CN110003883A - 具有增强的稳定性和发光效率的量子点纳米粒子 - Google Patents
具有增强的稳定性和发光效率的量子点纳米粒子 Download PDFInfo
- Publication number
- CN110003883A CN110003883A CN201910042350.7A CN201910042350A CN110003883A CN 110003883 A CN110003883 A CN 110003883A CN 201910042350 A CN201910042350 A CN 201910042350A CN 110003883 A CN110003883 A CN 110003883A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- nano particle
- core
- dot nano
- ligand
- 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.)
- Pending
Links
- 239000002096 quantum dot Substances 0.000 title claims abstract description 91
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 56
- 230000002708 enhancing effect Effects 0.000 title description 3
- 239000003446 ligand Substances 0.000 claims abstract description 76
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 23
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 9
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 6
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 6
- 235000021360 Myristic acid Nutrition 0.000 claims description 6
- -1 aryl hydrocarbon Chemical class 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000000862 absorption spectrum Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000000295 emission spectrum Methods 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 abstract description 14
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012990 dithiocarbamate Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 22
- 125000004429 atom Chemical group 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 150000001412 amines Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000010899 nucleation Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000006911 nucleation Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000006862 quantum yield reaction Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000011824 nuclear material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- 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 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- PFOXCVDDXSMFBE-UHFFFAOYSA-N indium;tetradecanoic acid Chemical compound [In].CCCCCCCCCCCCCC(O)=O PFOXCVDDXSMFBE-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical compound CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/701—Chalcogenides
- C09K11/703—Chalcogenides with zinc or cadmium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
- Y10S977/774—Exhibiting three-dimensional carrier confinement, e.g. quantum dots
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/81—Of specified metal or metal alloy composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/813—Of specified inorganic semiconductor composition, e.g. periodic table group IV-VI compositions
- Y10S977/815—Group III-V based compounds, e.g. AlaGabIncNxPyAsz
- Y10S977/818—III-P based compounds, e.g. AlxGayIn2P
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/813—Of specified inorganic semiconductor composition, e.g. periodic table group IV-VI compositions
- Y10S977/824—Group II-VI nonoxide compounds, e.g. CdxMnyTe
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/88—Manufacture, treatment, or detection of nanostructure with arrangement, process, or apparatus for testing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/882—Assembling of separate components, e.g. by attaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/89—Deposition of materials, e.g. coating, cvd, or ald
- Y10S977/892—Liquid phase deposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
- Y10S977/949—Radiation emitter using nanostructure
- Y10S977/95—Electromagnetic energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
Abstract
已经发现某些二硫代化合物是用于量子点(QD)纳米粒子的优秀封端配体。二硫代配体的实例包括二硫代氨基甲酸酯或盐配体。这些强结合的配体能够配位至纳米粒子表面上的正原子和负原子二者。所述配体是二齿的,并且因此它们向QD表面的接近不像单齿配体的接近那样是空间位阻的。这些配体因此可以完全充满QD表面。
Description
本申请是国际申请日为2015年2月6日、发明名称为“具有增强的稳定性和发光效率的量子点纳米粒子”、国际申请号为PCT/GB2015/050336并且中国国家申请号为201580007042.0的申请的分案申请。
相关申请的交叉引用:
本申请要求2014年2月7日提交的美国临时申请号61/937,073的权益。
关于联邦资助的研究或开发的声明:不适用
发明背景
发明领域
本发明总体上涉及半导体纳米粒子(“量子点”)。更具体地,其涉及在其外表面上具有封端配体的半导体纳米粒子。
2.包括根据37CFR 1.97和1.98公开的信息的相关领域的描述。
在通常被称为量子点(QD)和/或纳米晶体的具有大约2-100nm的等级的化合物半导体粒子的制备和表征方面,已经存在相当大的兴趣。这主要是因为它们的尺寸可调节的电子、光学和化学性质。例如,许多QD在电磁波谱的可见光区中显示出相对强的发射。此外,吸收和发射的光的波长是QD的尺寸的函数。由于它们独特的光学性质,QD是用于多种商业应用的有前景的材料,例如生物标记、太阳能电池、催化、生物成像、发光二极管、以及许多新型和新兴应用。
迄今为止,最多研究和制备的半导体材料是II-VI材料,即ZnS、ZnSe、CdS、CdSe、CdTe——最值得一提的是CdSe,这是由于其在光谱的可见光区中的可调性。如提到的,半导体纳米粒子是学术和商业上令人感兴趣的,这是由于它们与相同半导体材料的相应晶体大块形式的性质相比独特的性质。均与单个纳米粒子的尺寸有关的两个基本因素是造成其独特性质的原因。第一个是大的表面与体积比。随着粒子变得更小,表面原子的数量与内部原子的数量的比率增加。这导致表面性质在小粒子的总体性质中起着重要的作用。第二个因素是,对于半导体纳米粒子来说,存在着材料的电子性质随粒子尺寸的变化。具体地,随着粒子尺寸减小,带隙逐渐变宽。这种带隙的变化是因为量子限制效应(quantumconfinement effect)。这种效应是“盒中电子(electron in a box)”的限制的结果,其产生类似于在原子和分子中观察到的离散能级,而不是在相应的大块半导体材料中观察到的连续能带。因此,对于半导体纳米粒子来说,通过光子的吸收而产生的“电子和空穴”比在相应的粗晶材料中更靠近在一起,引起电子和空穴之间的不可忽略的库伦相互作用。这导致了取决于粒度和组成的窄带宽发射。因此,量子点具有比相应的粗晶材料更高的动能,并且第一激子跃迁(带隙)的能量随着粒径减小而增加。因此,具有较小直径的量子点比具有较大直径的量子点吸收和发射更高能量的光。换句话说,可以根据粒径“调节”吸收和发射的光的颜色。
归因于在位于纳米粒子表面上导致非辐射电子-空穴复合的缺陷和悬挂键(dangling bond)处发生的电子-空穴复合,由单一半导体材料组成的单一核纳米粒子倾向于具有较低的量子效率。消除缺陷和悬挂键的一种方法是在核粒子表面上生长具有宽带隙的第二半导体材料的壳以制备“核-壳粒子”。壳半导体材料优选具有与核材料的小晶格错配从而使两种材料之间的界面最小化。核-壳粒子将被限制在核中的电荷载流子从表面状态中分离,否则表面状态会起非辐射复合中心的作用。常见的实例是在CdSe核的表面上生长的ZnS。过度的应变可能会进一步造成导致低量子效率的缺陷和非辐射电子-空穴复合。
已经报道了多种用于制备半导体纳米粒子的合成方法。早期途径应用常规胶体水性化学,而较近的方法涉及使用有机金属化合物的纳米微晶的动力学控制的沉淀。
因为QD的光学性质是尺寸依赖性的,通常理想的是制备具有高单分散度(即具有在群中的QD的尺寸的高均匀度)的QD群。此外,具有高量子产率(QY,发射的光子与吸收的光子的比率)的QD群是理想的。已经报道了制备具有高单分散性并且具有大于50%的量子产率的半导体QD的方法。这些方法中的大多数基于由Murray、Norris和Bawendi,M.G.J.Am.Chem.Soc.1993,115,8706描述的最初的“成核和生长”方法。Murray等人最初使用金属-烷基(R2M)(M=Cd、Zn、Te;R=Me、Et和三正辛基硫化/硒化膦(TOPS/Se))溶解在三正辛基膦(TOP)中的有机金属溶液。将这些前体溶液在120-400℃的温度范围内注入至热的三正辛基氧化膦(TOPO)中。这制备了TOPO涂布/封端的II-VI材料的半导体纳米粒子。可以通过温度、所使用的前体的浓度、和合成的时间长度来控制粒子的尺寸。这种有机金属途径具有超过其他合成方法的优点,包括接近的单分散性和高的粒子结晶度。
在常规QD中使用的镉和其他受限的重金属是高毒性的并且在商业应用中表现出严重的担忧。含镉QD的固有毒性妨碍了它们在包括动物或人的任何用途中使用。例如,近期研究显示,除非受到保护,由镉硫属化物半导体材料制成的QD在生物环境中可能是细胞毒性的。具体地,通过多种途径的氧化或化学侵蚀可能会导致可以被释放至周围环境中的QD表面上的镉离子的形成。尽管表面涂层如ZnS可以明显地降低毒性,但它不可能将其完全消除,因为QD可以长时间在细胞中停留或在身体中积累,在此期间,它们的涂层可能会经历将富镉核暴露的某类降解。
毒性还影响包括光电子和通讯在内的应用,因为重金属系材料广泛用于包括家用电器如IT和电信设备、照明设备、电学和电子工具、玩具、休闲和运动设备在内的许多商业产品。在世界的许多区域已经实施了限制或禁止商业产品中某些重金属的法规。例如,被称为“在电子设备中限制使用有害物质”(或RoHS)的欧盟指令2002/95/EC禁止了含有大于某些水平的铅、镉、汞、六价铬以及多溴联苯(PBB)和多溴二苯醚(PBDE)阻燃剂的电气和电子设备的销售。作为该命令的结果,制造商需要寻找备选材料并且开发用于形成常见电子设备的新型工程工艺。另外,在2007年6月1日,关于化学品及其安全使用的欧共体法规开始生效(EC 1907/2006)。该法规涉及化学物质的注册、评估、授权和限制,并且被称为“REACH”。REACH法规赋予企业更多的责任,以管控来自化学品的风险并且提供关于物质的安全性信息。预计类似的法规将会扩大到世界范围。因此,存在明显的经济刺激以开发II-VI QD材料的替代方案。
归因于它们增加的共价性质,III-V和IV-VI高结晶性半导体纳米粒子更难以制备并且通常需要长得多的退火时间。然而,现在有以与用于II-VI材料的方式相似的方式制备III-VI和IV-VI材料的报道。这样的III-VI和IV-VI材料的实例包括GaN、GaP、GaAs、InP、InAs以及PbS和PbSe。
对于全部以上方法来说,快速的粒子成核和随后的缓慢的粒子生长对于窄粒度分布来说是必需的。所有这些合成方法基于Murray等人的最初的有机金属“成核和生长”方法,其涉及将前体快速注入至路易斯碱配位溶剂(封端剂)的热溶液中。较冷的溶液的加入降低了反应温度并且辅助粒子生长但是抑制了进一步成核。之后将温度维持一段时间,并且所得粒子的尺寸取决于反应时间、温度、和封端剂与所使用的前体的比率。将所得溶液冷却,接着加入过量的极性溶剂(甲醇或乙醇或有时丙酮)以产生可以通过过滤或离心分离的粒子的沉淀。通常,较大粒子比较小粒子更容易沉淀。因此,沉淀提供了将量子点根据其尺寸分离的手段。需要多个沉淀步骤以实现窄粒度分布。
根本上,这些现有技术制品依赖于粒子成核之后接着生长的原理。该原理依赖于纳米粒子成核步骤(在高温下)与纳米粒子生长步骤(在较低温度下)的分离以获得单分散性。这样的步骤的分离通过将前体之一或二者快速注入至引发粒子成核的热配位溶剂(如果不另外存在的话,含有另一种前体)中来实现。在注入时突然加入较冷的溶液随后降低了反应温度(所加入的溶液的体积为总溶液的约1/3)并且抑制了进一步成核,维持了窄纳米粒子尺寸分布。对于其中可以将一种溶液迅速加入至另一种中同时在整个反应中保持均匀温度的小规模合成来说,这种方法可以良好地进行。然而,在其中需要将大体积的溶液迅速注入至彼此中的较大的制备规模上,可能会在反应中出现温度差,这可能会导致大的粒度分布。此外,对于大量QD的制备来说,对进行多个尺寸选择性纯化步骤的需求是不实际的。
其全部内容通过引用结合于此的美国专利号7,588,828、7,803,423、7,985,446、和8,062,703(在本文中统称为“加晶种(seeding)专利”)描述了不依赖于上述热注入方法和尺寸选择性纯化步骤的用于制备单分散QD群的合成方法。简而言之,所述方法涉及使用充当用于QD半导体材料在溶液中成核的模板的分子簇“晶种”化合物。簇化合物起晶种或可以启动纳米粒子生长的成核点的作用。以这种方式,对于引发纳米粒子生长来说,高温成核步骤不是必需的,因为已经通过分子簇在体系中提供了适合的成核部位。通过提供比在上述方法中采用的成核部位更均匀的成核部位,该合成提供了基本上单分散的QD群。分子加晶种方法的明显优点是其可以容易地增加规模。
无论如何制备QD纳米粒子,在外部无机表面原子周围的原子的结合都是不完全的。表面被高度反应性的“悬挂键”占据,这可能会导致粒子聚集。这些未配位的表面原子还可以提供可以为辐射发射提供备选复合途径的表面态的激子。这样的途径是不希望的并且导致较低的发光。此外,未配位原子的可能会对氧化更敏感。
可以用保护性有机基团将“裸露”表面原子钝化(封端)来部分克服与未配位的悬挂键相关的问题。粒子的封端或钝化不仅防止粒子聚集出现,其还保护粒子不受其周围化学环境影响并且为粒子提供电子稳定(钝化)。封端剂通常是与粒子的最外无机层的表面金属原子结合(例如,与核-壳QD粒子的最外壳结合)的路易斯碱化合物或其他给电子化合物。当在给电子溶剂如TOP/TOPO中进行QD壳合成时,封端剂可以仅为粘附至QD表面的溶剂分子。在使用非给电子溶剂的情况下,可以将富含电子的封端剂加入至壳合成中。例如,如果将溶剂如THERMINOL用于包壳(shelling)反应,加入给电子化合物(如将肉豆蔻酸至反应混合物中)以提供封端配体可能会是必需的。
尽管给电子封端配体提供一些稳定性和表面钝化,这些配体中的许多仅弱地粘附至QD纳米粒子的表面。封端配体的脱附在表面上留下了空隙,这可能会导致聚集、沉淀,并且对QD的量子效率不利。解决弱结合的封端配体的问题的一种方式是使用含有对QD表面上的原子具有特异性结合亲和力的官能团的封端配体。例如,硫醇化合物的硫对于通常为QD壳半导体材料(如ZnS和ZnSe)的组分的许多金属原子(如锌)具有亲和力。因此,已经广泛使用硫醇作为用于QD的封端配体。但是硫醇封端配体也可能脱附,在QD表面上留下有问题的空隙。硫醇配体脱附的一种可能的机制是经由在QD表面上相邻硫醇之间的二硫键的形成以及随后的二硫化物的脱附。硫醇封端配体的另一个问题是,在一些情况下,空间位阻可能会阻碍完整的表面覆盖。换句话说,在得到一定的表面覆盖后,空间上阻碍额外的硫醇分子到达QD的表面而结合,即使在表面仍然留下大量的悬挂键未被填充。因此,为了使QD材料的性能和稳定性最大化,存在着对更有效的用于QD封端配体的需求。
发明概述
在本文中所公开的二硫代配体解决了上述问题。二硫代配体的实例包括二硫代氨基甲酸酯或盐配体。在本文中所描述的强结合的配体能够配位至纳米粒子表面上的正原子和负原子二者。所述配体是二齿的,并且因此它们向QD表面的接近不像单齿配体的接近那样是空间位阻的。公开的配体因此可以完全充满QD表面。
根据一个实施方案,将具有结合QD表面的正电性原子的基团的第一配体加入至QD中并且之后加入具有结合负电性原子的基团的第二配体。例如,如果最外壳包含ZnS,则一个配体可以优选与壳表面上的正电性的Zn原子结合,并且第二配体可以优选与更加负电性的S原子结合。通过在QD表面上结合更大数量的可用结合位点,在本文中所公开的二硫代氨基甲酸酯或盐配体提高了QD纳米粒子的稳定性和光学特征。
本发明的第一方面提供一种量子点(QD)纳米粒子,所述QD纳米粒子包含多个第一二硫代氨基甲酸酯或盐封端配体。所述二硫代氨基甲酸酯或盐封端配体可以具有选自由下列各项组成的组的式:
其中R是官能团。R可以包含亲水基团或两亲性部分。QD纳米粒子还可以包含多个具有以下式的第二二硫代氨基甲酸酯或盐封端配体:
其中R’是烷基,如乙基,并且R选自由包含亲水基团的官能团和包含两亲性部分的官能团组成的组。
本发明的第二方面提供一种量子点(QD)纳米粒子,所述QD纳米粒子包含多个第一二硫代碳酸酯或盐封端配体。所述二硫代碳酸酯或盐封端配体可以具有以下通式结构
其中R和R’是官能团。R和R’可以是烃。所述R基团可以是在C12位置具有羧酸官能性的C12烃链。
本发明的第三方面提供一种用于制备包含多个第一二硫代氨基甲酸酯或盐封端配体的量子点(QD)纳米粒子的方法,所述方法包括下列步骤:使核材料前体在分子簇化合物的存在下反应以制备纳米粒子核;将所述核分离;使分离的核与壳前体反应以在所述核上生长至少一个半导体壳;将封端配体结合至纳米粒子的最外半导体表面;以及将所述封端配体的至少一部分与二硫代配体交换。所述方法还可以包括监测与所述核的尺寸相关的光学性质并且当所述核达到预先选择的尺寸时停止反应。光学性质可以是吸收光谱或发射光谱。可以通过过滤将所述核分离。所述方法还可以包括将非溶剂加入至反应混合物中以引起所述核的沉淀。所述方法还可以包括在使所述核与所述壳前体反应前,从所述核蚀刻少量材料。可以使用氢氟酸蚀刻所述核。所述方法还可以包括在包壳反应期间加入配位配体以稳定所述包壳反应。所述配位配体可以是肉豆蔻酸。
附图的多个视图的简述
图1是用于制备具有二硫代氨基甲酸酯或盐配体的QD的根据本发明的方法的流程图。
发明详述
可以使用在本文中所描述的二硫代氨基甲酸酯或盐配体作为用于通常任何类型的半导体QD纳米粒子的封端配体。尤其有用的QD纳米粒子是如其全部内容通过引用结合于此的美国专利号7,588,828、7,803,423、7,985,446、和8,062,703(在本文中统称为“加晶种专利”)中所述制备的。图1图示了这样的制备QD纳米粒子的方法。简而言之,该方法涉及使核材料前体在起用于晶体生长的晶种作用的分子簇化合物的存在下反应(101)。加晶种专利描述了多种前体材料和分子簇化合物。例如,用于InP系核的适合的前体化合物必须提供铟源和磷源。例如,铟源可以是肉豆蔻酸铟并且磷源可以是三(三甲基甲硅烷基)膦。应该理解的是,可以使用其他铟源和磷源。
可以在分子加晶种化合物的存在下进行核形成反应。在以上引用的加晶种专利中详细地描述了适合的分子加晶种化合物。适合的分子加晶种化合物的一个实例是美国专利号8,062,703中描述的硫化锌系分子加晶种化合物。将核前体化合物和分子加晶种化合物在加晶种专利和美国专利公布号2010/0068522(其全部内容通过引用结合于此)中描述的条件下在溶剂中加热。通常,将非给电子溶剂用于反应。适合的溶剂的一个实例是(SOLUTIA INC.,ST.LOUIS MISSOURI 63141)。是已知的传热流体。
在核的合成期间监测核生长102(例如,通过QD核的光学性质)可以是适宜的。例如,可以在QD核生长时监测吸收光谱并且可以当核到达适当尺寸以产生所需吸收和/或发射光谱时停止反应。一旦得到理想的光学值并且停止反应,就可以将核分离103,例如,通过过滤。将非溶剂加入至反应混合物中以引起核的沉淀可以是适宜的。一旦将核分离,就可以将它们与壳前体反应104以在核上生长一个或多个半导体壳。将核预处理可以是适宜的,例如,通过在使核与壳前体反应前从核蚀刻少量材料。可以使用酸(如氢氟酸)蚀刻核。
壳前体发生反应以在QD核上形成半导体材料的壳。如果在包壳反应期间使用非配位溶剂,在包壳反应期间加入配位配体如肉豆蔻酸以使包壳反应稳定可能会是必需的。如果使用配位溶剂如TOP/TOPO,则溶剂分子本身可以起配体的作用以使包壳反应稳定。在任一种情况中,QD的最外半导体表面与封端配体结合。
下一个步骤是将封端配体的至少一部分与所公开的二硫代配体交换。二硫代配体具有通式结构(1):
二硫代配体的实例包括二硫代氨基甲酸酯或盐配体。适合的第一二硫代氨基甲酸酯或盐封端配体的实例由结构(2)和(3)表示:
其他适合的二硫代配体包括具有通式结构(4)的烷基二硫代碳酸酯或盐(即,黄原酸酯或盐)配体:
一个或多个R基团可以是任何官能团,并且通常是烃。实例包括烷基或芳基。一个实例是乙基。根据一些实施方案,一个或多个R基团可以含有具有调节QD的亲水性(例如使得QD在亲水性环境中更可溶)的能力的官能团。这样的R基团的实例是在C12位置具有羧酸官能性的C12烃链。一旦羧酸被合适地配位至点的表面,就可以用碱将羧酸去质子化并且将点转移至亲水性介质。备选地,一个或多个R基团可以是两亲性基团如PEG(聚乙二醇)。
可以交换第一二硫代封端配体以结合至表面上的正电性原子。例如,第一二硫代封端配体可以结合至ZnS表面或ZnSe表面上的锌。第一二硫代封端配体化合物(1)-(4)可以作为钠或钾的盐提供。二硫代配体可以作为粉末或在溶剂如中提供。
适合的二硫代配体的另一个实例由结构(5)表示:
在结构(5)中,R是如以上所定义的并且R’通常是烷基。结构(5)的化合物可以以单体和二聚体形式二者存在。当R’是乙基时,单体形式是主要物种。根据结构(5)的化合物具有配位至表面硫离子(sulfide)和/或硒离子的高潜力,从而满足了金属(Zn)原子的优选配位。
已经使用二硫代氨基甲酸锌,如以上结构(5)中图示的,作为用于ZnS纳米粒子的单一源前体。那些化合物是用于在InP核纳米粒子上沉积ZnS壳的单一源前体的可行的候选物。然而,二硫代氨基甲酸锌需要高温以使其分解。这样的高温负面影响InP核纳米粒子的性能。如果在胺的存在下提供二硫代氨基甲酸锌,则分解温度明显较低。然而,将胺加入至InP纳米粒子中对辐射效率具有特别急剧的猝灭作用。
申请人已经发现,如果将二硫代氨基甲酸锌“预配位”至胺,可以使用锌二硫代化合物,如结构(2)、(3)和(4)的锌复合物和结构(5)作为单一源包壳前体(即,在核纳米晶体上提供ZnS壳的元素的单一源前体)。另一种适合的包壳前体是胺配位的烷基硫代磷酸锌(zinc alkylthiophosphate),即具有以下结构(6)的二硫代配体的胺配位的化合物:
将胺与二硫代氨基甲酸锌预配位允许在包壳期间以胺与二硫代氨基甲酸锌的1∶1比率将胺和二硫代氨基甲酸锌引入至纳米粒子核的溶液中。因此,没有游离的胺可用于参加与核表面的猝灭反应。胺适宜地降低了二硫代氨基甲酸锌的分解温度,但是没有当存在游离胺时观察到的不利的猝灭作用。适合的胺的实例包括具有长烃成分的胺。特别适合的胺是油胺。
实施例
实施例1.
通过在存在和不存在油胺的情况下将InP合金系核包壳,说明了游离胺的猝灭作用。基本上如美国专利号7,558,828中所述制备InPZnS合金系核。将InP合金系核的两个样品各自悬浮在中。将乙酸锌(0.862g)加入至每个混合物中并且将混合物加热至230℃达2小时。将十二烷硫醇(1.69mL)加入至两个混合物中并且向混合物中的一个加入油胺(0.2mL)。使两个混合物反应另外1 1/2小时。
在不存在油胺的情况下包壳的量子点在644nm展现出具有94nm的半高全宽(fullwidth at half maximum,FWHM)和75%的量子产率(QY)的光致发光。在存在油胺的情况下包壳的量子点在644nm展现出具有90的FWHM和62%的量子产率(QY)的光致发光。在存在胺的情况下包壳的样品的较低的QY说明了胺的猝灭作用。
实施例2.
如美国专利号7,588,828中一般所述制备InPZnS合金系核。将核悬浮在(40mL)中,还向其中加入乙酸锌(5.76g)、肉豆蔻酸(1.5g)、硬脂酸锌(11.32g)。将混合物在180℃加热并且之后加入二乙基二硫代氨基甲酸锌(2.295g)并静置20分钟。观察到高混浊度并且反应混合物的光致发光保持非常低,说明在该温度下的低反应性/溶解度。将混合物加热至230℃并静置3小时并且粉末逐渐溶解但是QY始终保持非常低。
实施例3.
在实施例2中描述的相同条件下将InPZnS合金系核包壳,不同之处在于在180℃加入二乙基二硫代氨基甲酸酯或盐之后将油胺(5mL)加入至混合物中。将混合物在180℃加热额外20分钟,得到在523nm具有FWHM为53nm并且QY为73%的光致发光峰的量子点。实施例2和3之间的差异表明胺对包壳是至关重要的。
实施例4.
根据实施例3中描述的,将如美国专利号7,588,828中一般所述制备的InPZnS合金系核包壳,不同之处在于在加入至包壳反应前首先将二乙基二硫代氨基甲酸锌与油胺通过在氮下使用设定为50℃的水浴将两者预混合在一起来复合。包壳反应得到具有75%的发光QY的量子点。类似的反应得到具有高至85%的发光QY的量子点。
实施例5.
根据实施例4中描述的,将如美国专利号7,588,828中一般所述制备的InPZnS合金系核包壳,不同之处在于使用二乙基黄原酸锌代替二乙基二硫代氨基甲酸锌。将InPZnS合金系核(500mg)、肉豆蔻酸(1.5g)、乙酸锌(2.4g)、和硬脂酸锌(5.3g)在真空下在中在100℃搅拌1小时,并且之后加热至215℃,之后冷却至140℃。将乙基黄原酸锌(0.97g)和油胺1.05(mL)在(5mL)中的预混合溶液加入至核溶液中。将溶液搅拌1hr,之后在180℃搅拌一小时。加入辛醇(2.4mL)并且将溶液搅拌额外30分钟。反应得到具有85%的发光QY的量子点。
尽管已经示出并描述了本发明的具体的实施方案,它们并非意在限制本专利涵盖的内容。本领域技术人员将理解,可以在不背离如由以下权利要求在文字上和等价地涵盖的本发明的范围的情况下进行多种变化和改变。
Claims (21)
1.一种量子点纳米粒子,所述量子点纳米粒子包含多个第一二硫代碳酸酯或盐封端配体。
2.权利要求1中所述的量子点纳米粒子,其中所述第一二硫代碳酸酯或盐封端配体具有以下通式结构
其中R和R’是官能团。
3.权利要求2中所述的量子点纳米粒子,其中R和R’是烃。
4.权利要求2中所述的量子点纳米粒子,其中所述R基团是在C12位置具有羧酸官能性的C12烃链。
5.权利要求2中所述的量子点纳米粒子,其中R和R’中至少一个是两亲性基团。
6.权利要求5中所述的量子点纳米粒子,其中所述两亲性基团是聚乙二醇。
7.权利要求1中所述的量子点纳米粒子,其中所述多个第一二硫代碳酸酯或盐封端配体结合至所述量子点纳米粒子的ZnS或ZnSe表面。
8.权利要求1中所述的量子点纳米粒子,其中所述纳米粒子具有包含InP的核。
9.权利要求1中所述的量子点纳米粒子,所述量子点纳米粒子还包含第二封端配体。
10.权利要求9中所述的量子点纳米粒子,其中所述多个第二封端配体包含三辛基膦、三辛基氧化膦和油胺中的一种或多种。
11.一种用于制备包含多个第一二硫代碳酸酯或盐封端配体的核-壳纳米粒子的方法,所述方法包括:
使核纳米粒子与壳前体反应以在所述核上生长至少一个半导体壳,以形成核-壳纳米粒子;
将封端配体结合至核-壳纳米粒子的最外半导体表面;以及
将所述封端配体的至少一部分与所述第一二硫代碳酸酯或盐封端配体交换。
12.权利要求11中所述的方法,其中所述第一二硫代碳酸酯或盐封端配体具有以下通式结构
其中R和R’是官能团。
13.权利要求12中所述的方法,其中R和R’中至少一个是烷基或是芳基烃。
14.权利要求12中所述的方法,其中R和R’中至少一个是在C12位置具有羧酸官能性的C12烃链。
15.权利要求12中所述的方法,其中R和R’中至少一个是两亲性基团。
16.权利要求11中所述的方法,所述方法还包括监测与所述核的尺寸相关的光学性质并且当所述核达到预先选择的尺寸时停止反应。
17.权利要求15中所述的方法,其中所述光学性质是吸收光谱和发射光谱中的任一个。
18.权利要求11中所述的方法,所述方法还包括在使所述核与所述壳前体反应前,蚀刻所述核。
19.权利要求11中所述的方法,所述方法还包括在包壳反应期间加入配位配体以稳定所述包壳反应。
20.权利要求19中所述的方法,其中所述配位配体是肉豆蔻酸。
21.一种量子点纳米粒子,所述量子点纳米粒子包含第一配体和第二配体,所述第一配体包含结合到正电性原子的基团,所述第二配体包含结合到负电性原子的基团。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201461937073P | 2014-02-07 | 2014-02-07 | |
US61/937,073 | 2014-02-07 | ||
CN201580007042.0A CN105992807B (zh) | 2014-02-07 | 2015-02-06 | 具有增强的稳定性和发光效率的量子点纳米粒子 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580007042.0A Division CN105992807B (zh) | 2014-02-07 | 2015-02-06 | 具有增强的稳定性和发光效率的量子点纳米粒子 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110003883A true CN110003883A (zh) | 2019-07-12 |
Family
ID=52469241
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580007042.0A Active CN105992807B (zh) | 2014-02-07 | 2015-02-06 | 具有增强的稳定性和发光效率的量子点纳米粒子 |
CN201910042350.7A Pending CN110003883A (zh) | 2014-02-07 | 2015-02-06 | 具有增强的稳定性和发光效率的量子点纳米粒子 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580007042.0A Active CN105992807B (zh) | 2014-02-07 | 2015-02-06 | 具有增强的稳定性和发光效率的量子点纳米粒子 |
Country Status (7)
Country | Link |
---|---|
US (2) | US9666768B2 (zh) |
EP (2) | EP3473692B1 (zh) |
JP (2) | JP6483716B2 (zh) |
KR (2) | KR101819573B1 (zh) |
CN (2) | CN105992807B (zh) |
TW (2) | TWI580763B (zh) |
WO (1) | WO2015118346A1 (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110564404A (zh) * | 2019-08-30 | 2019-12-13 | 苏州星烁纳米科技有限公司 | 量子点的制备方法及量子点、量子点组合物和彩膜 |
CN110776917A (zh) * | 2019-11-19 | 2020-02-11 | 宁波纳鼎新材料科技有限公司 | 一种量子点及其合成方法 |
CN110980634A (zh) * | 2019-11-29 | 2020-04-10 | 京东方科技集团股份有限公司 | 纳米粒子图形化的方法、显示屏、显示装置 |
CN114672315A (zh) * | 2020-12-25 | 2022-06-28 | Tcl科技集团股份有限公司 | 量子点配体交换方法、量子点薄膜的制备方法和qled器件 |
WO2023159993A1 (zh) * | 2022-02-28 | 2023-08-31 | Tcl科技集团股份有限公司 | 量子点材料及制备方法、发光二极管 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110832618B (zh) | 2017-04-18 | 2023-09-12 | 芝加哥大学 | 光活性无机配体覆盖的无机纳米晶体 |
JP7202352B2 (ja) * | 2017-07-11 | 2023-01-11 | ティーシーエル テクノロジー グループ コーポレーション | 量子ドット及び量子ドットの製造方法 |
US11427756B2 (en) * | 2017-10-13 | 2022-08-30 | Merck Patent Gmbh | Semiconducting light emitting material |
CN109694704A (zh) * | 2017-10-20 | 2019-04-30 | Tcl集团股份有限公司 | 粒子及其制备方法和qled器件 |
JP6959119B2 (ja) | 2017-12-04 | 2021-11-02 | 信越化学工業株式会社 | 量子ドット及びその製造方法、並びに樹脂組成物、波長変換材料、発光素子 |
KR102659274B1 (ko) | 2018-06-05 | 2024-04-18 | 삼성전자주식회사 | 양자점, 이를 포함한 조성물 또는 복합체, 그리고 이를 포함한 전자 소자 |
KR102173712B1 (ko) * | 2018-07-09 | 2020-11-03 | 단국대학교 천안캠퍼스 산학협력단 | 전자적으로 비편재화된 카바메이트 유도체를 이용한 발광 나노결정체 |
JP2022508726A (ja) | 2018-10-15 | 2022-01-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | ナノ粒子 |
CN111849456B (zh) * | 2019-04-26 | 2021-12-14 | 纳晶科技股份有限公司 | 一种ii-iii-v-vi族量子点及其制备方法 |
EP3872146A1 (en) * | 2020-02-25 | 2021-09-01 | Rijksuniversiteit Groningen | Colloidal nanoparticle inks for printing of active layers in an optoelectronic device |
KR102564200B1 (ko) * | 2020-10-15 | 2023-08-08 | 단국대학교 천안캠퍼스 산학협력단 | 양자점, 이의 제조방법 및 이를 포함하는 qd-led 소자 |
CN116103046A (zh) * | 2021-11-09 | 2023-05-12 | Tcl科技集团股份有限公司 | 量子点薄膜、量子点发光二极管及其制备方法、显示装置 |
WO2024079905A1 (ja) * | 2022-10-14 | 2024-04-18 | シャープディスプレイテクノロジー株式会社 | 量子ドット溶液、量子ドット層の形成方法、発光素子、表示装置、および量子ドット溶液の製造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101168663A (zh) * | 2007-11-30 | 2008-04-30 | 中国科学院上海技术物理研究所 | 硒化镉/硫化镉/硫化锌核壳量子点的制备方法 |
US20100009071A1 (en) * | 2008-07-08 | 2010-01-14 | Xerox Corporation | Bimodal metal nanoparticle ink and applications therefor |
CN102201506A (zh) * | 2010-03-22 | 2011-09-28 | 三星电子株式会社 | 包括量子点-嵌段共聚物混合物的发光装置及其制造方法 |
CN103113882A (zh) * | 2013-02-20 | 2013-05-22 | 杭州纳晶科技有限公司 | 具有核-壳结构的纳米晶量子点及其制备方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61246760A (ja) * | 1985-04-25 | 1986-11-04 | Canon Inc | 静電荷像現像用電荷付与材 |
US6309701B1 (en) * | 1998-11-10 | 2001-10-30 | Bio-Pixels Ltd. | Fluorescent nanocrystal-labeled microspheres for fluorescence analyses |
US7558828B1 (en) | 2003-05-29 | 2009-07-07 | Aol Llc, A Delaware Limited Liability Company | Enabling electronic logging using an instant message system |
US7588828B2 (en) * | 2004-04-30 | 2009-09-15 | Nanoco Technologies Limited | Preparation of nanoparticle materials |
GB0409877D0 (en) * | 2004-04-30 | 2004-06-09 | Univ Manchester | Preparation of nanoparticle materials |
US7803568B2 (en) | 2005-04-20 | 2010-09-28 | Purdue Research Foundation | Carbodithioate ligands for nanotechnology and biosensing applications |
GB2429838B (en) | 2005-08-12 | 2011-03-09 | Nanoco Technologies Ltd | Nanoparticles |
GB0813273D0 (en) | 2008-07-19 | 2008-08-27 | Nanoco Technologies Ltd | Method for producing aqueous compatible nanoparticles |
GB0814458D0 (en) | 2008-08-07 | 2008-09-10 | Nanoco Technologies Ltd | Surface functionalised nanoparticles |
JP5604835B2 (ja) * | 2008-09-30 | 2014-10-15 | 東レ株式会社 | 半導体ナノ粒子及びその製造方法 |
EP2599898A1 (en) | 2011-12-01 | 2013-06-05 | Bayer Intellectual Property GmbH | Continuous synthesis of high quantum yield InP/ZnS nanocrystals |
WO2013114308A1 (en) | 2012-02-03 | 2013-08-08 | Koninklijke Philips N.V. | Dual site surface capping for highly improving quantum efficiency and life time of luminescent nano particles |
-
2015
- 2015-02-05 US US14/615,243 patent/US9666768B2/en active Active
- 2015-02-06 JP JP2016550505A patent/JP6483716B2/ja active Active
- 2015-02-06 CN CN201580007042.0A patent/CN105992807B/zh active Active
- 2015-02-06 TW TW104104132A patent/TWI580763B/zh active
- 2015-02-06 TW TW105116320A patent/TWI621692B/zh active
- 2015-02-06 WO PCT/GB2015/050336 patent/WO2015118346A1/en active Application Filing
- 2015-02-06 KR KR1020167020226A patent/KR101819573B1/ko active Application Filing
- 2015-02-06 EP EP18189532.7A patent/EP3473692B1/en active Active
- 2015-02-06 CN CN201910042350.7A patent/CN110003883A/zh active Pending
- 2015-02-06 KR KR1020187000924A patent/KR101912782B1/ko active IP Right Grant
- 2015-02-06 EP EP15704090.8A patent/EP3102649B1/en active Active
-
2017
- 2017-04-25 US US15/496,712 patent/US10468559B2/en active Active
-
2018
- 2018-09-14 JP JP2018172010A patent/JP2019023297A/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101168663A (zh) * | 2007-11-30 | 2008-04-30 | 中国科学院上海技术物理研究所 | 硒化镉/硫化镉/硫化锌核壳量子点的制备方法 |
US20100009071A1 (en) * | 2008-07-08 | 2010-01-14 | Xerox Corporation | Bimodal metal nanoparticle ink and applications therefor |
CN102201506A (zh) * | 2010-03-22 | 2011-09-28 | 三星电子株式会社 | 包括量子点-嵌段共聚物混合物的发光装置及其制造方法 |
CN103113882A (zh) * | 2013-02-20 | 2013-05-22 | 杭州纳晶科技有限公司 | 具有核-壳结构的纳米晶量子点及其制备方法 |
Non-Patent Citations (3)
Title |
---|
A. Z. WILCZEWSKA等: "Surface-Initiated RAFT/MADIX Polymerization on Xanthate-Coated Iron Oxide Nanoparticles", 《MACROMOL. CHEM. PHYS.》 * |
GUARISE C等: "Reversible aggregation/deaggregation of gold nanoparticles induced by a cleavable dithiol linker", 《LANGMUIR》 * |
LIU SIYU等: "Determination of copper(II) and cadmium(II) based on ternary CuInS2 quantum dots", 《ANALYTICAL METHODS》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110564404A (zh) * | 2019-08-30 | 2019-12-13 | 苏州星烁纳米科技有限公司 | 量子点的制备方法及量子点、量子点组合物和彩膜 |
CN110776917A (zh) * | 2019-11-19 | 2020-02-11 | 宁波纳鼎新材料科技有限公司 | 一种量子点及其合成方法 |
CN110776917B (zh) * | 2019-11-19 | 2023-07-21 | 南通惟怡新材料科技有限公司 | 一种量子点及其合成方法 |
CN110980634A (zh) * | 2019-11-29 | 2020-04-10 | 京东方科技集团股份有限公司 | 纳米粒子图形化的方法、显示屏、显示装置 |
CN110980634B (zh) * | 2019-11-29 | 2021-03-02 | 京东方科技集团股份有限公司 | 纳米粒子图形化的方法、显示屏、显示装置 |
CN114672315A (zh) * | 2020-12-25 | 2022-06-28 | Tcl科技集团股份有限公司 | 量子点配体交换方法、量子点薄膜的制备方法和qled器件 |
WO2023159993A1 (zh) * | 2022-02-28 | 2023-08-31 | Tcl科技集团股份有限公司 | 量子点材料及制备方法、发光二极管 |
Also Published As
Publication number | Publication date |
---|---|
US20170229618A1 (en) | 2017-08-10 |
EP3473692A1 (en) | 2019-04-24 |
TW201536895A (zh) | 2015-10-01 |
US10468559B2 (en) | 2019-11-05 |
JP2019023297A (ja) | 2019-02-14 |
US9666768B2 (en) | 2017-05-30 |
JP6483716B2 (ja) | 2019-03-13 |
CN105992807B (zh) | 2019-02-12 |
EP3473692B1 (en) | 2020-12-09 |
TW201631120A (zh) | 2016-09-01 |
US20150228866A1 (en) | 2015-08-13 |
EP3102649B1 (en) | 2018-10-10 |
JP2017513960A (ja) | 2017-06-01 |
EP3102649A1 (en) | 2016-12-14 |
KR20160103068A (ko) | 2016-08-31 |
KR20180007013A (ko) | 2018-01-19 |
WO2015118346A1 (en) | 2015-08-13 |
KR101912782B1 (ko) | 2018-10-29 |
TWI580763B (zh) | 2017-05-01 |
KR101819573B1 (ko) | 2018-01-18 |
TWI621692B (zh) | 2018-04-21 |
CN105992807A (zh) | 2016-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105992807B (zh) | 具有增强的稳定性和发光效率的量子点纳米粒子 | |
JP6730474B2 (ja) | カドミウムフリー量子ドットナノ粒子 | |
CN107338048B (zh) | InP/GaP/ZnS核壳量子点及其制备方法 | |
US9343301B2 (en) | Quantum dots made using phosphine | |
CN102272217B (zh) | 表面功能化的纳米颗粒 | |
KR102066423B1 (ko) | Iii-v/아연 칼코겐 화합물로 합금된 반도체 양자점 | |
CN101365828B (zh) | 纳米颗粒 | |
Gao et al. | Synthesis of N-acetyl-L-cysteine-capped ZnCdSe quantum dots via hydrothermal method and their characterization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190712 |
|
WD01 | Invention patent application deemed withdrawn after publication |