CN113388397B - Red fluorescent material containing rare earth element and preparation method and application thereof - Google Patents
Red fluorescent material containing rare earth element and preparation method and application thereof Download PDFInfo
- Publication number
- 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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- Prior art keywords
- red fluorescent
- equal
- rare earth
- fluorescent material
- earth element
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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
- 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
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a red fluorescent material containing rare earth elements, a preparation method and application thereof. The red fluorescent material has the composition of mSm 2 O 3 :nPr 6 O 11 :aMO:bY 2 O 3 :cE 2 O:xSiO 2 :yGO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is selected from at least one of Mg or Ba, E is selected from one or more alkali metal elements, and G is selected from one of Zr, ti or Ge; m, n, a, b, c, x and y represent Sm respectively 2 O 3 、Pr 6 O 11 、MO、Y 2 O 3 、E 2 O、SiO 2 And GO 2 The amount of the substance of (a); 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 is less than or equal to 0.4. The red fluorescent material provided by the invention can emit red fluorescence under the excitation of blue light.
Description
Technical Field
The invention relates to a red fluorescent material containing rare earth elements, a preparation method and application thereof, in particular to a red fluorescent glass material containing rare earth elements, a preparation method and application thereof.
Background
The light emitting diode is used as a novel light source, has the advantages of energy conservation, environmental protection, long service life, high starting speed and the like which are incomparable with the traditional light source, and is widely applied to the aspects of mobile phones, cameras, displays, indicator lamps and the like at present. In the white LED device, the performance of the fluorescent material directly determines the performance of the white LED such as luminous efficiency, conversion efficiency, color temperature, color coordinates, color rendering property, etc., so the fluorescent material is a very important technology. At present, a blue light chip is used for exciting Ce, YAG yellow fluorescent powder to generate white light to be used as a main commercialized mode of a white light LED. However, this white light has a high color temperature due to the lack of red light components, and has poor color rendering properties.
CN103045258A discloses a red phosphor for white LED, the chemical composition of the phosphor is (Y 3-x-y- z M y )MgAl 3 SiO 12 :Ce x Prz, wherein M is one of La, tb, gd. The fluorescent powder takes aluminosilicate as a matrix and Ce 3+ And Pr (Pr) 3+ Is an activator.
Lv Yanpeng et al studied a Ca 3 Y 2 Si 3 O 12 :Pr 3+ Red phosphor (see "red phosphor Ca 3 Y 2 Si 3 O 12 :Pr 3+ Is prepared from the following materials, material guide B: study, 5 months of 2015 (below) volume 29, phase 5, pages 5-8). The fluorescent powder is Pr 3+ The doped main crystal phase is Ca 3 Y 2 Si 3 O 12 Silicate phosphor of (2).
Disclosure of Invention
In view of the above, an object of the present invention is to provide a red fluorescent material containing rare earth elements, which emits red fluorescence upon excitation of blue light, of a new composition. Further, the rare earth element-containing red fluorescent material of the present invention has high luminous intensity and high visible light transmittance.
The invention also aims to provide a preparation method of the rare earth element-containing red fluorescent material, which is simple in process, and the obtained rare earth element-containing red fluorescent material has high luminous intensity and visible light transmittance.
It is still another object of the present invention to provide the use of the above-mentioned rare earth element-containing red fluorescent material as a light emitting diode lamp packaging material.
In one aspect, the present invention provides a rare earth element-containing red fluorescent material having a composition as shown below:
mSm 2 O 3 :nPr 6 O 11 :aMO:bY 2 O 3 :cE 2 O:xSiO 2 :yGO 2
wherein M is selected from at least one of Mg or Ba, E is selected from one or more alkali metal elements, and G is selected from one of Zr, ti or Ge;
wherein m, n, a, b, c, x and y each represent Sm 2 O 3 、Pr 6 O 11 、MO、Y 2 O 3 、E 2 O、SiO 2 And GO 2 The amount of the substance of (a); 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。
The rare earth element-containing red fluorescent material according to the present invention, preferably, E is Li; g is at least one selected from Ti and Ge.
The rare earth element-containing red fluorescent material according to the present invention is preferably 0.5a+0.25b+0.25c=x+y.
The rare earth element-containing red fluorescent material according to the present invention preferably has (m: n) represented by Sm 2 O 3 With Pr 6 O 11 The molar ratio of (2) is more than or equal to 0.5 and less than or equal to (m: n).
The rare earth element-containing red fluorescent material according to the present invention preferably (b: m) represents Y 2 O 3 With Sm 2 O 3 The molar ratio of (b: m) is less than or equal to 1500 and less than or equal to 2000.
The red fluorescent material containing rare earth elements according to the present invention is preferably 0<m.ltoreq.0.01, 0< n.ltoreq.0.01, 0< a.ltoreq.0.3, 0.7.ltoreq.b.ltoreq.1, 0< c.ltoreq. 0.3,0.05.ltoreq.x.ltoreq.0.5, 0< y.ltoreq.0.3.
The rare earth element-containing red fluorescent material according to the present invention, preferably, m is more than or equal to 0.0002 and less than or equal to 0.0007,0.0002, n is more than or equal to 0.0007,0.002, a is more than or equal to 0.09,0.7, b is more than or equal to 0.95,0.0001, c is more than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.4,0.003, y is more than or equal to 0.04.
The rare earth element-containing red fluorescent material according to the present invention preferably has a composition represented by one of the following formulas:
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01TiO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01ZrO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Na 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02K 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0001Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0001Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.15BaO:0.68Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.15MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.06GeO 2 。
in another aspect, the present invention provides a method for preparing the rare earth element-containing red fluorescent material, comprising the steps of:
(1) Forming a first material from boric acid and a raw material obtained from the composition of a red fluorescent material containing a rare earth element; the consumption of boric acid is 1-6wt% of the weight of the raw material;
(2) Burning the first material at 1100-1800 ℃ for 2-8 hours, and then cooling to obtain a second material;
(3) And (3) carrying out heat treatment on the second material for 2-8 hours in an inert atmosphere at 500-1000 ℃ to obtain the red fluorescent material containing rare earth elements.
In still another aspect, the present invention provides an application of the red fluorescent material containing rare earth elements as a packaging material of a light emitting diode lamp.
The invention provides a new-composition red fluorescent material containing rare earth elements, which can emit red fluorescence under the excitation of blue light. Further, the glass component and the red fluorescent component are matched with each other, so that the red fluorescent material containing the rare earth element has higher luminous intensity and visible light transmittance.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
< Red fluorescent Material containing rare earth element >
The red fluorescent material containing rare earth elements is a glass material capable of generating red fluorescence under the excitation of blue light. Blue excitation means that the wavelength of excitation light can be in the range of 425 to 500 nm. Preferably, the wavelength range of the maximum intensity of the excitation light is between 435 and 495 nm. The wavelength range of the emitted light can be between 560 and 665 nm. Preferably, the wavelength range of the maximum intensity of the emitted light is between 600 and 610 nm.
The rare earth element-containing red fluorescent material of the present invention has the composition shown below:
mSm 2 O 3 :nPr 6 O 11 :aMO:bY 2 O 3 :cE 2 O:xSiO 2 :yGO 2
wherein M represents one or more alkaline earth metal elements, E represents one or more alkali metal elements, and G represents one or more group IVA metal elements or group IVB metal elements. m, n, a, b, c, x and y represent Sm respectively 2 O 3 、Pr 6 O 11 、MO、Y 2 O 3 、E 2 O、SiO 2 And GO 2 The amount or molar ratio of the substances of (a). m, n, a, b, c, x and y are both relative amounts of the components.
Sm 2 O 3 Represents samarium sesquioxide. In the present invention, 0<m is less than or equal to 0.1; preferably 0<m is less than or equal to 0.01; more preferably, 0.0002.ltoreq.m.ltoreq.0.0007. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
Pr 6 O 11 Which means hexapraseodymium undecanoxide. In the present invention, 0<n is less than or equal to 0.1; preferably 0<n is less than or equal to 0.01; more preferably, 0.0002.ltoreq.n.ltoreq.0.0007. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
In the present invention, (m: n) represents Sm 2 O 3 With Pr 6 O 11 The molar ratio of (2) is more than or equal to 0.5 and less than or equal to (m: n); preferably, 0.8.ltoreq.m.n.ltoreq.1.7; more preferably, 1.ltoreq.m.ltoreq.n.1.5. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
M represents one or more alkaline earth metal elements. M is selected from at least one of Mg or Ba. In certain embodiments, M is Mg. In other embodiments, M is Ba. In the invention, 0<a is less than or equal to 0.7; preferably 0<a is less than or equal to 0.3; more preferably, 0.002.ltoreq.a.ltoreq.0.09. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
Y 2 O 3 Represents trioxygenAnd (3) yttrium oxide. In the present invention, 0.5.ltoreq.b<1, a step of; preferably 0.7.ltoreq.b<1, a step of; more preferably, 0.7.ltoreq.b.ltoreq.0.95. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
In the present invention, (b: m) represents Y 2 O 3 With Sm 2 O 3 The mol ratio of (b: m) is less than or equal to 1500 and less than or equal to 2000; preferably, 1600.ltoreq.b.m.ltoreq.1900; more preferably 1700.ltoreq.b.m.ltoreq.1800. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
E represents one or more alkali metal elements. Examples of alkali metal elements include, but are not limited to, li, na, or K. Preferably, E is selected from at least one of Li or Na. More preferably, E is Li. In the invention, 0<c is less than or equal to 0.5; preferably 0<c is less than or equal to 0.3; more preferably, 0.0001.ltoreq.c.ltoreq.0.05. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
SiO 2 Representing silica. In the invention, x is more than or equal to 0.01 and less than or equal to 0.7; preferably, x is more than or equal to 0.05 and less than or equal to 0.5; more preferably, 0.1.ltoreq.x.ltoreq.0.4. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
G represents one or more group IVA metal elements or group IVB metal elements. Preferably, G is selected from at least one of Zr, ti or Ge. More preferably, G is selected from at least one of Ti or Ge. In the invention, 0< y is less than or equal to 0.4; preferably, 0< y.ltoreq.0.3; more preferably, 0.003.ltoreq.y.ltoreq.0.04. This can improve the luminous intensity and the visible light transmittance of the red fluorescent glass material.
In certain embodiments 0<m.ltoreq.0.1, 0< n.ltoreq.0.1, 0< a.ltoreq. 0.7,0.5.ltoreq.b.ltoreq.1, 0< c.ltoreq.0.5, 0.01.ltoreq.x.ltoreq.0.7, 0< y.ltoreq.0.4. Preferably 0<m.ltoreq.0.01, 0< n.ltoreq.0.01, 0< a.ltoreq.0.3, 0.7.ltoreq.b.ltoreq.1, 0< c.ltoreq. 0.3,0.05.ltoreq.x.ltoreq.0.5, 0< y.ltoreq.0.3. More preferably, the process is carried out, m is more than or equal to 0.0002 and less than or equal to 0.0007,0.0002, n is more than or equal to 0.0007,0.002, a is more than or equal to 0.09,0.7, b is more than or equal to 0.95,0.0001, c is more than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.4,0.003, y is more than or equal to 0.04.
In other embodiments, 0.5a+0.25b+0.25c=x+y. Preferably, 0.5a+0.25b+0.25c=x+y, 0<m is equal to or less than 0.1,0< n is equal to or less than 0.1,0< a is equal to or less than 0.7,0.5 is equal to or less than 1,0< c is equal to or less than 0.5,0.01 is equal to or less than 0.7,0< y is equal to or less than 0.4. More preferably, 0.5a+0.25b+0.25c=x+y, 0<m.ltoreq.0.01, 0< n.ltoreq.0.01, 0< a.ltoreq.0.3, 0.7.ltoreq.b <1,0< c.ltoreq. 0.3,0.05.ltoreq.x.ltoreq.0.5, 0< y.ltoreq.0.3. Most preferably, 0.5a+0.25b+0.25c=x+y, m is more than or equal to 0.0002 and less than or equal to 0.0007,0.0002, n is more than or equal to 0.0007,0.002, a is more than or equal to 0.09,0.7, b is more than or equal to 0.95,0.0001, c is more than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.4,0.003, y is more than or equal to 0.04.
Specific examples of the rare earth element-containing red fluorescent material of the present invention include, but are not limited to, compositions represented by one of the following formulas:
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01TiO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01ZrO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Na 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02K 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0001Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0001Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.15BaO:0.68Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 ;
0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.15MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.06GeO 2 。
< preparation method >
The preparation method of the rare earth element-containing red fluorescent material comprises the following steps: forming boric acid and a raw material into a first material; burning the first material, and then cooling to obtain a second material; and carrying out heat treatment on the second material to obtain the red fluorescent material containing the rare earth elements. The red fluorescent material containing rare earth elements has the composition shown below: mSm 2 O 3 :nPr 6 O 11 :aMO:bY 2 O 3 :cE 2 O:xSiO 2 :yGO 2 The method comprises the steps of carrying out a first treatment on the surface of the In particular as described hereinbefore.
The consumption of boric acid is 1-6wt% of the weight of the raw material; preferably 2 to 5 wt.%; more preferably 3 to 5wt%. Thus, the luminous intensity and the visible light transmittance of the red fluorescent glass material can be improved.
In the present invention, the inert atmosphere may be provided by nitrogen or a rare gas; preferably nitrogen. The firing temperature can be 1100-1800 ℃; preferably 1400-1700 ℃; more preferably 1500 to 1700 ℃. The firing time can be 2-8 hours; preferably 2 to 5 hours; more preferably 3 to 5 hours. The temperature of the heat treatment may be 500 to 1100 ℃, preferably 700 to 900 ℃, more preferably 750 to 850 ℃. The heat treatment time may be 2 to 8 hours, preferably 3 to 7 hours, more preferably 3 to 5 hours. Thus, the luminous intensity and the visible light transmittance of the red fluorescent glass material can be improved.
The raw material of the invention contains rare earthThe composition of the elemental red phosphor is determined. The following is a detailed description. Sm (Sm) 2 O 3 The starting material of (a) may be selected from the group consisting of samarium oxide, samarium carbonate, samarium nitrate, samarium oxalate, samarium sulfate, samarium halide and samarium hydroxide. Specific examples include, but are not limited to, samarium sesquioxide, samarium carbonate, samarium nitrate, samarium sulfate, samarium oxalate, samarium halide, samarium hydroxide.
Pr 6 O 11 The raw material of (a) may be selected from the group consisting of an oxide of praseodymium, a carbonate of praseodymium, a nitrate of praseodymium, a sulfate of praseodymium, an oxalate of praseodymium, a halide of praseodymium, and a hydroxide of praseodymium. Specific examples include, but are not limited to, hexapraseodymium undecanoxide, praseodymium carbonate, praseodymium nitrate, praseodymium sulfate, praseodymium oxalate, praseodymium halide, praseodymium hydroxide.
The MgO raw material may be selected from magnesium oxide, magnesium carbonate, magnesium nitrate, magnesium sulfate, magnesium oxalate, magnesium halide, magnesium hydroxide. Specific examples include, but are not limited to, magnesium oxide, magnesium carbonate, magnesium nitrate, magnesium sulfate, magnesium oxalate, magnesium halide, magnesium hydroxide.
The starting material for BaO may be selected from the group consisting of barium oxides, barium carbonates, barium nitrates, barium sulfates, barium oxalates, barium halides, and barium hydroxides. Specific examples include, but are not limited to, barium oxide, barium carbonate, barium nitrate, barium sulfate, barium oxalate, barium halide, barium hydroxide.
Y 2 O 3 The starting material of (a) may be selected from the group consisting of yttrium oxide, yttrium carbonate, yttrium nitrate, yttrium sulfate, yttrium oxalate, yttrium halide, yttrium hydroxide. Y is Y 2 O 3 Examples of the raw materials of (a) include, but are not limited to, yttrium oxide, yttrium carbonate, yttrium nitrate, yttrium sulfate, yttrium oxalate, yttrium halide, yttrium hydroxide.
The raw materials of the alkali metal oxide can be alkali metal oxide, alkali metal carbonate, alkali metal nitrate, alkali metal sulfate, alkali metal oxalate, alkali metal halide and alkali metal hydroxide. Examples of alkali metal oxides include, but are not limited to, sodium oxide, lithium oxide, potassium oxide. Examples of alkali metal carbonates include, but are not limited to, lithium carbonate, sodium carbonate, potassium carbonate. Examples of alkali metal nitrates include, but are not limited to, lithium nitrate, sodium nitrate, potassium nitrate. Examples of alkali metal sulfates include, but are not limited to, lithium sulfate, sodium sulfate, potassium sulfate. Examples of alkali metal oxalates include, but are not limited to, lithium oxalate, sodium oxalate, potassium oxalate. Examples of alkali metal halides include, but are not limited to, lithium halides, sodium halides, potassium halides. Examples of alkali metal hydroxides include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide.
SiO 2 The raw material of (a) can be silicon oxide and other silicon-containing compounds, including but not limited to silicon dioxide (SiO) 2 ) The silicic acid comprises orthosilicic acid (H) 4 SiO 4 ) Metasilicic acid (H) 2 SiO 3 ) Disilicic acid (H) 2 Si 2 O 5 ) Silane, silicon tetrahalide (SiCl) 4 ) Silicon nitride (Si 3 N 4 ) Aminosilane, fluorosilicic acid (H) 2 SiF 6 )。
TiO 2 The raw materials of (a) include, but are not limited to, titanium dioxide (TiO) 2 ) Titanium pentoxide (Ti) 3 O 5 ) Titanium monoxide (TiO), titanic acid H 4 TiO 4 [TiO 2 ·xH 2 O or Ti (OH) 4 )]TiO (OH) meta-titanic acid 2 Titanium tetrachloride TiCl 4 Titanium trichloride TiCl 3 Titanium iodide TiI 4 Titanyl sulfate (TiOSO) 4 ·H 2 O)。
GeO 2 The raw materials of (a) include, but are not limited to germanium oxide (GeO) 2 ) Germanium tetrachloride (GeCl) 4 ) Germanium hydroxide (Ge (OH) 4 )。
ZrO 2 The raw materials of (a) include, but are not limited to, zirconium oxide (ZrO) 2 ) Zirconium halide (ZrF) 4 ,ZrI 4 ,ZrCl 4 ) Zirconium hydroxide (Zr (OH) 2 ) Zirconium oxychloride (ZrOCl) 2 ) Zirconium carbonate (3 ZrO) 2 ·CO 2 ·H 2 O), zirconium sulfate (Zr (SO) 4 ) 2 ) Zirconyl sulfate (ZrOSO) 4 ) Zirconium nitrate (Zr (NO) 3 ) 4 ·5H 2 O)。
< use >
The red fluorescent material containing rare earth elements generates red fluorescence under the excitation of blue light, so that the red fluorescent material can be used as a packaging material of a light-emitting diode lamp. The composition of the red fluorescent material containing the rare earth element is as described above. Preferably, the excitation light wavelength ranges between 425 and 500 nm. More preferably, the wavelength range of the maximum intensity of the excitation light is between 435 and 495 nm. Preferably, the wavelength of the emitted light is in the range of 580-660 nm. More preferably, the wavelength range of the maximum intensity of the emitted light is between 610 and 620 nm.
The wavelength range of the emitted light, the wavelength value of the maximum intensity, the relative luminous intensity, and the visible light transmittance of the red fluorescent material containing the rare earth element of the examples were tested by the following methods:
< wavelength Range of emitted light and wavelength value of maximum intensity >
The red fluorescent material containing rare earth elements of the following examples was used as an excitation light source with blue light, and the wavelength range of the emitted light and the wavelength value of the maximum intensity were detected. A quasi-monochromatic light of 460nm was used as excitation light source.
< relative luminous intensity >
The red fluorescent material containing rare earth elements obtained in the following examples was excited by using 460nm quasi-monochromatic light as an excitation light source, the generated fluorescence was collected and converted into an electrical signal by a photodetector, and the photoelectric value of the red fluorescent material containing rare earth elements was measured under the same conditions to calculate the relative luminescence intensity of the red fluorescent material containing rare earth elements.
< visible light transmittance >
The red fluorescent material containing rare earth elements of the following embodiments is irradiated by a wavelength-adjustable light source, and the sensor detects the incident light intensity of the light source and the light intensity (transmitted light intensity) of the light transmitted through the red fluorescent material containing rare earth elements, respectively, and the ratio of the transmitted light intensity to the incident light intensity is the visible light transmittance.
The following examples used the materials shown in the table below:
composition of the composition | Raw materials | Purity of raw materials |
Sm 2 O 3 | Sm 2 O 3 | 99.99wt% |
Pr 6 O 11 | Pr 6 O 11 | 99.99wt% |
MgO | MgCO 3 | Analytical grade |
BaO | BaCO 3 | Analytical grade |
Y 2 O 3 | Y 2 (CO 3 ) 3 | 99.99wt% |
Li 2 O | LiCl | Analytical grade |
Na 2 O | NaCl | Analytical grade |
K 2 O | KCl | Analytical grade |
SiO 2 | SiO 2 | Analytical grade |
ZrO 2 | ZrO 2 | Analytical grade |
TiO 2 | TiO 2 | Analytical grade |
GeO 2 | GeO 2 | Analytical grade |
Examples 1 to 10
The raw materials were selected and weighed according to the compositions of the red fluorescent materials containing rare earth elements in table 1. The starting material and boric acid (analytically pure) in an amount of 4% by weight of the starting material were formed into a first mass. The first material was burned at 1550 ℃ for 4 hours, and then casting and quenching were performed to obtain a second material. And (3) carrying out heat treatment on the second material for 4 hours at 800 ℃ under the protection of nitrogen, thereby obtaining the red fluorescent material containing the rare earth elements. The properties of the red fluorescent material containing rare earth elements are shown in table 2.
TABLE 1
Numbering device | Red fluorescent material containing rare earth element |
Example 1 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 |
Example 2 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 |
Example 3 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01TiO 2 |
Example 4 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01ZrO 2 |
Example 5 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Na 2 O:0.24SiO 2 :0.01GeO 2 |
Example 6 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02K 2 O:0.24SiO 2 :0.01GeO 2 |
Example 7 | 0.0005Sm 2 O 3 :0.0001Pr 6 O 11 :0.05MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 |
Example 8 | 0.0001Sm 2 O 3 :0.0004Pr 6 O 11 :0.05BaO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 |
Example 9 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.15BaO:0.68Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.01GeO 2 |
Example 10 | 0.0005Sm 2 O 3 :0.0004Pr 6 O 11 :0.15MgO:0.88Y 2 O 3 :0.02Li 2 O:0.24SiO 2 :0.06GeO 2 |
TABLE 2
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (8)
1. A rare earth element-containing red fluorescent material characterized by having the composition shown below:
mSm 2 O 3 : nPr 6 O 11 : aMO: bY 2 O 3 : cE 2 O: xSiO 2 : yGO 2
wherein M is selected from at least one of Mg or Ba, E is selected from at least one of Li, na or K, and G is selected from one of Zr, ti or Ge;
wherein m, n, a, b, c, x and y each represent Sm 2 O 3 、Pr 6 O 11 、MO、Y 2 O 3 、E 2 O、SiO 2 And GO 2 The amount of the substance of (a); 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. The rare earth element-containing red fluorescent material according to claim 1, wherein E is Li; g is at least one selected from Ti and Ge.
3. The rare earth element-containing red fluorescent material according to claim 1, wherein (m: n) represents Sm 2 O 3 With Pr 6 O 11 The molar ratio of (2) is more than or equal to 0.5 and less than or equal to (m: n).
4. The rare earth element-containing red fluorescent material according to claim 1, wherein (b: m) represents Y 2 O 3 With Sm 2 O 3 The molar ratio of (b: m) is less than or equal to 1500 and less than or equal to 2000.
5. The red fluorescent material containing rare earth elements according to claim 1, wherein, m is more than or equal to 0.0002 and less than or equal to 0.0007,0.0002, n is more than or equal to 0.0007,0.002, a is more than or equal to 0.09,0.7 and b is more than or equal to 0.95, and y is more than or equal to 0.003 and less than or equal to 0.04.
6. The rare earth element-containing red fluorescent material according to claim 1, wherein the rare earth element-containing red fluorescent material has a composition represented by one of the following formulas:
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05MgO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05BaO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05BaO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01TiO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05MgO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01ZrO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05MgO: 0.88Y 2 O 3 : 0.02Na 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05BaO: 0.88Y 2 O 3 : 0.02K 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0005Sm 2 O 3 : 0.0001Pr 6 O 11 :0.05MgO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0001Sm 2 O 3 : 0.0004Pr 6 O 11 :0.05BaO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.15BaO: 0.68Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.01GeO 2 ;
0.0005Sm 2 O 3 : 0.0004Pr 6 O 11 :0.15MgO: 0.88Y 2 O 3 : 0.02Li 2 O: 0.24SiO 2 : 0.06GeO 2 。
7. the method for producing a rare earth element-containing red fluorescent material according to any one of claims 1 to 6, comprising the steps of:
(1) Forming a first material from boric acid and a raw material obtained from the composition of a red fluorescent material containing a rare earth element; the consumption of boric acid is 1-6wt% of the weight of the raw material;
(2) Burning the first material at 1100-1800 ℃ for 2-8 hours, and then cooling to obtain a second material;
(3) And (3) carrying out heat treatment on the second material in an inert atmosphere at 500-1000 ℃ for 2-8 hours to obtain the red fluorescent material containing the rare earth elements.
8. Use of the rare earth element-containing red fluorescent material according to any one of claims 1 to 6 as a light emitting diode lamp packaging material.
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