JP2011256106A - Nanocrystal with multilayered structure and method for producing thereof - Google Patents
Nanocrystal with multilayered structure and method for producing thereof Download PDFInfo
- Publication number
- JP2011256106A JP2011256106A JP2011149538A JP2011149538A JP2011256106A JP 2011256106 A JP2011256106 A JP 2011256106A JP 2011149538 A JP2011149538 A JP 2011149538A JP 2011149538 A JP2011149538 A JP 2011149538A JP 2011256106 A JP2011256106 A JP 2011256106A
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- Japan
- Prior art keywords
- nanocrystal
- group
- alloy layer
- zinc
- cadmium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 193
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 70
- 239000000956 alloy Substances 0.000 claims abstract description 70
- 239000000126 substance Substances 0.000 claims abstract description 39
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 21
- -1 alkylthiol compound Chemical class 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 238000009792 diffusion process Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 9
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 9
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 241001455273 Tetrapoda Species 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910021478 group 5 element Inorganic materials 0.000 claims description 5
- 230000001965 increasing effect Effects 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 230000001629 suppression Effects 0.000 claims description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910021476 group 6 element Inorganic materials 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 4
- 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 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- LZSJBLXYNYSKPJ-UHFFFAOYSA-N 9-octyl-9h-fluorene Chemical class C1=CC=C2C(CCCCCCCC)C3=CC=CC=C3C2=C1 LZSJBLXYNYSKPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 claims description 2
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$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
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 2
- QVJAEHWIKHNTSX-UHFFFAOYSA-N C[Si](C)(C)[S] Chemical compound C[Si](C)(C)[S] QVJAEHWIKHNTSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910004613 CdTe Inorganic materials 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- 229910004262 HgTe Inorganic materials 0.000 claims description 2
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 2
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 2
- NPUVYHNDWLTMSW-UHFFFAOYSA-N OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.[AsH3].[AsH3] Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.[AsH3].[AsH3] NPUVYHNDWLTMSW-UHFFFAOYSA-N 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 229910002665 PbTe Inorganic materials 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 229910007709 ZnTe Inorganic materials 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- UUESRJFGZMCELZ-UHFFFAOYSA-K aluminum;2-methylquinoline-8-carboxylate;4-phenylphenolate Chemical compound [Al+3].C1=CC([O-])=CC=C1C1=CC=CC=C1.C1=CC=C(C([O-])=O)C2=NC(C)=CC=C21.C1=CC=C(C([O-])=O)C2=NC(C)=CC=C21 UUESRJFGZMCELZ-UHFFFAOYSA-K 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 2
- JMBNQWNFNACVCB-UHFFFAOYSA-N arsenic tribromide Chemical compound Br[As](Br)Br JMBNQWNFNACVCB-UHFFFAOYSA-N 0.000 claims description 2
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 claims description 2
- 229960002594 arsenic trioxide Drugs 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
- UJYLYGDHTIVYRI-UHFFFAOYSA-N cadmium(2+);ethane Chemical compound [Cd+2].[CH2-]C.[CH2-]C UJYLYGDHTIVYRI-UHFFFAOYSA-N 0.000 claims description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical group C[Zn]C AXAZMDOAUQTMOW-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
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 claims description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-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
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 2
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 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
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- DWUCCPNOMFYDOL-UHFFFAOYSA-N propyl(sulfanyl)silicon Chemical compound CCC[Si]S DWUCCPNOMFYDOL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- GOBNDSNLXZYUHQ-UHFFFAOYSA-N selenium;tributylphosphane Chemical compound [Se].CCCCP(CCCC)CCCC GOBNDSNLXZYUHQ-UHFFFAOYSA-N 0.000 claims description 2
- MJNSMKHQBIVKHV-UHFFFAOYSA-N selenium;trioctylphosphane Chemical compound [Se].CCCCCCCCP(CCCCCCCC)CCCCCCCC MJNSMKHQBIVKHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 2
- HTARNFAKZVZKEI-UHFFFAOYSA-N triphenylsilyloxyaluminum(2+) Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O[Al+2])C1=CC=CC=C1 HTARNFAKZVZKEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- AKJVMGQSGCSQBU-UHFFFAOYSA-N zinc azanidylidenezinc Chemical compound [Zn++].[N-]=[Zn].[N-]=[Zn] AKJVMGQSGCSQBU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- RTKMFQOHBDVEBC-UHFFFAOYSA-N 3-bromo-3-buten-1-ol Chemical compound OCCC(Br)=C RTKMFQOHBDVEBC-UHFFFAOYSA-N 0.000 claims 1
- IGPFOKFDBICQMC-UHFFFAOYSA-N 3-phenylmethoxyaniline Chemical compound NC1=CC=CC(OCC=2C=CC=CC=2)=C1 IGPFOKFDBICQMC-UHFFFAOYSA-N 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims 1
- MYPDMHWBPRKWAK-UHFFFAOYSA-N C(CCC)P(CCCC)CCCC.[S] Chemical compound C(CCC)P(CCCC)CCCC.[S] MYPDMHWBPRKWAK-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- AZKKVWMWAIFIBR-UHFFFAOYSA-N ON=O.ON=O.ON=O.[AsH3] Chemical compound ON=O.ON=O.ON=O.[AsH3] AZKKVWMWAIFIBR-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- RHKQUGZIMGIIEA-UHFFFAOYSA-N [S].CCCCCCCCP(CCCCCCCC)CCCCCCCC Chemical compound [S].CCCCCCCCP(CCCCCCCC)CCCCCCCC RHKQUGZIMGIIEA-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 1
- 229940075417 cadmium iodide Drugs 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- FMSYTQMJOCCCQS-UHFFFAOYSA-L difluoromercury Chemical compound F[Hg]F FMSYTQMJOCCCQS-UHFFFAOYSA-L 0.000 claims 1
- KBYOBAICCHNMNJ-UHFFFAOYSA-L diperchloryloxymercury Chemical compound [Hg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O KBYOBAICCHNMNJ-UHFFFAOYSA-L 0.000 claims 1
- 229910000373 gallium sulfate Inorganic materials 0.000 claims 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229940046892 lead acetate Drugs 0.000 claims 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims 1
- 229960002523 mercuric chloride Drugs 0.000 claims 1
- 229940075610 mercuric cyanide Drugs 0.000 claims 1
- 229960003671 mercuric iodide Drugs 0.000 claims 1
- 229940101209 mercuric oxide Drugs 0.000 claims 1
- 229940074994 mercuric sulfate Drugs 0.000 claims 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 claims 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims 1
- YFDLHELOZYVNJE-UHFFFAOYSA-L mercury diiodide Chemical compound I[Hg]I YFDLHELOZYVNJE-UHFFFAOYSA-L 0.000 claims 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims 1
- 229960003540 oxyquinoline Drugs 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims 1
- SCTHSTKLCPJKPF-UHFFFAOYSA-N selenium;triphenylphosphane Chemical compound [Se].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SCTHSTKLCPJKPF-UHFFFAOYSA-N 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 claims 1
- QNLQKURWPIJSJS-UHFFFAOYSA-N trimethylsilylphosphane Chemical compound C[Si](C)(C)P QNLQKURWPIJSJS-UHFFFAOYSA-N 0.000 claims 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000011162 core material Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 20
- 239000011257 shell material Substances 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 13
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 238000000295 emission spectrum Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000001443 photoexcitation Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004054 semiconductor nanocrystal Substances 0.000 description 4
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229940105296 zinc peroxide Drugs 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- DFIXSEWMIKVQNS-UHFFFAOYSA-L C(C)(=O)[O-].C(C)(=O)[O-].[Pb+2].[Hg+] Chemical compound C(C)(=O)[O-].C(C)(=O)[O-].[Pb+2].[Hg+] DFIXSEWMIKVQNS-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- IEMXCRCRFMZIJZ-UHFFFAOYSA-L [Br-].[Cd+2].C(C)(=O)[O-].[Cd+2] Chemical compound [Br-].[Cd+2].C(C)(=O)[O-].[Cd+2] IEMXCRCRFMZIJZ-UHFFFAOYSA-L 0.000 description 1
- SNMPINLMAPYRAZ-UHFFFAOYSA-N [O-]CC.[Ge+2].[Ge]=O.[O-]CC Chemical compound [O-]CC.[Ge+2].[Ge]=O.[O-]CC SNMPINLMAPYRAZ-UHFFFAOYSA-N 0.000 description 1
- WRYNUJYAXVDTCB-UHFFFAOYSA-M acetyloxymercury Chemical compound CC(=O)O[Hg] WRYNUJYAXVDTCB-UHFFFAOYSA-M 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- IKIBSPLDJGAHPX-UHFFFAOYSA-N arsenic triiodide Chemical compound I[As](I)I IKIBSPLDJGAHPX-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 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 description 1
- NRGIRRZWCDKDMV-UHFFFAOYSA-H cadmium(2+);diphosphate Chemical compound [Cd+2].[Cd+2].[Cd+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O NRGIRRZWCDKDMV-UHFFFAOYSA-H 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- PEHFFJSIXZRLAE-UHFFFAOYSA-J dizinc dicarbonate Chemical compound [Zn++].[Zn++].[O-]C([O-])=O.[O-]C([O-])=O PEHFFJSIXZRLAE-UHFFFAOYSA-J 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000003854 isothiazoles Chemical class 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- FQGYCXFLEQVDJQ-UHFFFAOYSA-N mercury dicyanide Chemical compound N#C[Hg]C#N FQGYCXFLEQVDJQ-UHFFFAOYSA-N 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- HSAJRDKFYZAGLU-UHFFFAOYSA-M perchloryloxymercury Chemical compound [Hg+].[O-]Cl(=O)(=O)=O HSAJRDKFYZAGLU-UHFFFAOYSA-M 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- UIQIFQQQNSUEBA-UHFFFAOYSA-N trimethylsilylphosphane Chemical compound C[Si](C)(C)P.C[Si](C)(C)P UIQIFQQQNSUEBA-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
- H10K30/352—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Abstract
Description
本発明は、多層構造のナノ結晶およびその製造方法に係り、より詳しくは、２種以上の物質からなるナノ結晶において、前記物質の合金層を含むことを特徴とする多層構造のナノ結晶およびその製造方法に関する。 The present invention relates to a multilayered nanocrystal and a method for producing the same, and more particularly, in a nanocrystal composed of two or more kinds of substances, including an alloy layer of the substance, and a multilayered nanocrystal thereof It relates to a manufacturing method.
ナノ結晶は、数ナノサイズの結晶構造を有する物質であって、数百〜数千個程度の原子から構成されている。このように小さいサイズの物質は、単位体積当たりの表面積が広く、多くの部分の原子が物質の表面に露出するので、物質自体の固有特性とは異なる独特な電気的、磁気的、光学的、化学的、機械的特性がナノ結晶の物理的サイズを調節することで多様に調節されうる。ナノ結晶を合成する方法としては、ＭＯＣＶＤ（ｍｅｔａｌ ｏｒｇａｎｉｃ ｃｈｅｍｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）やＭＢＥ（ｍｏｌｅｃｕｌａｒ ｂｅａｍ ｅｐｉｔａｘｙ）などのＣＶＤ法があり、最近では、界面活性剤の存在下に有機溶媒に前駆体物質を入れて結晶を成長させる化学的湿式方法が急速に発展しつつある。化学的湿式方法は、結晶が成長するときに界面活性剤が自然にナノ結晶の表面に配位されて分散剤の役割を担うようにすることにより、結晶の成長を調節する方法であって、ＭＯＣＶＤやＭＢＥなどのＣＶＤ法より一層容易かつ低廉な工程によってナノ結晶の大きさと形状の均一度を調節することができるという利点を持つ。 A nanocrystal is a substance having a crystal structure of several nanosizes, and is composed of several hundred to several thousand atoms. Such a small size material has a large surface area per unit volume, and since many parts of the atoms are exposed on the surface of the material, it has a unique electrical, magnetic, optical, Chemical and mechanical properties can be adjusted in various ways by adjusting the physical size of nanocrystals. As a method of synthesizing nanocrystals, there are CVD methods such as MOCVD (metal organic chemical deposition) and MBE (molecular beam epitaxy). Recently, a precursor material is put in an organic solvent in the presence of a surfactant. Chemical wet methods for growing crystals are developing rapidly. The chemical wet method is a method of controlling the growth of the crystal by allowing the surfactant to be naturally coordinated to the surface of the nanocrystal and play the role of a dispersing agent when the crystal grows, There is an advantage that the uniformity of the size and shape of the nanocrystals can be adjusted by a process that is easier and less expensive than CVD methods such as MOCVD and MBE.
特許文献１は、発光効率が増加したコア−シェル構造を有する半導体ナノ結晶物質を開示しており、特許文献２は、そのようなコア−シェル構造を有する半導体ナノ結晶物質を製造する方法を開示している。このように形成されたコア−シェル構造の化合物半導体ナノ結晶は発光効率が３０％〜５０％まで増加するものと報告された。前述した従来の技術では、半導体ナノ結晶は大部分エネルギーバンドギャップのエッジでのみ転移が起こるため、純粋な波長で高効率の光を発光する特性を利用してディスプレイまたはバイオイメージセンサとして応用することができると明らかにしている。 Patent Document 1 discloses a semiconductor nanocrystal material having a core-shell structure with increased luminous efficiency, and Patent Document 2 discloses a method for producing a semiconductor nanocrystal material having such a core-shell structure. is doing. It has been reported that the compound semiconductor nanocrystal having the core-shell structure formed in this way has an increase in luminous efficiency of 30% to 50%. In the above-mentioned conventional technology, semiconductor nanocrystals are mostly transferred only at the edge of the energy band gap, so that they can be applied as displays or bioimage sensors using the property of emitting highly efficient light at pure wavelengths. It is clarified that you can.
ところが、青色で発光するコア−シェルナノ結晶を前記従来の技術によって製造するには小さいサイズのコア（直径２ｎｍ以下）を使用しなければならず、このような小さい結晶は、シェルを形成する過程で非常に不安定であって互いに凝集するという問題点などがあった。 However, in order to manufacture a core-shell nanocrystal emitting blue light by the conventional technique, a small-sized core (diameter of 2 nm or less) must be used, and such a small crystal is formed in the process of forming a shell. There was a problem that they were very unstable and aggregated with each other.
そこで、本発明はこのような問題点に鑑みてなされたもので、その目的とするところは、青色領域で優れた発光効率を示すうえ、物質の安定性に優れた新しい構造のナノ結晶を提供することにある。 Therefore, the present invention has been made in view of such problems, and the object of the present invention is to provide a nanocrystal having a new structure that exhibits excellent luminous efficiency in the blue region and has excellent material stability. There is to do.
上記課題を解決するために、本発明の一形態によれば、２種以上の物質からなるナノ結晶において、前記物質の合金層を含むことを特徴とする、多層構造のナノ結晶が提供される。 In order to solve the above problems, according to one aspect of the present invention, there is provided a nanocrystal having a multilayer structure characterized in that a nanocrystal composed of two or more substances includes an alloy layer of the substances. .
また、本発明の他の形態によれば、（ａ）第１ナノ結晶を製造する段階と、（ｂ）前記（ａ）段階で得られた前記第１ナノ結晶の表面上に前記第１ナノ結晶とは異なる種類の第２ナノ結晶を成長させる段階と、（ｃ）前記第１ナノ結晶と前記第２ナノ結晶との界面に拡散によって合金層を形成する段階とを含む、多層構造のナノ結晶の製造方法が提供される。 According to another aspect of the present invention, (a) a step of manufacturing a first nanocrystal, and (b) the first nanocrystal on the surface of the first nanocrystal obtained in the step (a). A step of growing a second nanocrystal of a type different from the crystal; and (c) forming an alloy layer by diffusion at an interface between the first nanocrystal and the second nanocrystal. A method for producing a crystal is provided.
また、本発明のさらに他の形態によれば、前記製造方法で製造した多層構造のナノ結晶が提供される。 Moreover, according to the further another form of this invention, the nanocrystal of the multilayered structure manufactured with the said manufacturing method is provided.
また、本発明のさらに他の形態によれば、前記製造方法で製造した多層構造のナノ結晶を含む素子が提供される。 According to still another aspect of the present invention, there is provided an element including a multilayered nanocrystal manufactured by the above manufacturing method.
本発明に係る多層構造のナノ結晶は、互いに異なる結晶の間に合金層が存在するため、物質の安定性を増加させる。その結果、本発明によれば、青色領域で発光効率が非常に優れた物質を製造することができる。 The multi-layered nanocrystal according to the present invention increases the stability of the material because an alloy layer exists between different crystals. As a result, according to the present invention, it is possible to manufacture a substance having a very excellent luminous efficiency in the blue region.
以下、本発明についてより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明の一形態は、２種以上の物質からなるナノ結晶において、前記物質の合金（ａｌｌｏｙ）層を含むことを特徴とする、多層構造のナノ結晶に関するものである。 One embodiment of the present invention relates to a nanocrystal having a multilayer structure, wherein the nanocrystal includes two or more kinds of substances, and includes an alloy layer of the substances.
本発明に係る多層構造のナノ結晶に必須的に含まれる前記合金層は、ナノ結晶を構成する物質の界面の間に合金層として形成され、ナノ結晶を構成する物質の間に存在する格子定数の差を緩衝して物質の安定性を増進させる。 The alloy layer essentially included in the nanocrystal having a multilayer structure according to the present invention is formed as an alloy layer between the interfaces of the substance constituting the nanocrystal, and the lattice constant existing between the substances constituting the nanocrystal. Buffer the difference to increase the stability of the substance.
図１は本発明の一実施形態に係る多層構造の球状ナノ結晶の構造を示している。図１（ａ）を参照すると、３次元構造を有する球状の場合には、球の内部から外部に向かって、順次コア、合金層およびシェルから構成されている。この際、図１（ｂ）を参照すると、コア部分の体積が小さいかシェルがコアに拡散していく速度がさらに速い場合、合金層の拡散がコアの中心部分まで行われて合金コア−シェルの形を持つことができる。また、図１（ｃ）を参照すると、シェルの厚さが薄いかコアがシェルに拡散していく速度がさらに速い場合、合金層の拡散がシェルの外部まで行われてコア−合金シェルの形を持つことができる。 FIG. 1 shows the structure of a spherical nanocrystal having a multilayer structure according to an embodiment of the present invention. Referring to FIG. 1A, in the case of a spherical shape having a three-dimensional structure, a core, an alloy layer, and a shell are sequentially formed from the inside of the sphere toward the outside. In this case, referring to FIG. 1 (b), when the volume of the core portion is small or the speed at which the shell diffuses into the core is faster, the alloy layer is diffused to the center portion of the core, and the alloy core-shell Can have the shape of Referring to FIG. 1C, when the shell is thin or the core is diffused faster, the alloy layer is diffused to the outside of the shell to form the core-alloy shell. Can have.
図２は、本発明の球状ナノ結晶構造でそれぞれ当該合金層が均一な合金相を形成せず、物質組成の勾配を有するグラディエント（ｇｒａｄｉｅｎｔ）構造を示している。 FIG. 2 shows a gradient structure in which the alloy layers do not form a uniform alloy phase and have a material composition gradient in the spherical nanocrystal structure of the present invention.
図３は本発明の一実施形態に係る多層構造の棒状ナノ結晶の構造を示している。図３（ａ）を参照すると、２次元構造を有する棒状の場合には、長手方向に２種以上の物質が連結されて成長し、第１棒、合金層および第２棒から構成できる。また、図３（ｂ）を参照すると、上記合金層が均質な金層形態ではない物質組成の勾配を有するグラディエント構造の合金層形態に形成されることができる。また、図３（ｃ）を参照すると、棒状の場合でも、長手方向に２種以上の物質が連結されて成長するときに第１棒が短いか第２棒が第１棒に拡散していく速度がさらに速い場合、合金層の拡散が第１棒の端部まで行われて合金棒および第２棒の形で構成できる。 FIG. 3 shows a structure of a multi-layered rod-shaped nanocrystal according to an embodiment of the present invention. Referring to FIG. 3A, in the case of a rod having a two-dimensional structure, two or more kinds of substances are connected and grown in the longitudinal direction, and can be constituted by a first rod, an alloy layer, and a second rod. Referring to FIG. 3B, the alloy layer may be formed in a gradient alloy layer form having a material composition gradient that is not a homogeneous gold layer form. Referring to FIG. 3C, even in the case of a rod shape, when two or more kinds of substances are connected in the longitudinal direction and grown, the first rod is short or the second rod diffuses into the first rod. For higher speeds, the alloy layer can be diffused to the end of the first rod and configured in the form of an alloy rod and a second rod.
図４は本発明の一実施形態に係る多層構造の三脚状ナノ結晶の構造を示している。図４（ａ）を参照すると、三脚状の場合には順次コアの周囲に第１棒、第２棒および第３棒が構成され、コアと３つの棒との界面に合金層がある構造で構成できる。図４（ｂ）を参照すると、上記合金層が均質な金層形態ではない物質組成の勾配を有するグラディエント構造の合金層形態に形成されることができる。また、厚さ方向に２種以上の物質が連結されて成長するとき、コア棒、合金層およびシェル棒で構成できる。 FIG. 4 shows the structure of a tripod-like nanocrystal having a multilayer structure according to an embodiment of the present invention. Referring to FIG. 4A, in the case of a tripod, the first rod, the second rod, and the third rod are sequentially formed around the core, and an alloy layer is provided at the interface between the core and the three rods. Can be configured. Referring to FIG. 4B, the alloy layer may be formed in an alloy layer form having a gradient structure having a material composition gradient that is not a homogeneous gold layer form. Further, when two or more kinds of substances are connected and grown in the thickness direction, the core bar, the alloy layer, and the shell bar can be used.
図５は本発明の一実施形態に係る多層構造のチューブ状ナノ結晶を示している。図５（ａ）を参照すると、コア、合金層、シェルがチューブ状に形成されている。図５（ｂ）を参照すると、上記合金層が均質な金層形態ではない物質組成の勾配を有するグラディエント構造の合金層形態に形成されることができる。また、厚さ方向に２種以上の物質が連結されて成長するとき、コア棒の直径が小さいかシェル（外皮）が薄い場合、あるいはシェルとコアのいずれか一方の拡散速度がより速い場合、合金層の拡散によって合金コア棒−シェルの形またはコア棒−合金シェルの形を持つことができる。 FIG. 5 shows a tubular nanocrystal having a multilayer structure according to an embodiment of the present invention. Referring to FIG. 5A, the core, the alloy layer, and the shell are formed in a tube shape. Referring to FIG. 5B, the alloy layer may be formed in an alloy layer form having a gradient structure having a material composition gradient that is not a homogeneous gold layer form. In addition, when two or more kinds of substances are connected and grown in the thickness direction, when the diameter of the core rod is small or the shell (outer skin) is thin, or when the diffusion rate of either the shell or the core is faster, The diffusion of the alloy layer can have an alloy core rod-shell shape or a core rod-alloy shell shape.
より具体的に、図１に示すように、本発明に係る多層構造のナノ結晶は、順次コア、合金層およびシェルから構成されることにより、シェル物質またはコア物質が他方の内部に拡散していくにつれて発光コアの実際サイズが減少しながら発光波長が青色領域に移動するので、大きさが相対的に大きいコアを使用しても青色領域で発光する特性を持つ。また、発光波長の移動は、シェル物質またはコア物質が他方の内部に拡散していくにつれて発光コアの化学的組成が変わるために発生するものと推定される。 More specifically, as shown in FIG. 1, the nanocrystal having a multilayer structure according to the present invention is composed of a core, an alloy layer, and a shell, so that the shell material or the core material diffuses into the other. As the actual size of the light emitting core decreases with time, the emission wavelength shifts to the blue region, so that even if a relatively large core is used, light is emitted in the blue region. In addition, the shift of the emission wavelength is presumed to occur because the chemical composition of the light emitting core changes as the shell material or core material diffuses into the other.
また、シェルとして用いた物質がコアより広いバンドギャップを有する物質の場合、シェルによるパッシベーション（ｐａｓｓｉｖａｔｉｏｎ）および量子閉じ込め効果によって青色領域で発光効率が非常に向上した特性を持つ。 In addition, when the material used as the shell has a wider band gap than the core, the light emission efficiency is greatly improved in the blue region due to the passivation and quantum confinement effect by the shell.
一方、コアの周囲に形成された合金層は、コアとシェルとの間に存在する格子定数の差を緩衝するので、物質の安定性を増進させる特性を持つ。 On the other hand, the alloy layer formed around the core buffers the difference in the lattice constant existing between the core and the shell, and thus has the property of enhancing the stability of the material.
本発明に係るナノ結晶を構成する物質は、ＩＩ−ＶＩ族またはＩＩＩ−Ｖ族およびＩＶ−ＶＩ族の半導体化合物または前記物質の混合物よりなる群から選択できる。 The substance constituting the nanocrystal according to the present invention can be selected from the group consisting of II-VI or III-V and IV-VI group semiconductor compounds or mixtures of the aforementioned substances.
具体的に、ナノ結晶を構成する物質は、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＰｂＳ、ＰｂＳｅ、ＰｂＴｅ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＧａＮ、ＧａＰ、ＧａＡｓ、ＩｎＮ、ＩｎＰ、ＩｎＡｓおよび前記物質の混合物を例として挙げることができる。 Specifically, the materials constituting the nanocrystal are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, AlN, AlP, AlAs, GaN, GaP, GaAs, InN, Examples include InP, InAs and mixtures of the aforementioned substances.
一方、本発明に係る多層構造のナノ結晶の形状は、球状、正四面体（ｔｅｔｒａｈｅｄｒｏｎ）状、円筒状、棒状、三角状、円板（ｄｉｓｃ）状、三脚（ｔｒｉｐｏｄ）状、テトラポッド（ｔｅｔｒａｐｏｄ）状、立方体（ｃｕｂｅ）状、ボックス箱（ｂｏｘ）状、星（ｓｔａｒ）状およびチューブ（ｔｕｂｅ）状よりなる群から選択できるが、これらに限定されるものではない。 Meanwhile, the multilayered nanocrystal according to the present invention has a spherical shape, a tetrahedron shape, a cylindrical shape, a rod shape, a triangular shape, a disc shape, a tripod shape, a tetrapod shape, and a tetrapod shape. ) Shape, cube shape, box shape, star shape, and tube shape, but is not limited thereto.
以下、本発明に係る多層構造のナノ結晶を指すとき、「ＣｄＳｅ／／ＺｎＳ」で表示する。前記「ＣｄＳｅ／／ＺｎＳ」の表示は、ＣｄＳｅナノ結晶とＺｎＳナノ結晶との間に合金層が形成されていることを意味する。 Hereinafter, when referring to a nanocrystal having a multilayer structure according to the present invention, it is indicated by “CdSe // ZnS”. The indication of “CdSe // ZnS” means that an alloy layer is formed between the CdSe nanocrystal and the ZnS nanocrystal.
本発明の他の形態は、多層構造のナノ結晶の製造方法に関するものである。 Another embodiment of the present invention relates to a method for producing a multilayered nanocrystal.
すなわち、本発明の製造方法は、（ａ）第１ナノ結晶を製造する段階と、（ｂ）前記（ａ）段階で得られた第１ナノ結晶の表面上に第１ナノ結晶と異なる種類の第２ナノ結晶を成長させる段階と、（ｃ）前記第１ナノ結晶と前記第２ナノ結晶との間の界面に拡散によって合金層を形成する段階とを含む多層構造のナノ結晶の製造方法に関するものである。 That is, the production method of the present invention includes (a) a step of producing a first nanocrystal, and (b) a different kind of the first nanocrystal on the surface of the first nanocrystal obtained in the step (a). A method for producing a nanocrystal having a multilayer structure, comprising: growing a second nanocrystal; and (c) forming an alloy layer by diffusion at an interface between the first nanocrystal and the second nanocrystal. Is.
より具体的に、本発明の製造方法において、前記（ａ）段階の第１ナノ結晶は、金属前駆体とＶ族またはＶＩ族前駆体をそれぞれ溶媒および分散剤に仕込んだ後、これらを混合し反応させて形成し、前記（ｂ）段階の第２ナノ結晶は、金属前駆体とＶ族またはＶＩ族前駆体をそれぞれ溶媒および分散剤に仕込んだ後、これらを混合し反応させて第１ナノ結晶の表面上に成長させる。 More specifically, in the production method of the present invention, the first nanocrystal in the step (a) is prepared by adding a metal precursor and a group V or group VI precursor to a solvent and a dispersant, respectively, and then mixing them. The second nanocrystal in the step (b) is prepared by adding a metal precursor and a group V or VI group precursor to a solvent and a dispersing agent, and then mixing and reacting the first nanocrystal. Grows on the surface of the crystal.
すなわち、金属前駆体とＶ族またはＶＩ族前駆体をそれぞれ溶媒および分散剤に仕込み、これらを混合し反応させて第１ナノ結晶を形成した後、第２ナノ結晶の前駆体を溶媒および分散剤に仕込んだ溶液に、前記で合成した第１ナノ結晶を入れて反応させると、第１ナノ結晶の表面に第２ナノ結晶が成長し、第１ナノ結晶と第２ナノ結晶との界面に拡散によって合金層が形成される。 That is, a metal precursor and a group V or group VI precursor are charged in a solvent and a dispersant, respectively, mixed and reacted to form a first nanocrystal, and then a second nanocrystal precursor is used as a solvent and a dispersant. When the first nanocrystal synthesized above is put into the solution charged in the reaction and reacted, the second nanocrystal grows on the surface of the first nanocrystal and diffuses to the interface between the first nanocrystal and the second nanocrystal. Thus, an alloy layer is formed.
前記合金層は、前記第１ナノ結晶と前記第２ナノ結晶との界面において第２ナノ結晶を構成する物質が第１ナノ結晶の内部に拡散し、あるいは第１ナノ結晶を構成する物質が第２ナノ結晶の内部に拡散して形成されるが、拡散していく層が減少することにより、第１ナノ結晶と第２ナノ結晶との間に合金層が形成された新しい構造のナノ結晶を製造することができる。前記合金層は、ナノ結晶を構成する物質の間に存在する格子定数の差を緩衝して物質の安定性を増進させる。この際、拡散していく層が減少して完全に無くなることにより、第１ナノ結晶−合金層、合金層−第２ナノ結晶の形を持つこともできる。 In the alloy layer, a substance constituting the second nanocrystal diffuses into the first nanocrystal at the interface between the first nanocrystal and the second nanocrystal, or a substance constituting the first nanocrystal is the first. 2Diffusion is formed inside the nanocrystal, but the number of diffusing layers is reduced, so that a nanocrystal with a new structure in which an alloy layer is formed between the first nanocrystal and the second nanocrystal. Can be manufactured. The alloy layer increases the stability of the material by buffering a difference in lattice constant existing between materials constituting the nanocrystal. At this time, since the diffusing layer is reduced and completely eliminated, the first nanocrystal-alloy layer and the alloy layer-second nanocrystal can be formed.
一方、本発明の製造方法は、前記（ｂ）段階および（ｃ）段階を２回以上繰り返し行うことを含む。すなわち、コア−シェル構造の場合には、前記（ｂ）段階および（ｃ）段階によって製造された多層構造のナノ結晶を再び（ｂ）段階に投入して反応させると、その表面が成長しながら別の層を確保することができ、棒構造の場合には、三脚状またはテトラポッド状に形成できる。 On the other hand, the production method of the present invention includes repeating the steps (b) and (c) two or more times. That is, in the case of the core-shell structure, when the nanocrystal having the multilayer structure manufactured in the steps (b) and (c) is charged again in the step (b) and reacted, the surface grows. Another layer can be secured, and in the case of a rod structure, it can be formed in a tripod or tetrapod shape.
本発明に係る多層構造のナノ結晶の製造方法において、前記（ａ）および（ｂ）段階の金属前駆体としては、ジメチル亜鉛（ｄｉｍｅｔｈｙｌ ｚｉｎｃ）、ジエチル亜鉛（ｄｉｅｔｈｙｌ ｚｉｎｃ）、酢酸亜鉛（Ｚｉｎｃ ａｃｅｔａｔｅ）、亜鉛アセチルアセトナート（Ｚｉｎｃ ａｃｅｔｙｌａｃｅｔｏｎａｔｅ）、ヨウ化亜鉛（Ｚｉｎｃ ｉｏｄｉｄｅ）、臭化亜鉛（Ｚｉｎｃ ｂｒｏｍｉｄｅ）、塩化亜鉛（Ｚｉｎｃ ｃｈｌｏｒｉｄｅ）、フッ化亜鉛（Ｚｉｎｃ ｆｌｕｏｒｉｄｅ）、炭酸亜鉛（Ｚｉｎｃ ｃａｒｂｏｎａｔｅ）、シアン化亜鉛（Ｚｉｎｃ ｃｙａｎｉｄｅ）、窒化亜鉛（Ｚｉｎｃ ｎｉｔｒａｔｅ）、酸化亜鉛（Ｚｉｎｃ ｏｘｉｄｅ）、過酸化亜鉛（Ｚｉｎｃ ｐｅｒｏｘｉｄｅ）、過塩素酸亜鉛（Ｚｉｎｃ ｐｅｒｃｈｌｏｒａｔｅ）、硫酸亜鉛（Ｚｉｎｃ ｓｕｌｆａｔｅ）、ジメチルカドミウム（ｄｉｍｅｔｈｙｌ ｃａｄｍｉｕｍ）、ジエチルカドミウム（ｄｉｅｔｈｙｌ ｃａｄｍｉｕｍ）、酢酸カドミウム（Ｃａｄｍｉｕｍ ａｃｅｔａｔｅ）、カドミウムアセチルアセトナート（Ｃａｄｍｉｕｍ ａｃｅｔｙｌａｃｅｔｏｎａｔｅ）、ヨウ化カドミウム（Ｃａｄｍｉｕｍ ｉｏｄｉｄｅ）、臭化カドミウム（Ｃａｄｍｉｕｍ ｂｒｏｍｉｄｅ）、塩化カドミウム（Ｃａｄｍｉｕｍ ｃｈｌｏｒｉｄｅ）、フッ化カドミウム（Ｃａｄｍｉｕｍ ｆｌｕｏｒｉｄｅ）、炭酸カドミウム（Ｃａｄｍｉｕｍ ｃａｒｂｏｎａｔｅ）、硝酸カドミウム（Ｃａｄｍｉｕｍ ｎｉｔｒａｔｅ）、酸化カドミウム（Ｃａｄｍｉｕｍ ｏｘｉｄｅ）、過塩素酸カドミウム（Ｃａｄｍｉｕｍ ｐｅｒｃｈｌｏｒａｔｅ）、リン化カドミウム（Ｃａｄｍｉｕｍ ｐｈｏｓｐｈｉｄｅ）、硫酸カドミウム（Ｃａｄｍｉｕｍ ｓｕｌｆａｔｅ）、酢酸水銀（Ｍｅｒｃｕｒｙ ａｃｅｔａｔｅ）、ヨウ化水銀（Ｍｅｒｃｕｒｙ ｉｏｄｉｄｅ）、臭化水銀（Ｍｅｒｃｕｒｙ ｂｒｏｍｉｄｅ）、塩化水銀（Ｍｅｒｃｕｒｙ ｃｈｌｏｒｉｄｅ）、フッ化水銀（Ｍｅｒｃｕｒｙ ｆｌｕｏｒｉｄｅ）、シアン化水銀（Ｍｅｒｃｕｒｙ ｃｙａｎｉｄｅ）、硝酸水銀（Ｍｅｒｃｕｒｙ ｎｉｔｒａｔｅ）、酸化水銀（Ｍｅｒｃｕｒｙ ｏｘｉｄｅ）、過塩素酸水銀（Ｍｅｒｃｕｒｙ ｐｅｒｃｈｌｏｒａｔｅ）、硫酸水銀（Ｍｅｒｃｕｒｙ ｓｕｌｆａｔｅ）、酢酸鉛（Ｌｅａｄ ａｃｅｔａｔｅ）、臭化鉛（Ｌｅａｄ ｂｒｏｍｉｄｅ）、塩化鉛（Ｌｅａｄ ｃｈｌｏｒｉｄｅ）、フッ化鉛（Ｌｅａｄ ｆｌｕｏｒｉｄｅ）、酸化鉛（Ｌｅａｄ ｏｘｉｄｅ）、過塩素酸鉛（Ｌｅａｄ ｐｅｒｃｈｌｏｒａｔｅ）、硝酸鉛（Ｌｅａｄ ｎｉｔｒａｔｅ）、硫酸鉛（ｌｅａｄ ｓｕｌｆａｔｅ）、炭酸鉛（Ｌｅａｄ ｃａｒｂｏｎａｔｅ）、酢酸錫（Ｔｉｎ ａｃｅｔａｔｅ）、錫ビスアセチルアセトナート（Ｔｉｎ ｂｉｓａｃｅｔｙｌａｃｅｔｏｎａｔｅ）、臭化錫（Ｔｉｎ ｂｒｏｍｉｄｅ）、塩化錫（Ｔｉｎ ｃｈｌｏｒｉｄｅ）、フッ化錫（Ｔｉｎ ｆｌｕｏｒｉｄｅ）、酸化錫（Ｔｉｎ ｏｘｉｄｅ）、硫酸錫（Ｔｉｎ ｓｕｌｆａｔｅ）、四塩化ゲルマニウム（Ｇｅｒｍａｎｉｕｍ ｔｅｔｒａｃｈｌｏｒｉｄｅ）、酸化ゲルマニウム（ｇｅｒｍａｎｉｕｍ ｏｘｉｄｅ）、ゲルマニウムエトキシド（ｇｅｒｍａｎｉｕｍ ｅｔｈｏｘｉｄｅ）、ガリウムアセチルアセトナート（Ｇａｌｌｉｕｍ ａｃｅｔｙｌａｃｅｔｏｎａｔｅ）、塩化ガリウム（Ｇａｌｌｉｕｍ ｃｈｌｏｒｉｄｅ）、フッ化ガリウム（Ｇａｌｌｉｕｍ ｆｌｕｏｒｉｄｅ）、酸化ガリウム（Ｇａｌｌｉｕｍ ｏｘｉｄｅ）、硝酸ガリウム（Ｇａｌｌｉｕｍ ｎｉｔｒａｔｅ）、硫酸ガリウム（Ｇａｌｌｉｕｍ ｓｕｌｆａｔｅ）、塩化インジウム（Ｉｎｄｉｕｍ ｃｈｌｏｒｉｄｅ）、酸化インジウム（Ｉｎｄｉｕｍ ｏｘｉｄｅ）、硝酸インジウム（Ｉｎｄｉｕｍ ｎｉｔｒａｔｅ）および硫酸インジウム（Ｉｎｄｉｕｍ ｓｕｌｆａｔｅ）を例として挙げることができるが、これらに限定されるものではない。 In the method for producing a multilayered nanocrystal according to the present invention, the metal precursors in the steps (a) and (b) include dimethyl zinc, diethyl zinc, and zinc acetate. , Zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, cyanide, zinc acetate acetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate Zinc (cyanide), zinc nitride (Zinc nitrate), zinc oxide (Zinc oxide), zinc peroxide (Zinc peroxide), zinc perchlorate (Zinc pe) chlorate, zinc sulfate, dimethyl cadmium, diethyl cadmium, cadmium acetate, cadmium acetylacetonate, cadmium acetate, and cadmium acetate Cadmium bromide, cadmium chloride, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium oxide, cadmium oxide, cadmium oxide, cadmium oxide (Cadmium perchlorate), Cadmium phosphate, Cadmium sulfate, Mercury acetate, Mercury iodide, Mercury bromide chloride Mercury fluoride, Mercury cyanide, Mercury nitrate, Mercury oxide, Mercury perchlorate, Mercury sulfate, Mercury lead acetate acetate), lead bromide ), Lead chloride, lead fluoride, lead oxide, lead perchlorate, lead nitrate, lead sulphate, lead carbonate (lead sulphate), lead sulphate, lead sulphate, lead sulphate Lead carbonate, Tin acetate, Tin bisacetylacetonate, Tin bromide, Tin chloride, Tin fluoride, Tin oxide , Tin sulfate, germanium tetrachloride, germanium oxide Germanium ethoxide, Gallium acetylacetonate, Gallium chloride, Gallium fluoride, Gallium oxide, Gallium nitrate, Gallium nitrate Examples thereof include, but are not limited to, sulfate, indium chloride, indium oxide, indium nitrate, and indium sulfate.
また、本発明に係る多層構造のナノ結晶の製造方法において、前記（ａ）段階および（ｂ）段階のＶＩ族またはＶ族元素化合物としては、ヘキサンチオール、オクタンチオール、デカンチオール、ドデカンチオール、ヘキサデカンチオール、メルカプトプロピルシランなどのアルキルチオール化合物；サルファ−トリオクチルホスフィン（Ｓ−ＴＯＰ）、サルファ−トリブチルホスフィン（Ｓ−ＴＢＰ）、サルファ−トリフェニルホスフィン（Ｓ−ＴＰＰ）、サルファ−トリオクチルアミン（Ｓ−ＴＯＡ）、トリメチルシリルサルファ（ｔｒｉｍｅｔｈｙｌｓｉｌｙｌ ｓｕｌｆｕｒ）、硫化アンモニウム、硫化ナトリウム、セレン−トリオクチルホスフィン（Ｓｅ−ＴＯＰ）、セレン−トリブチルホスフィン（Ｓｅ−ＴＢＰ）、セレン−トリフェニルホスフィン（Ｓｅ−ＴＰＰ）、テルル−トリオクチルホスフィン（Ｔｅ− ＴＯＰ）、テルル−トリブチルホスフィン（Ｔｅ−ＴＢＰ）、テルル−トリフェニルホスフィン（Ｔｅ−ＴＰＰ）、トリメチルシリルホスフィン（ｔｒｉｍｅｔｈｙｌｓｉｌｙｌ ｐｈｏｓｐｈｉｎｅ）およびトリエチルホスフィン、トリブチルホスフィン、トリオクチルホスフィン、トリフェニルホスフィン、トリシクロヘキシルホスフィンを含むアルキルホスフィン（ａｌｋｙｌ ｐｈｏｓｐｈｉｎｅ）、酸化ヒ素（Ａｒｓｅｎｉｃ ｏｘｉｄｅ）、塩化ヒ素（Ａｒｓｅｎｉｃ ｃｈｌｏｒｉｄｅ）、硫酸ヒ素（Ａｒｓｅｎｉｃ ｓｕｌｆａｔｅ）、臭化ヒ素（Ａｒｓｅｎｉｃ ｂｒｏｍｉｄｅ）、ヨウ化ヒ素（Ａｒｓｅｎｉｃ ｉｏｄｉｄｅ）、酸化窒素（Ｎｉｔｒｉｃ ｏｘｉｄｅ）、硫酸（Ｎｉｔｒｉｃ ａｃｉｄ）および硝酸アンモニウム（Ａｍｍｏｎｉｕｍ ｎｉｔｒａｔｅ）などを例として挙げることができる。 In the method for producing a multilayered nanocrystal according to the present invention, the group VI or group V element compound in the steps (a) and (b) includes hexanethiol, octanethiol, decanethiol, dodecanethiol, hexadecane. Alkyl thiol compounds such as thiol and mercaptopropylsilane; sulfa-trioctylphosphine (S-TOP), sulfa-tributylphosphine (S-TBP), sulfa-triphenylphosphine (S-TPP), sulfa-trioctylamine (S -TOA), trimethylsilylsulfur, ammonium sulfide, sodium sulfide, selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-tol Phenylphosphine (Se-TPP), tellurium-trioctylphosphine (Te-TOP), tellurium-tributylphosphine (Te-TBP), tellurium-triphenylphosphine (Te-TPP), trimethylsilylphosphine (trimethylsilylphosphine) and triethylphosphine, Alkylphosphine including tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, arsenic oxide, arsenic chloride, arsenic sulfate, arsenic bromide ), Arsenic iodide, Nitric oxide Nitric Oxide), it may be mentioned as examples such as sulfuric acid (Nitric acid) and ammonium nitrate (Ammonium nitrate).
この際、前駆体の反応性に応じて前駆体の濃度および注入速度を適切に調節することにより、金属が粒子の形で剥離し、あるいは金属とＶＩ族またはＶ族の元素前駆体とが反応して別途に粒子を形成するなどの副反応が起こらないようにすることが好ましい。 At this time, by appropriately adjusting the concentration and injection rate of the precursor according to the reactivity of the precursor, the metal is separated in the form of particles, or the metal reacts with the group VI or V element precursor. Thus, it is preferable to prevent side reactions such as forming particles separately.
一方、本発明に係る多層構造のナノ結晶の製造方法において、前記（ａ）段階および（ｂ）段階の溶媒としては、炭素数６〜２２の第１級アルキルアミン、炭素数６〜２２の第２級アルキルアミン、炭素数６〜２２の第３級アルキルアミン、炭素数６〜２２の第１級アルコール、炭素数６〜２２の第２級アルコール、炭素数６〜２２の第３級アルコール、炭素数６〜２２のケトンおよびエステル、炭素数６〜２２の窒素または硫黄を含んだヘテロ環化合物（ｈｅｔｅｒｏｃｙｃｌｉｃ ｃｏｍｐｏｕｎｄ）、炭素数６〜２２のアルカン、炭素数６〜２２のアルケン、炭素数６〜２２のアルキン、トリオクチルホスフィンおよびトリオクチルホスフィンオキシドを例として挙げることができる。 On the other hand, in the method for producing a multilayered nanocrystal according to the present invention, as the solvent in the steps (a) and (b), a primary alkylamine having 6 to 22 carbon atoms and a solvent having 6 to 22 carbon atoms are used. Secondary alkylamine, tertiary alkylamine having 6 to 22 carbon atoms, primary alcohol having 6 to 22 carbon atoms, secondary alcohol having 6 to 22 carbon atoms, tertiary alcohol having 6 to 22 carbon atoms, C6-C22 ketones and esters, C6-C22 nitrogen or sulfur-containing heterocyclic compounds, C6-C22 alkanes, C6-C22 alkenes, C6-C22 Twenty-two alkynes, trioctylphosphine and trioctylphosphine oxide can be mentioned as examples.
また、本発明に係る多層構造のナノ結晶の製造方法において、前記（ａ）および（ｂ）段階の分散剤としては、末端にカルボキシル基（ＣＯＯＨ基）を有する炭素数６〜２２のアルカンまたはアルケン、末端にホスホン基（ＰＯＯＨ基）を有する炭素数６〜２２のアルカンまたはアルケン、末端にスルホン基（ＳＯＯＨ基）を有する炭素数６〜２２のアルカンまたはアルケン、および末端にアミン基（ＮＨ２基）を有する炭素数６〜２２のアルカンまたはアルケンを例として挙げることができる。 In the method for producing a multilayered nanocrystal according to the present invention, as the dispersant in the steps (a) and (b), an alkane or alkene having 6 to 22 carbon atoms having a carboxyl group (COOH group) at the terminal is used. An alkane or alkene having 6 to 22 carbon atoms having a phosphone group (POOH group) at the terminal, an alkane or alkene having 6 to 22 carbon atoms having a sulfone group (SOOH group) at the terminal, and an amine group (NH 2 group at the terminal) As an example, an alkane or alkene having 6 to 22 carbon atoms having) may be used.
具体的に、前記分散剤は、オレイン酸（ｏｌｅｉｃ ａｃｉｄ）、ステアリン酸（ｓｔｅａｒｉｃ ａｃｉｄ）、パルミチン酸（ｐａｌｍｉｔｉｃ ａｃｉｄ）、ヘキシルホスホン酸（ｈｅｘｙｌ ｐｈｏｓｐｈｏｎｉｃ ａｃｉｄ）、ｎ−オクチルホスホン酸（ｎ−ｏｃｔｙｌ ｐｈｏｓｐｈｏｎｉｃ ａｃｉｄ）、テトラデシルホスホン酸（ｔｅｔｒａｄｅｃｙｌ ｐｈｏｓｐｈｏｎｉｃ ａｃｉｄ）、オクタデシルホスホン酸（ｏｃｔａｄｅｃｙｌ ｐｈｏｓｐｈｏｎｉｃ ａｃｉｄ）、ｎ−オクチルアミン（ｎ−ｏｃｔｙｌ ａｍｉｎｅ）およびヘキサデシルアミン（ｈｅｘａｄｅｃｙｌ ａｍｉｎｅ）などを例として挙げることができる。 Specifically, the dispersant may include oleic acid, stearic acid, palmitic acid, hexyl phosphonic acid, n-octyl phosphonic acid. ), Tetradecylphosphonic acid, octadecylphosphonic acid, n-octylamine, hexadecylamine, and the like.
本発明に係る多層構造のナノ結晶の製造方法において、結晶成長を容易にし且つ溶媒の安定性を保障するための前記（ａ）段階および（ｂ）段階における好ましい反応温度範囲は、それぞれ１００℃〜４６０℃、より好ましくは１２０℃〜３９０℃、よりさらに好ましくは１５０℃〜３６０℃である。 In the method for producing a multilayered nanocrystal according to the present invention, preferred reaction temperature ranges in the steps (a) and (b) for facilitating crystal growth and ensuring the stability of the solvent are 100 ° C. to It is 460 degreeC, More preferably, it is 120 to 390 degreeC, More preferably, it is 150 to 360 degreeC.
また、本発明に係る多層構造のナノ結晶の製造方法において、反応速度の調節が容易な前記（ａ）段階および（ｂ）段階における反応時間は、それぞれ好ましくは５秒〜４時間、より好ましくは１０秒〜３時間、よりさらに好ましくは２０秒〜２時間である。 In the method for producing a multilayered nanocrystal according to the present invention, the reaction time in the step (a) and the step (b) in which the reaction rate can be easily adjusted is preferably 5 seconds to 4 hours, more preferably It is 10 seconds to 3 hours, more preferably 20 seconds to 2 hours.
一方、本発明に係る多層構造のナノ結晶の製造方法において、前記（ｂ）段階で反応温度、反応時間および第２ナノ結晶の金属前駆体物質の濃度を変化させることにより、前記（ｃ）段階における拡散速度を調節することができる。したがって、同じサイズの第１ナノ結晶物質を使用しても、発光波長が異なる物質を得ることができる。同じ原理により、異なるサイズの第１ナノ結晶物質を使用しても、拡散速度を調節することにより、同じ波長で発光する物質を得ることができる。 Meanwhile, in the method for producing a nanocrystal having a multilayer structure according to the present invention, the reaction temperature, the reaction time, and the concentration of the metal precursor material of the second nanocrystal are changed in the step (b). The diffusion rate in can be adjusted. Therefore, even if the first nanocrystal substance having the same size is used, substances having different emission wavelengths can be obtained. According to the same principle, even when the first nanocrystalline material having different sizes is used, a material that emits light at the same wavelength can be obtained by adjusting the diffusion rate.
また、前記（ｂ）段階で反応温度を段階的に変化させることにより、前記（ｃ）段階における拡散速度を調節することにより、同じサイズの第１ナノ結晶物質を使用しても、発光波長の異なる物質を得ることができる。 In addition, by changing the reaction temperature stepwise in the step (b) and adjusting the diffusion rate in the step (c), even if the first nanocrystal substance of the same size is used, the emission wavelength Different materials can be obtained.
一方、本発明に係る前記多層構造のナノ結晶の製造方法において、青色波長で発光効率を増加させるための（ｂ）段階の金属前駆体の濃度は、０．００１Ｍ〜２Ｍであることが好ましく、より好ましくは０．１Ｍ〜１．６Ｍである。 Meanwhile, in the method for producing a multilayered nanocrystal according to the present invention, the concentration of the metal precursor in the step (b) for increasing the light emission efficiency at a blue wavelength is preferably 0.001M to 2M, More preferably, it is 0.1M-1.6M.
また、本発明に係る前記多層構造のナノ結晶の製造方法において、青色波長で発光効率を増加させるための（ｂ）段階の金属前駆体に対するＶＩ族またはＶ族元素のモル比は、ＶＩ族またはＶ族元素：金属前駆体の比が１００：１〜１：５０であることが好ましく、より好ましくは５０：１〜１：１０である。 In the method for producing a multilayered nanocrystal according to the present invention, the molar ratio of the group VI or group V element to the metal precursor in the step (b) for increasing the light emission efficiency at a blue wavelength is a group VI or The ratio of group V element: metal precursor is preferably 100: 1 to 1:50, more preferably 50: 1 to 1:10.
本発明の他の形態は、前記製造方法によって製造された多層構造のナノ結晶に関するものである。前記ナノ結晶の形状は、球状、正四面体状、円筒状、棒状、三角状、円板状、三脚状、テトラポッド状、立方体状、箱状、星状およびチューブ状よりなる群から選択できるが、これらに限定されるものではない。 Another embodiment of the present invention relates to a nanocrystal having a multilayer structure manufactured by the manufacturing method. The nanocrystal shape can be selected from the group consisting of spherical, tetrahedral, cylindrical, rod, triangular, disc, tripod, tetrapod, cube, box, star and tube. However, it is not limited to these.
また、前記ナノ結晶の発光領域は、３５０ｎｍ〜７００ｎｍ、より好ましくは３８０ｎｍ〜４９０ｎｍであり、前記領域内で最大発光ピークを示しながら青色光を発する。このような青色光を発するナノ結晶の発光効率は、０．１％〜１００％、より好ましくは２０％〜１００％である。 The emission region of the nanocrystal is 350 nm to 700 nm, more preferably 380 nm to 490 nm, and emits blue light while exhibiting the maximum emission peak in the region. The luminous efficiency of such a nanocrystal emitting blue light is 0.1% to 100%, more preferably 20% to 100%.
一方、本発明の多層構造のナノ結晶は、ディスプレイ、センサ、エネルギー分野に様々に応用でき、特に青色発光素子の発光層の形成の際に有用である。 On the other hand, the nanocrystal having a multilayer structure of the present invention can be applied in various fields such as a display, a sensor and an energy field, and is particularly useful for forming a light emitting layer of a blue light emitting element.
すなわち、本発明の他の形態は、多層構造のナノ結晶を含む素子に関するものであり、具体的には、前記多層構造のナノ結晶を発光層に導入した有機無機電気発光素子に関するものである。 That is, another embodiment of the present invention relates to an element including a nanocrystal having a multilayer structure, and specifically relates to an organic / inorganic electroluminescent element in which the nanocrystal having the multilayer structure is introduced into a light emitting layer.
より具体的に、本発明の有機無機電気発光素子の構造は、図６に示すように、基板１０、正孔注入電極２０、正孔輸送層３０、発光層４０、電子輸送層５０および電子注入電極６０を順次含み、前記発光層４０が半導体である本発明の多層構造のナノ結晶を含むことを特徴とする。 More specifically, as shown in FIG. 6, the structure of the organic / inorganic electroluminescent device of the present invention includes a substrate 10, a hole injection electrode 20, a hole transport layer 30, a light emitting layer 40, an electron transport layer 50, and an electron injection. The electrode 60 is sequentially included, and the light emitting layer 40 includes a nanocrystal having a multilayer structure of the present invention which is a semiconductor.
必要であれば、本発明では、発光層４０と電子輸送層５０との間に正孔抑制層７０を導入してもよい。 If necessary, in the present invention, a hole suppression layer 70 may be introduced between the light emitting layer 40 and the electron transport layer 50.
本発明の電気発光素子に使用される基板１０は、通常用いられる基板を使用することができ、具体的に、透明性、表面平滑性、取扱容易性および防水性に優れたガラス基板または透明プラスチック基板が好ましい。さらに具体的な例としては、ガラス基板、テレフタル酸ポリエチレン基板、ポリカーボネート基板などがある。 As the substrate 10 used in the electroluminescent device of the present invention, a commonly used substrate can be used, and specifically, a glass substrate or transparent plastic excellent in transparency, surface smoothness, ease of handling and waterproofness. A substrate is preferred. More specific examples include a glass substrate, a polyethylene terephthalate substrate, and a polycarbonate substrate.
正孔注入電極２０を構成する材料は、伝導性金属またはその酸化物であって、具体的な例としてはＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）、ＩＺＯ（Ｉｎｄｉｕｍ Ｚｉｎｃ Ｏｘｉｄｅ）、ニッケル（Ｎｉ）、白金（Ｐｔ）、金（Ａｕ）、銀（Ａｇ）およびイリジウム（Ｉｒ）などを使用することができる。 The material constituting the hole injection electrode 20 is a conductive metal or an oxide thereof, and specific examples thereof include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), nickel (Ni), platinum (Pt ), Gold (Au), silver (Ag), iridium (Ir), and the like.
一方、本発明の正孔輸送層３０を構成する材料としては、通常用いられる物質であればいずれも使用することができ、その具体的な例としては、ポリ（３,４−エチレンジオフェン）（ＰＥＤＯＴ）／ポリスチレンパラスルフォネート（ＰＳＳ）、ポリ−Ｎ−ビニルカルバゾール（ｐｏｌｙ−Ｎ−ｖｉｎｙｌｃａｒｂａｚｏｌｅ）誘導体、ポリフェニレンビニレン（ｐｏｌｙｐｈｅｎｙｌｅｎｅｖｉｎｙｌｅｎｅ）誘導体、ポリパラフェニレン（ｐｏｌｙｐａｒａｐｈｅｎｙｌｅｎｅ）誘導体、ポリメタクリレート（ｐｏｌｙｍｅｔｈａａｃｒｙｌａｔｅ）誘導体、ポリ（９，９−オクチルフルオレン）（ｐｏｌｙ（９，９−ｏｃｔｙｌｆｌｕｏｒｅｎｅ））誘導体、ポリ（スピロ−フルオレン）（ｐｏｌｙ（ｓｐｉｒｏ−ｆｌｕｏｒｅｎｅ））誘導体、およびＴＰＤ（Ｎ，Ｎ’−ビス−（３−メチルフェニル）−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジン）を含むが、必ずしもこれらに限定されるものではない。本発明において、正孔輸送層の厚さは１０〜１００ｎｍが好ましい。 On the other hand, as a material constituting the hole transport layer 30 of the present invention, any of the commonly used substances can be used, and specific examples thereof include poly (3,4-ethylenediophene). (PEDOT) / polystyrene parasulfonate (PSS), poly-N-vinylcarbazole derivative, polyphenylene vinylene derivative, polyparaphenylene derivative, polymethacrylate derivative (9,9-octylfluorene) (poly (9,9-octylfluorene)) derivative, poly (spiro-fluorene) (poly (spiro-fluorene)) ) Derivatives, and TPD (N, N'-bis- (3-methylphenyl) -N, N'-bis- (phenyl) -benzidine)), but are not necessarily limited thereto. In the present invention, the thickness of the hole transport layer is preferably 10 to 100 nm.
本発明の電子輸送層５０を構成する材料としては、通常用いられる物質を使用することができる。その具体的な例としては、オキサゾール系化合物、イソオキサゾール系化合物、トリアゾール系化合物、イソチアゾール系化合物、オキシジアゾール系化合物、チアジアゾール系化合物、フリレン系化合物、およびトリス（８−ヒドロキシキノリン）−アルミニウム（Ａｌｑ３）、ビス（２−メチル−８−キノラート）（ｐ−フェニル−フェノラート）アルミニウム（Ｂａｌｑ）、ビス（２−メチル−８−キノリナート）（トリフェニルシロキシ）アルミニウム（ＩＩＩ）（Ｓａｌｑ）などのアルミニウム錯体を挙げることができるが、必ずしもこれらに限定されるものではない。本発明において、電子輸送層の厚さは１０〜１００ｎｍが好ましい。 As a material constituting the electron transport layer 50 of the present invention, a commonly used substance can be used. Specific examples thereof include oxazole compounds, isoxazole compounds, triazole compounds, isothiazole compounds, oxydiazole compounds, thiadiazole compounds, furylene compounds, and tris (8-hydroxyquinoline) -aluminum. (Alq3), bis (2-methyl-8-quinolate) (p-phenyl-phenolate) aluminum (Balq), bis (2-methyl-8-quinolinato) (triphenylsiloxy) aluminum (III) (Salq), etc. Although aluminum complex can be mentioned, it is not necessarily limited to these. In the present invention, the thickness of the electron transport layer is preferably 10 to 100 nm.
本発明の電子注入電極６０を構成する材料は、容易な電子注入のために仕事関数の小さい金属、すなわちＩ、Ｃａ、Ｂａ、Ｃａ／Ａｌ、ＬｉＦ／Ｃａ、ＬｉＦ／Ａｌ、ＢａＦ２／Ａｌ、ＢａＦ２／Ｃａ／Ａｌ、Ａｌ、Ｍｇ、Ａｇ：Ｍｇ合金などを含むが、必ずしもこれらに限定されるものではない。本発明において、好ましい電子注入電極の厚さは５０ｎｍ〜３００ｎｍである。 The material constituting the electron injection electrode 60 of the present invention is a metal having a small work function for easy electron injection, that is, I, Ca, Ba, Ca / Al, LiF / Ca, LiF / Al, BaF 2 / Al, Including, but not necessarily limited to, BaF 2 / Ca / Al, Al, Mg, Ag: Mg alloy. In the present invention, a preferable thickness of the electron injection electrode is 50 nm to 300 nm.
本発明の正孔抑制層７０を構成する材料は、当該技術分野で通常用いられる物質を使用することができる。具体的な例としては、３−（４−ビフェニイル）−４−フェニル−５−（４−ｔｅｒｔ−ブチルフェニル）−１，２，４−トリアゾール（ＴＡＺ）、２，９−ジメチル−１，１０−フェナントロリン（ＢＣＰ）、フェナントロリン（ｐｈｅｎａｎｔｈｒｏｌｉｎｅｓ）系化合物、イミダゾール系化合物、トリアゾール（ｔｒｉａｚｏｌｅｓ）系化合物、オキサジアゾール（ｏｘａｄｉａｚｏｌｅｓ）系化合物およびアルミニウム錯体などを含むが、必ずしもこれらに限定されるものではない。本発明において、好ましい正孔抑制層の厚さは５〜５０ｎｍである。 As a material constituting the hole suppression layer 70 of the present invention, a substance that is usually used in the technical field can be used. Specific examples include 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 2,9-dimethyl-1,10. -It includes, but is not necessarily limited to, phenanthroline (BCP), phenanthroline compounds, imidazole compounds, triazoles compounds, oxadiazoles compounds and aluminum complexes. In the present invention, the preferred hole suppression layer thickness is 5 to 50 nm.
以下、実施例によって本発明をより詳細に説明する。しかしながら、下記の実施例は、本発明を説明するためのもので、本発明を制限するものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for explaining the present invention and do not limit the present invention.
実施例１．ＣｄＳｅナノ結晶および多層構造のＣｄＳｅ／／ＺｎＳ合成
トリオクチルアミン（Ｔｒｉｏｃｔｙｌａｍｉｎｅ、以下「ＴＯＡ」という）１６ｇ、オクタデシルホスホン酸０.３ｇおよび酸化カドミウム０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込んだ後、攪拌しながら反応温度を３００℃に調節した。
Example 1. Synthesis of CdSe nanocrystals and multilayered CdSe // ZnS After charging 16 g of trioctylamine (hereinafter referred to as “TOA”), 0.3 g of octadecylphosphonic acid and 0.4 mmol of cadmium oxide into a 125 mL reflux condenser flask at the same time The reaction temperature was adjusted to 300 ° C. while stirring.
これとは別に、Ｓｅ粉末をトリオクチルホスフィン（ＴＯＰ）に溶解させてＳｅ濃度約２Ｍ程度のＳｅ−ＴＯＰ錯体溶液を作った。前記攪拌されている反応混合物に２Ｍ Ｓｅ−ＴＯＰ錯体溶液２ｍＬを速い速度で注入し、約２分間反応させた。 Separately, Se powder was dissolved in trioctylphosphine (TOP) to prepare a Se-TOP complex solution having a Se concentration of about 2M. To the stirred reaction mixture, 2 mL of 2M Se-TOP complex solution was injected at a high speed and allowed to react for about 2 minutes.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒（ｎｏｎ ｓｏｌｖｅｎｔ）としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させてＣｄＳｅナノ結晶溶液を合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize a CdSe nanocrystal solution.
ＴＯＡ８ｇ、オレイン酸０．１ｇおよび酢酸亜鉛０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。前記で合成したＣｄＳｅナノ結晶溶液を反応物に添加した後、Ｓ−ＴＯＰ錯体溶液をゆっくり加えて約１時間反応させることによりＣｄＳｅナノ結晶の表面上にＺｎＳナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。 8 g of TOA, 0.1 g of oleic acid and 0.4 mmol of zinc acetate were simultaneously charged into a 125 mL flask equipped with a reflux condenser, and the reaction temperature was adjusted to 300 ° C. while stirring. After adding the CdSe nanocrystal solution synthesized above to the reaction product, the S-TOP complex solution is slowly added and allowed to react for about 1 hour to grow ZnS nanocrystals on the surface of the CdSe nanocrystals and diffuse to the interface. Thus, an alloy layer was formed.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSe // ZnS.
こうして得られたナノ結晶は、３６５ｎｍＵＶランプの下で青色にて発光した。本実施例で得たコアＣｄＳｅナノ結晶と多層構造のＣｄＳｅ／／ＺｎＳナノ結晶の透過電子顕微鏡写真（ＴＥＭ）をそれぞれ図７および図８に示し、光励起発光スペクトルを調査して図９に示した。図９に示すように、発光波長の中心はそれぞれ４７０ｎｍ、４９６ｎｍであった。 The nanocrystals thus obtained emitted blue light under a 365 nm UV lamp. Transmission electron micrographs (TEM) of the core CdSe nanocrystal and the multilayer CdSe // ZnS nanocrystal obtained in this example are shown in FIG. 7 and FIG. 8, respectively, and the photoexcitation emission spectrum was investigated and shown in FIG. . As shown in FIG. 9, the centers of the emission wavelengths were 470 nm and 496 nm, respectively.
実施例２．反応温度による多層構造のＣｄＳｅ／／ＺｎＳ合成効果
ＴＯＡ８ｇ、オレイン酸０．１ｇおよび酢酸亜鉛０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度をそれぞれ２２０℃、２６０℃、３００℃および３２０℃に調節した。実施例１で合成したＣｄＳｅナノ結晶溶液を反応物に添加した後、Ｓ−ＴＯＰ錯体溶液をゆっくり加えて約１時間反応させることによりＣｄＳｅナノ結晶の表面上にＺｎＳナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。
Example 2 Synthetic effect of CdSe // ZnS with multilayer structure depending on reaction temperature 8 g of TOA, 0.1 g of oleic acid and 0.4 mmol of zinc acetate were charged simultaneously into a 125 mL flask equipped with a reflux condenser, and the reaction temperatures were 220 ° C., 260 ° C., 300 respectively while stirring. Adjusted to ℃ and 320 ℃. After the CdSe nanocrystal solution synthesized in Example 1 was added to the reaction product, the S-TOP complex solution was slowly added and reacted for about 1 hour to grow ZnS nanocrystals on the surface of the CdSe nanocrystals. An alloy layer was formed by diffusion.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSe // ZnS.
コアとして用いたＣｄＳｅの発光波長の中心が５２２ｎｍであり、反応後得られた多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳは反応温度によって異なる青色で発光した。反応温度による発光波長の変化を表１にまとめた。 The center of the emission wavelength of CdSe used as the core was 522 nm, and the nanocrystal CdSe // ZnS having a multilayer structure obtained after the reaction emitted light in a blue color different depending on the reaction temperature. Table 1 summarizes changes in the emission wavelength depending on the reaction temperature.
実施例３．反応時間による多層構造のＣｄＳｅ／／ＺｎＳ合成効果
ＴＯＡ８ｇ、オレイン酸０．１ｇおよび酢酸亜鉛０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。実施例１で合成したＣｄＳｅナノ結晶溶液を反応物に添加した後、Ｓ−ＴＯＰ錯体溶液をゆっくり加えてそれぞれ５分、２０分、４０分、１時間反応させることによりＣｄＳｅナノ結晶の表面上にＺｎＳナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。
Example 3 Synthetic effect of CdSe // ZnS having a multilayer structure depending on the reaction time 8 g of TOA, 0.1 g of oleic acid and 0.4 mmol of zinc acetate were charged simultaneously into a 125 mL flask equipped with a reflux condenser, and the reaction temperature was adjusted to 300 ° C. while stirring. After the CdSe nanocrystal solution synthesized in Example 1 was added to the reaction product, the S-TOP complex solution was slowly added and reacted for 5 minutes, 20 minutes, 40 minutes, and 1 hour, respectively, on the surface of the CdSe nanocrystals. ZnS nanocrystals were grown, and an alloy layer was formed by diffusion at the interface.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSe // ZnS.
こうして得られたナノ結晶は、３６５ｎｍＵＶランプの下で青色にて発光した。コアとして用いたＣｄＳｅの発光波長の中心が４９６ｎｍであり、こうして得られたナノ結晶は反応時間によって異なる青色で発光した。反応時間による発光波長の変化を表２にまとめた。 The nanocrystals thus obtained emitted blue light under a 365 nm UV lamp. The center of the emission wavelength of CdSe used as the core was 496 nm, and the nanocrystals thus obtained emitted blue light that differed depending on the reaction time. Table 2 summarizes changes in emission wavelength with reaction time.
実施例４．前駆体の濃度によるＣｄＳｅ／／ＺｎＳ合成効果
ＴＯＡ８ｇ、オレイン酸をそれぞれ０．０１ｇ、０．０５、０．１ｇ、および酢酸亜鉛をそれぞれ０．０４ｍｍｏｌ、０．２ｍｍｏｌ、０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。実施例１で合成したＣｄＳｅナノ結晶溶液を反応物に添加した後、Ｓ−ＴＯＰ錯体溶液をゆっくり加えて約３０分間反応させることによりＣｄＳｅナノ結晶の表面上にＺｎＳナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。
Example 4 CdSe // ZnS synthesis effect by precursor concentration TOA 8g, oleic acid 0.01g, 0.05, 0.1g and zinc acetate 0.04mmol, 0.2mmol, 0.4mmol respectively 125mL reflux at the same time The reaction temperature was adjusted to 300 ° C. while stirring in a flask with a condenser. After the CdSe nanocrystal solution synthesized in Example 1 was added to the reaction product, the S-TOP complex solution was slowly added and reacted for about 30 minutes to grow ZnS nanocrystals on the surface of the CdSe nanocrystals. An alloy layer was formed by diffusion.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSe // ZnS.
コアとして用いたＣｄＳｅの発光波長の中心が４９６ｎｍであり、反応後得られたナノ結晶は前駆体の濃度によって異なる青色で発光した。前駆体の濃度による発光波長の変化を表３にまとめた。 The center of the emission wavelength of CdSe used as the core was 496 nm, and the nanocrystals obtained after the reaction emitted light in blue depending on the concentration of the precursor. Table 3 summarizes changes in emission wavelength depending on the concentration of the precursor.
実施例５．追加反応温度の調節による多層構造のＣｄＳｅ／／ＺｎＳ合成
ＴＯＡ１６ｇ、オクタデシルホスホン酸０．３ｇおよび酸化カドミウム０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。これとは別途に、Ｓｅ粉末をトリオクチルホスフィン（ＴＯＰ）に溶解させてＳｅ濃度約２Ｍ程度のＳｅ−ＴＯＰ錯体溶液を作った。前記攪拌されている反応混合物に２Ｍ Ｓｅ−ＴＯＰ錯体溶液２ｍＬを速い速度で注入し、約２分間反応させた。
Example 5 FIG. Synthesis of multi-layered CdSe // ZnS by adjusting additional reaction temperature TOA (16 g), octadecylphosphonic acid (0.3 g) and cadmium oxide (0.4 mmol) were charged into a 125 mL reflux condenser flask at the same time, and the reaction temperature was adjusted to 300 ° C. with stirring. . Separately, Se powder was dissolved in trioctylphosphine (TOP) to prepare a Se-TOP complex solution having a Se concentration of about 2M. To the stirred reaction mixture, 2 mL of 2M Se-TOP complex solution was injected at a high speed and allowed to react for about 2 minutes.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させてＣｄＳｅナノ結晶溶液を合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize a CdSe nanocrystal solution.
ＴＯＡ８ｇ、オレイン酸０．１ｇおよび酢酸亜鉛０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を２６０℃に調節した。前記で合成したＣｄＳｅナノ結晶溶液を反応物に添加した後、Ｓ−ＴＯＰ錯体溶液をゆっくり加えて約１時間反応させた。１時間反応後、反応温度をゆっくり増加させて３００℃に合わせ、その温度で約１時間反応させてＣｄＳｅナノ結晶の表面上にＺｎＳナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。 8 g of TOA, 0.1 g of oleic acid and 0.4 mmol of zinc acetate were charged simultaneously into a 125 mL flask equipped with a reflux condenser, and the reaction temperature was adjusted to 260 ° C. while stirring. After the CdSe nanocrystal solution synthesized above was added to the reaction product, the S-TOP complex solution was slowly added and allowed to react for about 1 hour. After the reaction for 1 hour, the reaction temperature is slowly increased to 300 ° C., and the reaction is performed at that temperature for about 1 hour to grow ZnS nanocrystals on the surface of the CdSe nanocrystals, and an alloy layer is formed at the interface by diffusion. It was.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSe // ZnS.
コアとして用いたＣｄＳｅ、２６０℃で１時間反応させて得たナノ結晶、および２６０℃で１時間反応させ後３００℃で１時間反応させて得たナノ結晶の各光励起発光スペクトルを調査して図１０に示した。図１０に示すように、発光波長の中心はそれぞれ４９８ｎｍ、４９２ｎｍ、４６６ｎｍであった。 Each photoexcited emission spectrum of CdSe used as a core, a nanocrystal obtained by reacting at 260 ° C. for 1 hour, and a nanocrystal obtained by reacting at 260 ° C. for 1 hour and then reacted at 300 ° C. for 1 hour is shown in FIG. This is shown in FIG. As shown in FIG. 10, the centers of the emission wavelengths were 498 nm, 492 nm, and 466 nm, respectively.
実施例６．多層構造のＣｄＳｅ／／ＺｎＳｅ合成
ＴＯＡ８ｇ、オレイン酸０．１ｇおよび酢酸亜鉛０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。実施例１で合成したＣｄＳｅナノ結晶溶液を反応物に添加した後、Ｓｅ−ＴＯＰ錯体溶液をゆっくり加えて約１時間反応させることにより、ＣｄＳｅナノ結晶の表面上にＺｎＳｅナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。
Example 6 Synthesis of CdSe // ZnSe with multilayer structure 8 g of TOA, 0.1 g of oleic acid and 0.4 mmol of zinc acetate were charged simultaneously into a 125 mL flask equipped with a reflux condenser, and the reaction temperature was adjusted to 300 ° C. while stirring. After the CdSe nanocrystal solution synthesized in Example 1 was added to the reaction product, the Se-TOP complex solution was slowly added and reacted for about 1 hour to grow ZnSe nanocrystals on the surface of the CdSe nanocrystals. An alloy layer was formed by diffusion at the interface.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅ／／ＺｎＳｅを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSe // ZnSe.
こうして得られたナノ結晶は、３６５ｎｍＵＶランプの下で青色にて発光した。本実施例で得たナノ結晶とコアとして用いたＣｄＳｅの各光励起発光スペクトルを調査して図１１に示した。図１１に示すように、発光波長の中心はそれぞれ４７２ｎｍ、４９６ｎｍであった。 The nanocrystals thus obtained emitted blue light under a 365 nm UV lamp. Each photoexcitation emission spectrum of the nanocrystal obtained in this example and CdSe used as the core was investigated and shown in FIG. As shown in FIG. 11, the centers of the emission wavelengths were 472 nm and 496 nm, respectively.
実施例７．ＣｄＳｅＳナノ結晶の合成および多層構造のＣｄＳｅＳ／／ＺｎＳ合成
ＴＯＡ１６ｇ、オレイン酸０．５ｇおよび酸化カドミウム０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。
Example 7 Synthesis of CdSeS nanocrystals and multilayer CdSeS // ZnS synthesis 16 g of TOA, 0.5 g of oleic acid and 0.4 mmol of cadmium oxide were charged simultaneously into a 125 mL flask equipped with a reflux condenser, and the reaction temperature was adjusted to 300 ° C. with stirring.
これとは別に、Ｓｅ粉末をトリオクチルホスフィン（ＴＯＰ）に溶解させてＳｅ濃度約０．２５Ｍ程度のＳｅ−ＴＯＰ錯体溶液を作り、Ｓ粉末をＴＯＰに溶解させてＳ濃度約１．０Ｍ程度のＳ−ＴＯＰ錯体溶液を作った。前記攪拌されている反応混合物にＳ−ＴＯＰ錯体溶液０．９ｍＬとＳｅ−ＴＯＰ錯体溶液０．１ｍＬの混合物を速い速度で注入し、４分間さらに攪拌した。 Separately, Se powder is dissolved in trioctylphosphine (TOP) to form a Se-TOP complex solution having a Se concentration of about 0.25M, and S powder is dissolved in TOP to have an S concentration of about 1.0M. An S-TOP complex solution was made. A mixture of 0.9 mL of S-TOP complex solution and 0.1 mL of Se-TOP complex solution was poured into the stirred reaction mixture at a high speed, and further stirred for 4 minutes.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに１ｗｔ％溶液となるように分散させてＣｄＳｅＳナノ結晶溶液を合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene so as to be a 1 wt% solution to synthesize a CdSeS nanocrystal solution.
ＴＯＡ８ｇ、オレイン酸０．１ｇおよび酢酸亜鉛０．４ｍｍｏｌを同時に１２５ｍＬの還流コンデンサ付きフラスコに仕込み、攪拌しながら反応温度を３００℃に調節した。前記で合成したＣｄＳｅＳナノ結晶溶液を反応物に添加した後、Ｓ−ＴＯＰ錯体溶液をゆっくり加えて約１時間反応させることにより、ＣｄＳｅＳナノ結晶の表面上にＺｎＳナノ結晶を成長させ、その界面に拡散によって合金層を形成させた。 8 g of TOA, 0.1 g of oleic acid and 0.4 mmol of zinc acetate were simultaneously charged into a 125 mL flask equipped with a reflux condenser, and the reaction temperature was adjusted to 300 ° C. while stirring. After the CdSeS nanocrystal solution synthesized above is added to the reaction product, the S-TOP complex solution is slowly added and reacted for about 1 hour to grow ZnS nanocrystals on the surface of the CdSeS nanocrystals. An alloy layer was formed by diffusion.
反応が終結すると、反応混合物の温度をできる限り速く常温に降温し、非溶媒としてのエタノールを加えて遠心分離を行った。遠心分離された沈澱物を除いた溶液の上澄み液は捨て、沈澱物はトルエンに分散させて５ｎｍサイズの多層構造のナノ結晶ＣｄＳｅＳ／／ＺｎＳを合成した。 When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature as quickly as possible, and ethanol as a non-solvent was added for centrifugation. The supernatant of the solution excluding the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize 5 nm-sized multilayered nanocrystalline CdSeS // ZnS.
こうして得られたナノ結晶は、３６５ｎｍＵＶランプの下で青色にて発光した。本実施例で得たナノ結晶溶液とコアとして用いたＣｄＳｅＳ溶液の各光励起発光スペクトルを調査して図１２に示した。図１２に示すように、発光波長の中心はそれぞれ５２７ｎｍ、５４０ｎｍであった。 The nanocrystals thus obtained emitted blue light under a 365 nm UV lamp. Each photoexcitation emission spectrum of the nanocrystal solution obtained in this example and the CdSeS solution used as the core was investigated and shown in FIG. As shown in FIG. 12, the centers of the emission wavelengths were 527 nm and 540 nm, respectively.
実施例８．青色発光ＣｄＳｅ／／ＺｎＳナノ結晶を発光層として用いた有機無機ハイブリッド電気発光素子の製作
本実施例は、実施例１で製造したＣｄＳｅ／／ＺｎＳナノ結晶を電気発光素子の発光素材として用いた有機無機ハイブリッド電気発光素子の製造例である。
Example 8 FIG. Production of organic-inorganic hybrid electroluminescent device using blue light emitting CdSe // ZnS nanocrystal as light emitting layer In this example, organic material using CdSe // ZnS nanocrystal manufactured in Example 1 as a light emitting material of electroluminescent device was used. It is an example of manufacture of an inorganic hybrid electroluminescent element.
ガラス基板上にＩＴＯがパターニングされている基板の上部に、正孔伝達物質のＮ，Ｎ’−ビス−（３−メチルフェニル）−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジン（ＴＰＤ）３重量％で製造されたクロロホルム溶液と実施例１で製造したＣｄＳｅ／／ＺｎＳ１重量％で製造されたクロロホルム溶液とを混合してスピンコートし、これを乾燥させて正孔伝達層と発光層を形成した。 On the top of the substrate on which ITO is patterned on a glass substrate, the hole transport material N, N′-bis- (3-methylphenyl) -N, N′-bis- (phenyl) -benzidine (TPD) 3 A chloroform solution prepared at weight% and a chloroform solution prepared at 1% by weight of CdSe // ZnS prepared in Example 1 were mixed and spin coated, and dried to form a hole transport layer and a light emitting layer. did.
完全に乾燥させた前記ナノ結晶発光層の上部に正孔抑制層の３−（４−ビフェニイル）−４−フェニル−５−（４−ｔｅｒｔ−ブチルフェニル）−１，２，４−トリアゾール（ＴＡＺ）を１０ｎｍ蒸着し、電子輸送層のｔｒｉｓ−（８−ヒドロキシキノリン）アルミニウム（Ａｌｑ-３）を３０ｎｍの厚さに蒸着し、この上部に厚さ１ｎｍのＬｉＦを蒸着し、さらにアルミニウムを２００ｎｍの厚さに蒸着して陰極を形成することにより、電気発光素子を完成した。 The hole-inhibiting layer 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ) is formed on the nanocrystal light emitting layer that has been completely dried. ) Is evaporated to 10 nm, tris- (8-hydroxyquinoline) aluminum (Alq- 3 ) as an electron transporting layer is evaporated to a thickness of 30 nm, LiF having a thickness of 1 nm is evaporated on top of this, and aluminum is further added to a thickness of 200 nm. An electroluminescent device was completed by forming a cathode by vapor deposition to a thickness.
本実施例で得た有機無機ハイブリッド電気発光素子の構造を図６に示し、前記電気発光素子の電気発光スペクトルを調査して図１３に示した。図１３に示すように、発光波長は約４６０ｎｍであり、ＦＷＨＭは約３６ｎｍであり、明度は５００Ｃｄ／ｍ２、装置の効率は１．５Ｃｄ／Ａであった。 The structure of the organic-inorganic hybrid electroluminescent device obtained in this example is shown in FIG. 6, and the electroluminescent spectrum of the electroluminescent device was investigated and shown in FIG. As shown in FIG. 13, the emission wavelength was about 460 nm, the FWHM was about 36 nm, the brightness was 500 Cd / m 2 , and the efficiency of the device was 1.5 Cd / A.
１０ 基板、
２０ 正孔注入電極、
３０ 正孔輸送層、
４０ 発光層、
５０ 電子輸送層、
６０ 電子注入電極、
７０ 正孔抑制層。
10 substrates,
20 hole injection electrode,
30 hole transport layer,
40 light emitting layer,
50 electron transport layer,
60 electron injection electrode,
70 Hole suppression layer.
Claims (43)
（ｂ）前記（ａ）段階で得られた第１ナノ結晶の表面上に第１ナノ結晶とは異なる種類の第２ナノ結晶を成長させる段階と、
（ｃ）前記第１ナノ結晶と前記第２ナノ結晶との界面に拡散によって合金層を形成する段階とを含む、多層構造のナノ結晶の製造方法。 (A) producing a first nanocrystal;
(B) growing a second nanocrystal of a type different from the first nanocrystal on the surface of the first nanocrystal obtained in the step (a);
(C) A method for producing a nanocrystal having a multilayer structure, including a step of forming an alloy layer by diffusion at an interface between the first nanocrystal and the second nanocrystal.
前記（ｂ）段階において、第２溶媒および第２分散剤に第２ナノ結晶の前駆体を含む溶液に第１ナノ結晶を仕込んだ後にこれらを混合し、反応させて第１ナノ結晶の表面上に第２ナノ結晶が形成されることを特徴とする、請求項１０に記載の方法。 In the step (a), a first nanocrystal is formed by charging a metal precursor and a group V or group VI precursor into a first solvent and a first dispersant, and then mixing and reacting them.
In the step (b), the first nanocrystals are charged into a solution containing the second nanocrystal precursor in the second solvent and the second dispersant, and then mixed and reacted with each other on the surface of the first nanocrystal. The method according to claim 10, wherein second nanocrystals are formed on the surface.
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