KR101098337B1 - Process for preparing molybdate based red light emitting fluorescent material - Google Patents
Process for preparing molybdate based red light emitting fluorescent material Download PDFInfo
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- KR101098337B1 KR101098337B1 KR1020100004617A KR20100004617A KR101098337B1 KR 101098337 B1 KR101098337 B1 KR 101098337B1 KR 1020100004617 A KR1020100004617 A KR 1020100004617A KR 20100004617 A KR20100004617 A KR 20100004617A KR 101098337 B1 KR101098337 B1 KR 101098337B1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 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
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 229910052688 Gadolinium Inorganic materials 0.000 description 13
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 11
- 238000004020 luminiscence type Methods 0.000 description 11
- 238000000295 emission spectrum Methods 0.000 description 10
- 229910052727 yttrium Inorganic materials 0.000 description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 239000013543 active substance Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 5
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- -1 CaS: Eu Chemical compound 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
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- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
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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
- C09K11/77—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
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
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- F21V3/04—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
- F21V3/10—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by coatings
- F21V3/12—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by coatings the coatings comprising photoluminescent substances
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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Abstract
본 발명은 백색 발광 다이오드(백색 LED) 및 삼파장 형광등에 사용 가능한 적색발광 형광체의 제조방법에 관한 것으로, 하기 화학식 1로 표시되는 적색발광 형광체를 제조함에 있어서, 형광체의 원료 물질로서 Y(NO3)3 및 Gd2O3 중에서 1종 이상과, MoO3, Eu2O3 그리고 용융제(NH4F 등)를 사용하고, 전기로에서 850 내지 1,000℃의 온도로 소결함으로써, 대량으로 적색발광 형광체를 제조할 수 있는 방법을 제공한다.
[화학식 1]
(Gd1-xYx)2-y(MoO4)3:yEu
상기 식에서, 0.0 ≤ x ≤ 1.0, 0.32 ≤ y ≤ 0.48 이다.The present invention relates to a method of manufacturing a red light emitting phosphor that can be used for a white light emitting diode (white LED) and a three-wavelength fluorescent lamp. In manufacturing a red light emitting phosphor represented by the following Chemical Formula 1, Y (NO 3 ) is used as a raw material of the phosphor. The red light-emitting phosphor was mass-produced by sintering at a temperature of 850 to 1,000 ° C. in an electric furnace using at least one of 3 and Gd 2 O 3 , MoO 3 , Eu 2 O 3, and a melting agent (NH 4 F, etc.). Provided are methods that can be prepared.
[Formula 1]
(Gd 1-x Y x ) 2-y (MoO 4 ) 3 : yEu
Wherein 0.0 ≦ x ≦ 1.0, 0.32 ≦ y ≦ 0.48.
Description
본 발명은 산화물계 적색발광 형광체의 제조방법에 관한 것으로, 더욱 상세하게는 산화물의 일종인 몰리브데이트 계열 적색발광 형광체, 이의 제조방법, 그리고 이를 적용한 삼파장 백색 발광 다이오드 및 삼파장 형광등에 관한 것이다.The present invention relates to a method of manufacturing an oxide-based red light-emitting phosphor, and more particularly, to a molybdate-based red light-emitting phosphor, a method of manufacturing the same, and a three wavelength white light emitting diode and a three wavelength fluorescent lamp applied thereto.
본 발명은 하기와 같은 지식경제부 사업의 일환으로 수행한 연구로부터 도출된 것이다.The present invention is derived from the research conducted as part of the Ministry of Knowledge Economy as follows.
이 발명을 지원한 국가연구개발사업National R & D project supporting this invention
[과제고유번호]80744[Task unique number] 80744
[부처명] 지식경제부[Ministry of Knowledge] Ministry of Knowledge Economy
[연구사업명] 산업원천기술개발사업[Project name] Industrial source technology development project
[연구과제명] 적색 발광 신조성 양자점/나노 형광체 개발(1/2)[Project Name] Development of Red Light Emitting New Quantum Dot / Nano Phosphor (1/2)
[주관기관] 단국대학교[Organization] Dankook University
[연구기간] 2009년 3월 1일 ~ 2010년 02월 28일[Research Period] March 1, 2009 ~ February 28, 2010
형광체가 현재 사용되고 있는 영역은 디스플레이용, 광원용, 그리고 검지 용도이다. 디스플레이용 형광체로는 희토류 형광체를 사용한 것이 많은데, 이것의 발광 휘도가 높기 때문에 고휘도의 발광용 전자소재에 자주 사용된다. 따라서 청색, 적색, 녹색발광 형광체의 제조는 전자 소재 산업에서 필수적이며, 발광 성능이 좋은 형광체를 제조하는 것이 매우 중요하다.The areas where phosphors are currently used are for displays, light sources, and detection applications. In many cases, rare earth phosphors are used as display phosphors, and because of their high luminescence brightness, they are frequently used for high luminance light emitting electronic materials. Therefore, manufacturing of blue, red, and green light emitting phosphors is essential in the electronic material industry, and it is very important to prepare phosphors having good light emitting performance.
백색 발광 다이오드 및 삼파장 형광등에 사용되는 적색 형광체로는 일반적으로 CaS:Eu와 같은 황화물계 형광체를 사용한다. 이와 같이 기존의 적색 발광 형광체는 CaS:Eu와 같은 황화물계 형광체이므로, 열과 수분에 약하다.As a red phosphor used for a white light emitting diode and a three wavelength fluorescent lamp, a sulfide-based phosphor such as CaS: Eu is generally used. As such, the existing red light-emitting phosphor is a sulfide-based phosphor such as CaS: Eu, and therefore is weak to heat and moisture.
대한민국 특허 등록 제803620호에는 PDP 및 LED용 형광체 표면에, 금속산화물과 고분자로 이루어진 유, 무기 나노 복합체가 코팅된 것을 특징으로 하는 PDP 및 LED용 형광체가 개시되어 있다.Korean Patent Registration No. 803620 discloses a phosphor for PDP and LED, characterized in that an organic and inorganic nanocomposite composed of a metal oxide and a polymer is coated on the surface of the phosphor for PDP and LED.
대한 화학회 논문(Bull. Kor. Chem. Soc. 성혜진, 조영식, 허영덕, 도영락, 28, 1280 (2007))에는 백색 발광 다이오드에 사용되는 황화물계의 Ca1-xSrxS:Eu 적색 발광 형광체의 제조 및 형광체의 발광특성에 관한 연구가 개시되어 있다.Chemical Society of paper (Bull Kor Chem Soc seonghyejin, joyoungsik, heoyoungdeok, Toei Rock, 28, 1280 (2007)....), The Ca 1-x Sr x S of the sulfide to be used in a white light emitting diode for: Eu red light emitting The manufacture of phosphors and the study of the luminescence properties of phosphors are disclosed.
그러나 상술한 바와 같이, 상기 특허와 논문에서 백색 발광 다이오드 및 삼파장 형광등에 사용되는 황화물계의 적색발광 형광체는 광원에 의한 열 발생 및 수분에 매우 약한 단점이 있다.However, as described above, sulfide-based red light-emitting phosphors used in white light emitting diodes and three-wavelength fluorescent lamps in the above patents and papers have a very weak disadvantage in heat generation and moisture caused by the light source.
본 발명의 목적은 열과 수분에 약한 황화물계 형광체의 단점을 극복하고 우수한 발광 특성을 나타내는 몰리브데이트 계열 적색발광 형광체의 제조방법을 제공하는 것이다.SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a molybdate-based red light-emitting phosphor that overcomes the disadvantages of sulfide-based phosphors that are weak to heat and moisture and exhibits excellent luminescence properties.
본 발명의 다른 목적은 용융제를 사용하여 낮은 온도에서 소결할 수 있는 몰리브데이트 계열 적색발광 형광체의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing molybdate-based red light-emitting phosphor that can be sintered at a low temperature using a melting agent.
본 발명의 또 다른 목적은 발광효율이 최적화된 조성비를 갖는 몰리브데이트 계열 적색발광 형광체의 제조방법을 제공하는 것이다.Still another object of the present invention is to provide a method of manufacturing molybdate-based red light-emitting phosphors having an optimized composition ratio.
본 발명의 또 다른 목적은 몰리브데이트 계열 적색발광 형광체를 적용한 삼파장 백색 발광 다이오드 및 삼파장 형광등을 제공하는 것이다.Still another object of the present invention is to provide a three wavelength white light emitting diode and a three wavelength fluorescent lamp to which a molybdate-based red light emitting phosphor is applied.
본 발명은 상기 목적을 달성하기 위하여, Y(NO3)3 및 Gd2O3 중에서 1종 이상과, MoO3, Eu2O3 그리고 용융제를 균일하게 혼합하여 혼합물을 준비하는 단계; 및 혼합물을 전기로에서 소결하여 하기 화학식 1로 표시되는 몰리브데이트 계열 적색발광 형광체를 제조하는 단계를 포함하는, 몰리브데이트 계열 적색발광 형광체의 제조방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of preparing a mixture by uniformly mixing at least one of Y (NO 3 ) 3 and Gd 2 O 3 , MoO 3 , Eu 2 O 3 and the melting agent; And preparing a molybdate-based red light-emitting phosphor represented by Chemical Formula 1 by sintering the mixture in an electric furnace.
상기 식에서, 0.0 ≤ x ≤ 1.0, 0.32 ≤ y ≤ 0.48 이고,Wherein 0.0 ≦ x ≦ 1.0, 0.32 ≦ y ≦ 0.48,
Gd는 가돌리늄(gadolinium), Y는 이트륨(yttrium), Mo는 몰리브덴(molybdenum), Eu는 유로퓸(europium)이다.Gd is gadolinium, Y is yttrium, Mo is molybdenum, and Eu is europium.
본 발명에서 용융제는 불화암모늄, 염화나트륨, 불화나트륨, 불화칼슘, 불화바륨 및 염화암모늄 중에서 선택되는 1종 이상일 수 있으며, 도 7에서 확인할 수 있는 바와 같이, 불화암모늄인 것이 특히 바람직하다.In the present invention, the melting agent may be at least one selected from ammonium fluoride, sodium chloride, sodium fluoride, calcium fluoride, barium fluoride and ammonium chloride, and as shown in FIG. 7, ammonium fluoride is particularly preferable.
본 발명에서 용융제의 농도는 도 8에서 확인할 수 있는 바와 같이, 원료 전체 중량에 대하여 1 내지 10 중량%인 것이 바람직하며, 특히 3 중량%인 것이 더욱 바람직하다.As can be seen in Figure 8 the concentration of the melt in the present invention, preferably 1 to 10% by weight, more preferably 3% by weight relative to the total weight of the raw material.
본 발명에서 Gd와 Y의 조성비와 관련하여, 도 4에서 확인할 수 있는 바와 같이, 화학식 1에서 x는 바람직하게는 0.0 내지 1.0, 더욱 바람직하게는 0.2 내지 0.8, 가장 바람직하게는 0.4이다.With respect to the composition ratio of Gd and Y in the present invention, as can be seen in Figure 4, x in the formula (1) is preferably 0.0 to 1.0, more preferably 0.2 to 0.8, most preferably 0.4.
본 발명에서 활성제의 농도와 관련하여, 도 6에서 확인할 수 있는 바와 같이, 화학식 1에서 y는 0.32 내지 0.48인 것이 바람직하며, 특히 y는 0.4인 것이 더욱 바람직하다.Regarding the concentration of the active agent in the present invention, as can be seen in Figure 6, in the general formula (1) it is preferable that y is 0.32 to 0.48, in particular y is more preferably 0.4.
본 발명에서 소결온도는 도 2에서 확인할 수 있는 바와 같이, 850 내지 1,000℃인 것이 바람직하며, 특히 900℃인 것이 더욱 바람직하다.As can be seen in Figure 2 the sintering temperature in the present invention, preferably 850 to 1,000 ℃, more preferably 900 ℃.
본 발명에 따른 형광체의 입자크기는 1 내지 20 ㎛인 것이 바람직하다.The particle size of the phosphor according to the present invention is preferably 1 to 20 ㎛.
또한, 본 발명은 상술한 방법에 따라 제조되며, 상기 화학식 1로 표시되는 몰리브데이트 계열 적색발광 형광체를 제공한다.In addition, the present invention is prepared according to the above-described method, and provides a molybdate-based red light-emitting phosphor represented by the formula (1).
또한, 본 발명은 몰리브데이트 계열 적색발광 형광체가 청색 발광 다이오드 칩 위에 녹색 발광 형광체와 함께 도핑된 것을 특징으로 하는 삼파장 백색 발광 다이오드를 제공한다.The present invention also provides a three-wavelength white light emitting diode, characterized in that the molybdate-based red light-emitting phosphor is doped with the green light-emitting phosphor on the blue light emitting diode chip.
또한, 본 발명은 몰리브데이트 계열 적색발광 형광체가 형광등의 내부 벽에 청색, 녹색 발광 형광체와 함께 도핑된 것을 특징으로 하는 삼파장 형광등을 제공한다.In addition, the present invention provides a three-wavelength fluorescent lamp characterized in that the molybdate-based red light-emitting phosphor is doped with blue, green light-emitting phosphor on the inner wall of the fluorescent lamp.
본 발명에 따른 몰리브데이트 계열 적색발광 형광체는 청색(465 nm)을 잘 흡수하는 형광체이므로, 기존의 청색 발광 다이오드에 녹색 발광 형광체와 같이 도핑하면, 색 순도가 높은 삼파장 백색 발광 다이오드의 제조가 가능하다.Since the molybdate-based red light-emitting phosphor according to the present invention is a phosphor that absorbs blue (465 nm) well, it is possible to manufacture a three-wavelength white light emitting diode having high color purity by doping the existing blue light-emitting diode like a green light-emitting phosphor. Do.
또한, 본 발명에 따르면 용융제를 사용하여 낮은 온도에서 소결할 수 있는 몰리브데이트 계열 적색발광 형광체의 제조 조건을 확보할 수 있다.In addition, according to the present invention it is possible to ensure the manufacturing conditions of the molybdate-based red light-emitting phosphor that can be sintered at a low temperature using a melting agent.
또한, 본 발명에 따른 몰리브데이트 계열 적색발광 형광체는 자외선(254 nm)을 잘 흡수하는 형광체이므로, 형광등에 청색, 녹색 발광 형광체와 같이 도핑하면, 색 순도가 높은 삼파장 형광등을 제조할 수 있다.In addition, since the molybdate-based red light-emitting phosphor according to the present invention is a phosphor that absorbs ultraviolet rays (254 nm) well, a three-wavelength fluorescent lamp having high color purity can be manufactured by doping the fluorescent light with blue and green light-emitting phosphors.
또한, 본 발명에 따라 이트륨과 가돌리늄이 일정비로 혼합되어 발광효율이 최적화된 몰리브데이트 계열 적색발광 형광체의 제조 조건을 확보할 수 있다.In addition, according to the present invention, yttrium and gadolinium may be mixed in a predetermined ratio to secure the manufacturing conditions of the molybdate-based red light-emitting phosphor with optimized luminous efficiency.
또한, 본 발명에 따라 열과 수분에 약한 황화물계 형광체의 단점을 극복할 수 있는 몰리브데이트 계열 적색발광 형광체를 제조할 수 있다.In addition, according to the present invention, it is possible to prepare molybdate-based red light-emitting phosphors that can overcome the disadvantages of sulfide-based phosphors weak in heat and moisture.
본 발명은 삼파장 백색 발광 다이오드와 삼파장 형광등을 이용하는 디스플레이 분야에 적용될 수 있다.The present invention can be applied to a display field using a three wavelength white light emitting diode and a three wavelength fluorescent lamp.
구체적으로, 본 발명에 따른 적색발광 형광체를 청색 발광 다이오드 칩 위에 녹색 발광 형광체와 함께 도핑하여 삼파장의 백색 발광 다이오드를 만들 수 있다.Specifically, the red light emitting phosphor according to the present invention may be doped together with the green light emitting phosphor on the blue light emitting diode chip to make a white light emitting diode having three wavelengths.
또한, 본 발명에 따른 적색발광 형광체를 형광등의 내부 벽에 청색, 녹색 발광 형광체와 함께 도핑하여 삼파장의 형광등을 만들 수 있다.In addition, the red light-emitting phosphor according to the present invention can be doped with blue and green light-emitting phosphors on the inner wall of the fluorescent light to make a three-wavelength fluorescent light.
도 1은 소결용 도가니에 합성에 필요한 시료를 균일하게 혼합한 것을 나타낸 개략도이다.
도 2는 본 발명의 실시예 1-1 내지 1-4 및 비교예 1-1 내지 1-4에 따라 소결 온도를 변화시키면서 합성한 Gd1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼 및 발광 최대파장에서의 발광세기를 비교한 그래프이다.
도 3은 본 발명의 실시예 1-2에 따른 Gd1.6(MoO4)3:0.4Eu 형광체와 Gd2(MoO4)3 결정의 X-선 회절 스펙트럼이다.
도 4는 본 발명의 실시예 2-1 내지 2-6에 따라 가돌리늄과 이트륨의 조성비를 변화시키면서 합성한 (Gd1-xYx)1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼 및 발광 최대파장에서의 발광세기를 비교한 그래프이다.
도 5는 본 발명에 따른 (Gd0.67Y0.93)(MoO4)3:0.4Eu 형광체의 여기스펙트럼이다.
도 6은 본 발명의 실시예 3-1 내지 3-3 및 비교예 3-1 내지 3-3에 따라 활성제의 농도를 변화시키면서 합성한 Gd2-y(MoO4)3:yEu 형광체의 발광스펙트럼을 비교한 그래프이다.
도 7은 본 발명의 실시예 4-1 내지 4-3 및 비교예 4-1에 따라 용융제를 변화시키면서 합성한 Gd1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼을 비교한 그래프이다.
도 8은 본 발명의 실시예 5-1 내지 5-4 및 비교예 5-1 내지 5-2에 따라 용융제의 양을 변화시키면서 합성한 Gd1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼을 비교한 그래프이다.1 is a schematic view showing uniform mixing of a sample required for synthesis into a sinter crucible.
2 is a light emission spectrum and light emission of Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor synthesized according to Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 of the present invention while varying the sintering temperature This is a graph comparing the light emission intensity at the maximum wavelength.
3 is an X-ray diffraction spectrum of a Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor and a Gd 2 (MoO 4 ) 3 crystal according to Examples 1-2 of the present invention.
4 is a light emission spectrum and light emission of (Gd 1-x Y x ) 1.6 (MoO 4 ) 3 : 0.4Eu phosphors synthesized by varying the composition ratio of gadolinium and yttrium according to Examples 2-1 to 2-6 of the present invention. This is a graph comparing the light emission intensity at the maximum wavelength.
5 is an excitation spectrum of (Gd 0.67 Y 0.93 ) (MoO 4 ) 3 : 0.4Eu phosphor according to the present invention.
6 is a light emission spectrum of Gd 2-y (MoO 4 ) 3 : yEu phosphor synthesized according to Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3 of the present invention while varying the concentration of the active agent. This is a graph comparing.
FIG. 7 is a graph comparing emission spectra of Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphors synthesized while changing a melting agent according to Examples 4-1 to 4-3 and Comparative Example 4-1 of the present invention.
8 is a light emission spectrum of Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor synthesized according to Examples 5-1 to 5-4 and Comparative Examples 5-1 to 5-2 of the present invention while varying the amount of the melting agent. This is a graph comparing.
본 발명은 백색 발광 다이오드 및 삼파장 형광등에 사용 가능한 적색발광 형광체의 제조방법에 관한 것으로, 일반적인 고체상 반응을 이용하여 자외선 및 가시광선 영역의 빛을 흡수할 수 있는 형광체를 제조하는 방법에 관한 것이다.The present invention relates to a method of manufacturing a red light-emitting phosphor that can be used for white light emitting diodes and three-wavelength fluorescent lamps, and to a method for producing a phosphor capable of absorbing light in the ultraviolet and visible region using a general solid-phase reaction.
본 발명에 따른 적색발광 형광체는 활성제인 유로퓸의 역할에 많은 영향을 받는다. 가돌리늄 위치에 활성제인 유로퓸이 치환되어서 삽입되므로, 모결정인 (Gd1-xYx)2-y(MoO4)3의 결정성은 형광체의 발광 세기에 가장 큰 영향을 미친다. 따라서 모결정의 결정성을 안정하게 위한 소결온도와 소결시간 등의 합성조건이 발광효율에 영향을 미치며, 모체인 가돌리늄과 이트륨의 비율도 형광체의 발광효율에 영향을 주므로, 적절한 비율로 혼합하고 소결하게 되면 형광체의 휘도를 증가시킬 수 있다. 또한, 형광체를 구성하는 모결정의 소결 시에 녹는점을 낮추어서 결정 성장을 용이하게 해주는 용융제의 선택도 매우 중요하다.The red light emitting phosphor according to the present invention is greatly influenced by the role of europium which is an activator. Since europium, which is an activator, is substituted and inserted at the gadolinium position, the crystallinity of the parent crystal (Gd 1-x Y x ) 2-y (MoO 4 ) 3 has the greatest influence on the luminescence intensity of the phosphor. Therefore, synthesis conditions such as sintering temperature and sintering time to stabilize the crystallinity of the crystal affect the luminous efficiency, and the ratio of gadolinium and yttrium, which is the parent, also affects the luminous efficiency of the phosphor. This can increase the luminance of the phosphor. In addition, it is also very important to select a melting agent that facilitates crystal growth by lowering the melting point during the sintering of the mother crystal constituting the phosphor.
현재 사용되고 있는 적색발광 형광체의 모결정으로는 CaS, Y2O2S, La2O2S 등이 있고, 활성제로는 Eu, Tb, Sm, Ce, Pr 등이 사용된다. 이것들은 황화물계 조성을 갖고 있는 형광체로서, 열과 수분에 약한 단점이 있다고 알려져 있다. 본 발명은 이러한 단점을 극복하고 우수한 발광 특성을 보여주는 적색발광 형광체를 대량으로 제조하는 기술을 확보한 것을 특징으로 한다.Currently used mother crystals of red light-emitting phosphors include CaS, Y 2 O 2 S, La 2 O 2 S, and the like, and activators include Eu, Tb, Sm, Ce, Pr, and the like. These are phosphors having a sulfide-based composition, and are known to have a weak disadvantage in heat and moisture. The present invention is characterized by overcoming these shortcomings and securing a technique for producing a large amount of red light-emitting phosphor showing excellent light emission characteristics.
본 발명에 따른 몰리브데이트 계열 적색발광 형광체의 제조방법은 아래와 같다.A method of manufacturing molybdate-based red light-emitting phosphors according to the present invention is as follows.
(Gd1-xYx)2-y(MoO4)3:yEu 형광체는 도 1과 같은 소결용 도가니에 형광체의 조성비에 따라 Y(NO3)3 및 Gd2O3 중에서 1종 이상과, MoO3, Eu2O3 그리고 용융제를 균일하게 섞은 후, 고온의 전기로에서 소결하여 얻는다.(Gd 1-x Y x ) 2-y (MoO 4 ) 3 : yEu phosphors may be formed of one or more of Y (NO 3 ) 3 and Gd 2 O 3 according to the composition ratio of phosphors in a sintering crucible as shown in FIG. 1, MoO 3 , Eu 2 O 3 and a melt are mixed uniformly and then obtained by sintering in a high temperature electric furnace.
용융제로는 불화암모늄이 바람직하며(도 7 참조), 불화암모늄 이외에 염화나트륨, 불화나트륨, 불화칼슘, 불화바륨 및 염화암모늄 등이 사용될 수 있다. 용융제는 소결 시에 소모되어 최종 형광체에는 존재하지 않는다.Ammonium fluoride is preferred as the melting agent (see FIG. 7), and sodium chloride, sodium fluoride, calcium fluoride, barium fluoride, ammonium chloride and the like may be used in addition to ammonium fluoride. The melt is consumed during sintering and is not present in the final phosphor.
용융제의 농도는 바람직하게는 원료 전체 중량에 대하여 바람직하게는 1 내지 10 중량%, 가장 바람직하게는 3 중량%이다(도 8 참조).The concentration of the melting agent is preferably 1 to 10% by weight, most preferably 3% by weight, based on the total weight of the raw material (see FIG. 8).
Gd와 Y의 조성비와 관련하여, 화학식 1에서 x는 바람직하게는 0.0 내지 1.0, 더욱 바람직하게는 0.2 내지 0.8, 가장 바람직하게는 0.4이다(도 4 참조). 이와 같이, 이트륨과 가돌리늄이 일정비로 혼합되어 발광효율이 최적화된 몰리브데이트 계열 적색발광 형광체의 제조 조건을 확보할 수 있다.Regarding the composition ratio of Gd and Y, x in the formula (1) is preferably 0.0 to 1.0, more preferably 0.2 to 0.8, most preferably 0.4 (see Fig. 4). As described above, yttrium and gadolinium may be mixed in a predetermined ratio to secure the manufacturing conditions of the molybdate-based red light-emitting phosphor with optimized luminous efficiency.
활성제의 농도와 관련하여, 화학식 1에서 y는 바람직하게는 0.32 내지 0.48, 가장 바람직하게는 0.4이다(도 6 참조).Regarding the concentration of the active agent, y in the formula (1) is preferably 0.32 to 0.48, most preferably 0.4 (see Fig. 6).
전기로는 전열을 이용하여 가열하는 노로서, 금속 정제에 널리 쓰인다. 발열 방식에 따라 분류하면 저항로, 아크로, 유도로로 나눈다. 또한 박스형 전기로, 튜브형 전기로, 도가니형 전기로, 피트형 전기로 등이 있다.Electric furnaces are furnaces that use electric heat to heat and are widely used for metal refining. Divided by heating method, it is divided into resistance furnace, arc furnace and induction furnace. Furthermore, there are box type furnaces, tube type furnaces, crucible type furnaces, pit type electric furnaces, and the like.
소결온도는 바람직하게는 850 내지 1,000℃, 가장 바람직하게는 900℃이다(도 2 참조).Sintering temperature is preferably 850 to 1,000 ℃, most preferably 900 ℃ (see Figure 2).
소결시간은 바람직하게는 2 내지 10시간, 더욱 바람직하게는 4 내지 8시간, 가장 바람직하게는 6시간이다.The sintering time is preferably 2 to 10 hours, more preferably 4 to 8 hours, most preferably 6 hours.
이와 같이 제조되는 상기 화학식 1로 표시되는 적색발광 형광체는 1 내지 20 ㎛의 입자크기를 가지며, 산화물의 일종인 몰리브데이트 계열 적색발광 형광체로서, 열과 수분에 약한 황화물계 형광체의 단점을 극복할 수 있다.The red light-emitting phosphor represented by
도 5는 본 발명에 따른 (Gd0.67Y0.93)(MoO4)3:0.4Eu 형광체의 여기스펙트럼으로서, 본 발명에 따른 몰리브데이트 계열 적색발광 형광체는 청색(465 nm)을 잘 흡수하는 형광체이므로, 기존의 청색 발광 다이오드에 녹색 발광 형광체와 같이 도핑하면, 색 순도가 높은 삼파장 백색 발광 다이오드의 제조가 가능하다. 또한, 본 발명에 따른 몰리브데이트 계열 적색발광 형광체는 자외선(254 nm)을 잘 흡수하는 형광체이므로, 형광등에 청색, 녹색 발광 형광체와 같이 도핑하면, 색 순도가 높은 삼파장 형광등을 제조할 수 있다.5 is an excitation spectrum of (Gd 0.67 Y 0.93 ) (MoO 4 ) 3 : 0.4Eu phosphor according to the present invention, since the molybdate-based red light-emitting phosphor according to the present invention is a phosphor that absorbs blue (465 nm) well. If the conventional blue light emitting diode is doped like a green light emitting phosphor, it is possible to manufacture a three wavelength white light emitting diode having high color purity. In addition, since the molybdate-based red light-emitting phosphor according to the present invention is a phosphor that absorbs ultraviolet rays (254 nm) well, a three-wavelength fluorescent lamp having high color purity can be manufactured by doping the fluorescent light with blue and green light-emitting phosphors.
본 발명에 따른 적색발광 형광체는 삼파장 백색 발광 다이오드와 삼파장 형광등을 이용하는 디스플레이 분야에 적용될 수 있다.The red light emitting phosphor according to the present invention can be applied to a display field using a three wavelength white light emitting diode and a three wavelength fluorescent lamp.
구체적으로, 본 발명에 따른 적색발광 형광체를 청색 발광 다이오드 칩 위에 녹색 발광 형광체와 함께 도핑하여 삼파장의 백색 발광 다이오드를 만들 수 있으며, 또한 본 발명에 따른 적색발광 형광체를 형광등의 내부 벽에 청색, 녹색 발광 형광체와 함께 도핑하여 삼파장의 형광등을 만들 수 있다.Specifically, the red light emitting phosphor according to the present invention may be doped together with the green light emitting phosphor on the blue light emitting diode chip to make a white light emitting diode having three wavelengths, and the red light emitting phosphor according to the present invention may be blue or green on the inner wall of the fluorescent lamp. It can be doped with the luminescent phosphor to make a three-wavelength fluorescent lamp.
이하, 실시예를 참조하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to Examples.
이하의 실시예들은 본 발명을 예시하기 위한 것으로서, 본 발명을 국한시키는 것으로 이해되어서는 안 될 것이다.The following examples are intended to illustrate the invention and should not be construed as limiting the invention.
[실시예 1 및 비교예 1]Example 1 and Comparative Example 1
소결온도Sintering Temperature
표 1과 같은 조성비로 각 화합물을 볼밀(ball mill) 장치에 넣은 후 2시간 동안 돌려서 균일하게 혼합한 다음, 도 1과 같은 도가니에 넣고, 박스형 전기로에서 소결함으로써, Gd1.6(MoO4)3:0.4Eu 형광체를 제조하였다.Each compound was added to a ball mill device at a composition ratio as shown in Table 1, and then mixed for 2 hours to be uniformly mixed. Then, the compound was placed in a crucible as shown in FIG. 1 and sintered in a box-type electric furnace, thereby obtaining Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor was prepared.
본 실시예 및 비교예에서는 소결온도를 변화시키면서 Gd1.6(MoO4)3:0.4Eu 형광체를 제조하였으며, 요구되는 화합물의 함량(단위: 몰수) 및 소결조건은 표 1과 같다.In the present example and the comparative example, Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor was prepared while changing the sintering temperature, and the content (unit: moles) and sintering conditions of the required compound are shown in Table 1.
(Rhodia Chimie)Gd 2 O 3
(Rhodia Chimie)
(Aldrich)MoO 3
(Aldrich)
(Rhodia Chimie)Eu 2 O 3
(Rhodia Chimie)
(Aldrich)NH 4 F
(Aldrich)
(hour)Sintering time
(hour)
(℃)Sintering Temperature
(℃)
1-1Comparative example
1-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
1-2Comparative example
1-2
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
1-1Example
1-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
1-2Example
1-2
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
1-3Example
1-3
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
1-4Example
1-4
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
1-3Comparative example
1-3
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
1-4Comparative example
1-4
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
도 2는 실시예 1-1 내지 1-4 및 비교예 1-1 내지 1-4에 따라 소결온도를 변화시키면서 합성한 Gd1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼 및 발광 최대파장에서의 발광세기를 비교한 그래프로서, 소결온도가 850 내지 1,000℃일 때 발광세기가 우수하였으며, 특히 소결온도가 900℃일 때(실시예 1-2) 발광세기가 가장 우수한 적색발광 형광체를 얻을 수 있었다.2 is a light emission spectrum and maximum emission wavelength of Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor synthesized according to Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 with varying sintering temperatures. As a graph comparing the luminescence intensity of, the luminescence intensity was excellent when the sintering temperature is 850 to 1,000 ℃, especially when the sintering temperature is 900 ℃ (Example 1-2), the red luminescent phosphor having the best luminescence intensity can be obtained. there was.
도 3은 본 발명의 실시예 1-2에 따른 Gd1.6(MoO4)3:0.4Eu 형광체와 Gd2(MoO4)3 결정의 X-선 회절 스펙트럼이다.3 is an X-ray diffraction spectrum of a Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor and a Gd 2 (MoO 4 ) 3 crystal according to Examples 1-2 of the present invention.
[실시예 2][Example 2]
가돌리늄과 이트륨의 조성비Composition ratio of gadolinium and yttrium
본 실시예에서는 가돌리늄(Gd)과 이트륨(Y)의 조성비를 변화시키면서 (Gd1-xYx)1.6(MoO4)3:0.4Eu 형광체를 제조하였으며, 요구되는 화합물의 함량(단위: 몰수) 및 소결조건은 표 2와 같다. Gd2O3 (99.99%, Rhodia Chimie), Y(NO3)3·6H2O (99.9%, Aldrich), MoO3 (99.5%, Aldrich), Eu2O3 (99.99%, Rhodia Chimie), NH4F (99.99%, Aldrich)을 사용하였다.In this embodiment, (Gd 1-x Y x ) 1.6 (MoO 4 ) 3 : 0.4Eu phosphor was prepared while varying the composition ratio of gadolinium (Gd) and yttrium (Y), and the required compound content (unit: moles) And sintering conditions are shown in Table 2. Gd 2 O 3 (99.99%, Rhodia Chimie), Y (NO 3 ) 3 6H 2 O (99.9%, Aldrich), MoO 3 (99.5%, Aldrich), Eu 2 O 3 (99.99%, Rhodia Chimie), NH 4 F (99.99%, Aldrich) was used.
(hour)Sintering time
(hour)
(℃)Sintering Temperature
(℃)
2-1Example
2-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
2-2Example
2-2
mmol0.96
mmol
mmol1.92
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol2.08
mmol
2-3Example
2-3
mmol1.92
mmol
mmol1.44
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol2.24
mmol
2-4Example
2-4
mmol2.88
mmol
mmol0.96
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol2.40
mmol
2-5Example
2-5
mmol3.84
mmol
mmol0.48
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol2.56
mmol
2-6Example
2-6
mmol4.80
mmol9.00
mmol
mmol0.60
mmol
mmol2.70
mmol
도 4는 실시예 2-1 내지 2-6에 따라 가돌리늄과 이트륨의 조성비를 변화시키면서 합성한 (Gd1-xYx)1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼 및 발광 최대파장에서의 발광세기를 비교한 그래프로서, 몰비율로 표현되는 x가 0.2 내지 0.8일 때 발광세기가 보다 우수하였으며, 특히 x가 0.4일 때(실시예 2-3) 발광세기가 가장 우수한 적색발광 형광체를 얻을 수 있었다.Figure 4 shows the emission spectrum and maximum emission wavelength of (Gd 1-x Y x ) 1.6 (MoO 4 ) 3 : 0.4Eu phosphor synthesized by varying the composition ratio of gadolinium and yttrium according to Examples 2-1 to 2-6 As a graph comparing the light emission intensity of, the light emission intensity was better when x represented by the molar ratio is 0.2 to 0.8, especially when x is 0.4 (Example 2-3), the red light emitting phosphor having the best light emission intensity was obtained. Could get
[실시예 3 및 비교예 3]Example 3 and Comparative Example 3
활성제의 농도Concentration of active agent
본 실시예 및 비교예에서는 활성제의 농도를 변화시키면서 Gd2-y(MoO4)3:yEu 형광체를 제조하였으며, 요구되는 화합물의 함량(단위: 몰수) 및 소결조건은 표 3과 같다.In this Example and Comparative Example, Gd 2-y (MoO 4 ) 3 : yEu phosphor was prepared while changing the concentration of the active agent, the content of the required compound (unit: mole number) and the sintering conditions are shown in Table 3.
(hour)Sintering time
(hour)
(℃)Sintering Temperature
(℃)
3-1Comparative example
3-1
mmol2.88
mmol
mmol9.00
mmol
mmol0.12
mmol
mmol1.92
mmol
3-2Comparative example
3-2
mmol2.76
mmol
mmol9.00
mmol
mmol0.24
mmol
mmol1.92
mmol
3-3Comparative example
3-3
mmol2.64
mmol
mmol9.00
mmol
mmol0.36
mmol
mmol1.92
mmol
3-1Example
3-1
mmol2.52
mmol
mmol9.00
mmol
mmol0.48
mmol
mmol1.92
mmol
3-2Example
3-2
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
3-3Example
3-3
mmol2.28
mmol
mmol9.00
mmol
mmol0.72
mmol
mmol1.92
mmol
도 6은 실시예 3-1 내지 3-3 및 비교예 3-1 내지 3-3에 따라 활성제의 농도를 변화시키면서 합성한 Gd2-y(MoO4)3:yEu 형광체의 발광스펙트럼을 비교한 그래프로서, 활성제의 농도가 모체의 가돌리늄의 몰수에 대하여 16 내지 24 몰%(y=0.32-0.48)일 때 발광세기가 우수하였으며, 특히 활성제의 농도가 모체의 가돌리늄의 몰수에 대하여 20 몰%(y=0.4)(실시예 3-2)일 때 발광세기가 가장 우수한 적색발광 형광체를 얻을 수 있었다.6 is a light emission spectrum of the Gd 2-y (MoO 4 ) 3 : yEu phosphor synthesized by changing the concentration of the active agent according to Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3 As a graph, the luminescence intensity was excellent when the concentration of the activator was 16 to 24 mol% (y = 0.32-0.48) with respect to the number of moles of gadolinium in the parent, and the concentration of the active agent was 20 mol% (with respect to the number of moles of gadolinium in the parent). y = 0.4) (Example 3-2), the red light-emitting phosphor having the best luminescence intensity was obtained.
[실시예 4 및 비교예 4]Example 4 and Comparative Example 4
용융제의 유무와 종류Presence and Type of Melting Agent
본 실시예 및 비교예에서는 용융제의 유무와 종류에 따라 Gd1.6(MoO4)3:0.4Eu 형광체를 제조하였으며, 요구되는 화합물의 함량(단위: 몰수) 및 소결조건은 표 4와 같다.In the present example and the comparative example, Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor was prepared according to the presence or absence of the melting agent, the content (unit: mole number) and the sintering conditions of the required compound are shown in Table 4.
종류Melt
Kinds
(hour)Sintering time
(hour)
(℃)Sintering Temperature
(℃)
4-1Comparative example
4-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
4-1Example
4-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
4-2Example
4-2
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
4-3Example
4-3
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
도 7은 실시예 4-1 내지 4-3 및 비교예 4-1에 따라 용융제를 변화시키면서 합성한 Gd1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼을 비교한 그래프로서, 용융제로서 NH4F(실시예 4-1)를 사용했을 때 발광세기가 가장 우수한 적색발광 형광체를 얻을 수 있었다.FIG. 7 is a graph comparing emission spectra of Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphors synthesized while changing a melter according to Examples 4-1 to 4-3 and Comparative Example 4-1. When NH 4 F (Example 4-1) was used, a red light-emitting phosphor having the best luminescence intensity could be obtained.
[실시예 5 및 비교예 5]Example 5 and Comparative Example 5
용융제의 양Amount of flux
본 실시예 및 비교예에서는 용융제의 양을 변화시키면서 Gd1.6(MoO4)3:0.4Eu 형광체를 제조하였으며, 요구되는 화합물의 함량(단위: 몰수) 및 소결조건은 표 5와 같다.In the present Example and Comparative Example, Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphor was prepared while changing the amount of the melting agent, the content (unit: mole number) and the sintering conditions of the required compound are shown in Table 5.
(hour)Sintering time
(hour)
(℃)Sintering Temperature
(℃)
5-1Comparative example
5-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol0.064
mmol
5-1Example
5-1
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol0.64
mmol
5-2Example
5-2
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol1.92
mmol
5-3Example
5-3
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol3.20
mmol
5-4Example
5-4
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol6.40
mmol
5-2Comparative example
5-2
mmol2.40
mmol
mmol9.00
mmol
mmol0.60
mmol
mmol12.8
mmol
도 8은 실시예 5-1 내지 5-4 및 비교예 5-1 내지 5-2에 따라 용융제의 양을 변화시키면서 합성한 Gd1.6(MoO4)3:0.4Eu 형광체의 발광스펙트럼을 비교한 그래프로서, 용융제의 양이 원료 전체 중량에 대하여 1 내지 10 중량%일 때 발광세기가 우수하였으며, 특히 용융제의 양이 3 중량%(1.92 mmol)(실시예 5-2)일 때 발광세기가 가장 우수한 적색발광 형광체를 얻을 수 있었다.FIG. 8 compares emission spectra of Gd 1.6 (MoO 4 ) 3 : 0.4Eu phosphors synthesized while varying the amount of the melting agent according to Examples 5-1 to 5-4 and Comparative Examples 5-1 to 5-2. As a graph, the luminescence intensity was excellent when the amount of the melter was 1 to 10% by weight based on the total weight of the raw material, and particularly when the amount of the melter was 3% by weight (1.92 mmol) (Example 5-2). The best red light emitting phosphor was obtained.
1: 도가니 뚜껑
2: 도가니
3: Y(NO3)3
4: Gd2O3
5: MoO3
6: Eu2O3
7: NH4F1: crucible lid
2: crucible
3: Y (NO 3 ) 3
4: Gd 2 O 3
5: MoO 3
6: Eu 2 O 3
7: NH 4 F
Claims (12)
혼합물을 전기로에서 소결하여 하기 화학식 1로 표시되는 몰리브데이트 계열 적색발광 형광체를 제조하는 단계를 포함하며,
용융제의 양은 원료 전체 중량에 대하여 1 내지 10 중량%이고,
소결온도는 850 내지 1,000℃인 것을 특징으로 하는,
몰리브데이트 계열 적색발광 형광체의 제조방법.
[화학식 1]
(Gd1-xYx)2-y(MoO4)3:yEu
(상기 식에서, 0.2 ≤ x ≤ 0.8, 0.32 ≤ y ≤ 0.48 이다.)Preparing a mixture by uniformly mixing one or more of Y (NO 3 ) 3 and Gd 2 O 3 , MoO 3 , Eu 2 O 3, and a melter; And
Sintering the mixture in an electric furnace to prepare a molybdate-based red light-emitting phosphor represented by the formula
The amount of the melting agent is 1 to 10% by weight based on the total weight of the raw material,
Sintering temperature is characterized in that 850 to 1,000 ℃,
Method for producing molybdate-based red light-emitting phosphor.
[Formula 1]
(Gd 1-x Y x ) 2-y (MoO 4 ) 3 : yEu
(In the above formula, 0.2 ≦ x ≦ 0.8, 0.32 ≦ y ≦ 0.48.)
[화학식 1]
(Gd1-xYx)2-y(MoO4)3:yEu
(상기 식에서, 0.2 ≤ x ≤ 0.8, 0.32 ≤ y ≤ 0.48 이다.)Molybdate-based red light-emitting phosphor represented by Formula 1 below.
[Formula 1]
(Gd 1-x Y x ) 2-y (MoO 4 ) 3 : yEu
(In the above formula, 0.2 ≦ x ≦ 0.8, 0.32 ≦ y ≦ 0.48.)
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