CN106047341B - A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device - Google Patents
A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device Download PDFInfo
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- CN106047341B CN106047341B CN201610384438.3A CN201610384438A CN106047341B CN 106047341 B CN106047341 B CN 106047341B CN 201610384438 A CN201610384438 A CN 201610384438A CN 106047341 B CN106047341 B CN 106047341B
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- Prior art keywords
- fluorescent powder
- oxide
- carbonate
- rare earth
- phosphate
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- 239000000843 powder Substances 0.000 title claims abstract description 147
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 29
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title abstract description 9
- -1 rare earth ion Chemical class 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 19
- 230000008859 change Effects 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000011777 magnesium Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000011575 calcium Substances 0.000 claims description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000008246 gaseous mixture Substances 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000005121 nitriding Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 9
- 229910001626 barium chloride Inorganic materials 0.000 claims description 9
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 9
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 9
- LYSTYSFIGYAXTG-UHFFFAOYSA-L barium(2+);hydrogen phosphate Chemical compound [Ba+2].OP([O-])([O-])=O LYSTYSFIGYAXTG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 9
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 9
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 9
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 9
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 9
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 9
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 239000011368 organic material Substances 0.000 claims description 9
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 9
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 9
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 9
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 9
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 9
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 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 claims description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 5
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 5
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 5
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 5
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 5
- CMVOJSWILFNLFI-UHFFFAOYSA-L magnesium;dibromate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-]Br(=O)=O.[O-]Br(=O)=O CMVOJSWILFNLFI-UHFFFAOYSA-L 0.000 claims description 5
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- HKSVWJWYDJQNEV-UHFFFAOYSA-L strontium;hydron;phosphate Chemical compound [Sr+2].OP([O-])([O-])=O HKSVWJWYDJQNEV-UHFFFAOYSA-L 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 4
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000006259 organic additive Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 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 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- 239000001506 calcium phosphate Substances 0.000 claims 1
- 229960001714 calcium phosphate Drugs 0.000 claims 1
- 235000011010 calcium phosphates Nutrition 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 150000002222 fluorine compounds Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims 1
- 239000004137 magnesium phosphate Substances 0.000 claims 1
- 229960002261 magnesium phosphate Drugs 0.000 claims 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims 1
- 235000010994 magnesium phosphates Nutrition 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 235000007686 potassium Nutrition 0.000 claims 1
- 239000011698 potassium fluoride Substances 0.000 claims 1
- 235000003270 potassium fluoride Nutrition 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011775 sodium fluoride Substances 0.000 claims 1
- 235000013024 sodium fluoride Nutrition 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 235000011008 sodium phosphates Nutrition 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000009877 rendering Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005286 illumination Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 32
- 239000002994 raw material Substances 0.000 description 30
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 28
- 239000000377 silicon dioxide Substances 0.000 description 21
- 229910052581 Si3N4 Inorganic materials 0.000 description 18
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 15
- 238000004321 preservation Methods 0.000 description 15
- 229940119177 germanium dioxide Drugs 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 238000010792 warming Methods 0.000 description 14
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 13
- 229910001195 gallium oxide Inorganic materials 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 230000005284 excitation Effects 0.000 description 11
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 10
- BIXHRBFZLLFBFL-UHFFFAOYSA-N germanium nitride Chemical compound N#[Ge]N([Ge]#N)[Ge]#N BIXHRBFZLLFBFL-UHFFFAOYSA-N 0.000 description 10
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 229910001940 europium oxide Inorganic materials 0.000 description 8
- 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 8
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000005538 encapsulation Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007836 KH2PO4 Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910020073 MgB2 Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 4
- 229910016064 BaSi2 Inorganic materials 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 239000005084 Strontium aluminate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- XCNHXROWMVKLEB-UHFFFAOYSA-N [Ge+2].[O-2].[O-2].[Ti+4] Chemical compound [Ge+2].[O-2].[O-2].[Ti+4] XCNHXROWMVKLEB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7735—Germanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of rare earth doping fluorescent powder, its synthetic method and its applications on the led device, belong to luminescent material technical field.The fluorescent powder chemical general formula is MS2‑yAyO2+yN2‑y‑4z/ 3Cz:Rx, the compound of the present invention C4‑Replace N3‑, since C is smaller compared with N electronegativity, C4‑Compare N3‑Electron cloud bulking effect become apparent from, aggravate rare earth ion 5d engery level cracking, Stokes shift can also change, and the fluorescence parameters such as the Fluorescent peal of powder, full half-peak breadth change.By adjusting the generation of above-mentioned Doped ions, the photochromic fluorescent powder with quantum efficiency of different fluorescence can be obtained.The fluorescent powder is also disclosed in the present invention applied to LED component field, the colour rendering index which is applied to facilitate using blue led or ultraviolet LED as the White-light LED illumination utensil or light-emitting component of light source device improves.
Description
Technical field
The present invention relates to luminescent material technical field, in particular to a kind of rare earth doping fluorescent powder and synthetic method, and its
Application on the led device.
Background technique
There is low power consuming, high electro-optical efficiency, the long-life, high brightness, small in size, right using the white light LEDs of chemiluminescence
Environmental nonpollution, response it is fast many advantages, such as, be considered replace the traditional lightings tool such as incandescent lamp and fluorescent lamp become have both province
The new lighting source of electricity and environmental protection, has been widely used in illumination, traffic signals, backlight, laser, communication, automobile, instrument instrument
The various lighting areas such as table, plant culture, decoration.
Fluorescent powder has decisive role in solid-state lighting LED technology, and performance determines the luminous light of white light LEDs
The critical technical parameters such as spectrum, luminous efficiency, colour rendering index, colour temperature and service life.LED is often with white light implementation at present
InGaN chip issues blue light and excites YAG:Ce3+The blue light that the yellow light and chip for issuing it penetrate is combined into white light.Due to such
The white light colour rendering index that method obtains is not high, it is difficult to more than 80.The LED white light for obtaining high color rendering index (CRI), often passes through blue chip
The blue light that the light that excitated red fluorescent powder and green emitting phosphor issue the two is penetrated with chip again is combined into white light, or passes through
The recovery synthesis white light that ultraviolet chip excitated red fluorescent powder, green emitting phosphor and blue colour fluorescent powder issue three.In addition, if
It is expected that obtaining the white light of more high color rendering index (CRI) (being greater than 95), other than red, green, blue three-color phosphor, bluish-green, yellow or orange glimmering
Light powder is also needed.Therefore, acquisition luminous efficiency is high, chemical stability is good and the multicolor phosphor of good heat stability becomes
Obtain high color rendering index (CRI), the necessary condition of especially high-power white-light LED with high color rendering index lamp.
Use and develop at present more for rouge and powder, green powder and bloom, the exploitation photochromic for other fluorescence is less, especially
It is bluish-green powder.Patent CN103242834A discloses a kind of rear-earth-doped Sr4Al14O25The fluorescent powder of strontium aluminate, but the powder is only capable of
Just there is stronger fluorescence under ultraviolet light, and its long afterglow qualities limits its application on LED.The silicate of Eu doping
Ba5Si8O21(emission peak 480nm) and BaSi2O5(emission peak 505nm) can also emit blue green light under ultraviolet excitation, but due to
The stability of silicate is limited, which applies and unwelcome in actual package.The oxygen fluoride Sr of Ce doping3AlO4F exists
There is excitation bimodal respectively in 460nm and 502nm under ultraviolet excitation, and fluorescent powder quantum efficiency with higher, still
The fluorescent powder is restricted its use also due to thermal stability is not excellent.
The method for preparing nitric oxide fluorescent powder at present mainly has solid phase method, microwave method, vapour phase reduction nitriding.Microwave method
Raw material should not obtain and toxic, carrying cost height.Before vapour phase reduction nitriding need to use the preparation of organic/inorganic solution finely dispersed
Body is driven, cost of material is high, is easily introduced impurity in complex process and synthesis process.Also there is researcher will by plasma discharging (SPS)
In its study on the synthesis for being used in such fluorescent powder, though this method in ceramic post sintering using more mature, make in powder synthesis
Easily make powder sintering blocking with this method, the fluorescence intensity, quantum efficiency and fluorescence that powder is substantially reduced in shattering process are steady
Qualitative equal fluorescence properties, this method synthesizes also immature in fluorescent powder.
In fact, solid phase method is the method generally used in current fluorescent powder industrial production, this method simple process is easily-controllable
System, and large-scale production easy to accomplish.But its defect is that this method synthesis is easy to produce impurity phase, obtains powder and generates group
Poly-, being crushed reunion reduces the fluorescence property of fluorescent powder.Therefore, develop a kind of optimization side of the fluorescence property of system fluorescent powder
Method, under conditions of keeping volume production, to improve luminous efficiency, the fluorescence property for increasing fluorescent powder is necessary.
White light is made of the mixing of a variety of monochromatic light, common white light LEDs by ultraviolet LED or blue LED die with it is glimmering
The combination of light powder, fluorescent powder absorb the light emitted after the light that chip issues and mix and obtain white with the unabsorbed light of chip
Light.In order to improve the display index of White LED, it is desirable that the white light for obtaining continuous full spectrum as far as possible, in addition to using common Huang
Outside color, red and green emitting phosphor, more colorful fluorescent powder is also used in high display index LED component.Therefore, having must
The fluorescent powder of special color is developed, special fluorescence peak spike is long to be in the bluish-green emitting phosphor of 470~520nm.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention discloses a kind of rear-earth-doped MS2-yAyO2+yN2-y-4z/3Cz:
RxFluorescent powder, and provide the synthetic method and its application on the led device of the fluorescent powder, it is therefore intended that exploitation efficient stable
Fluorescent powder, and by it is simple and easy to control and can volume production process conditions, acquisition can be improved luminous efficiency, increase fluorescent powder
The synthetic method of fluorescence property, so that obtaining the colour rendering index that powder is conducive to further increase LED component.
C is successfully mixed MS by Design of Chemical Composition and technology controlling and process by the first purpose of this invention, the present invention2- yAyO2+yN2-y: among R, obtains rare earth and mix MS2-yAyO2+yN2-y-4z/3Cz:RxFluorescent powder uses C4-Replace N3-, since C is compared with N electronegativity
It is smaller, C4-Compare N3Electron cloud bulking effect become apparent from, incorporation after make rare earth ion 5d engery level cracking aggravate, stoke
This displacement increases, and Fluorescent peal red shift, half-peak breadth broadens, to obtain the system fluorescent powder of more high emission wavelength.
Due to the successful incorporation of C, to the mutual substitution between rear-earth-doped and alkaline-earth metal ions caused by crystal structure
Defect play the role of it is modified so that can optimize to the thermal stability of fluorescent powder while improving fluorescence emission peak wavelength.
A second object of the present invention is to provide the preparation methods of above-mentioned fluorescent powder.
Third object of the present invention is to solve to be capable of providing the excellent white light LED part of display index.Especially with indigo plant
The White LED of color LED or ultraviolet LED as the excitation light source of fluorescent powder.While guaranteeing the thermal stability of fluorescent powder, and energy
Enough realize the fluorescent powder of industrial scale production.
The rear-earth-doped MS synthesized using the present invention2-yAyO2+yN2-y-4z/3CzNitric oxide fluorescent powder has chemical stability
Height, luminous efficiency is high, excitation energy is low (blue light can be excited effectively), and emission spectrum is wide, and luminous efficiency is high, thermodynamic property
Good, hot-quenching is gone out temperature height.By adjusting the ratio of Mg, Ca, Sr, Ba and the ratio of S/A, can obtain bluish-green-yellowish green-orange-yellow
Fluorescent powder.The fluorescent powder is suitable for the white LED lamp of high color rendering index (CRI), the encapsulation including high-power LED lamp.
The technical scheme adopted by the invention is that:
A kind of rare earth doping fluorescent powder, molecular formula MS2-yAyO2+yN2-y-4z/3Cz:Rx, wherein in M=Mg, Ca, Sr, Ba
One or more, one of S Si, Ge or a variety of, A Al, one of Ga or a variety of, R are one in rare earth ion
Kind or a variety of, 0.001≤x≤0.2,0≤y≤0.8,0 < z≤0.1, O represent oxygen atom, and N represents nitrogen-atoms, and C represents carbon original
Son.
It is preferred that: 0.001≤x≤0.1,0≤y≤0.1,0 < z≤0.05.
It is preferred that: (Ca1-t-m-n-xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3Cz, wherein Re ' is trivalent rare earth ions Ce3 +、La3+、Pr3+、Sm3+、Tb3+、Dy3+One of or it is a variety of, L be alkali metal ion Li+、Na+, K+One of or it is a variety of, 0≤
M, n, t≤1,0.001≤x≤0.1.
It is preferred that: (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3Cz, wherein Re is bivalent rare earth ion Eu2+、Yb2 +、Sm2+One of or a variety of, 0≤m, n, t≤1,0.001≤x≤0.1.
The S is that Si or Si is combined with Ge, and A is the combination of Al or Al and Ga, Re Eu2+。
It is preferred that t=0, y=0.
The transmitting range of the fluorescent powder is 460nm~580nm, and fluorescence emission peak wavelength is between 470~520nm.
The preparation method of above-mentioned fluorescent powder is made using a step nitriding or two step nitridings,
The one step nitriding is the carbonate that raw material M is measured according to molecular formula, the oxide and S nitride of S, A oxygen
Compound, R oxide contain carbon simple substance or carbonaceous organic material, and additive synthesis is some mixes, grinding gained fluorescent powder after nitridation calcining
Body；
The step of two steps nitriding, aoxidizes to measure the carbonate of raw material M, the oxide of S, A according to molecular formula
Object, R oxide and containing obtaining presoma after carbon simple substance or carbonaceous organic material mixed calcining, after presoma is ground and S nitride
And additive synthesis mixing, nitridation calcining is then carried out again, also can get fluorescent powder；
Or the carbonate of raw material M, the oxide of S, A oxide and the mixing of R oxide are measured according to molecular formula and forged
Presoma is obtained after burning, after presoma is ground and S nitride, containing carbon simple substance or carbonaceous organic material and additive synthesis mixing, so
It carries out nitridation calcining again afterwards, also can get fluorescent powder.
Described is active powdered carbon or graphite powder containing carbon simple substance or carbonaceous organic material is sucrose, glucose or maltose.
Carbonate, S nitride, S oxide, R oxide, the A oxide of M is stoichiometrically (1.8~2.2):
(0.8~1.2): 1:(0.001~0.1): (0~0.8), auxiliary agent press quality proportioning, content be raw material sum 0.2%~
10%.
The auxiliary agent is one of fluoride, chloride, carbonate, phosphate, borate, oxide, boric acid or several
Kind.
The fluoride includes lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (CsF), calcirm-fluoride
(CaF2), magnesium fluoride (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminum fluoride (AlF3)。
The chloride includes lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), chlorination
Calcium (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl), aluminium chloride
(AlCl3)。
The carbonate includes lithium carbonate (Li2CO3), sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate
(Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg(OH)2·5H2O)。
The phosphate is including but not limited to lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid
Caesium (Cs3PO4), magnesium phosphate (Mg3(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3
(PO4)2), disodium-hydrogen (Na2HPO4), magnesium monohydrogen phosphate (MgHPO4), calcium monohydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4)、
Barium hydrogen phosphate (BaHPO4), lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), phosphorus
Acid dihydride magnesium (Mg (H2PO4)2), calcium dihydrogen phosphate (Ca (H2PO4)2)。
The borate includes lithium borate (Li3BO3), Boratex (Na3BO3), antifungin (MgB2O4)。
The oxide includes magnesia (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), scandium oxide (Sc2O3), oxidation
Yttrium (Y2O3)。
Wherein after nitridation calcining, then it is cooled to room temperature with the rate of temperature fall of 2~20 DEG C/min, obtains fluorescent powder or block
Block is placed on grinding or ball in grinding and clays into power and target product can be obtained by body.
Wherein nitridation calcination process be 1250~1600 DEG C at a temperature of calcine 2~20 hours in the protective atmosphere.
The calcination process for wherein obtaining presoma is that calcining 0.5~10 is small in protective atmosphere at 1000~1400 DEG C
When.
The protective atmosphere is one or more of argon gas, nitrogen, argon hydrogen gaseous mixture, nitrogen and hydrogen mixture or ammonia.
Application of the above-mentioned fluorescent powder in LED component.
The chip emission peak wavelength range of the LED component is between 200nm~520nm.
The compound of the present invention C4-Replace N3-, since C is smaller compared with N electronegativity, C4-Compare N3Electron cloud bulking effect
It becomes apparent from, aggravates rare earth ion 5d engery level cracking, Stokes shift can also change, the fluorescence of powder
The fluorescence parameters such as peak position, full half-peak breadth change.Therefore, by adjusting the generation of above-mentioned Doped ions, difference can be obtained
The photochromic fluorescent powder with quantum efficiency of fluorescence.
Alkaline-earth metal type and ratio are adjusted, the fluorescence spectrum of powder can be effectively adjusted, obtain the fluorescence of different colorations
Powder.The system belongs to the nitrogen oxides of silicon substrate, and Si-N and Si-O composition spatial network are as a result, pass through doped and substituted, such as Ge4+Replace
Si4+, Al-O (or Ga-O) replace Si-N, the lattice constant of crystal is changed, to change the coordination ring of luminescent center ion
The variation of centre of luminescence engery level cracking and the change of electron cloud effect are caused in border, so that the fluorescence spectrum of powder is obtained, hair
The parameters such as light efficiency change.
Fluorescent powder of the present invention specific the preparation method is as follows:
Above-mentioned MS2-yAyO2+yN2-y-4z/3CzFluorescent powder, a step nitriding comprise the following steps that
(1) according to chemical formula (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzOr (Ca1-t-m-n- 2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometric ratio is by alkaline earth metal carbonate, silicon nitride, germanium nitride, dioxy
SiClx, germanium dioxide, rare earth oxide, aluminium oxide and alkali carbonate and carbon dust proportion, additive synthesis press quality proportioning,
Its content is above-mentioned alkaline earth metal carbonate, silicon nitride, germanium nitride, silica, germanium dioxide, rare earth oxide, aluminium oxide
With the 0.5%~10% of alkali carbonate and carbon dust quality sum.Then it is uniformly mixed to get raw material mixed powder end.
(2) raw material mixed powder end is placed in crucible, under protective atmosphere, 3~30 DEG C of heating rate is imposed to crucible
After being warming up to 1250~1600 DEG C, heat preservation 2~20 hours, then it is cooled to room temperature, is obtained with the rate of temperature fall of 2~20 DEG C/min
Rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent powder or block.Powder or block are placed on grinding or ball grinds in grinding
End can needed for granularity MS2-yAyO2+yN2-y-4z/3Cz:RxOxynitride fluorescent powder.
According to the above scheme, (Ca in step (1)1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzStoichiometric ratio is matched
When than raw material, raw material proportioning is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silica+germanium dioxide): rare earth oxygen
Compound: (aluminium oxide+gallium oxide): carbon dust is (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~0.8): (0~
0.1) it matches.
According to the above scheme, (Ca in step (1)1-t-m-n-2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometry
When than proportion raw material, raw material proportioning is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silica+germanium dioxide): dilute
Native oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~0.8):
(0~0.1), to keep charge balance, the amount proportion of alkali carbonate and rare earth ion Re ' same substance.
According to the above scheme, additive synthesis is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), is fluorinated in step (1)
Caesium (CsF), calcirm-fluoride (CaF2), magnesium fluoride (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminum fluoride
(AlF3), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chloride (CaCl2), magnesium chloride
(MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl), aluminium chloride (AlCl3), lithium carbonate (Li2CO3)、
Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg
(OH)2·5H2O), lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid caesium (Cs3PO4), magnesium phosphate
(Mg3(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3(PO4)2), disodium-hydrogen
(Na2HPO4), magnesium monohydrogen phosphate (MgHPO4), calcium monohydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4), barium hydrogen phosphate (BaHPO4)、
Lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), magnesium dihydrogen phosphate (Mg
(H2PO4)2), calcium dihydrogen phosphate (Ca (H2PO4)2), lithium borate (Li3BO3), Boratex (Na3BO3), antifungin (MgB2O4), oxygen
Change magnesium (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), scandium oxide (Sc2O3), yttrium oxide (Y2O3) any one or a few.It is excellent
It is selected as potassium carbonate.
According to the above scheme, in step (1) the uniform method of mixing be in mortar grinding or ball mill in ball milling.
According to the above scheme, crucible described in step (2) is alumina crucible, molybdenum crucible or tungsten crucible.
According to the above scheme, protective atmosphere described in step (2) is inert atmosphere or reducing atmosphere.
According to the above scheme, protective atmosphere described in step (2) be high pure nitrogen, high-purity argon gas, nitrogen and argon gas gaseous mixture,
Nitrogen and hydrogen mixed gas, argon gas and hydrogen mixed gas.
Above-mentioned rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent powder, two step nitridings comprise the following steps that
(1) according to chemical formula (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzOr (Ca1-t-m-n- 2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometric ratio by alkaline earth metal carbonate, silica, germanium dioxide,
Rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate proportion, additive synthesis press quality proportioning, and content is above-mentioned alkali
Earth metal carbonate, silica, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate quality sum
0.5%~10%.Then by alkaline earth metal carbonate, silica, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and
Alkali carbonate matches salt and is uniformly mixed, i.e., preliminary mixed-powder；
(2) preliminary mixed raw material is placed in crucible, and under protective atmosphere, the heating rate for imposing 3~30 DEG C to crucible heats up
To 1000~1400 DEG C, after 0.5~10h of heat preservation is sufficiently decomposed, then it is cooled to room temperature with the rate of temperature fall of 2~20 DEG C/min,
Presoma is obtained, powder is worn by presoma is mixed, obtains presoma powder.
(3) by presoma powder and silicon nitride, germanium nitride and additive synthesis with the proportion of content described in step (1), uniformly
Mixing, obtains two step mixed-powders；
(4) two step mixed-powders are placed in crucible, under protective atmosphere, 3~30 DEG C of heating rate is imposed to crucible
After being warming up to 1250~1600 DEG C, heat preservation 2~20 hours, then it is cooled to room temperature, is obtained with the rate of temperature fall of 2~20 DEG C/min
Rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent powder or block.Fluorescent powder or block are placed on grinding or ball milling in grinding
It can be obtained the MS of required granularity at powder2-yAyO2+yN2-y-4z/3Cz:RxFluorescent powder.
According to the above scheme, with (Ca in step (1)1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzStoichiometric ratio
When matching raw material, raw material proportioning is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silica+germanium dioxide): rare earth
Oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~0.8): (0
~0.1) it matches.
According to the above scheme, with (Ca in step (1)1-t-m-n-2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzChemistry meter
When amount is than proportion raw material, raw material proportioning is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silica+germanium dioxide):
Rare earth oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~
0.8): (0~0.1), to keep charge balance, the amount proportion of alkali carbonate and rare earth ion Re ' same substance.
According to the above scheme, additive synthesis is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), is fluorinated in step (1)
Caesium (CsF), calcirm-fluoride (CaF2), magnesium fluoride (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminum fluoride
(AlF3), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chloride (CaCl2), magnesium chloride
(MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl) aluminium chloride (AlCl3), lithium carbonate (Li2CO3)、
Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg
(OH)2·5H2O, lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid caesium (Cs3PO4), magnesium phosphate (Mg3
(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3(PO4)2), disodium-hydrogen
(Na2HPO4), magnesium monohydrogen phosphate (MgHPO4), calcium monohydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4), barium hydrogen phosphate (BaHPO4)、
Lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), magnesium dihydrogen phosphate (Mg
(H2PO4)2), calcium dihydrogen phosphate (Ca (H2PO4)2), lithium borate (Li3BO3), Boratex (Na3BO3), antifungin (MgB2O4), oxygen
Change magnesium (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), scandium oxide (Sc2O3), yttrium oxide (Y2O3) any one or a few.It is excellent
It is selected as potassium carbonate.
According to the above scheme, the uniform method of mixing is the ball milling in grinding or ball mill in mortar in step (1) and (3).
According to the above scheme, crucible described in step (2) and (4) is alumina crucible, molybdenum crucible or tungsten crucible.
According to the above scheme, protective atmosphere described in step (2) and (4) is inert atmosphere or reducing atmosphere.
According to the above scheme, protective atmosphere described in step (2) and (4) is high pure nitrogen, and high-purity argon gas, nitrogen and argon gas are mixed
Close gas, nitrogen and hydrogen mixed gas, argon gas and hydrogen mixed gas.
Above-mentioned rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent powder, two second of step nitriding realizations comprise the following steps that
(1) according to chemical formula (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzOr (Ca1-t-m-n- 2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometric ratio matches alkaline earth metal carbonate, silica, titanium dioxide
Germanium, rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate, additive synthesis press quality proportioning, and content is above-mentioned alkaline earth
Metal carbonate, silica, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate quality sum
0.1%~10%.Then by alkaline earth metal carbonate, silica, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and
Alkali carbonate and additive synthesis are uniformly mixed to get preliminary mixed raw material；
(2) preliminary mixed raw material is placed in crucible, and under protective atmosphere, the heating rate for imposing 3~30 DEG C to crucible heats up
To 1000~1400 DEG C, after keeping the temperature abundant decomposition in 0.5~10 hour, room is then cooled to the rate of temperature fall of 2~20 DEG C/min
Then temperature obtains presoma powder or block, be ground into the powder of required granularity, obtains precursor powder.
(3) precursor powder and silicon nitride, germanium nitride grinding or ball milling are mixed, obtains two step mixed-powders；
(4) two step mixed-powders are placed in crucible, under protective atmosphere, 3~30 DEG C of heating rate is imposed to crucible
After being warming up to 1250~1600 DEG C, heat preservation 2~20 hours, then it is cooled to room temperature, is obtained with the rate of temperature fall of 2~20 DEG C/min
Rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent powder or block.Powder or block are placed on grinding or ball in grinding to clay into power
The MS of required granularity can be obtained2-yAyO2+yN2-y-4z/3Cz:RxFluorescent powder.
According to the above scheme, with (Ca in step (1)1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzStoichiometric ratio
When matching raw material, raw material proportioning is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silica+germanium dioxide): rare earth
Oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~0.8): (0
~0.1) it matches.
According to the above scheme, with (Ca in step (1)1-t-m-n-2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzChemistry meter
When amount is than proportion raw material, raw material proportioning is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silica+germanium dioxide):
Rare earth oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~
0.8): (0~0.1), to keep charge balance, the amount proportion of alkali carbonate and rare earth ion Re ' same substance.
According to the above scheme, additive synthesis is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), is fluorinated in step (1)
Caesium (CsF), calcirm-fluoride (CaF2), magnesium fluoride (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminum fluoride
(AlF3), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chloride (CaCl2), magnesium chloride
(MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl) aluminium chloride (AlCl3), lithium carbonate (Li2CO3)、
Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg
(OH)2·5H2O, lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid caesium (Cs3PO4), magnesium phosphate (Mg3
(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3(PO4)2), disodium-hydrogen
(Na2HPO4), magnesium monohydrogen phosphate (MgHPO4), calcium monohydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4), barium hydrogen phosphate (BaHPO4)、
Lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), magnesium dihydrogen phosphate (Mg
(H2PO4)2), calcium dihydrogen phosphate (Ca (H2PO4)2), lithium borate (Li3BO3), Boratex (Na3BO3), antifungin (MgB2O4), oxygen
Change magnesium (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), scandium oxide (Sc2O3), yttrium oxide (Y2O3) any one or a few.It is excellent
It is selected as potassium carbonate.
According to the above scheme, the uniform method of mixing is the ball milling in grinding or ball mill in mortar in step (1) and (3).
According to the above scheme, crucible described in step (2) and (4) is alumina crucible, molybdenum crucible or tungsten crucible.
According to the above scheme, protective atmosphere described in step (2) and (4) is inert atmosphere or reducing atmosphere.
According to the above scheme, protective atmosphere described in step (2) and (4) is high pure nitrogen, and high-purity argon gas, nitrogen and argon gas are mixed
Close gas, nitrogen and hydrogen mixed gas, argon gas and hydrogen mixed gas.
The implementation method of above-mentioned illuminating device is:
The LED adhesive of encapsulation includes but is not limited to silicone resin, and includes above-mentioned rear-earth-doped MS2-yAyO2+yN2-y-4z/ 3Cz:RxMain constituents of the fluorescent powder of fluorescent powder as encapsulating compound encapsulate blue light or UV LED chip, obtain white light LEDs
Device.
Compared with prior art, the beneficial effects of the present invention are:
First, present invention process is simple, and an especially step nitriding shortens synthesis cycle, and technique metaplasia easy to accomplish
It produces；
Second, by adjusting the type and content of additive synthesis, the crystallite dimension of powder can be flexibly controlled, crystallinity is brilliant
Lattice integrality and grain morphology.
Rear-earth-doped MS is prepared in third, the present invention2-yAyO2+yN2-y-4z/3Cz:RxThe excitation wavelength range of fluorescent powder is
250~520nm, excitation wavelength range is wide, and fluorescence intensity is high, can be used on UV LED chip or blue chip.
4th, rear-earth-doped MS is prepared in the present invention2-yAyO2+yN2-y-4z/3Cz:RxFluorescent powder and other color fluorescence powder,
Specifically with green powder, bloom, rouge and powder hybrid package blue light or UV LED chip, the excellent white light LEDs of display index are easily obtained
Device.
Detailed description of the invention
Fig. 1 is (Ba in embodiment one0.993-m-nSrmCanEu0.007)Si2O2N1.996C0.003Excitation and emission spectra figure.
Wherein curve 1 is m=0.1, n=0；Curve 2 is m=0.2, n=0；Curve 3 is m=0, n=0.1；Curve 4 is m=0, n=
0.4；Curve 5 is m=0.05, n=0.05；Curve 6 is m=0.1, n=0.1.
Fig. 2 is the excitation and emission spectra of gained sample in embodiment two and reference example one.
Fig. 3 is gained Sample Scan electron microscope display figure in embodiment two.
Fig. 4 shows figure for the scanning electron microscope of institute's sample in embodiment three.
Fig. 5 is gained sample and LuAG:Ce in embodiment two3+Green powder and (SrCa) AlSiN3:Eu2+Encapsulate blue-ray LED core
Spectrogram before and after piece 100W module group aging.
Fig. 6 is X-ray diffraction (XRD) figure of gained sample in example IV.
Fig. 7 is that the fluorescence spectrum of gained sample in example IV varies with temperature figure
Fig. 8 is gained sample heat stability testing result in example IV and reference example two.
Fig. 9 is the particle size distribution figure of gained sample in example IV.
Figure 10 be embodiment seven, in reference example three and reference example four white light LED part basic structure.Launch wavelength is
The InGaN blue chip 1 of 460nm is embedded in the groove 6 in lighttight encapsulating structure 10.1 one end of chip and electrode 3 are straight
Connect connected, the other end is connected through conducting wire 2 with electrode 4.It is filled in groove 6 with encapsulating compound 5, encapsulating compound is with fluorescent powder 7 and glue
Mainly to form.Fluorescent powder 7 includes rear-earth-doped MS in the present invention2-yAyO2+yN2-y-4z/3Cz:RxIt is formed with other fluorescent powders.It is recessed
The wall 8 of slot 6 has high reflection effect, to reflect the light that chip and fluorescent powder issue.9 protect mould for high light transmission.
Figure 11 is the spectrum of white light LEDs in embodiment seven and reference example three.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments.
Embodiment one
Reaction raw materials 35.24g barium carbonate, 2.96g strontium carbonate, 0g calcium carbonate, 5.64g silica, 15.24g silicon nitride,
0.24g europium oxide and 0.01g high purity graphite powder are placed in ground and mixed 30min in ceramic mortar and obtain mixture, by mixture mistake
It is fitted into alumina crucible after 100 meshes and is calcined in horizontal pipe furnace.Nitrogen-hydrogen gaseous mixture is passed through in calcination process
(hydrogen content 10%), throughput 0.3L/min, after being warming up to 1490 DEG C, heat preservation 8 hours with the heating rate of 8 DEG C/min,
Room temperature is cooled to the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.Slight ground 120 mesh of products therefrom warp,
Blue-green fluorescent powder (BaSr) Si can be obtained2O2N1.996C0.003:Eu2+.Curve 1 is to be somebody's turn to do (BaSr) in Fig. 1
Si2O2N1.996C0.003:Eu2+Excitation and emission spectra.
The proportion for adjusting barium carbonate, strontium carbonate, calcium carbonate can get blue-green-yellow fluorescence that different alkali metal replace
Powder.
Table 1 lists the composition quality of different composition ratio.
(the Ba of table 1, difference m, n value0.993‐m‐nSrmCanEu0.007)Si2O2N1.996C0.003Quality proportioning
Embodiment two
Reaction raw materials 64.68g barium carbonate, 9.31g silica, 25.14g silicon nitride, 0.40g europium oxide, 1.12g carbonic acid
Potassium and 0.015g high purity graphite powder are placed in ground and mixed 30min in ceramic mortar and obtain mixture, after mixture is sieved with 100 mesh sieve
It is fitted into alumina crucible and is calcined in horizontal pipe furnace.Nitrogen-hydrogen gaseous mixture (hydrogen content is passed through in calcination process
10%), throughput 0.3L/min, after being warming up to 1510 DEG C, heat preservation 8 hours with the heating rate of 8 DEG C/min, with 10 DEG C/min
Rate of temperature fall be cooled to 700 DEG C after cool to room temperature with the furnace.Indigo plant can be obtained through slight ground 120 mesh in products therefrom
Green emitting phosphor BaSi2O2N1.996C0.003:Eu2+.Curve 2 is the excitation and emission spectra of the sample in Fig. 2, compares reference example one
Spectrum, it can be seen that doped portion C replaces, fluorescence spectrum red shift, and fluorescence emission peak wavelength is mobile to long-wave band.Fig. 3 sample
Scanning electron microscope display figure.Comparative example three is as can be seen that adding assistant crystal growth is completely regular.Fig. 5 is the sample
And LuAG:Ce3+Green powder and (SrCa) AlSiN3:Eu2+Encapsulate blue-light LED chip 100W module group aging front and back spectrogram.
Reference example one
Reaction raw materials 64.68g barium carbonate, 9.31g silica, 25.14g silicon nitride, 0.40g europium oxide, 1.12g carbonic acid
Potassium is placed in ground and mixed 30min in ceramic mortar and obtains mixture, is fitted into alumina crucible after mixture is sieved with 100 mesh sieve
It is calcined in horizontal pipe furnace.Nitrogen-hydrogen gaseous mixture (hydrogen content 10%) is passed through in calcination process, throughput is
0.3L/min is cooled down after being warming up to 1510 DEG C, heat preservation 8 hours with the heating rate of 8 DEG C/min with the rate of temperature fall of 10 DEG C/min
Room temperature is cooled to the furnace after to 700 DEG C.Blue-green fluorescent powder can be obtained through slight ground 120 mesh in products therefrom
(BaEu)Si2O2N2.Curve 1 is the excitation and emission spectra of the sample in Fig. 2.
Embodiment three
Reaction raw materials 64.68g barium carbonate, 9.31g silica, 25.14g silicon nitride, 0.40g europium oxide and 0.015g high
Pure graphite is placed in ground and mixed 30min in ceramic mortar and obtains mixture, is packed into alumina crucible after mixture is sieved with 100 mesh sieve
In calcined in horizontal pipe furnace.Nitrogen-hydrogen gaseous mixture (hydrogen content 10%) is passed through in calcination process, throughput is
0.3L/min is cooled down after being warming up to 1510 DEG C, heat preservation 8 hours with the heating rate of 8 DEG C/min with the rate of temperature fall of 10 DEG C/min
Room temperature is cooled to the furnace after to 700 DEG C.Ground 120 mesh of mistake of products therefrom, can be obtained blue-green fluorescent powder (BaEu)
Si2O2N1.996C0.003。
Figure is shown in Fig. 4 for the scanning electron microscope of the sample.
Example IV
Reaction raw materials 130.64g barium carbonate, 18.83g silica, 0.82g europium oxide are placed in grind in ceramic mortar and mix
It closes 30min and obtains mixture, be fitted into alumina crucible after mixture is sieved with 100 mesh sieve and calcined in horizontal pipe furnace.
It is passed through in calcination process nitrogen-hydrogen gaseous mixture (hydrogen content 10%), throughput 0.2L/min, with the heating of 8 DEG C/min
After rate is warming up to 1190 DEG C, heat preservation 2 hours, room temperature is cooled to the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.
Products therefrom is sieved with 100 mesh sieve through slight grinding, i.e. acquisition precursor powder.By 120g precursor powder, 50.33g silicon nitride,
1.55g potassium carbonate and 0.03g high purity graphite are placed in ground and mixed 30min in ceramic mortar and obtain mixture, and mixture is crossed 100
It is fitted into alumina crucible after mesh and is calcined in horizontal pipe furnace.Nitrogen-hydrogen gaseous mixture (hydrogen is passed through in calcination process
Gas content 10%), throughput 0.3L/min, after being warming up to 1450 DEG C, heat preservation 8 hours with the heating rate of 8 DEG C/min, with 10
DEG C/rate of temperature fall of min cools to room temperature with the furnace after being cooled to 700 DEG C.Products therefrom also may be used through slight ground 120 mesh
Obtain the blue-green fluorescent powder of Eu doping.Fig. 6 is X-ray diffraction (XRD) map of the sample.Fig. 7 is the fluorescent spectrum
Vary with temperature figure.Fig. 8 curve 1 is the thermostabilization test result of the sample, and the sample heat compared in reference example two undoped with C is steady
Qualitative test is as a result, thermal stability optimization of the doping C when being greater than 200 DEG C is obvious.
Fig. 9 is the size distribution chart of the sample, and size distribution, which is shown, can be very good control particle size and particle ruler
Very little distribution.
Reference example two
Reaction raw materials 130.64g barium carbonate, 18.83g silica, 0.82g europium oxide are placed in grind in ceramic mortar and mix
It closes 30min and obtains mixture, be fitted into alumina crucible after mixture is sieved with 100 mesh sieve and calcined in horizontal pipe furnace.
It is passed through in calcination process nitrogen-hydrogen gaseous mixture (hydrogen content 10%), throughput 0.2L/min, with the heating of 8 DEG C/min
After rate is warming up to 1190 DEG C, heat preservation 2 hours, room temperature is cooled to the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.
Products therefrom is sieved with 100 mesh sieve through slight grinding, i.e. acquisition precursor powder.By 120g precursor powder, 50.33g silicon nitride,
1.55g potassium carbonate is placed in ground and mixed 30min in ceramic mortar and obtains mixture, and oxidation is packed into after mixture is sieved with 100 mesh sieve
It is calcined in horizontal pipe furnace in aluminium crucible.Nitrogen-hydrogen gaseous mixture (hydrogen content 10%), gas are passed through in calcination process
Flow is 0.3L/min, after being warming up to 1450 DEG C, heat preservation 8 hours with the heating rate of 8 DEG C/min, with the cooling speed of 10 DEG C/min
Rate cools to room temperature with the furnace after being cooled to 700 DEG C.The indigo plant of Eu doping also can be obtained through slight ground 120 mesh in products therefrom
Green emitting phosphor BaSi2O2N2:Eu2+.Curve 2 is the thermostabilization test result of the sample in Fig. 8.
Embodiment five
Reaction raw materials 39.07g barium carbonate, 5.74g silica, 13.68g silicon nitride, 0.21g germanium dioxide, 0.51g oxygen
Change aluminium, 0.35g europium oxide and 0.005g high purity graphite powder to be placed in ground and mixed 30min in ceramic mortar and obtain mixture, will mix
It closes to be fitted into alumina crucible after object sieves with 100 mesh sieve and be calcined in horizontal pipe furnace.Nitrogen-hydrogen is passed through in calcination process
Gaseous mixture (hydrogen content 10%), throughput 0.3L/min are warming up to 1450 DEG C with the heating rate of 8 DEG C/min, and heat preservation 8 is small
Shi Hou cools to room temperature with the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.Ground 120 mesh of mistake of products therefrom,
Bottle green fluorescent powder (BaEu) (SiGe) can be obtained1.95Al0.05O2.05N1.95C0.003。
Embodiment six
Reaction raw materials 38.64g barium carbonate, 0.30g strontium carbonate, 6.02g silica, 0.19g gallium oxide, 0.10g oxidation
Aluminium, 0.35g europium oxide are placed in ground and mixed 30min in ceramic mortar and obtain mixture, are packed into oxygen after mixture is sieved with 100 mesh sieve
Change and is calcined in horizontal pipe furnace in aluminium crucible.Nitrogen-hydrogen gaseous mixture (hydrogen content 10%) is passed through in calcination process,
Throughput is 0.2L/min, after being warming up to 1150 DEG C, heat preservation 2 hours with the heating rate of 8 DEG C/min, with the cooling of 10 DEG C/min
Rate cools to room temperature with the furnace after being cooled to 700 DEG C.Products therefrom is sieved with 100 mesh sieve through slight grinding, i.e. acquisition precursor powder.
35g precursor powder, 13.28g silicon nitride, 0.014g high purity graphite powder and 0.283g LiF are placed in grind in ceramic mortar and mixed
It closes 30min and obtains mixture, be fitted into alumina crucible after mixture is sieved with 100 mesh sieve and calcined in horizontal pipe furnace.
It is passed through in calcination process nitrogen-hydrogen gaseous mixture (hydrogen content 10%), throughput 0.3L/min, with the heating of 8 DEG C/min
After rate is warming up to 1400 DEG C, heat preservation 8 hours, room temperature is cooled to the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.
Bottle green fluorescent powder (BaSr) Si of Eu doping also can be obtained through slight ground 120 mesh in products therefrom1.98(AlGa)0.02O2.02N1.972C0.006:Eu2+。
Table 2 shows that the chemical composition and synthetic method and auxiliary agent selection of the sample in doping synthetic example.
Table 2, embodiment overview
Embodiment seven
Fluorescent powder (the emission peak λ that will be obtained by the synthetic method of embodiment twoem=501nm) and LuAG:Ce3+Green powder
(emission peak λem=525nm) and (SrCa) AlSiN3:Eu2+(emission peak λem=628nm) it is weighed with mass ratio 3.3:1.9:2.4,
With fluorescent powder: glue=0.13:0.87 mass ratio proportion encapsulates InGaN blue chip (λ after evenly mixingex=460nm), warp
After dispensing, baking, pressing mold, separation, the high display White-light LED illumination device comprising the invention fluorescent powder packaging is obtained.
Figure 10 is the basic structure of the encapsulation white light LED part.Launch wavelength is the InGaN blue chip 1 of 460nm,
It is embedded in the groove 6 in lighttight encapsulating structure 10.1 one end of chip is connected directly with electrode 3, and the other end is through conducting wire 2 and electricity
Pole 4 is connected.It is filled in groove 6 with encapsulating compound 5, it is mainly to form that encapsulating compound, which is with fluorescent powder 7 and glue,.Fluorescent powder 7 includes this
Rear-earth-doped MS in invention2-yAyO2+yN2-y-4z/3Cz:RxIt is formed with other fluorescent powders.The wall 8 of groove 6 has high reflection effect, with
Reflect the light that chip and fluorescent powder issue.9 protect mould for high light transmission.
501N# is added to the spectrum using the fluorescent powder packaging white light LEDs in Figure 11, and 501N# is added to use in table 3
15 kinds of colour rendering indexs of the fluorescent powder.
Reference example three
Use LuAG:Ce3+Green powder (emission peak λem=525nm) and (SrCa) AlSiN3:Eu2+(emission peak λem=628nm)
With mass ratio 2.1:2.4 weighing, with fluorescent powder: glue=0.12:0.88 mass ratio proportion, after evenly mixing, encapsulation InGaN is blue
Optical chip (λex=460nm), after dispensing, baking, pressing mold, separation, obtain the height comprising the invention fluorescent powder packaging show it is white
Light LED illumination device.Figure 10 is the basic structure of the encapsulation white light LED part.It is not added in Figure 11 to be no using the present invention
The spectrum of fluorescent powder packaging white light LEDs.15 kinds of colour rendering indexs to use the fluorescent powder are not added in table 3.Comparative example
White light LED part is obtained in seven, it is found that the display index using the white light LEDs of the fluorescent powder packaging of the invention obtained is exhausted
It is most of to improve, it averagely shows that index is promoted, represents saturated blue colors and show that index R12 is obviously improved.
Reference example four
Fluorescent powder (the emission peak λ that will be obtained by reference to the synthetic method of example oneem=500nm) and LuAG:Ce3+Green powder
(emission peak λem=525nm) and (SrCa) AlSiN3:Eu2+(emission peak λem=628nm) it is weighed with mass ratio 3.2:1.9:2.3,
With fluorescent powder: glue=0.13:0.87 mass ratio proportion encapsulates InGaN blue chip (λ after evenly mixingex=460nm), warp
After dispensing, baking, pressing mold, separation, the high display White-light LED illumination device comprising the invention fluorescent powder packaging is obtained.Figure 10 is
The basic structure of the encapsulation white light LED part.500N# is added to 15 kinds of display indexes of the encapsulation white light LEDs in table 3.It is right
Display exponent data than 501N#, it can be seen that the display index overwhelming majority of addition 501N# sample is improved, particularly
It is common display index (R1~R8).
Table 3 uses the present invention and the unused present invention and LuAG:Ce3+Green powder and (SrCa) AlSiN3:Eu2+Rouge and powder envelope
It fills white light LEDs and shows index contrast
| R1 | R2 | R3 | R4 | R5 | R6 | R7 | R8 | R9 | R10 | R11 | R12 | R13 | R14 | R15 | |
| 501N# addition | 96 | 97 | 99 | 98 | 96 | 95 | 98 | 96 | 89 | 96 | 96 | 81 | 96 | 98 | 92 |
| 500N# addition | 95 | 96 | 98 | 98 | 95 | 94 | 98 | 96 | 88 | 95 | 96 | 81 | 95 | 98 | 93 |
| It is not added with | 96 | 98 | 95 | 95 | 95 | 93 | 97 | 95 | 87 | 93 | 96 | 71 | 98 | 97 | 96 |
Claims (18)
1. a kind of rare earth doping fluorescent powder, molecular formula MS2-yAyO2+yN2-y-4z/3Cz:Rx, wherein in M=Mg, Ca, Sr, Ba
One or more, one of S Si, Ge or a variety of, one of A Al, Ga or a variety of, R is bivalent rare earth ion Eu2+、
Yb2+、Sm2+One of or a variety of or R be trivalent rare earth ions Ce3+、La3+、Pr3+、Sm3+、Tb3+、Dy3+One of or
A variety of, 0.001≤x≤0.2,0≤y≤0.8,0 < z≤0.1, O represent oxygen atom, and N represents nitrogen-atoms, and C represents carbon atom.
2. rare earth doping fluorescent powder according to claim 1, wherein 0.001≤x≤0.1,0≤y≤0.1,0 < z≤
0.05。
3. rare earth doping fluorescent powder according to claim 1, wherein molecular formula is (Ca1-t-m-n-xMgtSrmBanRe’xLx)
S2-yAyO2+yN2-y-4z/3Cz, wherein Re ' is trivalent rare earth ions Ce3+、La3+、Pr3+、Sm3+、Tb3+、Dy3+One of or it is more
Kind, L is alkali metal ion Li+、Na+, K+One of or a variety of, 0≤m, n, t≤1,0.001≤x≤0.1.
4. rare earth doping fluorescent powder according to claim 1, wherein molecular formula (Ca1-t-m-n-xMgtSrmBanRex)S2- yAyO2+yN2-y-4z/3Cz, wherein Re is bivalent rare earth ion Eu2+、Yb2+、Sm2+One of or a variety of, 0≤m, n, t≤1,
0.001≤x≤0.1。
5. rare earth doping fluorescent powder according to claim 4, wherein the S in molecular formula is that Si or Si is combined with Ge, A Al
Or the combination of Al and Ga, Re Eu2+。
6. rare earth doping fluorescent powder according to claim 5, wherein t=0, y=0.
7. rare earth doping fluorescent powder according to claim 5, the transmitting range of fluorescent powder is 460nm~580nm, fluorescence hair
It is long between 470~520nm to penetrate spike.
8. the preparation method of rare earth doping fluorescent powder as claimed in claim 1 to 7 is nitrogenized using a step nitriding or two steps
Method is made,
The one step nitriding is the carbonate that M is measured according to molecular formula, the oxide of S and the nitride of S, the oxide of A,
The oxide of R contains carbon simple substance or carbonaceous organic material, is mixed together with additive synthesis, grinding gained fluorescent powder after nitridation calcining；
The step of two steps nitriding is oxygen that the carbonate of M, the oxide of S, the oxide of A, R are measured according to molecular formula
Compound and containing obtaining presoma after carbon simple substance or carbonaceous organic material mixed calcining, after presoma is ground and the nitride of S and conjunction
It is mixed at auxiliary agent, then carries out nitridation calcining again, obtain fluorescent powder；
Or after measuring the oxide mixed calcining of the carbonate of M, the oxide of S, the oxide of A and R according to molecular formula
Obtain presoma, after presoma is ground and the nitride of S, containing carbon simple substance or carbonaceous organic material and additive synthesis mixing, then
Nitridation calcining is carried out again, obtains fluorescent powder.
9. preparation method according to claim 8, described is active powdered carbon containing carbon simple substance or graphite powder, carbonaceous organic material are
Sucrose, glucose or maltose.
10. preparation method according to claim 8, the wherein oxidation of the carbonate of M, the nitride of S, the oxide of S, R
The oxide of object, A is stoichiometrically (1.8~2.2): (0.8~1.2): 1:(0.001~0.1): (0~0.8), auxiliary agent
By quality proportioning, content is the carbonate of M, the oxide of S and the nitride of S, the oxide of A, the oxide of R, carbon containing list
The 0.2%~10% of matter or carbonaceous organic material summation.
11. preparation method according to claim 8, the auxiliary agent is fluoride, chloride, carbonate, phosphate, boric acid
One or more of salt, oxide, boric acid.
12. preparation method according to claim 11, the fluoride includes lithium fluoride, sodium fluoride, potassium fluoride, fluorination
Caesium, calcirm-fluoride, magnesium fluoride, strontium fluoride, barium fluoride, ammonium fluoride, aluminum fluoride；
The chloride includes lithium chloride, sodium chloride, potassium chloride, cesium chloride, calcium chloride, magnesium chloride, strontium chloride, barium chloride, chlorine
Change ammonium, aluminium chloride；
The carbonate includes lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, basic magnesium carbonate；
The phosphate includes lithium phosphate, sodium phosphate, potassium phosphate, phosphoric acid caesium, magnesium phosphate, calcium phosphate, strontium phosphate, barium phosphate, phosphorus
Sour a hydrogen sodium, magnesium monohydrogen phosphate, calcium monohydrogen phosphate, strontium monophosphate, barium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, biphosphate
Potassium, magnesium dihydrogen phosphate, calcium dihydrogen phosphate；
The borate includes lithium borate, Boratex, antifungin；
The oxide includes magnesia, zinc oxide, aluminium oxide, scandium oxide, yttrium oxide.
13. preparation method according to claim 8, wherein after nitridation calcining, it is cooling with the rate of temperature fall of 2~20 DEG C/min
To room temperature, fluorescent powder or block are obtained, block is placed on grinding or ball in grinding and clays into power and target product can be obtained.
14. preparation method according to claim 8, wherein nitridation calcination process be 1250~1600 DEG C at a temperature of at
It is calcined 2~20 hours in protective atmosphere.
15. preparation method according to claim 8, wherein the calcination process for obtaining presoma is at 1000~1400 DEG C
It is calcined 2~10 hours in protective atmosphere.
16. preparation method according to claim 14 or 15, the protective atmosphere is argon gas, nitrogen, argon hydrogen gaseous mixture, nitrogen
One or more of hydrogen gaseous mixture or ammonia.
17. application of the rare earth doping fluorescent powder as claimed in claim 1 to 7 in LED component.
18. application according to claim 17, the chip emission peak wavelength range of the LED component 200nm~
Between 520nm.
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