CN113388397B - 含有稀土元素的红色荧光材料及其制备方法和用途 - Google Patents
含有稀土元素的红色荧光材料及其制备方法和用途 Download PDFInfo
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- CN113388397B CN113388397B CN202010176469.6A CN202010176469A CN113388397B CN 113388397 B CN113388397 B CN 113388397B CN 202010176469 A CN202010176469 A CN 202010176469A CN 113388397 B CN113388397 B CN 113388397B
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- red fluorescent
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- fluorescent material
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005022 packaging material Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 description 17
- -1 samarium halide Chemical class 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 229910052777 Praseodymium Inorganic materials 0.000 description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229910005793 GeO 2 Inorganic materials 0.000 description 3
- 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
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical class [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical class [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical class [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- DABIZUXUJGHLMW-UHFFFAOYSA-H oxalate;samarium(3+) Chemical compound [Sm+3].[Sm+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DABIZUXUJGHLMW-UHFFFAOYSA-H 0.000 description 2
- 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 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 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
- 238000009877 rendering Methods 0.000 description 2
- QCZFMLDHLOYOQJ-UHFFFAOYSA-H samarium(3+);tricarbonate Chemical compound [Sm+3].[Sm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QCZFMLDHLOYOQJ-UHFFFAOYSA-H 0.000 description 2
- BCYBEIXXOVNETJ-UHFFFAOYSA-K samarium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sm+3] BCYBEIXXOVNETJ-UHFFFAOYSA-K 0.000 description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 2
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 2
- 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 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- 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 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 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
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical class [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- KDJOAYSYCXTQGG-UHFFFAOYSA-N disilicic acid Chemical compound O[Si](O)(O)O[Si](O)(O)O KDJOAYSYCXTQGG-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 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
- 229910052746 lanthanum Inorganic materials 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide 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
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 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
- DFIYWQBRYUCBMH-UHFFFAOYSA-N oxogermane Chemical compound [GeH2]=O DFIYWQBRYUCBMH-UHFFFAOYSA-N 0.000 description 1
- AZCUJQOIQYJWQJ-UHFFFAOYSA-N oxygen(2-) titanium(4+) trihydrate Chemical compound [O-2].[O-2].[Ti+4].O.O.O AZCUJQOIQYJWQJ-UHFFFAOYSA-N 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
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 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
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 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
- 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
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Abstract
本发明公开了一种含有稀土元素的红色荧光材料及其制备方法和用途。该红色荧光材料的组成为mSm2O3:nPr6O11:aMO:bY2O3:cE2O:xSiO2:yGO2;其中,M选自Mg或Ba中的至少一种,E选自一种或多种碱金属元素,G选自Zr、Ti或Ge中的一种;m、n、a、b、c、x和y分别表示Sm2O3、Pr6O11、MO、Y2O3、E2O、SiO2和GO2的物质的量;0<m≤0.1,0<n≤0.1,0<a≤0.7,0.5≤b<1,0<c≤0.5,0.01≤x≤0.7,0<y≤0.4。本发明的红色荧光材料能够在蓝光的激发下发出红色荧光。
Description
技术领域
本发明涉及一种含有稀土元素的红色荧光材料及其制备方法和用途,特别涉及一种含有稀土元素的红色荧光玻璃材料及其制备方法和用途。
背景技术
发光二级管作为一种新型光源,具有节能、环保、寿命长和启动速度快等传统光源无可比拟的优势,目前已经在手机、相机、显示器、指示灯等方面得到广泛应用。在白光LED器件中,由于荧光材料的性能直接决定白光LED的发光效率、转换效率、色温、色坐标及显色性等性能,因此荧光材料是一种非常重要的技术。目前以蓝光芯片激发Ce:YAG黄色荧光粉产生白光作为白光LED主流的商品化方式。但是这种白光由于缺少红光的成分使得色温较高,显色性差。
CN103045258A公开了一种白光LED用红色荧光粉,该荧光粉的化学组成为(Y3-x-y- zMy)MgAl3SiO12:Cex,Prz,其中M是La、Tb、Gd中的一种。该荧光粉以硅铝酸盐为基质,Ce3+和Pr3+为激活剂。
吕雁鹏等研究了一种Ca3Y2Si3O12:Pr3+红色荧光粉(参见“红色荧光粉Ca3Y2Si3O12:Pr3+的制备及其发光性能”,材料导报B:研究篇,2015年5月(下)第29卷第5期,第5-8页)。该荧光粉为Pr3+掺杂主晶相为Ca3Y2Si3O12的硅酸盐荧光粉。
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含有稀土元素的红色荧光材料,其在蓝光的激发下发出红色荧光。进一步地,本发明的含有稀土元素的红色荧光材料发光强度高且可见光透过率高。
本发明的另一个目的在于提供上述含有稀土元素的红色荧光材料的制备方法,其工艺简单,得到的含有稀土元素的红色荧光材料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含有稀土元素的红色荧光材料在作为发光二极管灯具封装材料中的用途。
一方面,本发明提供了一种含有稀土元素的红色荧光材料,该含有稀土元素的红色荧光材料具有如下所示的组成:
mSm2O3:nPr6O11:aMO:bY2O3:cE2O:xSiO2:yGO2
其中,M选自Mg或Ba中的至少一种,E选自一种或多种碱金属元素,G选自Zr、Ti或Ge中的一种;
其中,m、n、a、b、c、x和y分别表示Sm2O3、Pr6O11、MO、Y2O3、E2O、SiO2和GO2的物质的量;0<m≤0.1,0<n≤0.1,0<a≤0.7,0.5≤b<1,0<c≤0.5,0.01≤x≤0.7,0<y≤0.4。
根据本发明的含有稀土元素的红色荧光材料,优选地,E为Li;G选自Ti或Ge中的至少一种。
根据本发明的含有稀土元素的红色荧光材料,优选地,0.5a+0.25b+0.25c=x+y。
根据本发明的含有稀土元素的红色荧光材料,优选地,(m:n)表示Sm2O3与Pr6O11的摩尔比,0.5≤(m:n)≤2。
根据本发明的含有稀土元素的红色荧光材料,优选地,(b:m)表示Y2O3与Sm2O3的摩尔比,1500≤(b:m)≤2000。
根据本发明的含有稀土元素的红色荧光材料,优选地,0<m≤0.01,0<n≤0.01,0<a≤0.3,0.7≤b<1,0<c≤0.3,0.05≤x≤0.5,0<y≤0.3。
根据本发明的含有稀土元素的红色荧光材料,优选地,0.0002≤m≤0.0007,0.0002≤n≤0.0007,0.002≤a≤0.09,0.7≤b≤0.95,0.0001≤c≤0.05,0.1≤x≤0.4,0.003≤y≤0.04。
根据本发明的含有稀土元素的红色荧光材料,优选地,所述的含有稀土元素的红色荧光材料具有如下式之一所示的组成:
0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01TiO2;
0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2;
0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Na2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02K2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0001Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0001Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.15BaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.15MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06GeO2。
另一方面,本发明提供上述含有稀土元素的红色荧光材料的制备方法,包括如下步骤:
(1)将硼酸和根据含有稀土元素的红色荧光材料组成得到的原料形成第一物料;硼酸的用量为原料重量的1~6wt%;
(2)将第一物料在1100~1800℃灼烧2~8小时,然后冷却,得到第二物料;
(3)将第二物料在惰性气氛中,500~1000℃的条件下进行热处理2~8小时,得到含有稀土元素的红色荧光材料。
再一方面,本发明提供上述含有稀土元素的红色荧光材料在作为发光二极管灯具封装材料中的应用。
本发明提供了一种新组成的含有稀土元素的红色荧光材料,其在蓝光的激发下能够发出红色荧光。进一步地,本发明的玻璃成分与红色荧光成分相互配合,使含有稀土元素的红色荧光材料具有较高的发光强度和可见光透过率。
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。
<含有稀土元素的红色荧光材料>
本发明的含有稀土元素的红色荧光材料为一种在蓝光激发下能够产生红色荧光的玻璃材料。所谓蓝光激发,表示激发光波长范围可以在425~500nm之间。优选地,激发光最大强度的波长范围在435~495nm之间。发射光波长范围可以在560~665nm之间。优选地,发射光最大强度的波长范围在600~610nm之间。
本发明的含有稀土元素的红色荧光材料具有如下所示的组成:
mSm2O3:nPr6O11:aMO:bY2O3:cE2O:xSiO2:yGO2
其中,M表示一种或多种碱土金属元素,E表示一种或多种碱金属元素,G表示一种或多种IVA族金属元素或IVB族金属元素。m、n、a、b、c、x和y分别表示Sm2O3、Pr6O11、MO、Y2O3、E2O、SiO2和GO2的物质的量或摩尔比。m、n、a、b、c、x和y的取值范围均为各组分的相对含量。
Sm2O3表示三氧化二钐。在本发明中,0<m≤0.1;优选地,0<m≤0.01;更优选地,0.0002≤m≤0.0007。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
Pr6O11表示十一氧化六镨。在本发明中,0<n≤0.1;优选地,0<n≤0.01;更优选地,0.0002≤n≤0.0007。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
在本发明中,(m:n)表示Sm2O3与Pr6O11的摩尔比,0.5≤(m:n)≤2;优选地,0.8≤(m:n)≤1.7;更优选地,1≤(m:n)≤1.5。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
M表示一种或多种碱土金属元素。M选自Mg或Ba中的至少一种。在某些实施方式中,M为Mg。在另一些实施方式中,M为Ba。在本发明中,0<a≤0.7;优选地,0<a≤0.3;更优选地,0.002≤a≤0.09。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
Y2O3表示三氧化二钇。在本发明中,0.5≤b<1;优选地,0.7≤b<1;更优选地,0.7≤b≤0.95。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
在本发明中,(b:m)表示Y2O3与Sm2O3的摩尔比,1500≤(b:m)≤2000;优选地,1600≤(b:m)≤1900;更优选地,1700≤(b:m)≤1800。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
E表示一种或多种碱金属元素。碱金属元素的实例包括但不限于Li、Na或K。优选地,E选自Li或Na中的至少一种。更优选地,E为Li。在本发明中,0<c≤0.5;优选地,0<c≤0.3;更优选地,0.0001≤c≤0.05。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
SiO2表示二氧化硅。在本发明中,0.01≤x≤0.7;优选地,0.05≤x≤0.5;更优选地,0.1≤x≤0.4。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
G表示一种或多种IVA族金属元素或IVB族金属元素。优选地,G选自Zr、Ti或Ge中的至少一种。更优选地,G选自Ti或Ge中的至少一种。在本发明中,0<y≤0.4;优选地,0<y≤0.3;更优选地,0.003≤y≤0.04。这样能够提高红色荧光玻璃材料的发光强度和可见光透过率。
在某些实施方式中,0<m≤0.1,0<n≤0.1,0<a≤0.7,0.5≤b<1,0<c≤0.5,0.01≤x≤0.7,0<y≤0.4。优选地,0<m≤0.01,0<n≤0.01,0<a≤0.3,0.7≤b<1,0<c≤0.3,0.05≤x≤0.5,0<y≤0.3。更优选地,0.0002≤m≤0.0007,0.0002≤n≤0.0007,0.002≤a≤0.09,0.7≤b≤0.95,0.0001≤c≤0.05,0.1≤x≤0.4,0.003≤y≤0.04。
在另一些实施方式中,0.5a+0.25b+0.25c=x+y。优选地,0.5a+0.25b+0.25c=x+y,0<m≤0.1,0<n≤0.1,0<a≤0.7,0.5≤b<1,0<c≤0.5,0.01≤x≤0.7,0<y≤0.4。更优选地,0.5a+0.25b+0.25c=x+y,0<m≤0.01,0<n≤0.01,0<a≤0.3,0.7≤b<1,0<c≤0.3,0.05≤x≤0.5,0<y≤0.3。最优选地,0.5a+0.25b+0.25c=x+y,0.0002≤m≤0.0007,0.0002≤n≤0.0007,0.002≤a≤0.09,0.7≤b≤0.95,0.0001≤c≤0.05,0.1≤x≤0.4,0.003≤y≤0.04。
本发明的含有稀土元素的红色荧光材料的具体实例包括但不限于如下式之一表示的组成:
0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01TiO2;
0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2;
0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Na2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02K2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0001Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0001Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.15BaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2;
0.0005Sm2O3:0.0004Pr6O11:0.15MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06GeO2。
<制备方法>
本发明的含有稀土元素的红色荧光材料的制备方法包括如下步骤:将硼酸和原料形成第一物料;将第一物料灼烧,然后冷却,得到第二物料;将第二物料进行热处理,得到含有稀土元素的红色荧光材料。含有稀土元素的红色荧光材料具有如下所示的组成:mSm2O3:nPr6O11:aMO:bY2O3:cE2O:xSiO2:yGO2;具体如前文所述。
硼酸的用量为原料重量的1~6wt%;优选为2~5wt%;更优选为3~5wt%。这样可以提高红色荧光玻璃材料的发光强度和可见光透过率。
在本发明中,惰性气氛可以由氮气或稀有气体提供;优选为氮气。灼烧温度可以为1100~1800℃;优选为1400~1700℃;更优选为1500~1700℃。灼烧时间可以为2~8小时;优选为2~5小时;更优选为3~5小时。热处理的温度可以为500~1100℃,优选为700~900℃,更优选为750~850℃。热处理时间可以为2~8小时,优选为3~7小时,更优选为3~5小时。这样可以提高红色荧光玻璃材料的发光强度和可见光透过率。
本发明的原料由含有稀土元素的红色荧光材料的组成确定。下面进行详细描述。Sm2O3的原料可以选自钐的氧化物、钐的碳酸盐、钐的硝酸盐、钐的草酸盐、钐的硫酸盐、钐的卤化物或钐的氢氧化物。具体实例包括但不限于三氧化二钐、碳酸钐、硝酸钐、硫酸钐、草酸钐、卤化钐、氢氧化钐。
Pr6O11的原料可以选自镨的氧化物、镨的碳酸盐、镨的硝酸盐、镨的硫酸盐、镨的草酸盐、镨的卤化物、镨的氢氧化物。具体实例包括但不限于十一氧化六镨、碳酸镨、硝酸镨、硫酸镨、草酸镨、卤化镨、氢氧化镨。
MgO的原料可以选自镁的氧化物、镁的碳酸盐、镁的硝酸盐、镁的硫酸盐、镁的草酸盐、镁的卤化物、镁的氢氧化物。具体实例包括但不限于氧化镁、碳酸镁、硝酸镁、硫酸镁、草酸镁、卤化镁、氢氧化镁。
BaO的原料可以选自钡的氧化物、钡的碳酸盐、钡的硝酸盐、钡的硫酸盐、钡的草酸盐、钡的卤化物、钡的氢氧化物。具体实例包括但不限于氧化钡、碳酸钡、硝酸钡、硫酸钡、草酸钡、卤化钡、氢氧化钡。
Y2O3的原料可以选自钇的氧化物、钇的碳酸盐、钇的硝酸盐、钇的硫酸盐、钇的草酸盐、钇的卤化物、钇的氢氧化物。Y2O3的原料的实例包括但不限于三氧化二钇、碳酸钇、硝酸钇、硫酸钇、草酸钇、卤化钇、氢氧化钇。
碱金属氧化物的原料可以为碱金属氧化物、碱金属碳酸盐、碱金属硝酸盐、碱金属硫酸盐、碱金属草酸盐、碱金属卤化物、碱金属氢氧化物。碱金属氧化物的实例包括但不限于氧化钠、氧化锂、氧化钾。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。
SiO2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)。
TiO2的原料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)。
GeO2的原料包括但不限于氧化锗(GeO2),四氯化锗(GeCl4),氢氧化锗(Ge(OH)4)。
ZrO2的原料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)。
<用途>
本发明的含有稀土元素的红色荧光材料在蓝光的激发下产生红色荧光,因而可以作为发光二极管灯具的封装材料。含有稀土元素的红色荧光材料的组成如前文所述。优选地,激发光波长范围在425~500nm之间。更优选地,激发光最大强度的波长范围在435~495nm之间。优选地,发射光波长范围在580~660nm之间。更优选地,发射光最大强度的波长范围在610~620nm之间。
采用如下方法对实施例的含有稀土元素的红色荧光材料的发射光的波长范围、最大强度的波长值、相对发光强度和可见光透过率进行测试:
<发射光的波长范围和最大强度的波长值>
将以下实施例的含有稀土元素的红色荧光材料以蓝光为激发光源,检测发射光的波长范围和最大强度的波长值。采用460nm的准单色光作为激发光源。
<相对发光强度>
用460nm的准单色光作为激发光源,激发以下实施例所得到的含有稀土元素的红色荧光材料,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,在相同条件下测试含有稀土元素的红色荧光材料的光电流值,计算出含有稀土元素的红色荧光材料的相对发光强度。
<可见光透过率>
采用波长可调式光源照射以下实施例的含有稀土元素的红色荧光材料,感应器分别探测光源的入射光强和透过含有稀土元素的红色荧光材料后的光强(透过光强),透过光强与入射光强的比值即为可见光透过率。
以下实施例中各组成采用下表所示的原料:
组成 | 原料 | 原料纯度 |
Sm2O3 | Sm2O3 | 99.99wt% |
Pr6O11 | Pr6O11 | 99.99wt% |
MgO | MgCO3 | 分析纯 |
BaO | BaCO3 | 分析纯 |
Y2O3 | Y2(CO3)3 | 99.99wt% |
Li2O | LiCl | 分析纯 |
Na2O | NaCl | 分析纯 |
K2O | KCl | 分析纯 |
SiO2 | SiO2 | 分析纯 |
ZrO2 | ZrO2 | 分析纯 |
TiO2 | TiO2 | 分析纯 |
GeO2 | GeO2 | 分析纯 |
实施例1~10
按照表1中含有稀土元素的红色荧光材料的组成选择和称取原料。将原料和用量为原料重量4wt%的硼酸(分析纯)形成第一物料。将第一物料在1550℃的条件下灼烧4小时,然后浇铸急冷,得到第二物料。将第二物料在氮气保护下,在800℃的条件下,热处理4小时,得到含有稀土元素的红色荧光材料。含有稀土元素的红色荧光材料的性能如表2所示。
表1
编号 | 含有稀土元素的红色荧光材料 |
实施例1 | 0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2 |
实施例2 | 0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2 |
实施例3 | 0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01TiO2 |
实施例4 | 0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2 |
实施例5 | 0.0005Sm2O3:0.0004Pr6O11:0.05MgO:0.88Y2O3:0.02Na2O:0.24SiO2:0.01GeO2 |
实施例6 | 0.0005Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02K2O:0.24SiO2:0.01GeO2 |
实施例7 | 0.0005Sm2O3:0.0001Pr6O11:0.05MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2 |
实施例8 | 0.0001Sm2O3:0.0004Pr6O11:0.05BaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.01GeO2 |
实施例9 | 0.0005Sm2O3:0.0004Pr6O11:0.15BaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2 |
实施例10 | 0.0005Sm2O3:0.0004Pr6O11:0.15MgO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06GeO2 |
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 (8)
1. 一种含有稀土元素的红色荧光材料,其特征在于,其具有如下所示的组成:
mSm2O3: nPr6O11: aMO: bY2O3: cE2O: xSiO2: yGO2
其中,M选自Mg或Ba中的至少一种,E选自Li、Na或K中的至少一种,G选自Zr、Ti或Ge中的一种;
其中, m、n、a、b、c、x和y分别表示 Sm2O3、Pr6O11、MO、Y2O3、E2O、SiO2和GO2的物质的量;0<m≤0.0007,0<n≤0.0007, 0.002≤a≤0.3,0.5≤b≤0.95,0.0001≤c≤0.05,0.1≤x≤0.4,0.003≤y≤0.3,0.5a+0.25b+0.25c=x+y。
2.根据权利要求1所述的含有稀土元素的红色荧光材料,其特征在于,E为Li;G选自Ti或Ge中的至少一种。
3. 根据权利要求1所述的含有稀土元素的红色荧光材料,其特征在于,(m:n)表示Sm2O3与Pr6O11的摩尔比,0.5≤(m:n) ≤2。
4. 根据权利要求1所述的含有稀土元素的红色荧光材料,其特征在于,(b:m)表示Y2O3与Sm2O3的摩尔比,1500≤(b:m) ≤2000。
5. 根据权利要求1所述的含有稀土元素的红色荧光材料,其特征在于,0.0002≤m≤0.0007,0.0002≤n≤0.0007,0.002≤a≤0.09,0.7≤b≤0.95, 0.003≤y≤0.04。
6.根据权利要求1所述的含有稀土元素的红色荧光材料,其特征在于,所述的含有稀土元素的红色荧光材料具有如下式之一所示的组成:
0.0005Sm2O3: 0.0004Pr6O11:0.05MgO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.01GeO2;
0.0005Sm2O3: 0.0004Pr6O11:0.05BaO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.01GeO2;
0.0005Sm2O3: 0.0004Pr6O11:0.05BaO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.01TiO2;
0.0005Sm2O3: 0.0004Pr6O11:0.05MgO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.01ZrO2;
0.0005Sm2O3: 0.0004Pr6O11:0.05MgO: 0.88Y2O3: 0.02Na2O: 0.24SiO2: 0.01GeO2;
0.0005Sm2O3: 0.0004Pr6O11:0.05BaO: 0.88Y2O3: 0.02K2O: 0.24SiO2: 0.01GeO2;
0.0005Sm2O3: 0.0001Pr6O11:0.05MgO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.01GeO2;
0.0001Sm2O3: 0.0004Pr6O11:0.05BaO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.01GeO2;
0.0005Sm2O3: 0.0004Pr6O11:0.15BaO: 0.68Y2O3: 0.02Li2O: 0.24SiO2: 0.01GeO2;
0.0005Sm2O3: 0.0004Pr6O11:0.15MgO: 0.88Y2O3: 0.02Li2O: 0.24SiO2: 0.06GeO2。
7.根据权利要求1~6任一项所述的含有稀土元素的红色荧光材料的制备方法,其特征在于,包括如下步骤:
(1)将硼酸和根据含有稀土元素的红色荧光材料组成得到的原料形成第一物料;硼酸的用量为原料重量的1~6wt%;
(2)将第一物料在1100~1800℃灼烧2~8小时,然后冷却,得到第二物料;
(3)将第二物料在惰性气氛中,在500~1000℃下热处理2~8小时,得到含有稀土元素的红色荧光材料。
8.根据权利要求1~6任一项所述的含有稀土元素的红色荧光材料在作为发光二极管灯具封装材料中的应用。
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