Ink compositions and films using narrow-band emitting phosphor materials

Abstract

An ink composition is provided, the composition comprising a binder material and at least one narrow-band-emitting phosphor uniformly dispersed throughout the composition, the narrow-band-emitting phosphor having a D50 particle size of about 0.1 μm to about 15 μm, and a green-emitting U 6+ Contains phosphor, green emitting Mn 2+ Contains phosphor, Mn 4+ a red-emitting phosphor based on a complex fluorinated material activated by a fluorine-containing compound, and a mixture thereof. Color conversion films and devices are also provided.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a standard patent application and claims priority to U.S. Provisional Patent Application No. 63 / 009,800, entitled "GREEN-EMITTING PHOSPHORS AND DEVICES THEREOF," filed April 14, 2020; U.S. Provisional Patent Application No. 63 / 027,672, entitled "INK FORMULATIONS WITH NARROW BAND EMISSION PHOSPHOR MATERIALS," filed May 20, 2020; U.S. Provisional Patent Application No. 63 / 059,709, entitled "INK FORMULATIONS WITH NARROW BAND EMISSION PHOSPHOR MATERIALS," filed July 31, 2020; and U.S. Provisional Patent Application No. 63 / 073,391, entitled "GREEN-EMITTING PHOSPHORS AND DEVICES THEREOF," filed September 1, 2020. Each of these provisional patent applications is incorporated herein by reference in its entirety. [Background technology]

[0002] The subject matter described herein relates generally to ink formulations for phosphors and more particularly for forming color conversion films or color layers for lighting and display applications.

[0003] Narrow-band emitting phosphor materials are enabling high-quality color tones in LED-based lighting and displays. Next-generation displays are capable of producing human-visible light at very low drive currents, with wavelengths as low as 10,000 μm. 2 Mini LEDs and micro LEDs with active areas of about 100 μm to about 0.7 mm can be incorporated. Mini LEDs are LEDs with sizes from about 100 μm to about 0.7 mm. For micro LEDs, the display may be self-emitting or may include backlighting with an array of miniaturized, sub-100 μm LEDs.

[0004] To maximize the potential of mini-LED and micro-LED technology, new methods for applying phosphor materials to miniaturized LED elements on the micrometer scale must be developed. Coatings such as inkjet printing of phosphor materials and printed films, spin coating, and slot die coating are currently under development to create LEDs, including small-sized LEDs.

[0005] Inkjet-printable inks have been created using quantum dots. Quantum dot materials contain nanometer-sized particles with strong absorption coefficients. Challenges with quantum dots include low quantum efficiency (QE) and poor thermal stability, which significantly limit their practical applications.

[0006] Phosphors have improved properties compared to quantum dot materials. Phosphors for use in small-sized LEDs must be correspondingly small in size. Printing and coating compositions require stable dispersions, and phosphor materials using common organic solvents can produce undesirable sedimentation or phase separation for subsequent coating or printing processes. Additionally, small particle size phosphor materials tend to aggregate when mixed with commonly used solvents, making them unsuitable for ink compositions or formulations. Summary of the Invention [Means for solving the problem]

[0007] In one embodiment, an ink composition is provided. The composition includes a binder material and at least one narrow-band-emitting phosphor uniformly dispersed throughout the composition. The narrow-band-emitting phosphor has a D50 particle size of about 0.1 μm to about 15 μm, and is a green-emitting U 6+ Contains phosphor, green emitting Mn 2+ Contains phosphor, Mn 4+ red-emitting phosphors based on complex fluorinated materials activated by

[0008] In a further aspect, a film is provided, the film comprising at least one narrow-band-emitting phosphor dispersed in a binder matrix, the narrow-band-emitting phosphor having a D50 particle size of about 0.1 μm to about 15 μm and a green-emitting U 6+ Contains phosphor, green emitting Mn 2+ Contains phosphor, Mn 4+ red-emitting phosphors based on complex fluorinated materials activated by

[0009] In a further aspect, a black matrix and a device are provided. [Brief explanation of the drawings]

[0010] These and other features, aspects, and advantages of the present disclosure will be better understood from the following detailed description taken in conjunction with the accompanying drawings, in which like reference numerals represent like parts throughout.

[0011] [Figure 1A] 1 is a schematic cross-sectional view of a matrix device according to one embodiment of the present disclosure.

[0012] [Figure 1B] FIG. 1 is a plan view of a matrix device according to one embodiment of the present disclosure.

[0013] [Figure 2] 1 is a schematic cross-sectional view of a lighting device according to one embodiment of the present disclosure.

[0014] [Figure 3] 1 is a schematic cross-sectional view of a lighting device according to one embodiment of the present disclosure.

[0015] [Figure 4] 1 is a schematic cross-sectional view of a lighting device according to one embodiment of the present disclosure.

[0016] [Figure 5] 1 is a schematic perspective view of a backlight device according to one embodiment of the present disclosure.

[0017] [Figure 6A] 1 illustrates a liquid crystal display (LCD) with an edge-lit configuration, according to one embodiment of the present disclosure.

[0018] [Figure 6B] 1 illustrates a liquid crystal display (LCD) with a direct-lit configuration according to one embodiment of the present disclosure.

[0019] [Figure 7] 1 illustrates a liquid crystal display (LCD) with an edge-lit configuration, according to one embodiment of the present disclosure.

[0020] Unless otherwise indicated, the drawings provided herein are intended to illustrate features of embodiments of the present disclosure. These features are believed to be applicable in a wide variety of systems incorporating one or more embodiments of the present disclosure. Thus, the drawings are not intended to include all conventional features known to those skilled in the art that are required to practice the embodiments disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0021] In the following specification and claims, reference will be made to a number of terms that shall be defined to have the following meanings.

[0022] The singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. As used herein, the term "or" is not intended to be exclusive and refers to at least one of the referenced components that are present, and includes combinations of the referenced components that may be present, unless the context clearly dictates otherwise.

[0023] As used herein throughout the specification and claims, language expressing approximating values ​​may be applied to modify any quantitative expression that can be varied to an acceptable degree without resulting in a change in the basic function involved. Thus, values ​​modified by terms such as "about," "substantially," and "approximately" should not be limited to the exact value specified. In at least some instances, language expressing approximating values ​​may correspond to the precision of the instrument measuring the value. Here, and throughout the specification and claims, range limits may be combined and / or interchanged, and unless the context or language dictates otherwise, such ranges are specified and include all subranges contained therein.

[0024] Optionally, "optionally" or "optionally" means that a subsequently described event or circumstance may or may not occur, or that identified material may or may not be present, and the description is meant to include examples where the event or circumstance occurs or such material is present, as well as examples where the event or circumstance does not occur or such material is also absent.

[0025] The brackets in the formula indicate that at least one of the elements is present in the phosphor composition, and any combination of two or more of them may be present. For example, the formula [Ca,Sr,Ba]MgSiO:Eu 2+ , Mn 2+ contains at least one of Ca, Sr, or Ba, or any combination of two or more of Ca, Sr, or Ba. Examples include Ca3MgSi2O8:Eu 2+ , Mn 2+ ;Sr3MgSi2O8:Eu 2+ .Mn 2+ ; or Ba3MgSi2O8:Eu 2+ , Mn 2+Formulas with an activator after a colon (:) indicate that the activator is doped into the phosphor composition. Formulas with two or more activators separated by a comma after the colon (:) indicate that either one or both activators are doped into the phosphor composition. For example, the formula [Ca,Sr,Ba]3MgSi2O8:Eu 2+ , Mn 2+ is [Ca,Sr,Ba]3MgSi2O8:Eu 2+ , [Ca,Sr,Ba]3MgSi2O8:Mn 2+ , or [Ca,Sr,Ba]3MgSi2O8:Eu 2+ and Mn 2+ Includes.

[0026] In one embodiment, an ink composition is provided. The composition includes a binder material and at least one narrow-band-emitting phosphor uniformly dispersed throughout the composition. The narrow-band-emitting phosphor has a D50 particle size of about 0.1 μm to about 15 μm, and is a green-emitting U 6+ Contains phosphor, green emitting Mn 2+ Contains phosphor, Mn 4+ red-emitting phosphors based on complex fluorinated materials activated by

[0027] The ink composition or formulation is a solution and may be used to prepare a conversion film by coating or printing the ink composition, such as by inkjet printing, slot-die coating, or spin coating. In one embodiment, the film may be laminated or printed onto an LED, mini LED, OLED, or micro LED. The conversion film converts the wavelength of a light source, such as a blue LED, to another wavelength.

[0028] A liquid ink formulation may be prepared by combining a binder material, phosphor particles, and optionally a liquid vehicle, hi one embodiment, a liquid varnish is formed.

[0029] The composition includes a narrow-band emitting phosphor. High quality color hues for lighting and displays have been achieved with narrow-band emitting phosphor materials. Phosphors for use in ink formulations include small particle size narrow-band red-emitting phosphors and narrow-band green-emitting phosphors, which improve color conversion. In one embodiment, the narrow-band emitting phosphor includes a combination of a narrow-band red-emitting phosphor and a narrow-band green-emitting phosphor.

[0030] The narrow band emitting phosphor is green emitting U 6+ Contains phosphor, green emitting Mn 2+ Contains phosphor, Mn 4+ and mixtures thereof.

[0031] Green-emitting phosphors absorb radiation in the near-ultraviolet or blue region (wavelength range of about 400 nm to about 470 nm) and emit light in a narrow region with an emission peak centered in the wavelength range of about 510 nm to about 550 nm, particularly about 520 nm to about 535 nm.

[0032] In one embodiment, the narrow band-emitting phosphor is a green-emitting U 6+ Contains phosphor or Mn 2+ It may be a phosphor. Green emitting U 6+ The phosphor contains U in the phosphor compound host. 6+ or may contain the activator ion U 6+ In some embodiments, Mn 2+ , Mn 4+ , Ce 3+ , Sn 2+ , Bi 3+ , Sb 3+ , Cr 3+ , Tb 3+ , Pr 3+ ,EU 3+ ,EU 2+ , Ti 4+ , In + , Tl + , Dy 3+ and Pb 2+ Additional activator ions such as may be present.

[0033] In one embodiment, U 6+ The phosphor contained is (UO2) 2+ Mn 2+ Group and (UO2) 2+ The phosphor contains Mn, which is involved in the solubility in the ink composition. 2+ and (UO2) 2+ The ligands around the group are preferably (UO2). 2+ Examples of compositions include uranyl acetate, uranyl acetylacetonate, ammonium uranyl acetate, sodium magnesium uranyl acetate, uranyl benzoate, magnesium uranyl acetate, uranyl naphthenate, uranyl oxalate, uranyl sulfate, zinc uranyl acetate, and zinc sodium uranyl acetate. 2+ Examples of compounds include ((CH3)4N)MnX3 (where X = Br or Cl); MEA(MnX4)2 (where X = Br or Cl and MEA = ((CH3)4N(C2H5)4N)2NH4); (OPPh3)2MnBr2 (where Ph = phenyl); (OP(NMe2)3)2MnX2 (where X = Cl or Br and Me = methyl); (OPPh(NMe2)2)2MnX2 (where X = Cl or Br, Ph = phenyl and Me = methyl); DPEPOMnX2 (where X = Cl, Br or I and DPEPO = bis[2-(diphenylphosphino)-phenyl]ether-oxide; DBFDPOMnX2 (where X = Cl or Br and DBFDPO = 4,6-bis(diphenylphosphoryl)dibenzofuran); C 11 H 22 N2MnCl4;C4H 10 NMnBr3; and A2MnX4 (where X = Br, Cl, or I, and when X = Br, A = Et4N, Pr4N, BzBu3N, PhMe3N, Ph4P, MePh3P, EtPh3P, BzMe3N, K(Crypto-222), PrMe3N, MePPh3Br, PrMe3NBr, P14, PP14, CH 10 N2Br, C 10 H 16 N, Btz, BnPPh3, C nmim (n = 1, 2, 3), K (dibenzo-18-crown-6), BnMe3N, BnEt3N, Bn(C5H5N), C6H 14 N, C5H5N, C4H 10 N, and when X=Cl, A=EtN, PrN, BzBuN, PhMeN, PhP, EtPhP, BzMeN, (PPh)N, Btz, BnPPh, C n mim (n = 1, 2, 3), K (dibenzo-18-crown-6), CNH 10 When X=1, A=EtN, PrN, PhMeN, BzMeN, C4H 10 N, where Bz=benzoyl, Bn=benzyl, Pr=propyl, Me=methyl, Et=ethyl, Bu=butyl, Btz=benzothiazole, Cnmim=n-alkyl-methylimidazolium and Ph=phenyl.

[0034] In one embodiment, the green U 6+ The phosphor contained therein is, for example, [Ba,Sr,Ca,Mg][B,Al,Ga,In][P,V]O5:U 6+ ;Ba 2-x [Sr,Ca,Mg] x [P 1-y ,V y ]2O7:U 6+ (In this case, if 0≦x≦2, 0≦y≦1, and y=0, then x≠0);[Ba,Sr,Ca,Mg]4[P,V]2O9:U 6+ ;[Ba,Sr,Ca,Mg]3[P,V]4O 13 :U 6+ ;[Ba,Sr,Ca,Mg]4[B,Al,Ga,In][P,V]O8:U 6+ ;[Ba,Sr,Ca,Mg]6[B,Al,Ga,In]5[P,V]5O 26 :U 6+ ;Ba 3-x [Sr,Ca,Mg]x[P 1-y ,V y ]2O8:U 6+ ;(In this case, if 0≦x≦3, 0≦y≦1, and y=0, then x≠0);A2[Ba,Sr,Ca,Mg][P,V]2O7:U 6+;A[Ba,Sr,Ca,Mg][P,V]O4:U 6+ ;[Ba,Sr,Ca,Mg][P,V]2O6:U 6+ ;[Ba,Sr,Ca,Mg]3[B,Al,Ga,In][P,V]O7:U 6+ ; and [Ba,Sr,Ca,Mg] 10 [P,V]O 25 :U 6+ Such U 6+ Doped phosphate-vanadate phosphors, such as [Ba,Sr,Ca,Mg]X2:U 6+ ;A[Ba,Sr,Ca,Mg]X3:U 6+ ; and [Ba,Sr,Ca,Mg]2X4:U 6+ Such U 6+ Doped halide phosphors, such as [Ba,Sr,Ca,Mg]2[B,Al,Ga,In]O3X:U 6+ ;[Ba,Sr,Ca,Mg]2[P,V]O4X:U 6+ ;Ba 5-n [Sr,Ca,Mg] n [P 1-m ,V m ]3O 12 X:U 6+ (In this case, 0≦n≦5, 0≦m≦1, and when m=0, n≠0 and X=F);[Ba,Sr,Ca,Mg]5[B,Al,Ga,In]3O9X:U 6+ and [Ba,Sr,Ca,Mg]3[Si,Ge]O4X:U 6+ Such as U 6+ Doped oxyhalide phosphors, such as [Ba,Sr,Ca,Mg]2[Si,Ge]O4:U 6+ ;[Ba,Sr,Ca,Mg]3[Si,Ge]O5:U 6+ ;[Ba,Sr,Ca,Mg]3[Si,Ge]2O7:U 6+ ;[Ba,Sr,Ca,Mg][Si,Ge]O3:U 6+ ;[Ba,Sr,Ca,Mg][B,Al,Ga,In]2[Si,Ge]2O8:U 6+ ;[Ba,Sr,Ca,Mg]2[B,Al,Ga,In]2[Si,Ge]O7:U 6+; [Ba, Sr, Ca, Mg]3[B, Al, Ga, In]6[Si, Ge]2O 16 : U 6+ ; [Ba, Sr, Ca, Mg]3[B, Al, Ga, In]2[Si, Ge]O8: U 6+ ; [Ba, Sr, Ca, Mg] 11 [B, Al, Ga, In]2[Si, Ge]4O 22 : U 6+ ; [Ba, Sr, Ca, Mg]3[B, Al, Ga, In] 10 [Si, Ge]O 20 : U 6+ ; and [Ba, Sr, Ca, Mg] 6.5 [B, Al, Ga, In] 11 [Si, Ge]5O 33 : U 6+ such as U 6+ doped silica-germanate phosphors, and Ba,Sr,Ca,Mg][B,Al,Ga,In]4O7: U 6+ ; [Ba, Sr, Ca, Mg]3[B, Al, Ga, In]2O6: U 6+ ; [Ba, Sr, Ca, Mg][B, Al, Ga, In]6O 10 : U 6+ ; [Ba, Sr, Ca, Mg][B, Al, Ga, In]2O4: U 6+ ; [Ba, Sr, Ca, Mg]4[B, Al, Ga, In]2O7: U 6+ ; [Ba, Sr, Ca, Mg] 12 [B, Al, Ga, In] 14 O 33 : U 6+ ; A[Ba, Sr, Ca, Mg][B, Al, Ga, In]O3: U 6+ ; [Ba, Sr, Ca, Mg]O: U 6+ ; [Ba, Sr, Ca, Mg]2[B, Al, Ga, In, Sc]2O5: U 6+ ; A[Ba, Sr, Ca, Mg]2[B, Al, Ga, In]5O 10 : U 6+ ; and A[Ba, Sr, Ca, Mg]4[B, Al, Ga, In]3O9: U 6+ such as U 6+It may also be a doped alkali metal oxide phosphor, where A is Li, Na, K, Rb, Cs or a combination thereof, and X is F, Cl, Br or a combination thereof.

[0035] In another embodiment, U 6+ The phosphors contained therein are A2USiO6 (where A is Cs, Rb, or a combination thereof); A2(UO2)Si2O6 (where A is Cs, Rb, or a combination thereof); A2MnU3O 11 (where A is K, Rb, or a combination thereof); K4MU3O 12 (where M is Ca, Sr, or a combination thereof); M3UO6 (where M is Ca, Sr, or a combination thereof); Na 5-x M x UO6 (where M is Ca, Sr, Nd, or a combination thereof, and 0≦x≦3); LUO4 (where L is Ca, Mn, Fe, or a combination thereof); Na3MU6F 30 (where M is Al, Ga, Ti, V, Cr, Fe, or a combination thereof); Ba2MUO6 (where M is Cu, Ni, Zn, or a combination thereof); Na3A3(UO2)3(Si2O7)2-2H2O (where A is K, Rb, or a combination thereof); A3(U2O4)Ge2O7 (where A is Rb, Cs, or a combination thereof); Ba2(UO2)(TO4)2 (where T is P, As, or a combination thereof); K8U7O 24 ;Na4UO5;NiU2O6;K2UO4;Li 3.2 Mn 1.8 U6O 22 ;K8(K5F)U6Si8O40;Na9F2(UO2)3(Si2O7)2;Cs2Mn3U6O 22 ;BaK4U3O 12 ;Ba2Na 0.38 U 1.17 O6;Na 3.13 Mg 1.43 U6F 30 ;Na 2.5 Mn 1.75 U6F 30 ;K8U7O24 KUO3Cl; A(UO2)OCl (where A is Rb, Cs, Na, or a combination thereof); Na6Rb4(UO2)4Si 12 O 33 ;Cs2K(UO2)2Si4O 12 ;Cs8U(UO2)3(Ge3O9)3-3H2O;Cs2K(UO)2Si4O 12 ;Cs3(UO2)2(PO4)O2;Cs2(UO2)2(PO4)2;Cs2UO2Cl4;Ba3(UO2)2(HPO4)2(PO4)2;Ba(UO2)F(PO4);Na7(UO2)3(UO)2Si4O 16 ;CaO:U;SrMoO4:U;BaSO4:U;MgO:U;Li4MgWO6:U;Li4WO5:U;Li6Mg5Sb2O 13 :U;Li3NbO4:U;Li3SbO4:U;Li2SnO3:U;LiScO2:U;LiNbO3:U;LiSbO3:U;NaSbO3:U;Y6WO 12 :U; [Ca,Cd,Mg]WO4:U (where M is Ca, Sr, Cd, Mg, or a combination thereof); Li2WO4:U; Li3PO4:U; Ca2MgWO6:U; SrZnP2O7:U; R2TeO6:U (where R is Y, La, Gd, Lu, or a combination thereof); M3TeO6:U (where M is Mg, Ca, Sr, or a combination thereof); Ba2TeO5:U; and combinations thereof.

[0036] In another embodiment, U 6+ The contained phosphor is (A 2+ y M 1+ 2-2y )(UO2)2(ZO4)2-xH2O, where M is NH4, HO, Na, K, or a combination thereof; A is Fe, Co, Cu, Zn, Mg, Ca, Sr, Ba, Pb, or a combination thereof; Z is As, P, V, or a combination thereof; and 0≦y≦1 and 0≦x≦16; M 1+ (UO2)(SO4)(OH,F)-xH2O, where M is K, Na, or a combination thereof; 0≦x≦2; (A 2+2y M 1+ 4-4y )(UO2)(CO3)3-xH2O, (where M is Na, K, or a combination thereof; A is Mg, Ca, or a combination thereof; 0≦y≦1 and 0≦x≦18); (A 2+ )(UO2)4(ZO4)2(OH,F)4-xH2O (where A is Ca, Pb, or a combination thereof; Z is As, P, or a combination thereof; and 0≦x≦7); (A 2+ y M 1+ 2-2y )(UO2)6O4(OH,F)6-xH2O (where A is Ca, Ba, or a combination thereof, M is K, 0≦y≦1 and 0≦x≦8); (M 1+ )2(UO2)(SO4)2-xH2O (where M is NH4, Na, or a combination thereof; and 0≦x≦3); Al(UO2)2(ZO4)2(OH,F)-xH2O (where Z is As, V, P, or a combination thereof; and 0≦x≦11); (L 2+ 2y M 1+ 4-4y )(UO2)6(SO4)3(OH, F) 10 -xH2O (where L is Co, Ni, or a combination thereof; M is Na; 0≦y≦1 and 0≦x≦16); (A 2+ )2(UO2)3O2(PO4)2-xH2O (where A is Ca, Pb, or a combination thereof; and 0≦x≦7); (A 2+ y M 1+ 2-2y)(UO2)3(SeO3)2O2-xH2O (where M is Ba, Na, or a combination thereof; A is H3O, and 0≦x≦4 and 0≦y≦1); UO3-xH2O (where 0≦x≦2); UO4-xH2O (where 0≦x≦2); UO2CO3-xH2O (where 0≦x≦2); U(UO2)3(PO4)2(OH,F)6-xH2O (where 0≦x≦4); Ca(UO2)(CO3)2-xH2O (where 0≦x≦5); HAl(UO2)4(AsO4)4-xH2O (where 0≦x≦40); H 0.5 Al 0.5(UO2)2(PO4)2-xH2O (where 0≦x≦8); Cu(UO2)2(SO4)2(OH,F)2-xH2O (where 0≦x≦8); K2Ca3[(UO2)(CO3)3]2-xH2O (where 0≦x≦7); Na7(UO2)(SO4)4(SO3OH)-xH2O (where 0≦x≦3); Ca2Ba4[(UO2)3O2(PO4)2]3-xH2O (where 0≦x≦16); NaAl (UO2)2(SO4)4-xH2O (where 0≦x≦18); Na2Mg(UO2)2(SO4)4-xH2O (where 0≦x≦18); Na7(UO2)(SO4)4Cl-xH2O (where 0≦x≦2); [K,Na](UO2)(SiO3OH)-xH2O (where 0≦x≦1.5); Ca(UO2)2[SiO3[OH,F]]2-xH2O (where 0≦x≦5); Ca(UO2)3(MoO 4)3(OH,F)2-xH2O (where 0≦x≦11); Al2(UO2)(PO4)2[OH,F]2-xH2O (where 0≦x≦8); Al3(UO2)(PO4)3[OH,F]2-xH2O (where 0≦x≦13); Al(UO2)3(PO4)2[OH,F]3-xH2O (where 0≦x≦5.5); Al2(UO2)3(PO4)2[OH,F]6-xH2O (where 0≦x≦10); C a(UO2)4(SO4)2[OH,F]6-xH2O (where 0≦x≦6); K(UO2)2(SO4)[OH,F]3-xH2O (where 0≦x≦1); H2Pb3(UO2)6O4(PO4)4-xH2O (where 0≦x≦12); Na4(UO2)(SO4)3-xH2O (where 0≦x≦3); Ca(UO2)3(CO3)2O2-xH2O (where 0≦x≦6); Ca[(UO2)2SiO 12 [OH,F]2]-xH2O (where 0≦x≦3); (UO2)3(SeO3)2[OH,F]2-xH2O (where 0≦x≦5); (U)2(UO2)4O6[OH,F]4-xH2O (where 0≦x≦9); (UO2)8(SO4)[OH,F] 14-xH2O (where 0≦x≦13);(UO2)6(SO4)[OH,F] 10 -xH2O (where 0≦x≦5); Y2U4(CO3)3O 12 -xH2O (where 0≦x≦14.5); Mg(UO2)2(SO4)O2-xH2O (where 0≦x≦3.5); Pb[(UO2)3O3[OH,F]2]-xH2O (where 0≦x≦3); Pb 1.5 [(UO2) 10 )O6[OH,F] 11 ]-xH2O (where 0≦x≦11); Na5(UO2)(SO4)3(SO3OH)-xH2O (where 0≦x≦1); Ca(UO2)2Si6O 15 -xH2O (where 0≦x≦5); PbU7O 22 -xH2O (where 0≦x≦12); Ca2Cu(UO2)(CO3)4-xH2O (where 0≦x≦6); (H3O)3KCa(UO2)7O4(PO4)4-xH2O (where 0≦x≦8); (H3O)4Ca2(UO2)2(PO4)4-xH2O (where 0≦x≦5); Ca3Mg3(UO2)2(CO3)6[OH,F]4-xH2O (where 0≦x≦18); HAl(UO2)PO4[OH,F]3-xH2O (where 0≦x≦4); [(UO2)8O2[OH,F] 12 ]-xH2O (where 0≦x≦12); NaCa3(UO2)(SO4)(CO3)3F-xH2O (where 0≦x≦10); Ca(UO2)6(CO3)5[OH,F]4-xH2O (where 0≦x≦6); (UO2)2(SO4)2-xH2O (where 0≦x≦5); (H3O)2Mg(UO2)2(SiO4)2-xH2O (where where 0≦x≦4;(UO2)2SiO4-xH2O where 0≦x≦2;[Na,K](UO2)SiO3[OH,F]-xH2O where 0≦x≦1.5;(H3O)(UO2)(AsO4)-xH2O where 0≦x≦3;(UO2)6(SO4)O2[OH,F]6-xH2O where 0≦x≦14;Al 1-0.5(UO2)(PO4)2-xH2O(F≦1) (where 0≦x≦21); [Mg, Ca]4(UO2)4(Si2O5) 5.5 [OH,F]5-xH2O (where 0≦x≦13); Cu(UO2)(OH,F)4; [K ,Ba,Ca]2(UO2)2Si5O 13 -xH2O (where 0≦x≦1); K2Ca(UO2)7(PO4)4[OH,F]6-xH2O (where 0≦x≦6); Zn2(UO2)6(SO4)3[OH,F] 10 -xH2O (where 0≦x≦16); CaZn 11 (UO2)(CO3)3[OH,F]2O-xH2O (where 0≦x≦4); AxMFy:U 6+ , (where A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6, or 7) and combinations thereof.

[0037] In another embodiment, a green U 6+ The phosphor contained in the 1-a-b Sr a Ca b ] x [Mg,Zn] y (UO2) z ([P,V]O4) 2(x+y+z) / 3 (where 0≦a≦1, 0≦b≦0.5, 0.75≦x≦1.25, 0.75≦y≦1.25, 0.75≦z≦1.25); and [Ba 1-a-b Sr a Ca b ] p (UO2) q [P,V] r O (2p+2q+5r) / 2 (In this case, 0≦a≦1, 0≦b≦1, 2.5≦p≦3.5, 1.75≦q≦2.25, 3.5≦r≦4.5).

[0038] For example, BaMgUO2(PO4)2、BaZnUO2(PO4)2、Ba3(PO4)2(UO2)2P2O7、Ba2Sr(PO4)2(UO2)2P2O7、BaSr2(PO4 )2(UO2)2P2O7、Sr3(PO4)2(UO2)2P2O7、Ca3(PO4)2(UO2)2P2O7、BaMg2(PO4)2(UO2)2P2O7、Sr4AlPO8:U 6+ 、Ba4AlPO8:U 6+ 、Ca4AlPO8:U 6+ 、SrBa3AlPO8:U 6+ 、Sr2Ba2AlPO8:U 6+ 、Sr3BaAlPO8:U 6+ 、Ba6Al5P5O 26 :IN 6+ 、Ba6Ga5P5O 26 :IN 6+ 、Ba6In5P5O 26 :IN 6+ 、Ba6Al5V5O 26 :IN 6+ 、Ba6Ga5V5O 26 :IN 6+ 、Ba6In5V5O 26 :IN 6+ 、SrBPO5:U 6+ 、BaBPO5:U 6+ 、BaBP5:U 6+ 、MgAlPO5:U 6+ 、Ca2V2O7:U 6+ 、Ba2V2O7:U 6+ 、CaMgV2O7:U 6+ 、SrMgV2O7:U 6+ 、Sr4P2O9:U 6+ 、Ca4P2O9:U 6+ 、Ba3P4O 13 :IN 6+ 、Sr3P4O 13 :IN 6+ 、Ca 10 P6O 25 :IN 6+ 、Wed 10 P6O 25 :IN 6+ 、Mg3P2O8:U 6+ 、Ca3V2O8:U 6+ 、Ba3V2O8:U 6+、BaMg2V2O8:U 6+ 、Cs2CaP2O7:U 6+ 、Cs2SrP2O7:U 6+ 、Cs2CaV2O7:U 6+ 、Cs2SrV2O7:U 6+ 、Li2BaP2O7:U 6+ 、NaCaPO4:U 6+ 、LiSrPO4:U 6+ 、NaSrPO4:U 6+ 、KSrPO4:U 6+ 、KBaVO4:U 6+ 、KSrVO4:U 6+ 、KCaVO4:U 6+ 、BaP2O6:U 6+ 、CaV2O6:U 6+ 、Ba3BPO7:U 6+ 、Sr3BPO7:U 6+ 、CaF2:U 6+ 、BaF2:U 6+ 、BaFCl:U 6+ 、BaFBr:U 6+ 、LiBaF3:U 6+ 、BaMgF4:U 6+ 、Ca2BO3Cl:U 6+ 、Ca2PO4Cl:U 6+ 、Ca5(PO4)3Cl:U 6+ 、Ba5V3O 12 Cl:U 6+ 、Sr5(BO3)3Cl:U 6+ 、Sr3GeO4F:U 6+ 、Ca2SiO4:U 6+ 、Mg2SiO4:U 6+ 、Ca2GeO4:U 6+ 、Sr2GeO4:U 6+ 、Sr3SiO5:U 6+ 、Ca3SiO5:U 6+ 、Ca3Si2O7:U 6+ 、MgSiO3:U 6+ 、BaGeO3:U 6+ 、BaAl2Si2O8:U 6+ 、SrAl2Si2O8:U 6+ 、CaAl2Si2O8:U 6+ 、BaGa2Si2O8:U 6+<h2 style=";text-align:left;direction:ltr">、CaAl2SiO7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ba3B6Si2O<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> Ca<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> B2Si4O<h2 style=";text-align:left;direction:ltr"> 22 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Sr3Al<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> SiO<h2 style=";text-align:left;direction:ltr"> 20 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> Ba<h2 style=";text-align:left;direction:ltr"> 6.5 <h2 style=";text-align:left;direction:ltr"> Al<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si5O<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、CaAl2B2O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrAl2B2O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、BaAl2B2O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、CaB4O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrB4O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrAl3BO7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、CaAlB3O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ca3B2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Sr3B2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ba3B2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Sr3Al2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ca3Al2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ba2SrAl2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、BaSr2Al2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ba2SrB2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、BaSr2B2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ca3In2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Sr3In2O6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrB6O<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrAl2O4:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrAlBO4:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Sr4Al2O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、Ca4Al2O7:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> Sr<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> Ga6Sc4O<h2 style=";text-align:left;direction:ltr"> 25 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> Ca<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> Al<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> O<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、LiSrBO3:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、LiCaBO3:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、SrO:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、LiBa2B5O<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> :U<h2 style=";text-align:left;direction:ltr"> 6+and LiSr4B3O9:U 6+、Na2(UO2)2(AsO4)2-5H2O、K2(UO2)2(AsO4)2-6H2O、Ba(UO2)2(AsO4)2-(10-12)H2O、Co(UO2)2(AsO4)2-8H2O、Cu(UO2)2(AsO4)2-8H2O、Cu(UO2)2(AsO4)2-12H2O、Zn(UO2)2(AsO4)2-10H2O、Mg(UO2)2(AsO4)2-(4-8)H2O、Mg(UO2)2(AsO4)2-(10-12)H2O、Ca(UO2)2(AsO4)2-8H2O、Ca(UO2)2(AsO4)2-10H2O、Ba(UO2)2(AsO4)2-8H2O、Ba(UO2)2(AsO4)2-(10-12)H2O、(NH4,H3O)2(UO2)2(AsO4,PO4)2-6H2O、(NH4)2(UO2)2(PO4)2-6H2O、(H3O)2(UO2)2(PO4)2-6H2O、Na2(UO2)2(PO4)2-(6-8)H2O、Na2(UO2)2(PO4)2-(1 0-16)H2O、K2(UO2)2(PO4)2-6H2O、Fe(UO2)2(PO4)2-8H2O、Mg(UO2)2(PO4)2-8H2O、Mg(UO2)2(PO4)2-10H2O、Ca(UO2)2(PO4) )2-(2-6)H2O、Ca(UO2)2(PO4)2-11H2O、Ba(UO2)2(PO4)2-6H2O、Ba(UO2)2(PO4)2-8H2O、Ba(UO2)2(PO4)2-12H2O、Pb(UO2)2 (PO4)2-4H2O、Na2(UO2)2(VO4)2-6H2O、K2(UO2)2(VO4)2-(1-3)H2O、Ca(UO2)2(VO4)2-3H2O、K(UO2)(SO4)(OH)-H2O、Na(UO2 )(SO4)(OH)-2H2O, K4(UO2)(CO3)3, Na4(UO2)(CO3)3, Na2Ca(UO2)(CO3)3-6H2O, Mg2(UO2)(CO3)3-18H2O, CaMg(UO2)(CO3)3-12H2O, Ca2(UO2)(CO3)3-11H2O, Ca(UO2)4(AsO4)2(OH)4-6H2O, Pb(UO2)4(PO4)2(OH)4-7H2O, K2(UO2)6O4(OH)6-7H2O, Ca (UO2)6O4(OH)6-8H2O、Ba(UO2)6O4(OH)6-8H2O、(NH4)2(UO2)(SO4)2-2H2O、Na2(UO2)(SO4)2-3H2O、Al(UO2)2(AsO4)2(F,O H)-6.5H2O、Al(UO2)2(VO4)2(OH)-8H2O、Al(UO2)2(VO4)2(OH)-11H2O、Al(UO2)2(PO4)2(OH)-8H2O、Co2(UO2)6(SO4)3(OH), 10 -16H2O、Ni2(UO2)6(SO4)3(OH) 10 -16H2O、Na4(UO2)6(SO4)3(OH) 10<h2 style=";text-align:left;direction:ltr">-4H2O、Pb2(UO2)3O2(PO4)2-5H2O、Ca2(UO2)3O2(PO4)2-7H2O、Ba(UO2)3(SeO3)2O2-3H2O、Na(H3O)(UO2)3(SeO3)2O2-4H2O、K2SiF6:U<h2 style=";text-align:left;direction:ltr"> 6+ <h2 style=";text-align:left;direction:ltr"> 、UO3-0.75H2O、UO3-H2O、UO3-2H2O、UO4-2H2O、UO4-4H2O、UO2CO3、UO2CO3-H2O、(UO2)(CO3)-2H2O、U(UO2)3(PO4)2( OH)6-2H2O、U(UO2)3(PO4)2(OH)6-4H2O、Ca(UO2)(CO3)2-3H2O、Ca(UO2)(CO3)2-5H2O、HAl(UO2)4(AsO4)4-40H2O、H<h2 style=";text-align:left;direction:ltr"> 0.5 <h2 style=";text-align:left;direction:ltr"> Al<h2 style=";text-align:left;direction:ltr"> 0.5 <h2 style=";text-align:left;direction:ltr"> (UO2)2(PO4)2-8H2O、Cu(UO2)2(SO4)2(OH)2-8H2O、K2Ca3[(UO2)(CO3)3]2-7H2O、Na7(UO2)(SO4)4(SO3OH)-3H2O、Ca2Ba4[(UO2)3O2(PO4)2]3-16H2O、N aAl(UO2)2(SO4)4-18H2O、Na2Mg(UO2)2(SO4)4-18H2O、Na7(UO2)(SO4)4Cl-2H2O、[K,Na](UO2)(SiO3OH)-1.5H2O、Ca(UO2)2[SiO3(OH)]2-5H2O、Ca(UO2)3(MoO4)3(OH)2-11H2O、Al2(UO2)(PO4)2(OH)2-8H2O、Al3(UO2)(PO4)3(OH)2-13H2O、Al(UO2)3(PO4)2(OH)3-5.5H2O、Al2(UO2)3(PO4)2(OH)6-10H2O、C a(UO2)4(SO4)2(OH)6-6H2O、K(UO2)2(SO4)(OH)3-H2O、H2Pb3(UO2)6O4(PO4) )4-12H2O、Na4(UO2)(SO4)3-3H2O、Ca(UO2)3(CO3)2O2-6H2O、Ca[(UO2)2Si5O<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> (OH)2]-3H2O、(UO2)3(SeO3)2(OH)2-5H2O、(U)2(UO2)4O6(OH)4-9H2O、(UO2)8(SO4)(OH)<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> -3H2O、(UO2)6(SO4)(OH)<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> -5H2O、Y2U4(CO3)3O12 -14.5H2O、Mg(UO2)2(SO4)O2-3.5H2O、Pb[(UO2)3O3(OH)2]-3H2O、Pb 1.5 [(UO2) 10 )O6(OH) 11 ]-11H2O、Na5(UO2)(SO4)3(SO3OH)-H2O、Ca(UO2)2Si6O 15 -5H2O、PbU7O 22 -12H2O、Ca2Cu(UO2)(CO3)4-6H2O、(H3O)3KCa(UO2)7O4(PO4)4-8H2O、(H3O)4Ca2(UO2)2(PO4)4-5H2O、Ca3Mg3(UO2)2(CO3)6(OH)4-8H2O;、HAl(UO2)PO4(OH)3-4H2O、[(UO2)8O2(OH) 12 ]-12H2O、NaCa3(UO2)(SO4)(CO3)3F-10H2O、Ca(UO2)6(CO3)5(OH)4-6H2O、(UO2)2(SO4)2-5H2O、(H3O)2Mg(UO2)2(SiO4)2-4H2O、(UO2)2SiO4-2H2O、[Na,K](UO2)SiO3(OH)-1.5H2O、(H3O)(UO2)(AsO4)-3H2O、(UO2)6(SO4)O2(OH)6-14H2O、Al 0.5-1 (UO2)4(PO4)4-(20-21)H2O(F<1)、[Mg,Ca]4(UO2)4(Si2O5) 5.5 (OH)5-13H2O、Cu(UO2)(OH)4、[K,Ba,Ca]2(UO2)2Si5O 13 -H2O、K2Ca(UO2)7(PO4)4(OH)6-6H2O、Zn2(UO2)6(SO4)3(OH) 10 -16H2O、CaZn 11 (UO2)(CO3)3(OH) 2O -4H2O、CsUSiO6、RbUSiO6、Cs2(UO2)Si2O6、Rb2(UO2)Si2O6K2MnU3O 11 、Rb2MnU3O 11 K4CaU3O 12 、K4SrU3O 12 Ca3UO6、Sr3UO6Na3Ca 1.5 UO6、Na4.5 Nd 0.5 UO6CaUO4, MnUO4, FeUO4Na3GaU6F 30 , Na3AlU6F 30 , Na3TiU6F 30 , Na3VU6F 30 , Na3CrU6F 30 , and Na3FeU6F 30 , Ba2NiUO6, Ba2CuUO6, Na3K3(UO2)3(Si2O7)-2H2O, Na3Rb3(UO2)3(Si2O7)-2H2O Rb3(U2O4)Ge2O7, Cs3(U2O4)Ge2O7Ba2(UO2)(PO4)2, Ba2(UO2)(AsO4)2A(UO2)OCl, CaWO4:U, CdWO4:U, MgWO4:U, Y2TeO6:U and Gd2TeO6:U, Ca3TeO6:U, Sr3TeO6:U, Mg3TeO6:U, K8(K5F)U6Si8O 40 , SrZnP2O7:U, KUO3Cl, CsUO3Cl, NaUO3Cl, RbUO3Cl or combinations thereof.

[0039] In one embodiment, a green U 6+ The phosphor contained is of the formula γ-Ba2UO2(PO4)2, [Ba,Zn,Mg](UO2)2(PO4)2, Ba6Al5P5O 26 :U 6+ , Ba(UO2)P2O7, and Ba3(UO2)2P2O7(PO4)2 phosphors. Suitable narrow-band green-emitting phosphors and methods for making the same are described in U.S. Patent Application Publication Nos. 2019 / 0088827, 2019 / 0280165, and 2020 / 0028033, the entire contents of each of which are incorporated herein by reference.

[0040] In one embodiment, the U 6+The phosphor-containing material may be produced by firing the precursor mixture under an oxidizing atmosphere. Non-limiting examples of suitable precursors include appropriate metal oxides, hydroxides, alkoxides, carbonates, nitrates, aluminates, silicates, citrates, oxalates, carboxylates, tartrates, stearates, nitrites, peroxides, phosphates, pyrophosphates, and combinations thereof. Materials suitable for use as precursors include BaCl2·2H2O, BaCO3, BaHPO4, Ba3(PO4)2, Ba2P2O7, Ba2Zn(PO4)2, BaZnP2O7, Ba(OH)2, Ba(C2O4), Ba(C2H3O2)2, Ba3(C6H5O7)2, Ba(NO3)2, Eu2O3, Mg(C2O4), Mg(C2H3O2)2, Mg(C6H6O7), MgCO3, MgO, Mg(OH)2, Mg3(PO4)2, Mg2P2O7, Mg2Ba(PO4)2, MgHPO4, Mg(NO3)2, NH4VO3, (NH4)2HPO4, NH4 Examples of suitable phosphate ions include, but are not limited to, MgPO4, Zn(C2O4), Zn(C2H3O2)2, Zn3(C6H5O7)2, ZnCO3, Zn(OH)2, Zn3(PO4)2, Zn2P2O7, Zn2Ba(PO4)2, ZnHPO4, Zn(NO3)2, NH4ZnPO4, UO2, UO2(NO3)2, UO2(NO3)2·6H2O, (UO2)2P2O7, (UO2)3(PO4)2, NH4(UO2)PO4, UO2CO3, UO2(C2H3O2)2, UO2(C2O4), H(UO2)PO4, UO2(OH)2, and ZnUO2(C2H3O2)4. For example, the exemplary phosphor phase γ-Ba2UO2(PO4)2 may be produced by mixing appropriate amounts of BaHPO4 and UO2 with an appropriate amount of (NH4)2HPO4, followed by firing the mixture under an air atmosphere. In another example, Ba3(UO2)2(PO7)(PO4)2 may be produced by mixing appropriate amounts of BaCl2·2H2O and UO2(NO3)2·6H2O with an appropriate amount of (NH4)2HPO4, followed by firing the mixture under an air atmosphere. The precursors may be present in solid form or in solution. Non-limiting examples of solvents include water, ethanol, acetone, and isopropanol, the suitability of which depends primarily on the solubility of the precursor in the solvent.After firing, the phosphor may be crushed to break up any agglomerates that may have formed during the firing procedure.

[0041] The starting material mixture for producing the phosphor also includes one or more low-melting flux materials, such as boric acid, borate compounds such as lithium tetraborate, alkali phosphates, and combinations thereof. Non-limiting examples include LiPO, NaPO, NaBO-H, LiBO, KPO, NaPO, HBO, and BO. The flux can reduce the firing temperature and / or firing time of the phosphor. If a flux is used, it may be desirable to wash the final phosphor product with a suitable solvent to remove any residual soluble impurities that may be derived from the flux.

[0042] Calcination of the sample is generally carried out in air, which is necessary to obtain the highest oxidation state of uranium (U 6+ ), but may also be fired in O or other oxidizing atmospheres, including O or other oxidizing atmospheres, at oxygen partial pressures above 1 atmosphere, at about 900°C to about 1300°C, particularly about 1000°C to about 1200°C, for a time sufficient to convert the mixture to the phosphor. The firing time required may range from about 1 to about 20 hours, depending on the amount of mixture being fired, the degree of contact between the solids and the atmospheric gas, and the degree of mixing while the mixture is fired or heated. The mixture rapidly reaches and maintains the final temperature. Alternatively, the mixture may be heated to the final temperature at a slower rate, for example, about 2°C / min to about 200°C / min.

[0043] In one embodiment, the narrow band emitting phosphor is Mn 4+The red-emitting phosphor may be based on a complex fluorinated material activated by a method such as those described in U.S. Patent No. 7,497,973, U.S. Patent No. 7,648,649, U.S. Patent No. 8,906,724, U.S. Patent No. 8,252,613, U.S. Patent No. 9,698,314, U.S. Patent Application No. 2016 / 0244663, U.S. Patent Application Publication No. 2018 / 0163126, and U.S. Patent Application Publication No. 2020 / 0369956, the entire contents of each of which are incorporated herein by reference.

[0044] Suitable red-emitting phosphors include those represented by Formula I A x (MF y ):Mn +4( I) wherein A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; and x is (MF y ) is the absolute value of the charge of the ion; and y is 5, 6, or 7.

[0045] In one embodiment, the red-emitting phosphor is, for example, K2SiF6:Mn 4+ The red-emitting phosphor may be a manganese-doped potassium fluorosilicate (PFS), such as Na2SiF6:Mn. PFS has a narrow-band emission with multiple peaks having an average full width at half maximum (FWHM) of less than 4 nm. In another embodiment, the red-emitting phosphor is Na2SiF6:Mn 4+ (SFS) may also be used.

[0046] Examples of red-emitting phosphors of Formula I include K2(SiF6):Mn 4+ , K2(TiF6):Mn 4+ , K2(SnF6):Mn 4+ , Cs2(TiF6):Mn 4+ , Rb2(TiF6):Mn 4+ , Cs2(SiF6):Mn 4+, Rb2(SiF6):Mn 4+ , Na2(TiF6):Mn 4+ , Na2(SiF6):Mn 4+ , Na2(ZrF6):Mn 4+ , K3(ZrF7):Mn 4+ , K3(BiF7):Mn 4+ , K3(YF7):Mn 4+ , K3(LaF7):Mn 4+ , K3(GdF7):Mn 4+ , K3(NbF7):Mn 4+ , K3(TaF7):Mn 4+ These include, but are not limited to:

[0047] In one embodiment, the red-emitting phosphor may be further processed, such as by annealing, washing, roasting, or any combination of these treatments. Post-treatment processes for red-emitting phosphors are described in U.S. Patent No. 8,906,724, U.S. Patent No. 8,252,613, U.S. Patent No. 9,698,314, U.S. Patent Application Publication No. 2016 / 0244663, U.S. Patent Application Publication No. 2018 / 0163126, and U.S. Patent Application Publication No. 2020 / 0369956, the entire contents of each of which are incorporated herein by reference. In one embodiment, the red-emitting phosphor may be annealed, or may be processed with multiple washing treatments and roasted.

[0048] The amount of activator Mn (referred to as Mn%) incorporated into the red-emitting phosphor improves color conversion. Increasing the amount of Mn% incorporated improves color conversion by increasing the intensity of the red emission, maximizing absorption of the exciting blue light, and reducing the amount of unconverted blue light or bleed-through of blue light from the blue LED.

[0049] In one embodiment, the red-emitting phosphor has a Mn loading or Mn % of at least 1 wt %. In another embodiment, the red-emitting phosphor has a Mn loading or Mn % of at least 1.5 wt %. In another embodiment, the red-emitting phosphor has a Mn loading or Mn % of at least 2 wt %. In another embodiment, the red-emitting phosphor has a Mn % of at least 3 wt %. In another embodiment, the Mn % is greater than 3.0 wt %. In another embodiment, the Mn content in the red-emitting phosphor is from about 1 wt % to about 4 wt %.

[0050] In one embodiment, the narrow band-emitting phosphor has a particle size in the range of about 0.1 μm to about 15 μm. In another embodiment, the narrow band-emitting phosphor has a particle size in the range of about 0.1 μm to about 10 μm. In another embodiment, the narrow band-emitting phosphor has a particle size distribution with a D50 of less than 15 μm, particularly a D50 of less than 10 μm, particularly a D50 of less than 5 μm, or a D50 of less than 3 μm, or a D50 of less than 2 μm, or a D50 of less than 1 μm. In another embodiment, the particle size distribution D50 may be in the range of about 0.1 μm to about 5 μm. In another embodiment, the D50 particle size may be in the range of about 0.1 μm to about 3 μm. In another embodiment, the D50 particle size may be in the range of about 0.1 μm to about 1 μm. In another embodiment, the D50 particle size may be in the range of about 1 μm to about 5 μm. D50 (D 50 D90 or D 90 is the particle size of the volume distribution that is larger than the particle size of 90% of the particles in the distribution. D10 or D 10 is the particle size of a volume distribution that is larger than the size of 10% of the particles in the distribution. Phosphor particle size is conveniently measured by laser diffraction or optical microscopy, and commercially available software can generate particle size distributions and spans. Span is a measure of the width of the particle size distribution curve for particulate materials or powders, and is given by the formula:

number

[0051] The narrow-band emitting phosphor may be in particulate form. The phosphor may be conventionally powdered or milled to a small particle size having a D50 particle size of about 0.1 μm to about 15 μm. In another embodiment, the D50 particle size may be about 0.1 μm to about 10 μm. In another embodiment, the D50 particle size may be about 0.1 μm to about 5 μm. In another embodiment, the D50 particle size may be about 0.1 μm to about 3 μm. In another embodiment, the D50 particle size may be about 0.1 μm to about 1 μm.

[0052] The quantum efficiency (QE) of phosphors, especially red-emitting phosphors based on complex fluoride materials and with high Mn content, can be degraded by conventional milling and pulverization. In some embodiments, the particle size of the phosphor can be reduced by wet milling, which maintains the QE during milling and pulverization.

[0053] Even commonly used solvents can degrade the QE of a phosphor. In one embodiment, narrow-band emitting phosphors may be wet-milled using certain solvent media (e.g., oleic acid, dibutyl phosphate, bis(2-ethylhexyl) phosphate, and alkanes, including but not limited to hexane, heptane, and hexadecane).

[0054] The ink composition or film may include other luminescent or optical materials. These materials can reduce blue light bleed-through. The luminescent or optical materials may be added to the ink composition or incorporated into the film. In other embodiments, the luminescent material may be added as a separate filtering layer or coating in the light path. In one embodiment, the ink composition or film includes at least one color filter pigment capable of absorbing blue light. Color filter pigments suitable for use with red phosphors have high transmittance for red wavelengths and low transmittance for blue wavelengths. Color filter pigments suitable for use with green phosphors have high transmittance for green wavelengths and low transmittance for blue wavelengths.

[0055] The ink composition or film may further comprise one or more other luminescent materials. In one embodiment, the luminescent material may be a polyfluorene, such as poly(9,9-dioctylfluorene), and its copolymers, such as poly(9,9'-diosyl-fluorene-co-bis-N,N'-(4-butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole) and polyphenylenevinylene, and their derivatives. Additional luminescent materials, such as blue, yellow, red, orange, or other colored phosphors, may be included to customize the white color of the resulting light and generate specific spectral distributions. Suitable additional phosphors include ((Sr 1-z [Ca,Ba,Mg,Zn] z ) 1-(x+w) [Li,Na,K,Rb] w Ce x )3(Al 1-y Si y )O 4+y+3(x-w) F 1-y-3(x-w) (where 0≦x≦1.10, 0≦y≦0.5, 0≦0≦z≦0.5, 0≦w≦x); [Ca,Ce]3Sc2S3O 12 (CaSiG);[Sr,Ca,Ba]3Al 1-x Si x O 4+x F 1-x :Ce 3+(SASOF)); [Ba, Sr, Ca]5(PO4)3[Cl, F, Br, OH]:Eu 2+ , Mn 2+ ; [Ba, Sr, Ca]BPO5:Eu 2+ , Mn 2+ ; [Sr, Ca] 10 * (PO4)6 * vB2O3:Eu 2+ (in this case, 0 < v ≤ 1); Sr2Si3O8 * 2SrCl2:Eu 2+ ; [Ca, Sr, Ba]3MgSi2O8:Eu 2+ , Mn 2+ ; BaAl8O 13 :Eu 2+ ; 2SrO * 0.84P2O5 * 0.16B2O3:Eu 2+ ; [Ba, Sr, Ca]MgAl 10 O 17 :Eu 2+ , Mn 2+ ; [Ba, Sr, Ca]Al2O4:Eu 2+ ; [Y, Gd, Lu, Sc, La]BO3:Ce 3+ , Tb 3+ ; ZnS:Cu + , Cl - ; ZnS:Cu + , Al 3+ ; ZnS:Ag + , Cl - ; ZnS:Ag + , Al 3+ ; [Ba, Sr, Ca]2Si 1-n O 4-2n :Eu 2+ (in this case, 0 ≤ n ≤ 0.2); [Ba, Sr, Ca]2[Mg, Zn]Si2O7:Eu 2+ ; [Sr, Ca, Ba][Al, Ga, In]2S4:Eu 2+ ; [Y, Gd, Tb, La, Sm, Pr, Lu]3[Al, Ga][[ID=]](この場合、0≦a≦0.5である); [Ca, Sr]8[Mg, Zn](SiO4)4Cl2:Eu 2+ , Mn 2+ ​​​​; Na2Gd2B2O7:Ce 3+ , Tb 3+ ; [Sr,Ca,Ba,Mg,Zn]2P2O7:Eu 2+ , Mn 2+ ; [Gd,Y,Lu,La]2O3:Eu 3+ , Bi 3+ ; [Gd,Y,Lu,La]2O2S:Eu 3+ , Bi 3+ ; [Gd,Y,Lu,La]VO4:Eu 3+ , Bi 3+ ; [Ca,Sr]S:Eu 2+ , Ce 3+ ; SrY2S4:Eu 2+ ; CaLa2S4:Ce 3+ ; [Ba,Sr,Ca]MgP2O7:Eu 2+ , Mn 2+ ; [Y,Lu]2WO6:Eu 3+ , Mo 6+ ; [Ba,Sr,Ca] b Si g N m :Eu 2+ (In this case, 2b + 4g = 3m); Ca3(SiO4)Cl2:Eu 2+ ; [Lu,Sc,Y,Tb] 2-u-v Ce v Ca<000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​, 3.5MgO * 0.5MgF2 * GeO2:Mn 4+ ;Ca 1-c-f Ce c EU f Al 1+c Si 1-c N3, (where 0≦c≦0.2, 0≦f≦0.2); Ca 1-h-r Ce h EU r Al 1-h [Mg,Zn] h SiN3, (where 0≦h≦0.2, 0≦r≦0.2); Ca 1≦2s-t Ce s [Li,Na] s EU t AlSiN3, where 0 ≤ s ≤ 0.2, 0 ≤ t ≤ 0.2, and s + t > 0; [Sr,Ca]AlSiN3:Eu 2+ , Ce 3+ , and Li2CaSiO4:Eu 2+ In addition, the light-emitting layer may include blue, yellow, orange, green, or red phosphorescent dyes or metal complexes, quantum dot materials, color filter pigments, or combinations thereof. Materials suitable for use as phosphorescent dyes include, but are not limited to, tris(1-phenylisoquinoline)iridium(III) (red dye), tris(2-phenylpyridine)iridium (green dye), and iridium(III) bis(2-(4,6-difluorenephenyl-O-pyridinato-N,C2) (blue dye). ADS (American Dyes Fluorescent and phosphorescent metal complexes commercially available from ADS (Source, Inc.) may also be used. ADS green dyes include ADS060GE, ADS061GE, ADS063GE, ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

[0056] The ratio of each of the individual phosphors in the ink composition or film may be varied depending on the desired luminous output characteristics. The relative ratios of the individual phosphors in the various phosphors may be adjusted so that when the emissions of these phosphors are mixed and used in a device, such as a lighting device, they produce visible light at predetermined x and y values ​​on the CIE chromaticity diagram.

[0057] In another embodiment, the ink compositions and films may include quantum dots (QDs) that can absorb blue light and emit green or red light, and both may also be included to form hybrid color conversion articles. Exemplary QD materials include Group II-Group IV compound semiconductors such as CdS, CdSe, CdS / ZnS, CdSe / ZnS, or CdSe / CdS / ZnS, such as CdTe, ZnSe, ZnTe, ZnS, HgTe, HgS, HgSe, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, Cd Group II to Group VI elements such as HgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, for example, GaN, GaP, GaNP, GaNAs, GaPAs, GaAs, GaAlNP, GaAlNAs, GaAlPAs, GaI Group III-V or IV-VI compound semiconductors such as nNPs, GaInNAs, GaInPAs, AlN, AlNPs, AlNAs, AlP, AlPAs, AlAs, InN, InNPs, InP, InNAs, InPAs, InAS, InAlNPs, InAlNAs, InAlPAs, PbS / ZnS or PbSe / ZnS, Group IV semiconductors such as Si, Ge, SiC and SiGe, chalcopyrite type compounds including, but not limited to, CuInS2, CuInSe2, CuGaS2, CuGaSe2, AgInS2, AgInSe2, AgGaS2, AgGaSe2, ABX3 (where A is cesium, methylammonium or formamidinium, B is lead or tin, and C is chloride, bromide or iodide). In one embodiment, the perovskite quantum dots may be CsPbX3, where X is Cl, Br, I, or a combination thereof. The average size of the QD material may range from about 2 nm to about 20 nm.The QD particle surface may be further modified with ligands such as amine ligands, phosphine ligands, phospholipids, and polyvinylpyrimidines. In one embodiment, the red fluorophore may be a quantum dot material.

[0058] The QD material may be a core / shell QD comprising a core, at least one shell coated on the core, and an outer coating comprising one or more ligands, preferably organic polymeric ligands. Exemplary materials for preparing core-shell QDs include Si, Ge, Sn, Se, Te, B, C (including diamond), P, Co, Au, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, MnS, Mn Se, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si3N4, Ge3N4, Al2O 3、 [Al,Ga,In]2[S,Se,Te]3, and suitable combinations of two or more of these materials. Exemplary core-shell luminescent nanocrystals include, but are not limited to, CdSe / ZnS, CdSe / CdS, CdSe / CdS / ZnS, CdSeZn / CdS / ZnS, CdSeZn / ZnS, InP / ZnS, PbSe / PbS, PbSe / PbS, CdTe / CdS, and CdTe / ZnS.

[0059] The binder material provides a matrix for the phosphor particles in the film, and its viscosity can be adjusted to obtain a stable dispersion in the ink formulation. The binder material can also improve the performance of the ink composition and film, such as thermal stability and optical performance.

[0060] Binder materials for the ink compositions may include pre-binder materials such as thermoplastic polymers and copolymers, e.g., thermosetting or photocurable precursors. Exemplary binders include ethyl cellulose, polystyrene, polyacrylates and polymethacrylates, e.g., polymethyl acrylate (PMA) and polymethyl methacrylate (PMMA), polycarbonate, polyurethane, polyether ether ketone, polysulfone, polyphenylene sulfide, polyvinylpyrrolidone (PVP), polyethyleneimine (PEI), poly(1-naphthyl methacrylate), poly(vinyl phenyl sulfide) (PVPS), polyvinyl alcohol (PVA), poly(vinyl phenyl sulfide), polyvinyl alcohol (PVA), polyvinyl methyl acrylate (PMMA), polyvinyl phenyl sulfide (PVPS), polyvinyl alcohol (PVA), polyvinyl methyl acrylate (PMMA ... Examples of suitable oligomers / polymers / copolymers include, but are not limited to, polyvinyl butyral (PVB), poly(N-vinylphthalimine), polyvinylidene fluorinated polymers such as polyvinylidene fluoride (PDVF) or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), amine-based oligomers / polymers / copolymers, fluorine-based oligomers / polymers / copolymers, poly(phenylene vinylene), carbazole-based oligomers / polymers / copolymers, and phenyl-pyridine-based oligomers / polymers / copolymers.

[0061] In another embodiment, the binder material may include curable precursor materials, such as photocurable or UV curable precursor materials and thermosetting or heat-curable precursor materials. Exemplary heat-curable binder precursor materials include silicone materials, such as Sylgard™ 184, Sylgard™ 186, and Sylgard™ 527, and epoxy-based materials. Photocurable or UV curable materials include, for example, monofunctional groups such as isobornyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, stearyl acrylate, t-butylcyclohexyl acrylate, stearyl methacrylate, 2-phenoxyethyl methacrylate, cyclic trimethylolpropane formal acrylate, N-acryloylmorpholine, and diacetone acrylamide; monofunctional groups such as 1,4-butanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, and diacetone acrylamide; Precursor materials may include difunctional precursor materials such as glycerol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, and propoxylated (2) neopentyl glycol diacrylate; and polyfunctional precursor materials such as trimethylolpropane triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylolpropane triacrylate, and propoxylated (6) trimethylolpropane triacrylate. In one embodiment, precursor materials include pentaacrylate esters, epoxy resins, acrylic resins, acrylate resins, and urethane-based materials. In one embodiment, the binder material may include a photoinitiator for curing light-curable or UV-curable materials.

[0062] In another embodiment, the binder material may include photoresist materials, such as positive photoresist materials and negative photoresist materials. Positive resists are a type of photoresist in which portions of the photoresist exposed to light become more soluble in a photoresist developer. Unexposed portions of the photoresist remain insoluble in the photoresist developer. Negative photoresists are a type of photoresist in which portions of the photoresist exposed to light become insoluble in a photoresist developer. Unexposed portions of the photoresist are dissolved by the photoresist developer. Exemplary positive photoresist materials include, but are not limited to, polymethyl methacrylate (PMMA), Megaposit™, SPR™ series, diazonaphthoquinone (DNQ), and novolac resins. Exemplary negative photoresist materials include, but are not limited to, epoxy-based polymers, thiol-ene (OSTE) polymers, and crosslinking monomers, such as allylic monomers.

[0063] In another embodiment, the binder material may comprise a conjugated polymer containing fluorescence quenching units that absorb blue light and have negligible emission at the desired wavelength, such as a polyfluorene-based polymer. In one embodiment, the polyfluorene-based polymer may be a brilliant violet fluorophore or poly(5,5,10,10-tetrahexyl-5,10-dihydroindeno[2,1-a]indene-2,7-diyl) (PININE).

[0064] In one embodiment, the binder material may have a higher refractive index than the narrow-band-emitting phosphor material. 4+ In another embodiment, the binder material has a refractive index of at least 1.40. In another embodiment, the binder material has a refractive index of about 1.40 to about 1.45. In another embodiment, the binder material has a refractive index of at least 1.5. In another embodiment, the binder material has a refractive index of at least 0.05 Mn 4+In another embodiment, the binder material has a refractive index higher than that of a red-emitting phosphor based on a complex fluorinated material activated by Mn 4+ The refractive index of the red-emitting phosphor is higher than that of the red-emitting phosphor based on a complex fluorinated material activated by

[0065] In one embodiment, the binder material may have a lower refractive index than the narrow band emitting phosphor material. 6+ Contains phosphor or Mn 2+ The binder material includes a green-emitting phosphor containing phosphor, and the binder material includes a refractive index of at least 1.40. In another embodiment, the binder material includes a refractive index of about 1.40 to about 1.45. In another embodiment, the binder material includes a refractive index of at least 1.5. In another embodiment, the binder material includes a refractive index of at least 0.05. 6+ Contains phosphor or Mn 2+ In another embodiment, the binder material has a refractive index that is less than the refractive index of the green-emitting phosphor that contains the phosphor. 6+ Contains phosphor or Mn 2+ The refractive index is less than the refractive index of the green-emitting phosphor that contains the phosphor.

[0066] In one embodiment, a refractive index modifier may be added to the ink composition to increase the effective refractive index of the binder matrix and increase the refractive index difference between the PFS particles and their surrounding binder matrix. This increases light scattering, reduces blue light bleed-through, and increases the haze of the film. The scattering intensity of particles in a binder system is approximately proportional to the square of the refractive index difference of the particles relative to the matrix material.

[0067] In one embodiment, the refractive index modifier may be a high refractive index metal oxide or metal nanoparticle. In one embodiment, the metal oxide nanoparticles have a particle size of about 1 nm to about 10 nm. In another embodiment, the metal oxide nanoparticles have a particle size of less than about 10 nm. In another embodiment, the metal oxide nanoparticles have a particle size of less than about 5 nm. In one embodiment, the metal oxide nanoparticles may be zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, titanium dioxide, aluminum oxide, zinc oxide, carbides such as silicon carbide, nitrides such as boron nitride, sulfides such as carbon disulfide, and mixtures thereof. In one embodiment, the binder matrix comprises, based on the weight of the binder matrix, about 20 wt % to about 80 wt % of the binder material and about 20 wt % to about 80 wt % of the refractive index modifier. In another embodiment, the binder matrix comprises, based on the weight of the binder matrix, about 20 wt % to about 50 wt % of the binder material and about 50 wt % to about 80 wt % of the refractive index modifier. In one embodiment, the binder material containing the refractive index modifier has a refractive index of at least 1.6.

[0068] The ink composition is a stable solution containing narrow-band-emitting phosphor particles suspended and uniformly dispersed throughout the liquid composition. The particle size of the phosphor and the viscosity of the ink composition affect the stability of the composition. Reducing the particle size of the phosphor material and increasing the viscosity of the liquid composition improves the stability of ink formulations with very slow settling rates. In one embodiment, the composition has a settling rate of 1 mm / hr or less. In another embodiment, the composition has a settling rate of 0.5 mm / hr or less.

[0069] Increasing the loading of the narrow-band phosphor relative to the binder material in the ink formulation increases the absorption and photoconversion of blue light. In one embodiment, the ink composition may include the narrow-band-emitting phosphor in an amount of about 1% to about 60% by weight. In one embodiment, the ink composition may include the narrow-band-emitting phosphor in an amount of about 1% to about 50% by weight. In another embodiment, the narrow-band-emitting phosphor may be present in an amount of about 5% to about 40% by weight. In another embodiment, the narrow-band-emitting phosphor may be present in an amount of about 10% to about 30% by weight. In another embodiment, the narrow-band-emitting phosphor is present in an amount of about 20% to about 25% by weight. In some embodiments, the narrow-band-emitting phosphor is present in an amount less than 10% by weight. The loading of the narrow-band-emitting phosphor in the ink composition is based on the total weight of the ink composition.

[0070] In one embodiment, the ink composition comprises a binder in an amount of at least 2% by weight. In another embodiment, the binder is present in an amount of from about 3% to about 5% by weight. The binder loading in the ink composition is based on the total weight of the ink composition.

[0071] In one embodiment, the weight loading of the narrow band-emitting phosphor relative to the binder material is in the range of about 50% to about 95%. In another embodiment, the weight loading of the narrow band-emitting phosphor relative to the binder material is in the range of about 60% to about 95%. In another embodiment, the weight loading of the narrow band-emitting phosphor relative to the binder material is in the range of about 75% to about 95%. In another embodiment, the weight loading of the narrow band-emitting phosphor relative to the binder material is greater than 90%.

[0072] In one embodiment, the ink composition includes at least one solvent that can be evaporated after application of the ink or coating to a substrate. The solvent provides a liquid medium for the ink formulation and can modify the density and viscosity of the ink formulation at room temperature to provide a stable ink suspension of the narrow-band-emitting phosphor for uniform dispersion therein. In one embodiment, the liquid formulation has a stable dispersion with a settling rate of 1.0 mm per hour or greater.

[0073] In one embodiment, the solvent has a density of about 1.00 g / mL. In another embodiment, the solvent may have a melting point close to room temperature. In another embodiment, the solvent has a melting point below 40° C.

[0074] In one embodiment, the solvent may be an organic solvent. The organic solvent should not turn black after mixing with the phosphor. Exemplary solvents include chloroform, dibutyl phosphate, diethylene glycol methyl ether, bis(2-ethylhexyl)phosphate, isobutyric acid, isobornyl acrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, toluene, xylene, mesitylene, benzene, and chlorobenzene; aliphatic solvents such as hexane, cyclohexane, benzene, heptane, hexadecane, undecane, decane, dodecane, octadecane, tetradecane, and octane; alcoholic solvents such as ethanol, propanol, isopropanol, butanol, 2-butanol, tert-butanol, terpineol, ethylene glycol, propylene glycol, and glycerol; fluorinated alcohols such as 222-trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol (TFPO); ethyl acetate; Examples of suitable solvents include, but are not limited to, ester-based solvents such as butyl acetate (BA), tert-butyl acetate, 2-(2-butoxyethoxy)ethyl acetate (BEA), propylene glycol methyl ether acetate (PGMEA), ethylene glycol phenyl ether methacrylate, and ethyl benzoate (EB); ketone-based solvents such as 2-pentanone, 3-heptanone, methyl ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; N-containing solvents such as trimethylamine, pyridine, 4-tert-butylpyridine, acetonitrile, and N-methyl-2-pyrrolidone (NMP); ether-based solvents such as butyl ether, tetra(ethylene glycol) dimethyl ether, tetrahydrofuran, and dioxane; and sulfur-containing solvents such as dimethyl sulfoxide (DMSO).

[0075] In another embodiment, the solvent may include water. Although PFS particles may degrade when in contact with water, water may be used as a solvent when the particles have a water-resistant surface coating, such as MgF2. Alternatively, phosphate materials, such as potassium dihydrogen phosphate (KHP) or H3PO4, may be incorporated into the ink formulation to reduce degradation.

[0076] In another embodiment, the solvent may be a mixture of multiple solvents or co-solvents. A co-solvent may be added to a primary solvent to form a solvent mixture. A co-solvent may be added to adjust ink properties, such as viscosity, density, surface tension, ability to suspend particles and reduce settling velocity, and wetting and drying behavior of the film once coated. One or more co-solvents may be incorporated into the formulation to adjust surface energy and film-forming properties. In one embodiment, the co-solvent may be dibutyl phosphate or bis(2-ethylhexyl) phosphate. In another embodiment, the co-solvent mixture may be terpineol and 2-(2-butoxyethoxy)ethyl acetate (BEA). In another embodiment, the co-solvent mixture may be 2-(2-butoxyethoxy)ethyl acetate (BEA) and diethylene glycol methyl ether (DGME). In another embodiment, the ink is solvent-free and may be cured under UV or near-UV light.

[0077] Narrow-band emitting phosphors with small particle size tend to aggregate. 4+ Particles of red-emitting phosphors based on complex fluorinated materials activated by Mn exhibit random motion, known as Brownian motion, due to collisions with other particles and molecules in the fluid. Whether particles adhere to each other during each collision depends on surface properties, such as the zeta potential, which is the potential difference between the dispersion medium and the stationary layer of fluid that adheres to the dispersed particles. The magnitude of the zeta potential indicates the degree of electrostatic repulsion between adjacent, similarly charged particles in the dispersion. Colloids with a high zeta potential (negative or positive) are electrically stable, while colloids with a low zeta potential tend to coagulate or slowly aggregate. Mn4+ Particles of red-emitting phosphors based on complex fluorinated materials activated by have a low or neutral zeta potential and tend to aggregate or loosely aggregate.

[0078] In one embodiment, Mn 4+ The red-emitting phosphors based on complex fluorinated materials activated by phosphors can be at least partially coated with a surface coating to enhance the stability of the phosphor particles and to modify the particle surface to prevent aggregation and increase the zeta potential of the particles. In one embodiment, the surface coating can be a metal fluoride, silica, or organic coating. In one embodiment, Mn 4+ A red-emitting phosphor based on a complex fluoride material activated by a phosphor is at least partially coated with a metal fluoride to increase the positive zeta potential and reduce agglomeration. In one embodiment, the metal fluoride coating comprises MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AlF3, or a combination thereof. In another embodiment, the metal fluoride coating is present in an amount of about 0.1% to about 10% by weight. In another embodiment, the metal fluoride coating is present in an amount of about 0.1% to about 5% by weight. In another embodiment, the metal fluoride coating is present in an amount of about 0.3% to about 3% by weight. The metal fluoride-coated Mn 4+ Red-emitting phosphors based on complex fluorinated materials activated by are prepared as described in WO 2018 / 093832 and U.S. Patent Application Publication No. 2020 / 0369956, the entire contents of each of which are incorporated herein by reference.

[0079] In one embodiment, the coated phosphor has an MgF2 or CaF2 surface coating and a surface zeta potential of at least |±20 mV| when measured in isopropanol. In another embodiment, the coated phosphor has a zeta potential of at least |±30 mV| when measured in isopropanol.

[0080] In one embodiment, Mn 4+ The red-emitting phosphors based on complex fluorinated materials activated by phosphors are at least partially coated with an organic coating, e.g., polymerized oleic acid, which may be used to coat the phosphor particles by solvothermal synthesis or processing, e.g., co-adsorption processing.

[0081] In some embodiments, surfactants, such as small molecule surfactants or dispersants, may be incorporated to improve dispersion and reduce aggregation in the ink composition. Dispersants reduce aggregation of phosphor powders while minimizing their impact on optical performance and reliability. Dispersants contain functional groups for surface anchoring, such as hydroxyl (-OH), carboxyl (-COOH), sulfonic acid, sulfate, ammonium, amino (-NH), or imino (-NH-) groups, as well as buoyant moieties that help maintain a uniform and consistent dispersion. In addition, dispersants with appropriate functional groups can also improve wetting capabilities. Liquids with low surface tension tend to wet particles better than liquids with high surface tension. Dispersants can reduce the surface tension of the liquid and the interfacial tension between the liquid and the dispersed particles.

[0082] In one embodiment, the dispersant may be an anionic polymer, a nonionic polymer, a cationic polymer, or a zwitterionic polymer. Anionic dispersants include, but are not limited to, potassium oleate, alkyl sulfonates, polyesters, phosphate and carboxylate esters, polyoxyethylene (10) ether phosphates, polyol-derivatized phosphate esters, phosphate salts, 2-(octen-1-yl)-succinic acid, and polyacrylate salts such as acrylates derived from structured or controlled polymerization techniques (CPT), e.g., polyol-functionalized polyacrylates. In another embodiment, the dispersant is zwitterionic, e.g., a comb-type zwitterionic copolymer functionalized with amine and acid groups. In one aspect, the nonionic dispersant may be a polyurethane-based dispersant. In another embodiment, the cationic dispersant may be a polyamine dispersant, including cationic hyperbranched polyamines. In one embodiment, the dispersant may be a polymeric dispersant such as TEGO® 689 and TEGO® 690, which has a pigment affinity group such as a polymer containing an amine group, e.g., dodecanoic acid, which is a polymer with OH / ether groups and a pigment affinity group. In one embodiment, the dispersant may be a polyester composed of polyhydroxystearic acid stearate. In another embodiment, the dispersant may be an EO / PO block copolymer.

[0083] In one embodiment, the dispersant may be a solution of modified urea (BYK®-7410-ET from BYK Additives and Instruments).

[0084] In one embodiment, the dispersant or surfactant may be present in an amount of up to 10% by weight. In another embodiment, the dispersant or surfactant may be present in an amount of from about 0.1% by weight to about 10% by weight. In another embodiment, the dispersant or surfactant may be present in an amount of from about 1% by weight to about 5% by weight. The amount of dispersant or surfactant is based on the total weight of the ink composition.

[0085] In one embodiment, the ink composition may include a rheology modifier. The rheology modifier may be used to provide desirable rheological properties to the ink composition, such as adjusting the viscosity of the composition, improving dispersion stability and phosphor particle suspension, and controlling the rheological profile of the composition with respect to film-forming properties and ink printability. In one embodiment, the rheology modifier has a viscosity of greater than 100 centipoise at 20°C. In one embodiment, the rheology modifier includes silica nanoparticles and a clay-based material. In another embodiment, the silica nanoparticles may be fumed silica, precipitated silica, or surface-modified hydrophobic silica.

[0086] In another embodiment, the rheology modifier comprises a gelling agent containing at least one crosslinking group. In another embodiment, the gelling agent may gel at a temperature below 30°C. In another embodiment, the gelling agent may gel at a temperature ranging from about 20°C to about 30°C. Gelling agents, such as waxes with polymerizable functional groups, can be added to the ink composition to form gel dispersions with good room temperature stability and low settling. This results in a coatable, printable liquid with a significantly reduced viscosity upon heating. Exemplary waxes include, but are not limited to, di(hexadecyl) fumarate, oleyl cinnamide, di(4-vinyloxybutyl) octadecane dioate, non-polar acrylate waxes such as octadecyl cinnamide, and functionalized waxes such as dodecyl cinnamide.

[0087] Additive materials may be added to the ink composition to adjust the rheological properties and viscosity and to optimize coatability or film-forming ability and printability. In one embodiment, high thermal conductivity materials, such as aluminum nitride nanoparticles and microparticles, may be added to the ink composition. In another embodiment, one or more electrolytes or polyelectrolytes may be added to the ink composition.

[0088] In one embodiment, the ink composition may include scattering particles. In one embodiment, the scattering particles have a particle size of at least 1 μm. In another embodiment, the scattering particles have a particle size of about 1 μm to about 10 μm. In another embodiment, the scattering particles may include titanium dioxide, aluminum oxide (Al2O3), zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF), aluminum fluoride (AlF3), or combinations thereof.

[0089] In a further aspect, a film is provided, the film comprising at least one narrow-band-emitting phosphor dispersed in a binder matrix, the narrow-band-emitting phosphor having a D50 particle size of about 0.1 μm to about 15 μm and a green-emitting U 6+ Contains phosphor, green emitting Mn 2+ Contains phosphor, Mn 4+ red-emitting phosphors based on complex fluorinated materials activated by

[0090] In one aspect, a color conversion film is provided. The film may be formed by depositing an ink composition on a substrate. In one embodiment, the film may be formed by coating the ink composition on a substrate in any conventional manner. In one embodiment, the film may be formed by coating the ink composition by spreading the ink composition across the substrate surface using wet coating, spin coating, slot die coating, spray coating, dipping, or doctor blading. In another embodiment, the film may be formed by printing the ink composition, for example, by inkjet printing. In one embodiment, the film may be deposited or printed on an LED, mini LED, or micro LED. In another embodiment, the film may be deposited on a display substrate, for example, a glass substrate, a silicon substrate, or a polymer substrate such as a thermoplastic substrate. The film has high light conversion efficiency.

[0091] The film includes particulate narrow-band-emitting phosphors dispersed within a binder matrix. The phosphor material absorbs light at a first wavelength and emits light at a second wavelength. The narrow-band-emitting phosphors may be red-emitting phosphors, green-emitting phosphors, or a combination of red-emitting and green-emitting phosphors. The narrow-band-emitting phosphors absorb light from a light source, such as blue light from a blue LED, and generate red, green, or white light. In some embodiments, the blue LED may be a micro LED or a mini LED.

[0092] The binder material forms a solid binder matrix that holds the phosphor particles dispersed within the matrix. After the ink composition is deposited, the film is dried or cured to form a solid binder matrix that holds the phosphor particles dispersed within. In one embodiment, the binder material is a polymer, and the binder matrix forms upon drying of the film and evaporation of any volatile or liquid materials. In one embodiment, heating may be used to evaporate the volatile or liquid materials. In another embodiment, the film may be heated by baking in an oven or hot plate, or with infrared lamps. In another embodiment, the film may be dried on a dry bed or under vacuum.

[0093] In one embodiment, the binder matrix comprises a crosslinked polymer. In another embodiment, the binder material comprises a curable material, such as a photocurable binder material, a UV-curable binder material, a thermosetting binder material, or a combination. The thermosetting binder material polymerizes or crosslinks when the film is heat-treated to form a cured resin binder matrix. Exemplary thermosetting binder materials include silicone materials, such as Sylgard 184, Sylgard 186, and Sylgard 527, and epoxy-based materials. In one embodiment, the film can be cured by heating. In another embodiment, the film is heated to a temperature of at least 100°C. In another embodiment, the film is heated to a temperature of about 100°C to about 200°C. In another embodiment, the film is heated to a temperature of about 100°C to about 150°C. In another embodiment, the film is heated to a temperature of about 100°C to about 130°C. The photocurable or UV curable binder material polymerizes or crosslinks to form a UV curable binder matrix when the film is irradiated with an electromagnetic beam or UV or blue light.

[0094] In one embodiment, the binder matrix may include a refractive index modifier, as previously described. In one embodiment, the binder matrix includes about 20% to about 80% by weight of the binder material and about 20% to about 80% by weight of the refractive index modifier, based on the weight of the binder matrix. In another embodiment, the binder matrix includes about 20% to about 50% by weight of the binder material and about 50% to about 80% by weight of the refractive index modifier.

[0095] In one embodiment, the film comprises a narrow-band-emitting phosphor in an amount of about 20 wt % to about 98 wt % and a binder matrix in an amount of about 2 wt % to about 20 wt %, based on the total weight of the film. In another embodiment, the narrow-band-emitting phosphor may be present in an amount of about 30 wt % to about 98 wt % based on the total weight of the film. In another embodiment, the narrow-band-emitting phosphor may be present in an amount of about 40 wt % to about 98 wt % based on the total weight of the film. In another embodiment, the narrow-band-emitting phosphor may be present in an amount of about 50 wt % to about 98 wt % based on the total weight of the film. In another embodiment, the narrow-band-emitting phosphor may be present in an amount of about 80 wt % to about 98 wt % based on the total weight of the film. In another embodiment, the narrow-band-emitting phosphor may be a narrow-band-emitting phosphor in an amount of about 90 wt % to about 98 wt % based on the total weight of the film, and the binder matrix may be in an amount of about 2 wt % to about 10 wt %. In another embodiment, the binder matrix may be present in an amount of about 2 wt % to about 10 wt % based on the total weight of the film. In another embodiment, the binder matrix may be present in an amount of about 2% to about 5% by weight. In another embodiment, the binder matrix may be present in an amount of about 5% to about 8% by weight, based on the total weight of the film. In another embodiment, the binder matrix may be present in an amount of about 10% to about 20% by weight, based on the total weight of the film.

[0096] In another embodiment, the ink composition or film comprises quantum dots. In one embodiment, the film comprises quantum dots in an amount of up to about 8 wt % based on the weight of the film. In another embodiment, the film comprises quantum dots in an amount of about 1 wt % to about 7 wt % based on the weight of the film. In another embodiment, the film comprises quantum dots in an amount of about 4 wt % to about 6 wt % based on the weight of the film.

[0097] The film or phosphor-containing layer may have any desired thickness suitable for its use or application. In one embodiment, the film may have a thickness of 250 micrometers or less. In another embodiment, the film or layer may have a thickness of about 1 micrometer to about 150 micrometers. In another embodiment, the film may have a thickness of about 10 micrometers to about 150 micrometers. In another embodiment, the film may have a thickness of about 10 micrometers to about 100 micrometers. In another embodiment, the film may have a thickness of about 10 micrometers to about 50 micrometers. In another embodiment, the film may have a thickness of about 20 micrometers to about 50 micrometers. In another embodiment, the film may have a thickness of about 30 micrometers to about 50 micrometers. In another embodiment, the film may have a thickness of about 1 micrometer to about 10 micrometers. In another embodiment, the film or layer has a thickness of 20 micrometers or less. In another embodiment, the film may have a thickness of about 2 micrometers to about 5 micrometers.

[0098] Phosphors, including narrow-band-emitting phosphors, absorb blue light from a light source, e.g., blue light, and generate red, green, or white light. The degree of blue light absorption and the amount of blue light that passes through the color conversion film are referred to as bleed-through. Depending on the application requirements, partial bleed-through of the blue light to produce white light is desirable. In other embodiments, minimal bleed-through of the blue light requires significant absorption by the phosphor. In one embodiment, the blue light may be an LED, e.g., a mini-LED or micro-LED.

[0099] Ink formulations and ingredients can be adjusted to provide final color conversion films and layers with desirable color conversion, absorption (blue to red conversion and blue to green conversion), blue light bleed-through, and haze. In one embodiment, bleed-through can be reduced by increasing the loading of narrow-band emitting phosphors to the binder matrix or by adding other luminescent materials.

[0100] In one embodiment, the film includes a refractive index modifier as previously described. In one embodiment, the film includes the refractive index modifier in an amount of about 20 wt % to about 40 wt % based on the total weight of the film. In another embodiment, the refractive index modifier is present in an amount of about 25 wt % to about 30 wt % based on the total weight of the film.

[0101] In one embodiment, the film comprises, based on the total weight of the film, a narrow-band-emitting phosphor in an amount of about 20% to about 78% by weight, a binder matrix in an amount of about 2% to about 20% by weight, and a refractive index adjuster in an amount of about 20% to about 40% by weight. In another embodiment, the film comprises, based on the total weight of the film, a narrow-band-emitting phosphor in an amount of about 30% to about 78% by weight, a binder matrix in an amount of about 2% to about 10% by weight, and a refractive index adjuster in an amount of about 20% to about 40% by weight. In another embodiment, the film comprises, based on the total weight of the film, a narrow-band-emitting phosphor in an amount of about 40% to about 78% by weight, a binder matrix in an amount of about 2% to about 10% by weight, and a refractive index adjuster in an amount of about 20% to about 40% by weight.

[0102] In one embodiment, the color conversion film has a high conversion efficiency. In one embodiment, the film has a color conversion efficiency of greater than 25%. In another embodiment, the film has a color conversion efficiency of greater than 35%. In another embodiment, the film has a color conversion efficiency of greater than 40%. In another embodiment, the film has a color conversion efficiency of greater than 50%. In another embodiment, the film has a blue absorption of greater than 60%. In another embodiment, the film has a blue absorption of greater than 70%.

[0103] Films prepared from the ink composition are substantially free of uniformity or mura defects. A mura defect is a non-uniformity in brightness or color over a long, uneven area. Uniformity defects are perceived as brightness or color contrast. Methods and apparatus for identifying and classifying mura defects are described in U.S. Pat. No. 5,917,935. In one embodiment, the film is free of visible aggregates. In another embodiment, the film is uniform in color and brightness. In one embodiment, if the film is free of visible aggregates and has uniformity in color and / or brightness, it is substantially free of uniformity or mura defects.

[0104] In one embodiment, the ink composition may be deposited onto a substrate by printing, for example, inkjet printing or slot die coating. The ink composition includes a narrow-band-emitting phosphor having good suspension stability and a small particle size with reduced aggregation, which provides good printability or jettability. In one embodiment, the narrow-band-emitting phosphor has a D50 particle size of up to about 10 μm. In one embodiment, the narrow-band-emitting phosphor has a D50 particle size of up to about 5 μm. In another embodiment, the phosphor has a D50 particle size of less than 5 μm. In another embodiment, the phosphor has a D50 particle size of less than 3 μm. In another embodiment, the phosphor has a D50 particle size of less than 1 μm. In another embodiment, the phosphor has a D50 particle size of up to about 2 μm.

[0105] In one embodiment, the ink composition may be used for inkjet printing. In one embodiment, inkjet printing may be performed at a temperature of from about 20° C. to about 100° C. In another embodiment, inkjet printing may be performed at a temperature of from about 20° C. to about 50° C.

[0106] In one embodiment, the ink composition for inkjet printing has a viscosity in the range of 0.5 centipoise to 40 centipoise at operating temperatures and printing conditions. In another embodiment, the ink composition has a viscosity in the range of about 5 centipoise to about 30 centipoise. In another embodiment, the ink composition has a viscosity in the range of about 4 centipoise to about 20 centipoise. In another embodiment, the ink composition has a viscosity in the range of 35 centipoise at 25°C to about 20 centipoise at 50°C. In another embodiment, the ink composition has a viscosity of less than 30 centipoise.

[0107] In one embodiment, the ink composition for jet printing may include a solvent. In another embodiment, the ink formulation includes a solvent having a viscosity greater than 1 centipoise at room temperature. In another embodiment, the solvent has a viscosity greater than 10 centipoise at room temperature. In one embodiment, the solvent may be ethanol, water, propylene glycol methyl ether acetate (PGMEA), propanol, ethylene glycol, terpineol, 2-(2-butoxyethoxy)ethyl acetate (BEA), or a mixture thereof. In one embodiment, the solvent or mixture of solvents used may have a low vapor pressure or a slow evaporation rate under printing conditions to prevent undesired drying at the nozzle orifice.

[0108] The rheological properties and ink formulation may need to be adjusted for different printers or nozzles with different surface coatings. The surface tension should be between 28 dynes / cm and 40 dynes / cm. For good printability, the contact angle should be greater than 50° at the nozzle plate surface. In one embodiment, the printer orifice may be approximately 20 μm and the jet velocity may be approximately 4 m / s.

[0109] In one embodiment, the ink composition may be applied or deposited onto a substrate surface by inkjet printing. Other printing techniques, such as aerosol jet and spray coating, may be used to print ink formulations with even higher viscosities. For example, for aerosol jet printing, the viscosity of the ink formulation may range from 0.5 centipoise to 2000 centipoise.

[0110] In one embodiment, the composition may cover at least a portion of the LED. In another embodiment, the ink composition may be printed in a pattern onto a substrate, such as an LED, a glass substrate, a silicon substrate, or a polymeric material, such as a thermoplastic substrate, by inkjet printing. In some embodiments, the ink composition may be disposed over multiple light sources, such as an array of mini-LEDs or micro-LEDs. FIGS. 1A and 1B show a portion of a black matrix 1 according to one embodiment of the present disclosure. The black matrix minimizes crosstalk or optical interference between adjacent pixels, providing good display contrast and resolution. The black matrix 1 includes multiple light sources 2 or an array of light sources 2 arranged on a substrate 3, with each light source 2 spatially separated from the other light sources 2 in the array, and non-transparent regions 4 between the spatially separated light sources 2. In one embodiment, the light sources 2 may be separated by about 1 μm to about 1 mm. In another embodiment, the light sources 2 may be separated by about 1 μm to about 500 μm. In another embodiment, the light sources 2 may be separated by about 5 μm to about 300 μm. In another embodiment, the light sources 2 may be separated by about 10 μm to about 200 μm. In another embodiment, the light sources 2 may be separated by about 20 μm to about 50 μm. In one embodiment, the non-transmitting regions 4 between the light sources 2 may be about 1 μm to about 1 mm. In another embodiment, the non-transmitting regions 4 between the light sources 2 may be about 1 μm to about 500 μm. In another embodiment, the non-transmitting regions 4 between the light sources 2 may be about 5 μm to about 300 μm. In another embodiment, the non-transmitting regions 4 between the light sources 2 may be about 10 μm to about 200 μm. In another embodiment, the non-transmitting regions 4 between the light sources 2 may be about 20 μm to about 50 μm.

[0111] As described herein, the color conversion film 5 may be laminated onto each light source 2 by printing, such as inkjet printing. The light sources 2 may be light-emitting diodes, such as mini-LEDs or micro-LEDs. The color conversion film 5 includes a narrow-band-emitting phosphor 6 dispersed within a matrix 7. The non-transmissive regions 4 are substantially free of the color conversion film 5 and are substantially non-transmissive to the light generated by the multiple light sources 2. The non-transmissive regions 4 may be filled with a black matrix material including one or more non-transmissive materials dispersed within a black matrix binder. The non-transmissive material may include, but is not limited to, carbon black powder, a dielectric oxide such as aluminum oxide, or metal particles such as Ni, Co, Fe, Cr, Cu, Pd, Au, Pt, Sn, Zn, and combinations thereof. In one embodiment, the black matrix binder may include a binder material such as those previously described. In another embodiment, the black matrix binder may be a silicone material, a thermoplastic polymer, or a thermoplastic copolymer. In one embodiment, the optical density of the non-transmissive region 4 at wavelengths of light corresponding to the emission spectrum of the narrow-band-emitting phosphor 6 is at least 1.0. In another embodiment, the optical density is at least 2.0. In another embodiment, the optical density is at least 3.0. In one embodiment, the non-transmissive region is black or dark in color.

[0112] In some embodiments, the non-transmissive regions 4 surround each light source 2 or light sources 2 with the printed film 5 arranged thereon, as shown in FIG. 1B. In one embodiment, the black matrix material may be filled to a height substantially the same as the height of the light sources 2 and color conversion film 5, such that the black matrix has a substantially flat surface, as shown in FIG. 1A. In one embodiment, the non-transmissive regions 4 have a depth of up to about 100 μm. In another embodiment, the non-transmissive regions 4 have a depth of about 1 μm to about 100 μm. In another embodiment, the non-transmissive regions 4 have a depth of about 10 μm to about 30 μm.

[0113] A device or LED package according to the present disclosure includes a light source optically or radiatively coupled to a color conversion film, which, as previously described, includes a narrow-band light-emitting phosphor. FIG. 2 shows a device 10 according to one embodiment of the present disclosure. The device 10 includes a light source 12 and a color conversion film 14. In the device 10, the color conversion film 14 is optically or radiatively coupled to the light source 12. Optically or radiatively coupled or optically or radiatively coupled means that radiation from the light source 12 can excite the phosphor material in the color conversion film 14, causing the color conversion film 14 to emit light in response to excitation by the radiation. The color conversion film 14 may be aligned with at least a portion of the light source 12 or may be positioned a certain distance away from the light source 12.

[0114] The light source 12 may be an inorganic LED light source or an organic LED light source. As used herein, the term "LED light source" is intended to encompass all LED light sources, such as semiconductor laser diodes (LDs), inorganic light-emitting diodes, organic light-emitting diodes (OLEDs), or hybrids of LEDs and OLEDs. LEDs use pn junction diodes to emit light when activated by electroluminescence. The color of the light corresponds to the photon energy according to the energy bandgap of the semiconductor material. Additionally, LED light sources may be chip CSPs (chip-scale packages), mini LEDs, or micro LEDs, which may be used in self-emissive displays. Mini LEDs are submillimeter light-emitting diodes with sizes ranging from about 100 μm to about 0.7 mm. Micro LEDs have sizes smaller than 100 micrometers. In another embodiment, micro LEDs have sizes smaller than 50 micrometers. With micro LEDs, LED backlights may be miniaturized and arrayed with individual LEDs, where each LED element is individually addressed and driven to emit light in a manner similar to self-emissive OLEDs.

[0115] Furthermore, unless otherwise specified, it should be understood that the LED light source may be replaced, supplemented, or augmented by another radiation source, and references to semiconductors, semiconductor LEDs, or LED chips are merely intended to represent any suitable radiation source, including, but not limited to, LDs and OLEDs.

[0116] In one embodiment, the light source 12 is coated or covered with a color conversion film 14. In one embodiment, the color conversion coating or film is applied by inkjet printing to coat or cover the light source 12. In further embodiments, the color conversion film 14 may have multiple layers laminated onto the surface of the light source 12.

[0117] In one embodiment, light source 12 may include a UV or blue emitting LED. In another embodiment, light source 12 may include a mini LED or a micro LED. In some embodiments, light source 12 produces blue light in the wavelength range of about 440 nm to about 460 nm.

[0118] In some embodiments, device 10 may be a backlight unit for display applications. LED backlight units (BLUs) for use in displays are based on a combination of blue LEDs, e.g., mini- or micro-LEDs, and phosphors, including green- and red-emitting phosphors, to provide white light from the device. In one embodiment, the green phosphor is a green-emitting U 6+ Containing phosphor, or narrow band green emitting Mn 2+ In one embodiment, the red phosphor is Mn 4+ In another embodiment, the phosphor comprises a narrow band red-emitting phosphor based on a complex fluorinated material activated by Mn 4+ Narrow-band red-emitting phosphor based on composite fluorinated materials activated by Mn 2+ and narrowband green emitting U 6+ Containing phosphor or narrow band green emitting Mn 2+ This includes combinations with phosphors.

[0119] In one embodiment, the lighting device comprises a device. Figure 3 shows a lighting device or lamp 20 according to some embodiments. The lighting device 20 includes a light source 22, e.g., an LED chip, and leads 24 electrically attached to the light source 22. The leads 24 may include thin wires supported by one or more thicker lead frames 26, or the leads 24 may include self-supporting electrodes, or the lead frame may be omitted. The leads 24 provide electrical current to the light source 22, which causes it to emit light. In one embodiment, the LED chip may be a mini LED chip or a micro LED chip.

[0120] The light source 22 may be encapsulated within an envelope 28. The envelope 28 may be formed of, for example, glass or plastic. The light source 22 may be surrounded by an encapsulant 32. The encapsulant 32 may be a low-temperature glass or a polymer or resin known in the art, such as, for example, an epoxy, a silicone, an epoxy-silicone, an acrylate, or a combination thereof. In an alternative embodiment, the lighting device 20 may not include the envelope 28 and may include only the encapsulant 32. Both the envelope 28 and the encapsulant 32 must be transparent to allow light to pass through these elements.

[0121] 3, the color conversion film 34 is disposed on the light emitting surface of the light source 22 as previously described. The film 34 may be disposed in any suitable manner, such as by coating or printing. As shown, the layer 34 may be coated and disposed directly on the surface of the light source 22, such as by coating or printing and drying or curing the coating over the LED light source 22. Light emitted from the light source 22 mixes with light emitted from the color conversion film 34 to produce the desired emission.

[0122] In some other embodiments, instead of being formed on the light source 22 (FIG. 3), the color conversion film 38 is coated onto the surface of the envelope 28, as shown in FIG. 4, which illustrates an exemplary embodiment of a lighting device 40. As shown, the film 38 is coated onto the inner surface 29 of the envelope 28. However, if desired, the film 38 may be coated onto the outer surface of the envelope 28. The film 38 may be coated onto the entire surface of the envelope 28, or may be coated onto only the upper portion of the inner surface 29 of the envelope 28. Light emitted from the light source 22 mixes with light emitted from the film 38, and the mixed light is transmitted out. The color conversion film may be located in either or both locations as shown in FIGS. 3 and 4, or in any other suitable location, such as a remote location, e.g., a location remote from the envelope 28 or integrated into the light source 22.

[0123] In any or all of the above configurations, the lighting device 20 or 40 shown in Figures 3 or 4, respectively, may also include a plurality of scattering particles (not shown) embedded in the encapsulant material 32. The scattering particles may include, for example, alumina, silica, zirconia, or titania. The scattering particles scatter the directional light emitted from the light source 22, preferably with a negligible amount of absorption.

[0124] In one embodiment, the lighting device 20 or 40 shown in FIG. 3 or FIG. 4 may be a backlight device. In another embodiment, the backlight device comprises a backlight unit 10. Some embodiments relate to a backlight device 50 shown in FIG. 5. The backlight device 50 includes surface-mounted device (SMD) light-emitting diodes for backlighting or display applications. The SMD is "side-emitting" and includes a light-emitting window 52 in the protruding portion of the light-guiding member 54. The SMD package may include an LED chip and a color conversion film. In one embodiment, the backlight device may be an edge-lit or side-lit device. In another embodiment, the backlight device may be a direct-lit device. Backlight devices and related devices are described in U.S. Patent Application Publication No. 2017 / 0254943 and PCT Patent Application Publication No. 2018 / 190827, the entire contents of each of which are incorporated herein by reference.

[0125] The film may be used in direct-lit and edge-lit LCD display devices. Figure 6A shows one embodiment of a single-mode liquid crystal display with an edge-lit backlight configuration. The LCD 100A includes an illumination or backlight unit 102, a light guide panel 106, and an LCD panel 120, as previously described in Figures 3 and 4. The LCD 100A uses an electronically controllable LCD panel 120 and backlight unit 102 to generate color images. The backlight unit 102 provides white light and corresponds to multiple backlight units 102 along one or more edges of the LCD 100A. The LCD 100A uses an electronically controllable LCD panel 120 and LED backlight 100 to generate color images.

[0126] The LCD panel 120 includes color filters 122 arranged into subpixels, such as red, green, and blue filters. The red, green, and blue filters 122 transmit light having specific wavelengths of white light incident from the backlight device 102. The filters 122 transmit the wavelengths of light corresponding to the color of each filter and absorb other wavelengths.

[0127] The LCD panel 120 may include a front polarizer 118, a rear polarizer 114, thin film transistors (TFTs) 126, and liquid crystals 116, as well as electrodes (not shown). A color filter 122 may be disposed between the liquid crystals 116 and the front polarizer 118. The thin film transistors 126 may be disposed between the liquid crystals 116 and the rear polarizer 114. Each pixel has a corresponding transistor or switch for controlling the voltage applied to the liquid crystals 116. The front polarizer 118 and the rear polarizer 114 may be set at a right angle. In one embodiment, the LCD panel 120 is opaque. When a voltage is applied across the liquid crystals 116, the rod-like polymers modify their twist in response to the electric field, and as a result, the electric field controls the luminous output from the front polarizer 118. For example, when a voltage is applied to the liquid crystals 116, the liquid crystals 116 rotate such that there is luminous output from the front polarizer 118.

[0128] White light from the backlight device 102 travels towards the light guide panel (LGP) 106 through the diffuser film 110 and prisms 108, as well as a double brightness enhanced film (DBEF) 124, which provides a uniformly illuminated backlight for the LCD panel 120.

[0129] The LED backlight 102 and LCD 100A may include additional components typical of an optical stack. In one embodiment, a diffuser, reflector, or glass filter may be provided. In a further embodiment, a cover glass may cover the optical stack.

[0130] Figure 6B shows an embodiment of a single-mode LCD 100B with a direct-view / direct-lit backlight configuration. The direct-lit backlight configuration is similar to the edge-lit backlight configuration shown in Figure 6A, except for the light guide panel 106 and LED arrangement. Multiple backlight devices 102 are arranged to provide light directly to a diffuser plate 128, which may support a diffuser film 110.

[0131] FIG. 7 shows an exemplary embodiment of a backlight unit or module 200 including the light source 12 previously described in FIG. 2, a light guide panel (LGP) 204, a color conversion film 206, a dichroic filter 210, and the LCD panel 120 previously described in FIG. 6A. The backlight unit 200 also optionally includes a prism 212 and a dual brightness enhancement film (DBEF) 214. The light source 12 is a blue-emitting LED, which may be a mini-LED or micro-LED. To generate uniform illumination, the blue light from the light source 12 first passes through the light guide panel 204, which scatters the blue light. Typically, an air gap exists between the LCD panel 120 and the dual brightness enhancement film (DBEF) 214. The dual brightness enhancement film is a reflective polarizer film that is unpolarized on the backside but increases efficiency by repeatedly reflecting any light that would otherwise be absorbed by the LCD's rear polarizer 118. The dual brightness enhancement film 214 is disposed behind the LCD panel 120 without any other intervening films. The dual brightness enhancement film 214 may be attached with its transmission axis substantially parallel to that of the rear polarizer 118. The dual brightness enhancement film 214 serves to recycle white light 220 that would normally be absorbed by the rear polarizer 118 of the LCD panel 120. This therefore increases the brightness of the LCD panel 120 and the light 222 emitted from the LCD panel 120. In another embodiment, the prism 212 may be eliminated and replaced with other brightness enhancement components. In a further aspect, the dual brightness enhancement film may be eliminated.

[0132] The backlight unit or module 200 includes a color conversion film 206 positioned a distance away from the light source 12. The color conversion film 206 includes a phosphor that includes particles of narrow-band emitting phosphors. The phosphors include a green-emitting phosphor 208A and a red-emitting phosphor 208B. In one embodiment, the green-emitting phosphor is a green-emitting U 6+ Containing phosphor, or narrow band green emitting Mn 2+ In another embodiment, the red-emitting phosphor comprises Mn 4+ The color conversion film 206 includes a narrow-band red-emitting phosphor based on a composite fluorinated material activated by a compound fluorinated material. The color conversion film 206 is distinct in the sense that the primary light source and the phosphor are separate elements, and the phosphor is not integrated with the primary light source as a single element. Primary light is emitted from the primary light source and travels through one or more external media to radiatively or optically couple light source 12 to the phosphor of the color conversion film 206.

[0133] Those skilled in the art will appreciate that the configuration of a backlight unit or module according to embodiments of the present disclosure may be varied, for example, a direct-lit configuration similar to that shown in FIG.

[0134] A display device, or display, converts electrical signals into a pixelated, multicolored display to present information or images from a processor or other type of information management system. Displays may be self-emissive, such as microLEDs or organic light-emitting diode displays (OLEDs) with a light-generating organic light-emitting diode layer. Liquid crystal displays (LCDs) use backlighting, such as from an LED light source and individual liquid crystal cells. In one embodiment, a display device includes the color conversion film previously described. Examples of devices that include backlit or direct-emitting displays include: televisions, plasma screens, home and theater projections, digital photo frames, tablets, automotive displays, e-readers, electronic dictionaries, digital cameras, computers, laptops, computer monitors, electronic keyboards, cellular or traditional phones, smartphones, tablet computers, gaming devices, and other small devices with displays and screens. This list of applications is intended to be illustrative only and is not intended to be exhaustive. [Example]

[0135] 33.2 g of terpineol and 16.6 g of 2-(2-butoxyethoxy)ethyl acetate (BEA) were mixed at room temperature and stirred for 30 minutes to prepare a mixture of solvents called T / BEA.

[0136] PFS(K2SiF6:Mn 4+ Two phosphors were used in this example: PFS Sample No. 395 powder (F2531-120-2) and F2531-120-2. PFS Sample No. F2531-120-2 has a D10 / D50 / D90 particle size distribution of 8.9 / 10.5 / 12.3 μm.

[0137] PFS Sample No. 395 was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours under a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The powder was sonicated to a D50 particle size of 7.9 μm with a D10 / D50 / D90 particle size distribution of 6.9 / 7.9 / 9.2 μm, as measured with a Horiba particle size analyzer. The Mn% of this powder is 3.55.

[0138] By surface coating the PFS powder with 2.5% MgF2, PFS sample number 425 (K2SiF6:Mn 4+ PFS sample number F2531-120-2 was prepared from K2SiF6. PFS sample number 425 was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh and washed in a secondary wash step in a nearly saturated 49% HF solution of K2SiF6 for 30 minutes. The PFS sample has a D50 particle size of 12.0 μm (without sonication).

[0139] The powder was coated with MgF2 as follows: 12 mL of a 0.22 g / mL solution of MgSiF6·6H2O in 17.5% aqueous H2SiF6 solution was added to a magnetic stir bar, and 240 mL of a 49% saturated aqueous HF solution containing K2SiF6:Mn 4+The phosphor cake was added over 30 minutes to a reaction mixture containing 25g of acetone. The mixture was vigorously stirred (300 rpm) for 30 seconds, after which the stirring was reduced to 120 rpm. After the addition was complete, the stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to settle for 5 minutes. The supernatant was decanted and discarded. It was mixed with 150 mL of a 49% HF saturated aqueous solution containing K2SiF6. The wash mixture was allowed to settle for 5 minutes, after which the supernatant was decanted and discarded. It was transferred to a plastic Buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off, and the phosphor cake was washed five times with a total of 500 mL of acetone, agitating the solids before each wash. The product was dried under vacuum for 3 days and then sieved through a 170 mesh membrane to obtain the final coated product (Mn%=2.13, 0.67% MgF2 coated PFS sample number F2531-120-2).

[0140] Four ethylcellulose (EC) materials (hereafter referred to as EC-L, EC-M, EC-H, and EC-HH, respectively) obtained from Aldrich with product numbers 200646, 46070, 46080, and 200654 were used as received without any further purification. All ECs have similar amounts (48.0–49.5% (w / w) ethoxylate major content), an optical refractive index of 1.47, and a density of 1.14 g / mL at 25 °C. The EC materials have different molecular weights and viscosities measured as 5 wt% solutions in toluene / ethanol (80:20) at 25 °C (Error! Reference source not found, 1). [Table 1] [Example]

[0141] A 3.3 wt% EC-M solution was prepared by mixing 0.35 g of EC-M (see Example 1) in 10.25 g of T / BEA solvent mixture (see Example 1), hereafter referred to as T-BEA_EC-M (3.3%). A 3.3 wt% EC-H solution was prepared by mixing 0.42 g of EC-H (see Example 1) in 12.3 g of T / BEA solvent mixture, hereafter referred to as T-BEA_EC-H (3.3%). The two solutions were stirred overnight at 80°C to completely dissolve the ethyl cellulose. They were then cooled to room temperature for the following experiments.

[0142] 0.15 g of PFS sample number F2531-120-2 (see Example 1) was mixed with 3 g of T / BEA_EC_M (3.3%) varnish to prepare a PFS-containing dispersion designated T / BEA_EC_M (3.3%)-PFS (5%); 0.19 g of PFS sample number F2531-120-2 was mixed with 3.8 g of T / BEA_EC_H (3.3%) varnish to prepare a PFS-containing dispersion designated T / BEA_EC_H (3.3%)-PFS (5%); A PFS-containing dispersion designated T / BEA_EC_M(3.3%)-PFS395(5%) was prepared by mixing 0.2215 g of PFS Sample No. 395 (see Example 1) with 4.28 g of T / BEA_EC_M(3.3%) varnish; a PFS-containing dispersion designated T / BEA_EC_H(3.3%)-PFS395(5%) was prepared by mixing 0.2215 g of PFS Sample No. 395 (see Example 1) with 3.76 g of T / BEA_EC_H(3.3%) varnish. All dispersions with a 5 wt% PFS loading were first stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates and rolling on a bottle roller at 60 rpm for 2 hours. The homogeneous dispersions were stirred at 80°C for an additional 2 hours and then cooled to room temperature for sedimentation testing. The dry film coated with the dispersion had a PFS to binder (EC) ratio of 60:40.

[0143] At 60 min, sample T / BEA_EC-M(3.3%)-PFS395(5%) showed some sedimentation, while sample T / BEA_EC-H(3.3%)-PFS395(5%) showed no sedimentation. At 61 min, sample T / BEA_EC-M(3.3%)-PFS(5%) showed some sedimentation, while sample T / BEA_EC-H(3.3%)-PFS(5%) showed no sedimentation. At 120 min, sample T / BEA_EC-M(3.3%)-PFS395(5%) showed increased sedimentation, while sample T / BEA_EC-H(3.3%)-PFS395(5%) showed minimal sedimentation. At 198 minutes, the sedimentation of sample T / BEA_EC-M (3.3%)-PFS (5%) increased, while sample T / BEA_EC-H (3.3%)-PFS (5%) showed no sedimentation at all.

[0144] All four dispersions show improved dispersion stability compared to PFS dispersed in T / BEA alone. The EC-H-based dispersions (i.e., T / BEA_EC-H(3.3%)-PFS(5%) and T / BEA_EC-H(3.3%)-PFS395(5%)) show better dispersion stability than the EC-M-based dispersions (i.e., T / BEA_EC-M(3.3%)-PFS(5%) and T / BEA_EC-M(3.3%)-PFS395(5%)). This is due to the higher viscosity of the EC-H-based dispersions. In comparison, PFS sample number F2531-120-2, which contains the MgF2 coating, has better dispersion stability than PFS sample number 395, which does not contain the MgF2 coating. This can be partly explained by the fact that the PFS with MgF2 coating has a more positive zeta potential (57.2 mV for sample number F2531-120-2) than the PFS without MgF2 coating (4.6 mV for sample number 395), since aggregation can be inhibited by a more positive zeta potential. [Example]

[0145] A PFS-containing dispersion designated T / BEA_EC_M(3.3%)-PFS(40%) was prepared by mixing 1.63 g of PFS sample number F2531-120-2 (see Example 1) with 2.45 g of T / BEA_EC_M(3.3%) varnish (see Example 2); a PFS-containing dispersion designated T / BEA_EC_H(3.3%)-PFS(40%) was prepared by mixing 1.95 g of PFS sample number F2531-120-2 with 2.93 g of T / BEA_EC_H(3.3%) varnish (see Example 2). The two dispersions were first stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates and rolling on a bottle roller at 60 rpm for 2 hours. The homogeneous dispersion was stirred at 80°C for an additional 2 hours and then cooled to room temperature for the sedimentation test.

[0146] At 130 min, sample T / BEA_EC-M(3.3%)-PFS(40%) had precipitated approximately 30%, and sample T / BEA_EC-H(3.3%)-PFS(40%) had precipitated approximately 25%. At 188 min, sample T / BEA_EC-M(3.3%)-PFS(40%) had precipitated approximately 50%, and sample T / BEA_EC-H(3.3%)-PFS(40%) had precipitated approximately 30%.

[0147] Both samples show improved dispersion stability relative to PFS dispersed in T / BEA alone. The T / BEA_EC-H(3.3%)-PFS(40%) dispersion has better dispersion stability than the T / BEA_EC-M(3.3%)-PFS(40%) dispersion due to its higher viscosity.

[0148] Both dispersions were used to spin-coat PFS:EC films. Pre-cleaned glass slides were used as substrates for spin-coating in air. Approximately 0.7 mL of the dispersion was applied onto the substrate and spun for 60 seconds to obtain a wet film. Different spin speeds were used to control the film thickness. Prior to testing, the coated substrates were baked for 10 minutes on a preheated hotplate at 150°C. The spin-coated films were then placed inside an integrating sphere and optically pumped using a 450 nm blue LED. The refractive power in the blue region (400-550 nm) and red region (550-700 nm) was recorded. The blue-to-red conversion efficiency was measured using

number

[0149] The results for spin-coated films using the T / BEA_EC-H (3.3%)-PFS (40%) dispersion are shown in Table 2. The final dried film consists of approximately 92% PFS and approximately 8% EC-H. The film is free of uniformity defects. [Table 2] [Example]

[0150] The binder, 0.2686 g of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), was mixed with 15.18 g of cyclohexanone (CH) and stirred overnight at 80 °C to obtain a clear solution. The solution, designated CH_PVDF-HFP, had a viscosity of 15.37 cP at 25 °C and was prepared from 2 μm K2SiF6:Mn 4+ For particles this translates to a settling velocity of less than 1 mm / hour.

[0151] By surface coating the PFS powder with 2.5% MgF2, PFS sample number 466 (K2SiF6:Mn 4+ PFS sample number F2664-43-1 was prepared from K2SiF6. PFS sample number 466 was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The PFS sample had a D50 particle size of 9.96 μm without ultrasonic treatment and 9.4 μm with ultrasonic treatment.

[0152] The powder was coated with MgF2 as follows: 35.48 mL of a 0.22 g / mL solution of MgSiF6·6H2O in 17.5% aqueous H2SiF6 solution was added to a magnetic stir bar, and 665 mL of a 49% saturated aqueous HF solution containing K2SiF6:Mn 4+ The phosphor cake was added to a reaction mixture containing 70 g of acetone over a 30-minute period. The mixture was vigorously stirred (300 rpm) for 30 seconds, after which the stirring was reduced to 120 rpm. After the addition was complete, the stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to settle for 5 minutes. The supernatant was decanted and discarded. It was mixed with 250 mL of a 49% saturated aqueous HF solution containing K2SiF6. The wash mixture was allowed to settle for 5 minutes, after which the supernatant was decanted and discarded. It was transferred to a plastic Buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off, and the phosphor cake was washed five times with a total of 1 L of acetone, agitating the solids before each wash. The product was dried under vacuum for 3 days and then sieved through a 170 mesh membrane to give the final coated product (Mn%=2.49, 1.65% MgF2 coated PFS sample number F2664-43-1) with a D10 / D50 / D90 particle size distribution of 7.9 / 9.4 / 11.1 μm.

[0153] A 40 wt% PFS dispersion, designated CH_PVDF-HFP-PFS (40%), was prepared by mixing 2.28 g of PFS sample number F2664-43-1 with 3.45 g of CH_PVDF-HFP varnish. The dispersion, with a 5 wt% PFS loading, was first stirred at room temperature for 2 h, followed by vigorously mixing in a vortex mixer for 1–2 min to reduce particle agglomerates and rolling on a bottle roller at 60–70 rpm for 2 h. The homogeneous dispersion was stirred for an additional 2 h at 80 °C and then cooled to room temperature for film coating.

[0154] The dispersion containing PVDF-HFP is very stable, showing almost no settling after 30 minutes. In contrast, most of the PFS particles in the cyclohexanone dispersion without PVDF-HFP settle to the bottom within 10 minutes.

[0155] The dispersion CH_PVDF-HFP-PFS (40%) was then used to spin-coat a PFS:PVDF-HFP film. A pre-cleaned glass slide was used as the substrate for spin-coating in air. Approximately 0.7 mL of the mixture was added onto the substrate. The liquid was then spread by spinning at 700 rpm for 20 seconds, followed by 1500 rpm for 60 seconds (without stopping), to obtain a wet film. The wet film was baked for 10 minutes on a preheated hotplate at 150 °C before testing. The baked final film, consisting of 97.4% PFS in 2.6% PVDF-HFP, had a thickness of approximately 35 μm and a blue-to-red conversion efficiency of 36.8%. [Example]

[0156] Two samples were prepared using PFS sample number 395 (see Example 1). wA 40 wt% binder material, poly(methyl acrylate) (PMA) toluene solution, was purchased from Aldrich and used as received. To prepare the first sample, 1 g of PFS sample No. 395 (hereafter referred to as PFS-toluene) was combined with 4 g of toluene to obtain a 20 wt% dispersion. To prepare the second sample, 1 g of PFS sample No. 395 (hereafter referred to as PFS-toluene) was combined with 4.6 mL of a 40 wt% PMA solution in toluene to obtain a 15 wt% dispersion. A volume of 4.6 mL was selected for the PFS-PMA-toluene mixture to ensure the same total volume as the PFS-toluene mixture. Each sample was vortexed, thoroughly mixed, and allowed to settle to observe its settling behavior. The sample PFS-toluene (toluene only) settled by approximately 15% in 30 min, whereas PFS-toluene-PMA (toluene and 40 wt % poly(methyl acrylate)) showed no apparent settling in the same time frame. [Example]

[0157] Two samples were prepared using PFS sample number 320. This sample was made of PFS (K2SiF6:Mn) with a D10 / D50 / D90 particle size distribution of 9.0 / 13.6 / 20.2 μm. 4+ ) Product number 363065, 146,000-186,000 M w Polyvinyl alcohol (PVA), a binder material having the formula: was purchased from Aldrich and used as received.

[0158] PFS Sample No. 320 was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh screen and washed in a 49% HF solution nearly saturated with K2SiF6 for 30 minutes. The powder was subjected to a "roasting" process and, after the secondary washing, an additional low-temperature anneal at 150°C for 4 hours in a 20% fluorine:80% nitrogen atmosphere. The powder had a D50 particle size of 13.6 μm as measured by SEM. The powder had an Mn% of approximately 1.32.

[0159] To prepare the first sample, hereafter referred to as "5 Control," 0.4 g of Sample No. 320 was dispersed in 2 mL of 2,2,3,3-tetrafluoro-1-propanol (TFPO). To prepare the second sample, hereafter referred to as "5D," 0.5 g of Sample No. 320 and 0.03 g of PVA were dispersed in 2 mL of TFPO and mixed well. Both samples were vortexed for 30 seconds to form a dispersion, then allowed to settle and observe settling behavior.

[0160] At 30 minutes after sample preparation, sample "5 Control" had completely settled, while sample "5D" had not settled at all. The addition of PVA dramatically reduced the settling rate while significantly improving dispersion stability. [Example]

[0161] 0.3772 g of the binder material polyvinyl butyral (PVB) was mixed with 12.15 g of T / BEA (see Example 1) and stirred overnight at 80°C to obtain a clear solution. The solution, designated T / BEA_PVB, has a viscosity of 42.1 cP at 25°C and is obtained by mixing 2 μm K2SiF6:Mn 4+ For particles this translates to a settling velocity of less than 0.5 mm / hr.

[0162] 2.23 g of PFS sample number F2664-43-1 (from Example 4) was mixed with 3.35 g of T / BEA_PVB varnish. The dispersion, designated sample 030820-B, with a 5 wt. % PFS loading was first stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates and rolling on a bottle roller at 60-70 rpm for 2 hours. The homogeneous dispersion was stirred for an additional 2 hours at 80°C and then cooled to room temperature. [Example]

[0163] For this example, PFS sample number PFS GRC082718SSTGA(316 / 318) was used. PFS sample K2SiF6:Mn 4+ (PFS) was prepared. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh sieve and washed in a 49% nearly saturated HF solution of K2SiF6 for 30 minutes in a secondary washing step. The powder had a D10 / D50 / D90 particle size distribution of 9.8 / 14.4 / 21.8 μm.

[0164] In a plastic vial, 0.5 g of PFS sample number PFS GRC082718SSTGA (316 / 318) was mixed with 1.5 g of premixed Sylgard 184 thermosetting binder (1.36 g of part A and 0.14 g of part B). The PFS loading relative to Sylgard 184 (A + B) was 25 wt%. The mixture was gently mixed using a wooden Q-tip stick to obtain a uniform mixture with no visible agglomerates. The mixture was degassed under vacuum for 5 minutes. A pre-cleaned glass slide was used as the substrate for spin-coating in air. A glass substrate (1" x 1", or 25 mm x 25 mm) was placed on the chuck of the spinner. Approximately 0.5 mL of the mixture was first dispensed onto the substrate. This was followed by spinning at 500 rpm for 15 seconds, followed by spinning at 3000 rpm for 60 seconds (without stopping) to obtain a wet film. The coated substrate was baked on a preheated hotplate for 30 seconds to completely dry any volatile materials. The coated substrate was placed in a preheated oven and the film was cured at 125°C for 30 minutes. The resulting film had a thickness of approximately 55 μm. The film had a blue-to-red conversion efficiency of 42.3%.

[0165] Another film was prepared using Sylgard 184 diluted with toluene. In a plastic vial, 2 g of Sylgard 184 Part A was diluted with 1 g of toluene and mixed thoroughly. In a weighing dish, 0.5 g of Sylgard 184 Part B was diluted with 0.25 g of toluene and mixed thoroughly. 0.3 g of diluted Part B was added to diluted Part A to prepare a mixture of Sylgard 184 (A + B, A:B = 10:1 by weight) and mixed thoroughly. 0.73 g of Sample No. 316 / 318 was mixed with the diluted Sylgard 184 (A + B), and the mixture was gently mixed with a wooden stick to obtain a uniform dispersion. The mixture was degassed under vacuum for 5 minutes. A pre-cleaned glass slide was used as the substrate for spin-coating in air. Approximately 0.5 mL of the mixture was first applied to the substrate. This was followed by spinning at 500 rpm for 15 seconds, followed by spinning at 3000 rpm for 60 seconds (without stopping) to obtain a wet film. The coated substrate was baked on a preheated hotplate for 30 seconds to completely dry any volatile materials. The coated substrate was placed in a preheated oven, and the film was cured at 125°C for 30 minutes. The resulting film was approximately 35 μm thick. The film had a blue-to-red conversion efficiency of 41.7%. [Example]

[0166] A stock solution of the photoinitiator Igracure® 819 was prepared by dissolving 80 mg of Igracure® 819 in 1 mL of 2,2,3,3-tetrafluoro-1-propanol (TFPO).

[0167] 1.06 g of PFS sample number F2531-120-2 (see Example 1) was mixed with 1.63 g of binder material ethoxylated trimethylolpropane triacrylate (trade name SR454 obtained from Sartomer America) to obtain a dispersion with a PFS loading of 40 wt %. This dispersion was then mixed with 0.20 mL of Igracure® 819 TFPO stock solution to obtain a 40 wt % PFS dispersion (designated SR454-PFS-Dispersion-1).

[0168] 1.176 g of PFS Sample No. 395 (see Example 1) was mixed with 1.77 g of the binder material ethoxylated trimethylolpropane triacrylate (SR454) to obtain a 40 wt % PFS dispersion, which was then mixed with 0.22 mL of Igracure® 819 TFPO stock solution to obtain a 40 wt % PFS dispersion (referred to as SR454-PFS-Dispersion-2).

[0169] The two dispersions were first stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates, and then rolling on a bottle roller at 60-70 rpm for 2 hours. The homogenous dispersions were stirred for an additional 2 hours at 50°C, followed by cooling to room temperature.

[0170] Pre-cleaned glass slides were used as substrates for spin-coating in air. After spin-coating, the PFS-coated substrates were baked on a hotplate preheated to 110 °C for 10 min, and then baked in air at 39 mW / cm. 2 The spin-coated films were UV-cured under a UV intensity of 1000 uV. The final films were approximately 50 μm thick and consisted of approximately 40% PFS in a cross-linked acrylate matrix. The spin-coated films of both samples had good blue-to-red conversion efficiencies of 44% and were stable under UV irradiation. [Example]

[0171] Five commercially available photoresist inks were tested as binder materials: 0.30 g of K2SiF6:Mn, with particle sizes of approximately 3–5 μm as measured by SEM; 4+ (PFS) C011817VGAT(241) was mixed with 2.7 g of each photoresist material to produce a coatable liquid formulation with a 10 wt% loading of PFS. PFS Sample No. C011817VGAT(241) was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540 °C for 8 hours under a 20% fluorine:80% nitrogen atmosphere. Each mixture was mixed manually using a Q-tip. Coatings were produced using spin coating. Coating thickness was controlled by varying the spin speed. 4-inch glass and silicon wafers, pre-cleaned with isopropanol, were used as base substrates.

[0172] PFS:photoresist films were prepared by directly spin-coating a single layer of the corresponding liquid formulation onto pre-cleaned glass and silicon wafer substrates, although the mixture did not provide the desired uniform coating.

[0173] A two-layer structure was constructed. A layer of phosphor-free photoresist material (A) was coated onto a substrate. The substrate could be a glass or silicon wafer. A layer of photoresist material (B) was mixed with 10 wt% PFS and coated onto the substrate over the photoresist A coating. The film coverage and uniformity are shown in Table 3. [Table 3] [Example]

[0174] A mixture of 55.4 g of terpineol, the primary solvent, and 27.7 g of 2-(2-butoxyethoxy)ethyl acetate (BEA), the cosolvent, was mixed to prepare a solvent mixture designated T / BEA (see Example 1). The mixture was stirred at room temperature for 30 minutes. A 3 wt% ethyl cellulose (EC-H) solution designated T / BEA_EC-H (3%) was prepared by mixing 0.3088 g of ethyl cellulose (EC-H), the binder material (see Example 1), with 9.98 g of the solvent mixture, T / BEA. The solution was stirred overnight at 80°C to completely dissolve the EC-H, followed by cooling to room temperature. 0.3355 g of PFS sample number F2531-120-2 (see Example 1) was mixed with 3.1 g of T / BEA_EC-H(3%) varnish to form a 10 wt % PFS dispersion, designated T / BEA_EC-H(3%)-PFS(10%).

[0175] A mixture of 33 g of terpineol, the primary solvent, and 16.5 g of diethylene glycol methyl ether (DGME), the cosolvent, was prepared as T / DGME (T / DGME). 0.303 g of ethyl cellulose (EC-H), the binder material, was mixed with 9.8 g of the T / DGME solvent mixture to prepare a 3 wt% ethyl cellulose (EC-H) solution, designated T / DGME_EC-H(3%). The solution was stirred overnight at 80 °C to completely dissolve the EC-H, followed by cooling to room temperature. 0.4632 g of PFS sample number F2531-120-2 was mixed with 4.2 g of T / DGME_EC-H(3%) varnish to form a 10 wt% PFS dispersion, designated T / DGME_EC-H(3%)-PFS(10%).

[0176] Both dispersions were stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates, and rolling on a bottle roller at 60 rpm for 2 hours. The homogeneous dispersions were stirred at 80°C for an additional 2 hours, and then cooled to room temperature for sedimentation testing.

[0177] As shown in Table 4, varying the co-solvent is one way to adjust the rheological properties of the ink, such as viscosity, which subsequently affects the stability and settling rate of the ink. [Table 4] [Example]

[0178] The following dispersions containing PFS sample number F2531-120-2 were prepared in a manner similar to that disclosed in Example 1 (T / BEA_PVP(3%)-PFS(10%), T / BEA_EC-HH(3%)-PFS(10%), and T / BEA_PEI(3%)-PFS(10%)).

[0179] A 3 wt% PVP solution, designated T / BEA_PVP(3%), was prepared by mixing 0.29 g of PVP with 9.4 g of the T / BEA solvent mixture. A 10 wt% PFS dispersion, designated T / BEA_PVP(3%)-PFS(10%), was prepared by mixing 0.5098 g of PFS sample number F2531-120-2 with 4.6 g of the T / BEA_PVP(3%) varnish.

[0180] A 3 wt% EC-HH solution, designated T / BEA_EC-HH(3%), was prepared by mixing 0.766 g of EC-HH with 24.78 g of the T / BEA solvent mixture. A 10 wt% PFS dispersion, designated T / BEA_EC-HH(3%)-PFS(10%), was prepared by mixing 0.4528 g of PFS sample number F2531-120-2 with 4.1 g of the T / BEA_EC-HH(3%) varnish.

[0181] A 3 wt% PVP solution, designated T / BEA_PEI(3%), was prepared by mixing 0.32 g of PEI in 10.6 g of the T / BEA solvent mixture. A 10 wt% PFS dispersion, designated T / BEA_PEI(3%)-PFS(10%), was prepared by mixing 0.4649 g of PFS sample number F2531-120-2 with 4.2 g of T / BEA_PEI(3%) varnish.

[0182] All dispersions were first stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates, and then rolling on a bottle roller at 60 rpm for 2 hours. The homogeneous dispersions were stirred at 80°C for an additional 2 hours and cooled to room temperature for sedimentation testing.

[0183] At 78 minutes, the sample T / BEA_PVP(3%)-PFS(10%) had precipitated by approximately 10%, the sample T / BEA_EC-HH(3%)-PFS(10%) had not precipitated at all, and the sample T / BEA_PEI(3%)-PFS(10%) had precipitated by approximately 70%. At 120 minutes, the sample T / BEA_PVP(3%)-PFS(10%) had precipitated by approximately 10%, the sample T / BEA_EC-HH(3%)-PFS(10%) had not precipitated at all, and the sample T / BEA_PEI(3%)-PFS(10%) had precipitated by approximately 80%. At 16 hours, sample T / BEA_PVP(3%)-PFS(10%) had precipitated approximately 50%, sample T / BEA_EC-HH(3%)-PFS(10%) had precipitated approximately 15%, and sample T / BEA_PEI(3%)-PFS(10%) had precipitated.

[0184] As shown in Table 5, modifying the binder material is a more effective approach to adjust the rheological properties of the ink, such as viscosity, which subsequently affects the ink stability and settling rate. [Table 5] [Example]

[0185] A 20 mL dry vial containing a stir bar was charged with 2-butanol (8.26 g), water (0.203 g, 11.3 mmol), and isobutyric acid (0.2933 g, 2.8 mmol) at room temperature. After stirring the mixture for approximately 15 minutes, tantalum ethoxide (0.844 g, 2.1 mmol) was added dropwise to the stirred solution. The homogeneous solution was allowed to stir at room temperature for 22 hours, yielding a solution of 2 nm Ta2O5 nanoparticles. In a flask, the Ta2O5 nanoparticle solution was mixed with 6.19 g of T / BEA varnish containing 3 wt% EC-H binder material, followed by rotary evaporation to strip the 2-butanol from the homogeneous solution. The remaining solution, designated T / BEA_EC-H_Ta2O5, was optically clear and had a viscosity of 249.9 cP at 25 °C. The solution has 6.9 wt% Ta2O5 and 3.0 wt% binder (or stated another way, the solid binder compound is composed of 70% Ta2O5 and 30% binder). The solution has an effective refractive index of 1.62 (Table 18). By adjusting the content of metal oxide dispersed in the binder (Example 1 in Table 6) or by replacing Ta2O5 with other metal oxides with lower densities, such as ZrO2 and TiO2 (Example 2 in Table 6), the effective refractive index of the binder material can be further optimized for optimal performance. [Table 6] [Example]

[0186] 0.725 g of PFS sample number F2531-120-2 (see Example 1) was mixed with 2.9 g of T / BEA_EC-H_Ta2O5 (from Example 13) as sample 0305-Ta. The dispersion with a 5 wt% PFS loading was first stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates and rolling on a bottle roller at 60-70 rpm for 2 hours. The homogeneous dispersion was stirred for an additional 2 hours at 80°C and then cooled to room temperature for film coating. [Example]

[0187] A 250 mL dry flask equipped with a stir bar was charged with isopropanol (IPA) (90 mL), water (1.16 g, 64.4 mmol), and isobutyric acid (IBA) (1.7 g, 16.2 mmol) at room temperature. After stirring the mixture for 30 minutes, tantalum ethoxide (5.8 g, 14.4 mmol) was added dropwise to the stirred solution. The homogeneous solution was stirred at room temperature for 21 hours, yielding a solution of 2.2 nm Ta2O5 nanoparticles. In the flask, the Ta2O5 nanoparticle solution was mixed with 3.15 g of ethoxylated trimethylolpropane triacrylate (trade name SR454), a binder material. The isopropanol was stripped from the clear solution using rotary evaporation. The low-boiling solvents (IPA / H2O / IBA) were further stripped using nitrogen blowing. The final clear solution (11.6 g) contained 3.15 g of acrylate and 3.15–3.18 g of Ta2O5 nanoparticles. The weight percentage of the solid content is 1 part acrylate to 1 part Ta2O5 in the final solution. [Example]

[0188] Several waxes containing polymerizable functional groups were combined with 4 g of propylene glycol methyl ether acetate (PGMEA) and heated using a heat gun to produce a homogeneous solution (see Table 7). These samples were cooled and allowed to stand to determine which waxes induced gelation and increased viscosity in the solvent.

[0189] Sample F2664-5-8 crystallized upon cooling to a stiff paste-like consistency, and was diluted with an additional 4 g of PGMEA and heated again until homogenous. Upon cooling a second time, a stable, opaque dispersion with fewer crystals formed.

[0190] 1 g of PFS Sample No. 395 (see Example 1) was added to Sample F2664-5-12, and 2 g of PFS Sample No. 395 was added to Sample F2664-5-8 to produce a dispersion containing 21 wt. % solids and 2 wt. % wax. These samples were heated to re-dissolve the wax and then vortexed to thoroughly mix. Sample F2664-5-3 (20 wt. % PFS in PGMEA without wax) was further vortexed to mix again, and all three samples were allowed to settle to observe their settling behavior. After approximately 7 minutes, approximately 50% of the solids in Sample F2664-5-3 had settled, while approximately 15% of the solids in Sample F2664-5-12 had settled, and approximately 10% of the solids in Sample F2664-5-8 had settled. At 10.5 minutes, sample F2664-5-12 had settled approximately 15% further, while sample F2664-5-8 had settled approximately 10% further. [Table 7] [Example]

[0191] 0.1 g of wax Sample 2280-129 (di(octadecyl) fumarate) was combined with 4 g of isobornyl acrylate (Sample No. F2664-5-15), and 0.09 g of wax Sample 2280-116 (octadecyl cinnamide) was combined with 4 g of isobornyl acrylate (Sample No. F2664-5-16). Both samples were heated with a heat gun until homogeneous, then cooled and allowed to stand. Upon cooling, F2664-5-15 gelled, while F2664-5-16 crystallized. 1 g of PFS Sample No. 395 (see Example 1) was added to F2664-5-15, and the sample was heated to remelt the wax and vortexed to mix thoroughly. Upon cooling, the mixture formed a thick, fluid dispersion. However, the solids in F2664-5-15 settled at approximately the same rate as sample F2664-5-1, which contained no wax. [Example]

[0192] 0.1 g of functionalized wax Sample 2280-121 (dodecyl cinnamide) was dissolved in 2 g of ethylene glycol phenyl ether methacrylate (1.85 mL, Sample No. F2664-5-17), 2 g of polypropylene glycol dimethacrylate (1.98 mL, Sample No. F2664-5-18), and 2 g of triethylene glycol dimethacrylate (1.83 mL, Sample No. F2664-5-19). The samples were heated until homogeneous, cooled, and allowed to settle. Samples F2664-5-18 and F2664-5-19 remained homogeneous upon cooling, while Sample F2664-5-17 formed an opaque, thick dispersion. 0.5 g of PFS Sample No. 395 (see Example 1) was added to Sample F2664-5-17. Separate samples of 0.5 g of PFS Sample No. 395 and 2 g of ethylene glycol phenyl ether methacrylate (Sample No. F2664-5-20) were prepared. Sample No. F2664-5-17 was heated to melt the wax, and Samples Nos. F2664-5-17 and F2664-5-20 were vortexed to mix thoroughly and allowed to cool and settle.

[0193] After 25 minutes, approximately 15-20% of the solids in sample F2664-5-20, which contained no wax, had settled, while the solids in sample F2664-5-17, which contained 4% wax by weight, had not yet begun to settle. Both samples were inverted at approximately 25 minutes. This resulted in flow of the dispersion for sample F2664-5-20, while the wax-containing sample (sample F2664-5-17) did not flow toward the cap of the vial; instead, it remained at the bottom of the vial. The samples were then returned to their original orientation (cap up) and allowed to stand for an additional hour. At 105.5 minutes, settling was observed in sample F2664-5-20, but not in sample F2664-5-17. As previously noted, sample number F2664-5-20 flowed toward the cap upon inversion, whereas sample number F2664-5-17 did not flow toward the cap but remained at the bottom of the vial (top of the inverted vial). [Example]

[0194] Five solvent-based dispersants were received and used as received (see Table 8). [Table 8]

[0195] PFS sample number 395 (see Example 1) was dispersed in isopropanol (IPA) to prepare A series samples (10 wt % PFS) with and without dispersant (Table 9). [Table 9]

[0196] PFS sample number F2531-120-2 (see Example 1) containing an MgF2 coating was dispersed in IPA to prepare B series samples (10 wt% PFS) with and without dispersant (Table 10). [Table 10]

[0197] All dispersions were initially stirred at room temperature for 2 hours, followed by vigorously mixing on a vortex mixer for 1-2 minutes to reduce particle agglomerates, and then rolling on a bottle roller at 60-70 rpm for 2 hours. The homogeneous dispersions were stirred at 80°C for an additional 2 hours and cooled to room temperature for sedimentation testing.

[0198] The PFS particles in sample A-3, which contained TEGO 687, immediately settled to the bottom. This indicates that the TEGO 687 dispersant acts like a flocculant, interacting with the PFS particles through either hydrogen bonding or van der Waals forces to form large, loose aggregates. After 9 minutes, most of the PFS particles in the control sample, A-6, settled to the bottom. In contrast, sample A-5, which contained TEGO 690, showed almost no settling. In terms of stability, the order of stability from highest to lowest is TEGO 690 > TEGO 689 > control > TEGO 655 > TEGO 685 > TEGO 687. A similar trend was observed for PFS sample number F2531-120-2. [Example]

[0199] 0.5 g of PFS Sample No. 395 (see Example 1) and 97.6 mg of dispersant BYK®-7410-ET (a denatured urea solution available from BYK Additives and Instruments) were combined in a 3-dram vial with 2.535 mL (2 g) of absolute ethanol to form Sample No. F2664-5-22, which had a 3.8% dispersant loading. 0.5 g of PFS Sample No. 395 and 44.0 mg of dispersant BYK®-7410-ET were combined in a 3-dram vial with 2.535 mL (2 g) of absolute ethanol to form Sample No. F2664-5-23, which had a 1.7% dispersant loading. The vial was vortexed and allowed to settle to observe settling behavior. Both samples containing BYK®-7410-ET at 3.8% and 1.7% loadings gelled. The results showed no particle settling within 5 minutes, except for the solvent-only sample, sample number F2664-5-24, which showed approximately 70% settling. Samples F2664-5-22 and F2664-5-23 were then inverted for 5 minutes. The gel in F2664-5-22 did not move, but approximately 10% (top) of the gel in F2664-5-23 flowed toward the vial cap. [Example]

[0200] An example of using MgF2 coating to increase the zeta potential of PFS is shown in Table 11. All samples were from the same batch of PFS (PFS sample number 40C180101-01ATS, D10 / D50 / D90 = 16.7 / 26.1 / 39.3 μm), but differed in the amount and thickness of the MgF2 coating.

[0201] PFS sample number 40C180101-01ATS was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The powder had a D50 particle size of 26.1 μm as measured by SEM. The powder has a Mn % content of approximately 1.58%.

[0202] PFS sample number 40C180101-01ATS was surface coated with different amounts of MgF2, as shown in Table 11. A typical procedure for coating the phosphor was to add 100 mL of a 0.22 g / mL solution of MgSiF6·6H2O in a 17.5% aqueous solution of H2SiF6, using a magnetic stir bar, and K2SiF6:Mn in 400 mL of a 49% saturated aqueous solution of HF containing K2SiF6. 4+The phosphor cake was added over 30 minutes to a reaction mixture containing 50g of MgSiF6·6H2O. The mixture was vigorously stirred (300 rpm) for 30 seconds, then the stirring was reduced to 120 rpm. After the addition was complete, the stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to settle for 5 minutes. The supernatant was decanted and discarded. It was then transferred to a plastic Buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off, and the phosphor cake was washed five times with a total of 600 mL of acetone, stirring the solids before each wash. The product was dried under vacuum for 3 days and then sieved through a 170-mesh membrane to obtain the final coated product. The appropriate amount of MgSiF6·6H2O in a 17.5% H2SiF6 aqueous solution was used to prepare 40C180101-01ATS-F1934-75-Mg10 as described in Table 12 to obtain the desired MgF2 content.

[0203] Zeta potential was measured in ethanol using a folded capillary cell. PFS with a higher weight of MgF2 coating tended to increase the zeta potential. The addition of the MgF2 surface coating was also evidenced by reduced QE degradation and increased particle stability after 200 hours of testing at 85°C and 85% RH. [Table 11] [Example]

[0204] The stability of PFS Sample No. 395 (see Example 1), which does not contain an MgF2 coating and has a zeta potential of approximately 4.1 mV when measured in isopropanol, was compared with that of PFS Sample No. F2531-120-2 (see Example 1), which contains an MgF2 coating and has a zeta potential of 57.2 mV when measured in isopropanol. The two powders were dispersed and thoroughly mixed in each of the following solvents: 2-butanol, isopropanol, and ethanol, and then allowed to stand for a sedimentation test. Regardless of the solvent, the suspension of PFS Sample No. 395, which does not contain an MgF2 coating, quickly settled to the bottom, while the suspension of PFS Sample No. F2531-120-2, which contains an MgF2 coating, settled by less than 10% over the same period. [Example]

[0205] PFS(K2SiF6:Mn 4+ The haze of films containing 1.41% Sylgard™ 184A / B silicone encapsulant from Dow Chemical was evaluated. Two silicone binder materials were used: a two-part silicone encapsulant with a refractive index (RI) of 1.41 (product name: Sylgard™ 184A / B) from Dow Chemical and a two-part LED silicone encapsulant with a RI of 1.54 (product name: SCR-1011A / B) from Shin-Etsu Chemical Corporation.

[0206] All PFS samples listed in Table 12 were prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. Mn content was determined by XRF.

[0207] For Comparative Example 1, 0.78 g of PFS (Sample ID 040-1700501) was added to a premixed blend of Sylgard™ 184A (2.10 g) and Sylgard™ 184B (0.21 g). The mixture was thoroughly mixed using a thin wooden stick to obtain a uniform blend. This was then used to degas for 30 minutes to remove any air bubbles. 0.70 g of the mixture was manually poured into a mold to create a circular tape with a diameter of 2.87 cm, which was then cured at 90°C for 30 minutes. A digital caliper was used to measure the thickness to be 793 μm.

[0208] All other films were prepared using a doctor blade with a gap height of 127 μm. For samples with a 25 wt% loading (Comparative Examples 1-4 and Inventions 1-2), 0.25 g of PFS was added to a premixed blend of 0.70 g of Sylgard™ 184A and 0.07 g of Sylgard™ 184B. For samples with a 50 wt% PFS loading, 0.77 g of PFS was added to a premixed blend of 0.70 g of Sylgard™ 184A and 0.07 g of Sylgard™ 184B (Comparative Examples 5-7, Inventions 3-4), or to a premixed blend of 0.38 g of SCR-1011A and 0.38 g of SCR-1011B (Examples 8-10 and Inventions 5-6). Each mixture was thoroughly mixed using a thin wooden stick to obtain a uniform blend. This was then used to degas for 30 minutes to remove any air bubbles. Approximately 1.0 mL of each mixture was applied to a pre-cleaned 2" x 3" glass slide and processed with a doctor blade using a 127 μm gap to produce a 127 μm thick wet film. This was cured at 90°C for 30 minutes to yield a dry film with a thickness of 127 μm.

[0209] Haze measurements were performed using a home-made Hazemeter. The Hazemeter consists of an 8-inch integrating sphere and a collimated LED light source. The film sample was placed at the entrance of the integrating sphere. Each measurement measures two transmission values ​​at 450 nm, with either the exit sealed with a cap [total transmission, shown as T%(total)] or the exit without a cover cap [scattered transmission, shown as T%(scattered)]. The haze value is the ratio of T%(scattered) divided by T%(total). As shown in Table 12, the haze of PFS-containing films can be optimized by varying Mn%, particle size, and scattering intensity through controlling the refractive index of the matrix. [Table 12]

[0210] The amount of activator Mn incorporated into the phosphor (referred to as Mn%) has a significant effect on the color conversion. The color conversion characteristics of a film of PFS (25 wt%) dispersed in silicone illuminated with a blue LED are shown in Table 13. Increasing the degree of incorporation of Mn% in PFS reduces the bleed-through of blue light and increases the intensity of red emission. [Table 13] [Example]

[0211] Poly(vinyl phenyl sulfide) (PVPS) with a refractive index of 1.657 (purchased from Aldrich (product number 640212) and used as received) was mixed with 8.7 g of T / BEA (see Example 1), designated T / BEA_PVPS (3%), and stirred overnight at 80 °C to obtain a clear solution. 1.44 g of PFS sample number F2664-43-1 (see Example 4) was mixed with 2.16 g of T / BEA_PVPS varnish to obtain a suspension with a PFS concentration of 40 wt % designated T / BEA_PVPS-PFS (40%). The suspension with a PFS loading of 5 wt % was first stirred at room temperature for 2 h, followed by vigorously mixing in a vortex mixer for approximately 2 min to reduce particle agglomerates and rolling on a bottle roller at 60-70 rpm for 2 h. The homogeneous suspension was stirred at 80°C for an additional 2 hours and cooled to room temperature for film coating.

[0212] The T / BEA_PVPS-PFS (40%) suspension was then used to spin-coat a PFS:PVPS film. A pre-cleaned glass slide was used as the substrate for spin-coating, which was performed in air. Approximately 0.5 mL of the suspension was added to the substrate and spun for 60 seconds to obtain a wet film. The film thickness could be adjusted by using different spin speeds. Prior to testing, the coated substrate was baked on a hotplate preheated to 150 °C for 10 minutes. The dried final film consisted of 93 wt% PFS dispersed in 7 wt% PVPS and had a thickness of 13 μm. The film had a blue absorption of 41% and a blue-to-red conversion efficiency of 17%. [Example]

[0213] 25 mg of CsSe / ZnS core-shell type green-emitting quantum dot material (QD) (purchased from Aldrich with product number 748056) was added to 1.0 g of T / BEA_PVPS-PFS(40%) (according to Example 24) and mixed well to prepare a new suspension with 38.8% PFS and 3.0% QDs, designated T / BEA_PVPS-PFS(39.0%)-QD(2.4%). The suspension was used to spin-coat PFS:PVPS:QD films. Pre-cleaned glass slides were used as substrates for spin-coating in air. Approximately 0.5 mL of the suspension was added onto the substrate and spun for 60 seconds to obtain a wet film. The film thickness could be adjusted by using different spin speeds. Before testing, the coated substrates were baked on a preheated hotplate at 150 °C for 10 minutes. The final dried film was approximately 45 μm thick and consisted of 90.3 wt% PFS, 5.6% QDs, and 4.1% PVPS. The film had a blue absorption of 89%. [Example]

[0214] 1.5 g of Sylgard™ 184 and 0.33 g of PFS (K2SiF6:Mn 4+ ) (see Table 14) to provide an 18% fill weight of PFS, and the formulation was coated onto a pre-cleaned 3" x 2" glass plate using a doctor blade (see Table 14). For PFS sample number 320, see Example 6.

[0215] PFS sample number F2539-33 was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours under a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The powder was coated with MgF2 as follows: 75.0 mL of a 0.22 g / mL MgSiF6·6H2O solution in a 17.5% H2SiF6 aqueous solution was added to a magnetic stir bar and a 1.425 L solution of K2SiF6:Mn in 49% HF saturated aqueous solution. 4+ The phosphor cake was added to a reaction mixture containing 125 g of acetone over a 30-minute period. The mixture was vigorously stirred (300 rpm) for 30 seconds, after which the stirring was reduced to 120 rpm. After the addition was complete, the stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to settle for 10 minutes. The supernatant was decanted and discarded. It was mixed with 400 mL of a 49% HF-saturated aqueous solution containing K2SiF6. The wash mixture was allowed to settle for 10 minutes, after which the supernatant was decanted and discarded. It was transferred to a plastic Buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off, and the phosphor cake was washed five times with a total of 800 mL of acetone, agitating the solids before each wash. The product was dried under vacuum for 3 days and subsequently sieved through a 170 mesh membrane to obtain the coated final product (Mn%=2.35, 18.8 μm unsonicated D50 particle size, 2.5% MgF 2を The coated PFS sample number F2539-33 was obtained.

[0216] PFS sample number F2531-73B was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a 49% HF solution nearly saturated with K2SiF6 and annealed at 540°C for 8 hours under a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh and washed in a secondary wash step in a 49% HF solution nearly saturated with K2SiF6 for 30 minutes. The PFS sample had a D50 particle size of 16.0 μm (without sonication). The PFS sample was coated in PGMEA containing 2.5 wt% Hypermer™ KD4 as described in Example 36. [Table 14]

[0217] Film uniformity was analyzed using a Radiant Vision Systems imaging colorimeter with TrueTest™ software. Illuminant (Lv) uniformity measurements are based on 100% uniformity. Higher measurements indicate more uniform films. Films with very low overall contrast and color difference are preferred. Table 15 shows the results. [Table 15] [Example]

[0218] The effect of grinding media, typical solvents, wetting agents, additives, MgF2 coating, and grinding time on particle size and quantum efficiency (QE) is shown in Table 16. Hansen parameters for each solvent are also included in Table 16.

[0219] The following is a typical wet-milling process: At room temperature, 36 g of spherical grinding beads (Fisher, diameter: 1.44 mm), 10 mL of liquid medium, and optionally 1.5 mL of wetting agent (e.g., 20% TEGO® 689 in butyl acetate), other additives (e.g., dipotassium hydrogen phosphate, K2HP), were placed in a dry 25 mL NALGENE bottle. 2.5 g of PFS sample number GRC030620BTGA474 (K2SiF6:Mn 4+ ) was added to the bottle, the bottle was sealed, and placed on a roller mill at 78 rpm for 10 to 40 hours or at 1000 rpm for 2 to 4 hours. After drying under vacuum for 24 hours, the milled PFS powder was obtained by a centrifugation or filtration process.

[0220] PFS sample number GRC030620BTGA474 (K2SiF6:Mn) with 3.48% Mn% was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. 4+ ) was prepared. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The PFS powder has a Mn content of 3.48%.

[0221] However, the performance of PFS particles during milling is sensitive to the solvent medium used to facilitate milling and pulverization, especially for PFS with high Mn% loadings (Table 16). Commonly used solvents such as methanol, ethanol, and acetone significantly degrade the performance of PFS. Milling of PFS particles, especially those with high Mn%, may be accomplished using solvents such as oleic acid, dibutyl phosphate, hexane, heptane, and hexadecane, as shown in Table 16. [Table 16] [Example]

[0222] PFS powders, especially those with small particle sizes, tend to agglomerate. For example, the particle sizes (D10 / D50 / D90) of GRC101819ATGA(450) measured with a Horiba particle size analyzer after no sonication, 3 minutes of sonication, and 7 minutes of sonication were (10.3 / 32.1 / 87.5 μm), (7.3 / 11.0 / 16.9 μm), and (7.3 / 8.5 / 9.9 μm), respectively. The significant decrease in particle size upon sonication indicates substantial agglomeration of GRC101819ATGA(450).

[0223] Oleic acid (OA) was used to coat PFS particles via solvothermal synthesis or a simple mixed adsorption process. 2.5 mL (7.1 mmol) of oleic acid (Sigma-Aldrich / 364525) was dissolved in 7.5 mL of absolute absolute ethanol (Sigma-Aldrich / 459836). 0.8405 g of PFS sample number GRC101819ATGA(450) was dispersed in the above solution and stirred for 20 minutes. After 20 hours of stirring at 40 °C, the suspension was placed in a 25 mL hydrothermal reactor and heated at 140 °C for 6 hours. The suspension was cooled to room temperature, diluted with 10 mL of isopropanol (IPA), and centrifuged at 6,000 rpm for 10 minutes. The crude product was washed with IPA and centrifuged twice more. After drying under vacuum for 24 hours, 0.682 g of OA-coated PFS powder was prepared.

[0224] Two other PFS samples, Sample No. GRC101819ATGA(474) and Sample No. GRC101819ATGA(395), were processed in a similar manner, and the results are shown in Table 17. After processing, the differences in particle size and span (B) measured without and with 7 minutes of sonication were small relative to the respective control materials. The samples maintained good %QE (quantum efficiency).

[0225] PFS sample numbers GRC101819ATGA(450), GRC101819ATGA(474), and GRC101819ATGA(395) were prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powders were washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powders were sieved through a 280 mesh screen. [Table 17] [Example]

[0226] A solvent mixture designated toluene / BEA was prepared by mixing 27.1847 g of toluene with 27.4994 g of 2-(2-butoxyethoxy)ethyl acetate (BEA). The solvent mixture was stirred at room temperature for 15-30 minutes. A 4.2% EC-HH solution designated toluene / BEA_EC-HH (4.2%) was prepared by mixing 0.4886 g of binder material, EC-HH (see Example 1), in 11.0682 g of the toluene / BEA solvent mixture. The varnish was stirred overnight at 80°C to completely dissolve the binder and then cooled to room temperature. The varnish had a viscosity of approximately 800 cP at 25°C. 1.4688 g of PFS sample number F2664-68-1 was mixed with 2.1545 g of Toluene / BEA_EC-HH(4.2%) varnish to obtain an ink formulation designated Toluene / BEA_EC-HH(4.2%) / PFS(40%)-061420-B.

[0227] PFS Sample No. F2664-68-1 was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours under a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh sieve. The powder was coated with MgF2 as follows: 11.75 mL of a 0.22 g / mL MgSiF6·6H2O solution in a 17.5% H2SiF6 aqueous solution was added to a magnetic stir bar and a 760 mL solution of K2SiF6:Mn in 49% HF saturated water. 4+ The resulting solution was added to a reaction mixture containing 77 g of K2SiF6 over a 30-minute period. The mixture was vigorously stirred (300 rpm) for 30 seconds, after which the stirring was reduced to 120 rpm. After the addition was complete, the stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to settle for 7 minutes. The supernatant was decanted and discarded. It was mixed with 380 mL of a 49% saturated aqueous HF solution containing K2SiF6. The wash mixture was allowed to settle for 7 minutes, after which the supernatant was decanted and discarded. It was transferred to a plastic Buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off, and the phosphor cake was washed five times with a total of 800 mL of acetone, agitating the solids before each wash. The product was dried under vacuum for 3 days and then sieved through a 170 mesh membrane to give the final coated product (PFS sample number F2664-68-1 with 3.08% Mn%, 101% relative QE, and 9.1 μm D50 particle size).

[0228] The toluene / BEA_EC-HH (4.2%) / PFS (40%)-061420-B suspension was stirred at room temperature for 2 hours, vigorously mixed on a vortex mixer for 1-2 minutes, and sonicated for 10 minutes to reduce particle agglomerations. It was then rotated on a bottle roller at 60 rpm for 2 hours. The homogenous suspension was stirred at 80 °C for an additional 2 hours and cooled to room temperature.

[0229] The formulations were used to spin-coat PFS:EC films. Pre-cleaned glass slides were used as substrates for spin-coating in air. Approximately 0.7 mL of the dispersion was applied onto the substrate and spun for 60 seconds to obtain a wet film, which was then dried on a preheated hotplate at 150°C for 10 minutes to obtain the final dried film. The spin-coating conditions and properties of the final dried film are summarized in Table 18. [Table 18]

[0230] 1.8965 g of PFS sample number GRC030620BTGA474 (see Example 27) was mixed with 2.8527 g of Toluene / BEA_EC-HH(4.2%) varnish to obtain an ink formulation designated Toluene / BEA_EC-HH(4.2%) / PFS(40%)-072920.

[0231] The PFS has a Mn% incorporation of approximately 3.48%. The suspension was stirred at room temperature for 2 hours, vigorously mixed on a vortex mixer for 1-2 minutes, sonicated for 10 minutes to reduce particle agglomerations, and then rolled on a bottle roller at 60 rpm for 2 hours. The homogenous suspension was stirred at 80°C for an additional 2 hours and cooled to room temperature.

[0232] The formulations were used to spin-coat PFS:EC films. Pre-cleaned glass slides were used as substrates for spin-coating in air. Approximately 0.7 mL of the dispersion was applied onto the substrate and spun for 60 seconds to obtain a wet film, which was then dried on a preheated hotplate at 150°C for 10 minutes to obtain the final dried film. The spin-coating conditions and properties of the final dried film are summarized in Table 19. [Table 19] [Example]

[0233] A solvent mixture designated toluene / BEA was prepared by mixing 27.1847 g of toluene with 27.4994 g of 2-(2-butoxyethoxy)ethyl acetate (BEA). The mixture was stirred at room temperature for 15-30 minutes. A 4.2% EC-HH solution designated toluene / BEA_EC-HH (4.2%) was prepared by mixing 0.4886 g of binder material, EC-HH (see Example 1), in 11.0682 g of the toluene / BEA solvent mixture. The varnish was stirred overnight at 80 °C to completely dissolve the binder and then cooled to room temperature.

[0234] 1.8965 g of PFS sample number GRC030620BTGA474 (from Example 27), having a relative QE greater than 93% and milled to a 4 μm D50 particle size, was mixed with 2.8527 g of Toluene / BEA_EC-HH(4.2%) varnish to yield an ink formulation designated Toluene / BEA_EC-HH(4.2%) / PFS(40%)-072920. The PFS had a Mn loading of approximately 3.48%. The suspension was stirred at room temperature for 2 hours, vigorously mixed on a vortex mixer for 1-2 minutes, sonicated for 10 minutes to reduce particle agglomerates, and then rolled on a bottle roller at 60 rpm for 2 hours. The homogeneous suspension was stirred for an additional 2 hours at 80°C and cooled to room temperature.

[0235] The formulations were used to spin-coat PFS:EC films. Pre-cleaned glass slides were used as substrates for spin-coating in air. Approximately 0.7 mL of the dispersion was applied onto the substrate and spun for 60 seconds to obtain a wet film, which was then dried on a preheated hotplate at 150°C for 10 minutes to obtain the final dried film. The spin-coating conditions and properties of the final dried film are summarized in Table 20. [Table 20] [Example]

[0236] Triethylene glycol monomethyl ether (TGME) obtained from Sigma-Aldrich (catalog number 317292) and diethylene glycol dimethyl ether (DGDE) were used as the solvent. The solvent was mixed with the binder material, ethyl cellulose EC-HH (see Example 1), to make a 1% binder varnish called TGME / DGME-1%EC-HH (see Table 21). 0.5776 g of PFS sample number 070820A (KSiF:Mn 4+ ) was mixed with TGME / DGME-EC-HH(1.0%) varnish to obtain 6.6703 g of an ink formulation designated TGME / DGME-EC-HH(1.0%) / PFS(8.0%).

[0237] PFS sample number 070820A was prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The PFS sample had a relative QE of 43%, and the powder was milled to a D50 particle size of 1.1 μm.

[0238] The TGME / DGME-EC-HH (1.0%) / PFS (8.0%) suspension was stirred at room temperature for 2 hours, vigorously mixed on a vortex mixer for 1-2 minutes, and sonicated for 10 minutes to reduce particle agglomerations. It was then rolled on a bottle roller at 60 rpm for 2 hours. The homogeneous suspension was stirred at 60°C for an additional 2 hours and cooled to room temperature for inkjet printing. A typical print was obtained using the TGME / DGME-EC-HH (1.0%) / PFS (8.0%) formulation. This formulation was inkjet printed into a pattern on a polyethylene terephthalate (PET) substrate. Commercially available MFL-003 ink from Fuji Film was used as a reference (see Table 21). [Table 21]

[0239] A Fuji Film Dimatix Materials Printer (DMP-2831) equipped with a 10 pL ink cartridge (DMC-11610, 16 nozzles, nozzle diameter 21 μm) was used. The nozzle plate was made of Si / SiO2 material, and the contact angle of water on the surface was 100°. [Example]

[0240] For Example 32, chemicals are listed in Table 22. [Table 22]

[0241] TiO2-1-Slurry: A 20 mL dry vial containing a stir bar was charged with sec-butanol (12 mL), water (0.3489 g, 19.4 mmol), and isobutyric acid (IBA) (0.3502 g, 4 mmol) at room temperature. After stirring the mixture for 30 minutes, titanium(IV) isopropoxide (0.87 g, 3 mmol) was added dropwise to the stirred solution. The homogeneous solution, designated TiO2-1-Slurry, was allowed to stir at room temperature. After 5 hours, the particle size, characterized by a Malvern Zetasizer Dynamic Light Scattering, was 2.45 nm, and after 28 hours, it was 3.04 nm.

[0242] TiO2-2-Slurry: A 50 mL dry vial containing a stir bar was charged with 2-propanol (18 mL), water (0.1856 g, 10.3 mmol), and lactic acid (0.35 g, 3.9 mmol) at room temperature. After stirring the mixture for 30 minutes, titanium(IV) isopropoxide (0.8269 g, 2.9 mmol) was added dropwise to the stirred solution. The homogeneous solution, designated TiO2-2-Slurry, was allowed to stir at room temperature. After 20 hours, the particle size, characterized by a Malvern Zetasizer Dynamic Light Scattering, was slightly greater than 3 nm.

[0243] TiO2-3-Slurry: A 50 mL dry vial containing a stir bar was charged with sec-butanol (18 mL), water (0.2109 g, 11.7 mmol), and lactic acid (0.3756 g, 4.16 mmol) at room temperature. After stirring the mixture for 30 minutes, titanium(IV) isopropoxide (0.9091 g, 3.2 mmol) was added dropwise to the stirred solution. The homogeneous solution, designated TiO2-3-Slurry, was allowed to stir at room temperature. After 20 hours, the particle size, characterized by a Malvern Zetasizer Dynamic Light Scattering, was slightly greater than 3 nm.

[0244] TiO2-4-Slurry: A 50 mL dry vial containing a stir bar was charged with 2-propanol (19.74 g), water (1.13 g, 63 mmol), and IBA (1.0 g, 11.3 mmol) at room temperature. After stirring the mixture for 30 minutes, titanium(IV) isopropoxide (5.11 g, 18 mmol) was added dropwise to the stirred solution. A homogeneous solution, designated TiO2-4-Slurry, was obtained by stirring at room temperature. The solution became cloudy and turned into a white slurry within 2-3 minutes, indicating the formation of aggregates. [Example]

[0245] Four different solvent samples (dibutyl phosphate (DBP), oleic acid (OA), bis(2-ethylhexyl) phosphate (BEHP), and terpineol) were evaluated for the removal of agglomerates and stabilization of TiO2 nanoparticles in isopropanol. Four glass vials were washed and dried. 2 mL of cloudy white TiO2-4-slurry (from Example 32) was added to each vial. One of the solvent samples to be evaluated (0.5 mL) was added to each vial.

[0246] The solvent DBP changed from a cloudy slurry to a clear suspension, while the solvents OA, BEHP, and terpineol (Vial-D) did not change the slurry (it remained cloudy white). All suspensions were sonicated for 10 minutes. After sonication, the suspension containing BEHP became clear. After 2 days of storage at ambient conditions, only the suspension containing DBP remained clear. The vial containing BEHP became cloudy again. The vials containing OA and terpineol exhibited settling and phase separation, suggesting particle aggregation.

[0247] The TiO2-4-slurry sample containing DBP was dried using a flowing atmosphere and further dried in an oven at 145 °C. The coarse solid powder was then ground to a finer powder using an agate mortar and pestle and analyzed using X-ray diffraction (XRD), which was performed using an Empyrean instrument at 45 kV*40 mA. The resulting TiO2 nanoparticles are considered amorphous and do not exhibit any crystalline phases. [Example]

[0248] Using a stream of N2, 3.9416 g of a TiO2 nanoparticle suspension sample, TiO2-1-slurry (from Example 32), was concentrated to 0.8186 g of a clear gel-like suspension containing 53.4% ​​(0.4375 g) of TiO2. This was then mixed in a flask with 1.5406 g of varnish containing the solvent mixture toluene / BEA (1:1) and 6.1 wt% ethyl cellulose EC-HH (see Example 1). The resulting suspension (2.3592 g = 1.5406 g + 0.8186 g) was optically clear and is hereafter referred to as toluene / BEA_EC-HH_TiO2. Subsequently, 2.1302 g of the toluene / BEA_EC-HH_TiO2 suspension was added to a vial containing 0.9897 g of PFS sample number GRC030620BTGA474, which had a relative QE of approximately 90% (see Example 27). PFS sample number GRC030620BTGA474 was milled to a D50 particle size of 4.3 μm using oleic acid (see Example 27) and mixed thoroughly. The solid content in the final suspension, hereafter referred to as toluene / BEA_EC-HH_TiO2-PFS-33, was 0.9897 g (46.5 wt %) of PFS, 0.395 g (18.5 wt %) of TiO2, and 0.0854 g (4.0 wt %) of EC-HH. The suspension with 5 wt% PFS loading was first stirred at room temperature for 2 h, followed by vigorously mixing on a vortex mixer for 1–2 min to reduce particle agglomerates, and then rolled on a bottle roller at 60–70 rpm for 2 h. It was stirred at 80 °C for an additional 2 h, and then cooled to room temperature for film coating.

[0249] PFS:PVPS films were then spin-coated using the toluene / BEA_EC-HH_TiO2-PFS-33 suspension. Pre-cleaned glass slides were used as substrates for spin-coating, which was performed in air. Approximately 0.3 mL of the suspension was applied to the substrate and spun for 60 seconds to obtain a wet film. Film thickness could be adjusted by using different spin speeds. Prior to testing, the coated substrates were baked on a preheated hotplate at 150 °C for 10 minutes. The dried final film contained 67.3 wt.% PFS and 26.9 wt.% TiO2 dispersed in 5.8 wt.% EC-HH.

[0250] The performance of the spin-coated films is summarized in Table 23. The films, spun at 0.8 krpm, were then characterized using a Titan Themis SEM / TEM. TEM samples were prepared by removing several small pieces of film from the glass substrate using a scalpel. These film pieces were then placed between two glass slides, and the slides were moved back and forth to reduce the size of the film pieces and reduce them to as much powder as possible. This film powder was placed on a 3 mm diameter carbon-coated copper grid. The compositional spectrum obtained by TEM confirmed the presence of TiO2 and PFS. [Table 23] [Example]

[0251] To 1.0 g of toluene / BEA_EC-HH_TiO2-PFS-33 prepared in Example 33, 0.10 g of dibutyl phosphate (DBP) was added. The final suspension, hereafter referred to as toluene / BEA_EC-HH_TiO2-DBP-PFS-34, was stirred at 80 °C for an additional 2 h, followed by vigorously mixing in a vortex mixer for 1–2 min to reduce particle agglomerates, and then cooled to room temperature for film coating. Spin coating was performed in the same manner as in Example 33. The dried final film consisted of 67.3 wt% PFS and 26.9 wt% TiO2 dispersed in 5.8% ethyl cellulose EC-HH as a binder. The performance of the spin-coated film is summarized in Table 24. [Table 24] [Example]

[0252] Three anionic dispersants from the Hypermer™ family from Croda Inc. were evaluated in propylene glycol methyl ether acetate (PGMEA) and isobornyl acrylate (IA): Hypermer™ KD4-LQ-(AP), designated KD4, is polyhydroxystearic acid stearate (octadecanoic acid, 12-hydroxy-homopolymer, octadecenoate, CAS number: 58128-22-6); Hypermer™ KD24-SS-(RB), designated KD24, is polyoxyethylene (10) ether phosphate (PEG-10 oleyl ether phosphate, CAS number: 39464-69-2); and Hypermer™ KD57-LQ-(JP), designated KD57, is a polyester composed of 2-(octen-1-yl)-succinic acid (CAS number: 28805-58-5).

[0253] PFS Sample No. 327 was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. K2SiF6:Mn 4+The powder was washed and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The powder was then washed for 30 minutes in a nearly saturated 49% HF solution of K2SiF6.

[0254] Samples with a total solids loading of 25 wt% were prepared by combining 2.5 wt% and 5 wt% (relative to PFS) anionic dispersant with PFS Sample No. 327 and PGMEA. The samples were briefly shaken to mix, spun at 80 rpm for 10 minutes, filtered through Whatman #4 filter paper, and washed with 20 mL of triple acetone. The first wash was used to rinse the sample bottle, and the solid filter cake was agitated after washes 1 and 2. After the final wash, the filter cake was transferred to a vacuum desiccator and dried under vacuum overnight. The samples were then sieved through a 170-mesh nylon screen and analyzed (see Table 25).

[0255] Each dispersant reduced the D50 particle size by 50-60%, narrowed the particle size distribution (e.g., span) by 30-50%, and reduced the degree of dispersion and aggregation in the sample, if desired.

[0256] All three anionic dispersant materials showed a 1-6% decrease in %QE. KD4 showed a 2-3% decrease in QE loss after 100 hours of HTHH relative to the control sample. KD24 and KD57 showed a 3-9% increase in QE loss after 100 hours of HTHH relative to the control sample. The lower %QE of PFS sample #327 suggests that some of the observed %QE degradation is due to the K2SiF6:Mn starting material. 4+ It was hypothesized that this was due to insufficient sample quality. [Table 25]

[0257] Anionic Hypermer™ dispersant or potassium oleate dispersant (2.5 wt. % dispersant loading based on PFS), PFS Sample No. 337 (K2SiF6:Mn4+ , annealed, treated, and roasted) and PGMEA to prepare samples with a total solids loading of 45 wt. %. Samples with a total solids loading of 40 wt. % were prepared by combining anionic Hypermer™ dispersant or potassium oleate dispersant (2.5 wt. % dispersant loading relative to PFS), 2.5 wt. % PFS Sample No. 337, and IA.

[0258] The samples were briefly shaken to mix, spun at 80 rpm for 30 minutes, filtered through Whatman #4 filter paper, and washed with 20 mL of 3x acetone. The first wash was used to rinse the sample bottle, and the solid filter cake was agitated after washes 1 and 2. After the final wash, the filter cake was transferred to a vacuum desiccator and dried under vacuum overnight. The samples were then sieved through a 170-mesh nylon screen and analyzed (see Table 26).

[0259] Each Hypermer™ dispersant reduced the D50 particle size by 30-45% and narrowed the particle size distribution (e.g., span) by 10-40%, reducing dispersity and agglomeration in the sample, if desired. Potassium oleate produced a low D50 particle size and narrow particle size distribution, reducing dispersity and agglomeration in the sample, if desired.

[0260] All three anionic Hypermer™ dispersant materials had a very low impact on %QE. KD24 increased %QE by less than 1%, while KD57, KD4, and potassium oleate decreased %QE by approximately 1-3%. HTHH data was not collected. [Table 26] [Example]

[0261] Dispersants from Lubrizol Corporation were evaluated in propylene glycol methyl ether acetate (PGMEA), ethyl acetate (EA), and ethanol. Solplus™ D540 or Solsperse™ 45000, Solplus™ D541, Solsperse™ 41000, Solsperse™ 65000, and Solsperse™ 85000 are anionic dispersants containing phosphate-based coordinating groups with polyol or polyester-polyol stabilizing groups of various lengths and various amounts of acid functionality on the phosphate. Solplus™ D570 is a partially neutralized polyacrylate with polyol stabilizing groups. Solsperse™ wv400 is a nonionic polyurethane-based material. Solsperse™ 71000 is a comb-shaped zwitterionic polymer or comb-shaped multifunctional copolymer with amine and acid groups.

[0262] PFS Sample No. 344 was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. K2SiF6:Mn 4+ The powder was washed and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh. The powder was then washed for 30 minutes in a nearly saturated 49% HF solution of K2SiF6. The powder was subjected to a "roasting" process, and after the second washing treatment, an additional low-temperature anneal was performed at 150°C for 4 hours in a 20% fluorine:80% nitrogen atmosphere.

[0263] PFS Sample No. 388 was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. K2SiF6:Mn 4+ The powder was washed and annealed in a 20% fluorine:80% nitrogen atmosphere at 540°C for 8 hours. The annealed powder was sieved through a 280 mesh sieve.

[0264] Samples with a total solids loading of 15 wt% were prepared by combining Solsperse™ wv400 or Solplus™ D540 dispersant at a 5 wt% dispersant loading (based on the PFS) with PFS Sample No. 344 and ethanol or EA. Samples with a total solids loading of 15 wt% were prepared by combining potassium oleate dispersant at a 2.5 wt% dispersant loading based on the PFS with PFS Sample No. 344 and ethanol.

[0265] The samples were briefly shaken to mix, spun at 80 rpm for 10 minutes, filtered through Whatman #4 filter paper, and washed with 20 mL of 2x ethanol and 20 mL of 3x acetone. The first wash was used to rinse the sample bottle, and the solid filter cake was agitated after washes 1-4. After the final wash, the filter cake was transferred to a vacuum desiccator and dried under vacuum overnight. The samples were then sieved through a 170-mesh nylon screen and analyzed (see Table 27).

[0266] Solsperse™ wv400 reduced the D50 particle size by approximately 55% in both solvents, but also reduced the particle size distribution by 35-40%, reducing dispersibility and agglomeration in samples where desired. Solplus™ D540 reduced the D50 particle size by 56% in ethyl acetate and approximately 40% in ethanol. It also reduced the particle size distribution (span) by 38% in ethyl acetate and approximately 12% in ethanol, reducing dispersibility and agglomeration in samples where desired. Potassium oleate reduced the D50 particle size by approximately 52% and the span by approximately 18%, reducing dispersibility and agglomeration in samples where desired.

[0267] Solplus™ D540 did not decrease the %QE of the PFS material. Solsperse™ wv400 decreased the %QE by approximately 4-5% in both solvents. Potassium oleate decreased the %QE by approximately 2%. [Table 27]

[0268] The remaining dispersant from Lubrizol was evaluated. Samples with a total solids loading of 25 wt. % were prepared by combining the dispersant (at 5 wt. % loading relative to PFS) with PFS Sample No. 388 and either PGMEA or ethanol.

[0269] K2SiF6:Mn 4+ After combining the and dispersion solutions, the samples were briefly shaken to mix and spun at 80 rpm for 10 minutes before being filtered through Whatman #4 filter paper and washed with 20 mL of 2x ethanol and 20 mL of 3x acetone. They were then transferred to a vacuum desiccator and dried overnight under vacuum. The first wash was used to rinse the sample bottle, and after washes 1-4, the solid filter cake was agitated. The samples were then sieved through a 170-mesh nylon screen and analyzed (see Table 28).

[0270] In ethanol, all dispersants performed well, reducing the D50 particle size by 55-65% (compared to PFS Sample No. 388 without solvent or dispersant and Sample No. 1 without dispersant), reducing the particle size distribution (e.g., span) by 50-80%, and, if desired, reducing the degree of dispersion and agglomeration in the sample. In PGMEA, all dispersants except Solsperse™ 85000 performed well, reducing the D50 particle size by 50-60% (compared to PFS Sample No. 388 without solvent or dispersant and Sample No. 8 without dispersant), reducing the particle size distribution by 50-60%, and, if desired, reducing the degree of dispersion and agglomeration in the sample. Solsperse™ 85000 reduced both the D50 particle size and particle size distribution, and, if desired, reducing the degree of dispersion and agglomeration in the sample, but was less effective than Sample No. 8 without dispersant. A comb-like zwitterionic copolymer (Solsperse™ 71000) bearing amine and acid functional groups was synthesized by the polymerization of K2SiF6:Mn in ethanol and PGMEA. 4+The acrylate salt of a polymer containing polyol stabilizing groups (Solplus™ D570) and one of the polyol-stabilized phosphate ester dispersants (Solsperse™ 41000) were also very effective.

[0271] In ethanol, the %QE effect was minimal, with a 0-1% decrease in %QE. The %QE loss after 100 hours of HTHH testing increased substantially compared to PFS Sample No. 388 without solvent or dispersant and Sample 1 without dispersant. In PGMEA, the %QE effect was minimal, with a change of less than 0.5% relative to PFS Sample No. 388 without solvent or dispersant. Similarly, the %QE loss after 100 hours of HTHH testing increased substantially for the dispersant-coated materials from the 40% decrease in QE for PFS Sample No. 388 without solvent or dispersant, and increased substantially by 49-61% for Sample 8 without dispersant. The comb-like zwitterionic copolymers exhibited the greatest %QE loss after 100 hours at 80°C and 80% RH. Further testing of the comb-like zwitterionic copolymers was performed and is described below. [Table 28] [Example]

[0272] Anionic dispersants obtained from BYK Additives and Instruments were evaluated, including phosphate and carboxylic acid esters (BYK®-W-9011, Disperbyk®-102, Disperbyk®-110, Disperbyk®-111, Disperbyk®-180, and Disperplast® 1142), polyacrylates (Disperbyk®-190 and Disperbyk®-2055), and structured or controlled polymerization technology (CPT) derived acrylates (Disperbyk®-2008, Disperbyk®-2012, and Disperbyk®-2013). Three nonionic polyurethane-based dispersants (BYK®-9077, Disperbyk®-168, and Disperbyk®-185) and several cationic hyperbranched polyamine dispersants (BYK®-9076, Disperbyk®-2152, Disperbyk®-2155, Disperbyk®-2157, Disperbyk®-2158, Disperbyk®-2200, and Disperbyk®-2205). Additional materials include small molecule surfactants (BYK®-1788 and BYK®-3410 (sodium docusate, CAS number: 577-11-7) and Disperbyk®-2117 and Disperbyk®-2118 (EO / PO block copolymers).

[0273] Disperbyk®-110, a phosphate polyester anionic dispersant, at 5 wt. % loading (based on PFS), PFS samples with various processing levels (PFS sample no. 386 (K2SiF6:Mn 4+ , annealed), PFS sample number 428 (K2SiF6:Mn 4+ , annealed and treated), PFS sample number 421 (K2SiF6:Mn 4+ , annealed), PFS sample number 421 (K2SiF6:Mn4+ , annealed and treated), PFS sample number 425 (K2SiF6:Mn 4+ , annealed and treated) and PFS sample no. 341 (K2SiF6:Mn 4+ , annealing, treating, and roasting) with ethanol or ethyl acetate to prepare samples with a total solids loading of 17 wt.%.

[0274] PFS samples were prepared using the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh screen. The annealed and treated PFS sample was then washed for 30 minutes in a nearly saturated 49% HF solution of K2SiF6. PFS sample No. 341 was subjected to a "roasting" process and, after a secondary washing treatment, an additional low-temperature anneal at 150°C for 4 hours in a 20% fluorine:80% nitrogen atmosphere.

[0275] K2SiF6:Mn 4+ After combining the and dispersion solutions, the samples were briefly shaken to mix and spun at 80 rpm for 10 minutes before being filtered through Whatman #4 filter paper and washed with 20 mL of 2x ethanol and 20 mL of 3x acetone. They were then transferred to a vacuum desiccator and dried overnight under vacuum. The first wash was used to rinse the sample bottle, and after washes 1-4, the solid filter cake was agitated. The samples were then sieved through a 170-mesh nylon screen and analyzed (see Table 29).

[0276] For the annealed PFS samples (Samples 1, 6, and 7), the dispersant coating reduced the D50 particle size by 60–70%, potentially reducing dispersion and agglomeration in the sample. Samples 6 and 7 reduced the particle size distribution by 40%, while Sample 1 exhibited a particle size distribution similar to that of solvent-free PFS Sample No. 386. For the annealed and treated phosphor materials, the dispersant coating reduced the D50 particle size by 35–60%, potentially reducing dispersion and agglomeration in the sample. Samples 2 and 3 reduced the particle size distribution by approximately 40%, while Sample 4 exhibited a particle size distribution similar to that of PFS Sample No. 425. The annealed, treated, and roasted phosphor PFS materials exhibited a 30% reduction in D50 particle size and a 10% reduction in particle size distribution, potentially reducing dispersion and agglomeration in the sample.

[0277] Regardless of the degree of processing of the PFS samples, the addition of Disperbyk®-110 resulted in a decrease in %QE of 1-3%. [Table 29]

[0278] A single PFS sample, No. 434 (K2SiF6:Mn), with a 5 wt% dispersant loading was used for PFS in ethanol at 25 wt% total solids loading and PFS in PGMEA at 21 wt% total solids loading. 4+ , annealed and treated) were used to evaluate the remaining dispersants obtained from BYK Additives and Instruments. Disperbyk®-168, Disperbyk®-2157, Disperbyk®-2158, Disperbyk®-2205 and BYK®-1788 were not soluble / miscible in ethanol, and BYK®-3410 was not soluble / miscible in PGMEA, and these dispersants were not tested in those solvents.

[0279] After combining the PFS sample with the dispersant solution, the sample was briefly shaken to mix and then rotated at 80 rpm for 10 minutes (ethanol sample) or 40 rpm for 15 minutes (PGMEA sample). The ethanol sample was then filtered through Whatman #4 filter paper, washed with 20 mL of 3x ethanol and 20 mL of 2x acetone, and then transferred to a vacuum desiccator and dried overnight under vacuum. The PGMEA sample was filtered through Whatman #4 filter paper, washed with 20 mL of 3x PGMEA and 20 mL of 2x acetone, and then transferred to a vacuum desiccator and dried overnight under vacuum. For both solvents, the first wash was used to rinse the sample bottle, and after washes 1 through 4, the solid filter cake was agitated. All samples were then sieved through a 170-mesh nylon screen and analyzed; the data are collected in Table 30 for the ethanol-coated sample and Table 31 for the PGMEA-coated sample.

[0280] The hyperbranched polyamine cationic dispersants (Samples 3–5) performed well in ethanol, producing a substantial reduction in D50 particle size (60–70%) and particle size distribution (17–47%) (compared to PFS Sample No. 434 without solvent or dispersant and Sample No. 1 without dispersant), potentially reducing sample dispersion and agglomeration. Coating Sample 2 with potassium oleate resulted in a substantial reduction in D50 particle size (53%) (compared to PFS Sample No. 434 without solvent or dispersant), potentially reducing sample dispersion and agglomeration, but increasing particle size distribution (see Table 30). The polyurethane-based nonionic dispersants (Samples 6 and 7) also performed well in ethanol, producing a very low D50 particle size (70% reduction) near 13.0 μm and a significant reduction in particle size distribution (44%), potentially reducing sample dispersion and agglomeration. Phosphate ester and carboxylate ester-based anionic dispersants (Samples 8–12) produced substantial reductions in D50 particle size (55–65%) and particle size distribution (0–25%), reducing dispersibility and aggregation in samples where desired. Polyacrylate and CPT-derived acrylate-based anionic dispersants (Samples 13–17) performed very well (compared to PFS Sample No. 434 and Sample 1), producing substantial reductions in D50 particle size (60–70%) and particle size distribution (17–47%), reducing dispersibility and aggregation in samples where desired. Sample 18, coated with a small molecule surfactant, exhibited substantial reductions in D50 particle size (70%) and particle size distribution (34%), reducing dispersibility and aggregation in samples where desired. Samples 19 and 20 coated with Disperbyk®-2117 and Disperbyk®-2118 showed a substantial reduction (50-60%) in the D50 particle size, reducing the degree of dispersion and agglomeration in the samples where desired, although the particle size distribution of these coated materials is similar to that of Sample 1.

[0281] Hyperbranched polyamine cationic dispersants (Samples 3-5) performed well in ethanol, exhibiting minimal impact on %QE of ±1% (see Table 30). Samples 3-5 showed a slight increase in QE loss (poor performance) relative to PFS Sample No. 434 and Sample 1 after 100 hours of HTHH testing at 80°C and 80% RH. Polyurethane-based nonionic dispersants (Samples 6 and 7) also performed well in ethanol, exhibiting no discernible impact on %QE. These dispersants also showed a slight increase in QE loss (poor performance) relative to PFS Sample No. 434 and Sample 1 after 100 hours of HTHH testing. Phosphate ester and carboxylate ester-based anionic dispersants (Samples 8-12) performed comparable to or very slightly better than PFS Sample No. 434 and Example 1, exhibiting minimal impact on %QE (±0-1.5%). These dispersants also showed a very slight increase (poor performance) in QE loss after 100 hours of HTHH testing relative to PFS Sample No. 434 and Sample 1. The polyacrylate and CPT-derived acrylate-based anionic dispersants (Examples 13-17) performed excellently when compared to PFS Sample No. 434 and Sample 1, exhibiting minimal impact on %QE (±1%). The acrylate-based dispersants exhibited a significant increase in QE loss after 100 hours of HTHH testing relative to PFS Sample No. 434 and Sample 1. Sample 18, coated with a small molecule surfactant, exhibited excellent %QE but the lowest %QE loss (48.6%) after 100 hours of HTHH testing. Samples 19 and 20 coated with Disperbyk®-2117 and Disperbyk®-2118 showed no effect on %QE and only a slight increase in %QE loss after 100 hours of HTHH testing. [Table 30]

[0282] Hyperbranched polyamine cationic dispersants (Samples 3–9) performed well in PGMEA, providing a substantial reduction in D50 particle size (60–70%) and particle size distribution (15–40%) (compared to PFS Sample No. 434 without dispersant or solvent and Sample No. 1 without dispersant), and reduced sample dispersion and aggregation, if desired. Coating Sample 2 with potassium oleate provided a substantial reduction in D50 particle size (71%) and span (36%) (compared to PFS Sample No. 434 without solvent or dispersant), and reduced sample dispersion and aggregation, if desired (see Table 31). Polyurethane-based nonionic dispersants (Samples 10 and 12) also performed well in PGMEA, providing a substantial reduction in D50 particle size (65–70%) and significant reduction in particle size distribution (27–39%) (compared to PFS Sample No. 434 without solvent or dispersant), and reduced sample dispersion and aggregation, if desired. Phosphate ester and carboxylate ester-based anionic dispersants (Samples 13-17) produced substantial reductions in D50 particle size (60-70%) and particle size distribution (5-40%), reducing dispersibility and aggregation in samples where desired. Polyacrylate and CPT-derived acrylate-based anionic dispersants (Samples 18-22) performed very well (compared to PFS Sample 434 and Sample 1), producing substantial reductions in D50 particle size (70%) and particle size distribution (34-44%), reducing dispersibility and aggregation in samples where desired. Sample 23, coated with a small molecule surfactant, exhibited excellent reductions in D50 particle size (70%) and particle size distribution (27%), reducing dispersibility and aggregation in samples where desired. Samples 24 and 25 coated with Disperbyk®-2117 and Disperbyk®-2118 showed a substantial reduction in D50 particle size (65-67%), reducing the degree of dispersion and agglomeration in the samples where desired, although the particle size distribution of these coated materials is comparable to Sample 1.

[0283] Hyperbranched polyamine cationic dispersants (Samples 3-9) performed well in PGMEA, exhibiting minimal impact on %QE of 0.5%. Samples 3-9 showed a slight to moderate increase in QE loss of 35-50% (poor performance) relative to PFS Sample 434 and Sample 1 after 100 hours of HTHH testing at 80°C and 80% RH. Polyurethane-based nonionic dispersants (Samples 10 and 12) also performed well in PGMEA, exhibiting no discernible impact on %QE. These dispersants also showed a moderate increase in QE loss of 37-47% (poor performance) relative to PFS Sample 434 and Sample 1 after 100 hours of HTHH testing. Phosphate ester and carboxylate ester based anionic dispersants (Samples 13-17) performed comparable to or slightly better than PFS Sample No. 434 and Example 1, with minimal impact on %QE (±0.5%). These dispersants also showed a moderate increase (poor performance) of 38-45% in QE loss after 100 hours of HTHH testing compared to PFS Sample No. 434 and Sample 1. Polyacrylate and CPT derived acrylate based anionic dispersants (Examples 18-22) performed superiorly compared to PFS Sample No. 434 and Sample 1, with minimal impact on %QE (±0.5%). These acrylate based dispersants showed a significant increase (39-50%) in QE loss after 100 hours of HTHH testing compared to PFS Sample No. 434 and Sample 1. Sample 23, coated with a small molecule surfactant, exhibited excellent %QE, but this sample also showed a high %QE loss of 41.7% after 100 hours of HTHH testing. Samples 24 and 25, coated with Disperbyk®-2117 and Disperbyk®-2118, showed no effect on %QE, with only a slight increase in %QE loss after 100 hours of HTHH testing. [Table 31] [Example]

[0284] Dispersants from Croda Inc., Lubrizol Corporation, and BYK Additives and Instruments and potassium oleate were evaluated. Dispersants (shown in Table 32) at 5 wt. % dispersant loading (relative to PFS) were combined with PFS Sample No. 421 and ethanol to prepare samples at 25 wt. % total solids loading.

[0285] After combining the PFS sample with the dispersant solution, the sample was vortexed to mix and spun at 80 rpm for 10 minutes. The sample was filtered through Whatman #4 filter paper, washed with 20 mL of 2x ethanol and 20 mL of 3x acetone, and then transferred to a vacuum desiccator and dried under vacuum overnight. The first wash was used to rinse the sample bottle, and after washes 1-4, the solid filter cake was agitated. All samples were sieved through a 170-mesh nylon screen and analyzed (see Table 32).

[0286] All dispersants showed a substantial reduction in D50 particle size (55-65%) and particle size distribution (30-80%), reducing the degree of dispersion and aggregation in the samples where desired.

[0287] All dispersants showed minimal impact on %QE (±0.8%) except for Sample 6. Samples 1, 7, and 10 showed slight increases (poor performance) in %QE loss relative to PFS Sample No. 421, while all other dispersants produced moderate to substantial increases (30-50%) in %QE loss after 100 hours of HTHH testing. [Table 32]

[0288] Five samples from Table 32 that produced the greatest reduction in D50 particle size, as well as the dispersant sodium dodecylbenzene sulfonate (NaSDBS), were evaluated. Selected dispersants from Table 32 (shown in Table 33) at dispersant loadings of 2.5 wt. % and 1 wt. % (relative to PFS) and PFS sample number 421 (K2SiF6:Mn 4+ Samples were prepared at a total solids loading of 25 wt.% by combining the dispersant sodium dodecylbenzenesulfonate (K2SiF6:Mn) with ethanol at dispersant loadings of 5 wt.%, 2.5 wt.%, and 1 wt.% (relative to PFS). 4+ , annealed and treated) and ethanol to prepare samples with a total solids loading of 25 wt. %.

[0289] After combining the PFS sample with the dispersant solution, the sample was vortexed to mix and spun at 80 rpm for 10 minutes. The sample was filtered through Whatman #4 filter paper, washed with 20 mL of 2x ethanol and 20 mL of 3x acetone, and then transferred to a vacuum desiccator and dried under vacuum overnight. The first wash was used to rinse the sample bottle, and after washes 1-4, the solid filter cake was agitated. All samples were sieved through a 170-mesh nylon screen and analyzed (see Table 33).

[0290] At lower loadings, these materials maintained their performance, exhibiting excellent D50 particle size reductions (60-70%). Samples 1, 2, 9, and 10 showed moderate reductions in particle size distribution (28-45%), while Samples 3-8 achieved excellent reductions in particle size distribution (75-80%), reducing dispersibility and agglomeration in the samples when desired. Sodium dodecylbenzenesulfonate performed comparable to Samples 1, 2, 9, and 10, producing substantial reductions in D50 particle size (55-60%) and substantial reductions in particle size distribution (27-37%), reducing dispersibility and agglomeration in the samples when desired. In this case, the 5 wt% and 2.5 wt% coated samples performed optimally with D50 particle sizes of 12.1-12.7 μm, respectively, while the 1 wt% coated sample exhibited a D50 particle size of 14.1 μm.

[0291] Dispersants also showed minimal impact on %QE (±1% change) for PFS Sample No. 421 at low loadings. Sodium dodecylbenzene sulfonate performed comparably to Samples 1, 2, 9, and 10, impacting %QE by less than 1%. In many cases, lowering the dispersant loading to 2.5 wt% or 1 wt% resulted in moderately good HTHH performance (e.g., low %QE drop for 5 wt% loading). Solplus™ D570 and Solsperse™ 71000 exhibited a 50% drop in %QE at 5 wt%, decreasing to 43% and 36%, respectively, at 1 wt%. Hypermer™ KD4 exhibited a 34% drop in QE at 5 wt%, decreasing to 28% at 1 wt% loading. However, Disperbyk®-2055, Disperbyk®-2013 and NaSDBS all exhibited similar or higher %QE reduction at 2.5 wt% or 1 wt% for 5 wt% loading. [Table 33] [Example]

[0292] The settling behavior of two PFS samples, PFS Sample No. 554 and PFS Sample No. F2699-17-3, was evaluated in the binder material ethoxylated trimethylolpropane triacrylate (trade name SR454, available from Sartomer Americas).

[0293] PFS sample number 554 was replaced with PFS sample number 1016BTGA (K2SiF6:Mn 4+ ). PFS Sample No. 1016BTGA was prepared by the process described in U.S. Patent Application Publication No. 2018 / 0163126. The powder was washed in a nearly saturated 49% HF solution of K2SiF6 and annealed at 540°C for 8 hours in a 20% fluorine:80% nitrogen atmosphere. The annealed powder was sieved through a 280 mesh screen.

[0294] Sample No. F2699-17-3 was also prepared from PFS Sample No. 1016BTGA (as above) and subsequently coated with an overcoat of MgF (2.5 wt%). The powder was coated with MgF as follows: 4.1 mL of a 0.22 g / mL MgSiF 6H O solution in a 17.5% H Si F aqueous solution was added to a magnetic stir bar, and 8.1 g of K SiF:Mn in 78 mL of a 49% saturated aqueous HF solution containing K SiF. 4+The phosphor cake was added to the reaction mixture containing K2SiF6 over a 30-minute period. The mixture was vigorously stirred (300 rpm) for 30 seconds, after which the stirring was reduced to 120 rpm. After the addition was complete, the stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to settle for 7 minutes. The supernatant was decanted and discarded. It was mixed with 35 mL of a 49% HF-saturated aqueous solution containing K2SiF6. The wash mixture was allowed to settle for 5 minutes, after which the supernatant was decanted and discarded. It was transferred to a plastic Buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off, and the phosphor cake was washed five times with a total of 100 mL of acetone, stirring the solids before each wash. The product was dried under vacuum for 3 days and then sieved through a 170-mesh membrane to obtain the final coated product.

[0295] 0.3 g of PFS powder was mixed separately with 4.5 g of SR454 to obtain two dispersants with a PFS loading of 6.3 wt%. The two mixtures were stirred at room temperature for 2 hours, followed by vortex mixing for 2 minutes and ultrasonic treatment for 10 minutes. Both mixtures were rotated on a bottle roller at 60 rpm for 2 hours. The suspensions were stirred at 60°C for an additional 2 hours and then cooled to room temperature for sedimentation testing.

[0296] As can be seen in Table 34, PFS Sample No. 554 had a low zeta potential and settled much faster than the estimated settling rate calculated based on its particle size. This indicates significant aggregation of PFS Sample No. 554 in suspension. Although the MgF2-coated sample, PFS Sample No. F2699-17-3, had a high zeta potential, it settled at a much slower rate than PFS Sample No. 554, even though it had a slightly larger particle size. Furthermore, the settling behavior of PFS Sample No. F2699-17-3 closely matched the calculated estimated settling rate, indicating no aggregation occurred in suspension. [Table 34]

[0297] This specification uses examples to disclose the invention, including the best mode, and also to enable those skilled in the art to practice the invention, including making and using any device or system and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they contain equivalent structural elements that do not differ substantially from the literal language of the claims.

Claims

1. An ink composition comprising a binder material and at least one narrow band-emitting phosphor uniformly dispersed throughout said composition, said narrow band-emitting phosphor having a D50 particle size of 0.1 μm to 15 μm, and Mn ４＋ a red-emitting phosphor based on a complex fluorinated material activated by the red-emitting phosphor has an Mn content of at least 1 wt. %; An ink composition having a viscosity in the range of at least 15 cP at 25°C to less than 20 cP at 50°C.

2. 2. The ink composition of claim 1, wherein the binder material is selected from the group consisting of diazonaphthoquinone, ethyl cellulose, novolac resins, poly(methyl acrylate), polyvinyl alcohol, polyvinyl butyral, polyvinylidene fluoride-co-hexafluoropropylene, polyvinyl pyrrolidone, ethoxylated trimethylolpropane triacrylate, polymethyl methacrylate, propoxylated trimethylolpropane triacrylate, pentaacrylate esters, silicone materials, thiol-ene polymers, and mixtures thereof.

3. The ink composition of claim 1 , wherein the binder material comprises at least one of a thermally curable precursor, a photoresist material, or a UV-curable precursor.

4. 2. The ink composition of claim 1, wherein the at least one narrow band-emitting phosphor has a D50 particle size of 0.1 μm to 10 μm.

5. The at least one narrow band-emitting phosphor is a green-emitting U ６＋ The ink composition of claim 1 further comprising an incorporated fluorescent material.

6. The ink composition of claim 1 , further comprising a solvent.

7. 7. The ink composition of claim 6, wherein the solvent is selected from the group consisting of bis(2-ethylhexyl) phosphate, dibutyl phosphate, ethylene glycol phenyl ether methacrylate, isobutyric acid, isobornyl acrylate, isopropanol, propylene glycol methyl ether acetate, polypropylene glycol dimethacrylate, terpineol, triethylene glycol dimethacrylate, water, 2-(2-butoxyethoxy)ethyl acetate, 2,2,3,3-tetrafluoro-1-propanol, cyclohexanone, diethylene glycol methyl ether, toluene, and mixtures thereof.

8. The ink composition of claim 1 , wherein the composition further comprises a quantum dot material or a color filter pigment capable of absorbing blue light.

9. 10. The ink composition of claim 1, further comprising one of a number of additives selected from the group consisting of dispersants, rheology modifiers, electrolytes, metal oxide nanoparticles, scattering particles, and mixtures thereof.

10. The ink composition of claim 1 , wherein the binder material comprises metal oxide nanoparticles.

11. The ink composition of claim 9 , wherein the rheology modifier comprises a gelling agent.

12. The scattering particles have a particle size of more than 1 μm, and Al ２ O ３ 10. The ink composition of claim 9, wherein the inorganic oxide is selected from the group consisting of zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, titanium dioxide, zinc oxide, and combinations thereof.

13. 10. The ink composition of claim 9, wherein the metal oxide nanoparticles are selected from the group consisting of zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, titanium dioxide, zinc oxide, and combinations thereof.

14. The at least one narrow band emitting phosphor is γ-Ba ２ UO ２ (P.O. ４ ) ２ , [Ba, Zn, Mg] (UO ２ ) ３ (P.O. ４ ) ２ , Ba ６ Al ５ P ５ O ２６ :U ６＋ , Ba(UO ２ ) P ２ O ７ , Ba ３ (U.O. ２ ) ２ P ２ O ７ (P.O. ４ ) ２ and combinations thereof. ６＋ The ink composition of claim 1 further comprising an incorporated fluorescent material.

15. The at least one narrow band emitting phosphor has Formula I: A ｘ MF ｙ :Mn ４＋ I (In the formula, A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is MF ｙ is the absolute value of the charge of the ion; The ink composition of claim 1 , comprising a red fluorophore of formula (I), wherein y is 5, 6, or 7.

16. The at least one narrow band emitting phosphor is K ２ SiF ６ : Mn ４＋ or Na ２ SiF ６ : Mn ４＋ The ink composition of claim 1 , comprising:

17. The ink composition of claim 15, wherein the binder material has a higher refractive index than the red phosphor.

18. The ink composition of claim 15, wherein the red phosphor is at least partially coated with a surface coating comprising a metal fluoride or silica.

19. The metal fluoride is MgF ２ , CaF ２ , SrF ２ , BaF ２ , AgF, ZnF ２ , AlF ３ 20. The ink composition of claim 18, wherein the hydroxybenzoate is selected from the group consisting of:

20. 1. An ink composition comprising: a binder material; and at least one narrow-band-emitting phosphor uniformly dispersed throughout said composition, said narrow-band-emitting phosphor having a D50 particle size of 0.1 μm to 15 μm; ６＋ Contains phosphor, green emitting Mn ２＋ Containing phosphor, Mn ４＋ and mixtures thereof; The at least one narrow band-emitting phosphor is a green-emitting U ６＋ containing phosphor and Mn ４＋ and a red-emitting phosphor based on a complex fluorinated material activated by The ink composition, wherein the binder material comprises at least one of a photoresist material or a UV curable precursor.

21. 1. A film comprising at least one narrow-band-emitting phosphor dispersed in a binder matrix, the narrow-band-emitting phosphor having a D50 particle size of 0.1 μm to 15 μm, and Mn ４＋ a red-emitting phosphor based on a complex fluorinated material activated by the red-emitting phosphor has an Mn content of at least 1 wt. %; A film formed from an ink composition having a viscosity in the range of at least 15 cP at 25°C to less than 20 cP at 50°C.

22. 22. The film of claim 21, wherein the film is substantially free of uniformity defects.

23. 22. The film of claim 21, wherein the narrow band-emitting phosphor has a D50 particle size of 0.1 μm to 10 μm.

24. 22. The film of claim 21, wherein the binder matrix comprises a binder material selected from the group consisting of diazonaphthoquinone, ethyl cellulose, novolac resins, poly(methyl acrylate), polyvinyl alcohol, polyvinyl butyral, polyvinylidene fluoride-co-hexafluoropropylene, polyvinyl pyrrolidone, ethoxylated trimethylolpropane triacrylate, polymethyl methacrylate, propoxylated trimethylolpropane triacrylate, pentaacrylate esters, silicone materials, thiol-ene polymers, and mixtures thereof.

25. 22. The film of claim 21, wherein the binder matrix comprises a thermally cured resin, a UV cured resin, or a photoresist material.

26. The at least one narrow band-emitting phosphor is a green-emitting U ６＋ 22. The film of claim 21 further comprising an incorporated phosphor.

27. 22. The film of claim 21, wherein the film further comprises a quantum dot material or a color filter pigment capable of absorbing blue light.

28. 22. The film of claim 21, further comprising one of a number of additives selected from the group consisting of dispersants, rheology modifiers, electrolytes, metal oxide nanoparticles, scattering particles, and mixtures thereof.

29. 22. The film of claim 21, wherein the binder matrix comprises metal oxide nanoparticles.

30. 30. The film of claim 28, wherein the rheology modifier comprises a gelling agent.

31. The scattering particles have a particle size of more than 1 μm, and Al ２ O ３ 29. The film of claim 28, wherein the oxide is selected from the group consisting of zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, titanium dioxide, zinc oxide, and combinations thereof.

32. 30. The film of claim 28, wherein the metal oxide nanoparticles are selected from the group consisting of zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, titanium dioxide, zinc oxide, and combinations thereof.

33. The at least one narrow band emitting phosphor is γ-Ba ２ UO ２ (P.O. ４ ) ２ , [Ba, Zn, Mg] (UO ２ ) ３ (P.O. ４ ) ２ , Ba ６ Al ５ P ５ O ２６ :U ６＋ , Ba(UO ２ ) P ２ O ７ , Ba ３ (U.O. ２ ) ２ P ２ O ７ (P.O. ４ ) ２ and combinations thereof. ６＋ 22. The film of claim 21 further comprising an incorporated phosphor.

34. The at least one narrow band emitting phosphor is represented by Formula I A ｘ MF ｙ :Mn ４＋ I (In the formula, A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is MF ｙ is the absolute value of the charge of the ion; y is 5, 6, or 7.

35. The fluorophore of formula I is K ２ SiF ６ : Mn ４＋ or Na ２ SiF ６ : Mn ４＋ 35. The film of claim 34, wherein:

36. 35. The film of claim 34, wherein the binder matrix has a higher refractive index than the narrow-band emitting phosphor.

37. 35. The film of claim 34, wherein the at least one narrow band-emitting phosphor is at least partially coated with a surface coating comprising a metal fluoride or silica.

38. The metal fluoride is MgF ２ , CaF ２ , SrF ２ , BaF ２ , AgF, ZnF ２ , AlF ３ 38. The film of claim 37, wherein the film is selected from the group consisting of:

39. 22. The film of claim 21, wherein the at least one narrow band-emitting phosphor has a D50 particle size of 0.1 μm to 10 μm, and the film further comprises scattering particles and metal oxide nanoparticles having a particle size of 1 μm to 10 μm.

40. 1. A film comprising at least one narrow-band-emitting phosphor dispersed in a binder matrix, the narrow-band-emitting phosphor having a D50 particle size of 0.1 μm to 15 μm, and a green-emitting U ６＋ Contains phosphor, green emitting Mn ２＋ Containing phosphor, Mn ４＋ and mixtures thereof; The at least one narrow band-emitting phosphor is a green-emitting U ６＋ containing phosphor and Mn ４＋ and a red-emitting phosphor based on a complex fluorinated material activated by A film wherein the binder matrix comprises a UV curable resin or a photoresist material.

41. 22. An article comprising: a substrate; a plurality of spatially separated light sources arranged on the substrate; the film of claim 21 arranged on at least some of the plurality of light sources; and a non-transparent region surrounding at least some of the plurality of light sources.

42. 42. The article of claim 41, wherein at least some of the plurality of light sources are blue LEDs.

43. 42. The article of claim 41, wherein the non-transmissive regions have an optical density of at least 2.

0.

44. 42. The article of claim 41, wherein the non-transmissive regions comprise a black matrix material comprising a non-transmissive material dispersed in a black matrix binder.

45. 45. The article of claim 44, wherein the non-permeable material comprises carbon black particles, dielectric oxides, or metal particles selected from the group consisting of Ni, Co, Fe, Cr, Cu, Pd, Au, Pt, Sn, Zn, and combinations thereof.

46. 22. A device comprising an LED light source optically coupled and / or radiatively coupled to the film of claim 21.

47. A backlighting apparatus comprising the device of claim 46.

48. 47. A lighting apparatus comprising the device of claim 46.

49. A television comprising the backlight device of claim 47.

50. A mobile phone comprising the backlight device according to claim 47.

51. 48. A computer monitor comprising the backlight device of claim 47.

52. 10. A device comprising an LED light source optically coupled and / or radiatively connected to the ink composition of claim 1, wherein the ink composition is cured or dried.

53. A backlighting apparatus comprising the device of claim 52.

54. 53. A lighting apparatus comprising the device of claim 52.

55. A television comprising the backlight device of claim 53.

56. A mobile phone comprising the backlight device according to claim 53.

57. 54. A computer monitor comprising the backlight device of claim 53.

58. 47. The device of claim 46, wherein the LED light source comprises a mini LED or a micro LED.

59. 53. The device of claim 52, wherein the LED light source comprises a mini LED or a micro LED.

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