Hydrophobic coated phosphors and devices using the same

Abstract

The present disclosure relates to phosphor powders. In one implementation, the phosphor powder can include phosphor particles, a metal halide, and silane or siloxane. The phosphor particles can include at least one phosphor material. The at least one phosphor material can include a Mn4+ doped phosphor of formula I: Ax[MFy]:Mn4+ (I), where A is Li, Na, K, Rb, Cs, NH4, or any combination thereof, M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof, x is the absolute value of the charge of the [MFy] ion, and y is 5, 6 or 7. The present disclosure also includes ink compositions, films, and devices, that include one or more phosphor powders of the present disclosure. The present disclosure also includes methods of preparing phosphor powders of the present disclosure.

Description

RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 681,936, filed 12 August 2024.FIELD OF THE INVENTION

[0002] The subject matter described herein relates generally to compositions and films containing phosphor materials and scattering particles and devices using the same.BACKGROUND

[0003] Phosphors such as red-emitting manganese-doped complex fluoride material (e.g. those described in U.S. Pat. Nos. 7,358,542, 7,497,973, and 7,648,649) can be utilized in combination with yellow / green emitting phosphors such as YAG:Ce to achieve warm white light (CCTs<5000 K on the blackbody locus, color rendering index (CRI)>80) from a blue LED, equivalent to that produced by current fluorescent, incandescent and halogen lamps. These materials absorb blue light strongly and efficiently emit in a range between about 610 nm and 658 nm with little deep red / NIR emission. Therefore, luminous efficacy is maximized compared to red phosphors that have significant emission in the deeper red where eye sensitivity is poor. Quantum efficiency can exceed 85% under blue (440-460 nm) excitation. In addition, use of the red phosphors for displays can yield high gamut and efficiency.

[0004] The use of manganese doped potassium hexafluorosilicate (PFS, K_{2}SiF_{6}:Mn^{4+}) phosphors in micro-LED applications and luminescent color filters (in pixel color conversion) require printable inks that contain PFS particles with small sizes (<2 \mu m) and that have good dispersion stability. These printable inks typically contain organic solvents, acrylates, resins, or other non-aqueous, hydrophobic components as the main carrier for the ink (“ink base"). It is well established the fluorosilicate surfaces of PFS are hydrophilic, which leads to these powders being easily dispersed in water or aqueous solutions. Accordingly, there is a need to modify the PFS surfaces to make them hydrophobic to thereby improve their dispersibility and stability in ink resins.

[0005] Accordingly, there exists a need to develop new phosphor compositions that have improved dispersibility and / or stability in ink resins.SUMMARY OF THE INVENTION

[0006] It has been shown herein that hydrophobic coatings such as organic siloxane / silane and inorganic metal halide (e.g., magnesium fluoride) on phosphor particles increased hydrophobicity of the phosphor particles. Consequently, the coated phosphor particles demonstrated increased dispersibility in hydrophobic binders.

[0007] Accordingly, in one aspect, the present disclosure provides a phosphor powder including phosphor particles, the phosphor particles including at least one phosphor material comprising a Mn^{4+} doped phosphor of formula IA_{x}[MF_{y}]:Mn^{4}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0008] In another exemplary aspect, the present disclosure provides a composition that includes a phosphor powder of the present material and a binder. In some aspects, the composition can be an ink composition. In some aspects, the ink composition includes a phosphor powder including phosphor particles, the phosphor particles including at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I:A_{x}[MF_{y}]:Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the \{ME_{y}\} ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0009] In another exemplary aspect, the present disclosure provides a film that includes a first layer including one or more first polymers, a second layer including one or more second polymers, and at least one cured or semi-cured ink interposed between the first layer and the second layer, the at least one cured or semi-cured ink including phosphor particles. The phosphor particles include at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I:A_{x}[MF_{y}]:Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the [MF_{\gamma}] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0010] In another exemplary aspect, the present disclosure provides a film that includes at least one cured or semi-cured ink including phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I:Ax[ME_{y}]·Ma^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the \{MF_{y}\} ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0011] In another exemplary aspect, the present disclosure provides a device that includes an LED light source optically coupled and / or radiationally connected to at least one cured or semi-cured ink, the at least one semi or semi-cured ink including phosphor particles comprising at least one phosphor material comprising a mn^{4+} doped phosphor of formula IA_{x}(MF_{y}):Mn^{4+}wherein.A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0012] In another exemplary aspect, the present disclosure provides a lighting apparatus, a backlight apparatus, and / or a display apparatus that includes the device provided herein.

[0013] In another exemplary aspect, the present disclosure provides a television, a mobile phone, a computer monitor, a laptop, a tablet computer, and / or an automotive display that includes the device provided herein.

[0014] In another exemplary aspect, the present disclosure provides a process for producing a coated phosphor including combining at least one phosphor material with metal halide to form a first coated phosphor, the at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I:A_{3}[MF_{3}]:Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH_{4} or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles; andcombining the first coated phosphor with a silane or a siloxane to produce a second coated phosphor.

[0015] In another exemplary aspect, the present disclosure provides a method for inkjet printing, flexographic printing, microdispensing printing, screen printing, direct write printing, aerosol jet printing, or gravure printing, the method comprising printing an ink composition, wherein the ink composition comprises phosphor particles, the phosphor particles including at least one phosphor material comprising a mn^{4+} doped phosphor of formula I:A_{x}(MF_{y}):Mn^{4+}wherein.A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The aspects of the disclosure will now be described in greater detail with reference to the attached drawings in which:

[0017] FIG. 1 shows a graph of thermogravimetric analysis (TGA) traces of samples A112823ATMgGA(838)SiA (sample A-SiA) and A112823ATMgGA(838)SiB (sample A-SiB) under nitrogen flow from room temperature to 500^{\circ}C at a heating ramp of 10^{\circ}C / min. Mass loss values at 400^{\circ}C and 500^{\circ}C are indicated.

[0018] FIG. 2 shows reflectance IR spectra of silane coated PFS samples A112823ATMgGA(838)SiA (sample A-SiA) and A112823ATMgGA(838)SiB (sample A-SiB). Inset shows region of 2500 – 4000 cm-¹ where spectral features for both MgF_{2} and silane coatings are observed.

[0019] FIG. 3A is a schematic cross-sectional view of a device, in accordance with the teaching of the present disclosure. FIG. 3B is a schematic cross-sectional view of a device in accordance with the teaching of the present disclosure. FIG. 3C is a schematic cross-sectional view of a device in accordance with the teaching of the present disclosure. FIG. 3D is a schematic cross-sectional view of a device in accordance with the teaching of the present disclosure. FIG. 3E is a schematic cross-sectional view of a device in accordance with the teaching of the present disclosure.

[0020] FIG. 4 is a schematic cross-sectional view of a lighting apparatus, in accordance the teaching of the present disclosure.

[0021] FIG. 5 is a schematic cross-sectional view of a lighting apparatus, in accordance with the teaching of the present disclosure.

[0022] FIG. 6 is a cutaway side perspective view of a lighting apparatus, in accordance with the teaching of the present disclosure.

[0023] FIG. 7A is a schematic perspective view of a surface-mounted device (SMD), in accordance with the teaching of the present disclosure. FIG.7B is a schematic cross-sectional view of an SMD in accordance with the teaching of the present disclosure. FIG. 7C is a schematic cross-sectional view of a device in accordance with the teaching of the present disclosure.

[0024] FIGs. 8A-8D are schematic diagrams of a printing well arrangement, in accordance with the teaching of the present disclosure.

[0025] FIG. 9 is a schematic diagram of a bank arrangement, in accordance with the teaching of the present disclosure.

[0026] FIGs. 10A and 10B are a top view and a side view, respectively, of an example red-green-blue (RGB) pixel, in accordance with the teaching of the present disclosure.

[0027] Other features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating aspects of the disclosure, are given by way of illustration only and the scope of the claims should not be limited by these aspects, but should be given the broadest interpretation consistent with the description as a whole.DETAILED DESCRIPTION

[0028] Unless otherwise indicated, the definitions and aspects described in this and other sections are intended to be applicable to all aspects of the present disclosure herein described for which they are suitable as would be understood by a person skilled in the art.

[0029] The abbreviations used herein have their conventional meaning within the chemical and biological arts. The chemical structures and formulae set forth herein are constructed according to the standard rules of chemical valency known in the chemical arts.

[0030] The term "and / or" as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that "at least one of" or "one or more" of the listed items is used or present. The term “and / or” with respect to pharmaceutically acceptable salts and / or solvates thereof means that the compounds of the disclosure exist as individual salts and hydrates, as well as a combination of, for example, a solvate of a salt of a compound of the disclosure.

[0031] As used in the present disclosure, the singular forms “a”, “an” and “the” include plural references unless the content clearly dictates otherwise. For example, an aspect including "a phosphor" should be understood to present certain aspects with one compound, or two or more additional compounds.

[0032] In aspects comprising an "additional" or "second" component, such as an additional or second compound, the second component as used herein is chemically different from the other components or first component. A "third" component is different from the other, first, and second components, and further enumerated or "additional" components are similarly different.

[0033] In this disclosure, “comprises,” “comprising,” “containing" and "having" and the like can have the meaning ascribed to them in U.S. Patent law and can mean “includes," "including," and the like. "Consisting essentially of or "consists essentially" likewise has the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art aspects.

[0034] As used herein, the term "about" means a range of values including the specified value, which a person of ordinary skill in the art would consider reasonably similar to the specified value. In some aspects, about means within a standard deviation using measurements generally acceptable in the art. In aspects, about means a range extending to + / - 10% of the specified value. In some aspects, about includes the specified value.

[0035] The term “comparable phosphor powder” as used herein refers to a phosphor powder including phosphor particles coated with only magnesium fluoride.

[0036] The term "a mini-LED” as used herein, should be understood to mean an LED that is sized less than or equal to 250 microns. For example, a mini-LED can include an LED that has a length of 250 microns and a width of 250 microns.

[0037] The term "a micro-LED", as used herein, should be understood to mean an LED that is sized less than or equal to 50 microns. For example, a micro-LED can include an LED that has a length of 50 microns and a width of 50 microns

[0038] In one exemplary aspect, a phosphor powder including phosphor particles is provided. In some aspects, the phosphor particles include at least one phosphor material including a Mn doped phosphor of formula 1:A_{x}\{MF_{y}\}.Mn^{4+}\}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the \{MF_{y}\} ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0039] The Mn^{4+} doped phosphors of Formula I are complex fluoride materials, or coordination compounds, containing at least one coordination center surrounded by fluoride ions acting as ligands, and charge-compensated by counter ions as necessary. For example, in the exemplary phosphor particle K_{2}[SiF_{6}]:Mn^{4+}, the coordination center is Si and the counterion is K. Complex fluorides are occasionally written as a combination of simple, binary fluorides but such a representation does not indicate the coordination number for the ligands around the coordination center. The square brackets (occasionally omitted for simplicity) indicate that the complex ion they encompass is a new chemical species, different from the simple fluoride ion. The activator ion (Mn) also acts as a coordination center, substituting part of the centers of the host lattice, for example, Si. The host lattice (including the counter ions) can further modify the excitation and emission properties of the activator ion.

[0040] In particular aspects, the coordination center of the phosphor, that is, M in formula I, is Si, Ge, Sn, Ti, Zr, or a combination thereof. More particularly, the coordination center can be Si, Ge, Ti, or a combination thereof. The counterion, or A in formula I, can be Na, K, or a combination thereof, more particularly K. Examples of phosphors of formula I include K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+}, K_{2}[TiF_{6}]:Mn^{4+}, K_{2}[SnF_{6}]:Mn^{4+} Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}] Mn^{4+} Cs_{2}[SiF_{6}]:Mn^{4+}, Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4+} K_{3}[ZrF_{7}]:Mn^{4+}, K3[BIF6] K3[YF6]:Mn+, K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+} In some aspects, the Mn^{4+} doped phosphor can be at least one of K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+} K_{2}[TiF_{6}]:Mn^{4+} K_{2}[SnF_{6}]:Mn^{4+}, Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}]Mn^{4+}, Cs_{2}[SiF_{6}]:Mn^{4+}, Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4+}, K_{3}[ZrF_{7}]:Mn^{4+}, K3[BIF6] K_{3}[YF_{6}]:Mn^{4+} K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+} In certain aspects, the Mn^{4+} phosphor of formula I can be K_{2}SiF_{6}:Mn^{4+} or Na_{2}[SiFfi]:Mn^{4+} In particular aspects, the phosphor of formula I can be K_{2}[SiF_{6}]· Mn^{4}.

[0041] In some aspects, the phosphor powder can have a particle size distribution including a D50 value that is less than a D50 particle size distribution of a comparable phosphor powder. In some aspects, the D50 value of the phosphor powder can be about 0.5 \mu m to about 10 \mu m, about 0.5 \mu m to about 9 \mu m about 1 \mu m to about 8 \mu m, about 1 \mu m to about 7 \mu m, about 1 \mu m to about 5 \mu m, about 1 \mu m to about 4 \mu m about 1 \mu m to about 3.5 \mu m, about 1.5 \mu m to about 3.5 \mu m, about 2 \mu m to about 3 \mu m. about 4 \mu m to about 8 \mu m, about 4 \mu m to about 7.5 \mu m, or about 5 \mu m to about 6.5 \mu m, including all the subranges in between. In certain aspects, the particle size distribution can have a D50 value of about 0.1 \mu m, about 0.2 \mu m, about 0.3 \mu m, about 0.4 \mu m about 0.5 \mu m about 0.6 \mu m, about 0.7 \mu m, about 0.8 \mu m, about 0.9\mu m, about 1.0 \mu m, about 1.1 µm, about 1.2 \mu m, about 1.3\mu m about 1.4 \mu m, about 1.5 \mu m, about 1.6 \mu m, about 1.7 \mu m, about 1.8 \mu m, about 1.9 \mu m, about 2.0 \mu m, about 2.1\mu m about 2.2 \mu m, about 2.3 \mu m, about 2.4 \mu m, about 2.5 \mu m, about 2.6 \mu m. about 2.7 \mu m, about 2.8 \mu m about 2.9\mu m, about 3.0 \mu m, about 3.1 µm, about 3.2 \mu m, about 3.3 \mu m, about 3.4 \mu m about 3.5 \mu m, about 3.6 \mu m, about 3.7 \mu m, about 3.8 \mu m, about 3.9 \mu m, about 4.0 \mu m, about 4.1 \mu m. about 4.2 \mu m, about 4.3 \mu m, about 4.4 \mu m, about 4.5 \mu m. about 4.6 \mu m, about 4.7 \mu m, about 4.8 \mu m, about 4.9 \mu m, or about 5.0 \mu m.

[0042] In some aspects, the phosphor powder can have a particle size distribution including a D90 micron particle size that is less than a D90 particle size distribution of a comparable phosphor powder. In some aspects, the phosphor powder can have a D90 value of about 1 l\mu m to about 20 \mu m about 1 \mu m to about 18\mu m, about 1 \mu m to about 17 \mu m, about 1 \mu m to about 15 µm, about 1.5 \mu m to about 15 \mu m about 2 \mu m to about 13 \mu m, about 2 \mu m to about 10 \mu m, about 2 \mu m to about 8 \mu m, about 2 \mu m to about 7 \mu m, about 2 \mu m to about 6 \mu m, about 2 \mu m to about 5 µm, about 2.5 \mu m to about 5 \mu m, about 3 \mu m to about 5 \mu m, about 5 \mu m to about 13 \mu m, about 7 µm to about 13 \mu m, about 8 \mu m to about 12 \mu m, or about 9 \mu m to about 11 \mu m, including all the subranges in between.

[0043] In some aspects, the phosphor powder can have a greater quantum efficiency than a comparable phosphor powder at zero-hour. In some aspects, the phosphor particles can have a quantum efficiency of about 77% to about 95% at zero-hour. In some aspects, the powder particles can have a quantum efficiency of greater than about 90% at zero-hour. In some aspects, the powder particles can have a quantum efficiency of about 90% to about 99%, about 91% to about 98%, about 92% to about 97%, about 93% to about 96% at zero-hour, including all the subranges in between. In some aspects, the powder particles can have a quantum efficiency of greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94% at zero-hour.In some aspects, the at least one phosphor material includes an amount of manganese from about 0.5 wt% to about 4 wt% based on total phosphor powder weight, including all the subranges in between. In some aspects, the phosphor material includes an amount of manganese that is greater than about 2.5 wt% based on total phosphor powder weight. In certain aspects, the phosphor material includes an amount of manganese from about 2 wt% to about 3 wt% based on total phosphor powder weight, including all the subranges in between. In other aspects, the phosphor material can have a Mn loading or Mn % of at least 1 wt %. In another aspect, the phosphor material can have a Mn loading of at least 1.5 wt%. In another aspect, the phosphor material can have a Mn loading of at least 2 wt%. In another aspect, the phosphor material can have a Mn % of at least 3 wt%. In another aspect, the Mn % can be greater than 3.0 wt%. In another aspect, the content of Mn in the phosphor material can be from about 1 wt% to about 4 wt %.

[0044] In some aspects, at least a portion of the metal halide and at least a portion of the silane can be on the same surfaces of the phosphor particles. In some aspects, at least a portion of the metal halide can be on first surfaces of the phosphor particles and at least a portion of the silane can be on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different. In some aspects, the metal halides can be in the form of sol particles when deposited on the surfaces of phosphor particles.

[0045] Exemplary metal halides include, but are not limited to, magnesium fluoride. In one aspect, the metal halide can be magnesium fluoride.

[0046] In another exemplary aspect, the present disclosure provides a composition that includes a phosphor powder of the present material and a binder. In some aspects, the composition can be an ink composition. In some aspects, the ink composition includes phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mm^{4+} doped phosphor of formula I.A_{x}[MF_{y}\}:Mn^{4+}1wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the \{MF_{y}\} ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0047] In some aspects, the ink composition also includes a binder. Binders for use in the ink compositions described herein can include thermoplastic polymers and copolymers, pre-binder materials, such as thermally curable precursors or photocurable precursors. Exemplary binders include, but are not limited to, ethyl cellulose, polystyrene, polyacrylate, polymethacrylates, such as polymethyl acrylate (PMA) and polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate (PET), polyurethane, polyetherether ketone, polysulfone, polyphenylene sulfide, polyvinylpyrrolidone (PVP), polyethyleneimine (PEI), poly(1-naphthyl methacrylate), poly(vinyl phenyl sulfide) (PVPS), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), poly(N-vinylphthalimide), fluorinated polymers, such as polyvinylidene fluoride (PDVF) or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), amine-based oligomers / polymers / copolymers, fluorine-based oligomers / polymers / copolymers, poly(phenylene vinylene), carbazole-based oligomers / polymers / copolymers, phenyl-pyridine-based oligomers / polymers / copolymers. In certain aspects, the at least one binder can be at least one of an epoxy, acrylate, methacrylate, vinyl ester, siloxane, or polyethylene terethalate.

[0048] In some aspects, at least a portion of the metal halide and at least a portion of the silane can be on the same surfaces of the phosphor particles. In some aspects, at least a portion of metal halide can be on first surfaces of the phosphor particles and at least a portion of silane can be on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different. In some aspects, at least a portion of the metal halide and at least a portion of the siloxane can be on the same surfaces of the phosphor particles. In some aspects, at least a portion of the metal halide can be on first surfaces of the phosphor particles and at least a portion of the siloxane can be on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0049] In some aspects, the metal halide can be in the form of sol particles when deposited on the surfaces of phosphor particles. As used herein, a sol particle refers to solid particles in a continuous liquid medium forming a colloidal suspension.

[0050] In some aspects, the metal halide can be magnesium fluoride.

[0051] In some aspects, the ink composition can also include one or more scattering agents. For example, any of the phosphor materials described herein, can be at least partially coated with surface coatings to enhance stability of the phosphor particles and resist aggregation by modifying the surface of the particles and increase the zeta potential of the particles. In some aspects, the surface coatings can be a metal fluoride, silica or organic coating. In certain aspects, the phosphors described herein can be at least partially coated with a metal fluoride, which increases positive Zeta potential and reduces agglomeration. In certain aspects, the metal fluoride coating includes MgF_{2}, CaF_{2}, SrF_{2}, BaF_{2}, AgF, ZnF_{2} AlF_{3} or any combination thereof. In certain aspects, the metal fluoride coating can be present in an amount from about 0.1 wt% to about 10 wt %. In certain aspects, the metal fluoride coating can be present in an amount from about 0.1 wt% to about 5 wt %. In certain aspects, the metal fluoride coating can be present from about 0.3 wt% to about 3 wt %. Metal fluoride coated phosphors based on complex fluoride materials activated by Mn^{4+} can be prepared as described in WO 2018 / 093832 and US Publication No. 2020 / 0369956, which are incorporated by reference in their entireties.

[0052] In some aspects, the scattering agents can have a particle size of at least 1 \mu m. In certain aspects, the scattering agents can have a particle size from about 1 \mu m to about 10\mu m, including all the subranges in between. In certain aspects, the scattering agents can include titanium dioxide (TiO_{2}), aluminum oxide (Al_{2}O_{3}), zirconium oxide (ZrO_{2}), indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF_{2}), calcium fluoride (CaF_{2}), strontium fluoride (SrF_{2}) barium fluoride (BaF_{2}), silver fluoride (AgF), aluminum fluoride (AlF3) or combinations thereof.

[0053] In some aspects, the ink composition can have a viscosity from more than 2,000 cP to about 30,000 сР.

[0054] In some aspects, the phosphor particles can be present in an amount from about 5 wt% to about 70 wt%, based on the weight of the ink composition, including all the subranges in between.

[0055] In some aspects, the phosphor particles can be uniformly dispersed throughout the ink composition.

[0056] In some aspects, the phosphor particles can also include an additional phosphor. Suitable additional phosphors include, but are not limited to, (Y,Gd, Tb,La,Sm,Pr,Lu)3(Al,Ga)5- {}_{a}O_{12-3 / 2a}:Ce^{3+}(wherein 0\le a\le0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga,In)_{2}S_{4}:Eu^{2+}; alpha- SiAlON doped with Eu^{2+}and / or Ce^{3+}: Ca_{1-h-r}Ce_{h}Eu_{r}Al_{1-h}(Mg,Zn)_{h}SiN_{3} (where 0\le h\le0.2. 0\le r\le0.2); Sr(LiAl_{3}N_{4}):Eu^{2+}; (Ca,Sr)S:Eu^{2+} Ce^{3+}; (Ba,Sr,Ca)_{b}Si_{g}N_{m}:Eu^{2+}(wherein 2b+4g=3 m); or any combination thereof.

[0057] In some aspects, the phosphor particles can have a D50 value or about 0.1 microns to about 10 microns, including all the subranges in between. In certain aspects, the D50 value can be from about 0.1 microns to about 5 microns, including all the subranges in between. In certain aspects, the particle size distribution can have a D50 value of about 0.1\mu m, about 0.2 \mu m, about 0.3 \mu m, about 0.4 \mu m about 0.5 \mu m about 0.6 \mu m about 0.7 \mu m, about 0.8 \mu m, about 0.9\mu m, about 1.0 \mu m about 1.1 \mu m, about 1.2 \mu m, about 1.3 \mu m, about 1.4 \mu m, about 1.5 \mu m, about 1.6 µm, about 1.7 \mu m, about 1.8 \mu m, about 1.9\mu m, about 2.0 \mu m, about 2.1 \mu m, about 2.2 \mu m, about 2.3 \mu m, about 2.4 \mu m, about 2.5 \mu m, about 2.6 \mu m, about 2.7 \mu m, about 2.8 \mu m, about 2.9\mu m, about 3.0 \mu m, about 3.1\mu m, about 3.2 \mu m, about 3.3 \mu m, about 3.4 \mu m, about 3.5 \mu m, about 3.6 µm, about 3.7 \mu m, about 3.8 \mu m about 3.9\mu m about 4.0 \mu m, about 4.1\mu m, about 4.2 \mu m, about 4.3 \mu m, about 4.4 \mu m about 4.5 \mu m, about 4.6 \mu m. about 4.7 \mu m, about 4.8 \mu m, about 4.9 \mu m, or about 5.0 \mu m

[0058] In some aspects, the phosphor particles include an amount of manganese from about 0.5 wt% to about 4 wt % based on total phosphor particle weight, including all the subranges in between. In some aspects, the phosphor particles include an amount of manganese that is greater than about 2.5 wt% based on total phosphor particle weight. In certain aspects, the phosphor particles include an amount of manganese from about 2 wt% to about 3 wt% based on total phosphor particle weight, including all the subranges in between. In other aspects, the phosphor particles can have a Mn loading or Mn % of at least 1 wt %. In another aspect, the phosphor particles can have a Mn loading of at least 1.5 wt%. In another aspect, the phosphor particles can have a Mn loading of at least 2 wt %. In another aspect, the phosphor particles can have a Mn % of at least 3 wt %. In another aspect, the Mn % can be greater than 3.0 wt%. In another aspect, the content of Mn in the phosphor can be from about 1 wt% to about 4 wt %.

[0059] In some aspects, the phosphor particles can have a greater quantum efficiency than a comparable phosphor powder at zero-hour. In some aspects, the phosphor particles can have a quantum efficiency of about 77% to about 95% at zero-hour. In some aspects, the powder particles can have a quantum efficiency of greater than about 90% at zero-hour. In some aspects, the powder particles can have a quantum efficiency of about 90% to about 99%, about 91% to about 98%, about 92% to about 97%, about 93% to about 96% at zero-hour, including all the subranges in between. In some aspects, the powder particles can have a quantum efficiency of greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94% at zero-hour.

[0060] In some aspects, the ink composition can also include one or more other luminescent materials. In some aspects, the luminescent materials can be polyfluorenes, such as poly(9,9-dioctyl fluorene) and copolymers thereof, such as poly(9,9′-diocyl-fluorene-co-bis-N,N'-(4-butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole) and polyphenylenevinylene and their derivatives. Additional luminescent materials, such as blue, yellow, red, orange, or other color phosphors can be included to customize the white color of the resulting light and produce specific spectral power distributions.

[0061] In some aspects, the one or more luminescent materials can be quantum dot (QD) material. In certain aspects, the QD material can absorb blue light and generate green or red light or both can also be included to form a hybrid color conversion article. 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, such as CdTe, ZnSe, ZnTe, ZnS, HgTe, HgS, HgSe, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, group III-V or group IV-VI compound semiconductors such as GaN, GaP, GaNP, GaNAs, GaPAs, GaAs, GaAINP, GaAINAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, AIN, AINP, AINAs, AlP, AlPAs, AlAs, InN, InNP, InP, InNAs, InPAs, InAS, InAINP, InAINAs, 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 QDs having a formula of ABX3 where A is cesium, methylammonium or formamidinium, B is lead or tin and C is chloride, bromide or iodide. In one aspect, the perovskite quantum dot can be CsPbX3, where X is Cl, Br, I or a combination thereof. The mean size of the QD materials can range from about 2 nm to about 20 nm. The surface of QD particles can be further modified with ligands such as amine ligands, phosphine ligands, phosphatide and polyvinylpyridine. In one aspect, the quantum dot material can be perovskite quantum dots.

[0062] The QD materials can be a core / shell QD, including a core, at least one shell coated on the core, and an outer coating including one or more ligands, preferably organic polymeric 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, AIN, AIP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AIN, AIP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, 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, Cul, Si3N4, Ge3N4, Al2O3, [Al, Ga, In]2[S, Se, Te]3, and appropriate combinations of two or more such 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.

[0063] In some aspects, the ink composition can also include one or more additional phosphors. Suitable additional phosphors can include, but are not limited to: ((Sr_{1-z}[Ca, Ba, Mg, Zn]z)1-(x+w)[Li, Na, K, b]_{w}Ce_{x})_{3}(Al_{1-y}Si_{y})O_{4+y+3(x-w)}F_{1-y-3(x-w)}, (wherein 0\le x\le1.10, 0\le y\le0.5 0\le_{z}\le0.5, 0\le W\le\chi); [Ca,Ce]3Sc2S3O12 (CaSiG); [Sr,Ca,Ba]_{3}Al_{1-x}Si_{x}O_{4+x}F_{1-x}:Ce^{3+} (SASOF)); [Ba, Sr, Ca]5(PO4)3[Cl,F,Br,OH]:Eu2+,Mn2+; [Ba,Sr,Ca]BPO5:Eu2+,Mn2+, [Sr,Ca]_{10}(PO_{4})_{6}^{*}vB_{2}O_{3}:Eu^{2+} (wherein 0\le v\le1); Sr_{2}Si_{3}{O_{5}}^{*}{}_{2}SrCl_{2}:Eu^{2+}; [ Ca, Sr, Ba]3MgSi2O8:Eu2+, Mn^{2+}; BaAl_{8}O_{13:Eu^{2+}; 2SrO^{*}0.84P_{2}O_{5}^{*}0.16B_{2}O_{3}:Eu^{2+}; [ Ba, Sr CalMgAl_{10}O_{17:Eu^{2+}.M Mn^{2+}; [ Ba,Sr,Ca]Al_{2}O_{4}:Eu^{2+}; ZnS:Cu^{+} Cl¯; ZnS:Cu+, Al3+; ZnS:Ag^{+},Cl¯; ZnS:Ag^{+}, Al^{3+}; [Ba,Sr,Ca]_{2}Si_{1-n}O_{4-2n}:Eu^{2+} (wherein 0\le n\le0.2); [Ba,Sr,Ca]2[Mg,Zn]Si2O7:Eu2+; [Sr, Ca,Ba][Al,Ga,In]2S4:Eu2+; [Y,Gd, Tb, La, Sm,Pr,Lu]3 [Al,Ga]5-aO12-3 / 2a:Ce3+ (wherein (0\le a\le0.5); [ Ca, Sr]8[Mg,Zn](SiO4)4Cl2:Eu2+, Mn2+; Na2Gd2B2O7:Ce3+,Tb3+; [Sr, Ca, Ba, Mg, Zn]2 P2O7:Eu2+, Mn^{2+}; [Gd,Y,Lu,La]2O3:Eu3+,Bi³+; [Gd,Y,Lu,La]2O2S:Eu3+,Bi3+; [Gd,Y,Lu,La]VO4:Eu3+,Bi3+; [Ca,Sr]S:Eu2+,Ce3+; SrY_{2}S_{4}:Eu^{2+} CaLa_{2}S_{4}:Ce^{3+}; [Ba, Sr r,Ca]MgP_{2}O_{7}:Eu^{2+},Mn^{2+}; [Y,Lu]_{2}WO_{6}:Eu^{3+},Mo6+; [Ba, Sr, Ca]bSi8Nm:Eu2+ (wherein 2h+4 g=3m; Ca_{3}(SiO_{4})Cl_{2}:Eu^{2+}; [Lu, Sc, Y,Tb]2-u-v Cev Ca1+uLiwMg2-wPw(Si,Ge)3-wO12-u / 2 (where -0.5\le u\le1, 0<v<0.1 and 0\le w\le0.2); [Y,Lu, Gd]2-m[Y,Lu,Gd]CamSi4N6+mC1-m:Ce3+, (wherein 0\le m\le0.5); [Lu,Ca,Li,Mg,Y], alpha-SiAlON doped with Eu^{2+} and / or Ce^{3+}; Sr(LiAl_{3}N_{4}):Eu^{2+}, [Ca, Sr, Ba]SiO_{2}N_{2}:Eu^{2+},Ce3+; beta-SiAlON:Eu2+, 3.5MgO^{*}0.5MgF_{2}}^{*}GeO_{2}:Mn^{4+}; Ca_{1-c\_} {}_{f}Ce_{c}Eu_{f}Al_{1+c}Si_{1-c}N_{3}, (where 0\le c\le0.2, 0\le f\le0.2); Ca_{1-h-r}Ce_{h}Eu_{r}Al_{1-h}[Mg,Zn]_{h}SiN_{3}, (where N<h<0.2. 0\le r\le0.2); Ca_{1\le2s-t}Ces[Li,Na]_{5}Eu_{t}AlSiN_{3}, (where 0\le s\le0.2, 0\le t\le0.2, s+t>0); [Sr,Ca]AlSiN_{3}:Eu^{2+}Ce^{3+} and Li_{2}CaSiO_{4}:Eu^{2+}. In addition, the light emitting layer can include a blue, yellow, orange, green or red phosphorescent dye or metal complex, a quantum dot material, color filter pigments or a combination thereof. Materials suitable for use as the phosphorescent dye include, but are not limited to, tris(1-phenylisoquinoline) iridium (III) (red dye), tris(2-phenylpyridine) iridium (green dye) and Iridium (III) bis(2-(4,6-difluorephenyOpyridinato-N,C2) (blue dye). Commercially available fluorescent and phosphorescent metal complexes from ADS (American Dyes Source, Inc.) can also be used. ADS green dyes include ADS060GE, ADS061GE, ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

[0064] In another exemplary aspect, the present disclosure provides a film that includes a phosphor powder of the present material and a binder. In some aspects, the film includes a first layer including one or more first polymers, a second layer including one or more second polymers, and at least one cured or semi-cured ink interposed between the first layer and the second layer. It should be understood that reference to a cured ink indicates that the binder of the ink is in a cured state. Likewise, reference to a semi-cured ink indicates that the binder of the ink is in a semi-cured state.

[0065] In some aspects, the at least one cured or semi-cured ink includes a phosphor powder including phosphor particles, the phosphor particles including at least one phosphor material including a Mn^{4+} doped phosphor of formula I.A_{x}[MF_{y}]:Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is the absolute value of the charge of the \{\mathcal{N}\{E_{y}\} ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0066] In some aspects, the Mn^{4+} doped phosphor includes at least one of K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+}, K_{2}[TiF_{6}]:Mn^{4+} K_{2}[SnF_{6}]:Mn^{4+}, Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}]Mn^{4+}, Cs_{2}[SiF_{6}]:Mn^{4+} Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4+}, K_{3}[ZrF_{7}]:Mn^{4+}, K_{3}[BIF_{6}]K_{3}[YF_{6}]:Mn^{4+} K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+} In certain aspects, the Mn^{4+} phosphor of formula I can be K_{2}SiF_{6}:Mn^{4+} or Na_{2}[SiFfi]:Mn^{4+}.

[0067] In some aspects, the Mn^{4+} doped phosphor includes an amount of manganese from about 0.5 wt% to about 4 wt% based on total phosphor particle weight, including all the subranges in between. In some aspects, the phosphor particles include an amount of manganese that is greater than about 2.5 wt% based on total phosphor particle weight. In certain aspects, the phosphor particles include an amount of manganese from about 2 wt% to about 3 wt% based on total phosphor particle weight, including all the subranges in between. In other aspects, the phosphor particles can have a Mn loading or Mn % of at least 1 wt %. In another aspect, the phosphor particles can have a Mn loading of at least 1.5 wt%. In another aspect, the phosphor particles can have a Mn loading of at least 2 wt%. In another aspect, the phosphor particles can have a Mn % of at least 3 wt %. In another aspect, the Mn % can be greater than 3.0 wt%. In another aspect, the content of Mn in the phosphor can be from about 1 wt% to about 4 wt %.

[0068] In some aspects, the at least one phosphor material can be uniformly dispersed throughout the at least one cured or semi-cured ink.

[0069] In some aspects, the at least one cured or semi-cured ink also includes at least one binder. Binders for use in the at least one cured or semi-cured ink compositions described herein can include thermoplastic polymers and copolymers, pre-binder materials, such as thermally curable precursors or photocurable precursors. Exemplary binders include, but are not limited to, ethyl cellulose, polystyrene, polyacrylate, polymethacrylates, such as polymethyl acrylate (PMA) and polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate (PET), polyurethane, polyetherether ketone, polysulfone, polyphenylene sulfide, polyvinylpyrrolidone (PVP), polyethyleneimine (PEI), poly(1-naphthyl methacrylate), poly(vinyl phenyl sulfide) (PVPS), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), poly(N-vinylphthalimide), fluorinated polymers, such as polyvinylidene fluoride (PDVF) or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), amine-based oligomers / polymers / copolymers, fluorine-based oligomers / polymers / copolymers, poly(phenylene vinylene), carbazole-based oligomers / polymers / copolymers, phenyl-pyridine-based oligomers / polymers / copolymers. In certain aspects, the at least one binder can be at least one of an epoxy, acrylate, methacrylate, vinyl ester, siloxane, or polyethylene terethalate.

[0070] In some aspects, at least a portion of the metal halide and at least a portion of the silane can be on the same surfaces of the phosphor particles. In some aspects, at least a portion of metal halide can be on first surfaces of the phosphor particles and at least a portion of silane can be on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different. In some aspects, at least a portion of the metal halide and at least a portion of the siloxane can be on the same surfaces of the phosphor particles. In some aspects, at least a portion of the metal halide can be on first surfaces of the phosphor particles and at least a portion of the siloxane can be on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0071] In some aspects, the metal halide can be in the form of sol particles when deposited on the surfaces of phosphor particles.

[0072] In some aspects, the metal halide can be magnesium fluoride.

[0073] In some aspects, the at least one cured or semi-cured ink can also include one or more scattering agents. For example, any of the phosphor materials described herein, can be at least partially coated with surface coatings to enhance stability of the phosphor particles and resist aggregation by modifying the surface of the particles and increase the zeta potential of the particles. In some aspects, the surface coatings can be a metal fluoride, silica or organic coating. In certain aspects, the phosphors described herein can be at least partially coated with a metal fluoride, which increases positive Zeta potential and reduces agglomeration. In certain aspects, the metal fluoride coating includes MgF_{2}, CaF_{2}, SrF_{2}, BaF_{2}, AgF, ZnF_{2}, AlF_{3} or any combination thereof. In certain aspects, the metal fluoride coating can be present in an amount from about 0.1 wt% to about 10 wt%. In certain aspects, the metal fluoride coating can be present in an amount from about 0.1 wt% to about 5 wt%. In certain aspects, the metal fluoride coating can be present from about 0.3 wt% to about 3 wt%. Metal fluoride coated phosphors based on complex fluoride materials activated by Mn^{4+} can be prepared as described in WO 2018 / 093832 and US Publication No. 2020 / 0369956, which are incorporated by reference in their entireties.

[0074] In some aspects, the at least one cured or semi-cured ink can also include one or more other luminescent materials. In certain aspects, the one or more other luminescent materials can be quantum dot material. 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, such as CdTe, ZnSe, ZnTe, ZnS, HgTe, HgS, HgSe, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, group III-V or group IV-VI compound semiconductors such as GaN, GaP, GaNP, GaNAs, GaPAs, GaAs, GaAINP, GaAINAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, AIN, AINP, AINAs, AlP, AlPAs, AlAs, InN, InNP, InP, InNAs, InPAs, InAS, InAINP, InAINAs, 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, AgInSe_{2}, AgGaS_{2}, AgGaSe_{2} or perovskite QDs having a formula of ABX3 where A is cesium, methylammonium or formamidinium, B is lead or tin and C is chloride, bromide or iodide. In one aspect, the perovskite quantum dot can be CsPbX3, where X is Cl, Br, I or a combination thereof. The mean size of the QD materials can range from about 2 nm to about 20 nm. The surface of QD particles can be further modified with ligands such as amine ligands, phosphine ligands, phosphatide and polyvinylpyridine. In one aspect, the quantum dot material can be perovskite quantum dots.

[0075] In some aspects, the at least one cured or semi-cured ink can also include one or more additional phosphors. Suitable additional phosphors can include, but are not limited to: ((Sr1- 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)}, (wherein 0\le x\le1.10, 0\le y\le0.5, 0\le z\le0.5, 0\le W\le\chi); [Ca,Ce]_{3}Sc_{2}S_{3}O_{12}(CaSiG); [Sr,Ca,Ba]_{3}Al_{1-x}Si_{x}O_{4+x}F_{1} x:Ce^{3+} (SASOF)); [Ba, Sr,Ca]5(PO4)3[Cl,F,Br,OH]:Eu2+,Mn2+; [Ba,Sr,Ca]BPO_{5}:Eu^{2+},Mn^{2+}, [Sr,Ca]_{10}(PO_{4})_{6}^{*}vB_{2}O_{3}:Eu^{2+} (wherein 0\le v\le1,; Sr_{2}Si_{3}{O_{5}}^{*}{}_{2}SrCl_{2}:Eu^{2+}; [Ca,Sr,Ba]_{3}MgSi_{2}O_{8}:Eu^{2+},Mn^{2+} BaAl_{8}O_{13}:Eu^{2+} 2SrO^{*}0.84P_{2}O_{5}^{*}0.16B_{2}O_{3}:Eu^{2+}; [Ba, Sr, Ca]MgAl10017:Eu2+, Mn2+; [Ba,Sr,Ca]Al_{2}O_{4}:Eu^{2+}; [Y,Gd,Lu,Sc,La]BO_{3}:Ce^{3+},Tb^{3+} ZnS:Cu^{+} Cl; ZnS:Cu^{+},Al^{3+}; ZnS:Ag^{+},Cl¯; ZnS:Ag^{+}, Al3+; [Ba,Sr,Ca]_{2}Si_{1-n}O_{4-2n}:Eu^{2+} (wherein 0\le n\le0.2) [Ba, Sr,Ca]2[Mg,Zn]Si2O7:Eu2+; [Sr,Ca,Ba][Al,Ga,In]2S4:Eu2+; [Y,Gd, Tb,La, Sm,Pr,Lu]3 [Al,Ga]_{5-a}O_{12-3 / 2a}:Ce^{3+} (wherein (0\le a\le0.5); [ Ca, Sr]8[Mg,Zn](SiO4)4Cl2:Eu2+,Mn2+; Na_{2}Gd_{2}B_{2}O_{7}:Ce^{3+},Tb^{3+}; [Sr,Ca,Ba,Mg, Zn]2 P2O7:Eu2+, Mn2+; [Gd,Y,Lu,La]2O3:Eu3+,Bi³+; [Gd,Y,Lu,La]_{2}O_{2}S:Eu^{3+},Bi^{3}+; [Gd d,Y,Lu,La]VO_{4}:Eu^{3+},Bi^{3+}; [Ca,Sr]S:Eu2+, Ce^{3+}; SrY2S4:Eu2+; CaLa_{2}S_{4}:Ce^{3+}; [ Ba, Sr r.CalMgP_{2}O_{7}:Eu^{2+}. Mn^{2+}; [Y,Lu]_{2}WO_{6}:Eu^{3+} Mo^{6+}; [Ba, Sr r~Cal_{h}SieN_{m}:Eu^{2+} (wherein 2h+4 g=3m); Ca_{3}(SiO_{4})Cl_{2}:Eu^{2+}; [Lu,Sc, Y,Tb]2-u-v Cev 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 \mathcal{,}GdJCa_{m}Si_{4}N_{6+m}C_{1-m}:Ce^{3+}, (wherein 0<m<0.5); [Lu, Ca,Li, Mg,Y], alpha-SiAlON doped with Eu^{2+} and / or Ce³+; Sr(LiAl_{3}N_{4}):Eu^{2+}, [Ca, Sr, Ba]SiO2N2:Eu2+, Ce3+; beta-SiAlON:Eu2+, 3.5MgO^{*}0.5MgF_{2}}^{*}GeO_{2}:Mn^{4+}; Ca_{1-c-} {}_{f}Ce_{c}Eu_{f}Al_{1+c}Si_{1-c}N_{3}. (where 0\le c\le0.2, 0\le f\le0.2; Ca_{1-h-r}Ce_{h}Eu_{r}Al_{1-h}[Mg,Zn]_{h}SiN_{3}, (where 0≤h≤0.2, 0\le r\le0.2); Ca_{1\le2s-t}Ces[Li,Na]_{5}Eu_{t}AlSiN_{3}, (where 0<s<0.2, 0<t<0.2, s+t≥0); [Sr,Ca]AlSiN_{3}:Eu^{2+}Ce^{3+} and LisCaSiO_{4}· Eu^{2+}. In addition, the light emitting layer can include a blue, yellow, orange, green or red phosphorescent dye or metal complex, a quantum dot material, color filter pigments or a combination thereof. Materials suitable for use as the phosphorescent dye include, but are not limited to, tris(1-phenylisoquinoline) iridium (III) (red dye), tris(2-phenylpyridine) iridium (green dye) and Iridium (III) bis(2-(4,6-difluorephenyOpyridinato-N,C2) (blue dye). Commercially available fluorescent and phosphorescent metal complexes from ADS (American Dyes Source, Inc.) can also be used. ADS green dyes include ADS060GE, ADS061GE, ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

[0076] In some aspects, any of the phosphor powders described herein, the ink compositions described herein, and / or the films described herein can also include one or more agents on the surfaces of the phosphors. In some aspects, the phosphors can be at least partially coated with surface coatings to enhance stability of the phosphor particles and resist aggregation by modifying the surface of the phosphor particles and increase the zeta potential of the phosphor particles. In certain aspects, the coated phosphor can have a MgF_{2} or CaF_{2} surface coating and a surface Zeta potential of at least |20 mV| when measured in isopropanol. In certain aspec, the coated phosphor can have a Zeta potential of at least 30 mV when measured in isopropanol.

[0077] In some aspects, the surface coatings can be a metal fluoride, silica or organic coating. In certain aspects, the phosphors cam be at least partially coated with a metal fluoride, which increases positive Zeta potential and reduces agglomeration. In certain aspects, the metal fluoride coating includes MgF_{2}, CaF_{2}, SrF_{2}, BaF_{2}, AgF, ZnF_{2}, AlF_{3} or a combination thereof. In certain aspects, the metal fluoride coating can be present in an amount from about 0.1 wt% to about 10 wt%, including all the subranges in between. In certain aspects, the metal fluoride coating can be present in an amount from about 0.1 wt% to about 5 wt%, including all the subranges in between. In certain aspects, the metal fluoride coating can be present from about 0.3 wt% to about 3 wt%, including all the subranges in between. Metal fluoride coated Mn^{4+} doped phosphors can be prepared as described in WO 2018 / 093832 and US Publication No. 2020 / 0369956. The entire contents of each of which are incorporated herein by reference.

[0078] In some aspects, the phosphors can be at least partially coated with an organic coating, such as polymerized oleic acid. Oleic acid can be used to coat the phosphor particles via a solvothermal synthesis or treatment, such as by a mixing adsorption treatment.

[0079] In some aspects, any of the phosphor powders described herein, the ink compositions described herein, and / or the films described herein can further include one or more additives. In certain aspects, the additives can include surfactants, dispersants, rheology modifiers, scattering agents, and combinations thereof. In some aspects, surfactants, such as small molecule surfactants or dispersants can be incorporated to reduce dispersity and agglomeration in the ink compositions provided herein. Dispersants reduce agglomeration of phosphor powders with minimal impact to optical performance and reliability. Dispersants can have functional groups, such as hydroxyl (—OH), carboxyl (—COOH), sulfonate, sulfate, ammonium, amino (—NH2) or imino (—NH—) for anchoring on surfaces and a buoyant moiety, which helps to keep a dispersion uniform and homogeneous. In addition, dispersants with proper functional groups can also improve wetting ability. A liquid with lower surface tension tends to wet particles better than liquids with higher surface tension. Dispersants can lower the surface tension of a liquid and the interfacial tension between the liquid and dispersing particles.

[0080] In some aspects, the dispersants can be anionic, non-ionic, cationic or zwitterionic polymers. Anionic dispersants include, but are not limited to, potassium oleate, alkyl sulfonate, polyesters, phosphoric and carboxylic acid esters, polyoxyethylene (10) ether phosphate, polyol derivatized phosphate ester, phosphates, 2-(octen-1-yl)-butanedioic acid, polyacrylates including structured or controlled polymerization technology (CPT) derived acrylates, polyacrylate salt, such as a polyol functionalized polyacrylate. In other aspects, the dispersants are zwitterionic, such as a zwitterionic comb copolymer functionalized with amine and acid groups. In one aspect, the non-ionic dispersant can be a polyurethane based dispersant. In another aspect, the cationic dispersant can be a polyamine dispersant, including cationic hyperbranched polyamine. In one aspect, the dispersant can be one or polymers containing amine groups, polymer dispersants, such as TEGO® 689 and TEGO® 690 with pigment affinity groups, such as dodecanoic acid, polymers with OH / ether groups and pigment affinity groups. In one aspect, the dispersant can be a polyester composed of polyhydroxystearic acid stearate. In another aspect, the dispersant can be EO / PO block copolymers. In one aspect, the dispersant can be a solution of a modified urea (BYK®-7410-ET from BYK Additives and Instruments).

[0081] In some aspects, the dispersant or surfactant can be included in any of the phosphor powders described herein, the ink compositions described herein, and / or the films described herein in amounts up to 10 wt%. In some aspects, the dispersant or surfactant can be included in an amount from about 0.1 wt% to about 10 wt%, including all the subranges in between. In another aspect, the dispersant or surfactant can be included in an amount from about 1 wt% to about 5 wt%, including all the subranges in between. The dispersant or surfactant amount can be based on the total weight of the ink composition.

[0082] In some aspects, any of the phosphor powders described herein, the ink compositions described herein, and / or the films described herein can also include rheology modifiers. Rheology modifiers can be used to provide desirable rheological properties, such as adjusting the viscosity of the compositions, improving dispersion stability and phosphor particle suspension and controlling the rheology profile of the compositions for film forming characteristics and ink printability. In one aspect, the rheology modifier can have a viscosity greater than 100 centipoise at 20^{\circ} C. In one aspect, the rheology modifiers can include silica nanoparticles and clay-based materials. In other aspects, nanoparticles of silica can be fumed silica, precipitated silica or surface-modified hydrophobic silica.

[0083] In some aspects, the rheology modifiers can include gelators including at least one crosslinkable group. In some aspects, the gelators can gel at temperatures at less than 30^{\circ} C. In some aspects, the gelators can gel at temperatures in the range of about 20^{\circ} C to about 30^{\circ}c C, including all the subranges in between. Gelators, such as a wax with polymerizable functionality, can be added to any of the phosphor powders described herein, the ink compositions described herein, and / or the films described herein to form gel-like dispersions with good stability and low sedimentation at room temperature, which become coatable and printable liquids with much reduced viscosity upon heating. Exemplary waxes include, but are not limited to, di(hexadecyl) fumarate, oleyl cinnamide, di(4-vinyloxybutyl) octadecanedioate, non-polar acrylate waxes, such as octadecyl cinnamide, and functionalized waxes, such as dodecyl cinnamide.

[0084] In some aspects, additive materials can be added to any of the phosphor powders described herein, the ink compositions described herein, and / or the films described herein to adjust rheological properties, adjust viscosity and optimize coatability or film-forming capability and printability. In some aspect, materials with high thermal conductivity, such as aluminum nitride nanoparticles and microparticles can be added to the phosphor powders described herein, the ink compositions described herein, and / or the films described herein. In other aspects, one or more electrolytes or polyelectrolytes can be added to the phosphor powders described herein, the ink compositions described herein, and / or the films described herein.

[0085] In another exemplary aspect, the present disclosure provides a process for producing a coated phosphor as described herein. In certain aspects, the process includes combining at least one phosphor material described herein with metal halide to form a first coated phosphor, and combining the first coated phosphor with a silane or a siloxane to produce a second coated phosphor. In some aspects, combining at least one phosphor material with metal halide includes introducing the at least one phosphor material into a suspension of metal halide, wherein the metal halide is in the form of sol particles. In some aspects, combining the first coated phosphor with a silane or a siloxane includes combining the first coated phosphor with a silane. In some aspects, combining the first coated phosphor with a silane or a siloxane includes combining the first coated phosphor with a siloxane.

[0086] In another exemplary aspect, the present disclosure provides a method for inkjet printing, flexographic printing, microdispensing printing, screen printing, direct write printing, aerosol jet printing, or gravure printing. In some aspects, the method includes printing an ink composition, wherein the ink composition includes phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn^{4+} doped phosphor as described herein.

[0087] Devices according to the present disclosure can include an LED light source radiationally connected and / or optically coupled to any of the phosphor compositions described herein, the ink compositions described herein, and / or the films described herein. FIGs. 3A-3E show a device 10, according to various aspects of the present disclosure. Referring to FIG. 3A, the device 10 includes an LED light source 12 and the phosphor composition 14. The LED light source 12 can be a UV or blue emitting LED. In some aspects, the LED light source 12 produces blue light in a wavelength range from about 380 nm to about 460 nm, including all the subranges in between. In the device 10, the phosphor composition 14 is radiationally coupled and / or optically coupled to the LED light source 12. Radiationally connected or coupled or optically coupled means that radiation from the LED light source 12 is able to excite the phosphor composition 14, and the phosphor composition 14 is able to emit light in response to the excitation by the radiation. The phosphor composition 14 can be disposed on a part or portion of the LED light source 12 or located remotely at a distance from the LED light source 12. In some aspects, the device can be a backlight unit for display applications. In other aspects, the LED light source 12 can be a micro-LED and the device can be for a self-emissive display. FIG. 3B shows an exemplary aspect where the phosphor composition 14 is disposed on the LED light source 12. The LED light source 12 can be 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 can be any material suitable for reflecting light. In one aspect, the reflective layer 16 can be a metallic layer, such as aluminum, silver, silver alloys or aluminum alloys. FIG. 3C shows an exemplary aspect where the phosphor composition 14 is disposed on the LED light source 12. An encapsulant or barrier layer 18 can be disposed on the phosphor composition 14. The encapsulant or barrier layer 18 can be a low temperature glass, or a polymer or resin known in the art, for example, an epoxy, silicone, epoxy-silicone, acrylate or a combination thereof. The encapsulant or barrier layer 18 should be transparent to allow light to be transmitted through those elements. FIG. 3D shows an exemplary aspect where the LED light source 14 is depicted as an array of LED light sources 12. In some aspects, the LED light sources 12 can be mini-LEDs or micro-LEDs. FIG. 3E shows an exemplary aspect where the phosphor composition 14 is located remotely from the LED light source 12, which is depicted as an array of LED light sources 12.

[0088] The general discussion of the example LED light source discussed herein is directed toward an inorganic LED based light source. The most popular white LEDs are based on blue or UV emitting GalnN chips. In addition, to inorganic LED light sources, the term LED light source is meant to encompass all LED light sources, such as semiconductor laser diodes (LD), organic light emitting diodes (OLED) or a hybrid of LED and LD. The LED light source can be a mini-LED or micro-LED, which can be used in self-emissive displays. Further, it should be understood that the LED light source can be replaced, supplemented or augmented by another radiation source unless otherwise noted and that any reference to semiconductor, semiconductor LED, or LED chip is merely representative of any appropriate radiation source, including, but not limited to, LDs and OLEDs.

[0089] The phosphor composition 14 can be present in any form such as powder, glass, or composite, e.g., a phosphor-polymer composite or phosphor-glass composite. Further, the phosphor composition 14 can be used as a layer, sheet, film, strip, dispersed particulates, or a combination thereof. In some aspects, the phosphor composition 14 includes the uranium-based phosphor material in glass form. In some aspects, the device 10 can include the phosphor composition 14 in form of a phosphor wheel (not shown). The phosphor wheel can include the phosphor composition embedded in a glass. A phosphor wheel and related devices are described in WO 2017 / 196779, which is incorporated herein by reference.

[0090] The phosphor composition can be optically coupled or radiationally connected to an LED light source. In one aspect, a white light blend can be obtained by blending the red phosphor material and the green phosphor material with an LED light source, such as a blue or UV LED.

[0091] FIG. 4 illustrates a lighting apparatus or lamp 20, in accordance with the present teachings. In one aspect, the lighting apparatus 20 can be a backlight apparatus. The lighting apparatus 20 includes an LED chip 22 and leads 24 electrically attached to the LED chip 22. The leads 24 can include thin wires supported by a thicker lead frame(s) 26 or the leads 24 can include self-supported electrodes and the lead frame can be omitted. The leads 24 provide current to LED chip 22 and thus cause it to emit radiation.

[0092] A layer 30 of the phosphor composition can be disposed on a surface of the LED chip 22. The phosphor layer 30 can be disposed by any appropriate method, for example, using a slurry or ink composition prepared by mixing the phosphor composition and a binder material or solvent (as discussed above). In one such method, a silicone slurry in which the phosphor composition particles are randomly suspended or uniformly dispersed is placed around the LED chip 22. This method is merely exemplary of possible positions of the phosphor layer 30 and LED chip 22. The phosphor layer 30 can be coated over or directly on the light emitting surface of the LED chip 22 by coating and drying the slurry over the LED chip 22. The light emitted by the LED chip 22 mixes with the light emitted by the phosphor composition to produce desired emission.

[0093] With continued reference to FIG. 5, the LED chip 22 can be encapsulated within an envelope 28. The envelope 28 can be formed of, for example, glass or plastic. The LED chip 22 can be enclosed by an encapsulant material 32. The encapsulant material 32 can be a low temperature glass, or a polymer or resin known in the art, for example, an epoxy, silicone, epoxy-silicone, acrylate or a combination thereof. In some aspects, the lighting apparatus 20 only includes the encapsulant material 32 without the envelope 28. Both the envelope 28 and the encapsulant material 32 should be transparent to allow light to be transmitted through those elements.

[0094] In some aspects, the phosphor composition 36 can be interspersed within the encapsulant material 32, instead of being formed directly on the LED chip 22, as shown in FIG. 5. The phosphor composition 36 can be interspersed within a portion of the encapsulant material 32 or throughout the entire volume of the encapsulant material 32. Blue light or UV light emitted by the LED chip 22 mixes with the light emitted by phosphor composition 33, and the mixed light transmits out from the lighting apparatus 20.

[0095] In some aspects, a layer 34 of the phosphor composition can be coated onto a surface of the envelope 28, instead of being formed over the LED chip 22, as illustrated in FIG. 6. As shown, the phosphor layer 34 can be coated on an inside surface 29 of the envelope 28, although the phosphor layer 34 can be coated on an outside surface of the envelope 28, if desired. The phosphor layer 34 can be coated on the entire surface of the envelope 28 or only a top portion of the inside surface 29 of the envelope 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 transmits out. Of course, the phosphor composition can be located in any two or all three locations (as shown in FIGs. 4-6) or in any other suitable location, such as separately from the envelope 28, remote or integrated into the LED chip 22. In one aspect, the phosphor layer 34 can be a film and located remotely from the LED chip 22. In another aspect, the phosphor layer 34 can be a film and disposed on the LED chip 22. In some aspects, the phosphor layer 34 can be applied to the LED chip 22 as an ink composition. In some aspects, the phosphor layer 34 can be applied to the LED chip 22 as an ink composition and dried to form a film on the LED chip 22. In some aspects, the phosphor composition can be a single layer or multi-layered. In some aspects, the film is a multi-layered structure where each layer of the multi-layered structure includes at least one phosphor or quantum dot material.

[0096] In another aspect, a device structure includes a layer of a phosphor composition on an LED chip and a remote layer including a quantum dot material. In another aspect, a device structure includes a layer of a phosphor composition on an LED chip and a remote layer including a quantum dot material and phosphor material. In another aspect, a device structure includes a layer of a phosphor composition on an LED chip and a film including quantum dot material located remotely from the LED chip. In another aspect, a device structure includes a layer of a phosphor composition on an LED chip and a film including quantum dot material and phosphor material located remotely from the LED chip.

[0097] In any of the above structures, the lighting apparatus 20 (FIGS. 3-6) can also include a plurality of scattering particles (not shown), which are embedded in the encapsulant material 32. The scattering particles can comprise, for example, alumina, silica, zirconia, or titania. The scattering particles effectively scatter the directional light emitted from the LED chip 22, preferably with a negligible amount of absorption.

[0098] In one aspect, the lighting apparatus 20 shown in FIG. 5 or FIG. 6 can be a backlight apparatus. In another aspect, the backlight apparatus comprises a backlight unit 10. Some aspects include a surface mounted device (SMD) type light emitting diode 50, e.g., as illustrated in FIGs. 7A, 7B and 7C, for backlight applications. Referring to FIG. 7A, SMD is a “side-emitting type" and has a light-emitting window 52 on a protruding portion of a light guiding member 54. In some aspects, an SMD package includes an LED chip 56 as defined above, and a phosphor composition 58 as described herein. FIG. 7B shows the phosphor composition 58 disposed on the LED chip 56 and FIG. 7C shows the phosphor composition 58 disposed remotely from the LED chip 56. FIGs. 7B and 7C also show the LED chip 56 and the light guiding member 54 disposed on a reflective layer 59. The reflective layer 59 reflects light from the LED chip 56 and the light guiding member 54 toward the phosphor composition 58. The reflective layer 59 can be any material suitable for reflecting light. In one aspect, the reflective layer 59 can be a metallic layer, such as a silver, aluminum, aluminum alloy or silver alloy. In another aspect, the device can be a direct lit display. By use of the phosphor compositions described herein, devices can be provided producing white light for display applications, for example, LCD backlight units, having high color gamut and high luminosity. Alternately, devices can be provided producing white light for general illumination having high luminosity and high CRI values for a wide range of color temperatures of interest (2000 K to 10,000 K).

[0099] Devices of the present disclosure include lighting and display apparatuses for general illumination and display applications. Examples of display apparatuses include liquid crystal display (LCD) backlight units, televisions, computer monitors, vehicular displays, laptops, computer notebooks, mobile phones, smartphones, tablet computers and other handheld devices. Where the display is a backlight unit, the phosphor composition can be incorporated in a fdm, sheet or strip that is radiationally coupled and / or optically coupled to the LED light source, as described in US Patent Application Publication No. 2017 / 0254943, incorporated herein by reference. Examples of other devices include chromatic lamps, plasma screens, xenon excitation lamps, UV excitation marking sy stems, automotive headlamps, home and theatre projectors, laser pumped devices, and point sensors. In one aspect, the device can be a fast response display that does not include an LCD. The fast response display can be a self-emissive display including phosphor converted (PC) micro-LEDs. The list of these applications is meant to be merely exemplary and not exhaustive.

[0100] In some aspects, films including the phosphor composition can be disposed on small-size LEDs, such as micro-LEDs or mini-LEDs. In other aspects, the film includes phosphors with micron or sub-micron particle sizes. In other aspects, the film includes nano-sized particles. In one aspect, the film includes a Mn^{4+} doped phosphor having a D50 particle size less than 20 pm, less than 10 pm, particularly less than 5 pm, more particularly nano-sized. In another aspect, the D50 particle size can be from about 1 micron to about 20 microns. In another aspect, the D50 particle size is from about 1 micron to about 15 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 1 micron to about 10 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 1 micron to about 5 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 1 micron to about 3 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 50 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50 particle size is from about 100 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50 particle size is from about 200 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50 particle size is from about 250 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50 particle size is from about 500 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50 particle size is from about 750 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50 particle size is from about 50 nm to about 10 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 200 nm to about 5 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 250 nm to about 5 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 500 nm to about 5 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 750 nm to about 5 microns, including all the subranges in between. In another aspect, the D50 particle size is from about 750 nm to about 3 microns, including all the subranges in between.

[0101] FIGs. 8A-8C are schematic diagrams of a banked arrangement 200, in accordance with the present teachings. More particularly, FIGs. 8A-8C illustrate banked arrangement 200 at different phases of a dispensing or printing process. Both printing and transferring a high aspect ratio conversion layer on small-feature light emitting elements (e.g., mini-LEDs, and / or micro-LEDs) assembled over a plain substrate surface is challenging. Banked arrangement 200 enables a high aspect ratio conversion layer to be achieved on small-feature light emitting elements in a more efficient and cost-effective manner than current printing and / or dispensing technologies. For example, in some aspects, an aspect ratio of at least 0.1 (i.e., 1:10) can be achieved. In another aspect, the aspect ratio is from about 0.1 to about 10, including all the subranges in between. In another aspect, the aspect ratio is from about 0.1 to 5, including all the subranges in between. In another aspect, the aspect ratio is from about 0.5 to 5. In another aspect, the aspect ratio is from about 0.1 to 3, more particularly, 0.1 to 1 and 0.1 to 0.5, including all the subranges in between.

[0102] In FIG. 8A a plurality of light emitting elements 202 (e.g., LEDs, mini-LEDs, and / or micro-LEDs), operating at a desired color point (e.g., white light) are disposed on a substrate 210. In FIG. 8B, one or more walls 204 are disposed around each of the plurality of light emitting elements 202. In some aspects, each light emitting element 202 is surrounded by continuous walls 204. For example, each light emitting element 202 can be surrounded by a plurality of walls 204 which form a closed square, rectangle, or other shape, thereby forming a banked structure around each light emitting element 202. In the exemplary arrangement illustrated in FIGs. 8A-8D, each light emitting element 202 is surrounded by four walls 204 formed on planar structure 210, which form a banked structure 206. In other aspects, such as the example illustrated in FIG. 9, walls 204 are formed within a layer 244 that sits on top of the planar substrate 210, thereby forming a well structure 246. Therefore, banked arrangement 200 can include each light emitting element 202 surrounded by a banked structure 206 or a well structure 246. In some aspects, banked structure 206 or well structure 246 is formed via printing (e.g., using a contact stencil printing system or snap-off stencil printing system). In further aspects, snap-off printing can be desired, as it provides control over printing speed and with the appropriate opening dimensions, can lead to the right amount of material at the desired positioning to be transferred to fill well structures without any spill over to next pixel / color-filters. Further, in some aspects that include a well structure, a relatively thin stencil thickness can be used for better see-through to assist with alignment at a micron scale.

[0103] In some aspects, walls 204 include reflective materials, and therefore can act as reflectors. More particularly, walls 204 can be coated with a white surface which reflects back all the visible wavelengths that shine on it. The reflective material in walls 204 can increase the brightness of the light emitting elements. In some aspects, one or more walls 204 include a translucent material For example, in transparent display applications, walls 204 can include a translucent material.

[0104] In FIG. 8C, the banked structure, or alternatively the well structure, can be filled with an optically active material 230. The optically active material can include a down-conversion material, such as a phosphor material. In some aspects the banked structure, or alternatively, the well structure, can be filled by a dispensing and / or printing method. For example, in some aspects, the banked structure or the well structure can be filled using a contact stencil printing system or snap-off stencil printing system. Snap-off stencil printing system can enable the transfer of materials with high reproducibility and uniformity in a cost-effective manner. In other aspects, the well is filled via dispensing or printing methods known in the art.

[0105] FIG. 10A is a top view of an example red-green-blue (RGB) pixel 1000 that includes a blue subpixel 1010, a green subpixel 1020, and a red subpixel 1030. FIG. 10B is a side view of an example RGB pixel layout 1000. Each subpixel can include a well including a plurality of walls. An ink composition including blue-emitting phosphors can be deposited in blue subpixel 1010, an ink composition including green-emitting phosphors can be deposited in green subpixel 1022, and an ink composition including red- emitting phosphors can be deposited in red subpixel 1030. The ink compositions deposited into blue subpixel 1012, green subpixel 1020, and red subpixel 1030 can cure into a color filter parts 1012, 1022, and 1032, respectively. As such, blue subpixel 1010 can be configured to emit blue light 1016, green subpixel 1020 can be configured to emit green light 1026, and red subpixel 1030 can be configured to emit red light 1036. In some aspects, each subpixel, 1010, 1020, 1030 includes a color filter material 1014, 1024, 1034, respectively. In some aspects, stencil printing can be used to deposit the ink compositions. The stencil printing can be performed via a contact stencil printing system or a snap-off stencil printing system. The ink composition can be cured using hot air, UV light, and / or any other method known in the art.

[0106] In some aspects, a scattering agent can be added to a subpixel, as noted above. In some aspects, the scattering agent can include a refractive index of about 0. 1 to about 3, including all the subranges in between. In further aspects, the scattering agent can include a refractive index of about 1 to about 1.6, including all the subranges in between. In further aspects, the scattering agent can include a refractive index of about 1.50. In further aspects, the scattering agent can include a refractive index of about 1.51. A scattering agent having a relatively high refractive index increases the effective path length of excitation light 1040 (e.g., the blue light) for additional absorption.

[0107] In some aspects, a subpixel can be filled in part by a first ink composition, and in part by a second ink composition. The second ink composition can be located proximate to a portion of the pixel or subpixel through which excitation light enters (e.g., side 1002 in FIG. 16B). Excitation light 1040 can enter the pixel, and encounter the second ink composition and then subsequently, the first ink composition. The subpixel can be filled using a two-pass printing approach. The printing can be performed via a contact stencil printing system or snap-off stencil printing system. The ink composition can be cured using hot air, UV light, and / or any other method known in the art. The first ink composition and the second ink composition can include different refractive indexes. For example, in some aspects, the second ink composition includes a relatively low refractive index and the first ink composition comprising a relatively high refractive index. For example, in some aspects, the first ink composition includes a higher refractive index than the second ink composition. This causes 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 once coupled into the color filter part. In further aspects, the second ink composition includes a refractive index of about 0.1 to about 2, including all the subranges in between. In further aspects, the second ink composition includes a refractive index of about 0.1 to about 1.6, including all the subranges in between. In further aspects, the second ink composition includes a refractive index of about 0.1 to about 1.51, including all the subranges in between. In some aspects, the first ink composition includes a refractive index of greater than about 1. In further aspects, the first ink composition includes a refractive index of greater than about 1.3. In further aspects, the first ink composition includes a refractive index of greater than about greater than 1.50. In further aspects, the first ink composition includes a refractive index of greater than about 1.51.

[0108] In some aspects, quantum dots in a color filter (QDCF) can be utilized. QDCF can improve the color quality, viewing angle and energy efficiency of displays. By using a blue light source such as OLED, LED, mini -LED, or micro-LED, or a UV light source, and replacing traditional color filters with a QDCF material, at least a portion of the blue light gets converted to a higher wavelength range such as red and / or green light.

[0109] In some aspects, RGB pixel 1000 is part of a display device that includes a backlight unit (BLU) configured to emit a blue light 1040. In such aspects, QDCF can include scattering agent in blue subpixel 1010 and a quantum dot in the red subpixel 1030 and green subpixel 1020 to attain wide color gamut. In addition to the quantum dots in the red subpixel 1030 and green subpixel 1020, at least one binder, at least one scattering agent and / or an additional color filter material that absorbs blue light can be added to minimize blue light leakage through the subpixel, which would result in lower color gamut.

[0110] Suitable contact stencil printing system and snap-off stencil printing system include those described in WO2023 / 215433A1, the content of which is incorporated here by reference.

[0111] It is understood that the examples and aspects described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.EXAMPLES

[0112] The following non-limiting examples are illustrative of the present disclosure.Example 1: Synthesis of MgF_{2} Coated Phosphor

[0113] The synthesis of MgF_{2} coated potassium hexafluorosilicate (PFS) phosphor was based on modified methods described in the field. In the preparation of sample A, the MgF_{2} coating was introduced to the precipitated PFS as a suspension of MgF_{2} sol particles, which was created by first dissolving 5 g of Mg acetate tetrahydrate in 13 mL water and then adding 37 mL 49% hydrofluoric acid. Similar methodology was used to prepare sample B, however, a standard solution of MgF_{2} was used instead of sol particles.Example 2: Siloxane Coating (sample A112823ATMgGA(838)Sx)

[0114] Sample A-Sx was prepared by taking 5 grams of PFS (sample A) and 15 pieces of 5 mm YSZ ball media was placed in a 30 mL NalgeneTM bottle. Then, 0.1 g(2 wt%) HMS-991 (polymethylhydrosiloxane, trimethylsilyl terminated; Gelest) was added dropwise via pipet. The bottle was sealed and then manually shaken for several minutes. During this time, the walls of the bottle were scraped with a spatula to remove stuck powder and encourage mixing. After, 0.1 g (2 wt%) SIO6700.0 (octamethylcyclotetrasiloxane, 98%; Gelest) was added dropwise via pipet. The bottle was sealed and then manually shaken for several minutes. The product was then transferred to an aluminum dish and dried in a convection oven at 90^{\circ}C for 1 h and 120^{\circ}C for 1 h. Additional 0.1 g of each siloxane above was added (4 wt% each siloxane) and then the product was dried at 120^{\circ}C for 1 h.Example 3: Silane Coating

[0115] A solution of 15 mL of alcohol (e.g. isopropanol, terpineol) with optionally up to 5 wt% of deionized water was prepared. Then, 0.33 -0.66 g of a silane (from Gelest) was added to the alcohol solution and this silane solution was stirred for 5-15 min. 5 grams of PFS was added to the silane solution and mixed for 5-10 min. The mixture was then centrifuged and the supernatant was decanted. The PFS was then rinsed one time with 25 mL isopropanol and one time with 25 mL acetone. The silane coated PFS was then dried overnight at room temperature in a vacuum desiccator. The dried powder was sieved through a 60 mesh sieve and then cured in air for 10 min at 110^{\circ}C.Example 4: Characterization of Phosphor Powder

[0116] Optical performance including quantum efficiency (QE), blue light bleed through (BT), and R631 of PFS powders were measured as silicone tapes prepared and tested according to the standard operating procedure (SOP). PFS powder aggregate particle size analysis was measured using a HoribaTM Particle Counter according to the SOP. The carrier liquid was n-methyl pyrrolidone (NMP), which possessed a sufficient refractive index difference compared to PFS to allow for greater sensitivity when measuring submicron PFS (NMP RI=1.46; PFS RI= 1.40). Also, the polarity of NMP increased particle dispersion during measurement. Values are reported after sonication of PFS in NMP using the internal sonication horn at setting "5" for 3 min and stirring. The D50 was defined as the median particle size. The D10 and D90 values were defined as the particle sizes for a volume distribution greater than the particle size of 10% and 90% of the particles in the distribution, respectively. Scanning electron microscopy (SEM) was used to confirm aggregate size and primary PFS particle sizes. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to determine the elemental composition of PFS powders.Example 5: High Temperature, High Humidity (HTHH) Testing of the Phosphor Powder

[0117] Silicone tapes containing PFS were subjected to one (1) 30 h heating cycle at 80^{\circ}C and 60% relative humidity in a specially designed humidity chamber. After the heating cycle, the optical performance of the tapes was measured as above for quantum efficiency (QE), blue light bleed through (BT), and R631 and compared to the zero-hour data.Example 6: Results and DiscussionSiloxane coatings (sample A-Sx)

[0118] The parent sample A-PFS powder showed QE=90\% with aggregate D50<3.0 \mu m. Upon coating this powder with siloxanes, sample A-Sx showed increased QE compared to the parent PFS (Table 1), which was an unexpected result as prior coating experiments typically showed decreased QE upon coating. The aggregate size increased, however, after the coating process.Table 1. Summary of composition, aggregate size, and zero-hour (t=0) optical properties for the siloxane coated PFS powder characterized in this study.Silane Coatings

[0119] Table 2 summarizes the characterization of PFS samples coated with various silanes. Samples A-SiA and A-SiB showed increases in QE upon coating, which was similar to the siloxane trials above. Also, the D90 and D50 aggregate sizes for A-SiA and A-SiB decreased relative to the parent sample A PFS powder, which indicated that the silane coated powders were more easily dispersed in solvent.Table 2. Summary of composition, aggregate size, and zero-hour (t=0) optical properties for the silane coated PFS powders characterized in this study.

[0120] Additional characterization was carried out to confirm the surface functionalization of PFS powders with silanes. Figure 1 shows the thermogravimetric analysis (TGA) traces of A-SiA and A-SiB. The samples were heated under nitrogen with a heating ramp of 10^{\circ}C / min. Mass loss was observed at temperatures >350^{\circ}C, which indicated the presence of adsorbed species. The total mass loss at 500^{\circ}C was 0.77 – 0.95 wt% depending on the sample.

[0121] Infrared spectroscopy was used to analyze the surface functional groups present on the silane coated PFS powders (Figure 2). Many of the bands observed in the FTIR spectra are expected for PFS, including the presence of SiF_{6} and O-H stretches. The presence of Mg coating was confirmed by the appearance of a distinct Mg-OH stretch at 3700 cm^{-1}. The FTIR spectra also showed alkane C-H stretches in the 2800-3000 cm^{-1} region, which confirmed the PFS surface was successfully functionalized with organic silanes, in this case n-octyltrimethoxysilane. Overall, the spectroscopic evidence suggested the presence of both inorganic MgF2 and organic silane coatings on the surface of PFS.

[0122] The reliability of A-SiA and A-SiB were tested using a high temperature-high humidity (HTHH) test for 30 h under 60% relative humidity at 80^{\circ}C. After exposure to HTHH conditions, the QE decreased from 94% to 61% for both A-SiA and A-SiB, which indicated a major loss of quantum efficiency and poor reliability. This suggested the silane coating was not sufficient at the current concentrations (< 1 wt% according to TGA) to provide PFS with good HTHH stability.

[0123] Powders were functionalized with additional silanes of varying carbon chain lengths, including a phenyl functionality. Table 3 lists the different silanes studied and the resulting zero-hour optical properties including quantum efficiency, bleedthrough, and reflectivity at 631 nm.Table 3. Summary of zero-hour (t=0) optical properties for the silane coated PFS powders characterized in this study.

[0124] As shown herein, manganese doped phosphor, such as PFS powders, when coated with both inorganic metal halide (e.g., MgF2) and organic siloxane and / or silanes yielded phosphor powders that were better dispersed in resins and solvents, which is useful in the formulation of phosphor powder and inks. Results indicated the PFS surface was functionalized with both MgF_{2} and siloxane / silanes.

[0125] While the present disclosure has been described with reference to examples, it is to be understood that the scope of the claims should not be limited by the aspects set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.

[0126] In one embodiment, a phosphor powder comprises:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I:A_{3}[MF_{3}]:M_{n}^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0127] In one embodiment, at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles.

[0128] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the silane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0129] In one embodiment, at least a portion of the metal halide and at least a portion of the siloxane are on the same surfaces of the phosphor particles.

[0130] In one embodiment, at least a portion of metal halide is on first surfaces of the phosphor particles and at least a portion of siloxane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0131] In one embodiment, the metal halide is in the form of sol particles when deposited on the surfaces of phosphor particles.

[0132] In one embodiment, the metal halide comprises magnesium fluoride.

[0133] In one embodiment, the at least one phosphor material comprises an amount of manganese from about 0.5 wt% to about 4 wt% based on total phosphor material weight.

[0134] In one embodiment, the Mn^{4+} doped phosphor comprises at least one of K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+}, K_{2}[TiF_{6}]:Mn^{4+}, K_{2}[SnF_{6}]:Mn^{4+}, Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}] Mn^{4+}, Cs_{2}[SiF_{6}]:Mn^{4+}, Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+} Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4}+, K_{3}[ZrF_{7}]:Mn^{4+}, K_{3}[BIF_{6}]K_{3}[YF_{6}]:Mn^{4+}, K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+}.

[0135] In one embodiment, the Mn^{4+} phosphor of formula I is K_{2}SiF_{6}:Mn^{4+} or Na_{2}[SiFfi]:Mn^{4+}.

[0136] In one embodiment, an ink composition comprises:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mm^{4+} doped phosphor of formula I.A_{x}(MF_{y}):Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH_{4}, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0137] In one embodiment, the ink composition further comprises at least one binder.

[0138] In one embodiment, the at least one binder comprises at least one of an epoxy, acrylate, methacrylate, vinyl ester, or siloxane, polyethylene terethalate.

[0139] In one embodiment, at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles.

[0140] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the silane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0141] In one embodiment, at least a portion of the metal halide and at least a portion of the siloxane is on the same surfaces of the phosphor particles.

[0142] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the siloxane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0143] In one embodiment, the metal halide is in the form of sol particles when deposited on the surfaces of phosphor particles.

[0144] In one embodiment, the metal halide comprises magnesium fluoride.

[0145] In one embodiment, the ink composition further comprises scattering agents.

[0146] In one embodiment, the ink composition further comprises one or more other luminescent materials.

[0147] In one embodiment, the one or more other luminescent materials comprises quantum dot material.

[0148] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0149] In one embodiment, the Mn^{4+} doped phosphor comprises at least one of K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+}, K_{2}[TiF_{6}]:Mn^{4+}, K_{2}[SnF_{6}]:Mn^{4+}, Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}] Mn^{4+}, Cs_{2}[SiF_{6}]:Mn^{4+}, Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+} Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4+}, K_{3}[ZrF_{7}]:Mn^{4+}, K_{3}[BIF_{6}]K_{3}[YF_{6}]:Mn^{4+}, K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+}.

[0150] In one embodiment, the Mn^{4+} phosphor of formula I is K_{2}SiF_{6}:Mn^{4+} or Na_{2}[SiFfi]:Mn^{4+}.

[0151] In one embodiment, the ink composition further comprises a solvent.

[0152] In one embodiment, the at least one phosphor material comprises an amount of manganese from about 0.5 wt% to about 4 wt% based on total phosphor material weight.

[0153] In one embodiment, the metal halide comprises magnesium fluoride.

[0154] In one embodiment, a film comprises:a first layer comprising one or more first polymers, a second layer comprising one or more second polymers, and at least one cured or semi-cured ink interposed between the first layer and the second layer, the at least one cured or semi-cured ink comprising:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I.A_{x}[MF_{y}]:Mn^{4x}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0155] In one embodiment, a film comprises:at least one cured or semi-cured ink comprising:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Nn^{4+} doped phosphor of formula IA_{x}[ME_{y}]:M_{x}^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the ME_{y} ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0156] In one embodiment, the at least one phosphor material is uniformly dispersed throughout the at least one cured or semi-cured ink.

[0157] In one embodiment, the at least one cured or semi-cured ink further comprises at least one binder.

[0158] In one embodiment, the at least one binder comprises at least one of an epoxy, acrylate, methacrylate, vinyl ester, siloxane, polyethylene terethalate.

[0159] In one embodiment, at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles.

[0160] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the silane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0161] In one embodiment, at least a portion of the metal halide and at least a portion of the siloxane is on the same surfaces of the phosphor particles.

[0162] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the siloxane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0163] In one embodiment, the metal halide is in the form of sol particles when deposited on the surfaces of the phosphor particles.

[0164] In one embodiment, the metal halide comprises magnesium fluoride.

[0165] In one embodiment, the at least one cured or semi-cured ink further comprises scattering agents.

[0166] In one embodiment, the at least one cured or semi-cured ink further comprises one or more other luminescent materials.

[0167] In one embodiment, the one or more other luminescent material comprises quantum dot material.

[0168] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0169] In one embodiment, the Mn^{4+} doped phosphor comprises at least one of K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+}, K_{2}[TiF_{6}]:Mn^{4+}, K_{2}[SnF_{6}]:Mn^{4+}, Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}] Mn^{4+} Cs_{2}[SiF_{6}]:Mn^{4+} Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+} Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4+}, K_{3}[ZrF_{7}]:Mn^{4+}, K_{3}[BIF_{6}]K_{3}[YF_{6}]:Mn^{4+}, K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+}.

[0170]

[0171] In one embodiment, the Mn^{4+} phosphor of formula I is K_{2}SiF_{6}:Mn^{4+} or Na_{2}[SiFfi]:Mn^{4+}.

[0172] In one embodiment, the at least one phosphor material comprises an amount of manganese from about 0.5 wt% to about 4 wt% based on total phosphor material weight.

[0173] In one embodiment, a device comprises:an LED light source optically coupled and / or radiationally connected to at least one cured or semi-cured ink, the at least one semi or semi-cured ink comprising:phosphor particles comprising at least one phosphor material comprising a 3 / 9n^{4+} doped phosphor of formula I.A_{x}[MF_{y}]:Mn^{4}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [ME_{y}] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0174] In one embodiment, the at least one phosphor material is at least partially disposed on the LED light source.

[0175] In one embodiment, the at least one phosphor material is located remotely at a distance from the LED light source.

[0176] In one embodiment, the at least one phosphor material is uniformly dispersed throughout the at least one cured or semi-cured ink.

[0177] In one embodiment, the at least one cured or semi-cured ink further comprises at least one binder.

[0178] In one embodiment, the at least one binder comprises at least one of an epoxy, acrylate, methacrylate, vinyl ester, siloxane, or polyethylene terethalate.

[0179] In one embodiment, at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles.

[0180] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the silane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0181] In one embodiment, at least a portion of the metal halide and at least a portion of the siloxane is on the same surfaces of the phosphor particles.

[0182] In one embodiment, at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the siloxane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

[0183] In one embodiment, the metal halide is in the form of sol particles when deposited on the surfaces of phosphor particles.

[0184] In one embodiment, the metal halide comprises magnesium fluoride.

[0185] In one embodiment, the at least one cured or semi-cured ink further comprises scattering agents.

[0186] In one embodiment, the at least one cured or semi-cured ink further comprises one or more other luminescent materials.

[0187] In one embodiment, the one or more other luminescent material comprises quantum dot material.

[0188] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0189] In one embodiment, the Mn^{4+} doped phosphor comprises at least one of K_{2}[GeF_{6}]:Mn^{4+}, K_{2}[SiF_{6}]:Mn^{4+}, K_{2}[TiF_{6}]:Mn^{4+}, K_{2}[SnF_{6}]:Mn^{4+}, Cs_{2}[TiF_{6}]:Mn^{4+}, Rb_{2}[TiF_{6}] Mn^{4+}, Cs_{2}[SiF_{6}]:Mn^{4+}, Rb_{2}[SiF_{6}]:Mn^{4+}, Na_{2}[SiF_{6}]:Mn^{4+} Na_{2}[TiFfi]:Mn^{4+}, Na_{2}[ZrF_{6}]:Mn^{4+}, K_{3}[ZrF_{7}]:Mn^{4+}, K_{3}[BIF_{6}]K_{3}[YF_{6}]:Mn^{4+}, K_{3}[LaF_{6}]:Mn^{4+}, K_{3}[GdF_{6}]:Mn^{4+}, K_{3}[NbF_{7}]:Mn^{4+}, or K_{3}[TaF_{7}]:Mn^{4+}.

[0190] In one embodiment, the Mn^{4+} phosphor of formula I is K_{2}SiF_{6}· Mn^{4+} or Na_{2}[SiFfi]:Mn^{4+}.

[0191] In one embodiment, the at least one phosphor material comprises an amount of manganese from about 0.5 wt% to about 4 wt % based on total phosphor material weight.

[0192] In one embodiment, the LED light source is a blue emitting LED.

[0193] In one embodiment, the LED light source is a mini-LED or a micro-LED.

[0194] In one embodiment, the device is a self-emissive display.

[0195] In one embodiment, a lighting apparatus comprises the above-noted device.

[0196] In one embodiment, a display apparatus comprises the above-noted device.

[0197] In one embodiment, a backlight apparatus comprises the above-noted device.

[0198] In one embodiment, a television comprises the above-noted backlight apparatus.

[0199] In one embodiment, a mobile phone comprises the above-noted backlight apparatus.

[0200] In one embodiment, a computer monitor comprises the above-noted backlight apparatus.

[0201] In one embodiment, a laptop comprises the above-noted backlight apparatus.

[0202] In one embodiment, a tablet computer comprises the above-noted backlight apparatus.

[0203] In one embodiment, an automotive display comprises the above-noted backlight apparatus.

[0204] In one embodiment, a process for producing a coated phosphor comprises:combining at least one phosphor material with metal halide to form a first coated phosphor, the at least one phosphor material comprising a Mn^{4+} doped phosphor of formula IA_{x}[MF_{y}]:Mn^{4}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the (MF_{y}) ion, andy is 5, 6 or 7; andcombining the first coated phosphor with a silane or a siloxane to produce a second coated phosphor.

[0205] In one embodiment, combining at least one phosphor material with metal halide comprises introducing the at least one phosphor material into a suspension of metal halide, wherein the metal halide is in the form of sol particles.

[0206] In one embodiment, combining the first coated phosphor with a silane or a siloxane comprises combining the first coated phosphor with a silane.

[0207] In one embodiment, combining the first coated phosphor with a silane or a siloxane comprises combining the first coated phosphor with a siloxane.

[0208] In one embodiment, in a method for inkjet printing, flexographic printing, microdispensing printing, screen printing, direct write printing, aerosol jet printing, or gravure printing, the method comprises printing an ink composition, wherein the ink composition comprises phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn doped phosphor of formula I:A_{x}[MF_{y}]:Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [ME_{y}] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

[0209] All publications, patents and patent applications are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety. Where a term in the present disclosure is found to be defined differently in a document incorporated herein by reference, the definition provided herein is to serve as the definition for the term.

Claims

What is claimed is:

1. A phosphor powder comprising:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn doped phosphor of formula I:A_{x}[MF_{y}]:Mn^{4+}wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,Mis Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [ME_{y}] ion, andy is 5, 6 or 7; andmetal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

2. The phosphor powder of claim 1, wherein at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles3. The phosphor powder of claim 1, wherein at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the silane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

4. The phosphor powder of claim 1, wherein at least a portion of the metal halide and at least a portion of the siloxane are on the same surfaces of the phosphor particles.

5. The phosphor powder of claim 1, wherein at least a portion of metal halide is on first surfaces of the phosphor particles and at least a portion of siloxane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

6. An ink composition comprising:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn^{4+} doped phosphor of formula IAx[MF_{y}]:Ma^{4+}wherein:A is Li, Na, K, Rb, Cs, NH_{4}, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the ME_{y} ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

7. The ink composition of claim 6, further comprising at least one binder.

8. The ink composition of claim 7, wherein the at least one binder comprises at least one of an epoxy, acrylate, methacrylate, vinyl ester, or siloxane, polyethylene terethalate.

9. The ink composition of any one of claims 6 to 8, wherein at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles.

10. The ink composition of any one of claims 6 to 8, wherein at least a portion of the metal halide is on first surfaces of the phosphor particles and at least a portion of the silane is on second surfaces of the phosphor particles, the first surfaces and the second surfaces being different.

11. A film comprising.at least one cured or semi-cured ink comprising:phosphor particles, the phosphor particles comprising at least one phosphor material comprising a Mn^{4+} doped phosphor of formula I:A_{x}[MF_{y}]:M_{0}^{4+} }wherein:A is Li, Na, K, Rb, Cs, NH4, or any combination thereof,M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof,x is an absolute value of a charge of the [MF_{y}] ion, andy is 5, 6 or 7;metal halide on surfaces of the phosphor particles; andsilane or siloxane on surfaces of the phosphor particles.

12. The film of claim 11, wherein the at least one phosphor material is uniformly dispersed throughout the at least one cured or semi-cured ink.

13. The film of claim 11 or claim 12, wherein the at least one cured or semi-cured ink further comprises at least one binder.

14. The film of claim 13, wherein the at least one binder comprises at least one of an epoxy, acrylate, methacrylate, vinyl ester, siloxane, polyethylene terethalate.

15. The film of any one of claims 11 to 14, wherein at least a portion of the metal halide and at least a portion of the silane is on the same surfaces of the phosphor particles.

Images