CN108531185A - A kind of quantum dot and its synthetic method - Google Patents
A kind of quantum dot and its synthetic method Download PDFInfo
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- CN108531185A CN108531185A CN201810577676.5A CN201810577676A CN108531185A CN 108531185 A CN108531185 A CN 108531185A CN 201810577676 A CN201810577676 A CN 201810577676A CN 108531185 A CN108531185 A CN 108531185A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 97
- 238000010189 synthetic method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims description 78
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 62
- 229910052725 zinc Inorganic materials 0.000 claims description 62
- 229910052793 cadmium Inorganic materials 0.000 claims description 44
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000005864 Sulphur Substances 0.000 claims description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 27
- -1 ten sour cadmiums Chemical compound 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 11
- PVLBCXWFQZZIGP-UHFFFAOYSA-L zinc;nonanoate Chemical compound [Zn+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O PVLBCXWFQZZIGP-UHFFFAOYSA-L 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 7
- 229920005646 polycarboxylate Polymers 0.000 claims description 7
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 claims description 7
- 239000005639 Lauric acid Substances 0.000 claims description 6
- ZTSAVNXIUHXYOY-CVBJKYQLSA-L cadmium(2+);(z)-octadec-9-enoate Chemical compound [Cd+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O ZTSAVNXIUHXYOY-CVBJKYQLSA-L 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 4
- UMBZYKHJCJWCDP-UHFFFAOYSA-N cadmium;nonanoic acid Chemical compound [Cd].CCCCCCCCC(O)=O UMBZYKHJCJWCDP-UHFFFAOYSA-N 0.000 claims description 4
- PWVCIVRRMGKIKQ-UHFFFAOYSA-N cadmium;pentadecanoic acid Chemical compound [Cd].CCCCCCCCCCCCCCC(O)=O PWVCIVRRMGKIKQ-UHFFFAOYSA-N 0.000 claims description 4
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 4
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims description 4
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229940098697 zinc laurate Drugs 0.000 claims description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 2
- DSJCWPGSMYRVFC-UHFFFAOYSA-N heptadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCC(O)=O DSJCWPGSMYRVFC-UHFFFAOYSA-N 0.000 claims description 2
- MEFIJKOKCGRWSK-UHFFFAOYSA-N pentadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCC(O)=O MEFIJKOKCGRWSK-UHFFFAOYSA-N 0.000 claims description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims 1
- 238000002835 absorbance Methods 0.000 abstract description 11
- 230000007704 transition Effects 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 235000016804 zinc Nutrition 0.000 description 48
- 238000010792 warming Methods 0.000 description 29
- 239000003153 chemical reaction reagent Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000026267 regulation of growth Effects 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 235000019628 coolness Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- IPHJEASQVVMRBW-UHFFFAOYSA-N [Cd].C(CCCCCCCCCCCCCCCC)(=O)O Chemical compound [Cd].C(CCCCCCCCCCCCCCCC)(=O)O IPHJEASQVVMRBW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000021391 short chain fatty acids Nutrition 0.000 description 2
- 150000004666 short chain fatty acids Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000013904 zinc acetate Nutrition 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- CVCLJCPKZSIKTE-UHFFFAOYSA-N [S].C(CCC)P Chemical compound [S].C(CCC)P CVCLJCPKZSIKTE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical class [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- 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
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of quantum dot and its synthetic methods.It includes CdZnSeS quantum dots that the quantum dot, which has nucleocapsid, core therein, shell include coat the core successively the first CdZnS layers, the 2nd CdZnS layers, the first ZnS layers and the 2nd ZnS layers.The synthetic method includes：CdZnSeS quantum dots as core are provided, in wrapping up shell on the CdZnSeS quantum dots, the shell include the first CdZnS layers sequentially formed, the 2nd CdZnS layers, the first ZnS layers and the 2nd ZnS layers.The quantum dot of the present invention uses bilayer CdZnS alloy transition layers, raising efficiency and can improve stability while improving absorbance；Also, synthesising method reacting condition is mild, and application prospect is extensive.
Description
Technical field
The present invention relates to a kind of synthetic method of quantum dot, more particularly to a kind of high stable high efficiency high absorbance quantum dot
And its synthetic method, belong to technical field of nanometer material preparation.
Background technology
With the rapid development of science and technology, quantum dot application technology reaches its maturity.The pass that wherein quantum dot success uses
Key factor is the stability of quantum dot.In addition, reducing the usage amount of quantum dot, the absorption of quantum dot is promoted, reduces production cost
Can quantum dot be also determined apply on a large scale in our lives.As the quantum dot of luminescent layer, its luminous efficiency is to determine eventually
Hold the another important parameter of properties of product.
Therefore the quantum dot of success synthesizing efficient stabilization high absorbance is extremely urgent and industry research staff endeavours to solve
Direction.
Invention content
The main purpose of the present invention is to provide a kind of high stable high efficiency high absorbance quantum dot and its synthetic method, with
Overcome the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of quantum dots, it has nucleocapsid, and core therein includes CdZnSeS quantum
Point, shell include coat the core successively the first CdZnS layers, the 2nd CdZnS layers, the first ZnS layers and the 2nd ZnS layers.
The embodiment of the present invention additionally provides a kind of synthetic method of quantum dot comprising：
CdZnSeS quantum dots as core are provided；
In wrapping up shell on the CdZnSeS quantum dots, the shell includes the first CdZnS layers sequentially formed, second
CdZnS layers, the first ZnS layers and the 2nd ZnS layers.
Among certain preferred embodiments, the synthetic method includes：
Make comprising CdZnSeS quantum dots, the first cadmium source, the first zinc source and the first sulphur source hybrid reaction system in 280~
310 DEG C of 10~30min of reaction, CdZnS layers of formation the first；And
After completing the first CdZnS layers of growth, be added into the hybrid reaction system the second cadmium source, the second zinc source and
Second sulphur source, and 30min~2h, CdZnS layers of formation the 2nd are reacted in 280~310 DEG C.
Among certain preferred embodiments, the synthetic method includes：
After completing the 2nd CdZnS layer of growth, addition third zinc source and third sulphur source into hybrid reaction system, and in
280~310 DEG C of reaction 30min~1h, ZnS layers of growth formation the first；And
After completing the first ZnS layer of growth, the 4th zinc source of addition and the 4th sulphur source into hybrid reaction system, and in
200~310 DEG C of reaction 30min~2h, ZnS layers of growth formation the 2nd.
The embodiment of the present invention additionally provides the quantum dot synthesized by preceding method.
The embodiment of the present invention additionally provides purposes of the aforementioned quantum dot in preparing electrooptical device.
Compared with prior art, high stable high efficiency high absorbance quantum dot provided by the invention is closed using the double-deck CdZnS
Golden transition zone raising efficiency and can improve stability while improving absorbance；Meanwhile synthetic method of the invention, instead
Mild condition is answered, one CdZnS layers of growth regulation, which can play a protective role, is limited in hole and electronics in quantum dot core, growth regulation two
CdZnS layers can reduce R-SH capture hole abilities, improve quantum dot light emitting efficiency, in addition, the present invention using active zinc source come
ZnS layers of continued growth, can significantly improve the stability of quantum dot, and application prospect is extensive.
Description of the drawings
Fig. 1 for obtained high stable high efficiency high absorbance quantum dot in an of the invention typical embodiments transmitting and absorption
Spectrogram.
Fig. 2 is the TEM pictures of 1 obtained CdZnSeS/CdZnS/CdZnS/ZnS/ZnS quantum dots of the embodiment of the present invention.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
A kind of quantum dot that the one side of the embodiment of the present invention provides, it includes with nucleocapsid, core therein
CdZnSeS quantum dots, shell include coat the core successively the first CdZnS layers, the 2nd CdZnS layers, the first ZnS layers and
Two ZnS layers, structural formula can be expressed as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS.
Further, the size of the core is 5~7nm.
Further, the described first CdZnS layers thickness be 1~3nm.
Further, the described 2nd CdZnS layers thickness be 2~4nm.
Further, the described first ZnS layers thickness be 2~4nm.
Further, the described 2nd ZnS layers thickness be 2~4nm.
The embodiment of the present invention another aspect provides a kind of synthetic methods of quantum dot comprising：
CdZnSeS quantum dots as core are provided；
In wrapping up shell on the CdZnSeS quantum dots, the shell includes the first CdZnS layers sequentially formed, second
CdZnS layers, the first ZnS layers and the 2nd ZnS layers.
Among certain preferred embodiments, the synthetic method includes：
Make comprising CdZnSeS quantum dots, the first cadmium source, the first zinc source and the first sulphur source hybrid reaction system in 280~
310 DEG C of 10~30min of reaction, CdZnS layers of formation the first；And
After completing the first CdZnS layers of growth, be added into the hybrid reaction system the second cadmium source, the second zinc source and
Second sulphur source, and 30min~2h, CdZnS layers of formation the 2nd are reacted in 280~310 DEG C.
In some embodiments, the molar ratio in first cadmium source, the first zinc source and the first sulphur source is 1：1：2~1：3：4.
Further, the first cadmium source used in the first CdZnS layers of growth course is carboxylic acid cadmium, the carboxylic acid cadmium packet
Include cadmium oleate, heptadecanoic acid cadmium, hexadecylic acid cadmium, pentadecanoic acid cadmium, tetradecylic acid cadmium, lauric acid/dodecanoic acid cadmium, ten sour cadmiums, n-nonanoic acid cadmium, cadmium stearate
(Cd(St)2) and xanthic acid cadmium etc. in any one or two or more combinations, but not limited to this.
Further, the first zinc source used in the first CdZnS layers of growth course can be zinc polycarboxylate, the carboxylic acid
Zinc includes zinc oleate, heptadecanoic acid zinc, hexadecylic acid zinc, pentadecanoic acid zinc, tetradecylic acid zinc, zinc laurate, ten sour zinc, zinc pelargonate, diethyl
Any one in base zinc, xanthopone, zinc acetate and zinc propionate etc. or two or more combinations, but not limited to this.Its
In, first zinc source can be the amine aqueous solution of short chain fatty acids zinc.
Further, the first sulphur source used in the first CdZnS layers of growth course may include tri octyl phosphine sulphur, three
Any one in butyl phosphine sulphur and ethyl xanthate etc. or two or more combinations, but not limited to this.
In some embodiments, the molar ratio in second cadmium source, the second zinc source and the second sulphur source is 1：1：2~1：3：
15。
Further, the second cadmium source used in the 2nd CdZnS layers of growth course is carboxylic acid cadmium, the carboxylic acid cadmium packet
Include cadmium oleate, heptadecanoic acid cadmium, hexadecylic acid cadmium, pentadecanoic acid cadmium, tetradecylic acid cadmium, lauric acid/dodecanoic acid cadmium, ten sour cadmiums, n-nonanoic acid cadmium, cadmium stearate
(Cd(St)2) and xanthic acid cadmium etc. in any one or two or more combinations, but not limited to this.
Further, the second zinc source used in the 2nd CdZnS layers of growth course can be zinc polycarboxylate, the carboxylic acid
Zinc includes any one or two kinds in ten sour zinc, zinc pelargonate, diethyl zinc, xanthopone, zinc acetate and zinc propionate etc.
Above combination, but not limited to this.Wherein, first zinc source can be the amine aqueous solution of short chain fatty acids zinc.
In the present invention, the selection principle in zinc source is：Second zinc source is more active than the first zinc source, because with shell
Increase, the volume of quantum dot is increasing, is grown using inactive zinc source, it more difficult to which growth is got on so that the ingredient in CdZnS
More it is partial to CdS.
Further, it is R-SH that the second sulphur source used in the 2nd CdZnS layers of growth course, which can be chemical formula,
Compound, wherein R are the alkyl of 6~12 carbon atoms.
If only using one CdZnS layers of former approach growth regulation, TOP is as ligand, and element P is as coordination element, relatively
Coordination ability is weaker for S, and being easy to fall off reduces so as to cause luminous efficiency.If only using second method growth regulation two
CdZnS layers, then for R-SH themselves such that quantum dot generates cavitation damage, the hole in capture quantum dot leads to electronics in quantum dot
The probability reduction of exciton is generated with hole causes quantum dot light emitting effectively weaker.In addition R-SH, which participates in reacting, needs the regular hour
It is decomposed with temperature, if reaction controlling is bad, R-SH can form thicker S active layer around quantum dot, can cause in this way and sun
Only it will so cause matter crystal internal defect with outer layer S ionic reactions when ionic reaction, luminous efficiency is caused to decline.
The present invention with together, to distinguish one CdZnS layer of growth regulation and the 2nd CdZnS layers, gives birth to two methods first
Long first CdZnS layer can play a protective role and is limited in hole in quantum dot core with electronics, then with second method growth regulation
Two CdZnS layers can reduce the ability that R-SH captures hole, improve quantum dot light emitting efficiency.
Among certain preferred embodiments, the synthetic method includes：
After completing the 2nd CdZnS layer of growth, addition third zinc source and third sulphur source into hybrid reaction system, and in
280~310 DEG C of reaction 30min~1h, ZnS layers of growth formation the first；And
After completing the first ZnS layer of growth, the 4th zinc source of addition and the 4th sulphur source into hybrid reaction system, and in
200~310 DEG C of reaction 30min~2h, ZnS layers of growth formation the 2nd.
In some embodiments, the molar ratio of third zinc source and third sulphur source is 1：1~1：5.
In some embodiments, the molar ratio of the 4th zinc source and the 4th sulphur source is 1：1~1：5.
Further, the zinc source of the ZnS layers of use of growth the described first can be ten sour zinc, zinc pelargonate, diethyl zinc, ethyl
Any one in xanthic acid zinc, zinc acetate and zinc propionate etc. or two or more combinations, but not limited to this.
Further, the ZnS layer zinc source used of growth the described 2nd can be diethyl zinc, zinc acetate and zinc propionate etc.,
But not limited to this.
Growth ZnS can significantly improve the stability of quantum dot, but with the growth of shell, quantum dot volume is increasingly
Greatly, it is difficult up to grow, therefore carry out continued growth ZnS using active zinc with the substance of activity of the same race, it is higher to obtain
The quantum dot of stability.
Further, ZnS layers of growth the described first and the 2nd ZnS layers of sources S used can be chemical formulas for the change of R-SH
Object is closed, wherein R is the alkyl of 6~12 carbon atoms.
Wherein, method known to industry can refer to for the preparation of CdZnSe quantum dots, for example, can refer to document Highly
luminescent red emitting CdZnSe/ZnSe quantum dots synthesis and application
For quantum dot light emitting diodes (OPT MATEREXPRESS, 2017,7,3875) etc..
For example, among certain preferred embodiments, the preparation method of the CdZnSe quantum dots includes：Make to include oil
The hybrid reaction system of sour cadmium, zinc oleate and solvent reacts 30min~2h in 100~130 DEG C, later in 300~310 DEG C of additions
Tri-n-octyl phosphine selenium sulphur (TOPSeS) reacts 10~30min, forms CdZnSeS quantum dots.
Further, the solvent includes octadecylene (ODE), but not limited to this.
Further, the synthetic method further includes：Prior to 300~310 DEG C two are added into the hybrid reaction system
Tri-n-octyl phosphine selenium sulphur (TOPSeS) is added in Phenylphosphine later.
Further, the molar ratio of the cadmium oleate and zinc oleate is 1：2~1：30.
The other side of the embodiment of the present invention additionally provides the quantum dot synthesized by preceding method.
The other side of the embodiment of the present invention additionally provides purposes of the aforementioned quantum dot in preparing electrooptical device.
By above-mentioned technical proposal, quantum dot of the invention uses bilayer CdZnS alloy transition layers, can improve absorbance
While raising efficiency and improve stability；Also, synthesising method reacting condition is mild, and application prospect is extensive.
Technical scheme of the present invention is described in further details with reference to embodiment and attached drawing, but the present invention and not only
It is limited only to following embodiments.
The preparation method for some reaction reagents that following embodiment uses is as follows：
Cadmium oleate preparation method (Cd (OA)20.2M)
Cadmium oxide CdO 20mmol Alpha reagent 98%
Oleic acid OA 20ml Alpha reagent 90%
Octadecylene ODE 80ml Alpha reagent 90%
Above-mentioned raw materials are placed in 250ml three-neck flasks and is warming up to 120 DEG C and vacuumizes, until being warming up to 260 DEG C after bubble-free
Be cooled to after dissolving 80 DEG C it is spare.
Tetradecylic acid cadmium preparation method (Cd (MA)2)
Cadmium oxide CdO 20mmol Alpha reagent 98%
Tetradecylic acid MA 20ml Alpha reagent 90%
Octadecylene ODE 80ml Alpha reagent 90%
Above-mentioned raw materials are placed in 250ml three-neck flasks and is warming up to 120 DEG C and vacuumizes, until being warming up to 260 DEG C after bubble-free
Be cooled to after dissolving 80 DEG C it is spare.
Lauric acid/dodecanoic acid cadmium preparation method
Cadmium oxide CdO 20mmol Alpha reagent 98%
Lauric acid/dodecanoic acid MA 20ml Alpha reagent 90%
Octadecylene ODE 80ml Alpha reagent 90%
Above-mentioned raw materials are placed in 250ml three-neck flasks and is warming up to 120 DEG C and vacuumizes, until being warming up to 260 DEG C after bubble-free
Be cooled to after dissolving 80 DEG C it is spare.
Zinc polycarboxylate preparation method (0.5M) used herein
Zn(Ac)250mmol Alpha reagent 99.99%
Carboxylic acid 50ml Alpha reagent 90%
Octadecylene ODE 50ml Alpha reagent 90%
Above-mentioned raw materials are placed in 250ml three-neck flasks be warming up to 120 DEG C be evacuated to bubble-free after, obtain water white transparency
It is spare after being cooled to 80 DEG C after solution.
Zinc acetate solution preparation method：
Zn(Ac)250mmol Alpha reagent 99.99%
Oleyl amine 50ml Alpha reagent 98%
Octadecylene ODE 50ml Alpha reagent 90%
Zinc stearate solution preparation method：
Zinc stearate 50mmol Alpha reagent 90%
Octadecylene 100ml Alpha reagent 90%
Tri octyl phosphine selenium preparation method (TOPSe 2M)
TOP 20ml Alpha reagent 90%
Selenium powder Alpha reagent 99.999%
Above-mentioned raw materials are placed in 100ml three-neck flasks, be warming up to 120 DEG C be evacuated to bubble-free after obtain water white transparency
After solution, it is spare to be cooled to room temperature.
Tri octyl phosphine sulphur preparation method (TOPS 2M)
TOP 20ml Alpha reagent 90%
Sulphur powder Alpha reagent 99.999%
Above-mentioned raw materials are placed in 100ml three-neck flasks, be warming up to 120 DEG C be evacuated to bubble-free after obtain water white transparency
After solution, it is spare to be cooled to room temperature.
Embodiment 1
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 120 DEG C
1h is vacuumized to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 300 DEG C, fast injection TOPSeS 2M 1ml
Afterwards, it is maintained 30 minutes in 300 DEG C.Appropriate Cd (OA) is added dropwise simultaneously in 300 DEG C22ml、Zn(OA)20.8ml、TOPS 0.4ml,
After 20min, 300 DEG C are continued at using Cd (OA)20.3ml, zinc pelargonate 0.6ml and hexyl mercaptan 1ml, react 1h, after having grown in
300 DEG C use 10ml diethyl zincs and 2ml hexyl mercaptans using after 8ml zinc pelargonates and the growth of 1 hexyl mercaptan ZnS, 40min in 300 DEG C
Then growth ZnS reacts 1h, and reaction was completed for finally cooling, obtains the quantum dot with nucleocapsid, structural formula can be by table
It is the quantum dot as core, CdZnS/CdZnS/ZnS/ to state as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS, wherein CdZnSeS
ZnS is the quantum dot being coated on successively on core.
Embodiment 2
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 100 DEG C
1h is vacuumized to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 310 DEG C, in 310 DEG C of fast injection TOPSeS
After 2M1.2ml, maintained 30 minutes in 310 DEG C.Appropriate 2ml lauric acid/dodecanoic acids cadmium, 0.2ml Zn (OA) is added dropwise simultaneously in 300 DEG C2、
10min after TOPS0.4ml, continues at 300 DEG C using 5ml lauric acid/dodecanoic acids cadmiums, the sour zinc of 1ml ten and 1ml spicy thioalcohols, reaction 30min after
Continuous growth CdZnS, after grow in 310 DEG C using the sour zinc solutions of 8ml ten with after the growth of 1ml spicy thioalcohols ZnS, 30min in 310 DEG C
ZnS is then grown using 10ml diethyl zincs and 2ml spicy thioalcohols, reaction was completed for reaction 30min finally coolings, and obtaining has nucleocapsid
The quantum dot of structure, structural formula can be expressed as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS.
Embodiment 3
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 130 DEG C
It is evacuated to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 310 DEG C, and diphenylphosphine 1, which is added dropwise, in 310 DEG C drips,
After 310 DEG C of fast injection TOPSeS 2M 1.5ml, maintained 30 minutes in 300 DEG C.3mlCd (MA) is added dropwise simultaneously in 280 DEG C2、
2ml Zn(MA)2, 30min after 0.8ml TOPS, continue at 280 DEG C using 8ml Cd (MA)2、2.4ml Zn2Zinc pelargonate and 2ml
Lauryl mercaptan grows ZnS using 10ml zinc pelargonates and 1.2ml lauryl mercaptans in 280 DEG C after having grown, is used in 280 DEG C after 1h
10ml diethyl zincs then grow ZnS with 1.5ml lauryl mercaptans, and reaction was completed for reaction 2h finally coolings, and obtaining has nucleocapsid knot
The quantum dot of structure, structural formula can be expressed as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS.
Embodiment 4
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 120 DEG C
It is evacuated to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 300 DEG C, fast injection TOPSeS 2M 0.2ml
Afterwards, it is maintained 30 minutes in 300 DEG C.2ml Cd (MA) are added dropwise simultaneously in 280 DEG C2、0.6ml Zn(St)2, after TOPS 0.9ml
30min uses 4ml Cd (OA) in 280 DEG C2、0.8ml Zn(Ac)2With 0.8ml lauryl mercaptans, 2h continued growth CdZnS are reacted,
After having grown 4ml Zn (Ac) is used in 280 DEG C2With after the growth of 1ml lauryl mercaptans ZnS, 1h 8ml diethyl zincs are used in 280 DEG C
ZnS is then grown with 2.5ml lauryl mercaptans, reaction was completed for reaction 2h finally coolings, obtains the quantum dot with nucleocapsid,
Structural formula can be expressed as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS.
Embodiment 5
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 120 DEG C
1h is vacuumized to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 300 DEG C, fast injection TOPSeS 2M 1ml
Afterwards, it is maintained 30 minutes in 300 DEG C.Appropriate Cd (OA) is added dropwise simultaneously in 300 DEG C22ml、Zn(OA)20.8ml、TOPS 0.4ml,
After 20min, 300 DEG C are continued at using Cd (OA)20.3ml, diethyl zinc 1.2ml and hexyl mercaptan 1ml react 1h, after having grown
After 300 DEG C of use 8ml zinc pelargonates and the growth of 1 hexyl mercaptan ZnS, 40min 10ml diethyl zincs and the own sulphur of 2ml are used in 300 DEG C
Alcohol then grows ZnS reaction 1h, and reaction was completed for finally cooling, obtains the quantum dot with nucleocapsid, and structural formula can be by
It is expressed as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS.
Embodiment 6
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 120 DEG C
1h is vacuumized to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 300 DEG C, fast injection TOPSeS 2M 1ml
Afterwards, it is maintained 30 minutes in 300 DEG C.Appropriate Cd (OA) is added dropwise simultaneously in 300 DEG C22ml、Zn(OA)20.8ml、TOPS 0.4ml,
After 20min, 300 DEG C are continued at using Cd (OA)20.3ml, zinc laurate 1.2ml and hexyl mercaptan 1ml react 1h, after having grown
In 300 DEG C 10ml diethyl zincs and 2ml are used in 300 DEG C using 8ml zinc laurates with after the growth of 1ml hexyl mercaptans ZnS, 40min
Hexyl mercaptan then grows ZnS reaction 1h, and reaction was completed for finally cooling, obtains the quantum dot with nucleocapsid, structural formula can
To be expressed as CdZnSeS/CdZnS/CdZnS/ZnS/ZnS.
Comparative example 1
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 120 DEG C
1h is vacuumized to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 300 DEG C, fast injection TOPSeS 2M 1ml
Afterwards, it is maintained 30 minutes in 300 DEG C.Appropriate Cd (OA) is added dropwise simultaneously in 300 DEG C22ml、Zn(OA)20.8ml、TOPS 0.4ml,
After 20min, ZnS is grown using 8ml zinc pelargonates and 1 hexyl mercaptan in 300 DEG C, reaction was completed for finally cooling, and obtaining has nucleocapsid knot
The quantum dot of structure, wherein CdZnSeS are the quantum dot as core, and CdZnS/CdZnS/ZnS/ZnS is to be coated on core successively
Quantum dot.
The quantum dot with nucleocapsid is obtained, structural formula can be expressed as CdZnSeS/CdZnS/ZnS.
Comparative example 2
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 100 DEG C
1h is vacuumized to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 310 DEG C, in 310 DEG C of fast injection TOPSeS
After 2M1.2ml, maintained 30 minutes in 310 DEG C.Appropriate 2ml lauric acid/dodecanoic acids cadmium, 0.2ml Zn (OA) is added dropwise simultaneously in 300 DEG C2、
10min after TOPS0.4ml grows ZnS with 1ml spicy thioalcohols using the sour zinc solutions of 8ml ten in 310 DEG C after having grown, reacts 30min
Reaction was completed for finally cooling, obtains the quantum dot with nucleocapsid.The quantum dot with nucleocapsid is obtained, structural formula can
To be expressed as CdZnSeS/CdZnS/ZnS.
Comparative example 3：
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 130 DEG C
It is evacuated to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 310 DEG C, after 310 DEG C are added dropwise the drop of diphenylphosphine 1
After fast injection TOPSeS 2M 1.5ml, maintained 30 minutes in 300 DEG C.3ml Cd (MA) are added dropwise simultaneously in 280 DEG C2、2mlZn
(MA)2, 30min after 0.8ml TOPS, grow ZnS using 10ml zinc pelargonates and 1.2ml lauryl mercaptans in 280 DEG C after having grown,
ZnS is then grown using 10ml diethyl zincs and 1.5ml lauryl mercaptans in 280 DEG C after 1h, reaction was completed for reaction 2h finally coolings,
The quantum dot with nucleocapsid is obtained, structural formula can be expressed as CdZnSeS/CdZnS/ZnS/ZnS.
Comparative example 4：
By 1mlCd (OA)2With 10mlZn (OA)2It is placed in 100ml three-neck flasks with 10~20mlODE, is warming up to 120 DEG C
It is evacuated to bubble-free, after obtaining colourless transparent liquid, drum argon gas is warming up to 300 DEG C, fast injection TOPSeS 2M 0.2ml
Afterwards, it is maintained 30 minutes in 300 DEG C.2ml Cd (MA) are added dropwise simultaneously in 280 DEG C2、0.6ml Zn(St)2, after TOPS 0.9ml
30min uses 4ml Cd (OA) in 280 DEG C2、0.8ml Zn(Ac)2With 0.8ml lauryl mercaptans, 2h continued growth CdZnS are reacted,
After having grown 4ml Zn (Ac) is used in 280 DEG C2ZnS is grown with 1ml lauryl mercaptans, reaction was completed for reaction 2h finally coolings, obtains
The quantum dot with nucleocapsid is obtained, structural formula can be expressed as CdZnSeS/CdZnS/CdZnS/ZnS.
It is tested for the property by taking 1 obtained quantum dot of embodiment as an example below：
1. the test map of 1 obtained quantum dot of embodiment is seen shown in Fig. 1, TEM figures please refer to Fig. 2.
2. after tested, the PL intensity of 1 obtained quantum dot of embodiment is adjustable 460~630, FWHM<25, QY>90%.
3. Detection of Stability：
The chloroformic solution of 1 obtained quantum dot of embodiment is dispersed in formation quantum dispensing water in acrylic resin, by quantum
Point glue is coated in PET base material, and the other side is equally covered with PET base material and bonded, then ultraviolet light-initiated resin polymerization solidification
Obtain quantum dot enhancing film.Obtained QOEF (quantum dot enhancing film) is carried out under conditions of temperature is 85 DEG C, humidity is 85%
Test, test result show the excellent in stability of the obtained quantum dot of the present embodiment.
4. the luminous efficiency of the obtained quantum dots of embodiment 1-6 and comparative example 1-4 detects：
The detection method of quantum dot light emitting efficiency is：Using 450nm blue LED lamps as back light, integrating sphere is utilized
Blue backlight spectrum and the spectrum through quantum dot film are tested respectively, and calculating quantum dot light emitting using the integral area of spectrogram imitates
Rate.
Wherein, quantum dot light emitting efficiency=quantum dot absorb peak area/(Blue backlight peak area-through quantum dot film not
Absorbed blue peak area) * 100%.And survey starting efficiency and aging behind efficiency, testing result are as shown in table 1 respectively.
The luminous efficiency testing result of 1 the obtained quantum dot of embodiment 1-6 and comparative example 1-4 of table
In conclusion by above-mentioned technical proposal, high stable high efficiency high absorbance quantum dot of the invention, using bilayer
CdZnS alloy transition layers raising efficiency and can improve stability while improving absorbance.
In addition, mode of the inventor referring also to embodiment 1- embodiments 6, with the other raw materials listed in this specification
It is tested with condition etc., and the quantum dot of high stable high efficiency high absorbance has equally been made.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.Example
Such as, the part that do not address in the present specification is taken or is used for reference prior art and can be realized, therefore all according to spirit of that invention reality
Equivalent change or modification made by matter, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of quantum dot, it is characterised in that it has nucleocapsid, and core therein includes CdZnSeS quantum dots, and shell includes
The first CdZnS layers of the core, the 2nd CdZnS layers, the first ZnS layers and the 2nd ZnS layers are coated successively；Preferably, the core
Size be 5~7nm；Preferably, the described first CdZnS layers thickness be 1~3nm；Preferably, described 2nd CdZnS layers
Thickness is 2~4nm；Preferably, the described first ZnS layers thickness be 2~4nm；Preferably, the described 2nd ZnS layers thickness be 2
~4nm.
2. a kind of synthetic method of quantum dot, it is characterised in that including：
CdZnSeS quantum dots as core are provided；
In wrapping up shell on the CdZnSeS quantum dots, the shell includes the first CdZnS layers, the 2nd CdZnS sequentially formed
Layer, the first ZnS layers and the 2nd ZnS layers.
3. synthetic method according to claim 2, it is characterised in that including：
Make the hybrid reaction system comprising CdZnSeS quantum dots, the first cadmium source, the first zinc source and the first sulphur source in 280~310 DEG C
React 10~30min, CdZnS layers of formation the first；And
After completing the first CdZnS layers of growth, the second cadmium source, the second zinc source and second are added into the hybrid reaction system
Sulphur source, and 30min~2h, CdZnS layers of formation the 2nd are reacted in 280~310 DEG C.
4. synthetic method according to claim 3, it is characterised in that：First cadmium source, the first zinc source and the first sulphur source
Molar ratio be 1：1：2~1：3：4；And/or first cadmium source is carboxylic acid cadmium, the carboxylic acid cadmium includes cadmium oleate, heptadecanoic acid
Appointing in cadmium, hexadecylic acid cadmium, pentadecanoic acid cadmium, tetradecylic acid cadmium, lauric acid/dodecanoic acid cadmium, ten sour cadmiums, n-nonanoic acid cadmium, cadmium stearate and xanthic acid cadmium
Meaning a combination of one or more；And/or first zinc source is zinc polycarboxylate, the zinc polycarboxylate includes zinc oleate, heptadecanoic acid
Zinc, hexadecylic acid zinc, pentadecanoic acid zinc, tetradecylic acid zinc, zinc laurate, in any one or two or more combinations；And/or institute
It includes any one or the two or more groups in tri octyl phosphine sulphur, tributylphosphine sulphur and ethyl xanthate to state the first sulphur source
It closes.
5. synthetic method according to claim 3, it is characterised in that：Second cadmium source, the second zinc source and the second sulphur source
Molar ratio be 1：1：2~1：3：15；And/or second cadmium source includes carboxylic acid cadmium, the carboxylic acid cadmium includes cadmium oleate, ten
In seven sour cadmiums, hexadecylic acid cadmium, pentadecanoic acid cadmium, tetradecylic acid cadmium, lauric acid/dodecanoic acid cadmium, ten sour cadmiums, n-nonanoic acid cadmium, cadmium stearate and xanthic acid cadmium
Any one or two or more combinations；And/or second zinc source is zinc polycarboxylate, the zinc polycarboxylate includes ten sour zinc, nonyl
The combination of one or more of sour zinc, diethyl zinc, xanthopone, zinc acetate and zinc propionate；And/or it is described
Second sulphur source includes the compound that chemical formula is R-SH, and wherein R is the alkyl of 6~12 carbon atoms.
6. synthetic method according to claim 5, it is characterised in that including：
After completing the 2nd CdZnS layer of growth, addition third zinc source and third sulphur source into hybrid reaction system, and in 280
~310 DEG C of reaction 30min~1h, ZnS layers of growth formation the first；And
After completing the first ZnS layer of growth, the 4th zinc source of addition and the 4th sulphur source into hybrid reaction system, and in 200~
310 DEG C of reaction 30min~2h, ZnS layers of growth formation the 2nd.
7. synthetic method according to claim 6, it is characterised in that：Third zinc source and the molar ratio of third sulphur source are
1：1~1：5；And/or the molar ratio of the 4th zinc source and the 4th sulphur source is 1：1~1：5.
8. synthetic method according to claim 6, it is characterised in that：The zinc source for growing the described first ZnS layers of use includes
Any one in ten sour zinc, zinc pelargonate, diethyl zinc, xanthopone, zinc acetate and zinc propionate or two or more groups
It closes；And/or the zinc source of the ZnS layers of use of growth the described 2nd includes diethyl zinc, zinc acetate and zinc propionate；And/or growth institute
It includes chemical formula for the compound of R-SH to state the first ZnS layers and the 2nd ZnS layer sulphur source used, and wherein R is 6~12 carbon atoms
Alkyl.
9. the quantum dot synthesized by any one of claim 2-8 the methods.
10. purposes of the quantum dot of claim 1 or 9 in preparing electrooptical device.
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