutes (1 second on, 2 seconds off). The slurry was too thin. 0.4131g of PFS was added, followed by vortex mixing. The slurry was pulsed ultrasonically treated with an angular ultrasonic transducer for 3 minutes (1 second on, 2 seconds off), and then subjected to a 3-5 minute bath ultrasonic treatment. The slurry was then placed in a vacuum dryer for 15 minutes to degas it before coating.

[0211] Doctor blade coating on glass substrate

[0212] Ink was applied to a 1” x 1” Corning glass substrate with a thickness of 1.1 mm using an Erichsen Coatmaster 510 coater equipped with a vacuum stage. To obtain a final film thickness of 10–30 μm, a coater with a gap of 1–3 mils was used at a speed of 10 mm / s.

[0213] Glass substrates coated with a wet film were placed on a heating plate at 110°C to remove the solvent, and then they were UV cured for 2 minutes.

[0214] Table 4

[0215]

[0216]

[0217] Sample OS031022:

[0218] Weigh 6.1161g SFZ-1 + 3.0002g PFS into a 15ml (4 daphnes) amber vial. Vortex the mixture for 15-20 seconds and sonicate in a bath for 3-5 minutes. Add a portion of PFS (3.0064g) and vortex the mixture for 20-30 seconds. The mixture is too dry. Add 0.5112g DGME and vortex the mixture for 20-30 seconds. Add a third amount of PFS (3.0051g) and vortex mix. The mixture is too dry, so add 0.5141g DGME and mix again. Then, sonicate the slurry with an angle sonicator (1 second on, 2 seconds off) for 1 minute of effective sonication. The slurry is too thin. Add 1.0013g PFS and vortex mix; the slurry is still too thin. Add 0.5086g PFS, followed by vortex mixing and 3-5 minutes of bath sonication. Perform pulsed sonication on the slurry using an angle ultrasonic transducer (1 second on, 2 seconds off) to achieve 1 minute of effective sonication. Then place the slurry in a vacuum dryer for 15 minutes to degas it before coating.

[0219] Doctor blade coating on glass substrate

[0220] Ink was applied to a 1” x 1” Corning glass substrate with a thickness of 1.1 mm using an Erichsen Coatmaster 510 coater equipped with a vacuum stage. To obtain a final film thickness of 10–30 μm, a coater with a gap of 1–3 mils was used at a speed of 10 mm / s.

[0221] Glass substrates coated with a wet film were placed on a heating plate at 110°C to remove the solvent, and then they were UV cured for 2 minutes.

[0222] Table 5

[0223]

[0224] Example 2

[0225] The table below describes examples of inks containing small-sized, surface-modified phosphor materials developed according to the present invention. The ink embodiments listed in the table illustrate the versatility of this technology in producing fluids with customized viscosities and using solvents with proven printability. Furthermore, it illustrates how stable phosphor dispersions can be achieved using readily available resin systems from various commercial suppliers.

[0226] Experimental procedures for preparing inks in samples 1-4:

[0227] Add the resin to the glass vial using a disposable pipette. Add the solvent to the resin and vortex for 3 minutes or until the resin is completely dissolved in the solvent. In some embodiments, the solvent is optional. Visually inspect the bottom of the glass vial for corners where the resin may be difficult to agitate. Add YAG in increments of ~2g, vortexing the solution for 1 minute between each powder addition. Add PFS in increments of ~1-2g, vortexing the solution for 1 minute between each powder addition. Sonicate the solution with a probe sonicator at 25% power in pulse mode for 1 minute on and 2-second off (total run time ~3 minutes). Remove excess solvent in a rotary evaporator at a vacuum of 75 Torr at a speed between 100 and 170 RPM and a bath temperature of 45°C. Perform ink quality measurements at regular time intervals (e.g., hourly) and stop when the target viscosity is achieved.

[0228] Resin-free, low-viscosity ink. Sample ink 6 in the table above consists of a co-solvent mixture of triethylene glycol monomethyl ether (TGME) and diethylene glycol dimethyl ether (DGDE) in a 1:1 mass ratio. Ethyl cellulose (EC-HH, viscosity 300 Pa-s) is used as the binder material. Ethyl cellulose was added at 1 wt% to the TGME / DGDE co-solvent blend and mixed with a stirring rod until all the binder was dissolved. Then, PFS equal to 8 wt% of the co-solvent / binder blend was added. The suspension was stirred at room temperature to mix, then vortexed for 2 minutes. After vortexing, the suspension was subjected to bath sonication for 10 minutes to 1 hour to reduce the average agglomerate size. After sonication, the suspension was tumbled in a ball mill at 60 rpm for 2 hours. The solution was then transferred to an amber glass vial and stirred at 60°C for 2 hours.

[0229] Table 6

[0230]

[0231] The ink composition uses high-viscosity resins, solvents, and additives. Ink 4 in the table is an exemplary formulation using NOA68T. This embodiment may contain different types of high-viscosity resins, which may be photocurable or thermocurable and may have an initial viscosity ranging from 10,000 cP to 30,000 centipoise (cP). The amount of solvent added to the ink may vary between 0% and 50% by weight of the base resin. The type of solvent may be any of the types mentioned above. In exemplary inks 3 and 4, dimethylformamide (DMF) and acetone are used, respectively. The ink must contain 5% to 60% PFS phosphor material. The phosphor particle size (d50) may be in the range of 0.5-10 micrometers. Additives such as scattering agents (e.g., ZrO2) and auxiliary phosphor emitters such as YAG phosphors may be used in amounts that vary between 1% and 60%.

[0232] The ink compositions use medium-viscosity resins, solvents, and additives. Inks 1 and 2 in the table are exemplary formulations using NOA170 resin. This embodiment may contain different types of medium-viscosity resins, which may be photocurable or thermocurable and may have an initial viscosity ranging from 1,000 cP to 10,000 cP. The amount of solvent added to the ink may vary between 0% and 50% by weight of the base resin. The type of solvent may be any of the types mentioned above. In exemplary inks 1 and 2, acetone and DMF are used, respectively. The inks must contain 5% to 60% PFS phosphor material. The phosphor particle size (d50) may be in the range of 0.5-10 micrometers. Although exemplary inks 1 and 2 do not contain such molecules, additives such as scattering agents (e.g., ZrO2) and auxiliary phosphor emitters such as YAG phosphors may be used in the composition in amounts varying between 1% and 60%.

[0233] The ink composition uses low-viscosity resin, solvent, and additives. Ink 5 in the table above is an example of a low-viscosity formulation using SR454 resin. This embodiment may contain different types of low-viscosity resins, which may be photocurable or thermocurable, and may have an initial viscosity ranging from 10 cP to 1,000 cP. The amount of solvent added to the ink may vary between 0% and 10% of the weight of the base resin. The type of solvent may be any of the types mentioned above. In exemplary ink 5, no solvent is used. The ink must contain 5% to 60% PFS phosphor material. The phosphor particle size (d50) may vary between 0.5 and 5 micrometers. Although exemplary ink 5 does not contain additives, the additives may be present in amounts varying between 1% and 60%.

[0234] Figure 18Illustration 1200 shows a photoluminescence mapping of a blank substrate including blue, green, and red subpixels. More specifically, illustration 1200 shows the variation of the intensity (counts / second) 1204 of the blank substrate with wavelength (nm) 1202. As shown in illustration 1200, broad red light emission from the red subpixels and broad green light emission from the green subpixels are observed. Figure 19 A graph 1300 shows the variation of the intensity (counts / second) 1304 of the KSF-filled red subpixel as a function of wavelength (nm) 1302. As shown in Figure 1300, strong red light emission was observed for the KSF red subpixel at wavelengths above 580 nm, thus confirming the relationship with... Figure 18 Compared to the blank substrate, the light intensity of the red subpixels filled by KSF is increased.

[0235] Figure 20 A graph 1400 shows the relationship between the external quantum efficiency (EQE) 1404 as a percentage of the relevant form factor and the thickness measurement (μm) 1402 to understand product performance. EQE 1404 is proportional to the light absorption at 450 nm (LED or OLED) and the internal quantum efficiency. However, it is expected that the thinnest films will have a high EQE, as higher thickness is associated with higher self-absorption losses. Generally, however, for luminescent materials, the thinner the film, the lower the EQE. Nevertheless, ink formulations as described herein, and the systems and methods for dispensing and printing such ink formulations, achieve EQE improvements of 10% to 20%, thus enabling the use of thinner films.

[0236] Transparent displays, also known as see-through displays, are electronic displays that allow users to see the content displayed on a screen while still being able to see through the screen. The main applications of transparent displays are head-up displays, augmented reality systems, digital signage, and general large-scale spatial light modulation. Transparent displays bring many of the benefits of digital signage while allowing viewers to see the scene behind the display by mounting the light-emitting devices directly onto transparent glass as pixels. These see-through devices eliminate the need for backlighting or enclosures and are frequently used in applications including retail, corporate displays, museum exhibitions, prize / trophy displays, and head-up displays (including automotive applications). The light source for transparent displays can include LEDs, OLEDs, mini-EDS, and / or micro-LEDs. Generally, smaller LED arrays (such as mini-LEDs or micro-LEDs) allow for higher transparency and higher resolution compared to larger LEDs, and are potentially brighter than OLED-based transparent displays. However, generally, as the size of micro-LEDs decreases, the EQE (Equivalent Value of the LED) may also decrease. A typical display substrate consists of multiple individual micro-LEDs, OLEDs, mini-EDS, and / or micro-LEDs arranged in pixel groups, where each pixel group includes blue, green, and red light emitters. In embodiments according to this disclosure, a pixel group may include multiple blue light-emitting or UV light-emitting LEDs, OLEDs, mini-LEDs, and / or micro-LEDs, and utilize color conversion techniques to create other colors for the display. In many transparent display applications, it is desirable to maximize transparency by using small-sized LEDs, fine metallization lines, and transparent conductive materials (such as indium tin oxide) instead of metallization lines.

[0237] In some embodiments, the metallization layer may include an electrode layer and an optional barrier layer, but may also include other layers. In some embodiments, the thickness of the metallization layer is approximately 0.1-2 micrometers. The electrode layer may make ohmic contact with the GaN microLED and may be formed of a high work function metal (such as Ni, Au, Ag, Pd, and Pt). In some embodiments, the electrode layer may reflect light emission. In other embodiments, the electrode layer may be transparent to light emission. In some embodiments, the width of the lateral separation of the metallization layer is less than or equal to the width of the bottom surface of the micro pn diode array. The metallization layer is typically formed to have a uniform thickness and can be deposited by a variety of suitable methods, such as sputtering, electron beam evaporation, or deposition with a seed layer.

[0238] Using microLEDs with relatively large reflective surfaces and phosphor droplets allows for satisfactory light output with minimal loss of transparency. In some embodiments, the transparent display according to this disclosure may be at least 50% transparent, and in some cases at least 60% transparent, and in some cases at least 70% transparent. In some embodiments, the ink composition may include a relatively high refractive index. In one embodiment, the ink composition comprises KSF phosphor (K2SiF6:Mn). 4+ This KSF phosphor has a size of less than 5 micrometers and a Mn content of at least 1.5% by weight. This phosphor can be used with green or yellow emitting phosphors, such as (Y,Ga,Lu,Gd,Tb)3Al5O3. 12 :Ce 3+ The ink composition may include a refractive index greater than about 1.49 to form scattering with a KSF phosphor with a refractive index of about 1.4. This increases the effective path length of the blue light pump source and the dike-like micro-LED structure that transmits and reflects more than it absorbs, and therefore will have increased red and green light emission (lower CCT) and higher light output for a given phosphor load. This architecture produces a phosphor-converted micro-LED array with a color temperature higher than CCX > 0.2 and CCY > 0.2. Typical inks contain at least 20% phosphor load and may contain up to 70% phosphor load, where the green phosphor to red phosphor load ratio is typically at least about 2:1 (by weight) and up to about 20:1 (by weight).

[0239] In some embodiments, the viscosity of the ink composition used may be from about 100 cPs to about 30,000 cPs. In other embodiments, the viscosity of the ink composition may be from 500 cPs to 20,000 cPs. In some embodiments, located in dike structures (e.g., Figure 9 Each of the micro-LEDs within the dike structure 246 shown allows for lower viscosity inks down to approximately 100 cPs. High-quality, uniform printed parts are produced using inks ranging from 500 cPs to 20,000 cPs. The dike structure using lower viscosity inks allows for a more uniform phosphor-converted micro-LED array after printing via a degassing step before curing.

[0240] In some implementations, at least one reflective layer is formed around each LED, OLED, mini-LED, and / or micro-LED. At least one reflective layer enables higher conversion efficiency because it increases the probability of higher and / or multiple internal reflections of light, which increases the propagation path of light within the conversion layer, thus resulting in a higher conversion efficiency.

[0241] In some embodiments, at least one reflective layer is formed of a metal (such as Al and Ag) having high reflectivity in the visible light range and / or a metal (such as Al) forming a reflective or transparent oxide. In some embodiments, at least one reflective layer includes one or more dielectric mirrors and / or dichroic mirrors. The dielectric mirrors and / or dichroic mirrors can be adjusted to reflect specific spectral bands and can effectively reflect narrowband emission.

[0242] In some embodiments, at least one reflective layer is deposited around each LED, OLED, mini-LED, and / or micro-LED via screen printing / stencil printing (e.g., using a contact stencil printing system 100, a strip stencil printing system 150, etc.), high-resolution masking techniques, or inkjet printing. In some embodiments, at least one reflective layer is deposited prior to LED placement, possibly in the same step (and via the same deposition technique) as the metallization lines of the LED array, thereby avoiding additional steps and reducing process costs. Additionally or alternatively, a scattering agent, such as TiO2 or ZrO2, may be added. In another embodiment, the particle size of the scattering agent is from about 0.1 μm to about 4 μm.

[0243] Figure 21 This is a schematic diagram of the hybrid conductive mesh 1500. The hybrid conductive mesh 1500 can provide high reflectivity below and around the micro-LEDs 1502, and high transparency in the region between the micro-LEDs 1502. In some embodiments, the hybrid conductive mesh 1500 is produced by sputtering indium tin oxide (ITO) 1506 and Ag conductive segments 1504 in an alternating manner to form an interconnected conductive mesh with desired properties. The hybrid conductive mesh 1500 can enhance the reflective properties of at least one reflective layer discussed herein.

[0244] Figure 22 This is a chromaticity diagram of an example LED array including a dielectric microscope. A Konica Minolta CS-150 colorimeter and luminance meter were used to measure the color point of the phosphor deposit in the LED array. The color point was measured before (e.g., bare LEDs) and after (e.g., coated LEDs) phosphor application. For measurement, the colorimeter must be placed at a certain distance in front of the emitting surface. Typical color points for bare blue emitting LEDs were measured at CCX = 0.1640, CCY = 0.0130, with an emission peak appearing near 450 nm.

[0245] In the case of a transparent substrate, some emitted light may escape through the substrate to the back of the device. This effect is significant when phosphors are deposited on the transparent areas of the substrate. Measuring the luminance and color point emitted from both sides of the device can help assess how much light is lost through the substrate, as shown in Table 7. More specifically, Table 7 confirms that approximately 30% of the light in the example LED array is emitted from the back of the device (back of the column) compared to light emitted from the front side (column front) of the LED array, which includes the deposited phosphors, and its color point is further shifted away from the blue light emitting device (e.g., a bare LED). By placing a mirror behind the device, the luminance is returned to the front side and the overall color point is proportionally shifted (column reflections to the front side). Figure 22 This is a chromaticity diagram showing the data in Table 7.

[0246] Table 7

[0247] Bare LED front back Reflected on the front Brightness, cd / m2 not applicable 6888 3259 9715 ccx 0.1640 0.2190 0.2653 0.2334 ccy 0.0130 0.1172 0.0680 0.1427

[0248] The phosphor-converted LED array according to this disclosure may include multiple mini-LEDs or micro-LEDs having an ink composition comprising a phosphor material. The phosphor material may include rare-earth garnet phosphors and Mn... 4+ Doped phosphors. In some embodiments, rare earth garnet phosphors may be present in the phosphor material at an amount of about 80 wt% to about 100 wt%. Additionally, Mn4+ doped phosphors may be present in the phosphor material at an amount of about 20 wt% to about 0.1 wt%. In some embodiments, rare earth garnet phosphors may be present in the phosphor material at an amount of about 90 wt% to about 100 wt%. Additionally, Mn4+ doped phosphors may be present in the phosphor material at an amount of about 10 wt% to about 0.1 wt%. In some embodiments, rare earth garnet phosphors may be present in the phosphor material at an amount of about 95 wt% to about 100 wt%. Additionally, Mn4+ doped phosphors may be present in the phosphor material at an amount of about 5 wt% to about 0.1 wt%. The weight percentages of the phosphor material are based on the total weight of the phosphor material. In some embodiments, the rare earth garnet phosphors include YAG and the Mn4+ doped phosphors include PFS. In some embodiments, the phosphor-converted mini-LED array or phosphor-converted micro-LED is part of a display having a brightness of up to about 5,000 nits and a brightness uniformity of at least 60%, in some cases at least 80%, and in some cases at least 90%. In embodiments, the ink composition comprises greater than or equal to 90% rare-earth garnet phosphor and less than or equal to 10% Mn. 4+The phosphor is doped and deposited on a blue emitting LED, and its brightness gain is more than 4 times that of a standalone blue emitting LED, and in some cases, its brightness gain is more than 6 times that of a standalone blue LD, and in some cases, its brightness gain is more than 10 times that of a standalone blue emitting LED.

[0249] In some embodiments, where the ink composition comprises 80% or more of rare earth garnet phosphor and 10% or more of Mn4+ doped phosphor and is deposited on a blue light emitting LED, the phosphor-converted LED can result in light having a CCX measured of about 0.3 to about 0.35, and more particularly about 0.33, and a CCY in the range of about 0.31 to about 0.37, and more particularly about 0.34.

[0250] This written description uses examples to disclose the invention, including the best mode, and also enables those skilled in the art to practice the invention, including making and using any device or system and performing any combination of methods. The scope of the invention is defined by the claims and may include other examples that would occur to those skilled in the art. Such other examples are also intended to fall within the scope of the claims if their structural elements are identical to those of the claims, or if the equivalent structural elements included in such examples are not substantially different from those of the claims.

Claims

1. An ink composition comprising a phosphor material, said phosphor material being composed of Mn of Formula 1. 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the at least one rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

2. The ink composition according to claim 1, wherein the Mn of formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 20% by weight, based on the weight of the phosphor material.

3. The ink composition according to claim 1, wherein the at least one rare earth garnet phosphor is present in the phosphor material in an amount of at least about 90% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 10% by weight, based on the weight of the phosphor material.

4. The ink composition according to claim 1, wherein the at least one rare earth-containing garnet phosphor is doped with at least one of cerium, boron, SiAlON or quantum dots.

5. The ink composition according to claim 1, wherein the at least one rare earth garnet phosphor comprises yttrium aluminum garnet phosphor (YAG).

6. The ink composition according to claim 1, wherein the Mn 4+ The doped phosphor is selected from K2[GeF6]:Mn 4+ K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ Rb2[TiF6]Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4+ K3[BiF6], K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ and K3[TaF7]:Mn 4+ .

7. The ink composition according to claim 1, wherein the Mn of formula I 4+ The phosphor is K2SiF6:Mn 4+ Or Na2[SiF6]:Mn 4+ .

8. The ink composition according to claim 1, wherein the Mn of formula I 4+ The doped phosphor is coated with a surface coating containing metal fluorides.

9. The ink composition according to claim 8, wherein the metal fluoride is MgF2 or CaF2.

10. The ink composition of claim 1, wherein the ink composition further comprises an adhesive material and a solvent.

11. The ink composition of claim 10, wherein the adhesive material is one or more selected from epoxy resin, acrylate, methacrylate, vinyl ester and siloxane.

12. The ink composition according to claim 1, further comprising a scattering aid.

13. The ink composition according to claim 12, wherein the scattering aid is ZrO2 or TiO2 nanoparticles.

14. The ink composition of claim 1, wherein the ink composition further comprises one or more other luminescent materials.

15. The ink composition of claim 14, wherein the luminescent material comprises a quantum dot material.

16. The ink composition of claim 15, wherein the quantum dot material comprises perovskite quantum dots.

17. An apparatus comprising an LED light source, the LED light source being optically coupled and / or radiatively connected to a composition comprising a phosphor material, the phosphor material being composed of Mn of Formula 1. 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the at least one rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

18. The apparatus of claim 17, wherein the LED light source is a UV-emitting LED or a blue-emitting LED.

19. The apparatus according to claim 17, wherein the Mn of formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 20% by weight, based on the weight of the phosphor material.

20. The apparatus of claim 17, wherein the at least one rare earth garnet phosphor is present in the phosphor material in an amount of at least about 90% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 10% by weight, based on the weight of the phosphor material.

21. The apparatus of claim 17, wherein the at least one rare-earth-containing garnet phosphor is doped with at least one of cerium, boron, SiAlON or quantum dots.

22. The apparatus of claim 17, wherein the at least one rare earth garnet phosphor comprises yttrium aluminum garnet phosphor (YAG).

23. The apparatus of claim 17, wherein the Mn 4+ The doped phosphor is selected from K2[GeF6]:Mn 4+ K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ Rb2[TiF6]Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4+ K3[BiF6], K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ and K3[TaF7]:Mn 4+ .

24. The apparatus of claim 17, wherein Mn of formula I 4+ The phosphor is K2SiF6:Mn 4+ Or Na2[SiF6]:Mn 4+ .

25. The apparatus of claim 17, wherein Mn of formula I 4+ The doped phosphor is coated with a surface coating containing metal fluorides.

26. The apparatus of claim 25, wherein the metal fluoride is MgF2 or CaF2.

27. The apparatus of claim 17, wherein the composition further comprises an adhesive material and a solvent.

28. The apparatus of claim 27, wherein the adhesive material is one or more selected from epoxy resin, acrylate, methacrylate, vinyl ester, and siloxane.

29. The apparatus of claim 17, wherein the composition further comprises a scattering aid.

30. The apparatus of claim 29, wherein the scattering aid is ZrO2 or TiO2 nanoparticles.

31. The apparatus of claim 17, wherein the composition further comprises one or more other luminescent materials.

32. The apparatus of claim 31, wherein the light-emitting material comprises a quantum dot material.

33. The apparatus of claim 32, wherein the quantum dot material comprises perovskite quantum dots.

34. A lighting device comprising the means as described in claim 17.

35. A display device comprising the means as described in claim 17.

36. The apparatus of claim 17, wherein the LED light source is a mini LED or a micro LED.

37. A backlight device comprising the means as described in claim 17.

38. The backlight device including the apparatus of claim 17, wherein the backlight device has a brightness of at least about 5,000 nits.

39. The backlight device of claim 38, wherein the backlight device has a brightness uniformity of at least about 60%.

40. A television comprising the backlight device as claimed in claim 38.

41. A mobile phone comprising the backlight device as claimed in claim 38.

42. A computer monitor comprising the backlight device as claimed in claim 38.

43. A laptop computer comprising the backlight device as claimed in claim 38.

44. A tablet computer comprising the backlight device as described in claim 38.

45. An automotive display comprising the backlight device as claimed in claim 38.

46. ​​The apparatus of claim 17, wherein the apparatus is a self-emissive display.

47. A transparent display comprising the means as described in claim 17.

48. An automotive display comprising the transparent display as claimed in claim 47.

49. The automotive display of claim 48, wherein the automotive display is a windshield.

50. A vehicle taillight comprising the means as described in claim 17.

51. A light-emitting array comprising a plurality of mini LEDs or micro LEDs disposed on a substrate, wherein at least one mini LED or at least one micro LED is encapsulated in a dike structure or well structure, the dike structure or well structure being configured to contain a phosphor composition deposited within the dike structure or well structure, and at least a portion of the substrate contained in each of the dike structures or each of the well structures is coated with a reflective material. The phosphor composition comprises Mn of Formula 1. 4+ Phosphor material composition doped with phosphors, wherein Mn 4+ The D50 particle size of the doped phosphor is approximately 0.5 micrometers to approximately 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

52. The light-emitting array of claim 51, wherein each of the plurality of mini LEDs or each of the plurality of micro LEDs is a UV light emitting LED or a blue light emitting LED.

53. The light-emitting array of claim 51, wherein the reflective material comprises TiO2, ZrO2, BaSO4, or any combination thereof.

54. The light-emitting array of claim 51, wherein the phosphor material further comprises at least one rare-earth-containing garnet phosphor, wherein the rare-earth-containing garnet phosphor is doped with at least one of cerium, boron, SiAlON or quantum dots.

55. The light-emitting array of claim 54, wherein the at least one rare-earth garnet phosphor comprises yttrium aluminum garnet phosphor (YAG).

56. The light-emitting array of claim 54, wherein the at least one rare-earth garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 20% by weight, based on the weight of the phosphor material.

57. The light-emitting array of claim 54, wherein the at least one rare-earth garnet phosphor is present in the phosphor material in an amount of at least about 90% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 10% by weight, based on the weight of the phosphor material.

58. The light-emitting array of claim 51, wherein at least one wall of at least one dike structure or at least one well structure is coated with the reflective material.

59. A transparent display comprising a mini-LED array or micro-LED array disposed on a substrate, wherein at least one mini-LED in the mini-LED array or at least one micro-LED in the micro-LED array is encapsulated in a dike structure or well structure, the dike structure or well structure being configured to contain a phosphor composition deposited within the dike structure or well structure, and at least a portion of the substrate contained within each of the dike structure or each of the well structures is coated with a reflective material. The phosphor composition comprises Mn of Formula 1. 4+ Phosphor materials composed of doped phosphors, wherein Mn 4+ The D50 particle size of the doped phosphor is approximately 0.5 micrometers to approximately 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the ion's charge; and y is 5, 6, or 7. The transparent display has at least 60% transparency.

60. The transparent display of claim 59, wherein each mini-LED in the mini-LED array or each micro-LED in the micro-LED array is a UV-emitting LED or a blue-emitting LED.

61. The transparent display of claim 59, wherein the reflective material comprises TiO2, ZrO2, BaSO4, or any combination thereof.

62. The transparent display of claim 59, wherein the phosphor composition further comprises at least one rare-earth-containing garnet phosphor, wherein the rare-earth-containing garnet phosphor is doped with at least one of cerium, boron, SiAlON or quantum dots.

63. The transparent display of claim 62, wherein the at least one rare earth garnet phosphor comprises yttrium aluminum garnet phosphor (YAG).

64. The transparent display of claim 62, wherein the at least one rare earth garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 20% by weight, based on the weight of the phosphor material.

65. The transparent display of claim 62, wherein the at least one rare earth garnet phosphor is present in the phosphor material in an amount of at least about 90% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 10% by weight, based on the weight of the phosphor material.

66. The transparent display of claim 59, wherein at least one wall of at least one dike structure or at least one well structure is coated with the reflective material.

67. An automotive display comprising the transparent display as claimed in claim 59.

68. The automotive display of claim 67, wherein the automotive display is a windshield.

69. A vehicle taillight comprising a plurality of LED light sources arranged in a row, the plurality of LED light sources being optically coupled and / or radiatively connected to a composition comprising a phosphor material, the phosphor material being composed of Mn of Formula 1. 4+ The composition comprises a doped phosphor, wherein the D50 particle size of the phosphor material is from about 0.5 micrometers to about 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

70. The automotive taillight of claim 69, wherein the phosphor material is disposed at a distance on at least one of the plurality of LED light sources.

71. The automotive taillight of claim 70, wherein the phosphor material comprises a film.

72. The automotive taillight of claim 71, wherein a film is disposed at a distance on the plurality of LED light sources.

73. The automotive taillight of claim 71, wherein the plurality of LED light sources includes at least a first LED light source and a second LED light source, and a first film is disposed at a distance on the first LED light source, and a second film is disposed at a distance on the second LED light source.

74. The automotive taillight of claim 71, wherein the phosphor material is disposed at a distance and coated on at least one of the plurality of LED light sources.

75. The automotive taillight of claim 69, wherein the Mn 4+ The doped phosphor is selected from K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ Rb2[TiF6]Mn 4+ K2[GeF6]:Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4+ K3[BiF6], K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ and K3[TaF7]:Mn 4+ .

76. The automotive taillight of claim 69, wherein Mn of formula I 4+ The doped phosphor is K2SiF6:Mn 4+ Or Na2[SiF6]:Mn 4+ .

77. The automotive taillight of claim 69, wherein the phosphor composition further comprises a rare-earth-containing garnet phosphor doped with at least one of cerium, boron, SiAlON or quantum dots.

78. A vehicle taillight comprising a plurality of LED light sources, the plurality of LED light sources being optically coupled and / or radiatively connected to a composition comprising a phosphor material, the phosphor material being composed of Mn of Formula 1. 4+ The composition comprises a doped phosphor, wherein the phosphor material is coated on a glass, reflective surface, or flexible surface, wherein the Mn... 4+ The D50 particle size of the doped phosphor is from approximately 0.5 micrometers to approximately 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

79. The automotive taillight of claim 78, wherein the phosphor material is coated on the reflective surface, and the reflective surface comprises TiO2, ZrO2, ZnO2, BaSO4, or any combination thereof.

80. The automotive taillight of claim 78, wherein the phosphor material is coated on the flexible surface, and the flexible surface comprises a polymer material.

81. The automotive taillight of claim 78, wherein the Mn 4+ The doped phosphor is selected from K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ Rb2[TiF6]Mn 4+ K2[GeF6]:Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4+ K3[BiF6], K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ and K3[TaF7]:Mn 4+ .

82. The automotive taillight as claimed in claim 78, wherein Mn of formula I 4+ The doped phosphor is K2SiF6:Mn 4+ Or Na2[SiF6]:Mn 4+ .

83. The automotive taillight of claim 78, wherein the phosphor composition further comprises a rare-earth-containing garnet phosphor doped with at least one of cerium, boron, SiAlON or quantum dots.

84. A membrane comprising a phosphor material, said phosphor material being composed of Mn of Formula 1 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the at least one rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

85. The membrane according to claim 84, wherein the Mn of formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 20% by weight, based on the weight of the phosphor material.

86. The membrane according to claim 84, wherein the at least one rare earth garnet phosphor is present in the phosphor material in an amount of at least about 90% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 10% by weight, based on the weight of the phosphor material.

87. The membrane according to claim 84, wherein the at least one rare earth-containing garnet phosphor is doped with at least one of cerium, boron, SiAlON or quantum dots.

88. The membrane according to claim 84, wherein the at least one rare earth garnet phosphor comprises yttrium aluminum garnet phosphor (YAG).

89. The membrane according to claim 84, wherein the Mn 4+ The doped phosphor is selected from K2[GeF6]:Mn 4+ K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ Rb2[TiF6]Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4+ K3[BiF6], K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ and K3[TaF7]:Mn 4+ .

90. The membrane according to claim 84, wherein the Mn of formula I 4+ The phosphor is K2SiF6:Mn 4+ Or Na2[SiF6]:Mn 4+ .

91. The membrane according to claim 84, wherein the Mn of formula I 4+ The doped phosphor is coated with a surface coating containing metal fluorides.

92. The membrane according to claim 91, wherein the metal fluoride is MgF2 or CaF2.

93. The membrane according to claim 84, further comprising an adhesive material and a solvent.

94. The membrane according to claim 93, wherein the adhesive material is one or more selected from epoxy resin, acrylate, methacrylate, vinyl ester and siloxane.

95. The membrane according to claim 84, further comprising a scattering aid.

96. The membrane according to claim 95, wherein the scattering aid is ZrO2 or TiO2 nanoparticles.

97. The membrane according to claim 84, further comprising one or more other luminescent materials.

98. The membrane according to claim 97, wherein the luminescent material comprises a quantum dot material.

99. The membrane of claim 98, wherein the quantum dot material comprises perovskite quantum dots.

100. An apparatus comprising an LED light source, the LED light source being optically coupled and / or radiatively connected to a film comprising a phosphor material, the phosphor material being composed of Mn of Formula 1. 4+ The phosphor is composed of a doped phosphor and at least one rare-earth-containing garnet phosphor, wherein the at least one rare-earth-containing garnet phosphor is present in the phosphor material in an amount of at least about 80% by weight based on the weight of the phosphor material, and wherein the D50 particle size of the at least one rare-earth-containing garnet phosphor is from about 0.5 micrometers to about 15 micrometers. A x [MF y ]:Mn 4+ I Where A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is [MF y The absolute value of the charge of the ion; and y is 5, 6 or 7.

101. The apparatus of claim 100, wherein the LED light source is a UV-emitting LED or a blue-emitting LED.

102. The apparatus according to claim 100, wherein the Mn of formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 20% by weight, based on the weight of the phosphor material.

103. The apparatus of claim 100, wherein the at least one rare earth garnet phosphor is present in the phosphor material in an amount of at least about 90% by weight based on the weight of the phosphor material, and the Mn of Formula 1 4+ The doped phosphor is present in the phosphor material in an amount of about 0.1% to about 10% by weight, based on the weight of the phosphor material.

104. The apparatus of claim 100, wherein the at least one rare-earth-containing garnet phosphor is doped with at least one of cerium, boron, SiAlON or quantum dots.

105. The apparatus of claim 100, wherein the at least one rare earth garnet phosphor comprises yttrium aluminum garnet phosphor (YAG).

106. The apparatus of claim 100, wherein the Mn 4+ The doped phosphor is selected from K2[GeF6]:Mn 4+ K2[SiF6]:Mn 4+ K2[TiF6]:Mn 4+ K2[SnF6]:Mn 4+ Cs2[TiF6]:Mn 4+ Rb2[TiF6]Mn 4+ Cs2[SiF6]:Mn 4+ Rb2[SiF6]:Mn 4+ Na2[SiF6]:Mn 4+ Na2[TiF6]:Mn 4+ Na2[ZrF6]:Mn 4+ K3[ZrF7]:Mn 4+ K3[BiF6], K3[YF6]:Mn 4+ K3[LaF6]:Mn 4+ K3[GdF6]:Mn 4+ K3[NbF7]:Mn 4+ and K3[TaF7]:Mn 4+ .

107. The apparatus of claim 100, wherein Mn of formula I 4+ The phosphor is K2SiF6:Mn 4+ Or Na2[SiF6]:Mn 4+ .

108. The apparatus of claim 100, wherein Mn of formula I 4+ The doped phosphor is coated with a surface coating containing metal fluorides.

109. The apparatus of claim 108, wherein the metal fluoride is MgF2 or CaF2.

110. The apparatus of claim 100, wherein the membrane further comprises an adhesive material and a solvent.

111. The apparatus of claim 110, wherein the adhesive material is one or more selected from epoxy resin, acrylate, methacrylate, vinyl ester and siloxane.

112. The apparatus of claim 100, wherein the membrane further comprises a scattering aid.

113. The apparatus of claim 112, wherein the scattering aid is ZrO2 or TiO2 nanoparticles.

114. The apparatus of claim 100, wherein the film further comprises one or more other luminescent materials.

115. The apparatus of claim 114, wherein the luminescent material comprises a quantum dot material.

116. The apparatus of claim 115, wherein the quantum dot material comprises perovskite quantum dots.

117. A lighting device comprising the means as described in claim 100.

118. A display device comprising the means as described in claim 100.

119. The apparatus of claim 100, wherein the LED light source is a mini LED or a micro LED.

120. A backlight device comprising the means as described in claim 100.

121. The backlight device comprising the apparatus of claim 100, wherein the backlight device has a brightness of at least about 5,000 nits.

122. The backlight device of claim 121, wherein the backlight device has a brightness uniformity of at least about 60%.

123. A television comprising the backlight device as described in claim 120.

124. A mobile phone comprising the backlight device as claimed in claim 120.

125. A computer monitor comprising the backlight device as claimed in claim 120.

126. A laptop computer comprising the backlight device as claimed in claim 120.

127. A tablet computer comprising the backlight device as described in claim 120.

128. An automotive display comprising the backlight device as claimed in claim 120.

129. The apparatus of claim 100, wherein the apparatus is a self-emissive display.

130. A transparent display comprising the means as described in claim 100.

131. An automotive display comprising the transparent display as claimed in claim 130.

132. The automotive display of claim 131, wherein the automotive display is a windshield.

133. A vehicle taillight comprising the means as described in claim 100.

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