CN108281494A - A kind of quantum dot photovoltaic device and preparation method - Google Patents
A kind of quantum dot photovoltaic device and preparation method Download PDFInfo
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- CN108281494A CN108281494A CN201611259485.1A CN201611259485A CN108281494A CN 108281494 A CN108281494 A CN 108281494A CN 201611259485 A CN201611259485 A CN 201611259485A CN 108281494 A CN108281494 A CN 108281494A
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- CBKSKPBBKQQLOM-UHFFFAOYSA-N [S].C(CCCCCCCC=C/CCCCCCCC)(=O)O Chemical compound [S].C(CCCCCCCC=C/CCCCCCCC)(=O)O CBKSKPBBKQQLOM-UHFFFAOYSA-N 0.000 description 1
- RHKQUGZIMGIIEA-UHFFFAOYSA-N [S].CCCCCCCCP(CCCCCCCC)CCCCCCCC Chemical compound [S].CCCCCCCCP(CCCCCCCC)CCCCCCCC RHKQUGZIMGIIEA-UHFFFAOYSA-N 0.000 description 1
- JCURBQMROXDOLQ-KVVVOXFISA-N [S].CCCCCCCC\C=C/CCCCCCCCN Chemical compound [S].CCCCCCCC\C=C/CCCCCCCCN JCURBQMROXDOLQ-KVVVOXFISA-N 0.000 description 1
- QJYFNSGKKSUHQO-UHFFFAOYSA-N [Se].C(CCCCCCCC=C/CCCCCCCC)(=O)O Chemical compound [Se].C(CCCCCCCC=C/CCCCCCCC)(=O)O QJYFNSGKKSUHQO-UHFFFAOYSA-N 0.000 description 1
- GSXCWXWQRIEENF-KVVVOXFISA-N [Se].CCCCCCCC\C=C/CCCCCCCCN Chemical compound [Se].CCCCCCCC\C=C/CCCCCCCCN GSXCWXWQRIEENF-KVVVOXFISA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 1
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 1
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 description 1
- NRGIRRZWCDKDMV-UHFFFAOYSA-H cadmium(2+);diphosphate Chemical compound [Cd+2].[Cd+2].[Cd+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O NRGIRRZWCDKDMV-UHFFFAOYSA-H 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001577 copolymer Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical class C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- GOBNDSNLXZYUHQ-UHFFFAOYSA-N selenium;tributylphosphane Chemical compound [Se].CCCCP(CCCC)CCCC GOBNDSNLXZYUHQ-UHFFFAOYSA-N 0.000 description 1
- SCTHSTKLCPJKPF-UHFFFAOYSA-N selenium;triphenylphosphane Chemical compound [Se].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SCTHSTKLCPJKPF-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1832—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising ternary compounds, e.g. Hg Cd Te
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses a kind of quantum dot photovoltaic device and preparation method, quantum dot photovoltaic device include successively：Conductive substrates, electron transfer layer, quantum dot active layer, hole transmission layer, top electrode；The material of the quantum dot active layer is quanta point material, the quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, and the quantum-dot structure unit is the graded alloy component structure of level width variation or the in the radial direction consistent homogeneous components structure of level width in the radial direction.By the present invention in that using quanta point material and using quanta point material as quantum dot active layer, the photoelectric properties and stability of quantum dot photovoltaic device are improved, and simplify device architecture, saves cost of manufacture.
Description
Technical field
The present invention relates to field of photovoltaic devices more particularly to a kind of quantum dot photovoltaic device and preparation methods.
Background technology
As New Generation Optical electric material, quantum dot（Quantum dot）Extensive concern is obtained due to unique property.
Semiconductor crystal of the quantum dot as nano-scale, is wrapped up by surfactant, therefore can be disperseed in a solvent.Quantum dot can
To be prepared with solwution method, in addition to this for the application in terms of photovoltaic device, also there are photoelectric properties can pass through ruler
Very little and shape is come the advantages that adjusting.Application of the quantum dot in photovoltaic is exactly usually defined as light absorbing material
QDPV（Quantum dot photovoltaic device）.Directly using quantum dot as light absorbing layer, photoproduction current-carrying is being detached by building p-n structure
Son, to generate photoelectric current.
For QDPV, the nucleocapsid of quantum dot has vital influence for energy conversion efficiency.Pass through structure
Suitable nucleocapsid and level structure appropriate are built, on the one hand can be increased the service life of carrier, photoelectric current is improved；It is another
Aspect reduces the compound of carrier, improves short-circuit voltage.In addition, the optimization of quantum dot surface ligand, can not only reduce
The number of surface defect, and by improving dispersibility in the solution, can improve in device the pattern of quantum dot film and
Consistency, to effectively improve the properties of photovoltaic device.
Although the quantum dot part of nucleocapsid improves quantum dot performance, no matter from mentality of designing or from optimization side
In case or from the aspect of the efficiency based on promotion quantum dot itself, performance need to be improved, and does not in addition also consider
Other aspect particular/special requirements of QDPV devices for quanta point material.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of quantum dot photovoltaic device and preparation sides
Method, it is intended to solve the problems, such as that its photoelectric properties of existing QDPV are to be improved.
Technical scheme is as follows：
A kind of quantum dot photovoltaic device, wherein include successively：Conductive substrates, electron transfer layer, quantum dot active layer, hole pass
Defeated layer, top electrode；The material of the quantum dot active layer is quanta point material, and the quanta point material includes at least one in diameter
The quantum-dot structure unit arranged successively on direction, the quantum-dot structure unit are level width variation in the radial direction
The consistent homogeneous components structure of graded alloy component structure or in the radial direction level width.
The quantum dot photovoltaic device, wherein one layer is provided between the electron transfer layer and quantum dot active layer
Hole blocking layer.
The quantum dot photovoltaic device, wherein the quantum-dot structure unit is more outside energy level in the radial direction
The wider graded alloy component structure of width, and the energy level of quantum-dot structure unit adjacent in radial directions is continuous.
The quantum dot photovoltaic device, wherein the quanta point material includes at least three in radial directions successively
The quantum-dot structure unit of arrangement, wherein in at least three quantum-dot structures unit, be located at the quantum dot at center and surface
Structural unit is the graded alloy component structure that more outside level width is wider in the radial direction, and adjacent in radial directions
The energy level of quantum-dot structure unit of graded alloy component structure be continuous；Quantum-dot structure list positioned at center and surface
A quantum-dot structure unit between member is homogeneous components structure.
The quantum dot photovoltaic device, wherein the quanta point material includes two kinds of quantum-dot structure unit,
The quantum-dot structure unit of one of which type is the wider graded alloy component structure of more outside level width in the radial direction,
Another type of quantum-dot structure unit is the narrower graded alloy component structure of more outside level width in the radial direction, institute
It states two kinds of quantum-dot structure unit to be radially alternately distributed successively, and quantum dot knot adjacent in radial directions
The energy level of structure unit is continuous.
The quantum dot photovoltaic device, wherein the quantum-dot structure unit is more outside energy level in the radial direction
The wider graded alloy component structure of width, and the energy level of adjacent quantum-dot structure unit is discontinuous.
The quantum dot photovoltaic device, wherein the quantum-dot structure unit is more outside energy level in the radial direction
The narrower graded alloy component structure of width, and the energy level of adjacent quantum-dot structure unit is discontinuous.
The quantum dot photovoltaic device, wherein the quanta point material includes two amounts sub- point structural unit, wherein one
Kind quantum-dot structure unit is the wider graded alloy component structure of more outside level width in the radial direction, another quantum dot
Structural unit is homogeneous components structure, and the inside of the quanta point material includes one or more graded alloy component knot
The quantum-dot structure unit of structure, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions
It is continuous；The outside of the quanta point material includes the quantum-dot structure list of one or more homogeneous components structure
Member.
The quantum dot photovoltaic device, wherein the quanta point material includes two amounts sub- point structural unit, wherein one
Kind quantum-dot structure unit is homogeneous components structure, and another quantum-dot structure unit is more outside level width in the radial direction
The inside of wider graded alloy component structure, the quanta point material includes one or more homogeneous components structure
Quantum-dot structure unit, the outside of the quanta point material include the quantum of one or more graded alloy component structure
Point structural unit, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions is continuous
's.
The quantum dot photovoltaic device, wherein the quantum-dot structure unit be comprising II races and VI races element gradually
Become alloy compositions structure or uniform alloy compositions structure.
The quantum dot photovoltaic device, wherein the quantum-dot structure unit includes 2-20 layers of monoatomic layer, Huo Zhesuo
It includes 1-10 layer crystals born of the same parents' layer to state quantum dot light emitting unit.
The quantum dot photovoltaic device, wherein the glow peak wave-length coverage of the quanta point material be 400 nanometers extremely
700 nanometers.
The quantum dot photovoltaic device, wherein the peak width at half height of the glow peak of the quanta point material be 12 nanometers extremely
80 nanometers.
A kind of preparation method of quantum dot photovoltaic device as described above, wherein including step：
A, one layer of electron transfer layer is deposited on conductive substrates；
B, one layer of quantum dot active layer is deposited on the electron transport layer；The material of the quantum dot active layer is quanta point material,
The quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure
Unit is the graded alloy component structure of level width variation or in the radial direction consistent uniform of level width in the radial direction
Component structure；
C, one layer of hole transmission layer is deposited on quantum dot active layer；
D, one layer of top electrode is deposited on the hole transport layer, obtains quantum dot photovoltaic device.
The preparation method of the quantum dot photovoltaic device, wherein further include after the step A, before B：
One layer of hole blocking layer is deposited on the electron transport layer.
Advantageous effect：By the present invention in that using quanta point material and using quanta point material as quantum dot active layer, carry
The photoelectric properties and stability of high quantum dot photovoltaic device, and device architecture is simplified, save cost of manufacture.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of quantum dot photovoltaic device preferred embodiment of the present invention.
Fig. 2 is the level structure curve of quanta point material concrete structure 1 in quantum dot photovoltaic device of the present invention.
Fig. 3 is the level structure curve of quanta point material concrete structure 2 in quantum dot photovoltaic device of the present invention.
Fig. 4 is the level structure curve of quanta point material concrete structure 3 in quantum dot photovoltaic device of the present invention.
Fig. 5 is the level structure curve of quanta point material concrete structure 4 in quantum dot photovoltaic device of the present invention.
Fig. 6 is the level structure curve of quanta point material concrete structure 5 in quantum dot photovoltaic device of the present invention.
Fig. 7 is the level structure curve of quanta point material concrete structure 6 in quantum dot photovoltaic device of the present invention.
Fig. 8 is the level structure curve of quanta point material concrete structure 7 in quantum dot photovoltaic device of the present invention.
Fig. 9 is a kind of structural schematic diagram of quantum dot photovoltaic device embodiment 33 of the invention.
Specific implementation mode
A kind of quantum dot photovoltaic device of present invention offer and preparation method, to make the purpose of the present invention, technical solution and effect
Fruit is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only
Only to explain the present invention, it is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of structural schematic diagram of quantum dot photovoltaic device preferred embodiment of the present invention, as schemed institute
Show, includes successively：Conductive substrates 11, electron transfer layer 12, quantum dot active layer 13, hole transmission layer 14, top electrode 15；It is described
The material of quantum dot active layer 13 is quanta point material comprising at least one quantum dot knot arranged successively in radial directions
Structure unit, the quantum-dot structure unit are the graded alloy component structure or radial direction of level width variation in the radial direction
The consistent homogeneous components structure of upper level width.
The present invention utilizes the quantum dot of structure optimization, optimizes the level structure of quantum dot, not only increases carrier
Service life, and the compound of carrier is reduced, to improve the light conversion efficiency of QDPV, improve the photoelectric properties of QDPV.
One layer of hole blocking layer is provided between the electron transfer layer 12 and quantum dot active layer 13.The hole
The thickness on barrier layer is preferably 1 ~ 100 nm.The hole blocking layer can be selected from the organic material with cavity transmission ability,
Including but not limited to poly- (9,9- dioctyl fluorenes-CO-N- (4- butyl phenyls) diphenylamines)（TFB）, polyvinylcarbazole（PVK）, it is poly-
(bis- bis- (phenyl) benzidine of (4- butyl phenyls)-N, N'- of N, N')（poly-TPD）, it is poly- (double-N of 9,9- dioctyl fluorenes -co-s,
N- phenyl -1,4- phenylenediamines)（PFB）, 4,4 ', 4 ' '-three (carbazole -9- bases) triphenylamine（TCTA）, 4,4'- bis- (9- carbazoles) connection
Benzene（CBP）, N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,1 '-biphenyl -4,4 '-diamines（TPD）, N, N '-diphenyl-
N,N’-（1- naphthalenes）- 1,1 '-biphenyl -4,4 '-diamines（NPB）, doped graphene, undoped graphene, C60Or theirs is mixed
Close object；The material of the hole blocking layer is preferably PMMA materials.
The conductive substrates 11 refer to the substrate containing hearth electrode, and hearth electrode therein can be selected from indium doping tin oxide
（ITO）, fluorine-doped tin oxide（FTO）, antimony-doped tin oxide（ATO）, aluminium-doped zinc oxide（AZO）In it is one or more；It is excellent
Selection of land, the conductive substrates are ITO.
12 material of electron transfer layer is ZnO, TiO2、WO3、SnO2, the inorganic material such as AlZnO, ZnSnO, InSnO
And Alq3, TPBI (1,3,5- tri- (N- phenylbenzimidazol -2- bases) benzene) or TAZ (3- (4- xenyls) -4- phenyl -5- tert-s
Butyl phenyl -1,2,4- triazoles) etc. at least one of organic materials, preferably ZnO, the thickness of the electron transfer layer 12
Preferably 5 ~ 100 nm.
The thickness of the quantum dot active layer 13 is 10 ~ 400 nm；Preferably, the thickness of the quantum dot active layer 13
Degree is 50 ~ 200 nm.
The hole transmission layer 14 can be selected from the organic material with cavity transmission ability or inorganic material, wherein described
Including but not limited to poly- (9,9- dioctyl fluorenes-CO-N- (4- butyl phenyls) hexichol of the organic material with cavity transmission ability
Amine)（TFB）, polyvinylcarbazole（PVK）, poly- (bis- bis- (phenyl) benzidine of (4- butyl phenyls)-N, N'- of N, N')（poly-
TPD）, poly- (double-N of 9,9- dioctyl fluorenes -co-s, N- phenyl -1,4- phenylenediamines)（PFB）, 4,4 ', 4 ' '-three (carbazole -9- bases) three
Aniline（TCTA）, 4,4'- bis- (9- carbazoles) biphenyl（CBP）, N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,1 '-join
Benzene -4,4 '-diamines（TPD）, N, N '-diphenyl-N, N '-（1- naphthalenes）- 1,1 '-biphenyl -4,4 '-diamines（NPB）In one kind
Or it is a variety of；The inorganic material with cavity transmission ability includes but not limited to doped or non-doped WO3、NiO、MoO3、
V2O5In it is one or more；Preferably, the hole transmission layer is MoO3.The thickness of the hole transmission layer be 5 ~
100nm；Preferably, the thickness of the hole transmission layer is 10 ~ 50 nm.
The top electrode 15 be preferably metal electrode, the metal electrode can be selected from Al, Ag, Cu, Mo, Au or they
Alloy；Preferably, the metal electrode is Au.The thickness of the metal electrode is 50 ~ 500 nm；Preferably, described
The thickness of metal electrode is 100 ~ 200 nm.
Preferably, the quantum dot photovoltaic device is partial encapsulation, full encapsulation or does not encapsulate.
A kind of preparation method of quantum dot photovoltaic device as described above of the present invention comprising step：
S1, one layer of electron transfer layer is deposited on conductive substrates；
S2, one layer of quantum dot active layer is deposited on the electron transport layer；The material of the quantum dot active layer is quanta point material,
The quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure
Unit is the graded alloy component structure of level width variation or in the radial direction consistent uniform of level width in the radial direction
Component structure；
S3, one layer of hole transmission layer is deposited on quantum dot active layer；
S4, one layer of top electrode is deposited on the hole transport layer, obtains quantum dot photovoltaic device.
Further, further include after the step S1, before S2：
One layer of hole blocking layer is deposited on the electron transport layer.
Each layer（It is one or more in electron transfer layer, hole blocking layer, quantum dot active layer, hole transmission layer）It is heavy
Chemical method or Physical may be used in product method, and wherein chemical method includes but not limited to chemical vapour deposition technique, continuous ionic layer
Absorption with it is one or more in reaction method, anodizing, strike, coprecipitation；Physical includes but not limited to
Spin-coating method, print process, knife coating, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip
Rubbing method, thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vapour deposition (PVD)
It is one or more in method, atomic layer deposition method, pulsed laser deposition；Preferably, the deposition method is spin-coating method, print
Brush method, thermal evaporation coating method.
The structure of quanta point material of the present invention is described in detail below：
Quanta point material provided by the present invention, including at least one quantum-dot structure list arranged successively in radial directions
Member, the quantum-dot structure unit are the graded alloy component structure or in the radial direction can that level width changes in the radial direction
The consistent homogeneous components structure of level width.
That is in quanta point material provided by the invention, inside each quantum-dot structure unit from the inside to the outside radially
It is the knot with alloy compositions within the scope of the monoatomic layer of one layer of monoatomic layer on direction in any position or one layer or more
Structure.
Further, in the present invention, the quantum-dot structure unit includes II races and VI races element.The II races element packet
Include but be not limited to Zn, Cd, Hg, Cn etc.；VI races element includes but not limited to O, S, Se, Te, Po, Lv etc..Specifically, each
The alloy compositions group of quantum-dot structure unit becomes CdxZn1-xSeyS1-y, wherein 0≤x≤1,0≤y≤1, and when x with y differences
It is 0 and be asynchronously 1.It should be noted that the above situation is preferable case, for the quantum-dot structure of graded alloy component structure
For unit, component is alloy compositions；And for the quantum-dot structure unit of homogeneous components structure, component can be with
It is alloy compositions, can also be non-alloyed component, but currently preferred is alloy compositions, i.e., the described homogeneous components structure is equal
One alloy compositions structure, it is further preferred that comprising II races and VI races element, subsequent embodiment of the present invention is with uniform alloy compositions
It is illustrated for structure, it will be clear that can equally implement for unalloyed homogeneous components structure.
Radial direction herein refers to the center outwardly direction from quanta point material, it is assumed for example that quantum dot of the invention
Material is spherical or similar spherical structure, then the radial direction refers to along the direction of radius, the center of quanta point material（Or it is interior
Portion）Refer to the center of its physical arrangement, the surface of quanta point material（Or it is external）Refer to the surface of its physical arrangement.
Specifically, as shown in Fig. 2, the present invention provides a kind of quanta point material with funnel type level structure, it is located at
Quantum-dot structure unit composition of alloy ingredient inside the quanta point material corresponds to level width and is less than positioned at external quantum
Point structural unit composition of alloy ingredient corresponds to level width；Specifically, quanta point material provided by the invention includes at least one
A quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure unit are in the radial direction more to external enwergy
The wider graded alloy component structure of level width, and the quantum-dot structure of graded alloy component structure adjacent in radial directions
The energy level of unit is continuous；The structure of quanta point material shown in Fig. 2 is known as concrete structure 1 in subsequent embodiment.In Fig. 2
The level width of quanta point material, each adjacent quantum-dot structure unit has continuous structure, i.e., each adjacent quantum dot
The level width of structural unit has the characteristics that consecutive variations rather than mutation structure, that is to say, that the alloy compositions of quantum dot
It is with continuity, subsequent continuous structure principle is identical.
Further, in radial directions in adjacent quantum-dot structure unit, by paracentral quantum-dot structure unit
Level width is less than the level width of deep quantum-dot structure unit；That is, in the quanta point material, from
The level width of center to face gradually broadens, to form the funnel type structure that opening becomes larger, opening therein
It refers in level structure as shown in Figure 2 to become larger, and the energy level from quanta point material center to quanta point material surface is to connect
Continuous.Meanwhile the quanta point material in the present invention, the energy level of each adjacent quantum-dot structure unit are continuous, that is,
Say that the synthesis component of quantum dot also has the characteristic of consecutive variations, this characteristic, which is more advantageous to, realizes high luminous efficiency.
That is, the concrete structure 1 of the quanta point material be with from inside to outside radially it is continuous gradually
Become the quantum-dot structure of alloy compositions；This quantum-dot structure has radially continuous from inside to outside become in constituent
The characteristics of change；Correspondingly, also upper in energy level distribution have the characteristics that from inside to outside radially consecutive variations；This quantum
Point structure with energy level in constituent the characteristics of being distributed upper consecutive variations, relative to quantum dot core and shell with clear boundary
Relationship, quanta point material of the invention not only contributes to realize more efficient luminous efficiency, while also can more meet semiconductor
The comprehensive performance requirement of device and corresponding display technology to quanta point material is a kind of suitable semiconductor devices and display technology
Ideal quantum dot luminescent material.
Further, in the quanta point material provided such as Fig. 2, the alloy compositions of A points are Cdx0 AZn1-x0 ASey0 AS1-y0 A, B
The alloy compositions of point are Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points relative to B points closer to quanta point material center, and A points and
The composition of B points meets：x0 A>x0 B,y0 A >y0 B.That is, for any two points A points and B points in quanta point material, and A points
Relative to B points closer to quanta point material center, thenx0 A>x0 B,y0 A >y0 B, i.e. the Cd contents of A points are more than the Cd contents of B points, A
The Zn contents of point are less than the Zn contents of B points, and the Se contents of A points are more than the Se contents of B points, and the S contents of A points contain less than the S of B points
Amount.In this way, in the quanta point material, grading structure is just formd in radial directions, and due in radial directions, more
Outward（I.e. far from quanta point material center）Then Cd and Se contents are lower, Zn and S contents are higher, then according to these types of element
Characteristic, level width will be wider.
In the quanta point material of follow-up difference concrete structure, if quantum-dot structure unit is more outside energy level in the radial direction
The wider graded alloy component structure of width, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0, wherein the alloy of A points
Group is divided into Cdx0 AZn1-x0 ASey0 AS1-y0 A, the alloy compositions of B points are Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points relative to B points more
Close to quanta point material center, and the composition of A points and B points meets：x0 A>x0 B,y0 A >y0 B.If quantum-dot structure unit is radial direction side
The upward narrower graded alloy component structure of more outside level width, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0,
Wherein, the alloy compositions of C points are Cdx0 CZn1-x0 CSey0 CS1-y0 C, the alloy compositions of D points are Cdx0 DZn1-x0 DSey0 DS1-y0 D, wherein C
It puts relative to D points closer to quanta point material center, and the composition of C points and D points meets：x0 C＜x0 D,y0 C＜y0 D.If quantum dot knot
Structure unit is uniform alloy compositions structure（I.e. level width is consistent in the radial direction）, then its alloy compositions be both preferably
Cdx0Zn1-x0Sey0S1-y0, wherein the alloy compositions of E points are Cdx0 EZn1-x0 ESey0 ES1-y0 E, the alloy compositions of F points are
Cdx0 FZn1-x0 FSey0 FS1-y0 F, wherein E points are relative to F points closer to quanta point material center, and the composition of E points and F points is full
Foot：x0 E=x0 F,y0 E=y0 F。
Further, as shown in figure 3, having inner alloy constituent the present invention also provides one kind, to correspond to level width little
It is corresponded between level width and quantum-dot structure bosom and most external region containing at least one layer in exterior alloy constituent
The quanta point material of the quantum-dot structure unit of uniform alloy compositions structure；That is, quanta point material provided by the invention
The quantum-dot structure unit arranged successively in radial directions including at least three, wherein at least three quantum-dot structure
In unit, the quantum-dot structure unit positioned at center and surface is that the gradual change that more outside level width is wider in the radial direction is closed
Golden component structure, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions is continuous
, a quantum-dot structure unit between center and the quantum-dot structure unit on surface is uniform alloy compositions structure.
The structure of quanta point material shown in Fig. 3 is known as concrete structure 2 in subsequent embodiment.
Specifically, as Fig. 3 provide quanta point material in, it is described between center and the quantum-dot structure unit on surface
One layer of uniform alloy compositions structure quantum-dot structure unit on, the alloy compositions of any point are Cdx1Zn1-x1Sey1S1-y1,
In 0≤x1≤1,0≤y1≤1, and be 0 when x1 with y1 differences and be asynchronously 1, and x1 and y1 is fixed value.Such as it is a certain
The alloy compositions of point are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point also should be in the radial direction
Cd0.5Zn0.5Se0.5S0.5；In another example in the quantum-dot structure unit of a certain uniform alloy compositions structure certain point homogeneous components
For Cd0.7Zn0.3S, and the alloy compositions of another point also should be Cd in the quantum-dot structure unit0.7Zn0.3S；In another example a certain equal
The homogeneous components of certain point are CdSe in the quantum-dot structure unit of one alloy compositions structure, and another in the quantum-dot structure unit
The alloy compositions of any also should be CdSe.
Further, as in the quanta point material of Fig. 3 offers, the quantum-dot structure unit positioned at center and surface is radial direction
The wider graded alloy component structure of more outside level width on direction, and graded alloy component knot adjacent in radial directions
The energy level of the quantum-dot structure unit of structure is continuous；I.e. in the quantum-dot structure unit with graded alloy component structure
In, radially the corresponding level width of composition of alloy ingredient of upper any point is greater than adjacent and closer to quantum dot
The corresponding level width of composition of alloy ingredient of structure centre another point.The quantum dot knot with graded alloy component structure
Alloy compositions group in structure unit becomes Cdx2Zn1-x2Sey2S1-y2, wherein 0≤x2≤1,0≤y2≤1, and x2 and y2 differences
When be 0 and be asynchronously 1.Such as the alloy compositions of certain point are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point are
Cd0.3Zn0.7Se0.4S0.6。
Further, as shown in figure 4, the present invention also provides a kind of quantum of the full graded alloy component with quantum well structure
Point material；That is, quanta point material provided by the invention includes two kinds of quantum-dot structure unit（A1 types and A2
Type）, the wherein quantum-dot structure unit of A1 types is the wider graded alloy component of more outside level width in the radial direction
The quantum-dot structure unit of structure, A2 types is the narrower graded alloy component structure of more outside level width in the radial direction,
Described two quantum-dot structure units are radially alternately distributed successively, and quantum-dot structure list adjacent in radial directions
The energy level of member is continuous.That is, the quantum-dot structure cell distribution of the quanta point material can be：A1、A2、A1、
A2, A1 ... can also be A2, A1, A2, A1, A2 ..., that is, the quantum-dot structure unit originated can be A1 types, can also be
A2 types.In the quantum-dot structure unit of A1 types, level width is more more outside wider, in the quantum-dot structure of A2 types
In unit, level width is more more outside narrower, both level structures are like the form of wave is prolonged in radial directions
It stretches, the structure of quanta point material shown in Fig. 4 is known as concrete structure 3 in subsequent embodiment.
Further, as shown in figure 5, the present invention also provides a kind of alloy compositions of the quantum well structure with energy level mutation
Quanta point material, specifically, the quantum-dot structure unit are that the gradual change that more outside level width is wider in the radial direction is closed
Golden component structure, and the energy level of adjacent quantum-dot structure unit is discontinuous, i.e., each adjacent quantum-dot structure unit
Level width have the characteristics that discontinuous variation, that is, be mutated feature, that is to say, that the alloy compositions of quantum dot be also have it is prominent
Denaturation, subsequent mutation structure principle are identical；The structure of quanta point material shown in Fig. 5 is known as concrete structure in subsequent embodiment
4。
Specifically, quanta point material shown in fig. 5 is arranged successively by way of mutation by multiple quantum-dot structure units
Cloth is constituted, these quantum-dot structure units are the graded alloy component structure that more outside level width is wider in the radial direction.
Further, in the quanta point material, the level width by paracentral quantum-dot structure unit is less than deep quantum
The level width of point structural unit.It is gradual from the level width of center to face that is, in the quanta point material
It broadens, to form the intermittent funnel type structure for being open and becoming larger, certainly, in the quanta point material, also not
It is limited to aforesaid way, i.e., the level width of deep quantum-dot structure unit might be less that by paracentral quantum dot knot
The level width of structure unit, in this structure, the level width of adjacent quantum-dot structure unit has the place being overlapping.
Further, as shown in fig. 6, the present invention also provides the alloy compositions of another quantum well structure that there is energy level to be mutated
Quanta point material, specifically, the quantum-dot structure unit is the gradual change that more outside level width is narrower in the radial direction
Alloy compositions structure, and the energy level of adjacent quantum-dot structure unit is discontinuous, i.e., each adjacent quantum-dot structure list
The level width of member has the characteristics that discontinuous variation, that is, is mutated feature, that is to say, that the alloy compositions of quantum dot are also to have
Mutability, subsequent mutation structure principle are identical；The structure of quanta point material shown in Fig. 6 is known as specific knot in subsequent embodiment
Structure 5.
Specifically, quanta point material shown in fig. 6 is arranged successively by way of mutation by multiple quantum-dot structure units
Cloth is constituted, these quantum-dot structure units are the graded alloy component structure that more outside level width is narrower in the radial direction.
Further, in the quanta point material, the level width by paracentral quantum-dot structure unit is more than deep quantum
The level width of point structural unit.It is gradual from the level width of center to face that is, in the quanta point material
Narrow, to form the intermittent gradually smaller funnel type structure of opening, certainly, in the quanta point material, also not
It is limited to aforesaid way, i.e., the level width of deep quantum-dot structure unit, which can also be more than, leans on paracentral quantum dot knot
The level width of structure unit, in this structure, the level width of adjacent quantum-dot structure unit has the place being overlapping.
Further, as shown in fig. 7, the present invention also provides a kind of quanta point material, it is located inside the quanta point material
The level width of composition of alloy ingredient is become larger by center to outside, and quantum-dot structure most external region is uniform alloy group
Point；Specifically, the quanta point material includes two amounts sub- point structural unit（A3 types and A4 types）, wherein A3 types
Quantum-dot structure unit is the wider graded alloy component structure of more outside level width in the radial direction, the quantum dot of A4 types
Structural unit is uniform alloy compositions structure, and the inside of the quanta point material includes that one or more gradual change is closed
The quantum-dot structure unit of golden component structure, and the quantum-dot structure list of graded alloy component structure adjacent in radial directions
The energy level of member is continuous；The outside of the quanta point material includes the amount of one or more uniform alloy compositions structure
Son point structural unit；The structure of quanta point material shown in Fig. 7 is known as concrete structure 6 in subsequent embodiment.
Specifically, in quanta point material as shown in Figure 7, quantum-dot structure unit is distributed as A3 ... A3A4 ... A4,
The inside of the i.e. described quanta point material is made of the quantum-dot structure unit of A3 types, the outside of the quanta point material be by
The quantum-dot structure unit of A4 types forms, and the quantum-dot structure of the quantity and A4 types of the quantum-dot structure unit of A3 types
The quantity of unit is all higher than equal to 1.
Further, as shown in figure 8, the present invention also provides another quanta point material, it is located inside the quanta point material
Composition of alloy ingredient level width be it is uniform, be located at the quantum dot outside composition of alloy ingredient level width by
Center becomes larger to outside；Specifically, the quanta point material includes two amounts sub- point structural unit（A5 types and A6 classes
Type）, wherein the quantum-dot structure unit of A5 types is uniform alloy compositions structure, and the quantum-dot structure unit of A6 types is diameter
The inside of the wider graded alloy component structure of more outside level width on direction, the quanta point material includes one or one
The quantum-dot structure unit of a above uniform alloy compositions structure；The outside of the quanta point material include one or one with
On graded alloy component structure quantum-dot structure unit, and the amount of graded alloy component structure adjacent in radial directions
The energy level of son point structural unit is continuous；The structure of quanta point material shown in Fig. 8 is known as concrete structure in subsequent embodiment
7。
Specifically, in quanta point material as shown in Figure 8, monoatomic layer is distributed as A5 ... A5A6 ... A6 are that is, described
The inside of quanta point material is made of the quantum-dot structure unit of A5 types, and the outside of the quanta point material is by A6 types
Quantum-dot structure unit composition, and the quantum-dot structure unit of the quantity and A6 types of the quantum-dot structure unit of A5 types
Quantity is all higher than equal to 1.
Further, quantum-dot structure unit provided by the present invention includes 2-20 layers of monoatomic layer.Preferably, the amount
Son point structural unit includes 2-5 monoatomic layer, and the preferred number of plies can ensure that quantum dot realizes good photoluminescence quantum yield
And efficient charge injection efficiency.
Further, the quantum dot light emitting unit includes 1-10 layer crystals born of the same parents' layer, preferably 2-5 layer crystals born of the same parents layer；The structure cell layer
For minimum structural unit, i.e., its alloy compositions of each layer of structure cell layer are fixed, i.e., have the phase isomorphous in each structure cell layer
Lattice parameter and element, each quantum-dot structure unit are the closed unit cell curved surface of the connection of structure cell layer and composition, adjacent cell layer
Between level width have continuous structure or mutation structure.
The quanta point material of the present invention using the above structure, the photoluminescence quantum yield that can be realized ranging from 1% to 100%,
Preferred photoluminescence quantum yield ranging from 30% to 100% is capable of the good of guaranteed discharge point within the scope of preferred photoluminescence quantum yield
Good application.
The quanta point material, wherein the glow peak wave-length coverage of the quanta point material is 400 nanometers to 700 and receives
Rice.
The quanta point material of the present invention using the above structure, the glow peak wave-length coverage that can be realized are 400 nanometers to 700
Nanometer, preferred glow peak wave-length coverage are 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can protect
Card quanta point material realizes the photoluminescence quantum yield more than 30% within this range.
Further, in the present invention, the peak width at half height of the glow peak of the quanta point material is 12 nanometers to 80 nanometers.
Quanta point material provided by the present invention has the advantages that：First, help to reduce to the full extent not
With the lattice tension between the quantum dot crystal of alloy compositions and alleviate lattice mismatch, to reduce the formation of boundary defect, carries
The high luminous efficiency of quantum dot.Second, quanta point material provided by the present invention is formed by level structure and is more advantageous to pair
Effective constraint of electron cloud in quantum dot greatly reduces diffusion probability of the electron cloud to quantum dot surface, to greatly inhibit
The auger recombination loss of quantum dot radiationless transition, reduces quantum dot and flickers and improve quantum dot light emitting efficiency.Third, this hair
Bright provided quanta point material is formed by level structure and is more advantageous to quantum dot light emitting layer charge in raising semiconductor devices
Injection efficiency and efficiency of transmission；It can effectively avoid the aggregation of charge and resulting Exciton quenching simultaneously.4th, this
The there is provided quanta point material of invention, which is formed by easily controllable diversity level structure, can fully meet simultaneously coordination device
In the level structures of other functional layers efficiently partly led with realizing the matching of device entirety level structure to help to realize
Body device.
The present invention also provides a kind of preparation methods of quanta point material as described above, wherein including step：
The first compound is synthesized in pre-position；
Second of compound, the first described compound and second of compound are synthesized on the surface of the first compound
Alloy compositions are identical or different；
Make that cation exchange reaction formation quanta point material, the amount occur between the first compound and second of chemical combination object
Son point glow peak wavelength occur blue shift, red shift and it is constant in it is one or more.
Quantum dot SILAR synthetic methods incorporating quantum point one-step synthesis is generated quantum dot, tool by the preparation method of the present invention
Body is successively to be grown using quantum dot and form graded component transitional crust using quantum dot one-step synthesis.I.e. in precalculated position
Place, which is successively formed two layers, has identical or different-alloy component compound thin film, and sun occurs between two layers of compound by making
Ion-exchange reactions, to realize that the alloy compositions in pre-position are distributed.Repeating above procedure can constantly realize in diameter
It is distributed to the alloy compositions of direction pre-position.
Described the first compound and second of compound can be binary or the above compound of binary.
Further, when blue shift occurs in the glow peak wavelength of the quantum dot, illustrate that glow peak is moved to shortwave direction, energy
Level width broadens；When red shift occurs in the glow peak wavelength of the quantum dot, represents glow peak and moved to long wave direction, energy level is wide
Degree narrows；When the glow peak wavelength of the quantum dot is constant, illustrate that level width is constant.
The cationic presoma of the first described compound and/or second of compound includes：The presoma of Zn, institute
The presoma for stating Zn is zinc methide（dimethyl Zinc）, diethyl zinc（diethyl Zinc）, zinc acetate（Zinc
acetate）, zinc acetylacetonate（Zinc acetylacetonate）, zinc iodide（Zinc iodide）, zinc bromide（Zinc
bromide）, zinc chloride（Zinc chloride）, zinc fluoride（Zinc fluoride）, zinc carbonate（Zinc carbonate）、
Zinc cyanide（Zinc cyanide）, zinc nitrate（Zinc nitrate）, zinc oxide（Zinc oxide）, zinc peroxide（Zinc
peroxide）, zinc perchlorate（Zinc perchlorate）, zinc sulfate（Zinc sulfate）, zinc oleate（Zinc oleate）
Or zinc stearate（Zinc stearate）At least one of Deng, but not limited to this.
The cationic presoma of the first described compound and/or second of compound includes the presoma of Cd, institute
The presoma for stating Cd is dimethyl cadmium（dimethyl cadmium）, diethyl cadmium（diethyl cadmium）, cadmium acetate
（cadmium acetate）, acetylacetone,2,4-pentanedione cadmium（cadmium acetylacetonate）, cadmium iodide（cadmium iodide）、
Cadmium bromide（cadmium bromide）, caddy（cadmium chloride）, cadmium fluoride（cadmium fluoride）, carbon
Sour cadmium（cadmium carbonate）, cadmium nitrate（cadmium nitrate）, cadmium oxide（cadmium oxide）, perchloric acid
Cadmium（cadmium perchlorate）, cadmium phosphate（cadmium phosphide）, cadmium sulfate（cadmium sulfate）, oil
Sour cadmium（cadmium oleate）Or cadmium stearate（cadmium stearate）At least one of Deng, but not limited to this.
The anion presoma of the first described compound and/or second of compound includes the presoma of Se, example
It is formed by compound as Se is arbitrarily combined with some organic matters, specifically Se-TOP (selenium-
trioctylphosphine)、Se-TBP (selenium-tributylphosphine)、Se-TPP (selenium-
triphenylphosphine)、Se-ODE (selenium-1-octadecene)、Se-OA (selenium-oleic
acid)、Se-ODA (selenium-octadecylamine)、Se-TOA (selenium-trioctylamine)、Se-
In ODPA (selenium-octadecylphosphonic acid) or Se-OLA (selenium-oleylamine) etc.
At least one, but not limited to this.
The anion presoma of the first described compound and/or second of compound includes the presoma of S, such as
S is arbitrarily combined with some organic matters and is formed by compound, specifically S-TOP (sulfur-trioctylphosphine), S-
TBP(sulfur-tributylphosphine) 、S-TPP(sulfur-triphenylphosphine)、S-ODE
(sulfur-1-octadecene) 、S-OA (sulfur-oleic acid)、S-ODA(sulfur-octadecylamine)、
S-TOA (sulfur-trioctylamine), S-ODPA (sulfur-octadecylphosphonic acid) or S-OLA
At least one of (sulfur-oleylamine) etc., but not limited to this；The presoma of the S is alkyl hydrosulfide (alkyl
Thiol), the alkyl hydrosulfide is hexyl mercaptan (hexanethiol), spicy thioalcohol (octanethiol), decyl mercaptan
(decanethiol), lauryl mercaptan (dodecanethiol), hexadecyl mercaptan (hexadecanethiol) or mercaptos
At least one of propyl silane (mercaptopropylsilane) etc., but not limited to this.
The anion presoma of the first described compound and/or second of compound further includes the presoma of Te,
The presoma of the Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-
At least one of OLA.
In the preparation process in accordance with the present invention, the condition that cation exchange reaction occurs is to carry out heating reaction, such as heat
Temperature is between 100 DEG C to 400 DEG C, between preferred heating temperature is 150 DEG C to 380 DEG C.Heating time 2s to for 24 hours it
Between, preferred heating time is 5min between 4h.
Above-mentioned cation precursor and anion presoma can be formed according to final quanta point material to determine selection
It is one such or several：Such as it needs to synthesize CdxZn1-xSeyS1-yQuanta point material when, then need the presoma of Cd, Zn
The presoma of presoma, the presoma of Se, S；It such as needs to synthesize CdxZn1-xWhen the quanta point material of S, then the forerunner of Cd is needed
The presoma of body, the presoma of Zn, S；It such as needs to synthesize CdxZn1-xWhen the quanta point material of Se, then presoma, the Zn of Cd are needed
Presoma, Se presoma.
Heating temperature is higher, and the rate of cation exchange reaction is faster, the thickness range and exchange degree that cation exchanges
Also bigger, but thickness and extent and scope can progressively reach the degree of relative saturation；Similar, heating time is longer, and cation is handed over
The thickness range and exchange degree changed is also bigger, but thickness and extent and scope can also progressively reach the degree of relative saturation.Sun from
The thickness range and degree that son exchanges, which directly determine, is formed by the distribution of graded alloy component.Cation is exchanged and is formed by gradually
Become alloy compositions distribution also to be determined by the thickness for being respectively formed by binary or multi-element compounds nanocrystal simultaneously.
When forming each layer compound, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:50（Tool
Body is the molar feed ratio of cation and anion）, such as when forming first layer compound, cationic presoma and anion
The molar ratio of presoma is 100:1 to 1:50；When forming second layer compound, cationic presoma and anion presoma
Molar ratio is 100:1 to 1:50, preferred ratio is 20:1 to 1:10, preferred cation presoma and anion presoma
Molar ratio can ensure reaction rate in easily controllable range.
By the quanta point material prepared by above-mentioned preparation method, glow peak wave-length coverage is 400 nanometers to 700 and receives
Rice, preferred glow peak wave-length coverage are 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can ensure
Quantum dot realizes the photoluminescence quantum yield more than 30% within this range.
Quanta point material prepared by method made above, photoluminescence quantum yield ranging from 1% to 100% are preferred to shine
Quantum yield ranging from 30% to 100% is capable of the applications well of guaranteed discharge point within the scope of preferred photoluminescence quantum yield.
Further, in the present invention, the peak width at half height of the glow peak of the quanta point material is 12 nanometers to 80 nanometers.
Other than preparing the quanta point material of the present invention according to above-mentioned preparation method, the present invention also provides another such as
The preparation method of the upper quanta point material comprising step：
One or more kinds of cationic presomas are added in pre-position in radial directions；It is added simultaneously under certain condition
One or more kinds of anion presomas, makes cationic presoma react forming quantum dot material with anion presoma
Material, and the glow peak wavelength of the quanta point material occur during the reaction blue shift, red shift and it is constant in one kind or several
Kind, to realize that the alloy compositions in pre-position are distributed.
The difference of such method and former approach is, former is successively to form two layers of compound, is then sent out
Raw cation exchange reaction, to realize that alloy compositions needed for the present invention are distributed, and later approach is directly controlled predetermined
The cationic presoma and anion presoma of synthesis alloy compositions needed for being added at position, carry out reaction and form quantum dot material
Material, to realize that alloy compositions needed for the present invention are distributed.For later approach, reaction principle is the high cation of reactivity
Presoma and anion presoma first react, and occur after the low cationic presoma of reactivity and anion presoma anti-
It answers, and during the reaction, cation exchange reaction occurs for different cations, to realize alloy compositions needed for the present invention
Distribution.It has been described in detail in preceding method as the type of cationic presoma and anion presoma.As for reaction temperature, instead
Between seasonable and proportioning etc. can be different and different according to the quanta point material of synthesis needed for specific, with former side above-mentioned
Method is substantially the same, and is subsequently illustrated with specific embodiment.
Embodiment 1：Preparation based on CdZnSeS/CdZnSeS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn, the presoma of anion Se and anion S are noted
Enter into reaction system, forms CdyZn1-ySebS1-bLayer（Wherein 0≤y≤1,0≤b≤1）；Continue the forerunner of cationic Cd
Body, the presoma of cation Zn, the presoma of anion Se and the presoma of anion S are injected into reaction system, above-mentioned
CdyZn1-ySebS1-bLayer surface forms CdzZn1-zSecS1-cLayer（Wherein 0≤z≤1, and z is not equal to y, 0≤c≤1）；Certain
Heating temperature and the reaction conditions such as heating time under, ectonexine nanocrystal occurs（I.e. above-mentioned two layers of compound）Middle Cd and Zn
The exchange of ion；The probability migrated due to the limited and remoter migration distance of migration distance of cation with regard to smaller,
It can be in CdyZn1-ySebS1-bLayer and CdzZn1-zSecS1-cThe interface of layer is formed about the graded alloy component of Cd contents and Zn contents
Distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1,0≤a≤1.
Embodiment 2：Preparation based on CdZnS/CdZnS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion S is injected into reaction system,
It is initially formed CdyZn1-yS layers（Wherein 0≤y≤1）；Continue by the presoma of cationic Cd, cation Zn presoma and it is cloudy from
The presoma of sub- S is injected into reaction system, can be in above-mentioned CdyZn1-yS layer surfaces form CdzZn1-zS layers（Wherein 0≤z≤1,
And z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, ectonexine nanocrystal occurs（It is i.e. above-mentioned
Two layers of compound）The exchange of middle Cd and Zn ions；Since the limited and remoter migration distance of the migration distance of cation is moved
The probability of shifting, therefore can be in Cd with regard to smalleryZn1-yS layers and CdzZn1-zS layers of interface is formed about Cd contents and Zn contents gradually
Become alloy compositions distribution, i.e. CdxZn1-xS, wherein 0≤x≤1.
Embodiment 3：Preparation based on CdZnSe/CdZnSe quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion Se is injected into reaction system
It is initially formed CdyZn1-ySe layers（Wherein 0≤y≤1）；Continue the presoma and the moon of the presoma of cationic Cd, cation Zn
The presoma of ion Se is injected into reaction system, can be in above-mentioned CdyZn1-ySe layer surfaces form CdzZn1-zSe layers（Wherein 0≤z
≤ 1, and z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, Cd in ectonexine nanocrystal occurs
With the exchange of Zn ions；The probability migrated due to the limited and remoter migration distance of migration distance of cation with regard to smaller,
It therefore can be in CdyZn1-ySe layers and CdzZn1-zSe layers of interface is formed about the graded alloy component point of Cd contents and Zn contents
Cloth, i.e. CdxZn1-xSe, wherein 0≤x≤1.
Embodiment 4：Preparation based on CdS/ZnS quantum dots
First the presoma of the presoma of cationic Cd and anion S is injected into reaction system, is initially formed CdS layer；Continuing will
The presoma of cationic Zn and the presoma of anion S are injected into reaction system, can form ZnS layers on above-mentioned CdS layer surface；
Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd
Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation
The probability that migrates of the limited and remoter migration distance of migration distance with regard to smaller, therefore can be in CdS layer and ZnS layers of interface
Be formed about Cd contents it is radially outward gradually decrease, the radially outward graded alloy component gradually increased of Zn contents point
Cloth, i.e. CdxZn1-xS, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 0 from 1 monotone decreasing.
Embodiment 5：Preparation based on CdSe/ZnSe quantum dots
First the presoma of the presoma of cationic Cd and anion Se is injected into reaction system and is initially formed CdSe layers；Continuing will
The presoma of cationic Zn and the presoma of anion Se are injected into reaction system, can form ZnSe in above-mentioned CdSe layer surfaces
Layer；Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and with
Cation exchange reaction occurs for Cd cations, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from
The probability that the limited and remoter migration distance of migration distance of son migrates, therefore can be in CdSe layers and ZnSe layer with regard to smaller
Interface be formed about Cd contents it is radially outward gradually decrease, the radially outward graded alloy group gradually increased of Zn contents
Distribution, i.e. CdxZn1-xSe, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 0 from 1 monotone decreasing.
Embodiment 6：Preparation based on CdSeS/ZnSeS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of anion Se and anion S is injected into reaction system
It is initially formed CdSebS1-bLayer（Wherein 0≤b≤1）；Continue by the presoma of cationic Zn, anion Se presoma and it is cloudy from
The presoma of sub- S is injected into reaction system, can be in above-mentioned CdSebS1-bLayer surface forms ZnSecS1-cLayer（Wherein 0≤c≤1）；
Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd
Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation
The probability that migrates of the limited and remoter migration distance of migration distance with regard to smaller, therefore can be in CdSebS1-bLayer with
ZnSecS1-cThe interface of layer be formed about Cd contents it is radially outward gradually decrease, Zn contents are radially outward gradually increases
Graded alloy component distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1 and x is from inside to outside（Radial direction）From 1 monotone decreasing
It is 0,0≤a≤1.
Embodiment 7：Preparation based on ZnS/CdS quantum dots
First the presoma of the presoma of cationic Zn and anion S is injected into reaction system and is initially formed ZnS layers；Continuing will be positive
The presoma of ion Cd and the presoma of anion S are injected into reaction system, can form CdS layer in above-mentioned ZnS layer surfaces；
Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Zn sun
Cation exchange reaction occurs for ion, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation
The probability that the limited and remoter migration distance of migration distance migrates, therefore can be attached with the interface of CdS layer at ZnS layers with regard to smaller
It is close formed Zn contents it is radially outward gradually decrease, the radially outward graded alloy component gradually increased of Cd contents point
Cloth, i.e. CdxZn1-xS, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 1 from 0 monotonic increase.
Embodiment 8：Preparation based on ZnSe/CdSe quantum dots
First the presoma of the presoma of cationic Zn and anion Se is injected into reaction system and is initially formed ZnSe layer；Continuing will
The presoma of cationic Cd and the presoma of anion Se are injected into reaction system, can form CdSe on above-mentioned ZnSe layer surface
Layer；Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with
Cation exchange reaction occurs for Zn cations, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from
The probability that the limited and remoter migration distance of migration distance of son migrates, therefore can be in ZnSe layer and CdSe layers with regard to smaller
Interface be formed about Zn contents it is radially outward gradually decrease, the radially outward graded alloy group gradually increased of Cd contents
Distribution, i.e. CdxZn1-xSe, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 1 from 0 monotonic increase.
Embodiment 9：Preparation based on ZnSeS/CdSeS quantum dots
First the presoma of the presoma of cationic Zn, the presoma of anion Se and anion S is injected into reaction system
It is initially formed ZnSebS1-bLayer（Wherein 0≤b≤1）；Continue by the presoma of cationic Cd, anion Se presoma and it is cloudy from
The presoma of sub- S is injected into reaction system, can form CdSe in above-mentioned ZnSebS1-b layer surfacescS1-cLayer（Wherein 0≤c≤
1）；Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with
Cation exchange reaction occurs for Zn cations, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from
The probability that the limited and remoter migration distance of migration distance of son migrates, therefore can be in ZnSe with regard to smallerbS1-bLayer with
CdSecS1-cThe interface of layer be formed about Zn contents it is radially outward gradually decrease, Cd contents are radially outward gradually increases
Graded alloy component distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1 and x are from inside to outside 1 from 0 monotonic increase, 0≤a≤
1。
Embodiment 10：The preparation of blue quantum dot with concrete structure 1
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL
Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, after reacting 10 min, by trioctylphosphine sulfide presoma and cadmium oleate presoma respectively with 3 mL/h and
The rate of 10 mL/h is added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and nothing
Product is dissolved, is precipitated by water methanol repeatedly, is then centrifuged for purifying, and obtains the blue quantum dot with concrete structure 1（CdxZn1- xS）.
Embodiment 11：The preparation of green quantum dot with concrete structure 1
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet)2], 10
ML oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then it is cut
It changes under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4 mL
Octyl phosphine（Trio ctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three
Octyl phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by the vulcanization of 2mL
Tri octyl phosphine presoma is added dropwise to the rate of 8 mL/h in reaction system, until presoma has injected.After reaction,
After reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains having tool
The green quantum dot of body structure 1（CdxZn1-xSeyS1-y/CdzZn1-zS）, prepared green quantum is represented before "/" herein
The composition of the inside of point, "/" then represents the composition outside prepared green quantum dot below, and "/" representative is not
It is apparent boundary, but the structure of gradual change from inside to outside, this quantum dot representation method meaning subsequently occurred are identical.
Embodiment 12：The preparation of red quantum dot with concrete structure 1
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2],
14 mL oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then by it
It switches under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, it obtains
To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast
Speed is injected into reaction system, first generates CdxZn1-xSe, it is after reacting 10 min, selenizing tri octyl phosphine-vulcanization three of 2mL is pungent
Base phosphine presoma is added dropwise to the rate of 4 mL/h in reaction system.After reaction, after reaction solution is cooled to room temperature,
Product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains the red fluorescence quantum with concrete structure 1
Point（CdxZn1-xSeyS1-y/CdzZn1-zS）.
Embodiment 13：Influence of the cadmium oleate charge velocity to the blue quantum dot synthesis with concrete structure 1
On the basis of embodiment 10, the charge velocity by adjusting cadmium oleate can regulate and control the graded of quantum dot component
Slope, to influence its level structure, the final regulation and control realized to quantum dot light emitting wavelength.
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2],
8 mL oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C
Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generates CdxZn1-xS, react 10 min after, by trioctylphosphine sulfide presoma with 3 mL/h rates by
It is added dropwise in reaction system, while cadmium oleate presoma being added dropwise to different charge velocities in reaction system.Instead
After answering, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains
To the blue quantum dot with level structure 1（CdxZn1-xS/CdyZn1-yS）.
Based on identical quantum dot center（Alloy quantum dot glow peak 447nm）And the injection speed of different cadmium oleate presomas
Under rate, quantum dot light emitting wavelength tuning control is listed as follows：
Embodiment 14：Influence of the cadmium oleate injection rate to the blue quantum dot synthesis with concrete structure 1
On the basis of embodiment 10 and embodiment 13, by adjusting the injection rate of cadmium oleate presoma, quantum dot can be regulated and controled
Ingredient graded section, to influence the variation of its level structure, the final tune realized to quantum dot light emitting wavelength
Control.Based on identical quantum dot center（Alloy quantum dot glow peak 447nm）And the injection rate of different cadmium oleate presomas（It is identical
1 mmol/h under charge velocity）Under rate, quantum dot light emitting wavelength tuning control is listed as follows.
Embodiment 15：The preparation of blue quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL
Oleic acid（Oleic acid）With 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generates CdxZn1-xTemperature of reaction system is down to 280 DEG C, then by 2mL by S after reacting 10 min
Trioctylphosphine sulfide presoma and 6mL cadmium oleates presoma respectively with the rate of 3 mL/h and 10mL/h simultaneously be injected into reaction
In system.After injecting 40 min, temperature of reaction system is warming up to 310 DEG C, by 1mL trioctylphosphine sulfides presoma with 3 mL/h
Rate be injected into reaction system, after reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product
It dissolves, precipitate repeatedly, centrifugation purification obtains the blue quantum dot of concrete structure 2.
Embodiment 16：The preparation of green quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet) 2], 10
ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into
60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4mL
Octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains
To trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three
Octyl phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by reaction system temperature
Degree is down to 280 DEG C, then by the trioctylphosphine sulfide presoma of 1.2mL and 6mL cadmium oleates presoma respectively with 2 mL/h and
The rate of 10mL/h is injected into reaction system, until presoma has injected.Temperature of reaction system is warming up to 310 DEG C, by 0.8
ML trioctylphosphine sulfides presoma is injected into the rate of 2 mL/h in reaction system.After reaction, wait for that reaction solution is cooled to
After room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains the amount of green color with concrete structure 2
Sub- point.
Embodiment 17：The preparation of red quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2],
14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C
Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains
To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 0.3 mmol cadmium oxides（CdO）, 0.3mL oleic acid（Oleic acid）With 2.7 mL octadecylenes（1-
Octadecene）It is placed in 50 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast
Speed is injected into reaction system, first generates CdxZn1-xTemperature of reaction system is down to 280 DEG C, then by Se after reacting 10 min
By 1mL selenizings tri octyl phosphine-trioctylphosphine sulfide presoma and 3mL cadmium oleates presoma respectively with the speed of 2 mL/h and 6 mL/h
Rate is injected into reaction system.Temperature of reaction system is warming up to 310 DEG C, before 1mL selenizings tri octyl phosphine-trioctylphosphine sulfide
Body is driven to be injected into reaction system with the rate of 4 mL/h.After reaction, after reaction solution is cooled to room temperature, with toluene and nothing
Product is dissolved, is precipitated by water methanol repeatedly, and centrifugation purification obtains the red quantum dot with concrete structure 2.
Embodiment 18：The preparation of blue quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL
Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.2 mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 1 mL
（Trioctylphosphine）In, obtain selenizing tri octyl phosphine presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generates CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and trioctylphosphine sulfide presoma
It is continuously injected into 20 min to reaction system with the rate of 0.6 mmol/h, 4 mmol/h respectively.Then by cadmium oleate presoma,
Trioctylphosphine sulfide presoma and selenizing tri octyl phosphine presoma are respectively with 0.4 mmol/h, 0.6 mmol/h and 0.2 mmol/h
Rate be continuously injected into 1 h to reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and without water beetle
Product is dissolved, is precipitated by alcohol repeatedly, and centrifugation purification is obtained with Quantum Well（Concrete structure 3）Blue quantum dot
(CdZnS/CdZnS/CdZnSeS3)。
Embodiment 19：The preparation of green quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 6 mmol zinc acetates [Zn (acet)2], 10
ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into
60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in 4 mL's
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 0.1 mmol selenium powders（Selenium powder）, 0.3 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2.
By 0.8 mmol sulphur powders（Sulfur powder）, 0.8 mmol selenium powders（Selenium powder）It is dissolved in 3 mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 3.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three
Octyl phosphine presoma 1 is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 5 min, by the selenizing of 2mL
Tri octyl phosphine-trioctylphosphine sulfide presoma 2 is added dropwise to the rate of 6 mL/h in reaction system.Then, by the selenium of 3mL
Change the cadmium oleate presoma of tri octyl phosphine-trioctylphosphine sulfide presoma 3 and 6mL respectively with 3 mL/h and 6 mL/h rates after
It is continuous to be added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product
It dissolves, precipitate repeatedly, centrifugation purification obtains the green quantum dot (CdZn with concrete structure 33SeS3/Zn4SeS3/
Cd3Zn5Se4S4)。
Embodiment 20：The preparation of red quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2],
14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C
Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, it obtains
To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 0.9 mmol cadmium oxides（CdO）, 0.9 mL oleic acid（Oleic acid）With 8.1 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast
Speed is injected into reaction system, first generates CdxZn1-xSe, it is after reacting 10 min, selenizing tri octyl phosphine-vulcanization three of 2 mL is pungent
Base phosphine presoma is added dropwise to the rate of 2 mL/h in reaction system.When being injected into 30 min, before the cadmium oleate of 3 mL
Body is driven to be added dropwise in reaction system with 6 mL/h rates simultaneously.After reaction, after reaction solution is cooled to room temperature, first is used
Product is dissolved, is precipitated by benzene and absolute methanol repeatedly, and centrifugation purification obtains the red quantum dot with concrete structure 3
（CdxZn1-xSe/ZnSeyS1-y/CdzZn1-zSeS）.
Embodiment 21：The preparation of blue quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL
Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.2mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 1mL（Trioctylphosphine）
In, obtain selenizing tri octyl phosphine presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and selenizing tri octyl phosphine forerunner
Body is continuously injected into the rate of 0.6 mmol/h, 0.6 mmol/h in 20 min to reaction system respectively.It then will be before cadmium oleate
It drives body and trioctylphosphine sulfide presoma is continuously injected into 1h to reaction system with the rate of 0.4 mmol/h and 6 mmol/h respectively
In.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation carries
It is pure, it obtains with Quantum Well（Concrete structure 4）Blue quantum dot（CdZnS/CdZnSe/CdZnS）.
Embodiment 22：The preparation of green quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL
Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.4 mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 2 mL
（Trioctylphosphine）In, obtain selenizing tri octyl phosphine presoma.
By 0.8 mmol cadmium oxides（CdO）, 1.2 mL oleic acid（Oleic acid）With 4.8 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generates CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and selenizing tri octyl phosphine presoma
It is continuously injected into 40 min to reaction system with the rate of 0.6 mmol/h, 0.6 mmol/h respectively.Then by cadmium oleate forerunner
Body and trioctylphosphine sulfide presoma are continuously injected into 1 h to reaction system with the rate of 0.4 mmol/h and 6 mmol/h respectively
In.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation carries
It is pure, it obtains with Quantum Well（Concrete structure 4）Green quantum dot（CdZnS/CdZnSe/CdZnS）.
Embodiment 23：The preparation of red quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2],
14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C
Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 1.5 mmol selenium powders（Selenium powder）, 1.75 mmol sulphur powders（Sulfur powder）It is dissolved in 3mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 1 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains
To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.8 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2.
By 3 mmol cadmium oxides（CdO）, 3mL oleic acid（Oleic acid）With 6 mL octadecylenes（1-Octadecene）It is placed in
In 100 mL three-necked flasks, it is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent cadmium oleate presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three
Octyl phosphine presoma 1 is injected into reaction system, first generates CdxZn1-xSe, after reacting 10 min, by the selenizing trioctylphosphine of 2 mL
The cadmium oleate presoma of phosphine presoma and 3mL are added dropwise to the rate of 4 mL/h and 6 mL/h in reaction system respectively.Note
When entering to 30 min, by the cadmium oleate presoma of selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2 of 2mL and 3mL respectively with
2 mL/h and 3 mL/h rates are added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, toluene is used
Product is dissolved repeatedly with absolute methanol, is precipitated, centrifugation purification obtains the red quantum dot of concrete structure 4（CdxZn1-xSe/
CdZnSe/CdzZn1-zSeS）.
Embodiment 24：The preparation of blue quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL
Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 1 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generates CdxZn1-xS, after reacting 10 min, by 3 mL trioctylphosphine sulfides presomas with 3 mL/h's
Rate is continuously injected into 1h to reaction system, when trioctylphosphine sulfide presoma injects 20 min, by 2 mL cadmium oleate forerunners
Body is injected into 6 mL/h in reaction system, when trioctylphosphine sulfide presoma injects 40 min, by 4 mL cadmium oleate forerunners
Body is injected into 12 mL/h in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol
Product is dissolved repeatedly, is precipitated, centrifugation purification is obtained with Quantum Well（Concrete structure 5）Blue quantum dot
（CdZnS/ZnS/CdZnS）.
Embodiment 25：The preparation of green quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 6 mmol zinc acetates [Zn (acet)2], 10
ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into
60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in 4mL's
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three
Octyl phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, 3 mL are vulcanized three
Octyl phosphine presoma is continuously injected into the rate of 3 mL/h in 1h to reaction system, injects 20 in trioctylphosphine sulfide presoma
When min, 2 mL cadmium oleates presomas are injected into 6 mL/h in reaction system, inject 40 in trioctylphosphine sulfide presoma
When min, 4 mL cadmium oleates presomas are injected into 12 mL/h in reaction system.After reaction, wait for that reaction solution is cooled to room
Product is dissolved with toluene and absolute methanol, is precipitated by Wen Hou repeatedly, and centrifugation purification is obtained with Quantum Well（Specifically
Structure 5）Green quantum dot（CdZnSeS/ZnS/CdZnS）.
Embodiment 26：The preparation of red quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2],
14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C
Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains
To selenizing tri octyl phosphine presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast
Speed is injected into reaction system, first generates CdxZn1-xSe, after reacting 10 min, by trioctylphosphine sulfide presoma with 6 mmol/
The rate of h is continuously injected into 1h to reaction system, when S-TOP injects 20 min, by 0.2 mmol cadmium oleate presomas with 0.6
Mmol/h is injected into reaction system, when S-TOP injects 40 min, by 0.4 mmol cadmium oleates presoma with 1.2 mmol/h
It is injected into reaction system.After reaction, with toluene and absolute methanol that product is repeatedly molten after reaction solution is cooled to room temperature
Solution, precipitation, centrifugation purification, obtain with Quantum Well（Concrete structure 5）Red quantum dot（CdZnSe/ZnS/
CdZnS）.
Embodiment 27：The preparation of blue quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet) 2], 8 mL
Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C
60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-
Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil
Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted
Enter into reaction system, first generates CdxZn1-xS, after reacting 10 min, by trioctylphosphine sulfide presoma and cadmium oleate presoma
It is added dropwise in reaction system with the rate of 6mmol/h and 0.6 mmol/h respectively.After 30 min, temperature of reaction system is dropped
To 280 DEG C, by remaining trioctylphosphine sulfide presoma and cadmium oleate presoma respectively with the speed of 6mmol/h and 0.6 mmol/h
Rate is added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product
It dissolves, precipitate repeatedly, centrifugation purification obtains the blue quantum dot with concrete structure 6（CdxZn1-xS）.
Embodiment 28：The preparation of green quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet)2], 10
ML oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then it is cut
It changes under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4mL
Octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains
To trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three
Octyl phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by reaction system
Temperature is down to 280 DEG C, and trioctylphosphine sulfide presoma is added dropwise to the rate of 4 mL/h in reaction system.Reaction terminates
Afterwards, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification is had
The green quantum dot of concrete structure 6（CdxZn1-xSeyS1-y/ZnS）.
Embodiment 29：The preparation of red quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2],
14 mL oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then by it
It switches under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains
To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast
Speed is injected into reaction system, first generates CdxZn1-xTemperature of reaction system is down to 280 DEG C, by selenium by Se after reacting 10 min
Change tri octyl phosphine-trioctylphosphine sulfide presoma to be added dropwise in reaction system with the rate of 4 mL/h.After reaction, it waits for
After reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains having specific
The red quantum dot of structure 6（CdxZn1-xSe/ZnSeS）.
Embodiment 30：The preparation of green quantum dot with concrete structure 7
It is prepared by the first presoma of cadmium oleate：By 1 mmol cadmium oxides（CdO）, 1 mL oleic acid（Oleic acid）With 5 mL octadecylenes
（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then it switches it to
At under nitrogen atmosphere, and in being preserved at this temperature in case for use.
It is prepared by the second presoma of cadmium oleate：By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With
5.4 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 for 250 DEG C under nitrogen atmosphere
Mins obtains transparent the second presoma of cadmium oleate.
It is prepared by oleic acid zinc precursor：By 9 mmol zinc acetates [Zn (acet)2], 7 mL oleic acid（Oleic acid）And 10
ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then
It switches it under nitrogen atmosphere, and preservation is heated to reflux in case for use in lower 250 DEG C of nitrogen atmosphere.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur
Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In,
Obtain trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, the first presoma of cadmium oleate is warming up to 310 DEG C, sulphur octadecylene presoma is rapidly injected
Into reaction system, it is quickly generated CdS, after reacting 10 mins, oleic acid zinc precursor is all injected into reaction system, then by 3
The trioctylphosphine sulfide presoma of mL and 6 the second presomas of mL cadmium oleates are noted with the rate of 3 mL/h and 10 mL/h simultaneously respectively
Enter into reaction system.
After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated,
Centrifugation purification, obtains the blue quantum dot with Quantum Well.
Embodiment 31：The preparation of green quantum dot with concrete structure 7
It is prepared by cadmium oleate presoma：By 0.4 mmol cadmium oxides（CdO）, 1 mL oleic acid（Oleic acid）With 5 mL octadecylenes
（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then by it in nitrogen
Atmosphere is enclosed lower 250 DEG C and is heated to reflux, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, it is dissolved in the tri octyl phosphine of 4 mL
（Trioctylphosphine）In, obtain selenizing tri octyl phosphine.
It is prepared by oleic acid zinc precursor：By 8 mmol zinc acetates [Zn (acet)2], 9 mL oleic acid（Oleic acid）With 15
ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.In nitrogen
Atmosphere encloses lower 250 DEG C and is heated to reflux 120 mins, obtains transparent oleic acid zinc precursor.
By 2 mmol sulphur powders（Sulfur powder）With 1.6 mmol selenium powders（Selenium powder）It is dissolved in 2 mL
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate presoma is warming up to 310 DEG C, selenizing tri octyl phosphine presoma is rapidly injected
Into reaction system, it is quickly generated CdSe, after reacting 5 mins, oleic acid zinc precursor is all injected into reaction system, by 2
Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma of mL is added dropwise to the rate of 2 mL/h in reaction system, until before
Body is driven to have injected.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is heavy
It forms sediment, centrifugation purification obtains the green fluorescence quantum dot with Quantum Well.
Embodiment 32：The preparation of red quantum dot with concrete structure 7
It is prepared by cadmium oleate presoma：By 0.8 mmol cadmium oxides（CdO）, 4 mL oleic acid（Oleic acid）With 10 mL octadecylenes
（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then by it in nitrogen
Atmosphere is enclosed lower 250 DEG C and is heated to reflux, and in preservation at this temperature in case for use.
It is prepared by oleic acid zinc precursor：12 mmol zinc acetates [Zn (acet)2], 10 mL oleic acid（Oleic acid）With 10
ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.
By 0.8 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In,
Obtain selenizing tri octyl phosphine presoma.
By 1 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL's
Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate presoma is warming up to 310 DEG C, selenizing tri octyl phosphine presoma is rapidly injected
Into reaction system, it is quickly generated CdSe, after reacting 10 mins, oleic acid zinc precursor is all injected into reaction system, it will
Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma of 2 mL is added dropwise to the rate of 4 mL/h in reaction system.Reaction
After, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains
Red fluorescence quantum dot with Quantum Well.
Embodiment 33 is as shown in figure 9, a kind of quantum dot photovoltaic device, preparation process include the following steps：
(1) ITO is prepared on substrate 20（Hearth electrode 21）；
(2) the spin coating layer of ZnO layer on ITO（Electron transfer layer 22）, thickness is 30 nm；
(3) one layer PMMA layers of spin coating in ZnO layer（Hole blocking layer 23）, thickness is 5 nm；
(4) one layer of quanta point material of spin coating obtains quantum dot active layer 24 on PMMA layers, and thickness is 100 nm；Amount therein
The quantum dot of any one in son point material previous embodiment；
(5) one layer of MoO of spin coating on quantum dot active layer 243Layer（Hole transmission layer 25）, thickness is 10 nm；
(6) in MoO3The Au electrodes that a layer thickness is 150 nm are deposited on layer（Top electrode 26）, obtain quantum dot photovoltaic device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (15)
1. a kind of quantum dot photovoltaic device, which is characterized in that include successively：Conductive substrates, electron transfer layer, quantum dot activity
Layer, hole transmission layer, top electrode；The material of the quantum dot active layer is quanta point material, and the quanta point material includes extremely
A few quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure unit are energy level in the radial direction
The consistent homogeneous components structure of the graded alloy component structure of change width or in the radial direction level width.
2. quantum dot photovoltaic device according to claim 1, which is characterized in that the electron transfer layer and quantum dot activity
It is provided with one layer of hole blocking layer between layer.
3. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is
The wider graded alloy component structure of more outside level width in the radial direction, and quantum-dot structure adjacent in radial directions
The energy level of unit is continuous.
4. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quanta point material includes at least
Three quantum-dot structure units arranged successively in radial directions, wherein in at least three quantum-dot structures unit, position
Quantum-dot structure unit in center and surface is the graded alloy component knot that more outside level width is wider in the radial direction
Structure, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions is continuous；In being located at
A quantum-dot structure unit between the heart and the quantum-dot structure unit on surface is homogeneous components structure.
5. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quanta point material includes two kinds
The quantum-dot structure unit of type, the quantum-dot structure unit of one of which type are that more outside level width is more in the radial direction
Wide graded alloy component structure, another type of quantum-dot structure unit are that more outside level width is narrower in the radial direction
Graded alloy component structure, the quantum-dot structure unit of described two types is radially alternately distributed successively, and in diameter
The energy level of adjacent quantum-dot structure unit is continuous on direction.
6. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is
The wider graded alloy component structure of more outside level width in the radial direction, and the energy level of adjacent quantum-dot structure unit is
It is discontinuous.
7. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is
The narrower graded alloy component structure of more outside level width in the radial direction, and the energy level of adjacent quantum-dot structure unit is
It is discontinuous.
8. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quanta point material includes two kinds
Quantum-dot structure unit, one of which quantum-dot structure unit are the wider graded alloy of more outside level width in the radial direction
Component structure, another quantum-dot structure unit are homogeneous components structure, and the inside of the quanta point material includes one or one
The quantum-dot structure unit of a above graded alloy component structure, and graded alloy component structure adjacent in radial directions
The energy level of quantum-dot structure unit be continuous；The outside of the quanta point material includes one or more uniform group
The quantum-dot structure unit of separation structure.
9. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quanta point material includes two kinds
Quantum-dot structure unit, one of which quantum-dot structure unit are homogeneous components structure, and another quantum-dot structure unit is diameter
The inside of the wider graded alloy component structure of more outside level width on direction, the quanta point material includes one or one
The quantum-dot structure unit of a above homogeneous components structure, the outside of the quanta point material includes one or more
The quantum-dot structure unit of graded alloy component structure, and the quantum dot of graded alloy component structure adjacent in radial directions
The energy level of structural unit is continuous.
10. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is packet
The graded alloy component structure or uniform alloy compositions structure of race containing II and VI races element.
11. quantum dot photovoltaic device according to claim 10, which is characterized in that the quantum-dot structure unit includes 2-
20 layers of monoatomic layer or the quantum dot light emitting unit include 1-10 layer crystals born of the same parents' layer.
12. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the glow peak of the quanta point material
Wave-length coverage is 400 nanometers to 700 nanometers.
13. quantum dot photovoltaic device according to claim 1 or 2, which is characterized in that the glow peak of the quanta point material
Peak width at half height be 12 nanometers to 80 nanometers.
14. a kind of preparation method of quantum dot photovoltaic device as described in claim 1, which is characterized in that including step：
A, one layer of electron transfer layer is deposited on conductive substrates；
B, one layer of quantum dot active layer is deposited on the electron transport layer；The material of the quantum dot active layer is quanta point material,
The quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure
Unit is the graded alloy component structure of level width variation or in the radial direction consistent uniform of level width in the radial direction
Component structure；
C, one layer of hole transmission layer is deposited on quantum dot active layer；
D, one layer of top electrode is deposited on the hole transport layer, obtains quantum dot photovoltaic device.
15. the preparation method of quantum dot photovoltaic device according to claim 14, which is characterized in that the step A it
Afterwards, further include before B：
One layer of hole blocking layer is deposited on the electron transport layer.
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