Phosphor powder

Abstract

The present disclosure relates to milled phosphor powders and post-milling processes. The phosphor powders can include phosphor particles. 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 compositions, devices, and apparatuses that includes the one or more phosphor powders of the present disclosure. The present disclosure also includes methods of preparing the phosphor powder of the present disclosure.

Description

RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 681,912,filed 12 August 2024.BACKGROUND

[0002] Next generation micro-LED applications and luminescent color filters (in pixelcolor conversion) containing manganese doped potassium hexafluorosilicate (PFS,K2SiF6:Mn4+) phosphors will require printable inks that contain PFS particles with submicronsizes (< 1 µm) and quantum efficiencies (QE) > 85%. Previous work demonstrated thesynthesis of submicron PFS with good QE using a "bottom up" approach. These submicronPFS powders are currently being studied in ink formulations for printing development.

[0003] Alternatively, “top down” approaches to generate small size phosphors have beenproven for other compositions of phosphors, most notably yttrium aluminum garnet dopedwith Ce³+ (Y3Al5O12:Ce3+, YAG:Ce³+), which is a good candidate for both wet milling anddry milling in the presence of media. One specific operation for micronizing or fine grindingmaterials in various industries is jet milling. FIG. 1 is a general schematic of jet milloperation. First, the feedstock material enters the grind chamber where particles are impactedby high velocity gas (typically compressed air or inert gas) from the grind nozzles. Thiscauses particles to accelerate within the chamber and encourages high energy collisionsbetween particles. These particle-particle collisions induce particle size reduction. This isdifferent from ball or media milling in which particle size reduction is caused by collisionsbetween media and powder. Due to the lack of milling media, jet milling has the advantagesof reduced contamination and easier product collection. Indeed, jet milling of YAG:Ce3+ isfavorable because this phosphor is redox stable and is insensitive to impurities and humidity.Also, the crystal structure of YAG:Ce3+ is not prone to defects during milling operations.

[0004] Unlike YAG:Ce3+, however, jet milling of PFS has not been demonstratedbecause of this phosphor's sensitivity to Mn+ hydrolysis when new facets are exposed duringmilling. This hydrolysis leads to significant performance degradation. Also, PFS is verysensitive to impurities, which may be present after milling. Both wet milling and dry millingPFS in the presence of milling media were previously demonstrated. Wet milling of PFSwhile suspended in a solvent such as alcohol or butyl acetate reduced Mn+ and degradedoptical properties. On the other hand, hydrofluoric acid (HF) media provided a good millingenvironment for maintaining the Mn+ oxidation state. However, the solvation and removal ofMn⁴+ from the PFS host by HF and the agglomeration of milled particles during drying stillneed to be addressed. Dry milling PFS with milling media effectively broke down larger PFSparticles, but exposed facets increased the susceptibility of Mn⁴+ hydrolysis due to thereaction with moisture in air, which leads to lower PFS performance. Thus, there exists aneed to develop new phosphor compositions and methods of treating phosphor particles togenerate small size phosphors while maintaining high QE.SUMMARY OF THE INVENTION

[0005] The present disclosure demonstrates the feasibility of using jet milling as a "topdown" approach to synthesizing small size phosphor particles (e.g., PFS particles) from HFsoluble precursors. The present disclosure further demonstrates the use of post-millingtreatments (washing and annealing) to help recover one or more optical properties of thephosphor particles that were adversely effected due to the jet milling process.

[0006] Accordingly, in one exemplary aspect, the present disclosure provides a phosphorpowder including phosphor particles that are jet-milled. In some aspects, the phosphorparticles include a Mn doped phosphor of formula I:Ax[MF]:Mn+Iwherein: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 combinationthereof, x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns.

[0007] In another exemplary aspect, the present disclosure provides a phosphor powderincluding phosphor particles that are jet-milled washed with one or more solutions, andannealed is provided. In some aspects, the phosphor particles include a Mn+ doped phosphorof formula l:Ax[MFy]:Mn+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 combinationthereof, x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns.

[0008] In another exemplary aspect, the present disclosure provides a phosphor powderhaving a particle size distribution of a D50 value of less than about 10 microns is provided,where the phosphor powder is produced by reducing sizes of phosphor particles by jet millingthe phosphor particles, the phosphor particles including a Mn++ doped phosphor of formula I:Ax[MFy]:Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7,washing the phosphor particles with one or more solutions; and annealing the phosphorparticles.

[0009] In another exemplary aspect, the present disclosure provides a composition thatincludes a phosphor powder of the present material and a binder. In some aspects, thecomposition can be an ink composition. In some aspects, the ink composition includes aphosphor powder including phosphor particles that are jet-milled, the phosphor particlesincluding a Mn doped phosphor of formula I.Ax[MFy]: Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value ofless than about 10 microns.

[0010] In another exemplary aspect, the present disclosure provides an ink compositionthat includes a phosphor powder including phosphor particles that are jet-milled, washed withone or more solutions, and annealed. In some aspects, the phosphor particles include aMn+ doped phosphor of formula I:Ax[MF]:Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7, andwherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns.

[0011] In another exemplary aspect, the present disclosure provides a film that includes aphosphor powder of the present material and a binder. In some aspects, the film includes afirst layer including one or more first polymers, a second layer including one or more secondpolymers, and at least one cured or semi-cured ink interposed between the first layer and thesecond layer. In some aspects, the at least one cured or semi-cured ink includes a phosphorpowder including phosphor particles that are jet-milled, washed with one or more solutions,and annealed, the phosphor particles including a Mnt doped phosphor of formula I:Ax[MFy]:Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andat least one binder,wherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns.

[0012] In another exemplary aspect, the present disclosure provides a device that includesan LED light source optically coupled and / or radiationally connected to at least one phosphormaterial, the phosphor material including phosphor particles that are jet-milled, washed withone or more solutions, and annealed, the phosphor particles including a Mn+ doped phosphorof formula l:Ax[MFy]:Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns

[0013] 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.

[0014] In another exemplary aspect, the present disclosure provides a television, a mobilephone, a computer monitor, a laptop, a tablet computer, and / or an automotive display thatincludes the device provided herein.

[0015] In another exemplary aspect, the present disclosure provides a method of makingphosphor powder having a particle size distribution of a D50 value of less than about 10microns, the method including reducing sizes of phosphor particles by jet milling thephosphor particles, the phosphor particles including a Mnt doped phosphor of formula I:Ax[MF]:Mn+1wherein: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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7,washing the phosphor particles with one or more solutions; and annealing the phosphorparticles.BRIEF DESCRIPTION OF THE DRAWINGS

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

[0017] FIG. 1 shows an Illustration of an exemplary jet mill operation and the particlesize reduction mechanism within the grind chamber.

[0018] FIGs. 2A-2C show exemplary sample hierarchies illustrating the flow of processsteps for each sample described herein. FIG. 2A shows the processing steps of an unannealed(U) sample / starting material. FIG. 2B shows the processing steps of an annealed (A)sample / starting material. FIG. 2C shows the processing steps of an antisolvent precipitatedand annealed (ASP) sample / starting material for comparison.

[0019] FIGs. 3A and 3B show representative scanning electron micrographs of asreceived (FIG. 3A) and jet milled (FIG. 3B) exemplary annealed (A), unannealed (U), andantisolvent precipitated and annealed (ASP) samples.

[0020] FIG. 4 is a graphical diagram showing particle size distributions (PSD) of as-received (U and A) samples and jet milled (U1, U2, A3) samples, as measured by laserdiffraction. A sample prepared by antisolvent precipitation (ASP) is shown for comparison.

[0021] FIG. 5 is a graphical diagram showing quantum efficiency (QE), blue lightbleedthrough (BT), reflectivity at 631 nm (R631), and Mn wt% (measured via ICP) for theexemplary as-received, jet milled, and post-jet milled samples. Antisolvent precipitated(ASP) samples are shown as a comparison.

[0022] FIGs. 6A and 6B show representative scanning electron micrographs ofexemplary jet milled unannealed (U2FG, U2HG) and annealed (A3FG, A3HG) samplesfollowing post-jet milling treatment processes (FIG. 6A) and antisolvent precipitated andannealed (ASPF, ASPH) samples after treatment processes (FIG. 6B).

[0023] FIGs. 7A-7C are graphical diagrams showing changes in particle size distributions(PSD) of exemplary jet milled unannealed (U2, U2FG, U2HG; FIG. 7A), annealed (A3,A3FG, A3HG; FIG. 7B), and antisolvent precipitated and annealed (ASP, ASPF, ASPH)samples following post-jet milling treatment processes through laser diffraction analyses.

[0024] FIG. 8A is a schematic cross-sectional view of a device, in accordance with anexemplary aspect. FIG. 8B is a schematic cross-sectional view of a device in accordance withan exemplary aspect. FIG. 8C is a schematic cross-sectional view of a device in accordancewith an exemplary aspect. FIG. 8D is a schematic cross-sectional view of a device inaccordance with an exemplary aspect. FIG. 8E is a schematic cross-sectional view of a devicein accordance with an exemplary aspect.

[0025] FIG. 9 is a schematic cross-sectional view of a lighting apparatus, in accordancewith an exemplary aspect.

[0026] FIG. 10 is a schematic cross-sectional view of a lighting apparatus, in accordancewith an exemplary aspect.

[0027] FIG. 11 is a cutaway side perspective view of a lighting apparatus, in accordancewith an exemplary aspect.

[0028] FIG. 12A is a schematic perspective view of a surface-mounted device (SMD), inaccordance with an exemplary aspect. FIG. 12B is a schematic cross-sectional view of anSMD in accordance with an exemplary aspect. FIG. 12C is a schematic cross-sectional viewof a device in accordance with an exemplary aspect.

[0029] FIGs. 13A-13D are schematic diagrams of a printing well arrangement, inaccordance with an exemplary aspect.

[0030] FIG. 14 is a schematic diagram of a bank arrangement, in accordance with anexemplary aspect.

[0031] FIGs. 15A and 15B are a top view and a side view, respectively, of an examplered-green-blue (RGB) pixel, in accordance with an exemplary aspect.

[0032] Other features and advantages of the present disclosure will become apparentfrom the following detailed description. It should be understood, however, that the detailedde-scription and the specific examples, while indicating aspects of the disclosure, are givenby 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

[0033] Unless otherwise indicated, the definitions and aspects described in this and othersections are intended to be applicable to all aspects of the present disclosure herein describedfor which they are suitable as would be understood by a person skilled in the art.

[0034] The abbreviations used herein have their conventional meaning within thechemical and biological arts. The chemical structures and formulae set forth herein areconstructed according to the standard rules of chemical valency known in the chemical arts.

[0035] 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 ormore" of the listed items is used or present. The term "and / or" with respect topharmaceutically acceptable salts and / or solvates thereof means that the compounds of thedisclosure exist as individual salts and hydrates, as well as a combination of, for example, asolvate of a salt of a compound of the disclosure.

[0036] As used in the present disclosure, the singular forms "a", "an" and "the" includeplural references unless the content clearly dictates otherwise. For example, an aspectincluding "a phosphor" should be understood to present certain aspects with one compound,or two or more additional compounds.

[0037] In aspects including an "additional” or “second" component, such as an additionalor second compound, the second component as used herein is chemically different from theother components or first component. A "third" component is different from the other, first,and second components, and further enumerated or "additional" components are similarlydifferent.

[0038] In this disclosure, “comprises,” “comprising,” “containing” and “having” and thelike 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 themeaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence ofmore than that which is recited so long as basic or novel characteristics of that which isrecited is not changed by the presence of more than that which is recited, but excludes priorart aspects.

[0039] As used herein, the term "about" means a range of values including the specifiedvalue, which a person of ordinary skill in the art would consider reasonably similar to thespecified value. In some aspects, about means within a standard deviation usingmeasurements 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.

[0040] The term "comparable phosphor powder" as used herein refers to a phosphorpowder including phosphor particles coated with only magnesium fluoride.

[0041] The term "a mini-LED” as used herein, should be understood to mean an LEDthat is sized less than or equal to 250 microns. For example, a mini-LED can include an LEDthat has a length of 250 microns and a width of 250 microns.

[0042] The term "a micro-LED”, as used herein, should be understood to mean an LEDthat is sized less than or equal to 50 microns. For example, a micro-LED can include an LEDthat has a length of 50 microns and a width of 50 microns.

[0043] In one exemplary aspect, a phosphor powder including phosphor particles that arejet-milled is provided. In some aspects, the phosphor particles include a Mn dopedphosphor of formula I:A[MFy]:Mn++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 combinationthereof, x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.

[0044] In another exemplary aspect, a phosphor powder including phosphor particles thatare jet-milled washed with one or more solutions, and annealed is provided. In some aspects,the phosphor particles include a Mn¹ doped phosphor of formula IAx[MFy]:Mn+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 combinationthereof, x is the absolute value of the charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.

[0045] The Mn+ doped phosphors of Formula I are complex fluoride materials, orcoordination compounds, containing at least one coordination center surrounded by fluorideions acting as ligands, and charge-compensated by counter ions as necessary. For example, inthe exemplary phosphor particle K2[SiF6]:Mn, the coordination center is Si and thecounterion 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 theligands around the coordination center. The square brackets (occasionally omitted forsimplicity) indicate that the complex ion they encompass is a new chemical species, differentfrom 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 (includingthe counter ions) can further modify the excitation and emission properties of the activatorion.

[0046] In particular aspects, the coordination center of the phosphor, that is, M in formulaL, is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or any combination thereof. Thecounterion, or A in formula I, can be Li, Na, K, Rb, Cs, NH4, or any combination thereof. xin formula I is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. Examplesof phosphors of formula I include K2[SiF6]:Mn², K2[TiF6]:Mn, K2[SnF6]:Mn, Cs2[TiF6],Rb2[TiF6], Cs2[SiF6], Rb2[SiF6], Na2[TiF6]:Mn++, Na2[ZrF6]:Mn++, K3[ZrF7]:Mn++,K3[BiF6]:Mn, K3[YF6]:Mn, K3[LaF6]:Mn, K3[GdF6]:Mn+, K3[NbF7]:Mn+,K3[TaF7]:Mn.

[0047] In some aspects, the phosphor powder can have a D50 value or about 0.1 micronsto about 10 microns, including all the subranges in between. In certain aspects, the D50 valuecan be from about 0.1 microns to about 5 microns, including all the subranges in between. Incertain aspects, the particle size distribution can have a D50 value of about 0.1 µm, about 0.2µm, about 0.3 µm, about 0.4 µm, about 0.5 µm, about 0.6 µm, about 0.7 µm, about 0.8 µm,about 0.9 µm, about 1.0 µm, about 1.1 µm, about 1.2 µm, about 1.3 µm, about 1.4 µm, about1.5 µm, about 1.6 µm, about 1.7 µm, about 1.8 µm, about 1.9 µm, about 2.0 µm, about 2.1µm, about 2.2 µm, about 2.3 µm, about 2.4 µm, about 2.5 µm, about 2.6 µm, about 2.7 µm,about 2.8 µm, about 2.9 µm, about 3.0 µm, about 3.1 µm, about 3.2 µm, about 3.3 µm, about3.4 µm, about 3.5 µm, about 3.6 µm, about 3.7 µm, about 3.8 µm, about 3.9 µm, about 4.0µm, about 4.1 µm, about 4.2 µm, about 4.3 µm, about 4.4 µm, about 4.5 µm, about 4.6 µm,about 4.7 µm, about 4.8 µm, about 4.9 µm, or about 5.0 µm.

[0048] In some aspects, the phosphor powder includes an amount of manganese fromabout 0.5 wt% to about 4 wt% based on total phosphor powder weight, including all thesubranges in between. In some aspects, the phosphor powder includes an amount ofmanganese that is greater than about 2.5 wt% based on total phosphor powder weight. Incertain aspects, the phosphor powder includes an amount of manganese from about 2 wt% toabout 3 wt% based on total phosphor powder weight, including all the subranges in between.In other aspects, the phosphor powder can have a Mn loading or Mn % of at least 1 wt%. Inanother aspect, the phosphor powder can have a Mn loading of at least 1.5 wt%. In anotheraspect, the phosphor powder can have a Mn loading of at least 2 wt %. In another aspect, thephosphor powder can have a Mn % of at least 3 wt%. In another aspect, the Mn % can begreater than 3.0 wt%. In another aspect, the content of Mn in the phosphor can be from about1 wt% to about 4 wt %.

[0049] In some aspects, the phosphor powder can have a quantum efficiency that isgreater than about 95% under blue excitation. In certain aspects, the phosphor powder canhave a quantum efficiency that is about 99% under blue excitation.

[0050] In another exemplary aspect, a phosphor powder having a particle size distributionof a D50 value of less than about 10 microns is provided, where the phosphor powder isproduced by reducing sizes of phosphor particles by jet milling the phosphor particles, thephosphor particles including a Mn doped phosphor of formula I4+A.[MF]: Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7;washing the phosphor particles with one or more solutions, and annealing the phosphorparticles.

[0051] In some aspects, the step of washing the phosphor particles with one or moresolutions is performed after the step of reducing sizes of phosphor particles by jet milling thephosphor particles. In some aspects, the step of annealing the phosphor particles is performedafter the step of washing the phosphor particles with one or more solutions. In some aspects,the step of annealing the phosphor particles includes annealing the phosphor particles prior toreducing sizes of phosphor particles by jet milling the phosphor particles, followed by furtherannealing the phosphor particles after the step of washing the phosphor particles with one ormore solutions. In some aspects, the step of washing the phosphor particles with one or moresolutions includes at least one step of washing the phosphor particles with one or moresolutions. In certain aspects, the step of washing the phosphor particles with one or moresolutions includes two steps of washing the phosphor particles with one or more solutionsafter the step of reducing sizes of phosphor particles by jet milling the phosphor particles.

[0052] In some aspects, the one or more solutions for washing include HF and K2SiF6. Incertain aspects, the one or more solutions include 49% HF and K2SiF6. In certain aspects, theone or more solutions include 20% HF and K2SiF6.

[0053] In some aspects, annealing the washed, jet-milled phosphor particles includescontacting the washed, jet-milled phosphor particles with a fluorine-containing oxidizingagent in gaseous form at an elevated temperature. In some aspects, the fluorine-containingoxidizing agent can be F2, SF6, BrFs, NH4HF2, NH4F, KF, AIF3, SbF5, CIF3, BrF3, KrF, XeF2,XeF4, NF3, SiF4, PbF2, ZnF2, SnF2, CdF2 or any combination thereof. In certain aspects, thefluorine-containing oxidizing agent is F2.

[0054] In some aspects, prior to washing, the jet-milled phosphor particles can have aparticle size distribution of a D50 value of less than about 3 microns. In certain aspects, priorto washing, the jet-milled phosphor particles can have a particle size distribution of a D50value from about 1.5 microns to less than about 2.5 microns, including all the subranges inbetween. In certain aspects prior to washing, the jet-milled phosphor particles can have a D50value of about 1.5 µm, about 1.6 µm, about 1.7 µm, about 1.8 µm, about 1.9 µm, about 2.0µm, about 2.1 µm, about 2.2 µm, about 2.3 µm, about 2.4 µm, or about 2.5 µm.

[0055] In some aspects, prior to washing, manganese can be present in the jet milledphosphor particles in an amount of a first weight percent of the total weight of the jet milledphosphor particles, and subsequent to washing, manganese can be present in the washed, jet-milled phosphor particles in an amount of a second weight percent of the total weight of thejet milled phosphor particles, with the second weight percent being less than the first weightpercent.

[0056] In some aspects, the phosphor powder 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-aO12-3 / 2a:Ce3+(wherein 0≤a≤0.5); beta-SiAlON:Eu2+;(Sr, Ca, Ba)(Al, Ga, In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Ca1-h-rCehEurAl1-h (Mg, Zn)hSiN3 (where 0≤h≤0.2, 0≤r≤0.2); Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+, Ce3+;(Ba, Sr,Ca)b SigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0057] In some aspects, the phosphor powder can have a D50 value or about 0.1 micronsto about 10 microns, including all the subranges in between. In certain aspects, the D50 valuecan be from about 0.1 microns to about 5 microns, including all the subranges in between. Incertain aspects, the particle size distribution can have a D50 value of about 0.1 µm, about 0.2µm, about 0.3 µm, about 0.4 µm, about 0.5 µm, about 0.6 µm, about 0.7 µm, about 0.8 µm,about 0.9 µm, about 1.0 µm, about 1.1 µm, about 1.2 µm, about 1.3 µm, about 1.4 µm, about1.5 µm, about 1.6 µm, about 1.7 µm, about 1.8 µm, about 1.9 µm, about 2.0 µm, about 2.1µm, about 2.2 µm, about 2.3 µm, about 2.4 µm, about 2.5 µm, about 2.6 µm, about 2.7 µm,about 2.8 µm, about 2.9 µm, about 3.0 µm, about 3.1 µm, about 3.2 µm, about 3.3 µm, about3.4 µm, about 3.5 µm, about 3.6 µm, about 3.7 µm, about 3.8 µm, about 3.9 µm, about 4.0µm, about 4.1 µm, about 4.2 µm, about 4.3 µm, about 4.4 µm, about 4.5 µm, about 4.6 µm,about 4.7 µm, about 4.8 µm, about 4.9 µm, or about 5.0 µm.

[0058] In some aspects, the phosphor powder includes an amount of manganese fromabout 0.5 wt% to about 4 wt% based on total phosphor powder weight, including all thesubranges in between. In some aspects, the phosphor powder includes an amount ofmanganese that is greater than about 2.5 wt% based on total phosphor powder weight. Incertain aspects, the phosphor powder includes an amount of manganese from about 2 wt % toabout 3 wt% based on total phosphor powder weight, including all the subranges in between.In other aspects, the phosphor powder can have a Mn loading or Mn % of at least 1 wt %. Inanother aspect, the phosphor powder can have a Mn loading of at least 1.5 wt%. In anotheraspect, the phosphor powder can have a Mn loading of at least 2 wt %. In another aspect, thephosphor powder can have a Mn % of at least 3 wt%. In another aspect, the Mn % can begreater than 3.0 wt%. In another aspect, the content of Mn in the phosphor can be from about1 wt% to about 4 wt%.

[0059] In some aspects, the phosphor powder can have a quantum efficiency that isgreater than about 95% under blue excitation. In certain aspects, the phosphor powder canhave a quantum efficiency that is about 99% under blue excitation.

[0060] In another exemplary aspect, the present disclosure provides a composition thatincludes a phosphor powder of the present material and a binder. In some aspects, thecomposition can be an ink composition. In some aspects, the ink composition includes aphosphor powder including phosphor particles that are jet-milled, the phosphor particlesincluding a Mn* doped phosphor of formula I:Ax[MFy]:Mn++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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value ofless than about 10 microns.

[0061] In another exemplary aspect, the ink composition includes a phosphor powderincluding phosphor particles that are jet-milled, washed with one or more solutions, andannealed. In some aspects, the phosphor particles include a Mn* doped phosphor of formulai:Ax[MFy]:Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns.

[0062] Binders for use in the ink compositions described herein can include thermoplasticpolymers and copolymers, pre-binder materials, such as thermally curable precursors orphotocurable precursors. Exemplary binders include, but are not limited to, ethyl cellulose,polystyrene, polyacrylate, polymethacrylates, such as polymethyl acrylate (PMA) andpolymethyl 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) orpoly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), amine-basedoligomers / 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 canbe at least one of an epoxy, acrylate, methacrylate, vinyl ester, siloxane, or polyethyleneterethalate.

[0063] In some aspects, the ink composition can also include one or more scatteringagents. For example, any of the phosphor materials described herein, can be at least partiallycoated with surface coatings to enhance stability of the phosphor particles and resistaggregation by modifying the surface of the particles and increase the zeta potential of theparticles. In some aspects, the surface coatings can be a metal fluoride, silica or organiccoating. In certain aspects, the phosphors described herein can be at least partially coatedwith a metal fluoride, which increases positive Zeta potential and reduces agglomeration. Incertain aspects, the metal fluoride coating includes MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AlF3or any combination thereof. In certain aspects, the metal fluoride coating can be present in anamount from about 0.1 wt% to about 10 wt%. In certain aspects, the metal fluoride coatingcan be present in an amount from about 0.1 wt% to about 5 wt%. In certain aspects, themetal fluoride coating can be present from about 0.3 wt% to about 3 wt%. Metal fluoridecoated phosphors based on complex fluoride materials activated by Mn⁴+ can be prepared asdescribed in WO 2018 / 093832 and US Publication No. 2020 / 0369956, which areincorporated by reference in their entireties.

[0064] In some aspects, the scattering agents can have a particle size of at least 1 µm. Incertain aspects, the scattering agents can have a particle size from about 1 µm to about 10µm, including all the subranges in between. In certain aspects, the scattering agents caninclude titanium dioxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), indium tinoxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calciumfluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF),aluminum fluoride (AlF3) or combinations thereof.

[0065] In some aspects, the ink composition can have a viscosity from more than 2,000cP to about 30,000 cP.

[0066] In some aspects, the phosphor particles can be present in an amount from about 5wt% to about 70 wt%, based on the weight of the ink composition, including all thesubranges in between.

[0067] In some aspects, the phosphor powder can be uniformly dispersed throughout theink composition.

[0068] In some aspects, the one or more solutions for washing include HF and K2SiF6. Incertain aspects, the one or more solutions include 49% HF and K2SiF6. In certain aspects, theone or more solutions include 20% HF and K2SiF6.

[0069] In some aspects, the phosphor powder 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-aO12-3 / 2a:Ce3+(wherein 0≤a≤0.5); beta-SiAlON:Eu2+;(Sr, Ca, Ba)(Al, Ga, In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Ca1-h-rCehEurAl1-h (Mg, Zn)hSiN3 (where 0≤h≤0.2, 0≤r≤0.2); Sr(LiAl3N4):Eu2+; (Ca, Sr)S:Eu2+, Ce³+;(Ba, Sr,Ca)b SigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0070] In some aspects, the phosphor powder can have a D50 value or about 0.1 micronsto about 10 microns, including all the subranges in between. In certain aspects, the D50 valuecan be from about 0.1 microns to about 5 microns, including all the subranges in between. Incertain aspects, the particle size distribution can have a D50 value of about 0.1 µm, about 0.2µm, about 0.3 µm, about 0.4 µm, about 0.5 µm, about 0.6 µm, about 0.7 µm, about 0.8 µm,about 0.9 µm, about 1.0 µm, about 1.1 µm, about 1.2 µm, about 1.3 µm, about 1.4 µm, about1.5 µm, about 1.6 µm, about 1.7 µm, about 1.8 µm, about 1.9 µm, about 2.0 µm, about 2.1µm, about 2.2 µm, about 2.3 µm, about 2.4 µm, about 2.5 µm, about 2.6 µm, about 2.7 µm,about 2.8 µm, about 2.9 µm, about 3.0 µm, about 3.1 µm, about 3.2 µm, about 3.3 µm, about3.4 µm, about 3.5 µm, about 3.6 µm, about 3.7 µm, about 3.8 µm, about 3.9 µm, about 4.0µm, about 4.1 µm, about 4.2 µm, about 4.3 µm, about 4.4 µm, about 4.5 µm, about 4.6 µm,about 4.7 µm, about 4.8 µm, about 4.9 µm, or about 5.0 µm.

[0071] In some aspects, the phosphor powder includes an amount of manganese fromabout 0.5 wt% to about 4 wt% based on total phosphor powder weight, including all thesubranges in between. In some aspects, the phosphor powder includes an amount ofmanganese that is greater than about 2.5 wt% based on total phosphor powder weight. Incertain aspects, the phosphor powder includes an amount of manganese from about 2 wt% toabout 3 wt% based on total phosphor powder weight, including all the subranges in between.In other aspects, the phosphor powder can have a Mn loading or Mn % of at least 1 wt %. Inanother aspect, the phosphor powder can have a Mn loading of at least 1.5 wt%. In anotheraspect, the phosphor powder can have a Mn loading of at least 2 wt %. In another aspect, thephosphor powder can have a Mn % of at least 3 wt%. In another aspect, the Mn % can begreater than 3.0 wt%. In another aspect, the content of Mn in the phosphor can be from about1 wt% to about 4 wt%

[0072] In some aspects, the phosphor powder can have a quantum efficiency that isgreater than about 95% under blue excitation. In certain aspects, the phosphor powder canhave a quantum efficiency that is about 99% under blue excitation.

[0073] In another exemplary aspect, the present disclosure provides a film that includes aphosphor powder of the present material and a binder. In some aspects, the film includes afirst layer including one or more first polymers, a second layer including one or more secondpolymers, and at least one cured or semi-cured ink interposed between the first layer and thesecond layer. It should be understood that reference to a cured ink indicates that the binder ofthe ink is in a cured state. Likewise, reference to a semi-cured ink indicates that the binder ofthe ink is in a semi-cured state.

[0074] In some aspects, the at least one cured or semi-cured ink includes a phosphorpowder including phosphor particles that are jet-milled, washed with one or more solutions,and annealed, the phosphor particles including a Mn+ doped phosphor of formula IA.[MF]:Mn+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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andat least one binder;wherein the phosphor powder has a particle size distribution of a D50 value of less than about10 microns.

[0075] In some aspects, the film can have a thickness of no more than 250 micrometers.In certain aspects, the film can have a thickness of no more than 50 micrometers.

[0076] In some aspects, the film can be substantially free of uniformity or mura defects.

[0077] In some aspects, the at least one cured or semi-cured ink can also include one ormore scattering agents. In some aspects, the scattering agents can have a particle size of atleast 1 µm. In certain aspects, the scattering agents can have a particle size from about 1 µmto about 10 µm, including all the subranges in between. In certain aspects, the scatteringagents can include titanium dioxide (TiO2), aluminum oxide (Al2O3), zirconium oxide(ZrO2), indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride(MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silverfluoride (AgF), aluminum fluoride (AlF3) or combinations thereof.

[0078] In some aspects, any of the phosphor materials described herein, can be at leastpartially coated with surface coatings to enhance stability of the phosphor particles and resistaggregation by modifying the surface of the particles and increase the zeta potential of theparticles. In some aspects, the surface coatings can be a metal fluoride, silica or organiccoating. In certain aspects, the phosphors described herein can be at least partially coatedwith a metal fluoride, which increases positive Zeta potential and reduces agglomeration. Incertain aspects, the metal fluoride coating includes MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AlF3or any combination thereof. In certain aspects, the metal fluoride coating can be present in anamount from about 0.1 wt% to about 10 wt%. In certain aspects, the metal fluoride coatingcan be present in an amount from about 0.1 wt% to about 5 wt%. In certain aspects, themetal fluoride coating can be present from about 0.3 wt% to about 3 wt%. Metal fluoridecoated phosphors based on complex fluoride materials activated by Mn⁴+ can be prepared asdescribed in WO 2018 / 093832 and US Publication No. 2020 / 0369956, which areincorporated by reference in their entireties.

[0079] In some aspects, the at least one binder can be at least one of an epoxy, acrylate,methacrylate, vinyl ester, siloxane, or polyethylene terethalate.

[0080] In some aspects, the phosphor powder can be uniformly dispersed throughout theat least one cured or semi-cured ink.

[0081] In some aspects, the one or more solutions for washing include HF and K2SiF6. Incertain aspects, the one or more solutions can be 49% HF and K2SiF6. In certain aspects, theone or more solutions can be 20% HF and K2SiF6.

[0082] In some aspects, the phosphor powder of the cured or semi-cured ink of the filmcan also include an additional phosphor. Suitable additional phosphors include, but are notlimited to, (Y,Gd, Tb,La,Sm,Pr,Lu)3(Al,Ga)5-aO12-3 / 2a: Ce³+(wherein 0≤a≤0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Ca1-h-rCehEurAll-h (Mg,Zn)hSiN3 (where 0≤h≤0.2, 0≤r≤0.2); Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+,Ce³+; (Ba, Sr, Ca)bSigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0083] In some aspects, the phosphor powder of the cured or semi-cured ink of the filmcan have a D50 value or about 0.1 microns to about 10 microns, including all the subrangesin between. In certain aspects, the D50 value can be from about 0.1 microns to about 5microns, including all the subranges in between. In certain aspects, the particle sizedistribution can have a D50 value of about 0.1 µm, about 0.2 µm, about 0.3 µm, about 0.4µm, about 0.5 µm, about 0.6 µm, about 0.7 µm, about 0.8 µm, about 0.9 µm, about 1.0 µm,about 1.1 µm, about 1.2 µm, about 1.3 µm, about 1.4 µm, about 1.5 µm, about 1.6 µm, about1.7 µm, about 1.8 µm, about 1.9 µm, about 2.0 µm, about 2.1 µm, about 2.2 µm, about 2.3µm, about 2.4 µm, about 2.5 µm, about 2.6 µm, about 2.7 µm, about 2.8 µm, about 2.9 µm,about 3.0 µm, about 3.1 µm, about 3.2 µm, about 3.3 µm, about 3.4 µm, about 3.5 µm, about3.6 µm, about 3.7 µm, about 3.8 µm, about 3.9 µm, about 4.0 µm, about 4.1 µm, about 4.2µm, about 4.3 µm, about 4.4 µm, about 4.5 µm, about 4.6 µm, about 4.7 µm, about 4.8 µm,about 4.9 µm, or about 5.0 µm.

[0084] In some aspects, the phosphor powder of the cured or semi-cured ink of the filmincludes an amount of manganese from about 0.5 wt% to about 4 wt% based on totalphosphor powder weight, including all the subranges in between. In some aspects, thephosphor powder includes an amount of manganese that is greater than about 2.5 wt% basedon total phosphor powder weight. In certain aspects, the phosphor powder includes anamount of manganese from about 2 wt% to about 3 wt% based on total phosphor powderweight, including all the subranges in between. In other aspects, the phosphor powder canhave a Mn loading or Mn % of at least 1 wt %. In another aspect, the phosphor powder canhave a Mn loading of at least 1.5 wt%. In another aspect, the phosphor powder can have aMn loading of at least 2 wt %. In another aspect, the phosphor powder can have a Mn % of atleast 3 wt%. In another aspect, the Mn % can be greater than 3.0 wt%. In another aspect, thecontent of Mn in the phosphor can be from about 1 wt% to about 4 wt%

[0085] In some aspects, the phosphor powder of the cured or semi-cured ink of the filmcan have a quantum efficiency that is greater than about 95% under blue excitation. In certainaspects, the phosphor powder can have a quantum efficiency that is about 99% under blueexcitation.

[0086] In some aspects, any of the phosphor powders described herein, the inkcompositions described herein, and / or the films described herein can further include quantumdots (QDs) that can absorb blue light and generate green or red light or both to form a hybridcolor conversion article. Exemplary QD materials include, but are not limited to, group II-IVcompound 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-VIcompound 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 notlimited to, CuInS2, CuInSe2, CuGaS2, CuGaSe2, AgInS2, AgInSe2, AgGaS2, AgGaSe2 orperovskite QDs having a formula of ABX3 where A is cesium, methylammonium orformamidinium, B is lead or tin and C is chloride, bromide or iodide. In one aspect, theperovskite quantum dot can be CsPbX3, where X is Cl, Br, I or a combination thereof. Themean size of the QD materials can range from about 2 nm to about 20 nm. The surface of QDparticles can be further modified with ligands such as amine ligands, phosphine ligands,phosphatide and polyvinylpyridine. In one aspect, the phosphor can be a quantum dotmaterial.

[0087] In some aspects, the QD materials can be a core / shell QD, including a core, atleast 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 QDsinclude, but are not limited to, Si, Ge, Sn, Se, Te, B, C (including diamond), P, Co, Au, BN,BP, BAs, AIN, AlP, 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. Exemplarycore-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 / CdSand CdTe / ZnS.

[0088] In some aspects, any of the phosphor powders described herein, the inkcompositions described herein, and / or the films described herein can also include one ormore agents on the surfaces of the phosphors. In some aspects, the phosphors can be at leastpartially coated with surface coatings to enhance stability of the phosphor particles and resistaggregation by modifying the surface of the phosphor particles and increase the zeta potentialof the phosphor particles. In certain aspects, the coated phosphor can have a MgF2 or CaF2surface coating and a surface Zeta potential of at least |20 mV when measured inisopropanol. In certain aspec, the coated phosphor can have a Zeta potential of at least 30mV when measured in isopropanol.

[0089] In some aspects, the surface coatings can be a metal fluoride, silica or organiccoating. In certain aspects, the phosphors cam be at least partially coated with a metalfluoride, which increases positive Zeta potential and reduces agglomeration. In certainaspects, the metal fluoride coating includes MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AlF3 or acombination thereof. In certain aspects, the metal fluoride coating can be present in anamount from about 0.1 wt% to about 10 wt%, including all the subranges in between. Incertain 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 fluoridecoating can be present from about 0.3 wt% to about 3 wt%, including all the subranges inbetween. Metal fluoride coated Mn+ doped phosphors can be prepared as described in WO2018 / 093832 and US Publication No. 2020 / 0369956. The entire contents of each of whichare incorporated herein by reference.

[0090] In some aspects, the phosphors can be at least partially coated with an organiccoating, such as polymerized oleic acid. Oleic acid can be used to coat the phosphor particlesvia a solvothermal synthesis or treatment, such as by a mixing adsorption treatment.

[0091] In some aspects, any of the phosphor powders described herein, the inkcompositions described herein, and / or the films described herein can further include one ormore additives. In certain aspects, the additives can include surfactants, dispersants, rheologymodifiers, scattering agents, and combinations thereof. In some aspects, surfactants, such assmall molecule surfactants or dispersants can be incorporated to reduce dispersity andagglomeration in the ink compositions provided herein. Dispersants reduce agglomeration ofphosphor powders with minimal impact to optical performance and reliability. Dispersantscan have functional groups, such as hydroxyl (-OH), carboxyl (—COOH), sulfonate,sulfate, ammonium, amino (-NH2) or imino (—NH—) for anchoring on surfaces and abuoyant moiety, which helps to keep a dispersion uniform and homogeneous. In addition,dispersants with proper functional groups can also improve wetting ability. A liquid withlower 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 theliquid and dispersing particles.

[0092] In some aspects, the dispersants can be anionic, non-ionic, cationic or zwitterionicpolymers. Anionic dispersants include, but are not limited to, potassium oleate, alkylsulfonate, polyesters, phosphoric and carboxylic acid esters, polyoxyethylene (10) etherphosphate, polyol derivatized phosphate ester, phosphates, 2-(octen-1-yl)-butanedioic acid,polyacrylates including structured or controlled polymerization technology (CPT) derivedacrylates, polyacrylate salt, such as a polyol functionalized polyacrylate. In other aspects, thedispersants are zwitterionic, such as a zwitterionic comb copolymer functionalized withamine and acid groups. In one aspect, the non-ionic dispersant can be a polyurethane baseddispersant. In another aspect, the cationic dispersant can be a polyamine dispersant, includingcationic hyperbranched polyamine. In one aspect, the dispersant can be one or polymerscontaining amine groups, polymer dispersants, such as TEGO® 689 and TEGO® 690 withpigment affinity groups, such as dodecanoic acid, polymers with OH / ether groups andpigment affinity groups. In one aspect, the dispersant can be a polyester composed ofpolyhydroxystearic acid stearate. In another aspect, the dispersant can be EO / PO blockcopolymers. In one aspect, the dispersant can be a solution of a modified urea (BYK®-7410-ET from BYK Additives and Instruments).

[0093] In some aspects, the dispersant or surfactant can be included in any of thephosphor powders described herein, the ink compositions described herein, and / or the filmsdescribed herein in amounts up to 10 wt%. In some aspects, the dispersant or surfactant canbe included in an amount from about 0.1 wt% to about 10 wt%, including all the subrangesin between. In another aspect, the dispersant or surfactant can be included in an amount fromabout 1 wt% to about 5 wt%, including all the subranges in between. The dispersant orsurfactant amount can be based on the total weight of the ink composition.

[0094] In some aspects, any of the phosphor powders described herein, the inkcompositions described herein, and / or the films described herein can also include rheologymodifiers. Rheology modifiers can be used to provide desirable rheological properties, suchas adjusting the viscosity of the compositions, improving dispersion stability and phosphorparticle suspension and controlling the rheology profile of the compositions for film formingcharacteristics and ink printability. In one aspect, the rheology modifier can have a viscositygreater than 100 centipoise at 20° C. In one aspect, the rheology modifiers can include silicananoparticles and clay-based materials. In other aspects, nanoparticles of silica can be fumedsilica, precipitated silica or surface-modified hydrophobic silica.

[0095] In some aspects, the rheology modifiers can include gelators including at least onecrosslinkable group. In some aspects, the gelators can gel at temperatures at less than 30° С.In some aspects, the gelators can gel at temperatures in the range of about 20° C to about 30°C, including all the subranges in between. Gelators, such as a wax with polymerizablefunctionality, can be added to any of the phosphor powders described herein, the inkcompositions described herein, and / or the films described herein to form gel-like dispersionswith good stability and low sedimentation at room temperature, which become coatable andprintable liquids with much reduced viscosity upon heating. Exemplary waxes include, butare not limited to, di(hexadecyl) fumarate, oleyl cinnamide, di(4-vinyloxybutyl)octadecanedioate, non-polar acrylate waxes, such as octadecyl cinnamide, and functionalizedwaxes, such as dodecyl cinnamide.

[0096] In some aspects, additive materials can be added to any of the phosphor powdersdescribed herein, the ink compositions described herein, and / or the films described herein toadjust rheological properties, adjust viscosity and optimize coatability or film-formingcapability and printability. In some aspect, materials with high thermal conductivity, such asaluminum nitride nanoparticles and microparticles can be added to the phosphor powdersdescribed herein, the ink compositions described herein, and / or the films described herein. Inother aspects, one or more electrolytes or polyelectrolytes can be added to the phosphorpowders described herein, the ink compositions described herein, and / or the films describedherein.

[0097] Devices according to the present disclosure can include an LED light sourceradiationally connected and / or optically coupled to any of the phosphor compositionsdescribed herein, the ink compositions described herein, and / or the films described herein.FIGs. 8A-8E show a device 10, according to various aspects of the present disclosure.Referring to FIG. 8A, the device 10 includes an LED light source 12 and the phosphorcomposition 14. The LED light source 12 can be a UV or blue emitting LED. In someaspects, the LED light source 12 produces blue light in a wavelength range from about 380nm to about 460 nm, including all the subranges in between. In the device 10, the phosphorcomposition 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 LEDlight source 12 is able to excite the phosphor composition 14, and the phosphor composition14 is able to emit light in response to the excitation by the radiation. The phosphorcomposition 14 can be disposed on a part or portion of the LED light source 12 or locatedremotely at a distance from the LED light source 12. In some aspects, the device can be abacklight unit for display applications. In other aspects, the LED light source 12 can be amicro-LED and the device can for a self-emissive display. FIG. 8B shows an exemplaryaspect where the phosphor composition 14 is disposed on the LED light source 12. The LEDlight source 12 can disposed on a reflective layer 16. The reflective layer 16 reflects lightfrom 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, thereflective layer 16 can be a metallic layer, such as aluminum, silver, silver alloys oraluminum alloys. FIG. 8C shows an exemplary aspect where the phosphor composition 14 isdisposed on the LED light source 12. An encapsulant or barrier layer 18 can disposed on thephosphor 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 transparentto allow light to be transmitted through those elements. FIG. 3D shows an exemplary aspectwhere the LED light source 14 is depicted as an array of LED light sources 12. In someaspects, the LED light sources 12 can be mini-LEDs or micro-LEDs. FIG. 8E shows anexemplary aspect where the phosphor composition 14 is located remotely from the LED lightsource 12, which is depicted as an array of LED light sources 12.

[0098] The general discussion of the exemplary LED light source discussed herein isdirected toward an inorganic LED based light source. The most popular white LEDs arebased on blue or UV emitting GalnN chips. In addition, to inorganic LED light sources, theterm LED light source is meant to encompass all LED light sources, such as semiconductorlaser diodes (LD), organic light emitting diodes (OLED) or a hybrid of LED and LD. TheLED light source can be a mini-LED or micro-LED, which can be used in self-emissivedisplays. 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 anyreference to semiconductor, semiconductor LED, or LED chip is merely representative of anyappropriate radiation source, including, but not limited to, LDs and OLEDs.

[0099] The phosphor composition 14 can be present in any form such as a powder, glass,or composite, e.g., a phosphor-polymer composite or a phosphor-glass composite. Further,the phosphor composition 14 can be used as a layer, sheet, film, strip, dispersed particulates,or any combination thereof. In some aspects, the phosphor composition 14 includes auranium-based phosphor material in glass form. In some aspects, the device 10 can includethe phosphor composition 14 in form of a phosphor wheel (not shown). The phosphor wheelcan include the phosphor composition embedded in a glass. A phosphor wheel and relateddevices are described in WO 2017 / 196779, which is incorporated herein by reference.

[0100] The phosphor composition can be optically coupled or radiationally connected toan LED light source. In one aspect, a white light blend can be obtained by blending the redphosphor material and the green phosphor material with an LED light source, such as a blueor UV LED.

[0101] FIG. 9 illustrates a lighting apparatus or lamp 20, in accordance with the presentteachings. In one aspect, the lighting apparatus 20 can be a backlight apparatus. The lightingapparatus 20 includes an LED chip 22 and leads 24 electrically attached to the LED chip 22.In some aspects, the leads 24 can include thin wires supported by a thicker lead frame(s) 26or the leads 24 can include self-supported electrodes and the lead frame can be omitted. Theleads 24 provide current to LED chip 22 and thus cause it to emit radiation.

[0102] A layer 30 of the phosphor composition can be disposed on a surface of the LEDchip 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 powder or compositionand a binder material or solvent (as discussed above). In one exemplary method, a siliconeslurry in which the phosphor composition particles are randomly suspended or uniformlydispersed can be placed around the LED chip 22. This method is merely exemplary ofpossible positions of the phosphor layer 30 and LED chip 22. In some aspects, the phosphorlayer 30 can be coated over or directly on the light emitting surface of the LED chip 22 bycoating and drying the slurry over the LED chip 22. The light emitted by the LED chip 22mixes with the light emitted by the phosphor composition to produce desired emission.

[0103] With continued reference to FIG. 9, the LED chip 22 can be encapsulated withinan envelope 28. The envelope 28 can be formed of, for example, glass or plastic. In someaspects, the LED chip 22 can be enclosed by an encapsulant material 32. The encapsulantmaterial 32 can be a low temperature glass, or a polymer or resin known in the art, forexample, an epoxy, silicone, epoxy-silicone, acrylate or a combination thereof. In someaspects, the lighting apparatus 20 only includes the encapsulant material 32 without theenvelope 28. Both the envelope 28 and the encapsulant material 32 should be transparent toallow light to be transmitted through those elements.

[0104] In some aspects, the phosphor composition 36 is interspersed within theencapsulant material 32, instead of being formed directly on the LED chip 22, as shown inFIG. 10. The phosphor composition 36 can be interspersed within a portion of theencapsulant material 32 or throughout the entire volume of the encapsulant material 32. Bluelight or UV light emitted by the LED chip 22 mixes with the light emitted by phosphorcomposition 33, and the mixed light transmits out from the lighting apparatus 20.

[0105] In some aspects, a layer 34 of the phosphor composition is coated onto a surfaceof the envelope 28, instead of being formed over the LED chip 22, as illustrated in FIG. 11.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, ifdesired. In some aspects, the phosphor layer 34 can be coated on the entire surface of theenvelope 28 or only a top portion of the inside surface 29 of the envelope 28. The UV / bluelight emitted by the LED chip 22 mixes with the light emitted by the phosphor layer 34, andthe mixed light transmits out. Of course, the phosphor composition can be located in any twoor all three locations (as shown in FIGs. 9-11) or in any other suitable location, such asseparately 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 anotheraspect, the phosphor layer 34 can be a film and disposed on the LED chip 22. In someaspects, the phosphor layer 34 can be applied to the LED chip 22 as an ink composition. Insome aspects, the phosphor layer 34 can be applied to the LED chip 22 as an ink compositionand dried to form a film on the LED chip 22. In some aspects, the phosphor composition canbe a single layer or multi-layered. In some aspects, the film is a multi-layered structure whereeach layer of the multi-layered structure includes at least one phosphor or quantum dotmaterial.

[0106] In another aspect, a device structure includes a layer of a phosphor compositionon an LED chip and a remote layer including a quantum dot material. In another aspect, adevice structure includes a layer of a phosphor composition on an LED chip and a remotelayer including a quantum dot material and phosphor material. In another aspect, a devicestructure includes a layer of a phosphor composition on an LED chip and a film includingquantum dot material located remotely from the LED chip. In another aspect, a devicestructure includes a layer of a phosphor composition on an LED chip and a film includingquantum dot material and phosphor material located remotely from the LED chip.

[0107] In any of the above structures, the lighting apparatus 20 (FIGS. 9-11) can alsoinclude a plurality of scattering particles (not shown), which can be embedded in theencapsulant material 32. The scattering particles can include, for example, alumina, silica,zirconia, or titania. The scattering particles effectively scatter the directional light emittedfrom the LED chip 22, preferably with a negligible amount of absorption.

[0108] In some aspects, the lighting apparatus 20 shown in FIG. 10 or FIG. 11 can be abacklight apparatus. In certain aspects, the backlight apparatus includes a backlight unit 10.Some aspects include a surface mounted device (SMD) type light emitting diode 50, e.g., asillustrated in FIGs. 12A, 12B and 12C, for backlight applications. Referring to FIG. 12A,SMD is a "side-emitting type" and has a light-emitting window 52 on a protruding portion ofa light guiding member 54. In some aspects, an SMD package includes an LED chip 56 asdefined above, and a phosphor composition 58 as described herein. FIG. 12B shows thephosphor composition 58 disposed on the LED chip 56 and FIG. 12C shows the phosphorcomposition 58 disposed remotely from the LED chip 56. FIGs. 12B and 12C also show theLED chip 56 and the light guiding member 54 disposed on a reflective layer 59. Thereflective layer 59 reflects light from the LED chip 56 and the light guiding member 54toward the phosphor composition 58. The reflective layer 59 can be any material suitable forreflecting light. In some aspects, the reflective layer 59 can be a metallic layer, such as asilver, aluminum, aluminum alloy or silver alloy. In some aspects, the device can be a directlit display. By use of the phosphor compositions described herein, devices can be providedproducing white light for display applications, for example, LCD backlight units, having highcolor gamut and high luminosity. Alternately, devices can be provided for producing whitelight for general illumination having high luminosity and high CRI values for a wide range ofcolor temperatures of interest (2000 K to 10,000 K).

[0109] Devices of the present disclosure include lighting and display apparatuses forgeneral illumination and display applications. Examples of display apparatuses include, butare not limited to, liquid crystal display (LCD) backlight units, televisions, computermonitors, vehicular displays, laptops, computer notebooks, mobile phones, smartphones,tablet computers and other handheld devices. Where the display is a backlight unit, thephosphor composition can be incorporated in a fdm, sheet or strip that is radiationallycoupled and / or optically coupled to the LED light source, as described in US PatentApplication Publication No. 2017 / 0254943, incorporated herein by reference. Examples ofother devices include, but are not limited to, chromatic lamps, plasma screens, xenonexcitation lamps, UV excitation marking systems, automotive headlamps, home and theatreprojectors, laser pumped devices, and point sensors. In some aspects, the device can be a fastresponse 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 theseapplications is meant to be merely exemplary and not exhaustive.

[0110] In some aspects, films including the phosphor composition can be disposed onsmall-size LEDs, such as micro-LEDs or mini-LEDs. In other aspects, the film includesphosphors with micron or sub-micron particle sizes. In other aspects, the film includes nano-sized particles. In one aspect, the film includes a Mn⁴+ doped phosphor having a D50 particlesize less than 20 µm, less than 10 µm, particularly less than 5 µm, and more particularlynano-sized phosphors. In another aspect, the D50 particle size can be from about 1 micron toabout 20 microns, including all the subranges in between. In another aspect, the D50 particlesize is from about 1 micron to about 15 microns, including all the subranges in between. Inanother aspect, the D50 particle size is from about 1 micron to about 10 microns, includingall the subranges in between. In another aspect, the D50 particle size can be from about 1micron to about 5 microns, including all the subranges in between. In another aspect, the D50particle size is from about 1 micron to about 3 microns, including all the subranges inbetween. 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 about100 nm to about 1000 nm, including all the subranges in between. In another aspect, the D50particle 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 allthe subranges in between. In another aspect, the D50 particle size is from about 500 nm toabout 1000 nm, including all the subranges in between. In another aspect, the D50 particlesize is from about 750 nm to about 1000 nm, including all the subranges in between. Inanother aspect, the D50 particle size is from about 50 nm to about 10 microns, including allthe subranges in between. In another aspect, the D50 particle size is from about 200 nm toabout 5 microns. In another aspect, the D50 particle size is from about 250 nm to about 5microns, including all the subranges in between. In another aspect, the D50 particle size isfrom about 500 nm to about 5 microns, including all the subranges in between. In anotheraspect, the D50 particle size is from about 750 nm to about 5 microns, including all thesubranges in between. In another aspect, the D50 particle size is from about 750 nm to about3 microns, including all the subranges in between.

[0111] FIGs. 13A-13C are schematic diagrams of a banked arrangement 200, inaccordance with the present teachings. More particularly, FIGs. 13A-13C illustrate bankedarrangement 200 at different phases of a dispensing or printing process. Both printing andtransferring 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 ischallenging. Banked arrangement 200 enables a high aspect ratio conversion layer to beachieved on small-feature light emitting elements in a more efficient and cost-effectivemanner 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 ratiocan be 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 anotheraspect, the aspect ratio is from about 0.5 to 5, including all the subranges in between. Inanother aspect, the aspect ratio is from about 0.1 to 3, more particularly, 0.1 to 1 and 0.1 to0.5, including all the subranges in between.

[0112] In FIG. 13A 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 asubstrate 210. In FIG. 13B, one or more walls 204 are disposed around each of the pluralityof light emitting elements 202. In some aspects, each light emitting element 202 issurrounded by continuous walls 204. For example, each light emitting element 202 can besurrounded 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 exemplaryarrangement illustrated in FIGs. 13A-13D, each light emitting element 202 is surrounded byfour walls 204 formed on planar structure 210, which form a banked structure 206. In otheraspects, such as the example illustrated in FIG. 14, walls 204 are formed within a layer 244that 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 bankedstructure 206 or a well structure 246. In some aspects, banked structure 206 or well structure246 can be formed via printing (e.g., using a contact stencil printing system or snap-offstencil printing system). In further aspects, snap-off printing can be desired, as it providescontrol over printing speed and with the appropriate opening dimensions, can lead to the rightamount of material at the desired positioning to be transferred to fill well structures withoutany spill over to next pixel / color- filters. Further, in some aspects that include a wellstructure, a relatively thin stencil thickness can be used for better see-through to assist withalignment at a micron scale.

[0113] In some aspects, walls 204 are include reflective materials, and therefore can actas reflectors. More particularly, walls 204 can be coated with a white surface which reflectsback all the visible wavelengths that shine on it. The reflective material in walls 204 canincrease the brightness of the light emitting elements. In some aspects, one or more walls 204include a translucent material. For example, in transparent display applications, walls 204 caninclude a translucent material.

[0114] In FIG. 13C, the banked structure, or alternatively the well structure, can be filledwith 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, oralternatively, the well structure, can be filled by a dispensing and / or printing method. Forexample, in some aspects, the banked structure or the well structure can be filled using acontact stencil printing system or snap-off stencil printing system. Snap-off stencil printingsystem can enable the transfer of materials with high reproducibility and uniformity in a cost-effective manner. In other aspects, the well can be filled via dispensing or printing methodsknown in the art.

[0115] FIG. 15A is a top view of an exemplary red-green-blue (RGB) pixel 1000 thatincludes a blue subpixel 1010, a green subpixel 1020, and a red subpixel 1030. FIG. 15B is aside view of an exemplary RGB pixel layout 1000. Each subpixel can include a well thatincludes a plurality of walls. An ink composition including blue-emitting phosphors can bedeposited in blue subpixel 1010, an ink composition including green-emitting phosphors canbe deposited in green subpixel 1022, and an ink composition including red- emittingphosphors can be deposited in red subpixel 1030. The ink compositions deposited into bluesubpixel 1012, green subpixel 1020, and red subpixel 1030 can cure into color filter parts1012, 1022, and 1032, respectively. As such, blue subpixel 1010 can be configured to emitblue light 1016, green subpixel 1020 can be configured to emit green light 1026, and redsubpixel 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 beperformed via a contact stencil printing system or a snap-off stencil printing system. The inkcomposition can be cured using hot air, UV light, and / or any other method known in the art.

[0116] In some aspects, a scattering agent can be added to a subpixel, as noted above. Insome 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 arefractive index of about 1 to about 1.6, including all the subranges in between. In furtheraspects, 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 arelatively high refractive index increases the effective path length of excitation light 1040 (eg., the blue light) for additional absorption.

[0117] In some aspects, a subpixel can be filled in part by a first ink composition, and inpart by a second ink composition. The second ink composition can be located proximate to aportion of the pixel or subpixel through which excitation light enters (e.g., side 1002 in FIG.15B). Excitation light 1040 can enter the pixel, and encounter the second ink compositionand then subsequently, the first ink composition. The subpixel can be filled using a two-passprinting approach. The printing can be performed via a contact stencil printing system orsnap-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 inkcomposition can include different refractive indexes. For example, in some aspects, thesecond ink composition includes a relatively low refractive index and the first inkcomposition includes a relatively high refractive index. For example, in some aspects, thefirst ink composition includes a higher refractive index than the second ink composition. Thiscauses excitation light to first encounter the second ink composition resulting in lowreflection and then encounter the first ink composition, which increases the effectiveexcitation light path once coupled into the color filter part. In further aspects, the second inkcomposition includes a refractive index of about 0. 1 to about 2, including all the subrangesin between. In further aspects, the second ink composition includes a refractive index ofabout 0.1 to about 1.6, including all the subranges in between. In further aspects, the secondink composition includes a refractive index of about 0.1 to about 1.51, including all thesubranges in between. In some aspects, the first ink composition includes a refractive indexof greater than about 1. In further aspects, the first ink composition includes a refractiveindex of greater than about 1.3. In further aspects, the first ink composition includes arefractive index of greater than about greater than 1.50. In further aspects, the first inkcomposition includes a refractive index of greater than about 1.51.

[0118] In some aspects, quantum dots in a color filter (QDCF) can be utilized. QDCF canimprove the color quality, viewing angle and energy efficiency of displays. By using a bluelight source such as OLED, LED, mini -LED, or micro-LED, or a UV light source, andreplacing traditional color filters with a QDCF material, at least a portion of the blue lightgets converted to a higher wavelength range such as red and / or green light.

[0119] In some aspects, RGB pixel 1000 is part of a display device that includes abacklight unit (BLU) configured to emit a blue light 1040. In such aspects, QDCF caninclude scattering agent in blue subpixel 1010 and a quantum dot in the red subpixel 1030and green subpixel 1020 to attain wide color gamut. In addition to the quantum dots in thered subpixel 1030 and green subpixel 1020, at least one binder, at least one scattering agentand / or an additional color filter material that absorbs blue light can be added to minimizeblue light leakage through the subpixel, which would result in lower color gamut.

[0120] Suitable contact stencil printing system and snap-off stencil printing systeminclude those described in WO2023 / 215433A1, the content of which is incorporated here byreference.

[0121] It is understood that the examples and aspects described herein are for illustrativepurposes only and that various modifications or changes in light thereof will be suggested topersons skilled in the art and are to be included within the spirit and purview of thisapplication and scope of the appended claims. All publications, patents, and patentapplications cited herein are hereby incorporated by reference in their entirety for allpurposes.EXAMPLES

[0122] The following non-limiting examples are illustrative of the present disclosure.

[0123] SUMMARY: PFS with aggregate sizes of approximately D50 = 6 – 10 µm wasused as starting material. As shown herein, jet milling was successful in reducing theaggregate size to D50 ~2 µm and D90 ~3 µm after 1 to 3 passes in the jet mill under the mostaggressive milling conditions. This particle size was similar to synthesized PFS using theconventional antisolvent method. However, jet milled PFS exhibited poor quantum efficiency(QE) with values < 65%. This reduction in QE was attributed to newly exposed PFS facetswith reduced Mn species that serve as parasitic absorbers of blue light. Without being boundby theories, other potential factors for degraded performance included impurities from thestainless steel milling apparatus and / or crystallite damage during milling, which was apparentwith scanning electron microscopy (SEM) imaging. As demonstrated herein, attempts torecover PFS zero-hour (t=0) QE performance with post-jet milling treatments and annealingwere successful and the resulting powders exhibited QE > 98% with D50 < 4 µm.

[0124] More aggressive washing and full treatment followed by annealing resulted in QE> 101%, but this was achieved at the expense of lower Mn wt% (0.58 – 0.75 wt% Mn), whichwas significantly lower than the initial PFS powders (2.8 – 3.0 wt% Mn). Half treatmentfollowed by annealing provided the best balance of high QE (99%) and high Mn wt% (> 2.5wt% Mn). High temperature, high humidity (HTHH) reliability was also assessed for thesesamples for 60 h (cumulative over two 30 h cycles) at 80 °C and 60% relative humidity. Forall samples, a treatment step was necessary to prevent significant QE degradation post-HTHHexposure. Samples that underwent full treatment showed less QE degradation post-HTHHexposure than half treated samples, but this came at the expense of greater Mn+ removal.Low Mn wt% is expected to lead to low blue light absorption.Example 1: Jet Milling Process

[0125] PFS was received from Current Chemicals (Cleveland, Ohio) in the form of twosamples: unannealed powder (U, lot 0XX-2324901) and annealed powder (A, lot 0XX-2324902). These two powders were sent to Glen Mills, Inc. (Telford, PA) for jet milling on aModel 00 Jet-O-Mizer using a vibratory feeder, compressed air for the grinding fluid, filtersleeves for collection. The jet milling equipment was housed in a glove box due to PFStoxicity.

[0126] The jet milling data and sample weights collected are shown in Tables 1 and 2.Table 1: Particle Size Data (PSD)Sample IDRun ## of millpassesFeed rate(g / min)Grinding D50 (μm)ª D90 (μm)ªpressureUInitial feed N / AN / AN / A11.0036.24_b11Varies100__b__bU12161003.4157.296__C3161003.4447.820U24261002.8135.547AInitial feed N / AN / AN / A7.42418.86C__C5161003.0036.9706261002.2933.958A37361001.7593.043a) Particle size distribution analyzed on Coulter LS230; powder dispersed in IPA; Fraunhoferoptical modelb) Run #1 had feeding issues; no PSD data collectedc) PSD data only; sample underwent subsequent milling and was not collectedTable 2: Weight of Collected MaterialDescriptionWeightTotal Feed provided350 gRun #1*17.7 gSample U1 (Run #2)50.6 gSample U2 (Run #4)99.3 gSample A3 (Run #7)160.5 gTotal powder collected328.1 gTotal yield328.1 g / 350 g = 93.7% yield* Run #1 had feeding issues during jet milling.Example 2: Post-Jet Milling Full Treatment and Annealing

[0127] Samples U2FG and A3FG were prepared by adding 7 g of jet milled phosphor to70 mL 49% HF nearly saturated with K2SiF6 and stirred for approximately 22 min in separate250 mL centrifuge bottles with stir bars. The suspensions were centrifuged at 4000 rpm for 1min and then the supernatant was decanted. A second treatment using 70 mL 49% nearlysaturated with K2SiF6 was conducted for approximately 17 min. followed by centrifugationand decanting. The resulting powders were washed with 70 mL 20% HF for approximately30 min and then centrifuged and decanted. The powders were washed three times with 70 mLacetone before drying in a vacuum desiccator overnight. The dried powders were sievedthrough a 60 micron mesh plastic screen and then transferred to clean and dry PTFE boatsand placed in a drying oven. After three (3) pump-purge cycles with nitrogen, the sample wasleft under vacuum (approximately -28 in Hg) and heated to ~160 °C. The heat was turned offafter 2 h and the sample was allowed to cool to room temperature.Example 3: Post-Jet Milling Half Treatment and Annealing

[0128] Samples U2HG and A3HG were prepared by adding 7.7 g of jet milled phosphorto 23.5 mL 20% HF saturated with K2SiF6 and stirred for approximately 15 min in separate250 mL centrifuge bottles with stir bars. The suspensions were centrifuged at 4000 rpm for 1min and then the supernatant was decanted. The resulting powders were washed with 77 mL20% HF for approximately 1 min and then centrifuged and decanted. The powders werewashed three times with 77 mL acetone before drying in a vacuum desiccator overnight. Thedried powders were sieved, vacuum dried, and annealed as described above.Example 4: Characterization of Phosphor Powder

[0129] Optical performance including quantum efficiency (QE), blue light bleed through(BT), and R631 of PFS powders were measured as silicone tapes prepared and testedaccording to the standard operating procedure (SOP). PFS powder aggregate particle sizeanalysis was measured using a HoribaTM Particle Counter according to the SOP. The carrierliquid was n-methyl pyrrolidone (NMP), which possessed a sufficient refractive indexdifference 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 dispersionduring measurement. Values are reported after sonication of PFS in NMP using the internalsonication horn at setting "5" for 3 min and stirring. The D50 was defined as the medianparticle size. The D10 and D90 values were defined as the particle sizes for a volumedistribution 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 andprimary 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 PhosphorPowder

[0130] Silicone tapes containing PFS were subjected to two (2) 30 h heating cycles (60 hcumulative exposure) at 80 °C and 60% relative humidity in a specially designed humiditychamber. After each heating cycle, the optical performance of the tapes was measured asabove for quantum efficiency (QE), blue light bleed through (BT), and R631 and comparedto the zero-hour data.Example 6: Results and DiscussionSample Preparation and Synthesis

[0131] FIGs. 2A-2C summarize the sample process flow described herein and Table 3provides further processing details. The sample identification code is used for claritythroughout. It is important to note that sample U2 was prepared independently of sample U1.Both U1 and U2 were generated from sample U, as shown in FIG. 2A.Table 3. Sample identifiers, descriptions, and processing notes for the powders analyzed in this study.Sample IDUU1U2Sample DescriptionPFS, lot 0XX-2324901,unannealedSample U with 1 milling passSample U with 2 millingpasses (independent of U1)Processing NotesU2FGSample U2 followed by fulltreatment then annealed49% HF treatment 10mL / g,long duration 20% HF washfollowed by annealU2HGSample U2 followed by halftreatment then annealed20% HF half treatment3mL / g, 20% HF washfollowed by annealAA3A3FGPFS, lot 0XX-2324902,annealedSample A with 3 millingpassesSample A3 followed by fulltreatment then annealed run49% HF treatment 10mL / g,long duration 20% HF washfollowed by annealA3HGSample A3 followed by halftreatment then annealed20% HF half treatment3mL / g, 20% HF washfollowed by anneal50 g batchASPAntisolvent precipitated PFSand annealedASPFSample ASP followed by full 49% HF treatment 10mL / g,treatment (no additionalanneal)ASPH20% HF washSample ASP followed by half 20% HF half treatmenttreatment (no additional10mL / g, 20% HF washanneal)PFS Characterization: Zero-Hour Performance

[0132] FIGs. 3A and 3B show representative scanning electron micrographs of as-received and jet milled PFS samples and antisolvent precipitated PFS. Sample U showedlarger crystallites with more uniform cubic morphology than sample A, which showedsmaller, more polyhedral crystallites. After jet milling, the particle sizes of all powders werereduced, whether after a single milling pass (U1) or multiple passes (U2, A3). Also, all jetmilled powders showed similar particle morphologies with many particle fragments andphysically damaged crystallites, and heterogeneous shapes. This result was due to the jet millgrinding mechanism described above. As a comparison to jet milling, antisolvent precipitatedPFS exhibits comparable crystallite sizes while maintaining the cubic crystal structure.

[0133] Laser diffraction particle size analyses were completed to compare PFS (refractiveindex = 1.40) aggregate sizes when suspended in n-methyl pyrrolidone solvent (NMP, RI =1.46). Previous studies showed a good correlation between SEM particle size and laserdiffraction aggregate size. FIG. 4 illustrates the changes in sample particle size distributions(PSD) as a function of the number jet milling passes. The PSD for sample U showed largermean particle sizes than sample A. Upon milling, the aggregate sizes of both sample U andsample A were reduced to approximately similar sizes, with D50 values ~2 µm. A single jetmill pass was able to achieve most of the particle size reduction (U1), which is favorablefrom a commercialization perspective. Needing many passes to achieve the desired particlesize would be unfavorable. Diminishing reductions in particle size were apparent withadditional milling passes (U2, A3). Under the current milling conditions, three jet millingpasses achieved the smallest PFS aggregate sizes. Overall, these PSD results agreed with theSEM images. For comparison, a representative sample prepared by antisolvent precipitation(ASP) yielded a D50 of 2.77 µm, which was only slightly larger than the milled samples.

[0134] In addition to particle size reduction, the jet milling process also inducedsignificant reductions in sample quantum efficiency (QE). The QE of as-received U and Awere approximately 68% and 100%, respectively. Upon jet milling, however, the QE of Uand A decreased to approximately 50% and 65%, respectively (see, FIG. 5, U1, U2, A3). Itwas clear that jet milling damaged the as-received sample crystallites as shown in FIGS. 3Aand 3B. This process generated abundant PFS crystallite defects, which were the primaryreason for this QE detriment. Defects include reduced Mn species, which can easily begenerated at newly created particle surfaces during milling. The creation of these defectsyielded sub-optimal optical properties. Impurities such as iron gathered from jet milling in astainless-steel vessel may also have contributed to QE degradation in jet milled powders.This result was expected, and it was believed that post-jet milling processing of the powderwas needed to recover high QE for jet milled powders. Compared to the jet milled PFSsamples, the as-prepared ASP sample showed over 99% QE at similar particle sizes andsimilar %Mn. Therefore, the “zero-hour" performance of ASP was superior to both U2 andA3, and ASP did not need an additional milling step to reduce particle size, which isadvantageous for process economics.

[0135] Post-jet milling processing of powders entailed two steps: (1) stirring the jetmilled powders in HF solutions saturated with K2SiF6, from this point referred to as"treatment solutions,” and (2) subsequent annealing in F2 atmosphere (SRP process).Combined, these two steps were used to remove impurities, heal PFS defects, and convertreduced Mn species to the desired Mn4+ oxidation state. Indeed, for both U and A typepowders, the treated and annealed jet milled powders showed complete QE recovery (FIG.5). It was discovered that 49% HF full treatment solutions (U2FG, A3FG) removedsignificantly more Mn than 20% HF half treatment solutions (U2HG, A3HG), which wasexpected. Too much Mn removal, and hence, lower Mn wt% in the final powder, isdetrimental to blue light absorption. As such, it is desired to remove enough Mn to recoverQE without sacrificing blue light absorption. In this case, the 20% HF half treatment solution(U2HG, A3HG) provided the best balance of high QE (approx. 99%) while maintaining > 2.5wt% Mn. Similarly, ASPF and ASPH were treated and annealed. However, there was nosignificant difference in the zero-hour powder performance compared to ASP. This indicatedas-prepared ASP was already optimized for zero-hour performance without further treatmentsor processing. High temperature, high humidity (HTHH) reliability performance will bediscussed below.

[0136] Although microscopic defects were healed during the treatment and annealing ofjet milled powders, the particle morphology was not affected. Particles and particle fragmentsof varying shapes and sizes were still observed after the post-jet milling processing (FIG.6A). Thus, the particle and crystallite morphologies were nominal factors to obtain high QE.Similarly, the morphology of ASP did not change during subsequent treatment steps (FIG.6B). Particle and crystallite aggregation, however, were apparent in jet milled powders thatwere treated and annealed. Aggregation of PFS is common during the treatment process, andthe increase in PFS aggregate size was confirmed through laser diffraction analyses,including for the ASP sample (FIGs. 7A-7C).

[0137] Table 4 provides a tabulated summary of the zero-hour powder characterizationresults for as received, jet milled, and treated and annealed samples. Antisolvent precipitated(ASP) PFS is shown for comparison. Elemental analysis detected < 50 ppm of iron in somejet milled samples, but this impurity was mostly removed during post-jet mill treatments (2-6ppm). Copper contamination (<30 ppm) was detected in annealed samples, which is commondue to the firing of the PFS powders in copper boats.Table 4. Summary of composition, aggregate size, and zero-hour (t = 0) optical properties for the PFSpowders characterized in this study.ICPAggregate size (Horiba)Optical properties (t = 0)IDMn(wt%)Metals(ppm)D10(μm)D50(μm)D90(μm)QEBTR631Unannealed 69FU3.07%<LOD*3.65810.46116.95468.49%9.94%22.20%U13.10%Fe: 321.4862.3833.86150.28%5.78%30.50%U23.13%<LOD*1.462.1963.24851.65%5.69%31.90%U2FG0.75%Cu: 3-92.8184.8788.013102.05%27.17%34.80%U2HG2.58%Cu: 3-91.9963.8210.07798.77%8.42%34.40%Annealed 69FA2.84%Cu: 253.786.3459.943100.24%8.79%29.70%A32.88%Cu: 241.3471.9512.79464.76%5.14%33.80%A3FG0.58%Cu: 102.4864.0065.989101.91%33.11%34.80%A3HG2.71%Cu: 3-92.0993.8447.38799.66%8.63%33.60%Fe: 2-6Antisolvent precipitationASP3.04%Cu: 3-91.8802.7703.87499.25%5.93%37.25%ASPF2.83%<LOD*2.6124.47910.06899.38%6.53%36.90%ASPH2.97%<LOD*2.1323.4635.28498.73%6.34%37.15%* Less than limit of detectionPFS Characterization: HTHH Performance

[0138] Beyond zero-hour performance, there is interest in gauging the reliability of PFSafter extended use (~years) in relevant applications. To simulate this type of long-term use, ahigh temperature, high humidity (HTHH) protocol is used to intentionally accelerate PFSaging over several hours and QE is monitored to assess performance degradation. In thisstudy, two HTHH cycles of 30 h duration (60 h cumulative) were performed at 80 °C and60% relative humidity. The QE of each tape was measured after each HTHH cycle (Table 5).After the first HTHH exposure, the jet milled PFS samples (U1, U2, A3) all showed QElosses >46% after the first HTHH exposure, however, sample Ushowed a decrease of 9.69%QE. However, this has a very low t = 0 QE of 68%. These same jet milled samples did notshow appreciable QE degradation after the second HTHH exposure, however (< 1% loss).Clearly, as jet milled powders were not reliable, this further supported the need forsubsequent treatment and annealing steps. Indeed, U2FG and A3FG showed the best HTHHreliability. This can be explained by the aggressive removal of reduced Mn species, whichwas reflected in the ICP analysis of these samples (< 1 wt% Mn, Table 4). Although thesesamples exhibited high QE post-HTHH, the blue light absorption of these samples isexpected to be very low compared to the parent powders. Finally, ASPF showed both goodinitial performance and the best HTHH reliability, all while maintaining 2.8 wt% Mn. Atrade-off was observed when using a half treatment compared to a full treatment. For halftreatment powders, lower HTHH reliability was observed, but higher Mn wt% wasmaintained.Table 5. QE data for zero-hour (t = 0) performance and HTHH performance. For HTHH testing, tapeswere subjected to two (2) 30 h heating cycles (60 h cumulative exposure) at 80 °C and 60% relativehumidity.IDQEt=0QE post-HTHH#1AQE (t=0QE post-HTHH#1)HTHH #2ΔΟΕ(HTHH#1 →HTHH#2)total AQEUnannealed PFSU68.49%58.80%-9.69%57.90%-0.90%-10.59%U150.28%4.00%-46.28%3.41%-0.59%-46.87%U251.65%4.10%-47.55%3.35%-0.75%-48.30%U2FG102.05%87.80%-14.25%84.96%-2.84%-17.09%U2HG98.77%63.20%-35.57%58.38%-4.82%-40.39%Annealed PFSA100.24%81.30%-18.94%78.85%-2.45%-21.39%A364.76%4.10%-60.66%3.34%-0.76%-61.42%A3FG101.91%87.30%-14.61%85.39%-1.91%-16.52%A3HG99.66%64.10%-35.56%58.86%-5.24%-40.80%Antisolvent PrecipitationASP*93.87%66.40%-27.47%62.58%-3.82%-31.29%ASPF99.38%88.80%-10.58%85.26%-3.54%-14.12%ASPH98.73%82.00%-16.73%77.54%-4.46%-21.19%* The ASP QE data shown in this table was from a different tape than used in FIG. 5 and Table 4 above.

[0139] Aggressive jet milling of commercially available PFS was effective in decreasingaggregate sizes from D50 = 6 – 10 µm to D50 ~2 µm and d90~3 µm. These aggregates sizeswere achieved in only 1 to 3 passes, which is amenable for commercial practice. Theresulting sizes were comparable to currently synthesized PFS using the antisolventprecipitation method. Although jet milling induced crystallite damage, lattice defects, andreduced Mn species that caused low QE, post-jet mill treatments and annealing weresuccessful in recovering high, zero-hour QE (> 98%) performance at the expense of lowerMn wt% compared to the as-received PFS powder. For HTHH reliability, these powdersrequired subsequent treatments to maintain good performance. Overall, jet milling followedby subsequent treatment and annealing provides an alternative “top down" approach for smallsize PFS for micro-LED applications.

[0140] While the present disclosure has been described with reference to examples, it isto be understood that the scope of the claims should not be limited by the aspects set forth inthe examples, but should be given the broadest interpretation consistent with the descriptionas a whole.

[0141] In one embodiment, a phosphor powder comprises:phosphor particles that are jet-milled, the phosphor particles comprising a Mn dopedphosphor of formula I:Ax[MFy]:Mn+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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.

[0142] In one embodiment, a phosphor powder comprises:phosphor particles that are jet-milled, washed with one or more solutions, andannealed, the phosphor particles comprising a Mn¹ doped phosphor of formula I:Ax[MFy]:Mn+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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.

[0143] In one embodiment, the one or more solutions comprise HF and K2SiF6.

[0144] In one embodiment, the D50 value is from about 0.1 microns to about 10microns.

[0145] In one embodiment, the D50 value is from about 0.1 microns to about 5microns.

[0146] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 0.5 wt% to about 4 wt% based on total phosphor powder weight.

[0147] In one embodiment, the phosphor powder comprises an amount of manganesethat is greater than about 2.5 wt% based on total phosphor powder weight.

[0148] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 2 wt% to about 3 wt% based on total phosphor powder weight.

[0149] In one embodiment, the phosphor powder has a quantum efficiency that isgreater than about 95% under blue excitation.

[0150] In one embodiment, the phosphor powder has a quantum efficiency that is about99% under blue excitation.

[0151] In one embodiment, a phosphor powder has a particle size distribution of a D50value of less than about 10 microns. The phosphor powder may be produced by:reducing sizes of phosphor particles by jet milling the phosphor particles, thephosphor particles comprising a Mn doped phosphor of formula I.A[MFy]:Mn4+{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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7;washing the phosphor particles with one or more solutions; andannealing the phosphor particles.

[0152] In one embodiment, the step of washing the phosphor particles with one or moresolutions is performed after the step of reducing sizes of phosphor particles by jet milling thephosphor particles.

[0153] In one embodiment, the step of annealing the phosphor particles is performedafter the step of washing the phosphor particles with one or more solutions.

[0154] In one embodiment, the step of annealing the phosphor particles comprisesannealing the phosphor particles prior to reducing sizes of phosphor particles by jet millingthe phosphor particles, followed by further annealing the phosphor particles after the step ofwashing the phosphor particles with one or more solutions.

[0155] In one embodiment, the step of washing the phosphor particles with one or moresolutions comprises at least one step of washing the phosphor particles with one or moresolutions.

[0156] In one embodiment, the step of washing the phosphor particles with one or moresolutions comprises two steps of washing the phosphor particles with one or more solutionsafter the step of reducing sizes of phosphor particles by jet milling the phosphor particles.

[0157] In one embodiment, the one or more solutions comprise HF and K2SiF6.

[0158] In one embodiment, the one or more solutions comprise 49% HF and K2SiF6.

[0159] In one embodiment, the one or more solutions comprise 20% HF and K2SiF6.

[0160] In one embodiment, annealing the washed, jet-milled phosphor particlescomprises contacting the washed, jet-milled phosphor particles with a fluorine-containingoxidizing agent in gaseous form at an elevated temperature.

[0161] In one embodiment, the fluorine-containing oxidizing agent comprises F2, SF6,BrF5, NH4HF2, NH4F, KF, AIF3, SbF5, CIF3, BrF3, KrF, XeF2, XeF4, NF3, SiF4, PbF2, ZnF2,SnF2, CdF2 or any combination thereof.

[0162] In one embodiment, the fluorine-containing oxidizing agent is F2.

[0163] In one embodiment, prior to washing, the jet-milled phosphor particles have aparticle size distribution of a D50 value of less than about 3 microns.

[0164] In one embodiment, prior to washing, the jet-milled phosphor particles have aparticle size distribution of a D50 value from about 1.5 microns to less than about 2.5microns.

[0165] In one embodiment, prior to washing, manganese is present in the jet milledphosphor particles in an amount of a first weight percent of the total weight of the jet milledphosphor particles, and wherein, subsequent to washing, manganese is present in the washed,jet-milled phosphor particles in an amount of a second weight percent of the total weight ofthe jet milled phosphor particles, the second weight percent being less than the first weightpercent.

[0166] In one embodiment, the phosphor powder, further comprises an additionalphosphor comprising (Y,Gd, Tb,La,Sm,Pr,Lu)3(Al,Ga)5-aO12-3 / 2a:Ce³+(wherein 0≤a≤0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Ca1-h-rCehEurAll-h (Mg,Zn)hSiN3 (where 0≤h≤0.2, 0<r≤0.2); Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+,Се³+; (Ba, Sr, Ca)bSigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0167] In one embodiment, the D50 value is from about 0.1 microns to about 10microns.

[0168] In one embodiment, the D50 value is from about 0.1 microns to about 5microns.

[0169] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 0.5 wt% to about 4 wt% based on total phosphor powder weight.

[0170] In one embodiment, the phosphor powder comprises an amount of manganesethat is greater than about 2.5 wt% based on total phosphor powder weight.

[0171] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 2 wt% to about 3 wt% based on total phosphor powder weight.

[0172] In one embodiment, the phosphor powder has a quantum efficiency that isgreater than about 95% under blue excitation.

[0173] In one embodiment, the phosphor powder has a quantum efficiency that is about99% under blue excitation.

[0174] In one embodiment, an ink composition comprises:a phosphor powder comprising phosphor particles that are jet-milled, the phosphorparticles comprising a Mn doped phosphor of formula I.Ax[MF]:Mn+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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7, andat least one binder,wherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.

[0175] In one embodiment, an ink composition comprises:a phosphor powder comprising phosphor particles that are jet-milled, washed withone or more solutions, and annealed, the phosphor particles comprising a Mnt dopedphosphor of formula I:A.[MF]:Mn+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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andat least one binder,wherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.

[0176] In one embodiment, the ink composition further comprises scattering agents.

[0177] In one embodiment, the at least one binder comprises at least one of an epоху,acrylate, methacrylate, vinyl ester, siloxane, or polyethylene terethalate.

[0178] In one embodiment, the ink composition has a viscosity from more than 2,000cP to about 30,000 cP.

[0179] In one embodiment, the phosphor particles are present in an amount from about5 wt% to about 70 wt%, based on the weight of the ink composition.

[0180] In one embodiment, the phosphor powder is uniformly dispersed throughout theink composition.

[0181] In one embodiment, the one or more solutions comprise HF and K2SiF6.

[0182] In one embodiment, the one or more solutions comprise 49% HF and K2SiF6.

[0183] In one embodiment, the one or more solutions comprise 20% HF and K2SiF6.

[0184] In one embodiment, the ink composition further comprises an additionalphosphor comprising (Y,Gd, Tb,La,Sm,Pr,Lu)3(Al,Ga)5-aO12-3 / 2a:Ce³+(wherein 0<a≤0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga, In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce³+; Ca1-h-rCehEurAll-h (Mg, Zn)hSiN3 (where 0<h≤0.2, 0<r≤0.2); Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+,Ce³+; (Ba, Sr, Ca)bSigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0185] In one embodiment, the D50 value is from about 0.1 microns to about 10microns.

[0186] In one embodiment, the D50 value is from about 0.1 microns to about 5microns.

[0187] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 0.5 wt% to about 4 wt% based on total phosphor powder weight.

[0188] In one embodiment, the phosphor powder comprises an amount of manganesethat is greater than about 2.5 wt% based on total phosphor powder weight.

[0189] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 2 wt% to about 3 wt% based on total phosphor powder weight.

[0190] In one embodiment, the phosphor powder has a quantum efficiency that isgreater than about 95% under blue excitation.

[0191] In one embodiment, the phosphor powder has a quantum efficiency that is about99% under blue excitation.

[0192] In one embodiment, a film comprises:at least one cured or semi-cured ink comprising:a phosphor powder comprising phosphor particles that are jet-milled, washedwith one or more solutions, and annealed, the phosphor particles comprising aMn doped phosphor of formula I:Ax[MFy]:Mn++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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andat least one binder,wherein the phosphor powder has a particle size distribution of a D50 value ofless than about 10 microns.

[0193] In one embodiment, the film has a thickness of no more than 250 micrometers.

[0194] In one embodiment, the film has a thickness of no more than 50 micrometers.

[0195] In one embodiment, the film is substantially free of uniformity or mura defects.

[0196] In one embodiment, the at least one cured or semi-cured ink further comprisesscattering agents.

[0197] In one embodiment, the at least one binder comprises at least one of an epoxy,acrylate, methacrylate, vinyl ester, siloxane, or polyethylene terethalate.

[0198] In one embodiment, the phosphor powder is uniformly dispersed throughout theat least one cured or semi-cured ink.

[0199] In one embodiment, the one or more solutions comprise HF and K2SiF6.

[0200] In one embodiment, the one or more solutions comprise 49% HF and K2SiF6.

[0201] In one embodiment, the one or more solutions comprise 20% HF and K2SiF6.

[0202] In one embodiment, the at least one cured or semi-cured ink further comprisesan additional phosphor comprising (Y,Gd, Tb,La,Sm,Pr,Lu)3(Al,Ga)5-aO12-3 / 2a:Ce³+(wherein0≤a≤0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+; alpha-SiAlON doped withEu2+and / or Ce³+; Ca1-h-rCehEurAl1-h (Mg,Zn)hSiN3 (where 0≤h≤0.2, 0≤r≤0.2);Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+, Ce³+; (Ba,Sr,Ca)bSigNm:Eu2+(wherein 2b+4g=3m); or anycombination thereof.

[0203] In one embodiment, the particle size distribution D50 value is from about 0.1microns to about 10 microns.

[0204] In one embodiment, the particle size distribution D50 value is from about 0.1microns to about 5 microns.

[0205] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 0.5 wt% to about 4 wt% based on total phosphor powder weight.

[0206] In one embodiment, the phosphor powder comprises an amount of manganesethat is greater than about 2.5 wt% based on total phosphor powder weight.

[0207] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 2 wt% to about 3 wt% based on total phosphor powder weight.

[0208] In one embodiment, the phosphor powder has a quantum efficiency that isgreater than about 95% under blue excitation.

[0209] In one embodiment, the phosphor powder has a quantum efficiency that is about99% under blue excitation.

[0210] In one embodiment, a film comprises:a first layer comprising one or more first polymers, a second layer comprising one ormore second polymers, and at least one cured or semi-cured ink interposed between the firstlayer and the second layer, the at least one cured or semi-cured ink comprising:a phosphor powder comprising phosphor particles that are jet-milled, washedwith one or more solutions, and annealed, the phosphor particles comprising aMn doped phosphor of formula I:A[MFy]:Mn++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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andat least one binder,wherein the phosphor powder has a particle size distribution of a D50 value ofless than about 10 microns.

[0211] In one embodiment, a device comprises:an LED light source optically coupled and / or radiationally connected to at least onephosphor material, the phosphor material comprising:phosphor particles that are jet-milled, washed with one or more solutions, andannealed, the phosphor particles comprising a Mn+ doped phosphor of formula I:4+Ax[MFy] Mn++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 anycombination thereof, x is the absolute value of the charge of the [MFy] ion,andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value ofless than about 10 microns.

[0212] In one embodiment, the at least one phosphor material is at least partiallydisposed on the LED light source.

[0213] In one embodiment, the at least one phosphor material is located remotely at adistance from the LED light source.

[0214] In one embodiment, the one or more solutions comprise HF and K2SiF6.

[0215] In one embodiment, the one or more solutions comprise 49% HF and K2SiF6.

[0216] In one embodiment, the one or more solutions comprise 20% HF and K2SiF6.

[0217] In one embodiment, the phosphor material further comprises an additionalphosphor comprising (Y,Gd, Tb, La,Sm,Pr,Lu)3(Al,Ga)5-aO12-3 / 2a:Ce³+(wherein 0<a≤0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Ca1-h-rCehEurAl1-h (Mg, Zn)SiN3 (where 0≤h≤0.2, 0≤r≤0.2); Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+,Се³+; (Ba, Sr, Ca)SigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0218] In one embodiment, the D50 value is from about 0.1 microns to about 10microns.

[0219] In one embodiment, the D50 value is from about 0.1 microns to about 5microns.

[0220] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 0.5 wt% to about 4 wt% based on total phosphor powder weight.

[0221] In one embodiment, the phosphor powder comprises an amount of manganesethat is greater than about 2.5 wt% based on total phosphor powder weight.

[0222] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 2 wt% to about 3 wt% based on total phosphor powder weight.

[0223] In one embodiment, the phosphor powder has a quantum efficiency that isgreater than about 95% under blue excitation.

[0224] In one embodiment, the phosphor powder has a quantum efficiency that is about99% under blue excitation.

[0225] In one embodiment, the LED light source is a blue emitting LED.

[0226] In one embodiment, the LED light source is a miniLED or a micro-LED.

[0227] In one embodiment, the device is a self-emissive display.

[0228] In one embodiment, a lighting apparatus comprises the above-noted device.

[0229] In one embodiment, a backlight apparatus comprises the above-noted device.

[0230] In one embodiment, a display apparatus comprises the above-noted device.

[0231] In one embodiment, a television comprises the above-noted backlight apparatus.

[0232] In one embodiment, a mobile phone comprises the above-noted backlightapparatus.

[0233] In one embodiment, a computer monitor comprises the above-noted backlightapparatus.

[0234] In one embodiment, a laptop comprises the above-noted backlight apparatus.

[0235] In one embodiment, a tablet computer comprises the above-noted backlightapparatus.

[0236] In one embodiment, an automotive display comprises the above-noted backlightapparatus.

[0237] In one embodiment, in a method of making phosphor powder having a particlesize distribution of a D50 value of less than about 10 microns, the method comprises:reducing sizes of phosphor particles by jet milling the phosphor particles, thephosphor particles comprising a Mnt doped phosphor of formula I:Ax[MFy]:Mn+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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7;washing the phosphor particles with one or more solutions; andannealing the phosphor particles.

[0238] In one embodiment, the step of washing the phosphor particles with one or moresolutions is performed after the step of reducing sizes of phosphor particles by jet milling thephosphor particles.

[0239] In one embodiment, the step of annealing the phosphor particles is performedafter the step of washing the phosphor particles with one or more solutions.

[0240] In one embodiment, the step of annealing the phosphor particles comprisesannealing the phosphor particles prior to reducing sizes of phosphor particles by jet millingthe phosphor particles; followed by further annealing the phosphor particles after the step ofwashing the phosphor particles with one or more solutions.

[0241] In one embodiment, the step of washing the phosphor particles with one or moresolutions comprises at least one step of washing the phosphor particles with one or moresolutions.

[0242] In one embodiment, the step of washing the phosphor particles with one or moresolutions comprises two steps of washing the phosphor particles with one or more solutionsafter the step of reducing sizes of phosphor particles by jet milling the phosphor particles.

[0243] In one embodiment, the one or more solutions comprise HF and K2SiF6.

[0244] In one embodiment, the one or more solutions comprise 49% HF and K2SiF6.

[0245] In one embodiment, the one or more solutions comprise 20% HF and K2SiF6.

[0246] In one embodiment, annealing the washed, jet-milled phosphor particlescomprises contacting the washed, jet-milled phosphor particles with a fluorine-containingoxidizing agent in gaseous form at an elevated temperature.

[0247] In one embodiment, the fluorine-containing oxidizing agent comprises F2, SF6,BrF5, NH4HF2, NH4F, KF, AIF3, SbF5, CIF3, BrF3, KrF, XeF2, XeF4, NF3, SiF4, PbF2, ZnF2,SnF2, CdF2 or any combination thereof.

[0248] In one embodiment, the fluorine-containing oxidizing agent is F2.

[0249] In one embodiment, prior to washing, the jet-milled phosphor particles have aparticle size distribution of a D50 value of less than about 3 microns.

[0250] In one embodiment, prior to washing, the jet-milled phosphor particles have atotal particle size distribution of a D50 value from about 1.5 microns to less than about 2.5microns.

[0251] In one embodiment, prior to washing, manganese is present in the jet milledphosphor particles in an amount of a first weight percent of the total weight of the jet milledphosphor particles, and wherein, subsequent to washing, manganese is present in the washed,jet-milled phosphor particles in an amount of a second weight percent of the total weight ofthe jet milled phosphor particles, the second weight percent being less than the first weightpercent.

[0252] In one embodiment, the phosphor powder further comprises an additionalphosphor comprising (Y,Gd, Tb, La,Sm,Pr,Lu)3(Al,Ga)5-aO12-3 / 2a:Ce³+(wherein 0<a≤0.5); beta-SiAlON:Eu2+; (Sr,Ca,Ba)(Al,Ga, In)2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce³+; Ca1-h-rCehEurAll-h (Mg,Zn)hSiN3 (where 0<h≤0.2, 0<r≤0.2); Sr(LiAl3N4):Eu2+; (Ca,Sr)S:Eu2+,Ce³+; (Ba, Sr, Ca)SigNm:Eu2+(wherein 2b+4g=3m); or any combination thereof.

[0253] In one embodiment, the D50 value is from about 0.1 microns to about 10microns.

[0254] In one embodiment, the D50 value is from about 0.1 microns to about 5microns.

[0255] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 0.5 wt% to about 4 wt% based on total phosphor powder weight.

[0256] In one embodiment, the phosphor powder comprises an amount of manganesethat is greater than about 2.5 wt% based on total phosphor powder weight.

[0257] In one embodiment, the phosphor powder comprises an amount of manganesefrom about 2 wt% to about 3 wt% based on total phosphor powder weight.

[0258] In one embodiment, the phosphor powder has a quantum efficiency that isgreater than about 95% under blue excitation.

[0259] In one embodiment, the phosphor powder has a quantum efficiency that is about99% under blue excitation.

[0260] All publications, patents and patent applications are herein incorporated byreference in their entirety to the same extent as if each individual publication, patent or patentapplication was specifically and individually indicated to be incorporated by reference in itsentirety. Where a term in the present disclosure is found to be defined differently in adocument incorporated herein by reference, the definition provided herein is to serve as thedefinition for the term.

Claims

What is claimed is:1.A phosphor powder, comprising.phosphor particles that are jet-milled, the phosphor particles comprising a Mn dopedphosphor of formula I:Ax[MFy]:Mn+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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7; andwherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.2.A phosphor powder comprising:phosphor particles that are jet-milled, washed with one or more solutions, andannealed, the phosphor particles comprising a Mn doped phosphor of formula IAx[MFy]:Mnwherein: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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7, andwherein the phosphor powder has a particle size distribution of a D50 value of lessthan about 10 microns.3.The phosphor powder of claim 2, wherein the one or more solutions comprise HF and K2SiF6.4.The phosphor powder of claim 2 or 3, wherein the D50 value is from about 0.1microns to about 10 microns.5.The phosphor powder of any one of claims 2 to 4, wherein the D50 value is fromabout 0.1 microns to about 5 microns.6.The phosphor powder of any one of claims 2 to 5, wherein the phosphor powdercomprises an amount of manganese from about 0.5 wt% to about 4 wt% based on totalphosphor powder weight.7.The phosphor powder of any one of claims 2 to 5, wherein the phosphor powdercomprises an amount of manganese that is greater than about 2.5 wt% based on totalphosphor powder weight.8.The phosphor powder of any one of claims 2 to 5, wherein the phosphor powdercomprises an amount of manganese from about 2 wt% to about 3 wt% based on totalphosphor powder weight.9.The phosphor powder of any one of claims 2 to 8, wherein the phosphor powder has aquantum efficiency that is greater than about 95% under blue excitation.

10. The phosphor powder of any one of claims 2 to 9, wherein the phosphor powder has aquantum efficiency that is about 99% under blue excitation.

11. A phosphor powder having a particle size distribution of a D50 value of less thanabout 10 microns, the phosphor powder being produced by:reducing sizes of phosphor particles by jet milling the phosphor particles, thephosphor particles comprising a Mn doped phosphor of formula I.A[MFy]:Mnwherein: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 anycombination thereof, x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7,washing the phosphor particles with one or more solutions; andannealing the phosphor particles.12.The phosphor powder of claim 11, wherein the step of washing the phosphor particleswith one or more solutions is performed after the step of reducing sizes of phosphor particlesby jet milling the phosphor particles.

13. The phosphor powder of claim 11 or claim 12, where the step of annealing thephosphor particles is performed after the step of washing the phosphor particles with one ormore solutions.14.The phosphor powder of any one of claims 11 to 13, wherein the step of annealing thephosphor particles comprises annealing the phosphor particles prior to reducing sizes ofphosphor particles by jet milling the phosphor particles, followed by further annealing thephosphor particles after the step of washing the phosphor particles with one or moresolutions.

15. The phosphor powder of any one of claims 11 to 14, wherein the step of washing thephosphor particles with one or more solutions comprises at least one step of washing thephosphor particles with one or more solutions.

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