KR20130049653A - Method of core-shell structure quantum dots with thick shell and light conversion diode thereof - Google Patents
Method of core-shell structure quantum dots with thick shell and light conversion diode thereof Download PDFInfo
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- KR20130049653A KR20130049653A KR1020110114794A KR20110114794A KR20130049653A KR 20130049653 A KR20130049653 A KR 20130049653A KR 1020110114794 A KR1020110114794 A KR 1020110114794A KR 20110114794 A KR20110114794 A KR 20110114794A KR 20130049653 A KR20130049653 A KR 20130049653A
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- South Korea
- Prior art keywords
- group
- precursor solution
- metal precursor
- zinc
- cadmium
- Prior art date
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims description 33
- 239000011258 core-shell material Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 title description 20
- 239000002243 precursor Substances 0.000 claims abstract description 174
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 89
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- -1 zinc carboxylate Chemical class 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910021476 group 6 element Inorganic materials 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000011246 composite particle Substances 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 claims description 2
- IGPFOKFDBICQMC-UHFFFAOYSA-N 3-phenylmethoxyaniline Chemical compound NC1=CC=CC(OCC=2C=CC=CC=2)=C1 IGPFOKFDBICQMC-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 2
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- VQNPSCRXHSIJTH-UHFFFAOYSA-N cadmium(2+);carbanide Chemical compound [CH3-].[CH3-].[Cd+2] VQNPSCRXHSIJTH-UHFFFAOYSA-N 0.000 claims description 2
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 2
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 claims description 2
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 claims description 2
- UJYLYGDHTIVYRI-UHFFFAOYSA-N cadmium(2+);ethane Chemical compound [Cd+2].[CH2-]C.[CH2-]C UJYLYGDHTIVYRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 125000005265 dialkylamine group Chemical group 0.000 claims description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- UMTFPTCPRUEQHM-UHFFFAOYSA-N dicyanolead Chemical compound N#C[Pb]C#N UMTFPTCPRUEQHM-UHFFFAOYSA-N 0.000 claims description 2
- JUUVKOUSGRIGLL-UHFFFAOYSA-N diethyllead Chemical compound CC[Pb]CC JUUVKOUSGRIGLL-UHFFFAOYSA-N 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- XKSLEJLZTDEXGB-UHFFFAOYSA-N dimethyllead Chemical compound C[Pb]C XKSLEJLZTDEXGB-UHFFFAOYSA-N 0.000 claims description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical group C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 2
- XOYUVEPYBYHIFZ-UHFFFAOYSA-L diperchloryloxylead Chemical compound [Pb+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O XOYUVEPYBYHIFZ-UHFFFAOYSA-L 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 2
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims description 2
- FQGYCXFLEQVDJQ-UHFFFAOYSA-N mercury dicyanide Chemical compound N#C[Hg]C#N FQGYCXFLEQVDJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001987 mercury nitrate Inorganic materials 0.000 claims description 2
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 2
- 229910000370 mercury sulfate Inorganic materials 0.000 claims description 2
- SCTINZGZNJKWBN-UHFFFAOYSA-M mercury(1+);fluoride Chemical compound [Hg]F SCTINZGZNJKWBN-UHFFFAOYSA-M 0.000 claims description 2
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 claims description 2
- HIJSSUKZLPXDPU-UHFFFAOYSA-L mercury(2+);carbonate Chemical compound [Hg+2].[O-]C([O-])=O HIJSSUKZLPXDPU-UHFFFAOYSA-L 0.000 claims description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 2
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 claims description 2
- 229940105296 zinc peroxide Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 4
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims 1
- 229910000003 Lead carbonate Inorganic materials 0.000 claims 1
- HSAJRDKFYZAGLU-UHFFFAOYSA-M perchloryloxymercury Chemical compound [Hg+].[O-]Cl(=O)(=O)=O HSAJRDKFYZAGLU-UHFFFAOYSA-M 0.000 claims 1
- 235000003441 saturated fatty acids Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
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- 238000007254 oxidation reaction Methods 0.000 description 5
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- 238000002835 absorbance Methods 0.000 description 4
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- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
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- 239000005083 Zinc sulfide Substances 0.000 description 3
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Abstract
Description
본 발명은 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점의 제조 및 이를 포함하는 광변환 발광다이오드에 관한 것이다.
The present invention relates to the fabrication of a quantum dot of a nuclear-shell structure having a thick shell and a photoconversion light emitting diode comprising the same.
발광다이오드(LED, Light Emitting Diode)는 Ga(갈륨), P(인), As(비소)를 재료로 하여 만들어진 반도체로서 다이오드의 특성을 가지고 있다. 텅스텐전구나 네온램프 등 다른 발광 소자와 비교해서 전기에너지가 빛에너지로 바로 변환되어 빛의 변환효율이 양호하며, 열을 발하지 않고 소형, 경량이기 때문에 수명이 긴 것이 특징이다. 또한 전류가 흐르기 시작하고부터 발광하기까지의 시간이 짧고 응답특성도 좋아 다양한 모양으로 만들 수 있다.A light emitting diode (LED) is a semiconductor made of Ga (gallium), P (phosphorus), and As (arsenic) as a material, and has the characteristics of a diode. Compared with other light emitting devices such as tungsten lamps and neon lamps, electrical energy is directly converted into light energy, so the light conversion efficiency is good. In addition, the time from the start of the current to the light emission is short and the response characteristics are good, so that it can be made into various shapes.
발광색은 발광다이오드의 전극에 순방향으로 전압을 가하면, 사용된 화합물에 따라 붉은색, 녹색, 노란색, 청색 등을 나타내게 된다. 그러나 백색광은 직접 발산하지 못하기 때문에 청색 발광을 나타내는 발광다이오드 위에 형광체를 도포하여 백색광을 얻는 방식으로 백색 발광다이오드를 생산하고 있다. 상기 방법에 따라 생산되는 백색 발광다이오드는 효율이 우수하고 제조비용이 저렴하여 최근 들어 급속하게 시장이 커지고 있으며, 이와 관련한 연구 및 개발이 활발히 진행되고 있다.
The emission color is red, green, yellow, blue, etc. depending on the compound used when a voltage is applied in the forward direction to the electrode of the light emitting diode. However, since white light is not emitted directly, a white light emitting diode is produced by applying a phosphor on a light emitting diode that emits blue light to obtain white light. The white light emitting diodes produced according to the above method have an excellent efficiency and a low manufacturing cost, and thus the market is rapidly growing in recent years, and research and development on this are being actively conducted.
최근에는 기존 백색 발광다이오드 제조에 주로 사용되던 형광체 대신에 양자점(Quantum dot)을 이용하여 백색 발광다이오드를 구현시키려는 시도가 이루어지고 있다. 양자점은 빛 등의 에너지로 자극하면 빛을 발하는 나노 크기의 반도체 구조물 입자로써, 입자의 크기에 따라 방출하는 빛의 색상이 달라지는 물질이다. 구체적으로, 입자의 크기가 작아질수록 짧은 파장의 형광을 내며, 크기를 조절하여 원하는 파장의 가시광선영역의 형광을 거의 다 낼 수 있다. Recently, an attempt has been made to implement a white light emitting diode using a quantum dot instead of a phosphor mainly used for manufacturing a conventional white light emitting diode. Quantum dots are nano-sized semiconductor structure particles that emit light when stimulated with energy such as light, and the color of light emitted varies depending on the size of the particles. Specifically, as the size of the particles becomes smaller, the fluorescence of the shorter wavelength is emitted, and the fluorescence of the visible wavelength region of the desired wavelength can be almost adjusted by adjusting the size.
양자점은 일반적인 염료에 비해 흡광계수(Extinction coefficient)가 100 ~ 1000배 크고 양자효율(Quantum yield)도 높으므로 좁은 파장대에서도 매우 센 형광을 발생할 수 있다. 또한 전도대의 바닥진동상태에서 가전자대의 바닥진동상태로의 전이만을 관찰하므로 형광파장이 거의 단색광이다. 또한 일반적인 염료가 들뜬 상태에서 광화학반응에 의해 분해되어 광탈색(Photobleaching)현상이 일어나는 반면에, 양자점은 매우 안정하다.Quantum dots can generate very strong fluorescence even in a narrow wavelength range because the extinction coefficient is 100 to 1000 times higher and the quantum efficiency is higher than that of general dyes. In addition, since only the transition from the bottom vibration state of the conduction band to the bottom vibration state of the valence band is observed, the fluorescence wavelength is almost monochromatic light. In addition, quantum dots are very stable, while photobleaching occurs due to photochemical reactions in a state where a general dye is excited.
양자점을 이용한 백색 발광다이오드는 청색 발광다이오드 위에 녹색 및 적색 발광을 나타내는 양자점을 수지와 혼합하여 제조할 수 있다. 상기 방법으로 제조된 백색 발광다이오드는 기존의 형광체를 사용한 백색 발광다이오드에 비해 색재현성이 우수하고 색순수도가 우수하여, 조명 및 액정표시장치(LCD)용 배면광 등에 응용할 수 있다. A white light emitting diode using quantum dots can be prepared by mixing a quantum dot showing green and red light emission with a resin on a blue light emitting diode. The white light emitting diode manufactured by the above method is excellent in color reproducibility and color purity compared to the white light emitting diode using a conventional phosphor, and thus can be applied to illumination and backlight for liquid crystal display (LCD).
백색 발광다이오드 제조를 위해 사용되는 양자점은 주로 Ⅱ족 금속의 황화물, 셀렌화물 등이 사용된다. 상기의 Ⅱ족 금속은 외부의 수분이나 산소에 의해 산화가 잘 되는 조성이기 때문에 양자점을 이용해 제조한 백색 발광다이오드를 장시간 사용하는 경우 양자점의 산화에 의해 발광 강도가 감소하고, 색변이가 일어나는 문제점이 있다. 특히 청색 발광다이오드에 의해 양자점이 광여기되었을 경우 외부 환경인자에 의한 산화반응이 더욱 활발하게 발생하여 양자점의 수명을 더욱 감소시킬 수 있다.
The quantum dots used for manufacturing white light emitting diodes are mainly sulfides, selenides, and the like of Group II metals. Since the Group II metal is easily oxidized by external moisture or oxygen, when the white light emitting diode manufactured by using quantum dots is used for a long time, the emission intensity decreases due to oxidation of the quantum dots and color shift occurs. have. In particular, when the quantum dots are photoexcited by the blue light emitting diodes, oxidation reactions caused by external environmental factors are more actively generated, which may further reduce the lifetime of the quantum dots.
상기 문제점을 개선하기 위하여, [대한민국 공개특허 10-2011-0059855]에서는 반도체형 양자점을 합성하기 위한 방법을 개시하고 있다.In order to improve the above problem, Korean Patent Laid-Open Publication No. 10-2011-0059855 discloses a method for synthesizing a semiconductor quantum dot.
구체적으로 칼코겐을 함유하는 전구체 및 제 2그룹과 제 4그룹 메탈을 함유한 전구체로부터 유기용매 및 표면 모디피어(Modifier)를 사용하여 나노결정 중심체를 제조하며, 상기 모디피어로는 (아미노알킬)트리알콕시실란((Aminoalkyl)trialSpecifically, a nanocrystalline core is prepared by using an organic solvent and a surface modifier from a chalcogen-containing precursor and a precursor containing a second group and a fourth group metal, and the modifier is (aminoalkyl). Trialkoxysilane (Aminoalkyl)
coxysilane)을 사용하고, 150 ℃ ~ 250 ℃ 범위의 온도에서 15초 ~ 1시간을 유지하여 상기 중심체를 제조하고, 상기 나노결정 중심체를 함유하는 반응 혼합물을 자외선으로 1분 ~ 10분, 초음파로 5분 ~ 15분 정도 추가로 처리하는 방법을 제공하고 있다.coxysilane), and the core is prepared by maintaining the temperature for 15 seconds to 1 hour at a temperature in the range of 150 ° C to 250 ° C. It provides a way to process additional minutes to 15 minutes.
그러나 상기 반도체형 양자점을 합성하기 위한 방법의 경우, 무기물 형성을 위해 양자점의 표면 작용기를 개질하고 무기물 층을 형성시키는 과정에서 발광 강도가 상당히 감소하고 장시간의 반응 공정이 필요하다는 문제점이 있다. However, in the method for synthesizing the semiconductor quantum dots, there is a problem that the emission intensity is considerably reduced and a long time reaction process is required in the process of modifying the surface functional group of the quantum dots and forming the inorganic layer to form the inorganic material.
또한 제조된 양자점-무기물 복합 입자의 경우 그 크기가 수십 나노미터로 매우 작아 백색 발광다이오드 제조를 위해 수지와 함께 혼합하는 경우, 입자 간의 응집 등이 발생하기 쉬워서 균일한 혼합이 어려운 경우가 많고, 그 결과 발광 특성이 불균일해지는 문제점이 있다.
In addition, the manufactured quantum dot-inorganic composite particles are very small in size of several tens of nanometers, and when mixed with a resin to prepare a white light emitting diode, aggregation between particles is likely to occur, so that uniform mixing is often difficult. As a result, there is a problem in that the light emission characteristics become nonuniform.
최근에는 19층의 두꺼운 껍질을 가지는 핵-껍질(core-shell) 구조의 양자점이 우수한 환경 안정성을 가진다는 것이 보고되었다. 또한 핵-껍질 구조의 양자점에 있어서 껍질의 두께를 높이는 경우 발광의 재흡수나 발광의 깜빡임(blinking) 현상을 억제할 수 있기 때문에 발광다이오드나 태양전지 등 양자점의 각종 응용에 매우 유리하다.Recently, it has been reported that quantum dots of 19 layers of thick-shell core-shell structures have excellent environmental stability. In addition, in the case of increasing the thickness of the shell in the quantum dot of the nucleus-shell structure, reabsorption of luminescence and blinking of the luminescence can be suppressed, which is very advantageous for various applications of quantum dots such as light emitting diodes and solar cells.
두꺼운 껍질을 가지는 핵-껍질 구조의 양자점 제조를 위해서는 주로 이온층흡착 반응(SILAR, Successive Ionic Layer Adsorption and Reaction)이 사용된다.In order to prepare quantum dots of a thick-shelled nucleus-shell structure, a successive ionic layer adsorption reaction (SILAR) is mainly used.
[대한민국 공개특허 10-2010-0010424]에서는 열역학적 성장 조건에서 섬아연석 또는 암염 등의 면심입방 구조 결정상의 등방성 나노결정을 합성하여 동일한 반응성의 결정면이 표면에 고르게 분포된 핵을 제조하고, 그 표면에 적층형 껍질 성장을 유도하여 핵 표면에 균일하게 껍질이 성장된 핵-껍질 구조 나노결정을 제조하는 방법 및 각 층의 조성을 조절하여 핵-껍질 나노결정의 물성을 조절하는 방법을 제공하고 있다.[Korean Patent Laid-Open Patent Publication No. 10-2010-0010424] In the thermodynamic growth conditions, isotropic nanocrystals of face-centered cubic structure crystals such as splendid gelatin or rock salt are synthesized to prepare nuclei with evenly distributed crystal surfaces on the surface. The present invention provides a method for preparing a nucleus-shell structured nanocrystal in which a shell is uniformly grown on a surface of a nucleus by inducing layered shell growth, and a method of controlling the physical properties of the nucleus-shell nanocrystal by adjusting the composition of each layer.
구체적으로, 나노결정 전구체 용액의 온도를 상승시키면서 결정의 핵화 및 성장 반응을 진행시키고, 상기에서 제조된 핵 나노결정의 표면에 껍질 전구체 용액의 적하 및 어닐링 과정을 1회 이상 반복하여 껍질을 성장시킨다.Specifically, the nucleation and growth reaction of the crystal proceeds while raising the temperature of the nanocrystal precursor solution, and the shell is grown by repeating the dropping and annealing of the shell precursor solution one or more times on the surface of the prepared nuclear nanocrystal. .
상기의 방법은 매우 긴 시간과 복잡한 공정이 필요하고, 유기금속화합물 등은 고가이며, 폭발성이 있는 시약을 전구체로 사용하여야 한다. The above method requires a very long time and a complicated process, and an organometallic compound is expensive, and an explosive reagent must be used as a precursor.
특히 다층 껍질을 형성시키는 경우, 소요되는 시간 및 공정의 반복은 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점 합성에 있어서 걸림돌이 되고 있다. 예를 들어 황화아연 껍질을 형성시키는 경우, 합성 후 완전히 세정된 양자점을 용매에 분산시켜 200 ℃근처까지 가열한 후 천천히 아연 전구체용액을 주입하여 양자점 표면에 아연을 형성시킨 후 일정 시간 반응시키고 다시 황 용액을 천천히 주입하여 황화아연 단일층을 형성시켜야 한다. 다층형성을 위해 상기 방식을 사용하는 경우, 다량의 아연 및 황전구체가 이미 주입되었기 때문에 껍질층 형성과 별도로 황화아연 나노입자가 석출될 수 있어서 다시 완전히 세척한 후 처음 공정을 되풀이하여야 한다.
In particular, in the case of forming a multi-layer shell, repetition of time and process is an obstacle in quantum dot synthesis of a nucleus-shell structure having a thick shell. For example, in the case of forming a zinc sulfide shell, after synthesis, the fully cleaned quantum dots are dispersed in a solvent, heated to around 200 ° C., and then slowly injected with a zinc precursor solution to form zinc on the surface of the quantum dots. The solution should be injected slowly to form a zinc sulfide monolayer. In the case of using the above method for forming a multilayer, zinc sulfide nanoparticles may be precipitated separately from shell layer formation since a large amount of zinc and sulfur precursors have already been injected, and the first process must be repeated after complete washing.
이에 본 발명자들은 광안정성을 가지는 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 단시간에 제조하는 방법을 제공하고자 본 발명을 완성하였다.
Accordingly, the present inventors have completed the present invention to provide a method for preparing a quantum dot of a nuclear-shell structure having a thick shell having light stability in a short time.
본 발명은 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점 제조방법에 관한 것이다.The present invention relates to a method for producing a quantum dot of the nucleus-shell structure having a thick shell.
본 발명의 또 다른 목적은 상기 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 포함하는 광변환 발광다이오드를 제공하는데 있다.
Still another object of the present invention is to provide a photoconversion light emitting diode comprising a quantum dot of the nucleus-shell structure having the thick shell.
상기 목적을 달성하기 위하여, 250 ℃ ~ 350 ℃ 로 가열된 Ⅱ족 금속전구체 용액 또는 Ⅰ족과 Ⅲ족 원소의 혼합 금속전구체 용액에 Ⅵ족 전구체 용액을 첨가하되, 상기 금속전구체 용액 내의 금속전구체에 대한 Ⅵ족 전구체 용액 내의 Ⅵ족 전구체의 몰비율이 2 이상이고, 가열된 온도를 유지하면서 Ⅵ족 전구체 용액을 첨가하는 단계(단계 1);In order to achieve the above object, a Group VI precursor solution is added to a Group II metal precursor solution or a mixed metal precursor solution of a Group I and Group III element heated to 250 ° C. to 350 ° C., wherein the metal precursor in the metal precursor solution is Adding a Group VI precursor solution while maintaining a heated temperature at a molar ratio of Group VI precursor in the Group VI precursor solution (step 1);
상기 단계 1의 혼합용액을 180 ℃ ~ 240 ℃로 냉각시키는 단계(단계 2); 및Cooling the mixed solution of step 1 to 180 ° C. to 240 ° C. (step 2); And
상기 단계 2의 냉각된 혼합용액에 단계 1의 금속전구체 또는 혼합금속전구체 대비 0.5 ~ 1의 몰비율로 Ⅵ족 전구체 용액을 점적하는 단계(단계 3);Dropping a Group VI precursor solution into the cooled mixed solution of Step 2 at a molar ratio of 0.5 to 1 relative to the metal precursor or mixed metal precursor of Step 1 (Step 3);
를 포함하는 핵-껍질 구조의 양자점 제조방법을 제공한다.
It provides a method for producing a quantum dot of the nuclear-shell structure comprising a.
또한 본 발명은 상기의 제조방법에 따라 제조되는 핵-껍질 구조의 양자점을 제공한다.
The present invention also provides a quantum dot of the nucleus-shell structure produced according to the above production method.
또한 본 발명은 상기 양자점과 무기물 복합입자를 포함하며, 상기 무기물 복합입자는 SiO2, TiO2, ZrO2, ZnO, ITO 및 SnO로 구성되는 군에서 선택된 어느 하나인 것을 특징으로 하는 광변환 발광다이오드를 제공한다.
In another aspect, the present invention includes the quantum dots and inorganic composite particles, the inorganic composite particles are any one selected from the group consisting of SiO 2 , TiO 2 , ZrO 2 , ZnO, ITO and SnO. To provide.
상기 제조방법에 따라서, 핵-껍질 구조의 양자점을 제조하는 경우, 그 껍질의 두께를 조절할 수 있으며, 따라서 본 발명은 핵-껍질 구조의 양자점에 있어서 그 껍질의 두께를 두껍게 하는 방법을 제공한다.
According to the above production method, when manufacturing a quantum dot of the nucleus-shell structure, the thickness of the shell can be controlled, and thus the present invention provides a method for thickening the thickness of the shell in the quantum dot of the nuclear-shell structure.
본 발명에 따른, 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점 제조방법은 기존의 핵-껍질 구조의 양자점 제조에 있어서 핵과 껍질을 별도의 반응기에서 제조하는 방법과 달리 하나의 반응기 내에서 한번에 핵과 껍질을 제조함으로써 공정을 단순화할 수 있는 장점이 있다. 종래에는 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 제조하기 위하여 복수의 껍질층을 형성하는 방법을 사용하기도 하였으나, 이러한 경우 매우 긴 시간과 복잡한 공정이 필요하였다. According to the present invention, a method of manufacturing a quantum dot of a nuclear-shell structure having a thick shell is different from a method of manufacturing a nucleus and a shell in a separate reactor for preparing a quantum dot of a conventional nuclear-shell structure. Manufacturing has the advantage of simplifying the process. Conventionally, a method of forming a plurality of shell layers has been used to prepare a quantum dot having a thick shell with a nuclear shell structure, but in this case, a very long time and a complicated process are required.
본 발명은 한 개의 반응용기에서 온도조절을 통하여 반응이 이루어짐으로써 단시간내에 제조가 가능하고, 두께를 조절할 수 있는 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점 제조가 가능하다. 또한 양자점의 핵 표면에 껍질이 두꺼운 껍질층을 적층시킴으로써 양자점의 산화를 방지할 수 있어 광안정성이 우수한 광변환 백색 발광다이오드 제조에 제공될 수 있다.
The present invention can be produced in a short time by the reaction is made through the temperature control in one reaction vessel, it is possible to manufacture a quantum dot of the nucleus-shell structure having a thick shell that can control the thickness. In addition, it is possible to prevent the oxidation of the quantum dots by laminating a thick shell layer on the nucleus surface of the quantum dots can be provided for manufacturing a light conversion white light emitting diode having excellent light stability.
도 1은 본 발명의 실시형태에 따른 껍질의 두께가 두꺼운 핵-껍질형 양자점 제조 공정을 나타낸 모식도이다.
도 2는 본 발명의 비교예 1에 따라 제조된 양자점을 투과전자현미경으로 촬영한 사진이다.
도 3은 본 발명의 실시예 1에 따라 제조된 핵-껍질형 양자점을 투과전자현미경으로 촬영한 사진이다.
도 4는 본 발명의 실시예 2에 따라 제조된 핵-껍질형 양자점을 투과전자현미경으로 촬영한 사진이다.
도 5는 본 발명의 실시예 3에 따라 제조된 핵-껍질형 양자점을 투과전자현미경으로 촬영한 사진이다.
도 6은 비교예 1 및 실시예 1 ~ 3 에 따라 제조된 양자점의 파장에 따른 흡광도를 나타낸 그래프이다.
도 7은 비교예 1과 실시예 2에서 제조된 양자점을 이용하여 제조된 양자점 광변환 발광다이오드의 시간에 따른 발광 강도를 나타낸 그래프이다. 이 그래프에서 Y축은 시작시점에서의 양자점의 발광강도 값으로 각 시점에서 측정된 양자점의 발광강도 값으로 나눈 것을 의미한다.1 is a schematic diagram showing a process for producing a nuclear-shell quantum dot with a thick shell according to an embodiment of the present invention.
2 is a photograph taken with a transmission electron microscope of a quantum dot prepared according to Comparative Example 1 of the present invention.
3 is a photograph taken with a transmission electron microscope of a nuclear-shell quantum dot prepared according to Example 1 of the present invention.
4 is a photograph taken with a transmission electron microscope of a nuclear-shell quantum dot prepared according to Example 2 of the present invention.
5 is a photograph taken with a transmission electron microscope of a nuclear-shell quantum dot prepared according to Example 3 of the present invention.
6 is a graph showing the absorbance according to the wavelength of the quantum dots prepared according to Comparative Example 1 and Examples 1 to 3.
FIG. 7 is a graph showing luminescence intensity over time of quantum dot photoconversion light emitting diodes manufactured using quantum dots prepared in Comparative Examples 1 and 2. FIG. In this graph, the Y axis represents the light emission intensity value of the quantum dot at the starting point divided by the light emission intensity value of the quantum dot measured at each time point.
이하, 본 발명을 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은 250 ℃ ~ 350 ℃ 로 가열된 Ⅱ족 금속전구체 용액 또는 Ⅰ족과 Ⅲ족 원소의 혼합 금속전구체 용액에 Ⅵ족 전구체 용액을 첨가하되, 상기 금속전구체 용액 내의 금속전구체에 대한 Ⅵ족 전구체 용액 내의 Ⅵ족 전구체의 몰비율이 2 이상이고, 가열된 온도를 유지하면서 Ⅵ족 전구체 용액을 첨가하는 단계(단계 1);In the present invention, a Group VI precursor solution is added to a Group II metal precursor solution or a mixed metal precursor solution of Group I and Group III elements heated to 250 ° C. to 350 ° C., and a Group VI precursor solution to the metal precursor in the metal precursor solution. Adding a Group VI precursor solution while maintaining a heated temperature, wherein the molar ratio of Group VI precursor in the precursor is at least 2 (step 1);
상기 단계 1의 혼합용액을 180 ℃ ~ 240 ℃로 냉각시키는 단계(단계 2); 및Cooling the mixed solution of step 1 to 180 ° C. to 240 ° C. (step 2); And
상기 단계 2의 냉각된 혼합용액에 단계 1의 금속전구체 또는 혼합금속전구체 대비 0.5 ~ 1의 몰비율로 Ⅵ족 전구체 용액을 점적하는 단계(단계 3);Dropping a Group VI precursor solution into the cooled mixed solution of Step 2 at a molar ratio of 0.5 to 1 relative to the metal precursor or mixed metal precursor of Step 1 (Step 3);
를 포함하는 핵-껍질 구조의 양자점 제조방법을 제공한다.
It provides a method for producing a quantum dot of the nuclear-shell structure comprising a.
이하, 상기 제조방법을 단계별로 상세히 설명한다.
Hereinafter, the manufacturing method will be described step by step.
본 발명에 따른 제조방법에 있어서, 먼저 단계 1은 250 ℃ ~ 350 ℃로 가열된 Ⅱ족 금속전구체 용액 또는 Ⅰ족과 Ⅲ족 원소의 혼합 금속전구체 용액에 Ⅵ족 전구체 용액을 첨가하는 단계이다. 한편, 본 단계에서 형성되는 핵 또는 핵-껍질 구조의 양자점의 표면에는 과량으로 존재하는 금속전구체로 인하여 다량의 금속원자가 존재한다.In the manufacturing method according to the present invention, step 1 is a step of adding a Group VI precursor solution to a Group II metal precursor solution or a mixed metal precursor solution of Group I and Group III elements heated to 250 ° C. to 350 ° C. On the other hand, a large amount of metal atoms are present on the surface of the quantum dot of the nucleus or nucleus-shell structure formed in this step due to the excessive amount of the metal precursor.
상기 단계 1에서, 금속전구체 용액 내의 금속전구체와 Ⅵ족 전구체 용액내의 Ⅵ족 전구체의 몰비율은 2 이상이 되도록 하며, 바람직하게는 8이상이 되도록 하여 금속전구체가 혼합 용액 내애서 과량이 되도록 한다. 다만, 금속전구체가 Ⅵ족 전구체 대비 몰비율로 20을 초과하게 되면 금속입자가 생성되어 침전되는 문제가 생길 수 있다. 이렇게 과량으로 투입된 금속전구체는 생성되는 양자점의 표면에 존재하게 되고, 이후 단계 3에서 Ⅵ족 전구체 용액을 첨가하면 반응하여 양자점의 껍질을 형성하게 된다.
In step 1, the molar ratio of the metal precursor in the metal precursor solution and the Group VI precursor in the Group VI precursor solution is 2 or more, and preferably 8 or more so that the metal precursor is excessive in the mixed solution. However, when the metal precursor exceeds 20 in a molar ratio compared to the Group VI precursor, metal particles may be generated and precipitated. The metal precursor added in such an excess is present on the surface of the quantum dots to be produced, and then reacted to form a shell of the quantum dots by adding a Group VI precursor solution in step 3.
본 발명에 따른 핵-껍질 구조를 갖는 양자점 형성을 위해서 사용할 수 있는 금속전구체로는 Ⅱ족 금속전구체 용액 또는 Ⅰ족과 Ⅲ족 원소 혼합 금속전구체 용액을 사용할 수 있다. 상기 Ⅱ족 금속전구체로는 Ⅱ족 원소인 아연, 카드뮴, 수은, 및 납으로부터 선택되는 Ⅱ족 금속전구체를 사용할 수 있으며, 상기 전구체로서는 금속의 산화물 또는 염을 사용할 수 있다.As a metal precursor that can be used to form a quantum dot having a nuclear-shell structure according to the present invention, a group II metal precursor solution or a group I and group element mixed metal precursor solution may be used. As the Group II metal precursor, a Group II metal precursor selected from zinc, cadmium, mercury, and lead which are Group II elements can be used. An oxide or a salt of a metal can be used as the precursor.
구체적으로 상기 Ⅱ족 금속전구체로는 디메틸 아연, 디에틸 아연, 아연 카르복실레이트, 아연 아세틸아세토네이트, 아연 아이오다이드, 아연 브로마이드, 아연 클로라이드, 아연 플루오라이드, 아연 카보네이트, 아연 시아나이드, 아연 나이트레이트, 아연 옥사이드, 아연 퍼옥사이드, 아연 퍼클로레이트, 아연 설페이트, 디메틸 카드뮴, 디에틸 카드뮴, 카드뮴 옥사이드, 카드뮴 카보네이트, 카드뮴 아세테이트 디하이드레이트, 카드뮴 아세틸아세토네이트, 카드뮴 플루오라이드, 카드뮴 클로라이드, 카드뮴 아이오다이드, 카드뮴 브로마이드, 카드뮴 퍼클로레이트, 카드뮴 포스파이드, 카드뮴 나이트레이트, 카드뮴 설페이트, 카드뮴 카르복실레이트, 수은 아이오다이드, 수은 브로마이드, 수은 플루오라이드, 수은 시아나이드, 수은 나이트레이트, 수은 퍼클로레이트, 수은 설페이트, 수은 옥사이드, 수은 카보네이트, 수은 카르복실레이트, 디메틸 납, 디에틸 납, 납 카르복실레이트, 납 아세틸아세토네이트, 납 아이오다이드, 납 브로마이드, 납 클로라이드, 납 플루오라이드, 납 카보네이트, 납 시아나이드, 납 나이트레이트, 납 옥사이드, 납 퍼옥사이드, 납 퍼클로레이트 및 납 설페이트로 이루어진 군에서 선택될 수 있다.Specifically, the Group II metal precursors include dimethyl zinc, diethyl zinc, zinc carboxylate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, and zinc nitrate. Latex, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, dimethyl cadmium, diethyl cadmium, cadmium oxide, cadmium carbonate, cadmium acetate dihydrate, cadmium acetylacetonate, cadmium fluoride, cadmium chloride, cadmium iodide, Cadmium bromide, cadmium perchlorate, cadmium phosphide, cadmium nitrate, cadmium sulfate, cadmium carboxylate, mercury iodide, mercury bromide, mercury fluoride, mercury cyanide, mercury nitrate, mercury nitrate Chlorate, mercury sulfate, mercury oxide, mercury carbonate, mercury carboxylate, dimethyl lead, diethyl lead, lead carboxylate, lead acetylacetonate, lead iodide, lead bromide, lead chloride, lead fluoride, lead It may be selected from the group consisting of carbonate, lead cyanide, lead nitrate, lead oxide, lead peroxide, lead perchlorate and lead sulfate.
또한 Ⅰ족과 Ⅲ족 원소 혼합 금속전구체는 Ⅰ족 금속전구체와 Ⅲ족 금속전구체의 혼합물을 의미한다. Ⅰ족 원소로서 리튬, 나트륨, 칼륨, 루비듐 및 세슘 금속전구체와 Ⅲ족 원소인 알루미늄, 갈륨, 인듐 및 탈륨 금속전구체를 혼합하여 사용할 수 있다.In addition, the group I and group element mixed metal precursor means a mixture of a group I metal precursor and a group III metal precursor. Lithium, sodium, potassium, rubidium and cesium metal precursors as group I elements and aluminum, gallium, indium and thallium metal precursors as group III elements can be mixed and used.
상기 Ⅰ족 또는 Ⅲ족의 금속전구체로는 금속의 산화물, 수산화물, 할라이드, 알콕사이드, 포스페이트, 나이트레이트, 설페이트 등을 사용할 수 있다.
Examples of the metal precursors of the group I or group III may include oxides, hydroxides, halides, alkoxides, phosphates, nitrates, sulfates, and the like of metals.
상기 금속전구체 용액은 금속 전구체 외에 분산제를 더 포함할 수 있다.The metal precursor solution may further include a dispersant in addition to the metal precursor.
분산제는 양자점이 형성됨에 있어서 입자간에 서로 응집이 되는 것을 막고, 입자의 성장을 조절하여 과도하게 커지는 것을 막는다. 상기 지방산은 분산제로서 양자점 제조시 금속 분말들을 고르게 분산시키기 위하여 사용되며, 금속의 성장을 조절하는 역할을 한다.The dispersing agent prevents agglomeration between particles in forming quantum dots, and controls growth of particles to prevent excessive growth. The fatty acid is used as a dispersant to evenly disperse the metal powders in the production of quantum dots, and serves to control the growth of the metal.
한편, 분산제는 금속전구체 대비 2 ~ 5 배의 범위로 사용할 수 있다.On the other hand, the dispersant may be used in a range of 2 to 5 times compared to the metal precursor.
상기 분산제로는 C8 ~ C24 포화 또는 불포화 지방산 또는 C8 ~ C16의 모노알킬아민, 다이알킬아민, 또는 트리알킬아민, 또는 C2 ~ C18의 모노알킬포스포닉산, 다이알킬포스포닉산, 트리알킬포스포닉산, 테트라알킬포스포닉산을 사용할 수 있다. The dispersant may be a C 8 to C 24 saturated or unsaturated fatty acid or C 8 to C 16 monoalkylamine, dialkylamine, or trialkylamine, or C 2 to C 18 monoalkylphosphonic acid, dialkylphospho Nickel acids, trialkylphosphonic acids, tetraalkylphosphonic acids can be used.
구체적으로는 스테아릭산, 올레산, 옥틸아민, 헥사데실아민, 헥실포스포닉산, 옥틸포스포닉산, 옥타데실포스포닉산, 테트라데실포스포닉산 등을 사용할 수 있다.Specifically, stearic acid, oleic acid, octylamine, hexadecylamine, hexyl phosphonic acid, octyl phosphonic acid, octadecyl phosphonic acid, tetradecyl phosphonic acid, etc. can be used.
상기 단계 1은 고온반응에서 산화현상을 방지하고, 반응활성이 없는 분위기를 유지하기 위하여 비활성 기체 분위기에서 반응을 진행시키는 것이 바람직하다. In the step 1, it is preferable to proceed the reaction in an inert gas atmosphere in order to prevent oxidation in a high temperature reaction and maintain an atmosphere in which there is no reaction activity.
비활성기체로는 질소 가스, 아르곤 가스, 네온 가스, 헬륨 가스 등을 사용할 수 있다. 만약 비활성 분위기에서 반응을 진행시키지 않을 경우 용액 내에서 산화반응이 발생하고 용매의 일부가 연소되는 문제점이 발생할 수 있기 때문에 상기의 비활성 분위기는 단계 3까지 유지하는 것이 바람직하다. 비활성 분위기는 단계 3까지 유지하는 것이 바람직하다.
Nitrogen gas, argon gas, neon gas, helium gas, etc. may be used as the inert gas. If the reaction is not carried out in an inert atmosphere, it is preferable to maintain the inert atmosphere until step 3 because oxidation may occur in the solution and a part of the solvent may be burned. The inert atmosphere is preferably maintained up to step 3.
상기 금속전구체 용액에 Ⅵ족 전구체 용액을 첨가함에 있어서, 상기 금속전구체 용액은 처음 준비된 상태의 가열 온도를 유지하면서 첨가하는 것이 바람직하다. 실시예로서, 첨가를 위한 금속전구체 용액의 온도는 250 ℃ ~ 350 ℃ 이며, 바람직하게는 250 ℃ ~ 320 ℃로 가열한다.In adding the Group VI precursor solution to the metal precursor solution, the metal precursor solution is preferably added while maintaining the heating temperature of the first prepared state. By way of example, the temperature of the metal precursor solution for addition is from 250 ° C. to 350 ° C., preferably from 250 ° C. to 320 ° C.
상기 가열된 금속전구체 용액의 준비는 금속전구체와 지방산을 혼합한 다음, 유기용매에 용해시켜 가열함으로써 제조할 수 있다.Preparation of the heated metal precursor solution may be prepared by mixing a metal precursor and a fatty acid, then dissolving it in an organic solvent and heating it.
상기 유기용매는 고온에서 쉽게 기화되지 않는 물질로 선택하며, 파라핀이나 C6-18 알켄을 사용할 수 있으며, C6-18 알켄으로는 1-옥타데센을 사용할 수 있다. 상기 유기용매는 Ⅵ족 전구체 용액의 제조에도 동일하게 사용할 수 있다. 상기 유기용매는 그 점도에 따라서 금속전구체 용액에 Ⅵ족 전구체 용액을 주입할 때 그 속도를 조절하는 역할을 한다.
The organic solvent may be selected as a material that is not easily vaporized at a high temperature, paraffin or C 6-18 alkenes may be used, and C 6-18 alkenes may be 1-octadecene. The organic solvent can be similarly used for the preparation of the Group VI precursor solution. The organic solvent plays a role of controlling the speed when the Group VI precursor solution is injected into the metal precursor solution according to its viscosity.
상기 단계 1에 있어서, Ⅵ족 전구체 용액은 Ⅵ족전구체에 유기 포스핀계 화합물을 포함할 수 있다. 유기 포스핀계 화합물은 C2 ~ C18 트리알킬포스핀, 또는 C2 ~ C18 트리알킬포스핀옥사이드를 사용할 수 있으며, 구체적으로는 트리부틸포스핀, 트리옥틸포스핀, 트리부틸포스핀옥사이드 또는 트리옥틸포스핀옥사이드를 사용할 수 있다.In step 1, the Group VI precursor solution may include an organic phosphine compound in the Group VI precursor. The organic phosphine-based compound may be C 2 ~ C 18 trialkylphosphine, or C 2 ~ C 18 trialkyl phosphine oxide, specifically tributyl phosphine, trioctyl phosphine, tributyl phosphine oxide or Trioctylphosphine oxide can be used.
상기 유기 포스핀계 화합물은 Ⅵ족 전구체 대비하여 1 ~ 10배의 범위로 사용할 수 있다. 상기 유기 포스핀계 화합물은 양자점의 표면에 배위하여 양자점 크기의 성장 속도를 조절하는 역할을 한다.The organic phosphine compound may be used in a range of 1 to 10 times compared to the Group VI precursor. The organic phosphine-based compound serves to coordinate the surface of the quantum dots to control the growth rate of the quantum dot size.
상기 Ⅵ족 전구체 용액은 Ⅵ족 전구체에 유기 포스핀계 화합물을 혼합시킨 다음, 유기용매에 용해시켜 제조할 수 있다. 유기용매로는 앞서서 금속전구체 용액을 제조하는 과정에서 사용한 유기용매를 사용할 수 있으며, 서로 동일하거나 다른 유기용매를 사용하는 것도 가능하다. The Group VI precursor solution may be prepared by mixing an organic phosphine compound with a Group VI precursor and then dissolving it in an organic solvent. As the organic solvent, the organic solvent used in the process of preparing the metal precursor solution may be used, and the same or different organic solvents may be used.
상기 Ⅵ족 전구체용액 내에 포함되는 Ⅵ족 전구체는 산소, 황, 셀레늄, 텔루륨 및 폴로늄으로 이루어지는 군에서 선택되는 1종 이상의 전구체를 사용할 수 있으며 바람직하게는 황, 셀레늄, 텔루륨으로 구성된 칼코겐족 원소 중에서 선택 할 수 있다.The Group VI precursor contained in the Group VI precursor solution may be one or more precursors selected from the group consisting of oxygen, sulfur, selenium, tellurium, and polonium, and preferably chalcogenide elements composed of sulfur, selenium, and tellurium. You can choose from.
상기 Ⅵ족 전구체는 VI족 원소의 분말이나 VI족 원소를 포함하는 유기화합물을 사용할 수 있으며, 일반적으로는 분말을 사용한다. 유기화합물로는 알킬싸이올, 트리알킬포스핀 설파이드, 트리알케닐포스핀 설파이드 등이 사용될 수 있다. 상기 알킬은 C2 ~ C12의 알킬이 될 수 있다.
As the Group VI precursor, an organic compound containing a powder of a Group VI element or a Group VI element may be used, and powder is generally used. As the organic compound, alkylthiol, trialkylphosphine sulfide, trialkenylphosphine sulfide, or the like may be used. The alkyl may be C 2 ~ C 12 alkyl.
본 단계 1에서 첨가되는 VI족 전구체 용액에 있어서, VI족 전구체는 VI족 원소에서 선택되는 1종 또는 2종 이상의 혼합 VI족 전구체를 사용할 수 있다.In the Group VI precursor solution added in Step 1, the Group VI precursor may use one or two or more mixed Group VI precursors selected from Group VI elements.
1종을 사용하는 경우에는 양자점의 핵이 단계 1 및 단계 2를 통하여 형성되며, 2종의 혼합 전구체를 사용하는 경우에는 핵과 껍질을 갖거나 혼합된 2종의 VI족 원소가 하나는 내부에서 외부로, 다른 하나는 외부에서 내부로 농도 구배를 갖는 양자점의 핵이 형성될 수 있다.
If one species is used, the nuclei of the quantum dots are formed through steps 1 and 2, and if two species of mixed precursors are used, one of the two group VI elements having a nucleus and a shell or mixed therein is internally external. As the other, the nucleus of the quantum dots having a concentration gradient from the outside to the inside can be formed.
본 발명의 일 실시예에서는 2종의 혼합 VI족 전구체 용액을 사용하여 농도구배를 가지는 양자점의 핵을 형성하고 있다. 혼합되는 2종의 VI족 전구체는 반응성에 따라서 하나는 내부에서 그 농도가 높고, 외부에는 다른 하나의 농도가 더 높게 형성되는 양자점이 형성되게 된다.
In one embodiment of the present invention, two kinds of mixed Group VI precursor solutions are used to form nuclei of quantum dots having a concentration gradient. According to the reactivity of the two kinds of Group VI precursors to be mixed, quantum dots are formed at one concentration higher inside and the other concentration higher at the outside.
본 발명의 다른 실시예에서, 상기 Ⅵ족 전구체 용액을 구성하는 VI족 전구체는 제조하고자 하는 양자점의 핵을 구성하는 VI족 전구체와 껍질을 구성하는 VI족전구체의 혼합일 수 있다. 이 때, 2종의 Ⅵ족 전구체를 포함하는 Ⅵ족 전구체는 핵을 구성하는 VI족 원소 1몰에 대해서 껍질을 구성하는 족 원소 1 ~ 10몰을 포함할 수 있다. 1몰 미만을 사용하는 경우 껍질 구성이 거의 이루어지지 못하는 문제가 있으며, 10몰을 초과하는 경우에는 형성되는 핵의 크기가 너무 작아서 가시광선 발광에 적합하지 않게 되는 문제가 있을 수 있다.
In another embodiment of the present invention, the Group VI precursor constituting the Group VI precursor solution may be a mixture of the Group VI precursor constituting the nucleus of the quantum dots to be prepared and the Group VI precursor constituting the shell. In this case, the Group VI precursor including two kinds of Group VI precursors may include 1 to 10 mol of the group elements constituting the shell with respect to 1 mol of the Group VI elements constituting the nucleus. When less than 1 mole is used, there is a problem that the shell composition is hardly achieved, and when it exceeds 10 moles, the size of the nucleus formed may be too small to be suitable for visible light emission.
이하, 단계 2에 대해서 설명한다.Hereinafter, step 2 will be described.
상기 단계 2는 단계 1에서의 혼합용액을 냉각하는 단계이며 일 실시예로는 180 ℃ ~ 240 ℃로 냉각시킬 수 있고, 바람직하게는 200 ℃ ~ 230 ℃로 냉각시킬 수 있다. 180 ℃보다 낮게 냉각시키는 경우 침전이 발생하는 문제가 발생할 수 있으며, 240 ℃보다 높게 냉각시키는 경우에는 단계 1에서 제조된 양자점 내부의 조성이 고온에서의 확산현상으로 인하여 핵-껍질 형태의 조성분포를 가지지 못하고 균질한 조성을 가지게 되어 발광특성이 저하되는 문제가 발생할 수 있다.Step 2 is a step of cooling the mixed solution in step 1 and in one embodiment can be cooled to 180 ℃ ~ 240 ℃, preferably 200 ℃ to 230 ℃ it can be cooled. If the temperature is lower than 180 ° C, precipitation may occur. If the temperature is lower than 240 ° C, the composition inside the quantum dot prepared in step 1 may cause a nuclear-shell type composition distribution due to diffusion at high temperature. It may not have a homogeneous composition may cause a problem that the luminous properties are lowered.
상기 단계 2에서는 반응온도를 낮춤으로써, 단계 1에서 생성된 금속 원자가 노출된 양자점의 입성장을 방지하여 입자가 과도하게 커짐으로써 생성되는 양자점 크기의 불균일을 방지할 수 있다.
In the step 2, by lowering the reaction temperature, it is possible to prevent particle growth of the quantum dots exposed by the metal atoms generated in step 1 to prevent the non-uniformity of the quantum dot size generated by excessively large particles.
다음으로, 상기 단계 3은 상기 단계 2에서 냉각된 혼합용액에 Ⅵ족 전구체 용액을 점적하여 양자점의 껍질을 형성시키는 단계이다. 본 단계에서의 Ⅵ족 전구체용액의 첨가는 될 수 있는대로 천천히 하는 것이 바람직하며, 일반적으로 점적하여 수행된다. Next, step 3 is a step of forming a shell of the quantum dots by dropping the Group VI precursor solution in the mixed solution cooled in the step 2. The addition of the Group VI precursor solution in this step is preferably slowed down as much as possible, and is generally carried out by dropping.
구체적으로는 단계 2에서 냉각된 혼합용액에 금속전구체 대비 첨가하고자 하는 Ⅵ족 전구체가 0.5 ~ 1의 몰비율이 되도록 Ⅵ족 전구체 용액을 점적시킨다. 첨가하는 Ⅵ족 전구체 용액 내의 Ⅵ족 전구체는 단계 1에서 첨가한 Ⅵ족 전구체 용액 내의 Ⅵ족 전구체와 합한 양이 단계 1의 금속전구체 용액 내의 금속의 양과 동일한 수준이면 된다.Specifically, the Group VI precursor solution is added dropwise to the mixed solution cooled in Step 2 such that the Group VI precursor to be added to the metal precursor is in a molar ratio of 0.5 to 1. The amount of the Group VI precursor in the Group VI precursor solution to be added may be equal to the amount of the metal in the metal precursor solution of Step 1 in combination with the Group VI precursor in the Group VI precursor solution added in Step 1.
본 발명의 일 실시예로서 0.5 ~ 1의 몰비율이 되도록 첨가하게 되며, 0.5몰 미만이 되면, 미반응의 금속전구체가 남게 되고, 1몰 초과로 투입하게 되면, 금속전구체가 이미 다 반응하여 미반응의 Ⅵ족 전구체가 남게 된다.As an embodiment of the present invention is added so as to have a molar ratio of 0.5 to 1, when less than 0.5 mole, the unreacted metal precursor remains, and when added to more than 1 mole, the metal precursor is already reacted The Group VI precursor of the reaction remains.
단계 3에서 첨가되는 Ⅵ족 전구체 용액은 단계 1에서 첨가되는 Ⅵ족 전구체 용액과 Ⅵ족 전구체가 다르게 된다. 즉, 핵-껍질 구조를 갖는 양자점에 있어서, 핵의 구성 성분인 Ⅵ족 원소와 껍질의 구성 성분인 Ⅵ족 원소가 다름으로써 핵과 껍질 사이에 에너지 밴드갭의 차이가 발생할 수 있다.
The Group VI precursor solution added in Step 3 is different from the Group VI precursor solution added in Step 1. That is, in a quantum dot having a nucleus-shell structure, a difference in energy band gap may occur between the nucleus and the shell due to the difference between the Group VI element, which is a constituent of the nucleus, and the Group VI element, which is a constituent of the shell.
이렇게 하여 최종적으로 제조되는 양자점의 껍질은 종래의 방법으로 제조되는 0.5 ~ 1 nm 두께에 비해 두꺼운 2 ~ 3 nm 정도의 두꺼운 껍질을 갖는 핵-껍질구조의 양자점을 제조할 수 있다.
In this way, the shell of the finally produced quantum dot can be prepared a nuclear-shell structured quantum dot having a thick shell of about 2 ~ 3 nm thick compared to the 0.5 ~ 1 nm thickness prepared by the conventional method.
상기 단계 3에서 제조된 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점은 세정과정을 거쳐서 발광다이오드의 소재로서 응용 할 수 있다.
The quantum dots of the thick-shelled nucleus-shell structure prepared in step 3 may be applied as a material of the light emitting diode through a cleaning process.
또한 본 발명은 상기의 제조방법에 따라 제조되는 양자점을 무기물 복합입자와 결합하여 광변환 발광다이오드에 사용할 수 있으며, 상기 무기물로서는 SiO2, TiO2, ZrO2, ZnO, ITO 및 SnO로 구성되는 군에서 선택된 어느 하나를 사용할 수 있다.In addition, the present invention can be used in the photoconversion light emitting diode by combining the quantum dots prepared according to the above production method with the inorganic composite particles, the inorganic material group consisting of SiO 2 , TiO 2 , ZrO 2 , ZnO, ITO and SnO You can use any one selected from.
상기 제조방법에 따라서, 핵-껍질 구조의 양자점을 제공하는 경우, 그 껍질의 두께를 조절할 수 있으며, 따라서 본 발명은 핵-껍질 구조의 양자점에 있어서 그 껍질의 두께를 두껍게 하는 방법을 제공한다.
According to the above production method, in the case of providing a quantum dot of the nucleus-shell structure, the thickness of the shell can be adjusted, and thus the present invention provides a method of thickening the thickness of the shell in the quantum dot of the nucleus-shell structure.
<비교예 1> ≪ Comparative Example 1 &
금속전구체로서 카드뮴 옥사이드 32 mmol과 올레산 32 mL를 1-옥타데센 50 mL 에 혼합한 후 아르곤 가스 분위기 하에서 300 까지 가열하여 금속전구체 용액을 제조하였다. As a metal precursor, 32 mmol of cadmium oxide and 32 mL of oleic acid were mixed with 50 mL of 1-octadecene, and heated to 300 under an argon gas atmosphere to prepare a metal precursor solution.
또한 셀레늄 분말 1 mmol과 황 분말 3 mmol을 트리옥틸포스핀 8 mmol에 혼합한 후 용매로서 1-옥타데센 10 mL에 용해시켜 Ⅵ족 전구체 용액을 제조하였다.In addition, 1 mmol of selenium powder and 3 mmol of sulfur powder were mixed with 8 mmol of trioctylphosphine, and then dissolved in 10 mL of 1-octadecene as a solvent to prepare a Group VI precursor solution.
상기에서 제조된 Ⅵ족 전구체 용액을 주사기에 충진하여 300 ℃로 유지되고 있는 상기 금속전구체 용액에 재빨리 주입한 후 5분간 300 ℃로 반응시켰고 그 후 반응기의 온도를 225 ℃로 냉각시켰다. The Group VI precursor solution prepared above was filled into a syringe and quickly injected into the metal precursor solution maintained at 300 ° C., and then reacted at 300 ° C. for 5 minutes, and then the reactor temperature was cooled to 225 ° C.
상기 반응에서 생성된 양자점을 용매로부터 분리하고 세정하는 단계를 거쳐 양자점 제조반응을 완료하였다.
The quantum dot produced in the reaction was separated from the solvent and washed to complete the quantum dot production reaction.
<실시예 1>≪ Example 1 >
금속전구체로서 카드뮴 옥사이드 32 mmol과 올레산 32 mL를 1-옥타데센 50 mL 에 혼합한 후 아르곤 가스 분위기 하에서 300 ℃까지 가열하여 금속전구체 용액을 제조하였다. As a metal precursor, 32 mmol of cadmium oxide and 32 mL of oleic acid were mixed with 50 mL of 1-octadecene, and then heated to 300 ° C. under an argon gas atmosphere to prepare a metal precursor solution.
또한 셀레늄 분말 1 mmol과 황 분말 3 mmol을 트리옥틸포스핀 8 mmol에 혼합한 후 용매로서 1-옥타데센 10 mL에 용해시켜 핵-껍질 구조의 양자점 제조를 위한 족 전구체 용액을 제조하였다. In addition, 1 mmol of selenium powder and 3 mmol of sulfur powder were mixed with 8 mmol of trioctylphosphine, and then dissolved in 10 mL of 1-octadecene as a solvent to prepare a group precursor solution for preparing a quantum dot having a nuclear-shell structure.
상기에서 제조된 Ⅵ족 전구체 용액을 주사기에 충진하여 300 ℃로 유지되고 있는 상기 금속전구체 용액에 재빨리 주입한 후 5분간 300 ℃로 반응시켰고 그 후 반응기의 온도를 225 ℃로 냉각시켰다. The Group VI precursor solution prepared above was filled into a syringe and quickly injected into the metal precursor solution maintained at 300 ° C., and then reacted at 300 ° C. for 5 minutes, and then the reactor temperature was cooled to 225 ° C.
또한 황 분말 8 mmol을 트리옥틸포스핀 8 mmol에 혼합한 후 용매로서 1-옥타데센 10 mL에 용해시켜 껍질 형성을 위한 Ⅵ족 전구체 용액을 제조하였다. 다음으로, 상기에서 냉각된 양자점 용액에 Ⅵ족 전구체 용액을 점적한 뒤 30분 동안 반응시켜 추가적으로 양자점 표면에 껍질을 형성시켰다.In addition, 8 mmol of sulfur powder was mixed with 8 mmol of trioctylphosphine and dissolved in 10 mL of 1-octadecene as a solvent to prepare a Group VI precursor solution for shell formation. Next, a Group VI precursor solution was added to the cooled quantum dot solution and reacted for 30 minutes to form a shell on the surface of the quantum dot.
이후, 상기 반응에서 생성된 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 용매로부터 분리하고 세정하는 단계를 거쳐 본 발명에 따른 핵-껍질 구조의 양자점을 제조하였다.
Thereafter, the quantum dots of the nucleus-shell structure according to the present invention were prepared by separating and washing the quantum dots of the nucleus-shell structure having the thick husk produced in the reaction from a solvent.
<실시예 2> <Example 2>
냉각 후 점적하여 첨가하는 Ⅵ족 전구체 용액의 제조에서 황 분말을 12 mmol 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 제조하였다.
A quantum dot having a thick-shelled nucleus-shell structure was prepared in the same manner as in Example 1 except that 12 mmol of sulfur powder was used to prepare a Group VI precursor solution added after cooling.
<실시예 3> <Example 3>
냉각 후 점적하여 첨가하는 Ⅵ족 전구체 용액의 제조에서 황 분말을 24 mmol 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 제조하였다.
A quantum dot having a thick-shelled nucleus-shell structure was prepared in the same manner as in Example 1 except that 24 mmol of sulfur powder was used to prepare a Group VI precursor solution added after cooling.
<실험예 1> 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점의 형상 분석Experimental Example 1 Shape Analysis of Quantum Dots of Nuclear-Shell Structure with Thick Shells
상기 비교예 1에서 제조된 양자점과 실시예 1 ~ 3 에서 제조된 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점의 형상을 투과전자현미경 (제조사: JEOL, 모델명: JEM-2010F)을 이용하여 분석하였다.The shape of the quantum dots of the quantum dots prepared in Comparative Example 1 and the nucleus-shell structure prepared in Examples 1 to 3 was analyzed using a transmission electron microscope (manufacturer: JEOL, model name: JEM-2010F).
먼저 비교예 1과 실시예 1 ~ 3에서 제조된 양자점을 투과전자현미경 분석에 적절한 시편으로 전처리하였다. 전처리 방법으로서 상기 비교예 1과 실시예 1 ~ 3에서 제조된 양자점을 톨루엔에 각각 분산시킨 후 탄소로 코팅된 구리망에 상기 톨루엔에 분산시킨 양자점 용액을 1 ~ 2방울 떨어뜨린 후 건조하여 분석용 시편을 준비하였다.First, the quantum dots prepared in Comparative Example 1 and Examples 1 to 3 were pretreated with a specimen suitable for transmission electron microscope analysis. As a pretreatment method, the quantum dots prepared in Comparative Example 1 and Examples 1 to 3 were dispersed in toluene, respectively, and 1 to 2 drops of the quantum dot solution dispersed in toluene were dispersed in carbon coated copper mesh for analysis. The specimen was prepared.
상기에서 제조한 시편을 투과전자현미경으로 촬영하여 양자점의 형상을 파악하였으며 그 결과를 도 2 ~ 도 5에 나타내었다.
The specimen prepared above was taken with a transmission electron microscope to determine the shape of the quantum dot, and the results are shown in FIGS. 2 to 5.
먼저 도 2에서의 양자점은 단계 2에서의 냉각 반응 후에 별도로 Ⅵ족 전구체 용액을 첨가하지 않고 제조하는 핵-껍질 구조의 양자점으로 그 크기는 평균적으로 4 nm를 나타내었다.First, the quantum dot in FIG. 2 is a quantum dot of a nuclear-shell structure prepared without adding a Group VI precursor solution separately after the cooling reaction in step 2, and the size thereof was 4 nm on average.
상기 실시예 1에서 제조한 양자점은 추가적으로 황 분말 8 mmol이 더하여진 Ⅵ족 전구체 용액을 양자점 표면에 반응시킴으로써 평균적으로 5 nm의 크기를 가지는 양자점을 제조 할 수 있었다.The quantum dot prepared in Example 1 was able to prepare a quantum dot having an average size of 5 nm by reacting the Group VI precursor solution added with 8 mmol of sulfur powder on the quantum dot surface.
상기 실시예 2에서 제조한 양자점은 추가적으로 황 분말 12 mmol이 더하여진 Ⅵ족 전구체 용액을 양자점 표면에 반응시킴으로써 평균적으로 5 nm의 크기를 가지는 양자점을 제조 할 수 있었다.The quantum dot prepared in Example 2 was able to prepare a quantum dot having an average size of 5 nm by reacting the Group VI precursor solution added with 12 mmol of sulfur powder on the quantum dot surface.
또한 상기 실시예 3에서는 추가적으로 황 분말 24 mmol이 더하여진 Ⅵ족 전구체 용액을 양자점 표면에 반응시킴으로써 평균적으로 5 nm의 크기를 가지는 양자점을 제조 할 수 있었다.
In addition, in Example 3, a quantum dot having an average size of 5 nm could be prepared by reacting a Group VI precursor solution added with 24 mmol of sulfur powder to the quantum dot surface.
결국, 껍질에 해당하는 두께가 냉각 후 첨가하는 Ⅵ족 전구체의 양에 따라서 증가하는 것을 확인할 수 있었으며, 이는 껍질의 두께를 조절할 수 있음을 의미하였다. 따라서, 본 발명의 제조방법에 따라서 기존에 제조되는 핵-껍질구조의 양자점보다 두꺼운 껍질을 갖는 양자점을 제조할 수 있을 것이라 기대된다.
As a result, it was confirmed that the thickness corresponding to the shell increases with the amount of Group VI precursor added after cooling, which means that the thickness of the shell can be adjusted. Therefore, it is expected that according to the manufacturing method of the present invention, it is possible to produce a quantum dot having a thicker shell than the quantum dot of the nucleus-shell structure previously manufactured.
<실험예 2> 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점의 흡광 스펙트럼 분석Experimental Example 2 Analysis of Absorption Spectrum of Quantum Dots with Thick Shell-Nuclear Shell Structure
상기 비교예 1에서 제조된 양자점과 실시예 1 ~ 3 에서 제조된 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점의 흡광 스펙트럼을 자외선/가시광선/근적외선 분광계(제조사: Varian, 모델명: Cary 5000)를 이용하여 분석하였다.
Absorption spectra of the quantum dots of the quantum dots prepared in Comparative Example 1 and the nucleus-shell structure prepared in Examples 1 to 3 using an ultraviolet / visible / near infrared spectrometer (manufacturer: Varian, model name: Cary 5000) And analyzed.
측정용액으로서 상기 비교예 1에서 제조된 양자점과 실시예 1 ~ 3에서 제조된 양자점을 분산용매에 분산시킨 후, 두께 1cm의 석영 큐벳(Cuvette)에 넣은 후 흡광도를 측정하여 파장 300 nm ~ 700 nm 영역까지의 흡광스펙트럼을 얻었다.
As a measurement solution, the quantum dots prepared in Comparative Example 1 and the quantum dots prepared in Examples 1 to 3 were dispersed in a dispersion solvent, placed in a quartz cuvette having a thickness of 1 cm, and then absorbance was measured to measure a wavelength of 300 nm to 700 nm. Absorbance spectrum up to the region was obtained.
도 6의 흡수 스펙트럼은 상기 비교예 1 및 실시예 1 ~ 3 에 따라 제조된 양자점의 파장에 따른 흡광도를 나타낸 그래프이다. 도 6에서도 알 수 있듯이 비교예 1의 양자점에 비하여 본 발명인 실시예 1 ~ 3에서 제조된 양자점은 짧은 파장 영역에서도 매우 높은 흡광도를 나타냄을 알 수 있었고, 상기의 흡광스펙트럼으로부터 껍질의 두께가 두꺼워졌음을 확인 할 수 있었다.
6 is a graph showing absorbance according to the wavelength of the quantum dots prepared according to Comparative Example 1 and Examples 1 to 3 above. As can be seen from FIG. 6, the quantum dots prepared in Examples 1 to 3 of the present invention showed very high absorbance even in a short wavelength range, and the thickness of the shell was thickened from the absorbance spectrum. Could check.
<실험예 3> 두꺼운 껍질을 가지는 핵-껍질 구조의 양자점을 이용한 광변환 발광다이오드의 발광강도 분석Experimental Example 3 Analysis of Luminescence Intensity of Photoconversion Light Emitting Diode Using Quantum Dot of Nuclear-Heel Structure with Thick Shell
비교예 1과 실시예 2에 따라 제조된 양자점을 이용하여 광변환 발광다이오드를 제조하고 시간에 따른 밝기 변화를 측정 및 비교하였다.Photo conversion light emitting diodes were manufactured by using quantum dots prepared according to Comparative Example 1 and Example 2, and the brightness change with time was measured and compared.
먼저 비교예 1과 실시예 2에 따라 제조된 양자점을 이용하여 광변환 발광다이오드를 제작하였다. 상기 비교예 1과 실시예 2에 따라 제조된 양자점을 실리콘 인캡슐런트 수지(제조사: Dow Corning, 모델명: OE-6630)와 중량비로서 1:20의 비율로 혼합한 다음 진공 중에서 기포를 제거하고 테프론 수지로 제조된 반구형의 몰드에 중입한 후 청색발광다이오드(제조사: Perkin-Elmer, 모델명: ACULED)를 몰드 상부에 부착하고 150 ℃에서 2시간 가량 반응시켜 양자점 광변환 발광다이오드를 제조하였다.First, a photoconversion light emitting diode was manufactured using quantum dots prepared according to Comparative Example 1 and Example 2. Quantum dots prepared according to Comparative Example 1 and Example 2 were mixed with a silicon encapsulant resin (manufacturer: Dow Corning, model name: OE-6630) in a ratio of 1:20 by weight, and then bubbles were removed in vacuo and Teflon was removed. After loading into a hemispherical mold made of resin, a blue light emitting diode (manufacturer: Perkin-Elmer, model name: ACULED) was attached to the upper part of the mold, and reacted at 150 ° C. for about 2 hours to prepare a quantum dot photoconversion light emitting diode.
상기에서 제조한 양자점 발광다이오드에 100 mA의 전류를 공급하고 Gigaoptics사의 발광다이오드분석기를 사용하여 시간에 따른 양자점 광변환 발광다이오드의 발광 강도 변화를 분석하였다. A 100 mA current was supplied to the quantum dot light emitting diodes prepared above, and the change in emission intensity of the quantum dot photoelectric conversion light emitting diodes was analyzed using a light emitting diode analyzer of Gigaoptics.
도 7은 비교예 1과 실시예 2에서 제조된 양자점을 이용하여 제조된 양자점 광변환 발광다이오드의 시간에 따른 발광 강도 변화를 나타낸 그래프이다. 도 7에서 볼 수 있듯이 처음 방출되는 빛의 세기를 1.0으로 하였을 때 비교예 1에서 제조된 양자점을 이용한 광변환 발광다이오드의 경우 20분 뒤 발광 효율이 약 50 %정도로 급격히 감소하였으나, 실시예 2에서 제조된 양자점을 이용한 광변환 발광다이오드의 경우에는 80분 후에도 처음 발광 효율의 80 %를 유지하여 광안정성이 향상된 발광다이오드가 제작되었음을 알 수 있었다.FIG. 7 is a graph showing changes in luminescence intensity over time of quantum dot photoconversion light emitting diodes manufactured using quantum dots prepared in Comparative Examples 1 and 2. FIG. As shown in FIG. 7, the light emitting efficiency of the photoconversion light emitting diode using the quantum dot manufactured in Comparative Example 1 was rapidly decreased to about 50% after 20 minutes when the intensity of light emitted first was 1.0, but in Example 2 In the case of the photoconversion light emitting diode using the manufactured quantum dots, it was found that the light emitting diode having improved light stability was maintained after maintaining 80% of the light emission efficiency even after 80 minutes.
따라서 상기 실험예 3을 바탕으로 두꺼운 껍질을 가지는 핵-껍질 양자점은 장시간 사용에도 밝기 저하가 적은 광안정성을 가짐을 입증할 수 있었다.Therefore, the nucleus-shell quantum dot having a thick shell based on Experimental Example 3 was able to prove that it has light stability with low brightness deterioration even for long time use.
Claims (13)
상기 단계 1의 혼합용액을 180 ℃ ~ 240 ℃로 냉각시키는 단계(단계 2); 및
상기 단계 2의 냉각된 혼합용액에 단계 1의 금속전구체 또는 혼합금속전구체 대비 0.5 ~ 1의 몰비율로 Ⅵ족 전구체 용액을 점적하는 단계(단계 3);
를 포함하는 핵-껍질 구조의 양자점 제조방법.
A Group VI precursor solution is added to a Group II metal precursor solution or a mixed metal precursor solution of Group I and Group III elements heated to 250 ° C. to 350 ° C., but in the Group VI precursor solution to the metal precursor in the metal precursor solution. Adding a Group VI precursor solution while maintaining a heated temperature, wherein the molar ratio of the precursor is at least 2 (step 1);
Cooling the mixed solution of step 1 to 180 ° C. to 240 ° C. (step 2); And
Dropping a Group VI precursor solution into the cooled mixed solution of Step 2 at a molar ratio of 0.5 to 1 relative to the metal precursor or mixed metal precursor of Step 1 (Step 3);
Quantum dot manufacturing method of the nuclear-shell structure comprising a.
The method of claim 1, wherein the metal precursor solution of the metal precursor and C 8 ~ C 24 saturated or unsaturated fatty acids or C 8 ~ C 16 monoalkylamine, dialkylamine, or trialkylamine, or C 2 ~ C 18 Preparation of a quantum dot of the nucleus-shell structure, characterized in that it further comprises a mixture of monoalkyl phosphonic acid, dialkyl phosphonic acid, trialkyl phosphonic acid, tetraalkyl phosphonic acid, and then dissolved in an organic solvent Way.
The method of claim 1, wherein the group II metal precursor is a metal precursor selected from the group consisting of zinc, cadmium, mercury, and lead which are group II elements.
The method of claim 1, wherein the Group II metal precursor is dimethyl zinc, diethyl zinc, zinc carboxylate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide , Zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, dimethyl cadmium, diethyl cadmium, cadmium oxide, cadmium carbonate, cadmium acetate dihydrate, cadmium acetylacetonate, cadmium fluoride, cadmium chloride, cadmium i Odide, cadmium bromide, cadmium perchlorate, cadmium phosphide, cadmium nitrate, cadmium sulfate, cadmium carboxylate, mercury iodide, mercury bromide, mercury fluoride, mercury cyanide, mercury nitrate, mercury Perchlorate, mercury sulfate, mercury oxide, mercury carbonate, mercury carboxylate, dimethyl lead, diethyl lead, lead carboxylate, lead acetylacetonate, lead iodide, lead bromide, lead chloride, lead fluoride, lead carbonate , Lead cyanide, lead nitrate, lead oxide, lead peroxide, lead perchlorate and lead sulfate production method of quantum dot structure of the nuclear shell characterized in that it is selected from the group consisting of.
The metal precursor of claim 1, wherein the mixed metal precursor of the Group I and Group III elements is selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and a metal precursor selected from the group consisting of aluminum, gallium, indium and thallium. Quantum dot manufacturing method of the nucleus-shell structure, characterized in that the mixture.
The method of claim 1, wherein the Group VI precursor solution added in Step 1 and Step 3 is a precursor solution of different Group VI elements.
The method of claim 1, wherein the Group VI precursor solution further comprises an organic phosphine-based compound.
The method of claim 1, wherein the Group VI precursor included in the Group VI precursor solution is at least one precursor selected from the group consisting of sulfur, selenium, and tellurium.
The method of claim 7, wherein the organic phosphine-based compound is C 2 to C 18 trialkylphosphine, or C 2 to C 18 trialkylphosphine oxide.
The method of claim 1, wherein all the steps are carried out in an inert atmosphere.
Quantum dots of the nucleus-shell structure produced according to the method of claim 1.
The quantum dot and the inorganic composite particles of claim 11, wherein the inorganic composite particles are any one selected from the group consisting of SiO 2 , TiO 2 , ZrO 2 , ZnO, ITO and SnO.
상기 단계 1의 혼합용액을 180 ℃ ~ 240 ℃로 냉각시키는 단계(단계 2); 및
상기 단계 2의 냉각된 혼합용액에 단계 1의 금속전구체 또는 혼합금속전구체 대비 0.5 ~ 1의 몰비율로 Ⅵ족 전구체 용액을 점적하는 단계(단계 3);
를 포함하는 핵-껍질 구조의 양자점에 있어서 껍질을 두껍게 형성시키는 방법.
A Group VI precursor solution is added to a Group II metal precursor solution or a mixed metal precursor solution of Group I and Group III elements heated to 250 ° C. to 350 ° C., but in the Group VI precursor solution to the metal precursor in the metal precursor solution. Adding a Group VI precursor solution while maintaining a heated temperature, wherein the molar ratio of the precursor is at least 2 (step 1);
Cooling the mixed solution of step 1 to 180 ° C. to 240 ° C. (step 2); And
Dropping a Group VI precursor solution into the cooled mixed solution of Step 2 at a molar ratio of 0.5 to 1 relative to the metal precursor or mixed metal precursor of Step 1 (Step 3);
Method for forming a thick shell in the quantum dot of the nucleus-shell structure comprising a.
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