Phosphor ink compositions with scattering particles and devices using the same

Abstract

Phosphor ink compositions with scattering particles are disclosed. An ink composition in accordance with the present disclosure can include at least one phosphor material, at least one binder, first scattering particles having a first micron particle size, and second scattering particles having a second micron particle size that is smaller than the first micron particle size. 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, NFL, 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. Films, color filter parts, devices, light emitting arrays, and transparent displays containing the ink compositions of the present disclosure and methods of printing the ink compositions of the present disclosure are also disclosed.

Description

RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 681,974,filed 12 August 2024.FIELD OF THE INVENTION

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

[0003] Next generation displays can incorporate mini-LEDs and micro-LEDs havingactive areas of 10,000 µm² or less that are capable of generating light visible to the humaneye at very low drive currents. Mini-LEDs are LEDs with a size of about 100 µm to 0.7 mm.For micro-LEDs, the displays can be self-emissive or include miniaturized backlighting andarrayed with individual LEDs smaller than 100 μm.

[0004] In the past, quantum dots have been used in these next generation displays.Quantum dots have nanometer particle sizes with a strong absorption coefficient. Quantumdots, however, suffer from low quantum efficiency (QE) and poor thermal stability, whichsignificantly limit their practical applications.

[0005] Narrow band emission phosphor materials achieve high color quality in lightingand displays based on LEDs. Accordingly, there remains a need for improved phosphor inkcompositions that can enable the full potential of LED technologies.SUMMARY OF THE INVENTION

[0006] In certain aspects of the current subject matter, challenges associated withutilizing phosphor ink compositions in LED devices can be addressed by inclusion of one ormore of the features described herein or comparable / equivalent approaches as would beunderstood by one of ordinary skill in the art. Aspects of the current subject matter relate toink compositions and films that include phosphor material(s) and scattering particles.

[0007] In some implementations, one or more of the following features can optionally beincluded in any feasible combination.

[0008] In various implementations, an ink composition is disclosed. The ink compositionincludes at least one phosphor material, at least one binder, first scattering particles having afirst micron particle size, and second scattering particles having a second micron particle sizethat is smaller than the first micron particle size. The at least one phosphor material caninclude 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.

[0009] In various implementations, a film is disclosed. The film includes at least onecured or semi-cured ink. The at least one cured or semi-cured ink includes at least onephosphor material, at least one binder, and at least one of first scattering particles or secondscattering particles. The at least one phosphor material can include a Mn4+ doped phosphor offormula 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 isthe absolute value of the charge of the [MFy] ion, and y is 5, 6 or 7. The first scatteringparticles can have a first micron particle size, wherein the first scattering particles arepredominantly located at a first surface of the film, the first surface of the film configured tobe positioned proximate to or on a surface of an excitation source. The second scatteringparticles can have a second micron particle size that is smaller than the first micron particlesize, in which the second scattering particles are predominantly located at a second surface ofthe film, the second surface of the film configured to be positioned distal to the excitationsource.

[0010] In various implementations, a color filter part is disclosed. The color filter partincludes a well and at least one cured or semi-cured ink within the well. The at least onecured or semi-cured ink includes at least one phosphor material, at least one binder, and atleast one of first scattering particles or second scattering particles. The at least one phosphormaterial 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 first scattering particles can have a first micron particle size,in which the first scattering particles are predominantly located at a first surface of the film,the first surface of the film configured to be positioned proximate to or on a surface of anexcitation source. The second scattering particles can have a second micron particle size thatis smaller than the first micron particle size, in which the second scattering particles arepredominantly located at a second surface of the film, the second surface of the filmconfigured to be positioned distal to the excitation source.

[0011] In various implementations, a device including a LED light source opticallycoupled and / or radiationally connected to at least one cured or semi-cured ink is disclosed.aThe at least one cured or semi-cured ink includes at least one phosphor material, at least onebinder, and at least one of first scattering particles or second scattering particles. The at leastone 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 thecharge of the [MFy] ion, and y is 5, 6 or 7. The first scattering particles can have a firstmicron particle size, wherein the first scattering particles are predominantly located at a firstsurface of the at least one cured or semi-cured ink, the first surface of the at least one cured orsemi-cured ink is configured to be positioned proximate to or on a surface of the LED lightsource. The second scattering particles can have a second micron particle size that is smallerthan the first micron particle size, in which the second scattering particles are predominantlylocated at a second surface of the at least one cured or semi-cured ink, the second surface ofthe at least one cured or semi-cured ink is configured to be positioned distal to the LED lightsource.

[0012] In various implementations, a method for screen printing, direct write printing,aerosol jet printing, gravure printing, flexographic printing, or microdispensing printing isdisclosed. The method includes printing at least one ink composition. The at least one inkcomposition includes at least one phosphor material, at least one binder, and at least one offirst scattering particles or second scattering particles. The at least one phosphor material caninclude a Mn+ doped phosphor of formula I: Ax[MFy]:Mn4+ (I), where A is Li, Na, K, Rb,Cs, NH4, or any combination thereof, Mis Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta,Bi, Gd, or any combination thereof, x is the absolute value of the charge of the [MFy] ion,and y is 5, 6 or 7. The first scattering particles can have a first micron particle size, whereinthe first scattering particles are predominantly located at a surface through which excitationlight enters. The second scattering particles can have a second micron particle size that issmaller than the first micron particle size, in which the second scattering particles arepredominantly located distal to the surface through which the excitation light enters.

[0013] In various implementations, a method that includes depositing at least one inkcomposition into a well of a color filter part is disclosed. The at least one ink compositionincludes at least one phosphor material, at least one binder, and at least one of first scatteringparticles or second scattering particles. The at least one phosphor material can include a Mn+doped phosphor of formula I: Ax[MFy]:Mn4+ (I), where A is Li, Na, K, Rb, Cs, NH4, or anycombination 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, and y is 5, 6 or 7.The first scattering particles can have a first micron particle size, wherein the first scatteringparticles are predominantly located at a surface through which excitation light enters. Thesecond scattering particles can have a second micron particle size that is smaller than the firstmicron particle size, in which the second scattering particles are predominantly located distalto the surface through which the excitation light enters.

[0014] In various implementations, a light emitting array is disclosed. The light emittingarray includes a plurality of micro-LEDs, each micro-LED enclosed in a banked structure ora well structure, the banked structure or well structure configured to contain at least onecured or semi-cured ink. The at least one cured or semi-cured ink includes at least onephosphor material, at least one binder, and at least one of first scattering particles or secondscattering particles. The at least one phosphor material can include a Mn+ doped phosphor offormula 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 isthe absolute value of the charge of the [MFy] ion, and y is 5, 6 or 7. The first scatteringparticles can have a first micron particle size, in which the first scattering particles arepredominantly located at a first surface of the at least one cured or semi-cured ink, in whichthe first surface of the at least one cured or semi-cured ink configured to be positionedproximate to or on a surface of at least one micro-LED of the plurality of micro-LEDs. Thesecond scattering particles can have a second micron particle size that is smaller than the firstmicron particle size, in which the second scattering particles are predominantly located at asecond surface of the at least one cured or semi-cured ink, the second surface of the at leastone cured or semi-cured ink configured to be positioned distal to the surface of the at leastone micro-LED of the plurality of micro-LEDs.

[0015] In various implementations, a transparent display is disclosed. The transparentdisplay includes a micro-LED array and at least one cured or semi-cured ink positioned on orproximate to a surface of the micro-LED array. The transparent display has a transparency ofat least 50%. The at least one cured or semi-cured ink includes at least one phosphor material,at least one binder, and at least one of first scattering particles or second scattering particles.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 theabsolute value of the charge of the [MFy] ion, and y is 5, 6 or 7. The first scattering particlescan have a first micron particle size, in which the first scattering particles are predominantlylocated at the surface of the micro-LED array. The second scattering particles can have asecond micron particle size that is smaller than the first micron particle size, in which thesecond scattering particles are predominantly located distal to the surface of the micro-LEDarray.

[0016] The details of one or more variations of the subject matter described herein are setforth in the accompanying drawings and the description below. Other features and advantagesof the subject matter described herein will be apparent from the description and drawings,and from the claims. The claims that follow this disclosure are intended to define the scope ofthe protected subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings, which are incorporated in and constitute a part ofthis specification, show certain implementations of the subject matter disclosed herein and,together with the description, help explain some of the principles associated with thedisclosed implementations. The patent or application file contains at least one drawingexecuted in color. Copies of this patent or patent application with color drawing(s) will beprovided by the Office upon request and payment of the necessary fee. In the drawings:

[0018] FIG. 1A illustrates a block diagram of a film, consistent with implementations ofthe current subject matter;

[0019] FIG. 1B illustrates a block diagram of a multilayer structure that includes the filmof FIG. 1A, consistent with implementations of the current subject matter;

[0020] FIG. 2A illustrates a block diagram of a film, consistent with implementations ofthe current subject matter;

[0021] FIG. 2B illustrates a block diagram of a multilayer structure that includes the filmof FIG. 2A, consistent with implementations of the current subject matter;

[0022] FIG. 3 illustrates a graph of relative light scattering power versus rutile particlesize, consistent with implementations of the current subject matter;

[0023] FIGs. 4A and 4B are a top view and a side view, respectively, of an example red-green-blue (RGB) pixel, consistent with implementations of the current subject matter;

[0024] FIG. 5 illustrates a block diagram of a subpixel, consistent with implementationsof the current subject matter;

[0025] FIG. 6 illustrates a schematic cross-sectional view of a device, consistent withimplementations of the current subject matter;

[0026] FIG. 7 illustrates a schematic cross-sectional view of a device, consistent withimplementations of the current subject matter;

[0027] FIG. 8 illustrates a schematic cross-sectional view of a device, consistent withimplementations of the current subject matter;

[0028] FIG. 9 illustrates a schematic cross-sectional view of a device, consistent withimplementations of the current subject matter;

[0029] FIG. 10 illustrates a schematic cross-sectional view of a device, consistent withimplementations of the current subject matter;

[0030] FIG. 11 is illustrates schematic cross-sectional view of a lighting apparatus,consistent with implementations of the current subject matter;

[0031] FIG. 12 illustrates a cutaway side perspective view of a lighting apparatus,consistent with implementations of the current subject matter;

[0032] FIG. 13 illustrates a schematic perspective view of a surface-mounted device(SMD), consistent with implementations of the current subject matter;

[0033] FIG. 14 illustrates a schematic cross-sectional view of an SMD, consistent withimplementations of the current subject matter;

[0034] FIG. 15 illustrates a schematic cross-sectional view of a device, consistent withimplementations of the current subject matter;

[0035] FIGs. 16A-16D illustrate schematic diagrams of a printing well arrangement,consistent with implementations of the current subject matter; and

[0036] FIG. 17 illustrates a schematic diagram of a bank arrangement, consistent withimplementations of the current subject matter.

[0037] When practical, similar reference numbers denote similar structures, features, orelements.DETAILED DESCRIPTION

[0038] Implementations of the current subject matter include methods, apparatuses,articles of manufacture, and systems relating to phosphor ink compositions with micron-sizedscattering particles. For example, various implementations of ink compositions are describedherein that provide a number of benefits, including improved brightness. For example, byusing two different micron-sized scattering particles, creating two different phosphor inksurfaces with different scattering properties, optimal brightness and minimal loss can beachieved. The implementations of the current subject matter utilize mie scattering. In someaspects, at least one ink composition is provided on or proximate to a top surface of a bluelight source wherein, optic scattering is changed between two surfaces such that an emittedred color can be as strong as possible.

[0039] In general, the present ink compositions described herein include at least onephosphor material, at least one binder, first scattering particles having a first micron particlesize, and second scattering particles having a second micron particle size that is smaller thanthe first micron particle size.

[0040] In one aspect, an ink composition is provided. The ink composition can include atleast one phosphor material including a Mn+ doped phosphor of formula I and at least onebinder,Ax[MFy]:Mn+ Iwhere A is Li, Na, K, Rb, Cs, NH4, or a combination thereof: M is Si, Ge, Sn, Ti, Zr, Al, Ga,In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the chargeof the [MFy] ion; and y is 5, 6 or 7. In further aspects, the Mn+ doped phosphor can have aD50 particle size from about 0.5 microns to about 15 microns. Alternatively, or in addition,the ink composition can have a viscosity from more than 2000 cP to about 30,000 cP.

[0041] Square brackets in the formulas indicate that at least one of the elements is presentin the phosphor material, and any combination of two or more thereof can be present. Forexample, the formula [Ca, Sr, Ba]3MgSi2O8:Eu2+,Mn2+ encompasses at least one of Ca, Sr orBa or any combination of two or more of Ca, Sr or Ba. Examples includeCa3MgSi2O8:Eu2+.Mn2+; Sr3MgSi2O8:Eu2+.Mn2+; or Ba3MgSi2O8:Eu2+.Mn2+. Formula with anactivator after a colon indicates that the phosphor material is doped with the activator.Formula showing more than one activator separated by a after a colon indicates that thephosphor material is doped with either activator or both activators. For example, the formula[Ca, Sr, Ba]3MgSi2O8 :Eu2+, Mn2+ encompasses [Ca, Sr, Ba]3MgSi2O8:Eu2+,[Ca, Sr, Ba]3MgSi2O8:Mn2+ or [Ca, Sr, Ba]3MgSi2O8:Eu2+ and Mn2+.

[0042] The at least one phosphor material can include, but is not limited to: ((Sr1-z[Ca,Ba,Mg,Zn]z)i-(x|w)[Li,Na,K,Rb]wCex)3(Al1-ySiy)O4|y|3(x-w)F1-y-3(x-w), 0<x<0.10, 0≤y≤0.5,0≤z≤0.5, 0≤w≤x; [Ca,Ce]3Sc2Si3O12 (CaSiG); [Sr,Ca,Ba]3Al1-xSixO4+xF1-x:Ce3+ (SASOF));[Ba, Sr, Ca]5(PO4)3[Cl,F,Br,OH]:Eu2+, Mn2+; [Ba,Sr,Ca]BPO5:Eu2+, Mn2+;[Sr,Ca]10(PO4)6*vB2O3:Eu2+ (wherein 0<v≤l); Sr2Si3O8*2SrCl2:Eu2+;[Ca, Sr, Ba]3MgSi2O8:Eu2+, Mn2+; BaAl8O13:Eu2+; 2SrO*0.84P2O5*0.16B2O3:Eu2+;[Ba, ,Ca]MgAl10O17:Eu2+,Mn2+; [Ba,Sr,Ca]Al2O4:Eu2+; [Y,Gd,Lu,Sc,La]BO3:Ce3+,Tb3+;ZnS:Cu+,Cl; ZnS:Cut, Al3+; ZnS:Ag+, Cl-; ZnS:Ag+, Al3+; [Ba, Sr, Ca]2Si1-nO4-2n:Eu2+ (wherein0≤n≤0.2); [Ba, Sr,Ca]2[Mg,Zn]Si2O7:Eu2+; [Sr, Ca,Ba][Al,Ga,ln]2S4:Eu2+;[Y,Gd, Tb,La,Sm,Pr,Lu]3[Al,Ga]5-aO12-3 / 2a: Ce3+ (wherein 0≤a≤0.5);[Ca, Sr]8[Mg,Zn](SiO4)4C12:Eu2+,Mn2+; Na2Gd2B2O7:Ce3+,Tb3+;[Sr, Ca, Ba,Mg, Zn]2P2O7:Eu2+,Mn2+; [Gd,Y,Lu,La]2O3:Eu3+,Bi3+;[Gd,Y,Lu, La]2O2S:Eu3+, Bi³+; [Gd,Y,Lu,La]VO4:Eu3+,Bi³+; [Ca, Sr,Mg]S:Eu2+,Ce3+;SrY2S4:Eu2+; CaLa2S4: Ce³+; [Ba, Sr,Ca]MgP2O7:Eu2+,Mn2+; [Y,Lu]2WO6:Eu3+,Mo6+;[Ba, Sr, Ca]bSigNm:Eu2+ (wherein 2b+4g=3m); Ca3(SiO4)Cl2:Eu2+; [Lu, Sc, Y,Tb]2-u-vCevCa1+uLiwMg2-wPw[Si,Ge]3-wO12-u / 2 (where 0.5<u<l, 0<v≤0.1, and 0≤w≤0.2); [Y,Lu,Gd]2-m[Y,Lu,Gd]CamSi4N6+mC1-m:Ce3+, (wherein 0≤m≤0.5); [Lu,Ca,Li,Mg,Y], alpha-SiAlON dopedwith Eu2+ and / or Ce³+; Sr(LiAl3N4):Eu2+, [Ca, Sr,Ba]SiO2N2:Eu2+,Ce3+; beta-SiA1ON:Eu2+;3.5MgO*0.5MgF2*GeO2:Mn4+; Ca1-c-fCecEufAl1+cSi1-cN3, (where 0≤c≤0.2, 0<f≤0.2); Ca1-h-rCehEurAll-h(Mg,Zn)hSiN3, (where 0<h≤0.2, 0≤r≤0.2); Ca1-2s-tCes[Li,Na]sEutAlSiN3, (where0<s≤0.2, 0<t≤0.2, s+t>0); [Sr, Ca]AlSiN3: and Eu2+,Ce3+, Li2CaSiO4:Eu2+ .

[0043] In particular aspects, additional phosphors include:[Y,Gd,Lu,Tb]3[Al,Ga]5O12:Ce3+, β-SiAlON:Eu²¹, [Sr,Ca,Ba][Ga,Al]2S4:Eu2+, [Li,Ca]a-SiAlON:Eu2+, [Ba, Sr, Ca]2Si5N8:Eu2+, [Ca,Sr]AlSiN3:Eu2+, [Ba, Sr,Ca]LiAl3N4:Eu2+,[Sr, Ca,Mg]S:Eu2+, and [Ba, Sr, Ca]2Si2O4:Eu2+.

[0044] The at least one phosphor material can include at least one green-emittingphosphor. The green-emitting phosphor can include any suitable green-emitting phosphors,including a uranium phosphor. In one aspect, green-emitting uranium phosphors include, butare not limited to Ba3(PO4)2(UO2)2P2O7, Ba3(PO4)2(UO2)2V2O7, gamma y-Ba2UO2(PO4)2,BaMgUO2(PO4)2, BaZnUO2(PO4)2, Na2UO2P2O7, K2UO2P2O7, Rb2UO2P2O7,CS2UO2P2O7, K4UO2(PO4)2, K4UO2(VO4)2, or NaUO2P3O9, as described in US Patent No.11,254,864, the entire contents of which are incorporated herein by reference.

[0045] The ink composition can be tailored to a specific printing application. Forexample, the ink composition can be tailored to any one of the following printingapplications: inkjet printing, flexographic printing, or microdispensing printing, screenprinting, direct write printing, aerosol jet printing, gravure printing, and the like.Additionally, or alternatively, the ink composition can be tailored for extrusion. For example,low viscosity ink compositions can be tailored for inkjet printing, flexographic printing,and / or microdispensing printing; medium viscosity inks can be tailored for screen printing,direct write printing, aerosol jet printing, gravure printing, flexographic printing, and / ormicrodispensing printing; and high viscosity inks can be tailored for high viscosity screenprinting, direct write printing, and / or extruding.

[0046] The at least one phosphor material can be present in the ink composition fromabout 5 wt% to about 70 wt%. In another aspect, the phosphor material can be present fromabout 30 wt% to about 60 wt%. In another aspect, the phosphor material can present fromabout 10 wt% to about 50 wt%. The wt% for the at least one phosphor material is based onthe total weight of the ink composition.

[0047] In some aspects, the at least one phosphor material can have a D50 particle size ina range from about 0.5 to about 15 microns. In another aspect, the at least one phosphormaterial can include a D50 particle size in a range from about 0.5 micron to about 10microns. In another aspect, the D50 particle size can be in a range from about 0.5 micron toabout 5 microns.

[0048] D50 (also expressed as D50) is defined as the median particle size for a volumedistribution. D90 or D90 is the particle size for a volume distribution that is greater than theparticle size of 90% of the particles of the distribution. D10 or D10 is the particle size for avolume distribution that is greater than the particle size of 10% of the particles of thedistribution. Particle size of the phosphors can be conveniently measured by laser diffractionor optical microscopy methods, and commercially available software can generate theparticle size distribution and span. Span is a measure of the width of the particle sizedistribution curve for a particulate material or powder, and is defined according to theequation:Span (D90-D10)D50wherein D90, D10 and D50 are defined above. For phosphor particles, span of the particle sizedistribution is not necessarily limited and can be <1.0 in some aspects.

[0049] The Mn4+ 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, inK2SiF6:Mn4+, the coordination center is Si and the counterion is K. Complex fluorides areoccasionally written as a combination of simple, binary fluorides but such a representationdoes not indicate the coordination number for the ligands around the coordination center. Thesquare brackets (occasionally omitted for simplicity) indicate that the complex ion theyencompass is a new chemical species, different from the simple fluoride ion. The activatorion (Mn4+) also acts as a coordination center, substituting part of the centers of the hostlattice, for example, Si. The host lattice (including the counter ions) can further modify theexcitation and emission properties of the activator ion.

[0050] In particular aspects, the coordination center of the phosphor, that is, M in formulaI, is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. Moreparticularly, the coordination center can be Si, Ge, Ti, or a combination thereof. Thecounterion, or A in formula I, can be Li, Na, K, Rb, Cs, NH4, or a combination thereof, moreparticularly K or Na. Examples of phosphors of formula I include K2[SiF6]:Mn4+,K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, K2[GeF6]Mn4+, Rb2[TiF6] Mn4+,Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn+, Na2[SiF6]:Mn+, Na2[TiF6]:Mn+, Na2[ZrF6]:Mn+,K3[ZrF7]:Mn4+, K3[BiF6] K3[YF6]:Mn4+, K3[LaF6]:Mn+, K3[GdF6]:Mn4+, K3[NbF6]:Mn4+,K3[TaF7]:Mn4+. In particular aspects, the phosphor of formula I is K2SiF6:Mn4+ (PFS) orNa2[SiF6]:Mn4+ (NSF).

[0051] ,The amount of activator Mn incorporation in the Mn4+ doped phosphors (referredto as Mn%) improves color conversion. Increasing the amount of Mn% incorporationimproves color conversion by increasing the intensity of the red emission, maximizingabsorption of excitation blue light and reducing the amount of unconverted blue light orbleed-through of blue light from a blue LED.

[0052] In one aspect, the red-emitting Mn4+ doped phosphor has a Mn loading or Mn% ofat least 1 wt%. In another aspect, the red-emitting phosphor has a Mn loading of at least 1.5wt%. In another aspect, the red-emitting phosphor has a Mn loading of at least 2 wt%. Inanother aspect, the red-emitting phosphor has a Mn% of at least 3 wt%. In another aspect theMn% is greater than 3.0 wt%. In another aspect, the content of Mn in the red-emittingphosphor is from about 1 wt% to about 4 wt%. In another aspect, the red-emitting phosphormas a Mn% from about 2 wt% to about 5 wt%.

[0053] In one aspect, the Mn+ doped phosphor can be a manganese-doped potassiumfluorosilicate, such as K2SiF6:Mn4+ (PFS). PFS has a narrow band emission having multiplepeaks with an average full width at half maximum (FWHM) of less than 4 nm. In anotheraspect, the red-emitting phosphor can be Na2SiF6:Mn4+ (NFS).

[0054] In one aspect, the red-emitting phosphors based on complex fluoride materialsactivated by Mn⁴+ phosphors can be at least partially coated with surface coatings to enhancestability of the phosphor particles and resist aggregation by modifying the surface of theparticles and increase the zeta potential of the particles. In one aspect, the surface coatingscan be a metal fluoride, silica or organic coating. In one aspect, the red-emitting phosphorsbased on complex fluoride materials activated by Mn⁴+ phosphors are at least partially coatedwith a metal fluoride, which increases positive Zeta potential and reduces agglomeration. Inone aspect, the metal fluoride coating includes MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AlF3or a combination thereof. In another aspect, the metal fluoride coating is in an amount fromabout 0.1 wt% to about 10 wt%. In another aspect, the metal fluoride coating is present in anamount from about 0.1 wt% to about 5 wt%. In another aspect, the metal fluoride coating ispresent from about 0.3 wt% to about 3 wt%. Metal fluoride coated red-emitting phosphorsbased on complex fluoride materials activated by Mn⁴+ are prepared as described in WO2018 / 093832 and US Publication No. 2020 / 0369956. The entire contents of each of whichare incorporated herein by reference.

[0055] In one aspect, the red-emitting phosphors based on complex fluoride materialsactivated by Mn⁴+ phosphors are at least partially coated with an organic coating, such aspolymerized oleic acid. Oleic acid can be used to coat the phosphor particles via asolvothermal synthesis or treatment, such as by a mixing adsorption treatment.

[0056] In some aspects, surfactants, such as small molecule surfactants or dispersants canbe incorporated to reduce dispersity and agglomeration in the ink composition. Dispersantsreduce agglomeration of phosphor powders with minimal impact to optical performance andreliability. Dispersants can have functional groups, such as hydroxyl (-OH), carboxyl (—COOH), sulfonate, sulfate, ammonium, amino (-NH2) or imino (—NH-) for anchoring onsurfaces and a buoyant moiety, which helps to keep a dispersion uniform and homogeneous.In addition, dispersants with proper functional groups can also improve wetting ability. Aliquid with lower surface tension tends to wet particles better than liquids with higher surfacetension. Dispersants can lower the surface tension of a liquid and the interfacial tensionbetween the liquid and dispersing particles.

[0057] In one aspect, 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 another aspect,the dispersants 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 polymers containingamine groups, polymer dispersants, such as TEGO® 689 and TEGO® 690 with pigmentaffinity groups, such as dodecanoic acid, polymers with OH / ether groups and pigmentaffinity groups. In one aspect, the dispersant can be a polyester composed ofpolyhydroxystearic acid stearate. In another aspect, the dispersant can be EO / PO blockcopolymers.

[0058] In one aspect, the dispersant can be a solution of a modified urea (BYK®-7410-ET from BYK Additives and Instruments).

[0059] In one aspect, the dispersant or surfactant can be included in amounts up to 10 wt%. In another aspect, the dispersant or surfactant can be included in an amount from about0.1 wt% to about 10 wt %. In another aspect, the dispersant or surfactant can be included inan amount from about 1 wt% to about 5 wt%. The dispersant or surfactant amount is basedon the total weight of the ink composition.

[0060] In one aspect, the ink composition can include rheology modifiers. Rheologymodifiers can be used to provide desirable rheological properties to the ink composition, suchas adjusting the viscosity of the composition, improving dispersion stability and phosphorparticle suspension and controlling the rheology profile of the composition for film formingcharacteristics and ink printability. In one aspect, the rheology modifier has a viscositygreater than 100 centipoise at 20° C. In one aspect, the rheology modifiers include silicananoparticles and clay-based materials. In another aspect, nanoparticles of silica can befumed silica, precipitated silica or surface-modified hydrophobic silica.

[0061] In another aspect, the rheology modifiers include gelators including at least onecrosslinkable group. In another aspect, the gelators can gel at temperatures at less than 30° C.In another aspect, the gelators can gel at temperatures in the range of about 20° C. to about30° C. Gelators, such as a wax with polymerizable functionality, can be added to the inkcomposition to form gel-like dispersions with good stability and low sedimentation at roomtemperature, which become coatable and printable liquids with much reduced viscosity uponheating. Exemplary waxes include, but are not limited to, di(hexadecyl) fumarate, oleylcinnamide, di(4-vinyloxybutyl) octadecanedioate, non-polar acrylate waxes, such asoctadecyl cinnamide, and functionalized waxes, such as dodecyl cinnamide.

[0062] Additive materials can be added to the ink composition to adjust rheologicalproperties, adjust viscosity and optimize coatability or film-forming capability andprintability. In one aspect, materials with high thermal conductivity, such as aluminum nitridenanoparticles and microparticles can be added to the ink composition. In another aspect, oneor more electrolytes or polyelectrolytes can be added to the ink composition.

[0063] The at least one phosphor material can include additional phosphors, such as anYttrium Aluminum Garnet phosphor (YAG). The ratio of powders (YAG: PFS) can be tunedto reach a desired color point. The at least one phosphor material can include additionalphosphors, such as rare earth Garnet phosphors. The rare earth elements include: Sc, Y, La,Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. In one aspect, the rare earthGarnet phosphor can be an yttrium aluminum garnet phosphor (YAG). The ratio of the rareearth garnet phosphors to Mn+ doped phosphor can be tuned to reach a desired color point.In some aspects, the at least one phosphor can include a rare earth containing a Garnetphosphor doped with at least one of cerium or SiAION

[0064] The ink compositions described herein include at least one binder or at least onesolvent. In some aspects, the ink composition can include a binder, whereas in other aspects,the ink composition can include a binder and a solvent.

[0065] Binder for the ink composition can include thermoplastic polymers andcopolymers, pre-binder materials, such as thermally curable precursors or photocurableprecursors. Exemplary binders include, but are not limited to ethyl cellulose, polystyrene,polyacrylate, polymethacrylates, such as polymethyl acrylate (PMA) and polymethylmethacrylate (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), fluorinatedpolymers, such as polyvinylidene fluoride (PDVF) or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), amine-based oligomers / polymers / copolymers, fluorine-based oligomers / polymers / copolymers, poly(phenylene vinylene), carbazole-basedoligomers / polymers / copolymers, phenyl-pyridine-based oligomers / polymers / copolymers.

[0066] In one aspect, the binder includes a crosslinked polymer. In another aspect, thebinder includes curable materials, such as photocurable or UV-curable materials or thermallycurable or thermoset binder materials or any combination. A thermally curable or thermosetbinder will polymerize or crosslink and form a cured resin binder matrix. Exemplarythermoset and UV binder materials include epoxy, acrylate, methacrylate, vinyl ester andsiloxane families. Examples of suitable commercial resin systems include, but are not limitedto a Pixelligent UVG Curable ink base, Optical Adhesive (Norland 68T), Pixelligent PixJetSFZ-1 with 40 wt% ZrO2 in acrylic formulation.

[0067] In one aspect, the binder can be present in an amount up to about 75 wt%. Inanother aspect, the binder can be present in an amount up to about 70 wt%. In another aspect,the binder can be present in an amount from about 5 wt% to about 75 wt%. In another aspect,the binder is present in an amount of from about 10 wt% to about 70 wt%. In another aspect,the binder is present from about 20 wt% to about 50 wt%. The weight % is based on totalweight of the ink composition.

[0068] In some aspects, the at least one binder can have a refractive index from about1.52 or less. In certain aspects, the at least one binder can have a refractive index from about1.42 to 1.52. In other aspects, the at least one binder can have a refractive index from about1.42 to 1.58. In one aspects, the at least one binder can have a refractive index that does notexceed 1.58.

[0069]

[0070] In another aspect, the ink composition includes a first polymerization initiator anda second polymerization initiator for a 2-step curing process where during a first curing stepin photo-initiated polymerization process is initiated by a radiation wavelength less than 400nm (UV cure). The first polymerization initiator has a higher decomposition rate than thesecond polymerization initiator. The second curing process is free of UV radiation where thesecond polymerization initiator has a higher decomposition rate than the first polymerizationinitiator. The post cure phosphor treatment concentration increases by 5%, preferably 10%,and the print material decreases (shrinks) in volume by <20%, preferable <15%. The totalprint volume does not exceed 20vol% shrinkage. The ink composition can include a solvent.The amount of solvent, solvent polarity, and solvent vapor pressure can aid in making astable ink that meets viscosity, wettability, and optical density criteria of the ink composition.The solvent can be present in an amount effective for dissolving the phosphor material andany binder material and for adjusting the ink composition to a desired viscosity. In oneaspect, the solvent can be present from about 5 wt% to about 95 wt%. In another aspect, thesolvent can be present from about 10 wt% to about 75 wt%. In another aspect, the solvent ispresent from about 20 wt% to about 50 wt%. The %wt of the solvent is based on the weightof the ink composition.

[0071] The solvents can be polar or non-polar. Examples of solvents include, but are notlimited to acetone, glycol ethers, such as diethylene glycol methyl ether, propylene methylacrylates, such as propylene glycol dimethyl acrylate, cyclic aromatic solvents, such astoluene, xylenes and anisol, aliphatic solvents, such as hexane and tetradecane, alcohols, suchas ethanol, isopropanol, and octanol, glycols, such as ethylene glycol and propylene glycol,terpineol, acetates, such as butyl acetate, propylene glycol methyl ether acetate (PGMEA), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl formamide (DMF),diethylene glycol methyl ether (DGME) and 2-(2-Butoxyethoxy)ethyl acetate (BEA).

[0072] Co-solvents and mixture of solvents can also be used to improve fluid, printingprocess and film forming properties. Mixture of solvents can be composed of any two ormore of the solvents listed above and can also be comprised of small additions of commonorganic solvents into one of the solvents above.

[0073] In some aspects, the ink composition can have a viscosity from about 10 cP toabout 30,000 cP. In another aspect, the viscosity is from about 1,000 cP to about 30,000 cР.In another aspect, the viscosity can more than 2,000 cP to about 30,000 cP.

[0074] Additives can be added to the ink composition in an amount of from about 5 wt%to about 20 wt%, based on the weight of the ink composition.

[0075] The ink compositions can include, one or more other luminescent materials.Additional luminescent materials, such as blue, yellow, red, orange, or other color phosphorscan be used in the phosphor material to customize the white color of the resulting light andproduce specific spectral power distributions.

[0076] Other additional luminescent materials suitable for use in the ink composition caninclude electroluminescent polymers such as polyfluorenes, such as poly(9,9-dioctylfluorene) and copolymers thereof, such as poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole) and polyphenylenevinylene andtheir derivatives. In addition, the light emitting layer can include a blue, yellow, orange,green or red phosphorescent dye or metal complex, a quantum dot material, or a combinationthereof. Materials suitable for use as the phosphorescent dye include, but are not limited to,tris(1-phenylisoquinoline) iridium (III) (red dye), tris(2-phenylpyridine) iridium (green dye)and iridium (III) bis(2-(4,6-difluorephenyl)pyridinato-N,C2) (blue dye). Commerciallyavailable fluorescent and phosphorescent metal complexes from ADS (American DyesSource, Inc.) can also be used. ADS green dyes include ADS060GE, ADS061GE,ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes includeADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE,ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

[0077] In another aspect, the ink composition can include quantum dots (QDs) that canabsorb blue light and generate green or red light or both can also be included 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, GaAlNP,GaAINAs, GaAlPAs, GalnNP, GalnNAs, GalnPAs, AIN, A1NP, AINAs, A1P, AlPAs, AlAs,InN, InNP, InP, InNAs, InPAs, InAS, InAINP, InAINAs, InAlP As, 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. The quantum dotmaterial can include core-shell nanostructures having an Ag-In-Ga-S (AIGS) core and an Ag-Ga-S (AGS) shell.

[0078] In one aspect, the perovskite quantum dot can be CsPbX3, where X is Cl, Br, I ora combination thereof. The mean size of the QD materials can range from about 2 nm toabout 20 nm. The surface of QD particles can be further modified with ligands such as amineligands, phosphine ligands, phosphatide and polyvinylpyridine. In one aspect, the redphosphor can be a quantum dot material.

[0079] All of the semiconductor quantum dots can also have appropriate shells orcoatings for passivation and / or environmental protection. The QD materials can be acore / shell QD, including a core, at least one shell coated on the core, and an outer coatingincluding one or more ligands, preferably organic polymeric ligands. Exemplary materials forpreparing core-shell QDs include, but are not limited to, Si, Ge, Sn, Se, Te, B, C (includingdiamond), P, Co, Au, BN, BP, BAs, AIN, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN,InP, InAs, InSb, AIN, A1P, 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, Cui, Si3N4,Ge3N4, AI2O3, [Al, Ga, In]2[S, Se, Te]3, and appropriate combinations of two or more suchmaterials. Exemplary core-shell luminescent nanocrystals include, but are not limited to,CdSe / ZnS, CdSe / CdS, CdSe / CdS / ZnS, CdSeZn / CdS / ZnS, CdSeZn / ZnS, InP / ZnS, PbSe / PbS,PbSe / PbS, CdTe / CdS and CdTe / ZnS.

[0080] The ratio of each of the individual phosphors and other luminescent materials inthe ink composition can vary depending on the characteristics of the desired light output. Therelative proportions of the individual phosphors and other luminescent materials in thevarious ink compositions can be adjusted such that when their emissions are blended andemployed in a device, for example a lighting apparatus, there is produced visible light ofpredetermined x and y values on the CIE chromaticity diagram.

[0081] The ink compositions described herein include first scattering particles, secondscattering particles, or both, in which the first scattering particles have a first micron particlesize; and the second scattering particles have a second micron particle size that is smallerthan the first micron particle size. The first scattering particles are predominantly locatedwithin a first portion of the ink composition, and the second scattering particles arepredominantly located within a second portion of the ink composition, where the first portionis different than the second portion of the ink composition. As a result, the difference inparticle size between the first scattering particles and the second scattering particles incombination with their respective location within the ink composition are used to dictate therelative scattering power through the at least one cured or semi-cured ink prepared by the inkcomposition. In certain aspects, the first portion can be proximate to or at a first surface of theink composition and the second portion can be proximate to or at a second surface of the inkcomposition, in which the first surface allows excitation light to enter the ink composition.

[0082] As used herein, “predominantly located” when used to describe the location of thescattering particles present within the ink composition, within a cured or semi-cured ink, orwithin a film should be understood to mean that at least more than 50% of the scatteringparticles are located within a specific portion or region of the ink composition, within a curedor semi-cured ink, or within a film. In some aspects, more than 50% of the amount of firstscattering particles present in the ink composition can be positioned in a first portion of theink composition and more than 50% of the second scattering particles present in the inkcomposition can be positioned in a second portion of the ink composition. In some aspects,more than 75% of the amount of first scattering particles present in the ink composition canbe positioned in a first portion of the ink composition and more than 75% of the secondscattering particles present in the ink composition can be positioned in a second portion of theink composition. In some aspects, more than 95% of the amount of first scattering particlespresent in the ink composition can be positioned in a first portion of the ink composition andmore than 95% of the second scattering particles present in the ink composition can bepositioned in a second portion of the ink composition. It is also contemplated herein that allthe first scattering particles can be present in the first portion of the ink composition and allthe second scattering particles can be present in the second portion of the in composition.

[0083] In some aspects, the first micron particle size can be from about 0.25 microns toabout 0.3 microns. In one aspect, the first micron particle size can be about 0.3 microns. Insome aspects, the second micron particle size can be from about 0.1 to about 0.15 microns. Inone aspect, the second micron particle size can be about 0.15 microns. In certain aspects, thefirst micron particle size can be about 0.3 microns and the second micron particle size can beabout 0.15 microns.

[0084] Non-limiting examples of suitable scattering particles can include titaniumdioxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), indium tin oxide, ceriumoxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calcium fluoride (CaF2),strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF), aluminum fluoride(AlF3) or any combination thereof. In some aspects, the first scattering particles, the secondscattering particles, or both can include titanium dioxide micron particles. In one aspect, thetitanium dioxide is a rutile titanium dioxide. In other aspects, the first scattering particles, thesecond scattering particles, or both can include zirconia dioxide micron particles.

[0085] In some aspects, the first scattering particles can have a first micron particle sizeof about 0.3 microns and the second scattering particles can have a second micron particlesize of about 0.15 microns, in which the first scattering particles and the second scatteringparticles include titanium dioxide (e.g., rutile titanium dioxide).

[0086] In some aspects, the at least one phosphor can include K2SiF6:Mn4+, and the firstscattering particles can have a first micron particle size of about 0.3 microns, and the secondscattering particles can have a second micron particle size of about 0.15 microns.

[0087] In one aspect, films can be prepared from the ink compositions. The films can bedeposited on substrates, such as glass substrates. Films can be deposited on LEDs, such asmini-LEDs or micro-LEDs, such as by coating at least one ink composition, using a doctorsbade or by printing and thereafter cured, such as by UV light or heat curing. As such, thepresent films disclosed herein include at least one cured or semi-cured ink. In one aspect, afilm is prepared by coating the ink composition on a glass substrate with a doctors blade. Thesolvent can be removed, and the film is cured, such as by UV light or heat curing.

[0088] In general, the films disclosed herein include at least one cured or semi-cured ink.The at least one cured or semi-cured ink includes at least one phosphor material, at least onebinder, and at least one of first scattering particles or second scattering particles. In someaspects, the first scattering particles can have a first micron particle size, in which the firstscattering particles are predominantly located at a first surface of the film, the first surface ofthe film configured to be positioned proximate to or on a surface of an excitation source; andthe second scattering particles can have a second micron particle size that is smaller than thefirst micron particle size, in which the second scattering particles are predominantly locatedat a second surface of the film, the second surface of the film configured to be positioneddistal to the excitation source.

[0089] In some aspects, the excitation source can be a blue emitting LED. A blueemitting LED is configured to emit one or more wavelength that are in the range of about 380nm to about 460 nm.

[0090] In response to exposure from the excitation source, the first scattering particles areconfigured to allow a first light within a first range of wavelengths to pass through the firstsurface and into the film and inhibit a second light within a second range of wavelengths topass through the first surface and out of the film; and wherein, in response to exposure fromthe excitation source, the second scattering particles are configured to inhibit the first lightwithin the first range of wavelengths to pass through the second surface and out of the filmand allow the second light within the second range of wavelengths to pass through the secondsurface and out of the film.

[0091] In some aspects, the first range of wavelengths can be from about 380 nm to about460 nm. Alternatively, or in addition, the second range of wavelengths can be from about 620nanometers to about 750 nanometers.

[0092] In some aspects, the at least one cured or semi-cured ink can include a first curedor semi-cured ink, the at least one phosphor material can include a first phosphor material,and the at least one binder can include a first binder, in which the first cured or semi-curedink can include the first scattering particles and the second scattering particles.

[0093] In some aspects, the at least one cured or semi-cured ink can include a first curedor semi-cured ink and a second-cured ink in which the second cured or semi-cured ink isdisposed on at least a portion of the first cured or semi-cured ink. In such aspects, the firstcured or semi-cured ink can include a first phosphor material, a first binder, and the firstscattering particles; and the second cured or semi-cured ink can include a second phosphormaterial, a second binder, and the second scattering particles. In certain aspects, the firstphosphor material and the second phosphor material can be the same. Alternatively, or inaddition, the at least one first binder and the at least one second binder are the same.

[0094] In some aspects, the film can be part of a multilayer structure. The multi-layeredfilm can the film as disclosed herein, and a color filter material disposed on or proximate tothe second of the film. The color filter material can be configured to absorb light that passesthrough the second surface of the film, in which the light is in a range of wavelengths fromabout 380 nm to about 460 nm.

[0095] 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 comprise anLED that has a length of 250 microns and a width of 250 microns.

[0096] 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 comprise anLED that has a length of 50 microns and a width of 50 microns.

[0097] As the number of LEDs increase and the optical distance (OD) decreases, it can bepreferable to use a chip-scale package (CSP). A CSP is a type of integrated circuit (IC)package that is surface mountable. CSP chips can be directly applied to the PCB effectivelyshortening the heat flow path to the substrate and reducing the thermal resistance of the lightsource. Under the same current, CSP chips have higher intensity and lower current consumedcompared to SMD LED chips. And since the CSP LED chip has no chip holder or wiresconnected, two possible LED failure points are removed. Therefore, CSP LEDs featuresintegrated component features that do not need soldered wire connections which reducethermal resistance, reduce heat transfer path, reduce possible failure points, are smaller insize, have a high optical density, and do not require a substrate.

[0098] CSPs offer advantages like smaller size (reduced footprint and thickness), lesserweight, relatively easier assembly process, lower overall production costs, and improvementin electrical performance. They are also tolerant of chip size changes since a reduced chipsize can still be accommodated by the interposer design without changing the CSP's footprint.Further, a CSP LED can have a wider viewing angle of up to 180 degrees because thephosphor is applied on the sides too. This can be very important advantage for applicationssuch as backlight modules, replacement of traditional form factor lamps and tubes.

[0099] The CSP product features integrated component features that do not need solderedwire connections which reduce thermal resistance, reduce heat transfer path, and reducepossible failure points. Therefore, in some applications, it can be preferable to use CSPs.

[0100] Ink formulations described herein can be implemented in CSPs. In some aspects,such CSPs are used in applications such as LED headlights and various displays. In someaspects, CSP chips can replicate the size and location of the tungsten filament in halogenbulbs to create beam patterns much like halogen bulbs.

[0101] FIG. 1A is a block diagram of a film 110 radiationally coupled and / or opticallycoupled to a blue light source 100 in accordance with an aspect of the present disclosure. Thefilm 110 is formed of a cured or semi-cured ink that includes at least one phosphor material,at least one binder, and the first and second scattering particles 110a, 110b. Radiationallyconnected or coupled or optically coupled means that radiation from the blue light source isable to excite the at least one phosphor material, and the at least one phosphor matieral is ableto emit light in response to the excitation by the radiation. While the film 110 is illustrated asbeing in contact with a surface of the blue light source 100, in other aspects, the film 110 canbe located remotely at a distance from the blue light source 100.

[0102] In this illustrated implementation, the at least one phosphor can include a Mn4+doped phosphor of formula I: Ax[MFy]:Mn+ (I), where A is Li, Na, K, Rb, Cs, NH4, or anycombination 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, and y is 5, 6 or 7.

[0103] The first scattering particles 110a are predominantly located at a first surface ofthe film, and the second scattering particles 110b are predominantly located at a second,opposing surface of the film. While FIG. 1A illustrates that all the first scattering particles arelocated at the first surface and that all the second scattering particles are located at the secondsurface, in other implementations, more than 50%, but less than 100% of the first scatteringparticles can be located at the first surface, and likewise, more than 50%, but less than 100%of the second scattering particles can be located at the first surface.

[0104] While not illustrated, the first scattering particles have a first micron particle sizeand the second scattering particles have a second micron particle size that is smaller than thefirst micron particle size. As a result, prior to curing or semi-curing of the ink composition, toform the at least one cured or semi-cured ink, and thus the film 110, the location of the firstscattering particles and the second scattering particles can be effected by the Stokes settlingrate. In other words, the larger sizes scattering particles, which in this implementation are thefirst scattering particles, would settle faster within the ink composition than the smaller sizescattering particles, which in this implementation are the second scattering particles. This isreferred to as a gradient approach. As such, and as shown in FIG. 1A, given the position ofthe film relative to the blue light source, a larger fraction or percentage of the first scatteringparticles are at the first surface of the film, and therefore closer to the blue light sourcecompared to the second scattering particles. Further, a larger fraction or percentage of thesecond scattering particles are closer to the second surface of the film, and therefore furtheraway from the blue light source as compared to the first scattering particles.

[0105] In one aspect, the first micron particle size is about 0.3 microns and the secondmicron particle size is about 0.15 microns. As a result, during use, the first surface of the filmmaximizes red scatterance and minimizes blue scatterance, and the second surface of the filmmaximizes blue scatterance and minimizes red scatterance. This can increase the absorptionof the blue light within the film, even films with a relatively thin thickness, and thus, increasethe conversion of the blue light to red light.

[0106] FIG. 1B is a block diagram of a multilayer structure 130 radiationally coupledand / or optically coupled to the blue light source 100 in accordance with an aspect of thepresent disclosure. The multilayer structure 130 includes the film 110 of FIG. 1A and a colorfilter material 130 disposed on the second surface of the film, in which the color filtermaterial is configured to absorb light that passes through the second surface of the film.While the color filter material 130 is illustrated in FIG. 1B as being disposed on the secondsurface of the film, in other implementations, the color filter material can be remotely locatedat a distance from the film. In some aspects, the light can be in a range of wavelengths fromabout 380 nm to about 460 nm.

[0107] In use, the additional of the color filter material can help minimize any blue lightfrom passing completely through the film 110 (e.g., also known as bleed through). In otherwords, it is possible for an amount of blue light to pass through the film without beingconverted to red light (e.g., unconverted blue light), and in such instances, the emission ofthis unconverted blue light can compromise the red light emitted from the film (e.g., candecrease brightness, can generate a violet hue). As such, the color filter material can absorband therefore inhibit blue light from escaping out of multilayer structure.

[0108] FIG. 2A is a block diagram of a film 210 radiationally coupled and / or opticallycoupled to a blue light source 200 in accordance with an aspect of the present disclosure.While the film 210 is illustrated as being in contact with a surface of the blue light source200, in other aspects, the film can be located remotely at a distance from the blue lightsource. In this illustrated implementation, the film 210 is formed of a first cured or semi-cured ink 210a and a second cured or semi-cured ink 210b that is disposed on at least aportion of the first cured or semi-cured ink. As shown, the first cured or semi-cured ink 210ais positioned closer to the blue light source 200 than the second cured or semi-cured ink210b.

[0109] The first cured or semi-cured ink includes at least one first phosphor material, atleast one first binder, and first scattering particles. In certain aspects, the first scatteringparticles are uniformly dispersed (within manufacturing tolerances) through the first cured orsemi-cured ink, whereas in other aspects, the first scattering particle are not uniformlydispersed. The second cured or semi-cured ink includes at least one second phosphormaterial, at least one second binder, and second scattering particles. In certain aspects, thesecond scattering particles are uniformly dispersed (within manufacturing tolerances) throughthe second cured or semi-cured ink, whereas in other aspects, the second scattering particleare not uniformly dispersed. While not illustrated, the first scattering particles have a firstmicron particle size and the second scattering particles have a second micron particle sizethat is smaller than the first micron particle size.

[0110] In this illustrated implementation, the at least one first phosphor and the at leastone second phosphor can each include a Mn+ doped phosphor of formula I: Ax[MFy]:Mn+(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 ofthe charge of the [MFy] ion, and y is 5, 6 or 7. In one aspect, the at least one first phosphorand the at least one second phosphor are the same phosphor, whereas in other aspects, the atleast one first phosphor and the at least one second phosphor are different phosphors relativeto each other.

[0111] Further, in this illustrated implementation, the film 210 can be formed by using atwo-passing printing approach. For example, the film 210 can be manufactured by depositinga first ink composition onto a surface of the blue light source 200, and then curing the firstink composition to form a first cured or semi-cured ink, followed by depositing a second inkcomposition onto a surface of first cured or semi-cured ink, and thereafter curing the secondink composition to form a second cured or semi-cured ink.

[0112] FIG. 2B is a block diagram of a multilayer structure 230 radiationally coupledand / or optically coupled to the blue light source 100 in accordance with an aspect of thepresent disclosure. The multilayer structure 230 includes the film 210 of FIG. 2A and a colorfilter material 230 disposed on the second surface of the film, in which the color filtermaterial 230 is configured to absorb light that passes through the second surface of the film210. While the color filter material 230 is illustrated in FIG. 1B as being disposed on thesecond surface of the film 210, in other implementations, the color filter material can beremotely located at a distance from the film. In some aspects, the light can be in a range ofwavelengths from about 380 nm to about 460 nm.

[0113] In use, scattering of the blue and red light within the film 210 and multilayerstructure 230 illustrated in FIGS. 2A and 2B is similar to that of the film 110 and multilayerstructure 130 in FIGS. 1A and 1B, and therefore is not described in detail herein.

[0114] FIG. 3 is a graph of the relative scattering power of rutile titanium dioxide forblue, green, and red light as a function of rutile particle size in accordance with an aspect ofthe present disclosure. As shown in FIG. 3, rutile titanium dioxide micron particles having aparticle size of about 0.15 microns will scatter blue light about 3.55 times more (=1.6 / 0.45)than red light, e.g., if implemented as the second scattering particles 110b in film 110,allowing red light to exit and reflecting blue light back into the film 110. As further shown inFIG. 3, rutile titanium dioxide micron particles having a particle size of about 0.3 micronswill scatter blue light only 1.125 times more (=0.9 / 0.8) than red light, e.g., if implemented asthe first scattering particles 110a in film 110 of FIGS. 1A and 1B, which will better allowblue light to enter the film while more strongly scattering red to reflect it back towards thesecond surface of the film (e.g., the surface farthest away from the blue light source).Therefore, such an implementation would maximize blue scatterance / red scatterance ratio atthe second surface of the film while minimizing the ratio the first surface of the film, whichthe first surface is closer to the blue light source than the second surface. A person skilled inthe art would appreciate that the foregoing discussion is also applicable to film 210 of FIGS.2A and 2B.

[0115] The color filter pigment 120 on top of surface 2 (110b, 210b) can be embedded ina black or white matrix.

[0116] The ink compositions described herein can be deposited into one or more wells ofa color filter part, and then cured to form cured or semi-cured inks within the respective wellof the color filter part.

[0117] In general, a color filter part can include a well and at least one cured or semi-cured ink within the well. The at least one cured or semi-cured ink includes at least onephosphor material, at least one binder, and at least one of first scattering particles or secondscattering particles. The at least one phosphor material can include a Mn4+ doped phosphor offormula I: Ax[MFy]:Mn+ (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 isthe absolute value of the charge of the [MFy] ion, and y is 5, 6 or 7. The first scatteringparticles can have a first micron particle size, in which the first scattering particles arepredominantly located at a first surface of the film, the first surface of the film configured tobe positioned proximate to or on a surface of an excitation source. The second scatteringparticles can have a second micron particle size that is smaller than the first micron particlesize, in which the second scattering particles are predominantly located at a second surface ofthe film, the second surface of the film configured to be positioned distal to the excitationsource.

[0118] FIG. 4A is a top view of an example pixel layout 1000 that includes three colorfilter parts 1010, 1020, 1030 each having a respective well 1010a, 1020a, 1030c and at leastone respective cured or semi-cured ink 1005a, 1005b, 1005c within the respective well.While the illustrated pixel layout 1000 has three color filter parts 1010, 1020, 1030, it alsocontemplated herein that in other implements, a pixel layout can have one, two, or more thanthree color filter parts. FIG. 4B is a side view of the pixel layout 1000.

[0119] In this illustrated implementation, the pixel layout 1000 is a red-green-blue (RGB)pixel layout, in which the first color filter part 1010 includes at least one cured or semi-curedblue ink 1005a to thereby form a blue subpixel, the second color filter part 1020 includes atleast one cured or semi-cured green ink 1005b to thereby form a green subpixel, and the thirdcolor filter part 1030 includes at least one cured or semi-cured red ink 1005c to thereby forma red subpixel. As such, blue subpixel 1010 is configured to emit blue light 1016, the greensubpixel 1020 is configured to emit green light 1026, and red subpixel 1030 is configured toemit red light 1036 in response to exposure to respective excitation sources 1040. Theexcitation sources can be blue emitting LEDs.

[0120] In certain aspects, the at least one cured or semi-cured red ink includes at least onephosphor material, wherein the at least one phosphor mater can include a Mn+ dopedphosphor of formula I: Ax[MFy]:Mn4+ (I), where A is Li, Na, K, Rb, Cs, NH4, or anycombination 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, and y is 5, 6 or 7.Further, the at least one cured or semi-cured red ink includes the first and second scatteringparticles as discussed herein, wherein the first scattering particles have a micron particle sizeand the second scattering particles have a second micron particle size that is smaller than thefirst micron particle size. As such, in this implementation, the red subpixel would be similarto either film 110 or film 210 of FIGS. 1A and 2A, respectively, depending on themanufacturing approach, i.e., gradient or two-pass printing approach.

[0121] In some aspects, a color filter material 1014, 1024, 1034 can be deposited withinthe respective wells 1010a, 1020a, 1030c, respectively. The color filter material can beconfigured to absorb unconverted light that passes through the respective at least one cured orsemi-cured ink. For example, the light can in a range of wavelengths from about 380 nm toabout 460 nm.

[0122] In some aspects, stencil printing is used to deposit the ink compositions. Thestencil printing can be performed via contact stencil printing system 100 or snap-off stencilprinting system 200. The ink composition can be cured using hot air, UV light, and / or anyother method known in the art.

[0123] In some aspects, at least one film (not shown) is disposed over side of one or moresubpixels 1010, 1020, 1030 or over pixel 1000 through which excitation light enters (e.g.,side 1002). The at least one film can be configured to change the optical properties.Additionally, or alternatively, the at least one film can be configured to protect the cured orsemi-cured ink from at least one of oxygen or moisture.

[0124] In some aspects, quantum dots in a color filter (QDCF) are 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.

[0125] In some aspects, RGB pixel 1000 is part of a display device having a backlightunit (BLU) configured to emit a blue light 1040. In such aspects, QDCF can comprisescattering agent in blue subpixel 1010 and a quantum dot in the red subpixel 1030 and greensubpixel 1020 to attain wide color gamut. In addition to the quantum dots in the red subpixel1030 and green subpixel 1020, at least one binder, at least one scattering agent and / or anadditional color filter material that absorbs blue light can be added to minimize blue lightleakage through the subpixel, which would result in lower color gamut.

[0126] The nanometer size of the quantum dots, the high absorption cross section, and thesurface termination of the quantum dots with ligands has resulted in the commercialization ofQDCF containing display architectures. However, using a QDCF has some draw backs, suchas self-absorption losses. Further, encapsulation of the quantum dots is typically required inQDCF containing displays to prevent the degradation of the quantum dots due moistureand / or oxygen. The encapsulation can introduce parallax issues. Additionally, the necessarycoatings, shells, printing, and / or curing processing can decrease the quantum efficiency of thequantum dots in the QDCF part.

[0127] Additionally, in some aspects, one or more walls of a subpixel are coated with areflective (e.g., white) surface. For example, in some aspects, one or more walls of redsubpixel 1030 is coated with a reflective (e.g., white) surface. Additionally, in some aspects,well depth can be increased from about 8 microns to 16 microns.

[0128] FIG. 5 is a block diagram of a subpixel in accordance with an aspect of thedisclosure. As shown in FIG. 5, a red subpixel can be filled with a KSF ink composition(KSF, K2SiF6:Mn4+) and a color filter pigment (e.g., color filter material). While not shownfirst scattering particles are predominantly located at surface 1 and second scattering particlesare predominantly located at surface 2, in which the first scattering particles have a firstmicron particle size and the second scattering particles have a second micron particle sizethat is smaller than the first micron particle size. The first scattering particles and the secondscattering particles can address at less loss 1 at surface 1 and loss 3 at surface 2. While notshown, to mitigate sidewall loses (arrows labeled 2), the sidewalls can include a white matrixor the well depth can be decrease, e.g., less than about 6 microns. While not shown, tomitigate red emission from exciting incident side (arrow labeled 4), a dichroic filter or a highrefractive index ink can be positioned on or proximate to surface 1.

[0129] In one aspect, a lighting apparatus includes the device. In another aspect, abacklight apparatus includes the device. In another aspect, a display includes the device. Inanother aspect, the device is a self-emissive display and does not contain a liquid crystaldisplay (LCD). In one aspect, the display is a micro-LED display, such as a phosphor-converted micro-LED display.

[0130] Devices according to the present disclosure include an LED light sourceradiationally connected and / or optically coupled to the phosphor composition. FIGs. 6-10show a device 10, according to various aspects of the present disclosure. Referring to FIG. 6,the device 10 includes an LED light source 12 and the phosphor composition 14. The LEDlight source 12 can be a UV or blue emitting LED. In some aspects, the LED light source 12produces blue light in a wavelength range from about 380 nm to about 460 nm. In the device10, the phosphor composition 14 is radiationally coupled and / or optically coupled to the LEDlight source 12. Radiationally connected or coupled or optically coupled means that radiationfrom the LED light source 12 is able to excite the phosphor composition 14, and the phosphorcomposition 14 is able to emit light in response to the excitation by the radiation. Thephosphor composition 14 can be disposed on a part or portion of the LED light source 12 orlocated remotely at a distance from the LED light source 12. In some aspects, the device canbe a backlight unit for display applications. In other aspects, the LED light source 12 is amicro-LED and the device is for a self-emissive display. FIG. 7 shows an exemplary aspectwhere the phosphor composition 14 is disposed on the LED light source 12. The LED lightsource 12 is disposed on a reflective layer 16. The reflective layer 16 reflects light from theLED light source 12 toward the LED light source and the phosphor composition 14. Thereflective 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. 8 shows an exemplary aspect where the phosphor composition 14 isdisposed on the LED light source 12. An encapsulant or barrier layer 18 is 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. 9 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 are mini-LEDs or micro-LEDs. FIG. 10 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.

[0131] The general discussion of the example 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.

[0132] The phosphor composition 14 can be present in any form such as powder, glass,or composite e.g., phosphor-polymer composite or phosphor-glass composite. Further, thephosphor composition 14 can be used as a layer, sheet, film, strip, dispersed particulates, or acombination thereof. In some aspects, the phosphor composition 14 includes the uranium-based phosphor material in glass form. In some of these 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.

[0133] The phosphor composition is optically coupled or radiationally connected to anLED 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.

[0134] FIG. 11 illustrates a lighting apparatus or lamp 20, in accordance with someaspects. 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.The leads 24 can comprise thin wires supported by a thicker lead frame(s) 26 or the leads 24can comprise self-supported electrodes and the lead frame can be omitted. The leads 24provide current to LED chip 22 and thus cause it to emit radiation.

[0135] A layer 30 of the phosphor composition is disposed on a surface of the LED chip22. The phosphor layer 30 can be disposed by any appropriate method, for example, using aslurry or ink composition prepared by mixing the phosphor composition and a binder materialor solvent (as discussed above). In one such method, a silicone slurry in which the phosphorcomposition particles are randomly suspended or uniformly dispersed is placed around theLED chip 22. This method is merely exemplary of possible positions of the phosphor layer30 and LED chip 22. The phosphor layer 30 can be coated over or directly on the lightemitting surface of the LED chip 22 by coating and drying the slurry over the LED chip 22.The light emitted by the LED chip 22 mixes with the light emitted by the phosphorcomposition to produce desired emission.

[0136] In another aspect, 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. 12.As shown, the phosphor layer 34 is 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. The phosphor layer 34 can be coated on the entire surface of the envelope 28 or onlya top portion of the inside surface 29 of the envelope 28. The UV / blue light emitted by theLED chip 22 mixes with the light emitted by the phosphor layer 34, and the mixed lighttransmits out.

[0137] Some aspects include a surface mounted device (SMD) type light emitting diode50, e g., as illustrated in FIGs. 13, 14 and 15, for backlight applications. Referring to FIG. 13,SMD is a "side-emitting ty pe" and has a light-emitting window 52 on a protruding portion ofa light guiding member 54. An SMD package comprises an LED chip 56 as defined above,and a phosphor composition 58 as described herein. FIG. 14 shows the phosphor composition58 disposed on the LED chip 56 and FIG. 15 shows the phosphor composition 58 disposedremotely from the LED chip 56. FIGs. 14 and 15 also show the LED chip 56 and the lightguiding member 54 disposed on a reflective layer 59. The reflective layer 59 reflects lightfrom the LED chip 56 and the light guiding member 54 toward the phosphor composition 58.The reflective layer 59 can be any material suitable for reflecting light. In one aspect, thereflective layer 59 can be a metallic layer, such as a silver, aluminum, aluminum alloy orsilver alloy. In another aspect, the device can be a direct lit display.

[0138] 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 producing white lightfor general illumination having high luminosity and high CRI values for a wide range ofcolor temperatures of interest (2000 K to 10,000 K).

[0139] Devices of the present disclosure include lighting and display apparatuses forgeneral illumination and display applications. Examples of display apparatuses include liquidcrystal display (LCD) backlight units, televisions, computer monitors, vehicular displays,laptops, computer notebooks, mobile phones, smartphones, tablet computers and otherhandheld devices. Where the display is a backlight unit, the phosphor composition can beincorporated in a fdm, sheet or strip that is radiationally coupled and / or optically coupled tothe LED light source, as described in US Patent Application Publication No. 2017 / 0254943.Examples of other devices include chromatic lamps, plasma screens, xenon excitation lamps,UV excitation marking systems, automotive headlamps, home and theatre projectors, laserpumped devices, and point sensors. In one aspect, the device can be a fast response displaythat does not include an LCD. The fast response display can be a self-emissive displayincluding phosphor converted (PC) micro-LEDs. The list of these applications is meant to bemerely exemplary and not exhaustive.

[0140] 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 Mn+ doped phosphor having a D50 particlesize less than 20 µm, less than 10 µm, particularly less than 5 µm, more particularly nano-sized. In another aspect, the D50 particle size can be from about 1 micron to about 20microns. In another aspect, the D50 particle size is from about 1 micron to about 15 microns.In another aspect, the D50 particle size is from about 1 micron to about 10 microns. Inanother aspect, the D50 particle size is from about 1 micron to about 5 microns. In anotheraspect, the D50 particle size is from about 1 micron to about 3 microns.

[0141] In some aspects, walls 204 are comprised of a reflective materials, and thereforecan act as reflectors. More particularly, walls 204 are coated with a white surface whichreflects back all the visible wavelengths that shine on it. The reflective material in walls 204can increase the brightness of the light emitting elements. In some aspects, one or more walls204 are comprised of a translucent material For example, in transparent display applications,walls 204 can be comprised of a translucent material.

[0142] A see-through display or transparent display is an electronic display that allowsthe user to see what is shown on the screen while still being able to see through it. The mainapplications of a transparent display are head-up displays and augmented reality systems.Terminology

[0143] It will be appreciated that the terms "proximal" and "distal" are used herein torefer to relative locations of the referenced devices and / or components. Although “proximal"is generally used to refer to a location that is at or near a user when the device and / orcomponent is in use, and "distal" is generally used to refer to a location that is away from auser when the device and / or component is in use, these terms are not intended to be absolute.For example, a “proximal” end and / or a “distal” end of a component need not be the absolutefurthest points on the referenced ends, and can instead refer to a general region at or near thereferenced end. Further, opposing "proximal" ends and "distal" ends of a component need notbe completely and / or perfectly opposite each other, as the shapes of each end can differand / or the component cannot be perfectly linear (e.g., one or more longitudinal dimensions ofthe component can be of different lengths).

[0144] When a feature or element is herein referred to as being "on" another feature orelement, it can be directly on the other feature or element or intervening features and / orelements can also be present. In contrast, when a feature or element is referred to as being"directly on" another feature or element, there are no intervening features or elementspresent. It will also be understood that, when a feature or element is referred to as being"connected", "attached” or “coupled” to another feature or element, it can be directlyconnected, attached or coupled to the other feature or element or intervening features orelements can be present. In contrast, when a feature or element is referred to as being"directly connected”, “directly attached” or “directly coupled" to another feature or element,there are no intervening features or elements present.

[0145] 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.

[0146] Although described or shown with respect to one implementation, the features andelements so described or shown can apply to other implementations. It will also beappreciated by those of skill in the art that references to a structure or feature that is disposed"adjacent" another feature can have portions that overlap or underlie the adjacent feature.

[0147] Terminology used herein is for the purpose of describing particularimplementations and implementations only and is not intended to be limiting. For example,as used herein, the singular forms “a”, “an” and “the” are intended to include the plural formsas well, unless the context clearly indicates otherwise. It will be further understood that theterms "comprises” and / or “comprising," when used in this specification, specify the presenceof stated features, steps, operations, elements, and / or components, but do not preclude thepresence or addition of one or more other features, steps, operations, elements, components,and / or groups thereof. As used herein, the term "and / or" includes any and all combinations ofone or more of the associated listed items and can be abbreviated as " / ".

[0148] In the descriptions above and in the claims, phrases such as "at least one of" or"one or more of" can occur followed by a conjunctive list of elements or features. The term"and / or" can also occur in a list of two or more elements or features. Unless otherwiseimplicitly or explicitly contradicted by the context in which it used, such a phrase is intendedto mean any of the listed elements or features individually or any of the recited elements orfeatures in combination with any of the other recited elements or features. For example, thephrases "at least one of A and B;” “one or more of A and B;" and "A and / or B" are eachintended to mean “A alone, B alone, or A and B together." A similar interpretation is alsointended for lists including three or more items. For example, the phrases "at least one of A,B, and C;" "one or more of A, B, and C;" and "A, B, and / or C" are each intended to mean "Aalone, B alone, C alone, A and B together, A and C together, B and C together, or A and Band C together." Use of the term "based on," above and in the claims is intended to mean,"based at least in part on," such that an unrecited feature or element is also permissible.

[0149] Spatially relative terms, such as “forward”, “rearward”, “under”, “below”,"lower", "over", "upper" and the like, can be used herein for ease of description to describeone element or feature's relationship to another element(s) or feature(s) as illustrated in thefigures. It will be understood that the spatially relative terms are intended to encompassdifferent orientations of the device in use or operation in addition to the orientation depictedin the figures. For example, if a device in the figures is inverted, elements described as"under" or "beneath" other elements or features would then be oriented "over" the otherelements or features. Thus, the exemplary term "under" can encompass both an orientation ofover and under. The device can be otherwise oriented (rotated 90 degrees or at otherorientations) and the spatially relative descriptors used herein interpreted accordingly.Similarly, the terms “upwardly”, “downwardly”, “vertical”, “horizontal" and the like are usedherein for the purpose of explanation only unless specifically indicated otherwise.

[0150] Although the terms "first" and "second" can be used herein to describe variousfeatures / elements (including steps), these features / elements should not be limited by theseterms, unless the context indicates otherwise. These terms can be used to distinguish onefeature / element from another feature / element. Thus, a first feature / element discussed belowcould be termed a second feature / element, and similarly, a second feature / element discussedbelow could be termed a first feature / element without departing from the teachings providedherein.

[0151] As used herein in the specification and claims, including as used in the examplesand unless otherwise expressly specified, all numbers can be read as if prefaced by the word"about" or "approximately," even if the term does not expressly appear. The phrase "about"or "approximately" can be used when describing magnitude and / or position to indicate thatthe value and / or position described is within a reasonable expected range of values and / orpositions. For example, a numeric value can have a value that is + / - 0.1% of the stated value(or range of values), + / - 1% of the stated value (or range of values), + / - 2% of the statedvalue (or range of values), + / - 5% of the stated value (or range of values), + / - 10% of thestated value (or range of values), etc. Any numerical values given herein should also beunderstood to include about or approximately that value, unless the context indicatesotherwise. For example, if the value "10" is disclosed, then "about 10" is also disclosed. Anynumerical range recited herein is intended to include all sub-ranges subsumed therein. It isalso understood that when a value is disclosed that “less than or equal to” the value, "greaterthan or equal to the value" and possible ranges between values are also disclosed, asappropriately understood by the skilled artisan. For example, if the value "X" is disclosed the"less than or equal to X" as well as "greater than or equal to X" (e.g., where X is a numericalvalue) is also disclosed. It is also understood that the throughout the application, data isprovided in a number of different formats, and that this data, represents endpoints andstarting points, and ranges for any combination of the data points. For example, if a particulardata point "10" and a particular data point "15" are disclosed, it is understood that greaterthan, greater than or equal to, less than, less than or equal to, and equal to 10 and 15 areconsidered disclosed as well as between 10 and 15. It is also understood that each unitbetween two particular units are also disclosed. For example, if 10 and 15 are disclosed, then11, 12, 13, and 14 are also disclosed.

[0152] In one embodiment, an ink composition comprises:at least one phosphor material 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;at least one binder,first scattering particles having a first micron particle size; andsecond scattering particles having a second micron particle size that is smaller thanthe first micron particle size.

[0153] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise titanium dioxide micron particles.

[0154] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise zirconia dioxide micron particles.

[0155] In one embodiment, the first micron particle size is about 0.3 microns.

[0156] In one embodiment, the second micron particle size is about 0.15 microns.

[0157] In one embodiment, the first scattering particles are predominantly located withina first portion of the ink composition, and the second scattering particles are predominantlylocated within a second portion of the ink composition, the first portion being different thanthe second portion of the ink composition.

[0158] In one embodiment, the first portion is proximate to or at a first surface of the inkcomposition and the second portion is proximate to or at a second surface of the inkcomposition, wherein the first surface allows excitation light to enter the ink composition.

[0159] In one embodiment, the Mn+ doped phosphor has particle size distribution of aD50 value from about 0.5 microns to about 15 microns.

[0160] In one embodiment, the ink composition has a viscosity from more than 2,000 cPto about 30,000 сР.

[0161] In one embodiment, the at least one phosphor material is present in an amountfrom about 5 wt% to about 70 wt%, based on the weight of the ink composition.

[0162] In one embodiment, the Mn⁴+ doped phosphor comprises at least one ofK2[GeF6]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6]Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiFfi]:Mn+, Na2[ZrF6]:Mn4+,K3[ZrF7]:Mn4+, K3[BIF6] K3[YF6]:Mn4+, K3[LaF6]:Mn+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, orK3[TaF7]:Mn4+.

[0163] In one embodiment, the Mn+ phosphor of formula I is K2SiF6:Mn4+ orNa2[SiFfi]:Mn4+.

[0164] In one embodiment, the at least one phosphor material further comprises a rareearth containing a Garnet phosphor doped with at least one of cerium or SiAlON.

[0165] In one embodiment, the ink composition further comprises a solvent.

[0166] In one embodiment, the at least one binder comprises at least one of an epoxy,acrylate, methacrylate, vinyl ester, or siloxane, polyethylene terethalate.

[0167] In one embodiment, the Mn⁴+ phosphor of formula I is K2SiF6:Mn+, the firstmicron particle size is about 0.3 microns, and the second micron particle size is about 0.15microns.

[0168] In one embodiment, the at least one binder has a refractive index from about 1.52or less.

[0169] In one embodiment, the at least one binder has a refractive index from about 1.42to 1.52.

[0170] In one embodiment, the at least one binder has a refractive index that does notexceed 1.58.

[0171] In one embodiment, the ink composition further comprises one or more otherluminescent materials.

[0172] In one embodiment, the one or more other luminescent material comprisesquantum dot material.

[0173] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0174] In one embodiment, a film comprises:at least one cured or semi-cured ink comprising:at least one phosphor material comprising a Mn³+ doped phosphor offormula 1: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;at least one binder; andat least one of first scattering particles or second scattering particles,wherein:the first scattering particles have a first micron particle size, wherein the firstscattering particles are predominantly located at a first surface of the film, the firstsurface of the film configured to be positioned proximate to or on a surface of anexcitation source, andthe second scattering particles have a second micron particle size that issmaller than the first micron particle size, wherein the second scattering particles arepredominantly located at a second surface of the film, the second surface of the filmconfigured to be positioned distal to the excitation source.

[0175] In one embodiment, in response to exposure from the excitation source, the firstscattering particles are configured to allow a first light within a first range of wavelengths topass through the first surface and into the film and inhibit a second light within a secondrange of wavelengths to pass through the first surface and out of the film; and wherein, inresponse to exposure from the excitation source, the second scattering particles areconfigured to inhibit the first light within the first range of wavelengths to pass through thesecond surface and out of the film and allow the second light within the second range ofwavelengths to pass through the second surface and out of the film.

[0176] In one embodiment, the at least one cured or semi-cured ink comprises a firstcured or semi-cured ink, the at least one phosphor material comprises a first phosphormaterial, and the at least one binder comprises a first binder, wherein the first cured or semi-cured ink comprises the first scattering particles and the second scattering particles.

[0177] In one embodiment, the at least one cured or semi-cured ink comprises a firstcured or semi-cured ink, the at least one phosphor material comprises a first phosphormaterial, and the at least one binder comprises a first binder, wherein the first cured or semi-cured ink comprises the first scattering particles, and the at least one cured or semi-cured inkcomprises a second cured or semi-cured ink disposed on at least a portion of the first cured orsemi-cured ink, the at least one phosphor material comprises a second phosphor material, andthe at least one binder comprises a second binder, wherein the second cured or semi-curedink comprises the second scattering particles.

[0178] In one embodiment, the first phosphor material and the second phosphor materialare the same.

[0179] In one embodiment, the first binder and the second binder are the same.

[0180] In one embodiment, the excitation source is a blue emitting LED.

[0181] In one embodiment, the first range of wavelengths is from about 380 nm to about460 nm.

[0182] In one embodiment, the second range of wavelengths is from about 620nanometers to about 750 nanometers.

[0183] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise titanium dioxide micron particles.

[0184] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise zirconia dioxide micron particles.

[0185] In one embodiment, the first micron particle size is about 0.3 microns.

[0186] In one embodiment, the second micron particle size is about 0.15 microns.

[0187] In one embodiment, the Mn+ doped phosphor has particle size distribution of aD50 value from about 0.5 microns to about 15 microns.

[0188] In one embodiment, the at least one phosphor material is present in an amountfrom about 5 wt% to about 70 wt%, based on the weight of the ink composition.

[0189] In one embodiment, the Mn+ doped phosphor comprises at least one ofK2[GeF6]:Mn4+, K2[SiF6]:Mn+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6]Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn+, Na2[TiFfi]:Mn4+, Na2[ZrF6]:Mn4+,K3[ZrF7]:Mn4+, K3[BIF6] K3[YF6]:Mn4+, K3[LaF6]:Mn+, K3[GdF6]:Mn4+, K3[NbF7]:Mn+, orK3[TaF7]:Mn+.

[0190] In one embodiment, the Mn+ phosphor of formula I is K2SiF6:Mn+ orNa2[SiFfi]:Mn4+.

[0191] In one embodiment, the at least one phosphor material further comprises a rareearth containing a Garnet phosphor doped with at least one of cerium or SiAlON.

[0192] In one embodiment, the at least one binder comprises at least one of an epоху,acrylate, methacrylate, vinyl ester, or siloxane, polyethylene terethalate.

[0193] In one embodiment, the Mn+ phosphor of formula I is K2SiF6:Mn+, the firstmicron particle size is about 0.3 microns, and the second micron particle size is about 0.15microns.

[0194] In one embodiment, the at least one binder has a refractive index from about 1.52or less.

[0195] In one embodiment, the at least one binder has a refractive index from about 1.42to 1.52.

[0196] In one embodiment, the at least one binder has a refractive index that does notexceed 1.58.

[0197] In one embodiment, the at least one cured or semi-cured ink further comprises oneor more other luminescent materials.

[0198] In one embodiment, the one or more luminescent material comprises quantum dotmaterial.

[0199] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0200] In one embodiment, a multilayer structure comprises:the film as described above; anda color filter material disposed on or proximate to the second surface of the film, thecolor filter material configured to absorb light that passes through the second surface of thefilm, wherein the light is in a range of wavelengths from about 380 nm to about 460 nm.

[0201] In one embodiment, a color filter part comprises:a well; andat least one cured or semi-cured ink within the well, the at least one cured or semi-cured ink comprising.at least one phosphor material comprising a Mn¹ doped phosphor of formula1: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 an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7,at least one binder; andat least one of first scattering particles or second scattering particles,wherein:the first scattering particles have a first micron particle size, wherein the firstscattering particles are predominantly located at a first surface of the at least onecured or semi-cured ink, the first surface of the at least one cured or semi-cured inkconfigured to be positioned proximate to or on a surface of an excitation source; andthe second scattering particles have a second micron particle size that issmaller than the first micron particle size, wherein the second scattering particles arepredominantly located at a second surface of the at least one cured or semi-cured ink,the second surface of the at least one cured or semi-cured ink configured to bepositioned distal to the excitation source.

[0202] In one embodiment, a depth of the well is about 6 microns to about 20 microns.

[0203] In one embodiment, at least one wall of the well is coated with a reflective material.

[0204] In one embodiment, in response to exposure from the excitation source, the firstscattering particles are configured to allow a first light within a first range of wavelengths topass through the first surface and into the at least one cured or semi-cured ink and inhibit asecond light within a second range of wavelengths to pass through the first surface and out ofthe at least one cured or semi-cured ink; and wherein, in response to exposure from theexcitation source, the second scattering particles are configured to inhibit the first light withinthe first range of wavelengths to pass through the second surface and out of the at least onecured or semi-cured ink and allow the second light within the second range of wavelengths topass through the second surface and out of the at least one cured or semi-cured ink.

[0205] In one embodiment, the at least one cured or semi-cured ink comprises a firstcured or semi-cured ink, the at least one phosphor material comprises a first phosphormaterial, and the at least one binder comprises a first binder, wherein the first cured or semi-cured ink comprises the first scattering particles and the second scattering particles.

[0206] In one embodiment, the at least one cured or semi-cured ink comprises a firstcured or semi-cured ink, the at least one phosphor material comprises a first phosphormaterial, and the at least one binder comprises a first binder, wherein the first cured or semi-cured ink comprises the first scattering particles, and the at least one cured or semi-cured inkcomprises a second cured or semi-cured ink disposed on at least a portion of the first cured orsemi-cured ink, the at least one phosphor material comprises a second phosphor material, andthe at least one binder comprises a second binder, wherein the second cured or semi-curedink comprises the second scattering particles.

[0207] In one embodiment, the first phosphor material and the second phosphor materialare the same.

[0208] In one embodiment, the at least one first binder and the at least one second binderare the same.

[0209] In one embodiment, the excitation source is a blue emitting LED.

[0210] In one embodiment, the first range of wavelengths is from about 380 nm to about460 nm.

[0211] In one embodiment, the second range of wavelengths is from about 620nanometers to about 750 nanometers.

[0212] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise titanium dioxide micron particles.

[0213] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise zirconia dioxide micron particles.

[0214] In one embodiment, the first micron particle size is about 0.3 microns.

[0215] In one embodiment, the second micron particle size is about 0.15 microns.

[0216] In one embodiment, the Mn+ doped phosphor has particle size distribution of aD50 value from about 0.5 microns to about 15 microns.

[0217] In one embodiment, the at least one phosphor material is present in an amountfrom about 5 wt% to about 70 wt%, based on the weight of the ink composition.

[0218] In one embodiment, the Mn4+ doped phosphor comprises at least one ofK2[GeF6]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6]Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiFfi]:Mn+, Na2[ZrF6]:Mn4+,K3[ZrF7]:Mn4+, K3[BIF6] K3[YF6]:Mn4+, K3[LaF6]:Mn+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, orK3[TaF7]:Mn4+.

[0219] In one embodiment, the Mn+ phosphor of formula I is K2SiF6:Mn4+ orNa2[SiFfi]:Mn4+.

[0220] In one embodiment, the at least one phosphor material further comprises a rareearth containing a Garnet phosphor doped with at least one of cerium or SiAlON.

[0221] In one embodiment, the at least one binder comprises at least one of an epoxy,acrylate, methacrylate, vinyl ester, or siloxane, polyethylene terethalate.

[0222] In one embodiment, the Mn⁴+ phosphor of formula I is K2SiF6:Mn4+, the firstmicron particle size is about 0.3 microns, and the second micron particle size is about 0.15microns.

[0223] In one embodiment, the at least one binder has a refractive index from about 1.52or less.

[0224] In one embodiment, the at least one binder has a refractive index from about 1.42to 1.52.

[0225] In one embodiment, the at least one binder has a refractive index that does notexceed 1.58.

[0226] In one embodiment, the at least one cured or semi-cured ink further comprises oneor more other luminescent materials.

[0227] In one embodiment, the one or more luminescent material comprises quantum dotmaterial.

[0228] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0229] In one embodiment, the color filter part further comprises a color filter materialconfigured to absorb light that passes through the second surface of the at least one cured orsemi-cured ink, wherein the light is in a range of wavelengths from about 380 nm to about460 nm.

[0230] In one embodiment, the color filter material is disposed on the second surface ofthe at least one cured or semi-cured ink.

[0231] In one embodiment, a device comprises:a LED light source optically coupled and / or radiationally connected to at least onecured or semi-cured ink, the at least one cured or semi-cured ink comprising:at least one phosphor material comprising a Mn¹ doped phosphor of formula1:A[MF]:Mnwherein:A is Li, Na, K, Rb, Cs, 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,at least one binder; andat least one of first scattering particles or second scattering particles;wherein:first scattering particles having a first micron particle size, wherein the firstscattering particles are predominantly located at a first surface of the at least onecured or semi-cured ink, the first surface of the at least one cured or semi-cured inkconfigured to be positioned proximate to or on a surface the LED light source; andsecond scattering particles having a second micron particle size that is smallerthan the first micron particle size, wherein the second scattering particles arepredominantly located at a second surface of the at least one cured or semi-cured ink,the second surface of the at least one cured or semi-cured ink configured to bepositioned distal to the LED light source.

[0232] In one embodiment, in response to exposure from the LED light source, the firstscattering particles are configured to allow a first light within a first range of wavelengths topass through the first surface and into the at least one cured or semi-cured ink and inhibit asecond light within a second range of wavelengths to pass through the first surface and out ofthe at least one cured or semi-cured ink; and wherein, in response to exposure from the LEDlight source, the second scattering particles are configured to inhibit the first light within thefirst range of wavelengths to pass through the second surface and out of the at least one curedor semi-cured ink and allow the second light within the second range of wavelengths to passthrough the second surface and out of the at least one cured or semi-cured ink.

[0233] In one embodiment, the at least one cured or semi-cured ink comprises a firstcured or semi-cured ink, the at least one phosphor material comprises a first phosphormaterial, and the at least one binder comprises a first binder, wherein the first cured or semi-cured ink comprises the first scattering particles and the second scattering particles.

[0234] In one embodiment, the at least one cured or semi-cured ink comprises a firstcured or semi-cured ink, the at least one phosphor material comprises a first phosphormaterial, and the at least one binder comprises a first binder, wherein the first cured or semi-cured ink comprises the first scattering particles, and the at least one cured or semi-cured inkcomprises a second cured or semi-cured ink disposed on at least a portion of the first cured orsemi-cured ink, the at least one phosphor material comprises a second phosphor material, andthe at least one binder comprises a second binder, wherein the second cured or semi-curedink comprises the second scattering particles.

[0235] In one embodiment, the first phosphor material and the second phosphor materialare the same.

[0236] In one embodiment, the at least one first binder and the at least one second binderare the same.

[0237] In one embodiment, the excitation source is a blue emitting LED.

[0238] In one embodiment, the first range of wavelengths is from about 380 nm to about460 nm.

[0239] In one embodiment, the second range of wavelengths is from about 620nanometers to about 750 nanometers.

[0240] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise titanium dioxide micron particles.

[0241] In one embodiment, the first scattering particles, the second scattering particles, orboth comprise zirconia dioxide micron particles.

[0242] In one embodiment, the first micron particle size is about 0.3 microns.

[0243] In one embodiment, the second micron particle size is about 0.15 microns.

[0244] In one embodiment, the Mn+ doped phosphor has particle size distribution of aD50 value from about 0.5 microns to about 15 microns.

[0245] In one embodiment, the at least one phosphor material is present in an amountfrom about 5 wt% to about 70 wt%, based on the weight of the ink composition.

[0246] In one embodiment, the Mn+ doped phosphor comprises at least one ofK2[GeF6]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6]Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiFfi]:Mn+, Na2[ZrF6]:Mn4+,K3[ZrF7]:Mn4+, K3[BIF6] K3[YF6]:Mn4+, K3[LaF6]:Mn4+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, orK3[TaF7]:Mn4+.

[0247] In one embodiment, the Mn+ phosphor of formula I is K2SiF6:Mn+ orNa2[SiFfi]:Mn+.

[0248] In one embodiment, the at least one phosphor material further comprises a rareearth containing a Garnet phosphor doped with at least one of cerium or SiAlON.

[0249] In one embodiment, the at least one binder comprises at least one of an epoxy,acrylate, methacrylate, vinyl ester, or siloxane, polyethylene terethalate.

[0250] In one embodiment, the Mn+ phosphor of formula I is K2SiF6:Mn4+, the firstmicron particle size is about 0.3 microns, and the second micron particle size is about 0.15microns.

[0251] In one embodiment, the at least one binder has a refractive index from about 1.52or less.

[0252] In one embodiment, the at least one binder has a refractive index from about 1.42to 1.52.

[0253] In one embodiment, the at least one binder has a refractive index that does notexceed 1.58.

[0254] In one embodiment, the at least one cured or semi-cured ink further comprises oneor more other luminescent materials.

[0255] In one embodiment, the one or more luminescent material comprises quantum dotmaterial.

[0256] In one embodiment, the quantum dot material comprises perovskite quantum dots.

[0257] In one embodiment, the device further comprises a color filter material configuredto absorb light that passes through the second surface of the film, wherein the light is in arange of wavelengths from about 380 nm to about 460 nm.

[0258] In one embodiment, the color filter material is disposed on the first surface of theat least one cured or semi-cured ink.

[0259] In one embodiment, the LED light source is a blue emitting LED.

[0260] In one embodiment, the LED light source is a mini-LED or a micro-LED.

[0261] In one embodiment, the device is a self-emissive display.

[0262] In one embodiment, a lighting apparatus comprises the above-described device.

[0263] In one embodiment, a display apparatus comprises the above-described device.

[0264] In one embodiment, a backlight apparatus comprises the above-described device.

[0265] In one embodiment, a television comprises the above-noted backlight apparatus.

[0266] In one embodiment, a mobile phone comprises the above-noted backlightapparatus.

[0267] In one embodiment, a computer monitor comprises the above-noted backlightapparatus.

[0268] In one embodiment, a laptop comprises the above-noted backlight apparatus.

[0269] In one embodiment, a tablet computer comprises the above-noted backlightapparatus.

[0270] In one embodiment, an automotive display comprises the above-noted backlightapparatus. 114.

[0271] In one embodiment, a method for screen printing, direct write printing, aerosol jetprinting, gravure printing, flexographic printing, or microdispensing printing, the methodcomprising printing at least one ink composition, wherein the at least one ink compositioncomprises:at least one phosphor material comprising a Mn doped phosphor of formula I:Ax[MF]:Mnwherein:A is Li, Na, K, Rb, Cs, 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,at least one binder; andat least one of first scattering particles or second scattering particles;wherein:the first scattering particles have a first micron particle size, wherein the firstscattering particles are predominantly located at a surface through which excitationlight enters, andthe second scattering particles have a second micron particle size that issmaller than the first micron particle size, wherein the second scattering particles arepredominantly located distal to the surface through which the excitation light enters.

[0272] In one embodiment, the at least one ink composition comprises at least one inkcomposition according to the above-described ink composition.

[0273] In one embodiment, a method comprises depositing at least one ink compositioninto a well of a color filter part, wherein at least one ink composition comprises:at least one phosphor material comprising a Mn+ doped phosphor of formula 1:4+A[MFy]:Mn+wherein:A is Li, Na, K, Rb, Cs, 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;at least one binder; andat least one first scattering particles or second scattering particles,wherein:the first scattering particles have a first micron particle size, wherein the firstscattering particles are predominantly located at a surface through which excitation lightenters, andthe second scattering particles have a second micron particle size that is smaller thanthe first micron particle size, wherein the second scattering particles are predominantlylocated distal to the surface through which the excitation light enters.

[0274] A light emitting array comprising a plurality of micro-LEDs, each micro-LEDenclosed in a banked structure or a well structure, the banked structure or well structureconfigured to contain at least one cured or semi-cured ink, wherein at least one cured or semi-cured ink comprises:at least one phosphor material comprising a Mn+ doped phosphor of formula 1:A[MF]:Mnwherein:A is Li, Na, K, Rb, Cs, 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;at least one binder; andat least one of first scattering particles or second scattering particles,wherein:the first scattering particles have a first micron particle size, wherein the firstscattering particles are predominantly located at a first surface of the at least one cured orsemi-cured ink, the first surface of the at least one cured or semi-cured ink configured to bepositioned proximate to or on a surface of at least one micro-LED of the plurality of micro-LEDs; andthe second scattering particles have a second micron particle size that is smaller thanthe first micron particle size, wherein the second scattering particles are predominantlylocated at a second surface of the at least one cured or semi-cured ink, the second surface ofthe at least one cured or semi-cured ink configured to be positioned distal to the surface of theat least one micro-LED of the plurality of micro-LEDs.

[0275] In one embodiment, the at least one micro-LED of the plurality of micro-LEDs isa blue emitting micro-LED.

[0276] In one embodiment, a transparent display comprises a micro-LED array and atleast one cured or semi-cured ink positioned on or proximate to a surface of the micro-LEDarray, wherein the transparent display has a transparency of at least 50%, the at least onecured or semi-cured ink comprising.at least one phosphor material comprising a Mn+ doped phosphor of formula 1:A[MFy]:Mn+wherein:A is Li, Na, K, Rb, Cs, 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;at least one binder; andat least one first scattering particles or second scattering particles,wherein:the first scattering particles have a first micron particle size, wherein the firstscattering particles are predominantly located at the surface of the micro-LED array; andthe second scattering particles have a second micron particle size that is smaller thanthe first micron particle size, wherein the second scattering particles are predominantlylocated distal to the surface of the micro-LED array.

[0277] In one embodiment, the micro-LED array comprises at least one blue emittingmicro-LED.

[0278] Although various illustrative implementations are described above, any of anumber of changes can be made to various implementations without departing from theteachings herein. For example, the order in which various described method steps areperformed can often be changed in alternative implementations, and in other alternativeimplementations one or more method steps can be skipped altogether. Optional features ofvarious device and system implementations can be included in some implementations and notin others. Therefore, the foregoing description is provided primarily for exemplary purposesand should not be interpreted to limit the scope of the claims.

[0279] The examples and illustrations included herein show, by way of illustration andnot of limitation, specific implementations in which the subject matter can be practiced. Asmentioned, other implementations can be utilized and derived there from, such that structuraland logical substitutions and changes can be made without departing from the scope of thisdisclosure. Such implementations of the inventive subject matter can be referred to hereinindividually or collectively by the term "invention" merely for convenience and withoutintending to voluntarily limit the scope of this application to any single invention or inventiveconcept, if more than one is, in fact, disclosed. Thus, although specific implementations havebeen illustrated and described herein, any arrangement calculated to achieve the samepurpose can be substituted for the specific implementations shown. This disclosure isintended to cover any and all adaptations or variations of various implementations.Combinations of the above implementations, and other implementations not specificallydescribed herein, will be apparent to those of skill in the art upon reviewing the abovedescription.

Claims

What is claimed is:

1. An ink composition comprising:at least one phosphor material comprising a Mnt doped phosphor of formula I:Ax[MFy]: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 anycombination thereof,x is an absolute value of a charge of the [MFy] ion, andy is 5, 6 or 7;at least one binder;first scattering particles having a first micron particle size; andsecond scattering particles having a second micron particle size that is smaller thanthe first micron particle size.

2. The ink composition of claim 1, wherein the first scattering particles, the secondscattering particles, or both comprise titanium dioxide or zirconia dioxide micron particles.

3. The ink composition of any one of the preceding claims, wherein the first micronparticle size is about 0.3 microns, and the second micron particle size is about 0.15 microns.

4. The ink composition of any one of the preceding claims, wherein the first scatteringparticles are predominantly located within a first portion of the ink composition, and thesecond scattering particles are predominantly located within a second portion of the inkcomposition, the first portion being different than the second portion of the ink composition.

5. The ink composition of claim 4, wherein the first portion is proximate to or at a firstsurface of the ink composition and the second portion is proximate to or at a second surfaceof the ink composition, wherein the first surface allows excitation light to enter the inkcomposition.

6. The ink composition of any one of the preceding claims, wherein the Mn+ dopedphosphor has particle size distribution of a D50 value from about 0.5 microns to about 15microns.

7. The ink composition of any one of the preceding claims, wherein the ink compositionhas a viscosity from more than 2,000 cP to about 30,000 cP.

8. The ink composition of any one of the preceding claims, wherein the at least onephosphor material is present in an amount from about 5 wt% to about 70 wt%, based on theweight of the ink composition.

9. The ink composition of any one of the preceding claims, wherein the Mn+ dopedphosphor comprises at least one of K2[GeF6]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+,K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6] Mn+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+,Na2[SiF6]:Mn4+, Na2[TiFfi]:Mn+, Na2[ZrF6]:Mn4+, K3[ZrF7]:Mn4+, K3[BIF6] K3[YF6]:Mn+,K3[LaF6]:Mn4+, K3[GdF6]:Mn4+, K3[NbF7]:Mn+, or K3[TaF7]:Mn+.

10. The ink composition of any one of the preceding claims, wherein the Mn⁴+ phosphorof formula I is K2SiF6:Mn+ or Na2[SiFfi]:Mn4+.

11. The ink composition of any one of the preceding claims, wherein the at least onephosphor material further comprises a rare earth containing a Garnet phosphor doped with atleast one of cerium or SiAlON.

12. The ink composition of any one of the preceding claims, wherein the ink compositionfurther comprises a solvent.

13. The ink composition of any one of the preceding claims, wherein the at least onebinder comprises at least one of an epoxy, acrylate, methacrylate, vinyl ester, or siloxane,polyethylene terethalate.

14. The ink composition of any one of the preceding claims, wherein the Mn+ phosphorof formula I is K2SiF6:Mn4+, the first micron particle size is about 0.3 microns, and thesecond micron particle size is about 0.15 microns.

15. The ink composition of any one of the preceding claims, wherein the at least onebinder has a refractive index that does not exceed 1.58.

Images