CN113387565A - 荧光玻璃及其制备方法和用途 - Google Patents
荧光玻璃及其制备方法和用途 Download PDFInfo
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- CN113387565A CN113387565A CN202010176548.7A CN202010176548A CN113387565A CN 113387565 A CN113387565 A CN 113387565A CN 202010176548 A CN202010176548 A CN 202010176548A CN 113387565 A CN113387565 A CN 113387565A
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- fluorescent glass
- ltoreq
- mole fraction
- fluorescent
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- 239000011521 glass Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 230000005284 excitation Effects 0.000 claims abstract description 9
- 229910002637 Pr6O11 Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002834 transmittance Methods 0.000 description 17
- -1 rare earth carbonates Chemical class 0.000 description 16
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910002412 SrMoO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010386 TiI4 Inorganic materials 0.000 description 1
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- 229910009440 Y2(CO3)3 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 229910008047 ZrI4 Inorganic materials 0.000 description 1
- TYTOIPRGKQQICM-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].O.O.[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].O.O.[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3] TYTOIPRGKQQICM-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- PVDYMOCCGHXJAK-UHFFFAOYSA-H europium(3+);oxalate Chemical compound [Eu+3].[Eu+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O PVDYMOCCGHXJAK-UHFFFAOYSA-H 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- CQQZFSZWNXAJQN-UHFFFAOYSA-K europium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Eu+3] CQQZFSZWNXAJQN-UHFFFAOYSA-K 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- GGQZVHANTCDJCX-UHFFFAOYSA-N germanium;tetrahydrate Chemical compound O.O.O.O.[Ge] GGQZVHANTCDJCX-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- UHTYDNCIXKPJDA-UHFFFAOYSA-H oxalate;praseodymium(3+) Chemical compound [Pr+3].[Pr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHTYDNCIXKPJDA-UHFFFAOYSA-H 0.000 description 1
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- XIRHLBQGEYXJKG-UHFFFAOYSA-H praseodymium(3+);tricarbonate Chemical compound [Pr+3].[Pr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XIRHLBQGEYXJKG-UHFFFAOYSA-H 0.000 description 1
- ZLGIGTLMMBTXIY-UHFFFAOYSA-K praseodymium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Pr+3] ZLGIGTLMMBTXIY-UHFFFAOYSA-K 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- XLMQAUWIRARSJG-UHFFFAOYSA-J zirconium(iv) iodide Chemical compound [Zr+4].[I-].[I-].[I-].[I-] XLMQAUWIRARSJG-UHFFFAOYSA-J 0.000 description 1
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
本发明公开了一种荧光玻璃,所述荧光玻璃的组成如下式所示:mPr6O11:nEu2O3:xCaO:yY2O3:zE2O:dSiO2:eRO2;其中,E选自碱金属元素;R选自Zr、Ti和Ge中的一种或多种;m表示Pr6O11的摩尔分数,0.00001<m<0.01;n表示Eu2O3的摩尔分数,0.00005<n<0.05;x表示CaO的摩尔分数,0.0001<x<0.1;y表示Y2O3的摩尔分数,0.1<y<1;z表示E2O的摩尔分数,0.01<z<0.1;d表示SiO2的摩尔分数,0.01<d<0.5;e表示RO2的摩尔分数,0.005<e<0.07;且2x+y+z=4(d+e)。本发明的荧光玻璃在蓝光的激发下产生红色荧光。
Description
技术领域
本发明涉及一种荧光玻璃及其制备方法和用途。
背景技术
在大功率白光LED(发光二极管)灯具中,封装材料热稳定性差、热导率低和光折射率低,这样会严重影响灯具的发光性能及使用寿命。为解决这些问题,国内外科研人员加强了对高性能荧光体的研究。这些荧光体包括玻璃、陶瓷、晶体以及它们的复合体。
CN101619216A公开了一种钠、硅、钇复合掺杂SrMoO4:Eu3+的红色发光材料。该红色发光材料以SrMoO4:Eu3+型红色发光材料为基础掺杂改性,以Na+作为助熔剂和电荷补偿剂、Si4+作为调剂基质组成、并以Y3+作为敏化剂。
CN108277000A公开了一种红色荧光玻璃陶瓷由玻璃粉和红色荧光粉组成;玻璃粉的组成为SiO2、B2O3、ZnO和Na2O;红色荧光粉的组成为0%<Na2O+Li2O+K2O的总含量<6.65%,0%<MgO<8.65%,30%<WO3+MoO3的总含量<49.75%,5%<Gd2O3+La2O3+Y2O3的总含量<34.95%,0%<Eu2O3<22.28%。该红色荧光玻璃陶瓷为以Eu2+粒子激活的钨酸盐和钼酸盐型发光材料。
黄聪研究了Pr3+掺杂钛酸盐红色发光材料(参见“稀土掺杂钛酸盐的红色发光材料的制备与研究”,浙江工业大学化学工程与材料学院,2013年11月),采用Mg2+、Zn2+、Al3+、Cu2 +、Bi3+、Si4+分别对CaTiO3:Pr3+进行共掺杂改性。
发明内容
有鉴于此,本发明的一个目的在于提供一种新组成的荧光玻璃,该荧光玻璃在蓝光的激发下产生红色荧光。进一步地,本发明的荧光玻璃具有较高的发光强度和较高的可见光透过率。
本发明的另一个目的在于提供上述荧光玻璃的制备方法,其制备工艺简单,得到的荧光玻璃具有较高的发光强度和可见光透过率。
本发明的再一个目的在于提供上述荧光玻璃在作为发光二极管封装材料中的应用。
本发明通过如下技术方案实现上述技术目的。
一方面,本发明提供了一种荧光玻璃,该荧光玻璃的组成如式(Ⅰ)所示:
mPr6O11:nEu2O3:xCaO:yY2O3:zE2O:dSiO2:eRO2 (Ⅰ)
其中,E选自碱金属元素;R选自Zr、Ti和Ge中的一种或多种;m表示Pr6O11的摩尔分数,0.00001<m<0.01;n表示Eu2O3的摩尔分数,0.00005<n<0.05;x表示CaO的摩尔分数,0.0001<x<0.1;y表示Y2O3的摩尔分数,0.1<y<1;z表示E2O的摩尔分数,0.01<z<0.1;d表示SiO2的摩尔分数,0.01<d<0.5;e表示RO2的摩尔分数,0.005<e<0.07;且2x+y+z=4(d+e)。
根据本发明的荧光玻璃,优选地,所述的荧光玻璃在蓝光的激发下产生红色荧光。
根据本发明的荧光玻璃,优选地,0.01<x<0.1,0.6<y<1,0.01<z<0.06,0.1<d<0.5,且0.005<e<0.05。
根据本发明的荧光玻璃,优选地,0.00001<m<0.001,且0.00005<n<0.001。
根据本发明的荧光玻璃,优选地,0.7≤m/n≤2.8。
根据本发明的荧光玻璃,优选地,100≤x/n≤300。
根据本发明的荧光玻璃,优选地,2000≤y/n≤8000。
根据本发明的荧光玻璃,优选地,所述荧光玻璃具有如下式之一表示的组成:
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0006Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0003Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01TiO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Na2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02K2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.02CaO:0.88Y2O3:0.02Li2O:0.225SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.07CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.02GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.48Y2O3:0.02Li2O:0.14SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.04Li2O:0.24SiO2:0.015GeO2。
另一方面,本发明提供上述荧光玻璃的制备方法,包括如下步骤:
(1)将荧光玻璃的原料和助熔剂混合均匀,得到混合物;将混合物灼烧,然后冷却,得到灼烧产物;其中,所述的助熔剂为硼酸,灼烧温度为1300~1800℃,且灼烧时间为2~6小时;
(2)将灼烧产物在惰性气体保护下进行热处理,得到荧光玻璃;其中,热处理温度为700~1000℃,且热处理时间为2~6小时。
再一方面,本发明提供了上述荧光玻璃在作为发光二极管封装材料中的用途。
本发明提供了一种新的荧光玻璃,其在蓝光的激发下产生红色荧光。进一步地,本发明的荧光玻璃中各个元素相互配合,提高了荧光玻璃的发光强度和对可见光的透过率。
具体实施方式
下面结合具体实施例对本发明作进一步的说明,但本发明的保护范围并不限于此。
<荧光玻璃>
本发明的荧光玻璃的组成如式(Ⅰ)所示:
mPr6O11:nEu2O3:xCaO:yY2O3:zE2O:dSiO2:eRO2 (Ⅰ)。
式(Ⅰ)中,E表示一种碱金属元素;R表示一种IVB族或IVA族的金属元素。E和R所表示的具体含义如下文所述。
式(Ⅰ)中,m表示Pr6O11的摩尔分数或摩尔比;n表示Eu2O3的摩尔分数或摩尔比;x表示CaO的摩尔分数或摩尔比;y表示Y2O3的摩尔分数或摩尔比;z表示E2O的摩尔分数或摩尔比;d表示SiO2的摩尔分数或摩尔比;e表示RO2的摩尔分数或摩尔比。在本发明中2x+y+z=4(d+e)。上述组成的摩尔分数或摩尔比的取值范围如下文所述。
本发明的荧光玻璃在蓝光的激发下能够产生红色荧光。优选地,激发光(蓝光)的波长范围在425nm~500nm之间。更优选地,激发光谱的最大峰值的波长在435~495nm之间。优选地,发射光(红色荧光)的波长范围在590~650nm之间。更优选地,发射光谱的最大峰值的波长在610~620nm之间。
Pr6O11表示十一氧化六镨。在本发明中0.00001<m<0.01;优选地,0.00001<m<0.001;更优选地,0.0001<m<0.0007。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
Eu2O3表示三氧化二铕。在本发明中0.00005<n<0.05;优选地,0.00005<n<0.001;更优选地,0.0001<n<0.0005。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
m/n表示Pr6O11与Eu2O3的摩尔比。在本发明中0.7≤m/n≤2.8;优选地,1≤m/n≤2.5;更优选地,1.5≤m/n≤2.3。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
CaO表示氧化钙。在本发明中0.0001<x<0.1;优选地,0.01<x<0.1;更优选地,0.03<x<0.08。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
Y2O3表示三氧化二钇。在本发明中0.1<y<1;优选地,0.6<y<1;更优选地,0.7<y<1。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
E表示一种碱金属元素。E可以选自Li、Na和K中的至少一种。优选地,E选自Li或Na中的至少一种。更优选地,E为Li。E2O表示E的氧化物。在本发明中0.01<z<0.1;优选地,0.01<z<0.06;更优选地,0.01<z<0.04。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
x/n表示CaO与Eu2O3的摩尔比。在本发明中,100≤x/n≤300;优选地,200≤x/n≤300;更优选地,220≤x/n≤270。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
y/n表示Y2O3与Eu2O3的摩尔比。在本发明中,2000≤y/n≤8000;优选地,3000≤y/n≤5000;更优选地,4000≤y/n≤4800。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
SiO2表示二氧化硅。在本发明中0.01<d<0.5;优选地,0.1<d<0.5;更优选地,0.1<d<0.4。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
R表示一种IVB族或IVA族的金属元素。R可以选自Zr、Ti和Ge中的至少一种元素。优选地,R选自Ge或Ti中的至少一种元素。更优选地,R为Ge。RO2表示R元素的氧化物。在本发明中,0.005<e<0.07;优选地,0.005<e<0.05;更优选地,0.005<e<0.03。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
在某些实施方式中,0.00001<m<0.01,0.00005<n<0.05,0.0001<x<0.1,0.1<y<1,0.01<z<0.1,0.01<d<0.5,0.005<e<0.07,且2x+y+z=4(d+e)。在另一些实施方式中,0.00001<m<0.001,0.00005<n<0.001,0.01<x<0.1,0.6<y<1,0.01<z<0.06,0.1<d<0.5,0.005<e<0.05,且2x+y+z=4(d+e)。在再一些实施方式中,0.0001<m<0.0007,0.0001<n<0.0005,0.03<x<0.08,0.7<y<1,0.01<z<0.04,0.1<d<0.4,0.005<e<0.03,且2x+y+z=4(d+e)。
根据本发明的一个实施方式,E为Li,R为Ge,0.00001<m<0.01,0.00005<n<0.05,0.0001<x<0.1,0.1<y<1,0.01<z<0.1,0.01<d<0.5,0.005<e<0.07,且2x+y+z=4(d+e)。根据本发明的另一个实施方式,E为Li,R为Ge,0.00001<m<0.001,0.00005<n<0.001,0.01<x<0.1,0.6<y<1,0.01<z<0.06,0.1<d<0.5,0.005<e<0.05,且2x+y+z=4(d+e)。根据本发明的再一个实施方式,E为Li,R为Ge,0.0001<m<0.0007,0.0001<n<0.0005,0.03<x<0.08,0.7<y<1,0.01<z<0.04,0.1<d<0.4,0.005<e<0.03,且2x+y+z=4(d+e)。
本发明的荧光玻璃的具体实例包括但不限于如下式之一表示的组成:
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0006Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0003Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01TiO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Na2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02K2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.02CaO:0.88Y2O3:0.02Li2O:0.225SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.07CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.02GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.48Y2O3:0.02Li2O:0.14SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.04Li2O:0.24SiO2:0.015GeO2。
<制备方法>
本发明的荧光玻璃的制备方法包括灼烧产物的制备步骤及热处理步骤。
将荧光玻璃的原料和助熔剂混合均匀,得到混合物;将混合物灼烧,然后冷却,得到灼烧产物。所得到的荧光玻璃满足式(Ⅰ)所示的组成:
mPr6O11:nEu2O3:xCaO:yY2O3:zE2O:dSiO2:eRO2 (Ⅰ)。
式(Ⅰ)中E、R所表示的含义,m、n、x、y、z、d和e所表示的含义及取值范围,荧光玻璃的具体实例如前文所述。
制备荧光玻璃的原料可以为含有式(Ⅰ)所含有的金属元素和硅元素的氧化物或可热分解为氧化物的碳酸盐、硝酸盐、硫酸盐、草酸盐、卤化物或氢氧化物等。
稀土碳酸盐的实例包括但不限于碳酸钇、碳酸铕、碳酸镨。稀土硝酸盐实例包括但不限于硝酸钇、硝酸铕、硝酸镨。稀土硫酸盐的实例包括但不限于硫酸钇、硫酸铕、硫酸镨。稀土草酸盐的实例包括但不限于草酸钇、草酸铕、草酸镨。稀土卤化物的实例包括但不限于卤化钇、卤化铕、卤化镨。稀土氢氧化物的实例包括但不限于氢氧化钇、氢氧化铕、氢氧化镨。
氧化钙的原料可以为碳酸钙、硝酸钙、硫酸钙、草酸钙、卤化钙或氢氧化钙。
碱金属碳酸盐的实例包括但不限于碳酸锂、碳酸钠、碳酸钾。碱金属硝酸盐的实例包括但不限于硝酸锂、硝酸钠、硝酸钾。碱金属硫酸盐的实例包括但不限于硫酸锂、硫酸钠、硫酸钾。碱金属草酸盐的实例包括但不限于草酸锂、草酸钠、草酸钾。碱金属卤化物的实例包括但不限于卤化锂、卤化钠、卤化钾。碱金属氢氧化物的实例包括但不限于氢氧化锂、氢氧化钠、氢氧化钾。
二氧化硅的原料可以为硅的氧化物及其他含硅化合物,包括但不限于:二氧化硅(SiO2),硅酸包括原硅酸(H4SiO4),偏硅酸(H2SiO3),二硅酸(H2Si2O5),硅烷,四卤化硅(SiCl4),氮化硅(Si3N4),氨基硅,氟硅酸(H2SiF6)。
RO2为IVA族金属元素或IVB族金属元素形成的化合物,例如含钛化合物,含锆化合物或含锗化合物。含钛化合物的原料的实例包括但不限于二氧化钛(TiO2),五氧化三钛(Ti3O5),一氧化钛(TiO),钛酸H4TiO4[TiO2·xH2O或Ti(OH)4)],偏钛酸TiO(OH)2,四氯化钛TiCl4,三氯化钛TiCl3,碘化钛TiI4,硫酸氧钛(TiOSO4·H2O)。含锆化合物的原料的实例包括但不限于氧化锆(ZrO2),卤化锆(ZrF4,ZrI4,ZrCl4),氢氧化锆(Zr(OH)2),氧氯化锆(ZrOCl2),碳酸锆(3ZrO2·CO2·H2O),硫酸锆(Zr(SO4)2),硫酸氧锆(ZrOSO4),硝酸锆(Zr(NO3)4·5H2O)。含锗化合物的原料的实例包括但不限于氧化锗(GeO2),四氯化锗(GeCl4),氢氧化锗(Ge(OH)4)。
本发明中的助熔剂可以选自硼酸、氟化钡、氟化铵和氟化锂中的一种或多种。优选地,助熔剂选自硼酸、氟化钡、氟化铵中的一种或多种。更优选地,助熔剂为硼酸。这样能够提高荧光玻璃的发光强度和对可见光的透过率。
将灼烧产物在惰性气体保护下进行热处理,得到荧光玻璃。在本发明中,灼烧温度可以为1300~1800℃,优选为1400~1700℃,更优选为1500~1600℃。灼烧时间可以为2~6小时,优选为3~6小时,更优选为3~5小时。
在本发明中,惰性气体可以为氮气、氩气或氖气;优选为氮气。热处理的温度可以为700~1000℃,优选为700~900℃,更优选为750~850℃。热处理时间可以为2~6小时,优选为3~6小时,更优选为3~5小时。
<用途>
本发明的荧光玻璃可以单独或者与其它材料复合使用,作为发光二极管的封装材料。
实施例1
制备荧光玻璃的原料为Pr6O11(纯度99.99wt%)、Eu2O3(纯度99.99wt%)、CaCO3(分析纯)、Y2(CO3)3(纯度99.99wt%)、LiCl(分析纯)、SiO2(分析纯)和GeO2(分析纯)。按照表1的荧光玻璃的组成称取各原料。在原料中加入H3BO3(规格为分析纯,用量为各原料总重量的4wt%),混合均匀,得到混合物。
将混合物在1550℃的条件下灼烧4小时,然后浇注急冷,得到灼烧产物。
将灼烧产物在氮气保护下,在800℃的条件下,热处理4小时,得到荧光玻璃。
实施例2~11
根据表1的配方选择和称取实施例2~11的原料,按照实施例1的方法制备荧光玻璃。
表1
编号 | 荧光玻璃组成 |
实施例1 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例2 | 0.0006Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例3 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0003Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例4 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01TiO<sub>2</sub> |
实施例5 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01ZrO<sub>2</sub> |
实施例6 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Na<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例7 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02K<sub>2</sub>O:0.24SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例8 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.02CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.225SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例9 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.07CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.02GeO<sub>2</sub> |
实施例10 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.48Y<sub>2</sub>O<sub>3</sub>:0.02Li<sub>2</sub>O:0.14SiO<sub>2</sub>:0.01GeO<sub>2</sub> |
实施例11 | 0.0004Pr<sub>6</sub>O<sub>11</sub>:0.0002Eu<sub>2</sub>O<sub>3</sub>:0.05CaO:0.88Y<sub>2</sub>O<sub>3</sub>:0.04Li<sub>2</sub>O:0.24SiO<sub>2</sub>:0.015GeO<sub>2</sub> |
实验例
荧光玻璃以460nm的准单色光为激发光源,检测发射光的波长范围和最大强度的波长值。
采用如下方法对以上实施例的荧光玻璃的相对发光强度和可见光透过率进行测试:
相对发光强度:用460nm的准单色光作为激发光源,激发荧光玻璃,产生的荧光经收集后通过光电探测器将光信号转变为电信号,在相同条件下测试荧光玻璃的光电流值,计算出荧光玻璃的相对发光强度。
可见光透过率:采用波长可调式光源照射荧光玻璃,感应器分别探测光源的入射光强和透过荧光玻璃后的光强(透过光强),透过光强与入射光强的比值即为可见光透过率。
表2
本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。
Claims (10)
1.一种荧光玻璃,其特征在于,所述荧光玻璃的组成如式(Ⅰ)所示:
mPr6O11:nEu2O3:xCaO:yY2O3:zE2O:dSiO2:eRO2 (Ⅰ)
其中,E选自碱金属元素;R选自Zr、Ti和Ge中的一种或多种;m表示Pr6O11的摩尔分数,0.00001<m<0.01;n表示Eu2O3的摩尔分数,0.00005<n<0.05;x表示CaO的摩尔分数,0.0001<x<0.1;y表示Y2O3的摩尔分数,0.1<y<1;z表示E2O的摩尔分数,0.01<z<0.1;d表示SiO2的摩尔分数,0.01<d<0.5;e表示RO2的摩尔分数,0.005<e<0.07;且2x+y+z=4(d+e)。
2.根据权利要求1所述的荧光玻璃,其特征在于,所述的荧光玻璃在蓝光的激发下产生红色荧光。
3.根据权利要求1所述的荧光玻璃,其特征在于,0.01<x<0.1,0.6<y<1,0.01<z<0.06,0.1<d<0.5,且0.005<e<0.05。
4.根据权利要求1所述的荧光玻璃,其特征在于,0.00001<m<0.001,且0.00005<n<0.001。
5.根据权利要求1所述的荧光玻璃,其特征在于,0.7≤m/n≤2.8。
6.根据权利要求1所述的荧光玻璃,其特征在于,100≤x/n≤300。
7.根据权利要求1~6任一项所述的荧光玻璃,其特征在于,2000≤y/n≤8000。
8.根据权利要求1所述的荧光玻璃,其特征在于,所述荧光玻璃具有如下式之一表示的组成:
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0006Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0003Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01TiO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02Na2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.02K2O:0.24SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.02CaO:0.88Y2O3:0.02Li2O:0.225SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.07CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.02GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.48Y2O3:0.02Li2O:0.14SiO2:0.01GeO2;
0.0004Pr6O11:0.0002Eu2O3:0.05CaO:0.88Y2O3:0.04Li2O:0.24SiO2:0.015GeO2。
9.根据权利要求1~8任一项所述的荧光玻璃的制备方法,其特征在于,包括如下步骤:
(1)将荧光玻璃的原料和助熔剂混合均匀,得到混合物;将混合物灼烧,然后冷却,得到灼烧产物;其中,所述的助熔剂为硼酸,灼烧温度为1300~1800℃,且灼烧时间为2~6小时;
(2)将灼烧产物在惰性气体保护下进行热处理,得到荧光玻璃;其中,热处理温度为700~1000℃,且热处理时间为2~6小时。
10.根据权利要求1~8任一项所述的荧光玻璃在作为发光二极管封装材料中的用途。
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