Process for improved halide materials
A process for treating a luminescent halogen-containing material includes contacting the luminescent halogen-containing material with an atmosphere comprising a halogen-containing oxidizing agent for a period of at least about two hours. The luminescent halogen-containing material has a composition other than (i) A x [MF y ]:Mn 4+ , where A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MF y ] ion; and y is 5, 6 or 7; (ii) Zn 2 [MF 7 ]:Mn 4+ , where M is selected from Al, Ga, In, and combinations thereof; (iii) E[MF 6 ]:Mn 4+ , where E is selected from Mg, Ca, Sr, Ba, Zn, and combinations thereof; and where M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof; or (iv) Ba 0.65 Zr 0.35 F 2.70 :Mn 4+ .
1. A process for treating a luminescent halogen-containing material, the process comprising
contacting the luminescent halogen-containing material with an atmosphere comprising a halogen-containing oxidizing agent for a period of at least about two hours;
with the proviso that the luminescent halogen-containing material comprises a composition other than:
(i) Ax [MFy]:Mn4+, where A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7;
(ii) Zn2[MF7]:Mn4+, where M is selected from Al, Ga, In, and combinations thereof;
(iii) E[MF6]:Mn4+, where E is selected from Mg, Ca, Sr, Ba, Zn, and combinations thereof; and where M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof; or
(iv) Ba0.65Zr0.35F2.70:Mn4+.
2. A process according to claim 1 , wherein the luminescent halogen-containing material is selected from selected from the group consisting of doped halosilicates, doped halophosphates, doped halides, doped oxyhalides, doped haloborates, doped halogermanates, undoped halides, undoped halophosphates, and combinations thereof.
3. A process according to claim 1 , wherein the luminescent halogen-containing material is selected from LaSiO3Cl:Ce3+; LaSiO3Cl:Ce3+, Tb3+; Ca3 SiO4Cl2:Pb2+; Ca3SiO4Cl2:Eu2+; Ba5SiO4Cl6:Eu2+; Ba5SiO4Br6:Eu2+; Mg3SiO3F4:Ti4+; Sr5Si4O10Cl6:Eu2+; Na(Mg2-x; Mnx)LiSi4O10F2:Mn; where 0≤x≤100; Ca5(PO4)3F:Mn2+; Ca5(PO4)3F:Sb2+; Ca5(PO4)3F:Sn2+; Ca5(PO4)3Cl:Eu2+; Ca5(PO4)3Cl:Mn2+; Ca5(PO4)3Cl:Sb2+; Ca5(PO4)3Cl:Sn2+; Ca5(PO4)3(F;Cl):Sb; Mn; (Ba;Ca;Mg)5(PO4)3Cl:Eu2+; Cd5(PO4)3Cl:Mn2+; Sr5(PO4)3Cl:Eu2+; Sr5(PO4)3Cl:Mn2+; Sr5(PO4)3Cl:Sb2+; Sr5(PO4)3Cl:Sn2+; Srs(PO4)3Cl:Eu2+; Pr3+; Ba5(PO4)3Cl:Eu2+; Ba5(PO4)3Cl:U; Ca2Ba3(PO4)3Cl:Eu2+; 3Cd3(PO4)2.CdCl2:Mn2+; 3Ca3(PO4)2.Ca(F;Cl)2:Sb3+; Mn2+; 3Sr3(PO4)2.SrF2:Sn2+; Mn2+; 3Sr3(PO4)2.CaCl2:Eu2+; MgF2:Mn2+; CaF2:Ce3+; CaF2:Eu2+; CaF2:Mn2+; CaF2:Ce3+; Eu2+; CaF2:Ce3+, Tb3+; CaF2:U; CaCl2:Eu2+ in SiO2; CaCl2:Eu2+; Mn2+ in SiO2; BaCl2:Eu2+ in SiO2; CaI2:Eu2+ in SiO2; CaI2:Eu2+; Mn2+ in SiO2; SrF2:Eu2+; SrFBr:Eu2+; SrCl2:Eu2+ in SiO2; Sr(Cl; Br; I)2:Eu2+ in SiO2; CsI:Na+; CsI:T1; CsBr:Eu2+; KCl:Eu2+; RbBr:T1; RbBr:T1+; RbI:T1+; ZnF2:Mn2+; (Zn; Mg)F2:Mn2+; (Ba;Sr)F2:Eu2+; BaFBr:Eu2+; BaBr2:Eu2+; BaFCl:Eu2+; BaFCl:Eu2+; Pb2+; BaFI:Eu2+; Ba2Mg3F10:Eu2+; BaMg3F8:Eu2+; Mn2+; BaY2F8:Er3+, Yb3+; LaBr3:Ce3+; LaCl3:Ce3+; YF3:Mn2+; YF3:Mn2+, Th4+; YF3:Er3+, Yb3+; YF3:Em3+, Yb3+; NaYF4:Er3+, Yb3+; KMgF3:Eu2+; KMgF3:Mn2+; 3.5MgO.0.5MgF2.GeO2:Mn4+; LiAlF4:Mn2+; YOBr:Eu2+; YOCl:Eu2+; YOCl:Ce3+; YOF:Eu2+; YOF:Tb3+; LaOF:Eu3+; LaOCl:Bi3+; LaOCl:Eu3+; LaOBr:Bi3+, Tb3+; Pr3+; Ca2B5O9Br:Eu2+; Ca2B5O9Cl:Eu2+; Ca2B5O9Cl:Pb2+; SrFB2O3.5:Eu2+; Mg4(F)GeO6:Mn2+; Mg4(F)(Ge; Sn)O6:Mn2+; Mg8Ge2O11:Mn4+; BaF2; BaY2F8; CaF2; MgF2; SrF2; KMgF3; RbCaF3; LiYF4 (YLF); Nd:YLF; LiBaAlF6; LiCaAlF6; LiSrAlF6; CeF3; CsF; LaBr3; LaCl3; RbBr; KI; CsI; KCl; CuCl:NaCl; (ErCl3)0.25(BaCl2)0.75; Ca5(PO4)3F; Ca5(PO4)3Cl; Sr5(PO4)3Cl; and combinations thereof.
4. A process according to claim 1 , wherein the atmosphere comprises a fluorine-containing oxidizing agent selected from F2, anhydrous HF, BrF5, NH4HF2, NH4F, AlF3, SbF5, ClF3, BrF3 SbF6,KrF, XeF2, XeF4, NF3 or a combination thereof.
5. A process according to claim 1 , wherein the luminescent halogen-containing material is Mg3SiO3F4:Ti4+; Na(Mg2-x, Mnx)LiSi4O10F2:Mn, where 0≤x≤100; Ca5(PO4)3F:Mn2+; Ca5(PO4)3F:Sb2+; Ca5(PO4)3F:Sn2+; Ca5(PO4)3(F;Cl):Sb; Mn; 3Ca3(PO4)2.Ca(F;Cl)2:Sb3+; Mn2+; 3Sr3(PO4)2.SrF2:Sn2+; Mn2+; MgF2:Mn2+; CaF2:Ce3+; CaF2:Eu2+; CaF2:Mn2+; CaF2:Ce3+;Eu2+; CaF2:Ce3+, Tb3+; CaF2:U; SrF2:Eu2+; SrFBr:Eu2+; ZnF2:Mn2+; (Zn; Mg)F2:Mn2+; (Ba;Sr)F2:Eu2+; BaFBr:Eu2+; BaBr2:Eu2+; BaFCl:Eu2+; BaFCl:Eu2+, Pb2+, BaFI:Eu2+; Ba2Mg3F10:Eu2+; BaMg3F8:Eu2+, Mn2+, BaY2F8:Er3+, Yb3+, YF3:Mn2+; YF3:Mn2+, Th4+, YF3:Er3+, Yb3+, YF3:Em3+, Yb3+, NaYF4:Er3+, Yb3+, KMgF3:Eu2+, KMgF3:Mn2+, 3.5MgO.0.5MgF2 GeO2:Mn4+, LiAlF4:Mn2+; YOF:Eu2+, YOF:Tb3+, LaOF:Eu3+, SrFB2O3.5:Eu2+, Mg4(F)GeO6:Mn2+; Mg4(F)(Ge, Sn)O6:Mn2+; BaF2BaY2F8; CaF2; MgF2; SrF2; KMgF3; RbCaF3; LiYF4 (YLF); Nd:YLF; LiBaAlF6; LiCaAlF6; LiSrAlF6; CeF3; CsF; Ca5(PO4)3F, and combinations thereof.
6. A process according to claim 1 , wherein the luminescent halogen-containing material comprises a dopant.
7. A process according to claim 1 , wherein the luminescent halogen-containing material comprises Eu3+.
8. A process according to claim 1 , wherein the luminescent halogen-containing material is YOBr:Eu3+, YOCl:Eu3+, YOF:Eu3+, LaOF:Eu3, LaOCl:Eu3+, or a combination thereof.
9. A process according to claim 1 , additionally comprising annealing the phosphor at a temperature of at least about 250° C. while contacting the phosphor with the atmosphere comprising fluorine gas.
10. A process according to claim 9 , wherein the elevated temperature is any temperature in a range from about 500° C. to about 600° C.
11. A process according to claim 1 , wherein the halogen-containing oxidizing agent comprises a halogen gas selected from fluorine, chlorine, bromine, iodine, or a combination thereof.
12. A process according to claim 1 , wherein the halogen-containing oxidizing agent comprises fluorine gas.
13. A process according to claim 1 , wherein the atmosphere additionally comprises nitrogen, helium, neon, argon, krypton, xenon, or a combination thereof.
14. A luminescent halogen-containing material produced by a process according to claim 1 .
15. An apparatus comprising a semiconductor light source optically coupled to a luminescent halogen-containing material produced by a process according to claim 1 .
16. An apparatus according to claim 15 , comprising a backlight device.
17. A process according to claim 1 , wherein the luminescent halogen-containing material comprises fluorine.