CN106281311B - A kind of alloy quantum dot and preparation method thereof, electroluminescent diode and photoluminescent diode - Google Patents
A kind of alloy quantum dot and preparation method thereof, electroluminescent diode and photoluminescent diode Download PDFInfo
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- CN106281311B CN106281311B CN201610742723.8A CN201610742723A CN106281311B CN 106281311 B CN106281311 B CN 106281311B CN 201610742723 A CN201610742723 A CN 201610742723A CN 106281311 B CN106281311 B CN 106281311B
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 87
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000002347 injection Methods 0.000 claims abstract description 29
- 239000007924 injection Substances 0.000 claims abstract description 29
- 230000005540 biological transmission Effects 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- 229910052793 cadmium Inorganic materials 0.000 claims description 17
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052711 selenium Inorganic materials 0.000 claims description 16
- 239000011669 selenium Substances 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- -1 transition metal salt Chemical class 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000000862 absorption spectrum Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 238000004528 spin coating Methods 0.000 description 61
- 239000000243 solution Substances 0.000 description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 230000005525 hole transport Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000954 Polyglycolide Polymers 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 6
- 239000004633 polyglycolic acid Substances 0.000 description 6
- 229960002796 polystyrene sulfonate Drugs 0.000 description 6
- 239000011970 polystyrene sulfonate Substances 0.000 description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000003760 hair shine Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000004246 zinc acetate Substances 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
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Chemical compound C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QKCRCANNYXEEPC-UHFFFAOYSA-N acetic acid;vanadium Chemical compound [V].CC(O)=O QKCRCANNYXEEPC-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007850 fluorescent dye Substances 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
- 239000007791 liquid phase Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
-
- 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
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention provides a kind of alloy quantum dot and preparation method thereof and electroluminescent diode and photoluminescent diode.The present invention prepares alloy quantum dot using hot injection method combination one-pot synthesis involucrum, and reaction temperature is low, the reaction time is short；The alloy quantum dot being prepared is good at brilliant effect, and stability is good, and nanocrystalline size is easy to control and is evenly distributed；Using alloy quantum dot provided by the invention as luminescent layer, the electroluminescent diode and photoluminescent diode of preparation have very wide absorption spectrum and high-photoelectric transformation efficiency, and have the reproducibility of height.Preparation method provided by the invention is easy to operate, mild condition, low energy consumption, low in cost, technique is easily-controllable, is suitable for that large-scale industry is promoted.
Description
Technical field
The present invention relates to nano-functional material technical field, in particular to a kind of alloy quantum dot and preparation method thereof, with
And electroluminescent diode and photoluminescent diode.
Background technique
With the rapid development and progress of human sciences' civilization, the problem of energy crisis is 21 century mankind's urgent need to resolve.
Wherein lighting energy consumption occupies the 20% of energy wastage in bulk or weight, and there are also the trend risen, the primary illumination lights such as incandescent lamp, fluorescent lamp
That there are high energy consumption and efficiencies in source is low, the drawbacks such as not environmentally.
Semiconductor lighting, i.e., using semiconductor light-emitting-diode as the solid-state lighting of light source, as a kind of emerging illumination
Technology, because the advantages that its energy conservation and environmental protection and long service life is gradually taken seriously.There are glimmering with LED fluorescent material for lighting area at present
The problems such as light yield is not high, space chromacity uniformity is poor and at high cost, this is limited by the synthetic method of material, type, material knot
The many factors such as structure.Wherein, luminous organic material stability itself is poor, device architecture level-density parameter and preparation process are to shining
The influence of diode physical property is very big.
Alloy quantum dot has that absorption spectrum is wide, emission spectrum is narrow and symmetrical as a kind of new material, passes through adjusting group
It can be made to launch the fluorescence of different colours at partial size, the advantages that fluorescence intensity is high and fluorescent stability is good, overcome biography
Many deficiencies of system organic fluorescent dye.Currently, the preparation method of quantum dot mainly has three categories: (1) high temperature gas phase method synthesizes,
As chemical vapour deposition technique, or use laser method heat gas phase predecessor；(2) colloid method has in organic solvent with metal
Machine object is presoma, and at 350 DEG C prepared by back flow reaction；(3) reverse micro emulsion self-assemble mould board method passes through gas-liquid phase reaction system
The standby quantum dot with well-crystallized performance.
But the above method or there are reaction temperature height, the size and size distribution of quantum dot problems not easy to control, or deposit
It is long in the reaction time, the problem of stability difference.
Summary of the invention
The purpose of the present invention is to provide a kind of alloy quantum dot and preparation method thereof and electroluminescent diodes and light
Photoluminescence diode.
Preparation method reaction temperature provided by the invention is low, the reaction time is short, and the alloy quantum dot being prepared is stablized
Good, the even particle size distribution of property.
Electroluminescent diode and photoluminescent diode provided by the invention have very wide absorption spectrum and Gao Guang electricity
Transfer efficiency, and have the reproducibility of height.
The present invention provides a kind of preparation methods of alloy quantum dot, comprising the following steps:
(1) zinc source, cadmium source, transition metal salt, ligand solvent and non-coordinating solvent are mixed, heating obtains cationic forerunner
Body；
(2) sulphur source is injected in the cationic presoma that Xiang Suoshu step (1) obtains, before the first reaction of progress obtains quantum dot
Drive body；
(3) selenium source is added in the quantum dot presoma that Xiang Suoshu step (2) obtains, carries out the second reaction and obtains alloy quantum
Point.
Preferably, the molar ratio of metallic element is 10~100 in zinc source, cadmium source and transition metal salt in the step (1):
1:0.1~2.
Preferably, the temperature heated in the step (1) is 100~200 DEG C.
Preferably, the sulphur source in the step (2) and the molar ratio in cadmium source in the step (1) are 2~50:1.
Preferably, in the step (2) first reaction temperature be 280~320 DEG C, first reaction time be 5~
15min。
Preferably, the molar ratio in the selenium source in the step (3) and cadmium source in the step (1) is 1~30:1.
Preferably, in the step (3) second reaction temperature be 290~330 DEG C, second reaction time be 30~
90min。
The present invention also provides the alloy quantum dots of the preparation of preparation method described in above-mentioned technical proposal, have core-shell structure,
Including D:CdZnS nucleome and the ZnSe shell being coated on outside the nucleome, D is transition metal element.
The present invention also provides a kind of electroluminescent diodes, including the electro-conductive glass, hole injection layer, sky set gradually
Cave transport layer, luminescent layer, electron transfer layer and electrode, the luminescent layer include above-mentioned technical proposal preparation alloy quantum dot or
Alloy quantum dot described in above-mentioned technical proposal.
The present invention also provides a kind of photoluminescent diodes, the luminescent layer including ultraviolet chip and its surface, the hair
Photosphere includes alloy quantum dot described in alloy quantum dot prepared by above-mentioned technical proposal or above-mentioned technical proposal.
The present invention prepares alloy quantum dot using hot injection method combination one-pot synthesis involucrum, and reaction temperature is low, the reaction time
It is short；The alloy quantum dot being prepared is good at brilliant effect, and stability is good, and nanocrystalline size is easy to control and is evenly distributed；
Using the alloy quantum dot as luminescent layer, the electroluminescent diode and photoluminescent diode of preparation have very
Wide absorption spectrum and high-photoelectric transformation efficiency, and have the reproducibility of height.The experimental results showed that method system provided by the invention
Standby obtained alloy quantum dot yield is 75%, and partial size is 3~6nm, has preferable monodispersity and stability.
Detailed description of the invention
Fig. 1 is the TEM picture for the alloy quantum dot that embodiment 1 obtains；
Fig. 2 is the partial enlarged view of Fig. 1.
Specific embodiment
The present invention provides a kind of preparation methods of alloy quantum dot, comprising the following steps:
(1) zinc source, cadmium source, transition metal salt, ligand solvent and non-coordinating solvent are mixed, heating obtains cationic forerunner
Body；
(2) sulphur source is injected in the cationic presoma that Xiang Suoshu step (1) obtains, before the first reaction of progress obtains quantum dot
Drive body；
(3) selenium source is added in the quantum dot presoma that Xiang Suoshu step (2) obtains, carries out the second reaction and obtains alloy quantum
Point.
The present invention mixes zinc source, cadmium source, transition metal salt, ligand solvent and non-coordinating solvent, and heating obtains cation
Presoma.The not special restriction of operation of the present invention to the heating, using the skill of heating well known to those skilled in the art
Art scheme.In the present invention, the temperature of the heating is preferably 100~200 DEG C, more preferably 120~180 DEG C, optimal
It is selected as 140~160 DEG C.
In the present invention, the molar ratio of metallic element is preferably 10~100 in the zinc source, cadmium source and transition metal salt:
1:0.1~2, more preferably 30~80:1:0.12~0.18, most preferably 50~60:1:1.5~1.6.In the present invention, lead to
The doping of control transition metal is crossed to adjust the time of electronics and hole-recombination, i.e. fluorescence lifetime.In the present invention, pass through control
Reactant processed matches to improve the yield of alloy quantum dot.
In the present invention, the zinc source, the concentration of cadmium source and transition metal salt in ligand solvent and non-coordinating solvent are excellent
It is selected as 5~20mol/L, more preferably 10~15mol/L.In the present invention, the volume of the ligand solvent and non-coordinating solvent
Than being preferably 1~100:3, more preferably 10~50:3, most preferably 20~30:3.
In the present invention, the zinc source preferably includes one or more of zinc oxide and organic aliphatic acid zinc；It is described to have
Machine fatty acid zinc preferably includes one or more of zinc acetate, zinc stearate, tetradecylic acid zinc and zinc laurate.In the present invention
In, the cadmium source preferably includes one or more of cadmium oxide and organic aliphatic acid cadmium；The organic aliphatic acid cadmium preferably wraps
Include cadmium acetate and/or cadmium stearate.In the present invention, the transition metal salt preferably includes the fatty acid salt of transition metal；Institute
It states transition metal and preferably includes copper, manganese or vanadium.
In the present invention, the ligand solvent preferably includes one in oleic acid, organic phosphine ligand solvent and organic fat amine
Kind is a variety of；The organic phosphine ligand solvent preferably includes tributylphosphine and/or tri-n-octyl phosphine；The organic fat amine is preferred
Including oleyl amine and/or octadecylamine.In the present invention, the adjustable quantum dot crystal face of the ligand solvent and ligand solvent adsorb and
The dynamic rate to fall off changes the shape of quantum dot to promote some crystal face speed of growth of quantum dot faster than other crystal faces, control
Combinations type enables the energy level forbidden bandwidth of alloy quantum dot energy level and forbidden bandwidth and nano zine oxide to match, that is, is formed with
The hierarchic structure of sequence.
In the present invention, the non-coordinating solvent preferably includes 1- octadecylene and/or trioctylamine.
After obtaining cationic presoma, the present invention injects sulphur source into the cationic presoma, carries out first and reacts
To quantum dot presoma.In the present invention, sulphur source injection and the first reaction preferably under vacuum or inert gas shielding into
Row；The inert gas is preferably nitrogen or argon gas.
In the present invention, the sulphur source and the molar ratio in cadmium source described in above-mentioned technical proposal are preferably 2~50:1, more preferably
For 10~40:1, most preferably 20~30:1.The present invention does not have special restriction to the type of the sulphur source, using this field skill
The substance of S element is capable of providing known to art personnel.In the present invention, the sulphur source is preferably elemental sulfur, more preferably
Sulphur powder.In the present invention, the sulphur source is added preferably in the form of sulphur source solution；The concentration of the sulphur source solution is preferably
0.001~0.5mol/L, more preferably 0.01~0.1mol/L；Solvent in the sulphur source solution is preferably 1- octadecylene or three
Octylame.
In the present invention, the sulphur source is preferably disposably injected into cationic presoma.In the present invention, the sulphur source
The rate of injection is preferably 20~100mL/s, more preferably 40~80mL/s.In the present invention, the sulphur source inject when sun from
The temperature of sub- presoma is preferably 280~320 DEG C, and more preferably 290~310 DEG C.
In the present invention, the temperature of first reaction is preferably 280~320 DEG C, and more preferably 290~310 DEG C；It is described
The time of first reaction is preferably 5~15min, more preferably 8~12min.In the present invention, the product of first reaction is excellent
It is selected as D:CdZn nucleus；The partial size of the D:CdZn nucleus is preferably 4~6nm, more preferably 4.5~5.5nm.In the present invention
In, the crystallinity of alloy quantum dot is improved by control reaction temperature and time, adjusts the size of alloy quantum dot.
After obtaining quantum dot presoma, selenium source is added into the quantum dot presoma by the present invention, carries out second and reacts
To alloy quantum dot.In the present invention, the selenium source is added and the second reaction preferably carries out under vacuum inert gas shield；Institute
Stating inert gas is preferably nitrogen or argon gas.
In the present invention, the selenium source and the molar ratio in cadmium source described in above-mentioned technical proposal are preferably 1~30:1, more preferably
For 10~20:1, most preferably 12~16:1.The present invention does not have special restriction to the type of the selenium source, using this field skill
The substance of selenium element is capable of providing known to art personnel.In the present invention, the selenium source is preferably elemental selenium, more preferably
Selenium powder.In the present invention, the selenium source is added preferably in the form of selenium source solution；The concentration of the selenium source solution is preferably
0.001~0.5mol/L, more preferably 0.01~0.1mol/L；Solvent in the selenium source solution is preferably tributylphosphine, three
N-octyl phosphine, oleyl amine or octadecylamine.
In the present invention, the addition of the selenium source is preferably added dropwise；The rate of the dropwise addition is preferably 1~3mL/min.
In the present invention, the temperature of second reaction is preferably 290~330 DEG C, and more preferably 300~320 DEG C；It is described
The time of second reaction is preferably 30~90min, more preferably 50~70min.
The present invention is preferably cooled down second after the reaction was completed, and purification obtains alloy quantum dot.In the present invention, described cold
But the temperature after is preferably 40~60 DEG C, and more preferably 45~55 DEG C.The not special limit of operation of the present invention to the purification
It is fixed, using the technical solution of purification well known to those skilled in the art.In the present invention, the purification preferably includes to extract
It takes, be centrifuged and dry.
Split-phase extracts after the present invention preferably mixes the second reaction product with extractant.In the present invention, the extraction
Agent is taken to preferably include the mixture of one of n-hexane, toluene and chloroform with alcohols solvent；In the mixture just oneself
The volume ratio of alkane, toluene or chloroform and alcohols solvent is preferably 1:2~15, more preferably 1:5~10.
Product of the present invention preferably by the second reaction is mixed with extractant, obtains mixed solution.In the present invention, described mixed
Conjunction preferably carries out under agitation；The stirring is preferably magnetic agitation；The rate of the magnetic agitation is preferably 200~
2000r/min, more preferably 500~1500r/min, most preferably 800~1200r/min；The time of the magnetic agitation is excellent
It is selected as 4~6min.The present invention is preferably stood after the completion of the stirring, makes mixed solution split-phase.In the present invention, the split-phase
The upper layer of mixed solution is alloy quantum dot solution afterwards, and lower layer is the free ligand and alcohols solvent of impurity, not formed coordinate bond.
The present invention preferably removes the lower layer of the mixed solution, obtains alloy quantum dot solution.In the present invention, time of the extraction
Number preferably 4~6 times.
Acetone is added preferably into the alloy quantum dot solution by the present invention or second cyanogen is centrifuged.In the present invention, institute
The rate for stating centrifugation is preferably 8000~12000r/s, more preferably 9000~10000r/s；The time of the centrifugation is preferably 4
~6min.
Preferably the obtained solid that is centrifuged is dried by the present invention, and in the present invention, the drying is preferably vacuum
It is dry；The vacuum drying vacuum degree is preferably -25~-35Bar；The vacuum drying temperature is preferably 40~60 DEG C,
More preferably 45~55 DEG C；The vacuum drying time is preferably 25~35min.
The present invention also provides the alloy quantum dots of above-mentioned technical proposal preparation, have core-shell structure, including D:CdZnS core
Body and the ZnSe shell being coated on outside the nucleome, D is transition metal element.In the present invention, the grain of the D:CdZnS nucleome
Diameter is preferably 4~6nm, more preferably 4.5~5.5nm；The thickness of the ZnSe shell is preferably 2~4nm, and more preferably 2.5
~3.5nm.In the present invention, by containing transition metal element, keep the energy level of alloy quantum dot itself more abundant；Pass through control
It makes suitable shell thickness and reaches and suitably answer force request, improve transient state fluorescence length, while improving the stabilization of alloy quantum dot
Property.
It is saved in the present invention, it is preferred to disperse the alloy quantum dot in organic solvent.In the present invention, described to have
Solvent preferably includes one of n-hexane, toluene, dodecane and octane.
The present invention also provides a kind of electroluminescent diodes, including the electro-conductive glass, hole injection layer, sky set gradually
Cave transport layer, luminescent layer, electron transfer layer and electrode, the luminescent layer include above-mentioned technical proposal preparation alloy quantum dot or
Alloy quantum dot described in above-mentioned technical proposal.
Electroluminescent diode provided by the invention includes electro-conductive glass.In the present invention, the electro-conductive glass is preferably
ITO electro-conductive glass.
Electroluminescent diode provided by the invention includes hole injection layer.In the present invention, the hole injection layer is excellent
Choosing includes Polyglycolic acid fibre and poly styrene sulfonate.In the present invention, the Polyglycolic acid fibre and polystyrene
The mass ratio of sulfonate is preferably 1:1.5~5, more preferably 1:2~4.In the present invention, the thickness of the hole injection layer is excellent
It is selected as 30~80nm, more preferably 40~60nm.
Electroluminescent diode provided by the invention includes hole transmission layer.In the present invention, the hole transmission layer is excellent
Choosing includes the first hole transmission layer and the second hole transmission layer.In the present invention, first transport layer preferably includes 4- butyl-
The polymers such as N, N- diphenylaniline；The thickness of first hole transmission layer is preferably 50~80nm, more preferably 60~70nm.
In the present invention, second hole transmission layer is preferably polyvinyl carbazole；The thickness of second cave transport layer is preferably
80~120nm, more preferably 90~100nm.
Electroluminescent diode provided by the invention includes luminescent layer.In the present invention, the luminescent layer includes above-mentioned skill
The alloy quantum dot that preparation method described in alloy quantum dot described in art scheme or above-mentioned technical proposal obtains.In the present invention, institute
The thickness for stating luminescent layer is preferably 50~80nm, more preferably 60~70nm.
Electroluminescent diode provided by the invention includes electron transfer layer.In the present invention, the electron transfer layer is excellent
Choosing includes nano zine oxide or nano-titanium dioxide.In the present invention, the thickness of the electron transfer layer be preferably 80~
150nm, more preferably 100~120nm.
Electroluminescent diode provided by the invention includes electrode.In the present invention, the electrode preferably include gold, silver,
Platinum or aluminium electrode.In the present invention, the thickness of the electrode is preferably 80~140nm, more preferably 100~120nm.
The present invention does not have special restriction to the preparation method of the electroluminescent diode, using those skilled in the art
The well known technical solution for preparing electroluminescent diode.In the present invention, the electroluminescent diode prepare it is excellent
It is selected as: successively spin coating hole injection layer, the first hole transmission layer, the second hole transmission layer, luminescent layer and electricity on electro-conductive glass
Sub- transport layer, then electrode evaporation, obtains electroluminescent diode.
Present invention spin coating hole injection layer preferably on electro-conductive glass.In the present invention, the hole injection layer preferably with
The ethanol solutions of Polyglycolic acid fibre and poly styrene sulfonate mixture carry out spin coating.In the present invention, described poly-
The concentration of ethylenedioxy thiophene and poly styrene sulfonate in ethanol solution is preferably 0.5~2mol/L, more preferably 1~
1.5mol/L.In the present invention, the rate of the spin coating is preferably 3800~4800r/s, more preferably 4000~4500r/s；
The time of the spin coating is preferably 35~45s.
After the spin coating for completing the hole injection layer, the present invention is preferably dried, and obtains hole injection layer.In the present invention
In, the temperature of the drying is preferably 120~160 DEG C, and more preferably 130~150 DEG C；The time of the drying is preferably 10~
14min。
After obtaining hole injection layer, the present invention first hole transmission layer of spin coating preferably on the hole injection layer.At this
In invention, the spin coating of first hole transmission layer is preferably carried out under vacuum or inert gas shielding.In the present invention, described
First hole transmission layer is preferably with the chlorobenzene solution form spin coating of the polymers such as 4- butyl-N, N- diphenylaniline.In the present invention,
The concentration of the polymers in chlorobenzene solution such as 4- butyl-N, the N- diphenylaniline are preferably 6~10g/L, more preferably 7~
9g/L.In the present invention, the rate of the spin coating is preferably 2000~3000r/s, more preferably 2400~2600r/s；It is described
The time of spin coating is preferably 40~50s.
After the spin coating for completing first hole transmission layer, the present invention is preferably dried, and obtains the first hole transmission layer.
In the present invention, the temperature of the drying is preferably 50~200 DEG C, and more preferably 100~150 DEG C；The time of the drying is excellent
It is selected as 18~22min.
After obtaining the first hole transmission layer, the present invention second hole transport of spin coating preferably on first hole transmission layer
Layer.In the present invention, the spin coating of second hole transmission layer preferably carries out under vacuum or inert gas shielding.In the present invention
In, second hole transmission layer is preferably with the meta-xylene solution form spin coating of polyvinyl carbazole.In the present invention, described
Concentration of the polyvinyl carbazole in meta-xylene solution is preferably 1.2~1.8g/mL, more preferably 1.4~1.6g/mL.?
In the present invention, the rate of the spin coating is preferably 2000~3000r/s, more preferably 2400~2600r/s；The spin coating when
Between preferably 40~50s.
After the spin coating for completing second hole transmission layer, the present invention is preferably dried, and obtains the second hole transmission layer.
In the present invention, the temperature of the drying is preferably 150~190 DEG C, and more preferably 160~180 DEG C；The time of the drying is excellent
It is selected as 25~35min.
After obtaining the second hole transmission layer, present invention spin coating luminescent layer preferably in second transport layer.In the present invention
In, the spin coating of the luminescent layer preferably carries out under vacuum or inert gas shielding.In the present invention, the luminescent layer preferably with
The chloroformic solution form spin coating of alloy quantum dot.In the present invention, concentration of the alloy quantum dot in chloroformic solution is preferred
For 10~20g/L, more preferably 14~16g/L.In the present invention, the rate of the spin coating is preferably 2000~3000r/s, more
Preferably 2400~2600r/s；The time of the spin coating is preferably 40~50s.
After the spin coating for completing the luminescent layer, the present invention is preferably dried, and obtains luminescent layer.In the present invention, described
Dry temperature is preferably 80~200 DEG C, and more preferably 100~150 DEG C；The time of the drying is preferably 20~30min.
After obtaining luminescent layer, the present invention preferably spin coating electron transfer layer on the light-emitting layer.In the present invention, the electricity
The spin coating of sub- transport layer preferably carries out under vacuum or inert gas shielding.In the present invention, the electron transfer layer preferably with
The ethanol solutions spin coating of nano zine oxide or nano-titanium dioxide.In the present invention, the nano zine oxide or nanometer two
Concentration of the titanium oxide in ethanol solution is preferably 55~65g/L, more preferably 58~62g/L.
After the spin coating for completing the electron transfer layer, the present invention is preferably dried, and obtains electron-transport layer by layer.In this hair
In bright, the temperature of the drying is preferably 80~200 DEG C, and more preferably 100~150 DEG C；The time of the drying is preferably 20
~30min.
After obtaining electron transfer layer, the present invention preferably in the electron-transport layer surface electrode evaporation, obtains electroluminescent
Diode.In the present invention, the vacuum degree of the vapor deposition is preferably 3.5~4.5 × 10-6mbar；The temperature of the vapor deposition is preferred
It is 200~1300 DEG C, more preferably 500~1000 DEG C, most preferably 700~800 DEG C.
The present invention also provides a kind of photoluminescent diodes, the luminescent layer including ultraviolet chip and its surface, the hair
Photosphere includes alloy quantum dot described in alloy quantum dot prepared by above-mentioned technical proposal or above-mentioned technical proposal.
In the present invention, the luminescent layer preferably includes alloy quantum dot described in above-mentioned technical proposal or according to above-mentioned technology
The alloy quantum dot and poly- silicon nitrence based compound of scheme preparation；The quality of the alloy quantum dot and poly- silicon nitrence based compound
Than being preferably 1:1~100, more preferably 1:20~80, most preferably 1:50~60.In the present invention, the poly- silicon nitrence system
Compound preferably solidifies A, B glue.In the present invention, the thickness of the luminescent layer is preferably 10~100 μm, more preferably 30~
70 μm, most preferably 50~60 μm.
The present invention does not have special restriction to the type of the ultraviolet chip, using well known to those skilled in the art ultraviolet
The type of chip.In the present invention, the launch wavelength of the ultraviolet chip is preferably 345~380nm；The ultraviolet chip
Preferably InGaN/GaN or GaN ultraviolet chip.
The present invention does not have special restriction to the preparation method of the photoluminescent diode, using those skilled in the art
The well known technical solution for preparing photoluminescent diode.In the present invention, the photoluminescent diode prepare it is excellent
It is selected as: alloy quantum dot is mixed with poly- silicon nitrence based compound, be coated in ultraviolet chip surface, solidification obtains luminescence generated by light two
Pole pipe.
The present invention preferably mixes alloy quantum dot with poly- silicon nitrence based compound, obtains mixed material.In the present invention,
The mixing preferably carries out under agitation；The rate of the stirring is preferably 100~200r/min, more preferably 140~
160r/min；The time of the stirring is preferably 15~30min, more preferably 20~25min.
For the gas in removal mixed material, the mixed material is preferably vacuum-treated by the present invention.In the present invention
In, the vacuum degree of the vacuum processing is preferably -25~-35bar, more preferably -28~-32bar；The vacuum processing when
Between preferably 2~4h, more preferably 2.5~3.5h.
It completes after being vacuum-treated, the mixed material after the vacuum processing is preferably coated in ultraviolet chip table by the present invention
Face, solidification obtain photoluminescent diode.In the present invention, the cured temperature is preferably 120~180 DEG C, more preferably
140~160 DEG C；The cured time is preferably 20~40min, more preferably 25~35min.
In order to further illustrate the present invention, below with reference to embodiment to alloy quantum dot provided by the invention and its preparation side
Method and electroluminescent diode and photoluminescent diode are described in detail, but they cannot be interpreted as to this hair
The restriction of bright protection scope.
Embodiment 1:
10mmol zinc acetate, 1mmol cadmium oxide and 0.02mmol manganese acetate are dissolved in 3.5mL oleic acid and 10mL1- octadecylene
In, it is heated to 100 DEG C；40min is vacuumized with mechanical pump, leads to argon gas as reaction protection environment；
Continue to be warming up to 300 DEG C, the 2mmol sulphur powder solution of 1mL1- octadecylene, heat preservation are dissolved in the injection of most rapid rate
10min forms Mn:CdZnS nucleus；
310 DEG C are warming up to, the 1mmol selenium powder for being dissolved in 2mL tributylphosphine is added dropwise with 1mL/min rate, keeps the temperature 1h, is formed
Mn:CdZnS/ZnSe core-shell structure alloy quantum dot；
50 DEG C are cooled to, injects n-hexane and methanol volume ratio for the mixed solution of 1:2, with the stirring of 800r/min rate
After 5min, static 10min, mixed solution layering；Quantum dot solution is mixed in upper layer, impurity and unreacted ligand solvent and methanol
Solution is closed in lower layer, extracts lower layer methanol solution with syringe；After being repeated 4 times, acetone is added, with the centrifugation of 10000r/s rate
5min outwells upper layer supernatant, is put into -30bar in vacuum oven, and 50 DEG C of vacuum drying 30min obtain alloy quantum
Point, yield 75%.
Alloy quantum dot manufactured in the present embodiment is transmitted, obtain TEM picture as shown in Figure 1, Fig. 1 partial enlargement
Figure is as shown in Figure 2.
Alloy quantum dot partial size manufactured in the present embodiment is 8.2nm, and Mn:CdZnS core diameter is 5.2nm, ZnSe shell
With a thickness of 3nm.
Embodiment 2:
Polyglycolic acid fibre and poly styrene sulfonate are with the mixing of 1:1.5 mass ratio, according to the concentration system of 0.5mol/L
Standby ethanol solution, with the speed spin coating 40s of 4200r/s on electro-conductive glass, then in 140 DEG C of baking 12min, obtain with a thickness of
The hole injection layer of 30nm；
Electro-conductive glass with hole injection layer is put into glove box, in the 4- fourth of hole injection layer surface spin coating 8g/L
The chlorobenzene solution of base-N, N- diphenylaniline homopolymer, spin coating rate are 2500r/s, are put at 100 DEG C of vacuum oven and toast
20min obtains the first hole transmission layer with a thickness of 60nm；
In the meta-xylene solution of the polyvinyl carbazole of the first hole transport layer surface spin coating 1.5g/mL, spin coating rate
The second hole transmission layer with a thickness of 100nm is obtained in 170 DEG C of annealing 30min for 2500r/s, spin coating 45s；
In the chloroformic solution of alloy quantum dot prepared by the embodiment 1 of the second hole transport layer surface spin coating 15g/L, spin coating
Rate is 2500r/s, spin coating 45 seconds, in 100 DEG C of drying 20min, obtains the luminescent layer with a thickness of 60nm；
In the ethanol solution of the Zinc oxide nanoparticle for the layer surface spin coating 60g/L that shines, spin coating rate is 2500r/s, rotation
It applies 45 seconds, in 100 DEG C of drying 25min, obtains the electron transfer layer with a thickness of 100nm；
It is 4 × 10 in vacuum degree-6Mbar, temperature are silver electrode to be deposited in electron-transport layer surface, electrode is thick at 800 DEG C
Degree is 80nm, obtains electroluminescent diode.
Embodiment 3:
The mass ratio and solidification A of alloy quantum dot prepared by embodiment 1 by 1:3, B glue (1:1) mixing, with 120r/min
Rate stirs 20min, obtains mixed material；
Mixed material is put into vacuum oven 3h at vacuum degree -25bar, remaining bubble is discharged；
Mixed material after vacuum processing is coated in the InGaN/GaN ultraviolet chip of 380 nanometer emission wavelength, then
The lower 150 DEG C of heating 30min solidification of vacuum, obtains the photoluminescent diode that light emitting layer thickness is 50 μm.
Embodiment 4:
10mmol zinc oxide, 1mmol cadmium acetate and 0.02mmol copper acetate are dissolved in 3.5mL tributylphosphine and 10mL tri- is pungent
In amine, it is heated to 150 DEG C；40min is vacuumized with mechanical pump, leads to argon gas as reaction protection environment；
Continue to be warming up to 290 DEG C, the 2mmol sulphur powder solution of 1mL trioctylamine be dissolved in the injection of most rapid rate, keeps the temperature 10min,
Form Cu:CdZnS nucleus；
300 DEG C are warming up to, the 1mmol selenium powder for being dissolved in 2mL tributylphosphine is added dropwise with 1mL/min rate, keeps the temperature 1h, is formed
Cu:CdZnS/ZnSe core-shell structure alloy quantum dot；
50 DEG C are cooled to, injects toluene and methanol volume ratio for the mixed solution of 1:10, with the stirring of 1000r/min rate
After 5min, static 10min, mixed solution layering；Quantum dot solution is mixed in upper layer, impurity and unreacted ligand solvent and methanol
Solution is closed in lower layer, extracts lower layer methanol solution with syringe；After being repeated 4 times, acetone is added, with the centrifugation of 8000r/s rate
5min outwells upper layer supernatant, is put into -30bar in vacuum oven, and 50 DEG C of vacuum drying 30min obtain alloy quantum
Point, yield 73%.
Alloy quantum dot partial size manufactured in the present embodiment is 8.5nm, and Cu:CdZnS core diameter is 5.4nm, ZnSe shell
With a thickness of 3.1nm.
Embodiment 5:
Polyglycolic acid fibre and poly styrene sulfonate prepare second according to the concentration of 2mol/L with the mixing of 1:5 mass ratio
Alcoholic solution, then in 140 DEG C of baking 12min, is obtained with the speed spin coating 40s of 4200r/s on electro-conductive glass with a thickness of 50nm
Hole injection layer；
Electro-conductive glass with hole injection layer is put into glove box, in the 4- fourth of hole injection layer surface spin coating 8g/L
The chlorobenzene solution of base-N, N- diphenylaniline homopolymer, spin coating rate are 2500r/s, are put at 120 DEG C of vacuum oven and toast
20min obtains the first hole transmission layer with a thickness of 60nm；
In the meta-xylene solution of the polyvinyl carbazole of the first hole transport layer surface spin coating 1.5g/mL, spin coating rate
The second hole transmission layer with a thickness of 100nm is obtained in 170 DEG C of annealing 30min for 2500r/s, spin coating 45s；
In the chloroformic solution of alloy quantum dot prepared by the embodiment 4 of the second hole transport layer surface spin coating 15g/L, spin coating
Rate is 2500r/s, spin coating 45 seconds, in 110 DEG C of drying 25min, obtains the luminescent layer with a thickness of 60nm；
In the ethanol solution of the Zinc oxide nanoparticle for the layer surface spin coating 60g/L that shines, spin coating rate is 2500r/s, rotation
It applies 45 seconds, in 105 DEG C of drying 22min, obtains the electron transfer layer with a thickness of 100nm；
It is 4 × 10 in vacuum degree-6Mbar, temperature are silver electrode to be deposited in electron-transport layer surface, electrode is thick at 800 DEG C
Degree is 80nm, obtains electroluminescent diode.
Embodiment 6:
The mass ratio and solidification A of alloy quantum dot prepared by embodiment 4 by 1:100, B glue (1:1) mixing, with 140r/
Min rate stirs 23min, obtains mixed material；
Mixed material is put into vacuum oven 3h at vacuum degree -32bar, remaining bubble is discharged；
Mixed material after vacuum processing is coated in the GaN ultraviolet chip of 345 nanometer emission wavelength, then under vacuum
150 DEG C of heating 30min solidifications, obtain the photoluminescent diode that light emitting layer thickness is 100 μm.
Embodiment 7:
10mmol zinc stearate, 1mmol cadmium stearate and 0.2mmol acetic acid vanadium are dissolved in 3.5mL oleic acid and 10mL1- ten
In eight alkene, it is heated to 200 DEG C；40min is vacuumized with mechanical pump, leads to argon gas as reaction protection environment；
Continue to be warming up to 310 DEG C, the 2mmol sulphur powder solution of 1mL1- octadecylene, heat preservation are dissolved in the injection of most rapid rate
10min forms V:CdZnS nucleus；
320 DEG C are warming up to, the 1mmol selenium powder for being dissolved in 2mL tributylphosphine is added dropwise with 1mL/min rate, keeps the temperature 1h, forms V:
CdZnS/ZnSe core-shell structure alloy quantum dot；
50 DEG C are cooled to, injects n-hexane and methanol volume ratio for the mixed solution of 1:2, with the stirring of 800r/min rate
After 5min, static 10min, mixed solution layering；Quantum dot solution is mixed in upper layer, impurity and unreacted ligand solvent and methanol
Solution is closed in lower layer, extracts lower layer methanol solution with syringe；After being repeated 4 times, acetone is added, with the centrifugation of 10000r/s rate
5min outwells upper layer supernatant, is put into -30bar in vacuum oven, and 50 DEG C of vacuum drying 30min obtain alloy quantum
Point, yield 73%.
Alloy quantum dot partial size manufactured in the present embodiment is 9nm, and V:CdZnS core diameter is 5.8nm, ZnSe shell thickness
For 3.2nm.
Embodiment 8:
Polyglycolic acid fibre and poly styrene sulfonate are prepared with the mixing of 1:3 mass ratio according to the concentration of 1.5mol/L
Ethanol solution, with the speed spin coating 40s of 4200r/s on electro-conductive glass, then in 140 DEG C of baking 12min, obtain with a thickness of
The hole injection layer of 80nm；
Electro-conductive glass with hole injection layer is put into glove box, in the 4- fourth of hole injection layer surface spin coating 8g/L
The chlorobenzene solution of base-N, N- diphenylaniline homopolymer, spin coating rate are 2500r/s, are put at 110 DEG C of vacuum oven and toast
20min obtains the first hole transmission layer with a thickness of 60nm；
In the meta-xylene solution of the polyvinyl carbazole of the first hole transport layer surface spin coating 1.5g/mL, spin coating rate
The second hole transmission layer with a thickness of 100nm is obtained in 170 DEG C of annealing 30min for 2500r/s, spin coating 45s；
In the chloroformic solution of alloy quantum dot prepared by the embodiment 7 of the second hole transport layer surface spin coating 15g/L, spin coating
Rate is 2500r/s, spin coating 45 seconds, in 105 DEG C of drying 25min, obtains the luminescent layer with a thickness of 60nm；
In the ethanol solution of the Zinc oxide nanoparticle for the layer surface spin coating 60g/L that shines, spin coating rate is 2500r/s, rotation
It applies 45 seconds, in 110 DEG C of drying 20min, obtains the electron transfer layer with a thickness of 100nm；
It is 4 × 10 in vacuum degree-6Mbar, temperature are silver electrode to be deposited in electron-transport layer surface, electrode is thick at 800 DEG C
Degree is 80nm, obtains electroluminescent diode.
Embodiment 9:
The mass ratio and solidification A of alloy quantum dot prepared by embodiment 7 by 1:1, B glue (1:1) mixing, with 120r/min
Rate stirs 25min, obtains mixed material；
Mixed material is put into vacuum oven 3h at vacuum degree -30bar, remaining bubble is discharged；
Mixed material after vacuum processing is coated in the InGaN/GaN ultraviolet chip of 380 nanometer emission wavelength, then
The lower 150 DEG C of heating 30min solidification of vacuum, obtains the photoluminescent diode that light emitting layer thickness is 10 μm.
Claims (7)
1. a kind of preparation method of alloy quantum dot, comprising the following steps:
(1) by zinc source, cadmium source, transition metal salt, ligand solvent and non-coordinating solvent mix, 100~200 DEG C heating obtain sun from
Sub- presoma；
(2) sulphur source is injected in the cationic presoma that Xiang Suoshu step (1) obtains, and is carried out the first reaction and is obtained quantum dot forerunner
Body；The temperature of first reaction is 280~320 DEG C, and the time of the first reaction is 5~15min；
(3) selenium source is added in the quantum dot presoma that Xiang Suoshu step (2) obtains, carries out the second reaction and obtains alloy quantum dot；
The temperature of second reaction is 290~330 DEG C, and the time of the second reaction is 30~90min；The alloy quantum dot has core
Shell structure, including D:CdZnS nucleome and the ZnSe shell being coated on outside the nucleome, D is transition metal element, transition metal member
Element is copper, manganese or vanadium.
2. preparation method according to claim 1, which is characterized in that zinc source, cadmium source and transition metal in the step (1)
The molar ratio of metallic element is 10~100:1:0.1~2 in salt.
3. preparation method according to claim 1, which is characterized in that sulphur source and the step (1) in the step (2)
The molar ratio in middle cadmium source is 2~50:1.
4. preparation method according to claim 1, which is characterized in that selenium source and the step (1) in the step (3)
The molar ratio in middle cadmium source is 1~30:1.
5. the alloy quantum dot of the preparation of preparation method described in Claims 1 to 4 any one, has core-shell structure, including D:
CdZnS nucleome and the ZnSe shell being coated on outside the nucleome, D are transition metal element, transition metal element be copper, manganese or
Vanadium.
6. a kind of electroluminescent diode, including set gradually electro-conductive glass, hole injection layer, hole transmission layer, luminescent layer,
Electron transfer layer and electrode, the luminescent layer include the alloy quantum of the preparation of preparation method described in Claims 1 to 4 any one
Alloy quantum dot described in point or claim 5.
7. a kind of photoluminescent diode, the luminescent layer including ultraviolet chip and its surface, the luminescent layer includes claim 1
Alloy quantum dot described in the alloy quantum dot or claim 5 of the preparation of preparation method described in~4 any one.
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| US10096743B1 (en) * | 2017-05-26 | 2018-10-09 | Unique Materials Co., Ltd. | Gigantic quantum dots |
| CN107400507A (en) * | 2017-08-17 | 2017-11-28 | 厦门世纳芯科技有限公司 | A kind of nearly mid and far infrared alloy quantum dot and preparation method thereof |
| CN111384306B (en) * | 2018-12-29 | 2021-10-29 | Tcl科技集团股份有限公司 | Preparation method of quantum dot light-emitting diode |
| CN112300777B (en) * | 2019-07-26 | 2022-01-18 | 纳晶科技股份有限公司 | Core-shell quantum dot, preparation method thereof and quantum dot photoelectric device |
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