KR100912495B1 - Red phosphor based on zinc sulfide and preparation method thereof - Google Patents
Red phosphor based on zinc sulfide and preparation method thereof Download PDFInfo
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- KR100912495B1 KR100912495B1 KR1020080125107A KR20080125107A KR100912495B1 KR 100912495 B1 KR100912495 B1 KR 100912495B1 KR 1020080125107 A KR1020080125107 A KR 1020080125107A KR 20080125107 A KR20080125107 A KR 20080125107A KR 100912495 B1 KR100912495 B1 KR 100912495B1
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- layer
- red phosphor
- zns
- liquid
- zinc
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- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 82
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 47
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 21
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940049918 linoleate Drugs 0.000 claims abstract description 13
- 239000004246 zinc acetate Substances 0.000 claims abstract description 13
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 11
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims abstract description 8
- 235000020778 linoleic acid Nutrition 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 26
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- -1 linoleate compound Chemical class 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- WYPBVHPKMJYUEO-NBTZWHCOSA-M sodium;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Na+].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O WYPBVHPKMJYUEO-NBTZWHCOSA-M 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 29
- 150000001875 compounds Chemical class 0.000 abstract description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 abstract description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 59
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 31
- 239000002243 precursor Substances 0.000 description 14
- 235000002908 manganese Nutrition 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 12
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 230000007774 longterm Effects 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000012190 activator Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011162 core material Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- QVRFMRZEAVHYMX-UHFFFAOYSA-L manganese(2+);diperchlorate Chemical compound [Mn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O QVRFMRZEAVHYMX-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GIQAZSIUJMRIFW-NBTZWHCOSA-N ethanol;(9z,12z)-octadeca-9,12-dienoic acid Chemical compound CCO.CCCCC\C=C/C\C=C/CCCCCCCC(O)=O GIQAZSIUJMRIFW-NBTZWHCOSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940006486 zinc cation Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
- C09K11/572—Chalcogenides
- C09K11/574—Chalcogenides with zinc or cadmium
-
- 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
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
-
- 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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
본 발명은 망간 및 리튬을 함유하고 입자표면으로부터 중심방향으로 일정 두께의 비정질층을 형성하여 우수한 인광 장기안정성 및 발광효율을 갖는 황화아연계 적색형광체와 이의 제조방법에 관한 것이다.The present invention relates to a zinc sulfide-based red phosphor containing manganese and lithium and having a predetermined thickness of amorphous layer from the particle surface to a central direction, having excellent phosphorescence long-term stability and luminous efficiency, and a method of manufacturing the same.
형광체는 백색 광원, 디스플레이 등의 분야에서 폭넓게 사용되고 있는데 현재 상업적으로 사용하고 있는 형광체는 입경이 마이크로 사이즈인 벌크 형광체이다. 그러나 벌크 형광체의 경우 입자 크기가 가시광의 파장(400-700 nm) 보다 크기 때문에 형광이 전방 입자에 의해 후방 산란되어 빛의 추출 효율이 떨어지는 문제가 발생한다. Phosphors are widely used in the field of white light sources, displays, and the like, and commercially used phosphors are bulk phosphors having a micro size. However, in the case of the bulk phosphor, since the particle size is larger than the wavelength of visible light (400-700 nm), the fluorescence is scattered backward by the front particles, which causes a problem in that light extraction efficiency is lowered.
이처럼 빛의 후방 산란에 의한 손실을 줄이기 위한 방법 중 하나로 광 산란의 효과가 적은 나노 사이즈까지 입경을 작게 하는 방법이 제시되고 있다. 또한 나노 발광재료의 경우 화질의 고정밀화를 이룰 수 있고, 크기에 따라 광 파장을 변 화시킬 수 있으며, 사이즈를 균일하게 할 경우 광파장의 넓이를 줄일 수 있어 보다 선명하고 채도가 높은 빛을 낼 수 있다. 하지만 나노 형광체는 입자의 크기가 작아짐에 따라 부피에 비해 입자 표면의 상대적인 비율이 커지게 되고, 이러한 표면에 형성되는 결함에 의해 광 변환 효율이 저하되는 문제점을 지니고 있다. 따라서, 나노 형광체를 상업적으로 이용하기 위해서는 표면 개질이 필수적이라고 할 수 있다. As one of the methods for reducing the loss due to backscattering of light, a method of reducing the particle size to nano size with less light scattering effect has been proposed. In addition, in the case of nano light emitting materials, it is possible to achieve high definition of image quality, and to change the wavelength of light according to the size. When the size is uniform, the width of the light wavelength can be reduced, resulting in brighter and more saturated light. have. However, the nano-phosphor has a problem that as the particle size decreases, the relative ratio of the particle surface to the volume increases, and the light conversion efficiency decreases due to defects formed on the surface. Therefore, it can be said that surface modification is essential for commercial use of nano-phosphor.
나노 형광체의 표면 개질은 목표로 하는 나노 형광체를 합성한 뒤에 추가적으로 전구체를 도입하는 2단계 합성 방식이 주로 사용되고 있다. 이러한 2단계 합성 방법을 통해 나노 형광체 코어와 상기 코어 표면에 다른 물질을 코팅한 쉘 구조를 만들어 형광체 표면의 결함을 줄이고 광변환 효율을 향상시킬 수 있다. 그러나 이 방법은 두 단계에 거쳐 나노 형광체를 합성하기 때문에 제작비용이 너무 커서 상용화에 큰 문제가 있다는 단점이 있다.The surface modification of the nano-phosphor is mainly used a two-step synthesis method of synthesizing the target nano-phosphor and additionally introducing a precursor. Through the two-step synthesis method, a nanostructure core and a shell structure coated with another material on the surface of the core may be formed to reduce defects on the surface of the phosphor and to improve light conversion efficiency. However, this method has a disadvantage in that it is a big problem in commercialization because the manufacturing cost is too large because the nano-phosphor is synthesized in two steps.
구체적으로 관련문헌을 살펴보면, 대한민국 특허공개 제2007-0119104호에서는 셀렌화카드뮴 양자점 주위를 황화아연으로 둘러싼 양자점을 형성하거나 황화아연으로 둘러싼 셀렌화카드뮴 양자점을 형성하는 방법이 개시되어 있다. 이는 빠른 핵 생성과 느린 성장의 2단계 공정을 이용하여 균일한 코어를 생성하고 성장 온도와 시간에 따라 코어 주변을 쉘 물질로 성장시켜 코어-쉘 구조를 만드는 기술이다.Looking at the related documents in detail, Korean Patent Publication No. 2007-0119104 discloses a method of forming a quantum dot surrounded by zinc sulfide around the cadmium selenide quantum dots or a cadmium selenide quantum dot surrounded by zinc sulfide. This is a technology that creates a core core by using a two-step process of rapid nucleation and slow growth, and grows the core material around the core as a shell material according to the growth temperature and time.
또한 대한민국 특허공개 제2006-0006627호에서는 액상환원법을 이용하여 미세금속 입자의 표면 개질 방법에 대하여 개시되어 있다. 이는 입자를 분산시킨 용액과 금속을 용해시킨 용액을 혼합시켜 금속이온환원제 등을 첨가시키는 액상환원법을 이용하여 미세 금속입자를 제조하는 것이다.In addition, Korean Patent Publication No. 2006-0006627 discloses a method for surface modification of fine metal particles using a liquid reduction method. This is to produce fine metal particles using a liquid reduction method in which a solution in which particles are dispersed and a solution in which a metal is dissolved are mixed to add a metal ion reducing agent.
한편, 황화아연계 형광체는 휘도나 수명의 특성이 디스플레이 디바이스에 요구되는 특성을 완전히 만족하지 못하고 상당히 개선해야할 점이 있어 종래부터 개량을 위한 여러 가지 방법이 시도되어 왔다.On the other hand, since zinc sulfide-based phosphors need to be significantly improved without satisfactorily satisfying the characteristics required for display devices such as luminance and lifetime, various methods for improvement have been attempted.
예를 들면 황화아연의 경우 1020 ℃ 이상에서는 육방정계의 결정 구조가 되고, 그 이하에서는 입방정계의 결정 구조를 갖는 것으로 알려져 있으며 발광효율은 입방정계쪽이 높다. 단 처음부터 입방정계로 하는 것보다는 우선 육방정계를 제작하고, 그 후에 입방정계로 변환하는 쪽이 발광효율이 높아진다. 따라서, 일본특개 소61-296085호에는 황화아연계 형광체의 결정을 변환시키는 방법으로 부활제를 혼합한 황화아연에 알칼리 금속 원소의 화합물 및 알칼리토류 금속원소의 화합물을 첨가하여 육방정계의 중간체를 제작하고, 그 후 고압을 가해 입방정계의 황화아연계 전장 발광 형광체를 얻는 방법이 기재되어 있다. 일본특개 소57-145174호에는 상기에서 제시한 부활제 및 공부활제의 첨가량을 최적화하는 것에 의해 황화아연계 발광 형광체의 효율이나 수명을 향상시키는 방법이 기재되어 있다.For example, zinc sulfide is known to have a hexagonal crystal structure at 1020 ° C. or higher and a cubic crystal structure at a lower level. Rather than producing a cubic system from the beginning, a hexagonal system is produced first and then converted into a cubic system. Therefore, Japanese Patent Application Laid-Open No. 61-296085 has prepared a hexagonal intermediate by adding a compound of an alkali metal element and a compound of an alkaline earth metal element to zinc sulfide mixed with an activator by converting crystals of zinc sulfide-based phosphors. Thereafter, a method of applying a high pressure to obtain a cubic zinc sulfide-based electroluminescent phosphor is described. Japanese Patent Application Laid-Open No. 57-145174 discloses a method of improving the efficiency and lifespan of a zinc sulfide-based light-emitting phosphor by optimizing the amounts of the activator and the study agent described above.
상기와 같이 종래부터 황화아연계 발광 형광체의 발광 효율이나 수명 등의 특성을 향상시키기 위한 다양한 방법이 제시되고 있으나, 종래의 방법으로는 현재의 휘도나 수명에 대한 요구 레벨을 만족시킬 수 없다. 특히, 최근의 디스플레이 디바이스는 밝기나 수명 특성을 더욱 향상시키는 것이 요구되고 있기 때문에 상기 디스플레이 디바이스에 이용되는 발광 형광체의 휘도나 수명 등의 특성을 더욱 높 이는 것이 과제로 남아 있다.As described above, various methods for improving characteristics such as luminous efficiency and lifetime of zinc sulfide-based light-emitting phosphors have been proposed in the related art, but the conventional methods cannot satisfy the required level of luminance and lifetime. In particular, the recent display device is required to further improve the brightness and life characteristics, it remains a problem to further improve the characteristics such as the brightness and life of the light emitting phosphor used in the display device.
또한, 미국특허 제2,952,642호에는 부활제로서 납과 구리를 함유하고, 또 0.001%의 마그네슘을 함유하는 황화아연 형광체가 기재되어 있으나 납을 함유하는 황화아연 형광체는 발광 효율이나 수명 특성이 떨어져 디스플레이 디바이스에 요구되는 특성을 만족하는 레벨에는 이르지 못하는 실정이다.In addition, US Pat. No. 2,952,642 describes zinc sulfide phosphors containing lead and copper as an activator and 0.001% magnesium, but zinc sulfide phosphors containing lead have low luminous efficiency and lifetime characteristics. The situation does not reach the level that satisfies the required characteristics.
이에 본 발명자는 황화아연, 망간 및 리튬을 일정비로 함유하고 입자표면으로부터 중심방향으로 일정 두께의 비정질층 구조를 형성하는 형광체로, 인광 장기안정성 및 550-625 ㎚ 범위에서 발광특성이 우수하여 디스플레이 장치, LED 형광체, 고효율 램프 등의 전자재료 분야에서 유용한 신규의 황화아연계 적색형광체를 제시하고자 한다.Accordingly, the present invention is a phosphor containing zinc sulfide, manganese, and lithium in a certain ratio and forming an amorphous layer structure having a predetermined thickness from the particle surface to the center. The display device has excellent phosphorescence long-term stability and excellent light emission characteristics in the range of 550-625 nm. We propose a novel zinc sulfide-based red phosphor useful in the field of electronic materials such as LED, phosphor, and high efficiency lamp.
또한, 본 발명은 액체-고체-액체 합성법을 이용하여 상기 황화아연계 적색형광체를 제조하는 방법을 제시하고자 한다.In addition, the present invention is to propose a method for producing the zinc sulfide-based red phosphor using a liquid-solid-liquid synthesis method.
본 발명은 하기 화학식 1로 표시되는 황화아연계 적색형광체에 그 특징이 있다.The present invention is characterized by a zinc sulfide-based red phosphor represented by the following formula (1).
상기 화학식 1에서, x 및 y는 아연금속원자 1몰에 대한 각 금속의 원자몰비로, 0 < x < 0.5이고 0 < y < 0.5이다.In Formula 1, x and y are an atomic molar ratio of each metal to 1 mol of zinc metal atoms, and 0 <x <0.5 and 0 <y <0.5.
또한, 본 발명은 아연아세트산염, 망간질산염 및 리튬수산화물·수화물을 증류수에 용해시켜 액상의 1층을 제조하는 단계; 상기 액상의 1층 혼합물에, 리놀레 이트계 화합물을 첨가하여 액상의 1층과 고상의 2층을 형성하는 단계; 상기 액상과 고상의 2개의 층이 형성된 혼합물에, 티오아세트아마이트 및 에탄올에 용해된 리놀레산 용액을 첨가하여 액상의 1층, 고상의 2층 및 액상의 3층을 갖는 혼합물을 형성하는 단계; 상기 3개의 층을 갖는 혼합물을 85-95 ℃에서 9-12 시간동안 처리하여 Mn-Li-ZnS 나노입자를 형성하는 단계; 상기 형성된 Mn-Li-ZnS 나노입자를 회수하여 세척한 후 건조하는 단계; 및 상기 건조된 Mn-Li-ZnS 나노입자를 100-600 ℃에서 열처리하여 입자 표면으로부터 0.5-3 nm 범위의 비정질층을 갖는 상기 화학식 1로 표시되는 Mn-Li-ZnS 형광체 나노입자를 제조하는 단계를 포함하여 이루어진 것을 특징으로 하는 황화아연계 적색형광체의 제조방법에 또 다른 특징이 있다.In addition, the present invention comprises the steps of dissolving zinc acetate, manganese nitrate and lithium hydroxide hydrate in distilled water to prepare a single layer of a liquid; Adding a linoleate compound to the liquid layer mixture to form a liquid layer and a solid layer; Adding a linoleic acid solution dissolved in thioacetite and ethanol to the mixture in which the two layers of the liquid phase and the solid phase are formed to form a mixture having one layer of liquid phase, two layers of solid phase, and three layers of liquid phase; Treating the three layered mixture at 85-95 ° C. for 9-12 hours to form Mn-Li—ZnS nanoparticles; Recovering and washing the formed Mn-Li-ZnS nanoparticles and then drying them; And heat treating the dried Mn-Li-ZnS nanoparticles at 100-600 ° C. to prepare Mn-Li-ZnS phosphor nanoparticles represented by Chemical Formula 1 having an amorphous layer in the range of 0.5-3 nm from the particle surface. There is still another feature in the method for producing a zinc sulfide-based red phosphor, characterized in that it comprises a.
본 발명에 따른 황화아연계 적색형광체는 입자 표면으로부터 중심방향으로 일정 두께의 비정질층을 형성하여 인광 장기안정성 및 발광효율이 우수하며, 아연, 망간 및 리튬의 조성, 최적 화합물의 종류 및 열처리 온도 등을 적의 선택함으로써 종래에 비해 비교적 저온에서 균일한 크기의 황화아연계 적색형광체를 효과적으로 제조할 수 있으므로 원가절감의 효과가 있고, 제조공정이 단순하여 기존의 공정에 쉽게 적용시킬 수 있다는 장점이 있다. 따라서 본 발명에 따른 황화아연계 적색형광체 및 이의 제조방법은 PDP 등의 디스플레이 장치, LED 형광체, 고효율 램프 등에 우수한 적색 형광체로서 활용될 수 있다.The zinc sulfide-based red phosphor according to the present invention forms an amorphous layer having a predetermined thickness from the particle surface in the center direction, and thus has excellent phosphorescence long-term stability and luminous efficiency, composition of zinc, manganese and lithium, types of optimal compounds, heat treatment temperature, and the like. By selecting an appropriate amount of zinc sulfide-based red phosphor of a uniform size at a relatively low temperature can be effectively produced compared to the conventional, there is an effect of cost reduction, and the manufacturing process is simple and can be easily applied to an existing process. Therefore, the zinc sulfide-based red phosphor according to the present invention and a manufacturing method thereof may be utilized as a red phosphor excellent in a display device such as a PDP, an LED phosphor, a high efficiency lamp, and the like.
본 발명은 망간과 리튬을 함유하고 균일한 입경을 갖는 하기 화학식 1로 표시되는 황화아연계 적색형광체에 관한 것으로, 상기 형광체 입자의 표면으로부터 중심방향으로 일정 두께의 비정질층이 형성되어 인광 장기안정성 및 550-625 ㎚ 범위에서 발광특성이 우수한 신규의 황화아연계 적색형광체에 관한 것이다.The present invention relates to a zinc sulfide-based red phosphor represented by the following Chemical Formula 1 containing manganese and lithium and having a uniform particle diameter, wherein an amorphous layer having a predetermined thickness is formed from the surface of the phosphor particles in the center direction, and thus phosphorescent long-term stability and A novel zinc sulfide-based red phosphor having excellent luminescence in the range of 550-625 nm.
[화학식 1][Formula 1]
ZnS : Mnx, Liy ZnS: Mn x , Li y
상기 화학식 1에서, x 및 y는 아연금속원자 1몰에 대한 각 금속의 원자몰비로, 0 < x < 0.5이고 0 < y < 0.5이다. 바람직하기로는 0.005 < x < 0.2이고 0.01 < y < 0.2이며, 보다 바람직하기로는 0.005 < x < 0.05 이고 0.001 < y < 0.005 이다.In Formula 1, x and y are an atomic molar ratio of each metal to 1 mol of zinc metal atoms, and 0 <x <0.5 and 0 <y <0.5. Preferably it is 0.005 <x <0.2 and 0.01 <y <0.2, More preferably, it is 0.005 <x <0.05 and 0.001 <y <0.005.
일반적으로 형광체는 모체 이외에 활제, 부활제 및 융제 등으로 구성되며, 동일한 모체를 가지더라도 활제, 부활제 및 융제 성분의 종류 및 이들의 혼합비에 따라 발현되는 색, 발광파장, 결정성 등의 특성이 전혀 다르게 나타나 이들 형광체는 별개의 물질로 인식된다. 본 발명과 같이 황화아연을 모체로 사용하고 망간을 활성제로 사용한 형광체는 다양하게 알려져 있으나, 활성제 성분으로 망간과 동시에 아연을 사용하여 비정질층을 형성하는 구조를 가지며 적색을 발현하는 황화아연계 형광체는 아직 알려진 바 없는 신규의 형광체이다.In general, a phosphor is composed of a lubricant, an activator, and a flux in addition to the mother, and even though the same matrix has a characteristic such as color, light emission wavelength, and crystallinity expressed according to the type of lubricant, activator, and flux component, and the mixing ratio thereof. Appears to be completely different, these phosphors are recognized as separate substances. Phosphors using zinc sulfide as a parent and manganese as an activator are variously known as the present invention, but zinc sulfide-based phosphors having red structure and having a structure of forming an amorphous layer using zinc at the same time as an active ingredient are manganese. It is a novel phosphor that is not known yet.
또한, 본 발명의 황화아연계 적색형광체는 입자 표면으로부터 중심방향으로 0.5-3 nm 범위의 비정질층을 형성하는 바, 상기 비정질층은 형광체 표면의 결함을 완화시켜 전자-전공 비방사 결함을 감소하게 된다. 이와 같이 표면의 결함이 감소되면 안정적인 장기인광특성 및 발광효율의 증가 등을 나타난 다는 것은 당 분야에서 이미 알려져 있다[H. Yang and P. H. Holloway, Adv. Funct. Mater. 14, 152 (2004)].In addition, the zinc sulfide-based red phosphor of the present invention forms an amorphous layer in the range of 0.5-3 nm from the particle surface toward the center, and the amorphous layer mitigates defects on the surface of the phosphor to reduce electron-electron non-radiative defects. do. It is known in the art that when the surface defects are reduced, stable long-term phosphorescence characteristics and an increase in luminous efficiency are exhibited. Yang and P. H. Holloway, Adv. Funct. Mater. 14, 152 (2004).
다시 말하면, 일반적으로 형광체는 입자 표면의 결함이 적을수록 장기인광 및 발광특성이 증가된다는 것이 알려져 있는 바, 리튬(Li) 원자에 의해 표면의 비정질층을 형성하는 본 발명의 황화아연계 적색형광체는 종래 Li 원자를 함유하지 않은 형광체에 비해 상대적으로 입자 표면의 결함이 현저히 낮아 발광 효율이 증가한다. 또한 나노형광체가 오랜 시간 동안 작동할 경우 표면의 결함이 증가하여 발광 효율이 감소할 것인데, 리튬에 의해 표면이 개질된 본 발명에 따른 형광체의 경우는 개질되지 않은 형광체에 비해 표면 결합이 현저히 적어 동일한 시간동안 작동하는 경우 상대적으로 장기 인광 특성이 증가한다.In other words, in general, it is known that the phosphor has long-term phosphorescence and luminescence properties as the defects on the surface of the particles decrease, so that the zinc sulfide-based red phosphor of the present invention, which forms an amorphous layer on the surface by lithium (Li) atoms, Compared with the phosphor containing no conventional Li atom, defects on the surface of the particles are significantly lower, resulting in increased luminous efficiency. In addition, if the nanophosphor is operated for a long time, the surface defects will increase and the luminous efficiency will be reduced. In the case of the phosphor according to the present invention whose surface is modified by lithium, the surface bonding is significantly lower than that of the unmodified phosphor. When operating for a long time, the long-term phosphorescence characteristic is relatively increased.
한편, 본 발명의 액체-고체-액체 합성법을 이용하여 황화아연계 적색형광체를 제조하는 방법을 구체적으로 살펴보면 다음과 같다.Meanwhile, a method of preparing a zinc sulfide-based red phosphor using the liquid-solid-liquid synthesis method of the present invention will be described in detail.
본 발명에서 적용한 액체-고체-액체 합성법은 밀도차이 및 리놀레이트계 화합물을 이용함으로써 아래층에 존재하는 양이온과 위층에 존재하는 음이온 간의 반응이 계면에서 일어나도록 조절하여, 계면에서 형성되는 입자는 중력과 계면장력의 영향을 동시에 받으면서 서서히 크기가 커지게 되고 결국 특정 크기 이상으로 입자가 커지게 되면 중력의 영향이 우세해지면서 결국 입자는 아래로 가라앉게 되어 균 일한 크기의 입자를 얻을 수 있도록 하는 나노입자의 일반적 합성방법이다[X. Wang, J. Zhuang, Q. Peng, and Y. Li, Nature 437, 121 (2005)]. 이러한 원리를 이용하여 망간으로 도핑된 황화아연계 나노 형광체 입자를 제조하는 방법은 본 출원인에 의해 대한민국 특허등록 제0842376호에서 제시한 바 있다. 본 발명은 상기 대한민국 특허등록 제0842376호에서 제시된 방법과 유사한 액체-고체-액체 합성법으로 형광체 입자를 제조하나, 상기에서 전혀 개시 및 예측하지 못한 방법인 리튬 성분을 사용하여 입자 표면으로부터 일정두께의 비정질층을 형성하는 데 그 특징이 있는 것이다. 즉 이는 단순한 성분 추가가 아니라 일정 두께의 비정질층을 형성하기 위하여 특정의 금속성분으로 리튬을 선택 사용한 것이다.The liquid-solid-liquid synthesis method applied in the present invention controls the reaction between the cation present in the lower layer and the anion present in the upper layer by using a density difference and a linoleate-based compound, so that the particles formed at the interface may have gravity and Nanoparticles that gradually grow in size under the influence of interfacial tension, and eventually increase in size beyond a certain size, become more influenced by gravity and eventually settle down to obtain particles of uniform size. General synthesis of [X. Wang, J. Zhuang, Q. Peng, and Y. Li, Nature 437, 121 (2005)]. A method of manufacturing zinc sulfide-based nanophosphor particles doped with manganese using this principle has been presented in Korean Patent Registration No. 0842376 by the present applicant. The present invention is to produce the phosphor particles by a liquid-solid-liquid synthesis method similar to the method proposed in the Republic of Korea Patent Registration No. 0842376, but a certain thickness of amorphous from the particle surface using a lithium component which is a method that is not disclosed and predicted at all It is characteristic to form a layer. That is, lithium is selected as a specific metal component to form an amorphous layer having a predetermined thickness, rather than simply adding a component.
먼저, 아연아세트산염, 망간질산염 및 리튬수산화물·수화물을 증류수에 용해시켜 액상의 1층을 제조한다.First, zinc acetate, manganese nitrate, and lithium hydroxide hydrate are dissolved in distilled water to prepare a liquid single layer.
상기 아연아세트산염은 아연 양이온(Zn2+)을 제공하기 위한 최적의 전구체이고, 망간질산염은 도판트인 망간 양이온(Mn2+)을 제공하기 위한 최적의 전구체로 본 발명에서 사용된다. 또한, 리튬수산화물·수화물은 형광체 입자의 표면개질을 수행하는 촉진제로 리튬 양이온(Li+)을 제공하는 최적의 전구체로 사용된다. 아연 양이온, 망간 양이온 및 리튬 양이온을 공급하기 위하여 다른 조합을 사용할 경우에는 망간의 도핑양이 제한되는 경향을 보였으므로, 이 전구체들이 최선의 전구체라고 할 수 있다.The zinc acetate is an optimal precursor for providing a zinc cation (Zn 2+ ), and manganese nitrate is used in the present invention as an optimal precursor for providing a manganese cation (Mn 2+ ) which is a dopant. In addition, lithium hydroxide hydrate is used as an optimal precursor for providing a lithium cation (Li + ) as an accelerator for surface modification of the phosphor particles. When other combinations are used to supply zinc cations, manganese cations and lithium cations, the doping amount of manganese tends to be limited, so these precursors are the best precursors.
아연 양이온과 망간 양이온을 공급하기 위해 다른 조합을 사용하는 경우 망 간의 도핑양이 제한되는 경향을 보이므로, 본 발명의 제조방법에서는 상기 아연아세트산염과 망간질산염의 조합이 바람직하다.When other combinations are used to supply zinc cations and manganese cations, the amount of doping between manganeses tends to be limited. Thus, the combination of zinc acetate and manganese nitrate is preferable in the production method of the present invention.
본 발명의 제조방법에서 아연의 전구체로 공지의 디메틸 아연(dimethyl zinc), 디에틸 아연(diethyl zinc), 아연 아세틸아세토네이트(zinc acetylacetonate), 요오드화 아연(zinc iodide), 브롬화 아연(zinc bromide), 염화 아연(zinc chloride), 불화 아연(zinc fluoride), 탄산 아연(zinc carbonate), 시안화 아연(zinc cyanide), 질산 아연(zinc nitrate), 산화 아연 (zinc oxide), 과산화 아연(zinc peroxide), 과염화 아연(zinc perchlorate) 및 황산 아연(zinc sulfate)과 같은 아연을 포함하는 유기금속화합물과 그 염을 사용할 경우 균일상의 황화아연 이외에 다른 상(phase)이 형성될 가능성이 있으므로 바람직하지 못하고, 망간의 전구체로서 공지의 아세트산 망간(manganese acetate), 망간 아세틸아세토네이트(manganese acetylacetonate), 탄산 망간(manganese carbonate), 브롬화 망간(manganese bromide), 염화 망간(manganese chloride), 불화 망간(manganese fluoride), 산화 망간(manganese oxide), 황산 망간(manganese sulfate) 및 과염화 망간(manganese perchlorate)과 같은 망간을 포함하는 유기금속화합물과 그 염을 사용하는 경우 망간 도핑이 원활하지 않게 되는 문제점이 발생하여 바람직하지 못하다.Dimethyl zinc, diethyl zinc, zinc acetylacetonate, zinc iodide, zinc bromide, and the like are known as precursors of zinc in the preparation method of the present invention. Zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, perchlorate The use of organometallic compounds containing zinc, such as zinc perchlorate and zinc sulfate and salts thereof, is undesirable because there is a possibility that other phases may be formed in addition to the uniform zinc sulfide. Manganese acetate, manganese acetylacetonate, manganese carbonate, manganese bromide, manganese chloride, manganese fluoride as known precursors (Manganese fluoride), manganese oxide (manganese oxide), manganese sulfate and manganese perchlorate (organic metal compounds including manganese perchlorate (manganese perchlorate) and when using the salt and the manganese do not become smooth when using the salt This occurs and is undesirable.
리튬의 전구체는 당 분야에서 일반적으로 사용되는 것으로 Li2CO3, LiNO3, LiOH 및 LiOH·H2O 등과 같은 리튬을 포함하는 유기금속화합물과 그 염을 사용하는 경우에도 본 발명의 형광체 제조가 가능하나, Li2CO3, LiNO3, LiOH 등의 전구체를 사용하는 경우에는 황화아연 내에 리튬 도핑이 원활히 일어나지 않아 비정질층 형성이 용이하지 못하므로 목적으로 하는 형광체 특성 유지가 어려운 문제가 있으므로 바람직하지 못하다. 따라서 리튬수산화물의 수화물 형태인 LiOH·H2O을 사용하는 것이 좋다.Precursors of lithium are generally used in the art, even when organometallic compounds containing lithium such as Li 2 CO 3 , LiNO 3 , LiOH, and LiOH · H 2 O and salts thereof are used. However, in the case of using precursors such as Li 2 CO 3 , LiNO 3 , LiOH, lithium doping does not occur smoothly in the zinc sulfide, and thus it is not easy to form an amorphous layer. Can not do it. Therefore, it is preferable to use LiOH.H 2 O, which is a hydrate form of lithium hydroxide.
이러한 아연아세트산염, 망간질산염 및 리튬수산화물·수화물은 1 몰 : 0.001-0.5 몰 : 0.001-0.5 몰, 바람직하기로는 1 몰 : 0.005-0.2 몰 : 0.01-0.2 몰 범위, 보다 바람직하기로는 1 몰 : 0.005-0.05 몰 : 0.001-0.005 몰을 사용할 수 있다. 이의 범위는 상기 화학식 1에 표시된 바와 같은 비율을 갖도록 하기 위한 최적의 범위이며, 이의 범위에서 인광 및 발광 특성이 우수하게 된다. 특히 상기 리튬수산화물·수화물은 이의 사용량 변화에 따라 표면의 비정질층의 형성 정도가 크게 달라지는 바, 상기 범위를 유지할 때 본 발명이 목적으로 하는 두께의 비정질층 형성이 가능하다.Such zinc acetate, manganese nitrate and lithium hydroxide hydrate are in the range of 1 mol: 0.001-0.5 mol: 0.001-0.5 mol, preferably 1 mol: 0.005-0.2 mol: 0.01-0.2 mol, more preferably 1 mol: 0.005-0.05 mol: 0.001-0.005 mol can be used. Its range is the optimum range to have a ratio as shown in the formula (1), it is excellent in phosphorescence and luminescence properties in this range. In particular, the lithium hydroxide hydrate has a large change in the degree of formation of the amorphous layer on the surface according to the change in the amount of use thereof, so that the amorphous layer of the thickness of the present invention can be formed when the above range is maintained.
상기 아연아세트산염, 망간질산염 및 수산화리튬의 수용액을 오토클레이브 내열용기에 넣어 하층을 형성한다.The aqueous solution of zinc acetate, manganese nitrate and lithium hydroxide is placed in an autoclave heat resistant container to form a lower layer.
다음은 상기 액상의 1층 혼합물에, 리놀레이트계 화합물을 첨가하여 액상의 1층과 고상의 2층을 형성한다.Next, a linoleate compound is added to the liquid layer mixture to form a liquid layer and a solid layer.
상기 리놀레이트계 화합물은 본 발명에서 밀도차를 이용하여 반응속도를 조절하는 역할을 하여 균일한 나노입자를 만드는데 기여한다. 이 화합물로는 몇 가 지 형태의 메탈 리놀레이트 중에서 선택된 하나를 사용할 수 있으며, 바람직하기로는 소듐 리놀레이트를 사용할 수 있다.The linoleate-based compound serves to control the reaction rate by using the density difference in the present invention contributes to making uniform nanoparticles. The compound may be one selected from several forms of metal linoleate, and preferably sodium linoleate.
이러한 리놀레이트계 화합물은 알콜에 용해하여 0.001-0.01 g/mL 농도 범위, 바람직하기로는 0.004-0.007 g/mL 농도인 것을 사용한다. 상기 리놀레이트계 화합물은 액상의 1층 혼합물 1 중량에 대하여 0.05-0.5 중량비 범위, 바람직하기로는 0.08-0.1 중량비 범위로 사용하는 것이 좋다. 이때, 상기 알콜은 에탄올을 사용하고, 리놀레이트계 화합물은 소듐 리놀레이트를 사용하는 것이 바람직하다. Such linoleate compounds are dissolved in alcohol and used in a concentration range of 0.001-0.01 g / mL, preferably 0.004-0.007 g / mL. The linoleate compound may be used in the range of 0.05-0.5 weight ratio, preferably 0.08-0.1 weight ratio, based on 1 weight of the liquid one-layer mixture. At this time, the alcohol is used ethanol, the linoleate compound is preferably sodium linoleate.
다음으로 상기 액상과 고상의 2개의 층이 형성된 혼합물에, 티오아세트아마이트 및 에탄올에 용해된 리놀레산 용액을 첨가하여 액상의 1층, 고상의 2층 및 액상의 3층을 갖는 혼합물을 형성한다.Next, a linoleic acid solution dissolved in thioacetite and ethanol is added to the mixture in which the two layers of the liquid phase and the solid phase are formed to form a mixture having one layer of liquid phase, two layers of solid phase and three layers of liquid phase.
상기 티오아세트아마이드는 황을 제공하는 전구체 화합물로 몇 가지 형태의 다른 황화물 전구체를 사용할 수 있으나 본 발명의 티오아세트아마이드가 황화아연을 가장 안정적으로 만들 수 있는 전구체이다. 또한, 상기 리놀레산은 초기의 반응속도를 조절하는 역할로서 작용한다.The thioacetamide is a precursor compound for providing sulfur, but may be used in some forms of other sulfide precursors, but the thioacetamide of the present invention is the precursor which can make zinc sulfide the most stable. In addition, the linoleic acid acts to control the initial reaction rate.
이러한 티오아세트아마이드는 아연아세트산염 1몰에 대하여 0.9-1.1 몰비 범위로 사용하며, 리놀레산은 에탄올 1 중량에 대하여 0.01-0.5 중량비, 바람직하기로는 0.02-0.05 중량비 농도 범위를 유지하는 것이 좋다.Such thioacetamide is used in the range of 0.9-1.1 molar ratio with respect to 1 mole of zinc acetate, and linoleic acid is preferably maintained in a concentration range of 0.01-0.5 weight ratio, preferably 0.02-0.05 weight ratio, based on 1 weight of ethanol.
이 정도의 농도 범위로 사용할 때 도핑농도가 최적화되어 우수한 특성을 나타내게 된다. 최적화된 농도범위를 벗어나는 경우에는, 망간의 도핑이 저하되거나 또는 망간의 응집현상이 발생하여 발광특성이 나빠진다.When used in this concentration range, the doping concentration is optimized to show excellent characteristics. If it is out of the optimized concentration range, the doping of manganese is reduced or the coagulation phenomenon of manganese occurs, so that the luminescence property is deteriorated.
상기 농도의 리놀레산 에탄올 용액은 2층이 형성된 혼합물 1 중량에 대하여 0.001-0.1 중량비 범위, 바람직하기로는 0.005-0.01 중량비 범위로 사용하는 것이 좋다.The linoleic acid ethanol solution of the concentration is preferably used in the range of 0.001-0.1 weight ratio, preferably 0.005-0.01 weight ratio with respect to 1 weight of the mixture formed two layers.
이상과 같은 방법으로 본 발명의 제조 방법을 수행하게 되면, 액체(1층)-고체(2층)-액체(3층)의 구조가 형성되는데, 이는 층별 사용 용매의 밀도차이 및 리놀레이트계 유기물의 사용으로 가능하다. 이때, 이들 3단계에서 사용 가능한 용매는 증류수 및 에탄올 뿐만 아니라 밀도 차이를 형성할 수 있는 다양한 유기물이 될 수 있다. When the production method of the present invention is carried out as described above, a structure of liquid (1 layer) -solid (2 layer) -liquid (3 layer) is formed, which is a difference in density of the solvent used for each layer and a linoleate organic material. With the use of At this time, the solvent usable in these three steps may be a variety of organic materials that can form a difference in density as well as distilled water and ethanol.
다음으로 상기 3개의 층을 갖는 혼합물을 85-95 ℃에서 9-12 시간동안, 바람직하기로는 89-91 ℃에서 10-11 시간동안 처리하여 Mn-Li-ZnS 나노입자를 형성한다. 상기 3개의 층을 갖는 혼합물은 오토클래브 내열용기에서 처리한다.The mixture with the three layers is then treated at 85-95 ° C. for 9-12 hours, preferably at 89-91 ° C. for 10-11 hours to form Mn-Li—ZnS nanoparticles. The mixture having the three layers is treated in an autoclave heat resistant container.
이때 밀도차이 및 리놀레이트 유기물을 이용함으로써 아래층에 존재하는 양이온(Zn2+, Mn2+, Li+)과 위층에 존재하는 음이온(S2) 간의 반응이 계면에서 일어나, 계면에서 본 발명의 황화아연계 형광체 입자가 생성되며, 생성되는 입자는 중력과 계면장력의 영향을 동시에 받으면서 서서히 크기가 커지게 된다.결국 특정 크기 이상으로 입자가 커지게 되면 중력의 영향이 우세해지면서 결국 본 발명의 황화아연계 형광체 입자는 아래로 가라앉게 된다(도 1 참조).At this time, by using the difference in density and linoleate organic material cations present in the lower layer (Zn 2+ , The reaction between Mn 2+ , Li + ) and the anion (S 2 ) present in the upper layer occurs at the interface, and the zinc sulfide-based phosphor particles of the present invention are produced at the interface, and the generated particles simultaneously influence the effects of gravity and interfacial tension. When the particles are larger than a certain size, the influence of gravity becomes dominant and eventually the zinc sulfide-based phosphor particles of the present invention sink down (see FIG. 1).
다음으로 상기 형성된 Mn-Li-ZnS 나노입자를 회수하여 세척한 후 건조한다. 회수한 나노입자는 부산물과 유기물을 제거하기 위하여 에탄올을 사용하여 세척하 고 원심분리하여 침전물을 얻고, 다시 회수한 입자는 반복 수행하여 총 5회 이상, 바람직하기로는 5-9회의 세척과정을 수행한다. 또한 건조는 55-65 ℃에서 3-6 시간동안 수행한다.Next, the formed Mn-Li-ZnS nanoparticles are recovered, washed and dried. The recovered nanoparticles are washed with ethanol to remove by-products and organics, and centrifuged to obtain a precipitate. The recovered particles are repeatedly performed at least 5 times, preferably 5-9 times. do. Drying is also carried out at 55-65 ° C. for 3-6 hours.
다음으로 상기 건조된 Mn-Li-ZnS 나노입자를 100-600 ℃에서, 바람직하기로는 400-500 ℃에서 3-6 시간동안 열처리하여 입자 표면으로부터 0.5-3 nm 범위의 비정질층을 갖는 상기 화학식 1로 표시되는 Mn-Li-ZnS 형광체 나노입자를 제조한다. 이때, 열처리 시간은 승온속도 180-230 ℃/h에서 승온시간 약 2시간, 유지시간은 약 3시간동안 수행하는 것이 바람직하다. Next, the dried Mn-Li-ZnS nanoparticles are heat-treated at 100-600 ° C., preferably at 400-500 ° C. for 3-6 hours, to provide an amorphous layer in the range of 0.5-3 nm from the particle surface. To prepare a Mn-Li-ZnS phosphor nanoparticles represented by. At this time, the heat treatment time is a temperature increase time of about 2 hours, the holding time is about 3 hours at a temperature increase rate of 180-230 ℃ / h.
상기 첫 단계에서 첨가된 수산화리튬에 의해 리튬이 ZnS:Mn에 미량 도핑 되어있는 상태인데, 상기 열처리 과정 중에 리튬이 표면 개질의 촉진제로 작용하여 나노 형광체의 표면으로부터 중심으로 약 0.5-3 nm 두께의 비정질층을 형성하게 된다.Lithium is a small amount of lithium doped in ZnS: Mn by the lithium hydroxide added in the first step, and during the heat treatment process, lithium acts as a promoter for surface modification, which is about 0.5-3 nm thick from the surface of the nanophosphor. An amorphous layer is formed.
본 발명의 황화아연계 적색형광체는 입경이 5-20 nm인 균일한 입자로 입자 표면으로부터 중심방향으로 0.5-3 nm 두께의 비정질층을 형성하는 구조를 갖는다. 또한, 상기 적색형광체는 색좌표(CIE)의 X=0.51-0.53이고 Y=0.41-0.43이며, 발광파장이 550-625 nm이고, 인광 장기안정성 및 발광특성이 우수하여 PDP 등의 디스플레이 장치, 고효율 램프 등에 우수한 적색형광체로서 활용이 유용하다.The zinc sulfide-based red phosphor of the present invention has a structure of forming an amorphous layer having a thickness of 0.5-3 nm in the center direction from the particle surface as uniform particles having a particle diameter of 5-20 nm. In addition, the red phosphor has a color coordinate (CIE) of X = 0.51-0.53, Y = 0.41-0.43, a light emission wavelength of 550-625 nm, excellent phosphorescent long-term stability and light emission characteristics, and a high efficiency lamp such as a PDP. It is useful as a red phosphor excellent in the back.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실 시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연하다.Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.
실시예 1 : 적색 형광체Example 1: red phosphor
증류수 10 mL가 함유된 각각의 용기에, 아연아세트산염(Zn(CH3COO)2·2H2O) 0.66 g, 망간질산염(Mn(NO3)2) 0.05 g 및 수산화리튬·수화물(LiOH·H2O) 0.017 g을 각각 넣고 교반하여 충분히 용해시켰다.In each vessel containing 10 mL of distilled water, 0.66 g of zinc acetate (Zn (CH 3 COO) 2 .2H 2 O), 0.05 g of manganese nitrate (Mn (NO 3 ) 2 ), and lithium hydroxide hydrate (LiOH 0.017 g of H 2 O) were added and stirred to dissolve sufficiently.
상기에서 준비된 각각의 아연아세트산염 수용액, 망간질산염 수용액 및 수산화리튬 수용액을 혼합하고 이를 오토클래이브(autoclave) 내열용기에 가하여 액상의 1층을 형성시켰다. Each of the zinc acetate aqueous solution, manganese nitrate aqueous solution, and lithium hydroxide aqueous solution prepared above were mixed and added to an autoclave heat-resistant container to form a single layer of liquid phase.
소듐 리놀레이트(sodium linoleate, (C17H31)COONa)) 0.115 g을 에탄올 25 mL에 용해한 후 이를 1 mL 취하여 상기 액상의 1층 혼합물에 첨가하였다. 이때 밀도차에 의하여 액상의 1층과 고상의 2층을 형성하였다.0.115 g of sodium linoleate (C 17 H 31 ) COONa) was dissolved in 25 mL of ethanol, 1 mL of it was added to the liquid layer mixture. At this time, one layer of the liquid phase and two layers of the solid phase were formed by the density difference.
이후에 황(S)의 소스로 티오아세트아마이드(CH3CSNH2) 0.225 g을 에탄올 10 mL에 용해시켜 상기 고상의 2층에 가하고, 리놀레산(linoleic acid, (C17H31)COOH) 5 mL를 에탄올 20 mL에 용해시킨 이 용액을 0.20 mL 다시 가하여 액상의 1층, 고상의 2층 및 액상의 3층 구조를 갖는 용액을 제조하였다.Subsequently, 0.225 g of thioacetamide (CH 3 CSNH 2 ) as a source of sulfur (S) was dissolved in 10 mL of ethanol and added to the two layers of the solid phase, and 5 mL of linoleic acid (C 17 H 31 ) COOH). 0.20 mL of this solution dissolved in 20 mL of ethanol was added again to prepare a solution having a liquid 1 layer, a solid 2 layer, and a liquid 3 layer structure.
상기에서 제조한 3개의 층을 갖는 용액을 오토클래이브 내열용기에 넣고 밀봉하여 90 ℃에서 10 시간 동안 반응시켜 Mn-Li-ZnS 나노입자를 형성하였다.The solution having the three layers prepared above was placed in an autoclave heat resistant container, sealed, and reacted at 90 ° C. for 10 hours to form Mn-Li—ZnS nanoparticles.
이후에 상기에서 제조된 Mn-Li-ZnS 나노입자를 회수하고, 에탄올을 사용하여 5 회 원심분리 과정을 통해 부산물과 유기물을 제거하는 세척 과정을 수행하였다. 세척된 Mn-Li-ZnS 나노입자를 60 ℃에서 5 시간 동안 건조시킨 후, 210 ℃/시간 속도로 승온하고 450 ℃에서 3 시간 동안 열처리하여 입자 표면으로부터 약 1 ㎚ 범위의 비정질층을 갖는 Mn-Li-ZnS 형광체 나노입자를 제조하였다. 이때, 제조된 Mn-Li-ZnS 형광체 나노입자의 입경은 약 9 ㎚이었다.Thereafter, the prepared Mn-Li-ZnS nanoparticles were recovered, and a washing process of removing by-products and organics was performed by centrifugation five times using ethanol. The washed Mn-Li-ZnS nanoparticles were dried at 60 ° C. for 5 hours, then heated at 210 ° C./hour and heat-treated at 450 ° C. for 3 hours to form Mn- having an amorphous layer in the range of about 1 nm from the particle surface. Li-ZnS phosphor nanoparticles were prepared. At this time, the particle diameter of the prepared Mn-Li-ZnS phosphor nanoparticles was about 9 nm.
상기에서 제조된 Mn-Li-ZnS 형광체 나노입자의 구조를 분석하기 위하여 고해상도의 투과전자현미경(HRTEM: JEM3010, JEOL사)을 사용하여 관찰하였고, 유도결합 플라즈마(inductively coupled plasma, ICP1000IV, Shimadzu사) 분석은 시료의 화학적 조성을 결정하기 위해 수행되었다. 상기 투과전자 현미경 분석 결과는 도 2에 나타내었으며, 이를 통해 표면으로부터 약 1 ㎚의 비정질층이 존재함을 확인할 수 있다.In order to analyze the structure of the prepared Mn-Li-ZnS phosphor nanoparticles were observed using a high-resolution transmission electron microscope (HRTEM: JEM3010, JEOL), inductively coupled plasma (ICP1000IV, Shimadzu) The analysis was performed to determine the chemical composition of the sample. The transmission electron microscope analysis results are shown in FIG. 2, through which it can be seen that an amorphous layer of about 1 nm is present from the surface.
상기 투과전자 현미경에 의해 확인된 비정질층의 존재로부터, 실시예 1에서 제조된 Mn-Li-ZnS 형광체 나노입자는 Mn-ZnS으로 구성된 정질층의 표면에 Li-ZnS으로 구성된 비정질층이 둘러싼 코어-셀 구조를 형성한다는 것을 미루어 짐작할 수 있다. 이때, 표면의 비정질층은 XPS 장비를 통해 ZnS와 Li로 구성되어 있음을 추측할 수 있었다.From the presence of the amorphous layer confirmed by the transmission electron microscope, the Mn-Li-ZnS phosphor nanoparticles prepared in Example 1 is a core- surrounded by an amorphous layer composed of Li-ZnS on the surface of the amorphous layer composed of Mn-ZnS- It can be guessed that it forms a cell structure. At this time, it could be assumed that the amorphous layer of the surface is composed of ZnS and Li through the XPS equipment.
상기와 같이 비정질의 표면층을 형성하여 종래에 비해 표면결함이 현저히 낮아 H. Yang and P. H. Holloway, Adv. Funct. Mater. 14, 152 (2004) 등에 의하면 안정적인 장기인광성을 나타내고 발광 효율이 증가됨이 명백하므로 본 발명에 따른 황화아연계 적색형광체도 이러한 효과 발현이 가능할 것으로 보여진다.By forming the amorphous surface layer as described above, the surface defects are significantly lower than in the prior art H. Yang and P. H. Holloway, Adv. Funct. Mater. 14, 152 (2004), etc., it is apparent that stable long-term phosphorescence is exhibited and the luminous efficiency is increased, and thus the zinc sulfide-based red phosphor according to the present invention may be expressed.
또한, 상기 Mn-Li-ZnS 형광체 나노입자는 색좌표(CIE)의 X= 0.52이고 Y= 0.42이며 발광파장이 600 nm인 적색형광체임을 확인할 수 있었다. In addition, it was confirmed that the Mn-Li-ZnS phosphor nanoparticles were red phosphors having X = 0.52 of color coordinates (CIE), Y = 0.42, and emission wavelength of 600 nm.
실시예 2 : 리튬의 농도에 따른 변화Example 2 Change with Concentration of Lithium
상기 실시예 1과 동일하게 실시하되, 하기 표 1에 나타낸 바와 같이 리튬원자의 농도를 변화시켜 Mn-Li-ZnS 형광체 나노입자를 제조하였다.In the same manner as in Example 1, Mn-Li-ZnS phosphor nanoparticles were prepared by changing the concentration of lithium atoms as shown in Table 1 below.
상기와 같이 각각의 리튬 농도에 따른 광특성 변화를 PL 스펙트럼(FP6500, JASCO) 분석을 통해 확인하고 그 결과를 하기 도 3에 나타내었다. 이때, 도 3에서 표기된 농도는 ICP 분석을 통해 구해진 실제 리튬 도핑 농도를 나타낸다.As described above, the optical characteristic change according to each lithium concentration was confirmed through PL spectrum (FP6500, JASCO) analysis, and the results are shown in FIG. 3. At this time, the concentration indicated in Figure 3 represents the actual lithium doping concentration obtained through the ICP analysis.
도 3의 리튬 농도에 따른 광특성을 PL 스펙트럼 분석한 결과, PL의 강도는 합성 시 넣어준 리튬의 양이 10 원자%이고 ICP 분석 시 0.34 원자%일 때 최고치를 보였다. 즉 도핑한 리튬의 양에 의해서 표면 개질의 정도를 조절할 수 있으며, 특히 최적 조건의 표면 개질 정도가 존재함을 확인할 수 있었다.As a result of PL spectrum analysis of optical properties according to the lithium concentration of FIG. 3, the strength of PL was the highest when the amount of lithium added during synthesis was 10 atomic% and 0.34 atomic% in ICP analysis. That is, the degree of surface modification can be controlled by the amount of lithium doped, and it was confirmed that the degree of surface modification under optimum conditions exists.
비교예 1Comparative Example 1
대한민국 특허등록 제0842376호의 실시예 1(망간이 도핑된 황화아연 나노입자)Example 1 (Manganese-doped zinc sulfide nanoparticles) of Korean Patent Registration No. 0842376
비교예 2Comparative Example 2
상기 실시예 1과 동일하게 실시하되, LiOH·H2O 대신에 Li2CO3, LiNO3, LiOH을 사용하여 Mn-Li-ZnS 형광체 나노입자를 제조하였다. 각각의 리튬화합물은 입자의 표면 개질을 위한 전구체로 Li2CO3, LiNO3, LiOH 등도 사용이 가능하나 실제 개질 효율은 큰 차이를 나타내었으며, 이들 중 수산화리튬·수화물이 가장 우수한 개질효율을 보였다. Mn-Li-ZnS phosphor nanoparticles were prepared in the same manner as in Example 1, using Li 2 CO 3 , LiNO 3 , and LiOH instead of LiOH · H 2 O. Li 2 CO 3 , LiNO 3 , LiOH, etc. can be used as precursors for the surface modification of the particles, but the actual reforming efficiency showed a big difference. Among them, lithium hydroxide and hydrate showed the best reforming efficiency. .
비교예 3 Comparative Example 3
상기 실시예 1과 동일하게 실시하되, 수산화리튬·수화물 대신에 수산화알루미늄·수화물, 수산화나트륨·수화물 및 수산화칼륨·수화물을 사용하여 형광체 나노입자를 제조하였다.The phosphor nanoparticles were prepared in the same manner as in Example 1, using aluminum hydroxide hydrate, sodium hydroxide hydrate, and potassium hydroxide hydrate instead of lithium hydroxide hydrate.
그 결과, 도핑양이 아주 적고 비정질층이 제대로 형성되지 않아 본 발명에서 목적으로 하는 발광 특성이 발현되지 않음을 확인할 수 있었다.As a result, it was confirmed that the amount of doping was very small and the amorphous layer was not formed properly, so that the luminescent property of the present invention was not expressed.
실험예Experimental Example
상기 실시예 2에 나타낸 바와 같이 리튬의 양을 조절하여 제조된 형광체의 특성에 미치는 영향을 확인하였다.As shown in Example 2, it was confirmed that the effect on the characteristics of the phosphor prepared by adjusting the amount of lithium.
제조된 형광체는 PL 스펙트럼 분석방법을 사용하였으며, 방출 스펙트럼을 스펙트로플루오로메터(FP-6500, JASCO)로 측정하여 그 결과를 도 3에 나타내었다.The prepared phosphors were PL spectrometric method, and the emission spectrum was measured by spectrofluorometer (FP-6500, JASCO) and the results are shown in FIG. 3.
도 3에 나타낸 바와 같이, 종래 리튬이 사용하지 않은 비교예 1의 황화아연계 형광체에 비해 리튬이 함유된 황화아연계 적색형광체의 발광효율이 향상되었으며, 사용되는 리튬의 양이 증가할수록 발광효율이 증가한다는 것을 확인할 수 있었으며, 표면 개질을 통해 장기 발광 특성도 보다 향상된다는 것을 예측할 수 있다.As shown in FIG. 3, the luminous efficiency of the zinc sulfide-based red phosphor containing lithium was improved compared to the zinc sulfide-based fluorescent material of Comparative Example 1, which is not conventionally used in lithium, and the luminous efficiency was increased as the amount of lithium used was increased. It was confirmed that the increase, and the surface modification can be expected to improve the long-term light emission characteristics.
도 1은 본 발명에 따른 황화아연계 적색형광체의 제조방법을 나타낸 모식도이다.1 is a schematic diagram showing a method of manufacturing a zinc sulfide-based red phosphor according to the present invention.
도 2는 본 발명에 따른 황화아연계 적색형광체의 고배율(× 1,500,000) 투과전자현미경을 나타낸 것이다. Figure 2 shows a high magnification (x 1,500,000) transmission electron microscope of the zinc sulfide-based red phosphor according to the present invention.
도 3은 본 발명에 따른 황화아연계 적색형광체의 리튬농도에 따른 인광특성을 형광분석기로 분석한 것이다.Figure 3 is analyzed by the fluorescence spectroscopy phosphorescence characteristics of the lithium sulfide-based red phosphor according to the lithium concentration according to the present invention.
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| KR930002479A (en) * | 1991-07-03 | 1993-02-23 | 김정배 | ZnS-based phosphor |
| KR20030045500A (en) * | 2001-12-04 | 2003-06-11 | 한국화학연구원 | Preparing process for spherical red phosphor based on borates using hydrolysis |
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| KR930002479A (en) * | 1991-07-03 | 1993-02-23 | 김정배 | ZnS-based phosphor |
| KR20030045500A (en) * | 2001-12-04 | 2003-06-11 | 한국화학연구원 | Preparing process for spherical red phosphor based on borates using hydrolysis |
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| CN112397657A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Modified zinc sulfide, preparation method thereof and quantum dot light-emitting diode |
| CN112397657B (en) * | 2019-08-19 | 2022-05-03 | Tcl科技集团股份有限公司 | Modified zinc sulfide, preparation method thereof and quantum dot light-emitting diode |
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