CN108264894A - A kind of nano luminescent material, preparation method and semiconductor devices - Google Patents
A kind of nano luminescent material, preparation method and semiconductor devices Download PDFInfo
- Publication number
- CN108264894A CN108264894A CN201611256950.6A CN201611256950A CN108264894A CN 108264894 A CN108264894 A CN 108264894A CN 201611256950 A CN201611256950 A CN 201611256950A CN 108264894 A CN108264894 A CN 108264894A
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- CN
- China
- Prior art keywords
- luminescent material
- nano luminescent
- presoma
- cadmium
- zinc
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- 239000000463 material Substances 0.000 title claims abstract description 261
- 238000002360 preparation method Methods 0.000 title claims abstract description 73
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 155
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 155
- 238000006243 chemical reaction Methods 0.000 claims description 167
- 239000011701 zinc Substances 0.000 claims description 158
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 80
- ZTSAVNXIUHXYOY-CVBJKYQLSA-L cadmium(2+);(z)-octadec-9-enoate Chemical compound [Cd+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O ZTSAVNXIUHXYOY-CVBJKYQLSA-L 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 69
- 150000001875 compounds Chemical class 0.000 claims description 63
- 150000001450 anions Chemical class 0.000 claims description 46
- 229910052793 cadmium Inorganic materials 0.000 claims description 38
- 125000002091 cationic group Chemical group 0.000 claims description 35
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- -1 caddy Chemical compound 0.000 claims description 22
- 238000005341 cation exchange Methods 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims description 8
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 8
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 4
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 claims description 4
- 229940075417 cadmium iodide Drugs 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 4
- VQNPSCRXHSIJTH-UHFFFAOYSA-N cadmium(2+);carbanide Chemical compound [CH3-].[CH3-].[Cd+2] VQNPSCRXHSIJTH-UHFFFAOYSA-N 0.000 claims description 4
- UJYLYGDHTIVYRI-UHFFFAOYSA-N cadmium(2+);ethane Chemical compound [Cd+2].[CH2-]C.[CH2-]C UJYLYGDHTIVYRI-UHFFFAOYSA-N 0.000 claims description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 4
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- MJNSMKHQBIVKHV-UHFFFAOYSA-N selenium;trioctylphosphane Chemical group [Se].CCCCCCCCP(CCCCCCCC)CCCCCCCC MJNSMKHQBIVKHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 claims description 4
- 229940105296 zinc peroxide Drugs 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims description 4
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 3
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
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- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 100
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 92
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 82
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 82
- 239000011669 selenium Substances 0.000 description 78
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- ZJGSVSYBKAZJGP-KVVVOXFISA-N (z)-octadec-9-enoic acid;zinc Chemical compound [Zn].CCCCCCCC\C=C/CCCCCCCC(O)=O ZJGSVSYBKAZJGP-KVVVOXFISA-N 0.000 description 45
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- 150000001768 cations Chemical class 0.000 description 30
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 239000000090 biomarker Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
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- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- DWUCCPNOMFYDOL-UHFFFAOYSA-N propyl(sulfanyl)silicon Chemical compound CCC[Si]S DWUCCPNOMFYDOL-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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Abstract
The present invention discloses a kind of nano luminescent material, preparation method and semiconductor devices, wherein, the nano luminescent material includes at least two layers monoatomic layer arranged successively in radial directions, and 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 are formed between adjacent monoatomic layer.Nano luminescent material provided by the invention, it not only realizes more efficient nano luminescent material luminous efficiency, it also can more meet the comprehensive performance requirement of semiconductor devices and corresponding display technology to nano luminescent material simultaneously, be a kind of suitable semiconductor devices and the preferable nano luminescent material of display technology.
Description
Technical field
The present invention relates to a kind of field of light emitting materials more particularly to nano luminescent material, preparation method and semiconductor devices.
Background technology
Quantum dot is a kind of special material for being limited in nanometer scale in three dimensions, this significant
Quantum confined effect causes quantum dot to be provided with many unique nanometer properties:Launch wavelength is continuously adjusted, emission wavelength is narrow, is inhaled
Receive spectral width, luminous intensity height, fluorescence lifetime length and good biocompatibility etc..These features cause quantum dot to be shown in tablet
Show, the fields such as solid-state lighting, photovoltaic solar, biomarker are respectively provided with the prospect of being widely applied.It especially should in FPD
With aspect, the quanta point electroluminescent diode component based on quanta point material(Quantum dot light-emitting
Diodes, QLED)Characteristic and optimization by means of CdS quantum dots, in display image quality, device performance, manufacture cost
Etc. shown huge potentiality.Although the performance of QLED devices in all respects is continuously available promotion in recent years no matter
It is also to have phase with the requirement of commercial application in device efficiency or in the basic devices performance parameter such as device job stability
When gap, this also hinders the development and application of quanta point electroluminescent display technology significantly.In addition, it is not limited only to QLED devices
Part, in other areas, quanta point material are also gradually paid attention to relative to the characteristic of traditional material, such as photo luminescent devices,
Solar cell, display device, photodetector, bioprobe and device for non-linear optical etc., below only with QLED devices
It is illustrated for part.
Although quantum dot has been studied and developed more than 30 years as a kind of nano material of classics, quantum is utilized
The superior luminescence characteristics of point simultaneously apply the search time in QLED devices and corresponding display technology as luminescent material
It is also very short;Therefore the R and D of the QLED devices of the overwhelming majority are all based on the quantum dot for having classical architecture system at present
Material, the standard of screening and the optimization of corresponding quanta point material is also substantially from the luminescent properties such as quantum of quantum dot itself
The luminous peak width of point, solution quantum yield etc. set out.More than quantum dot is directly applied in QLED device architectures so as to obtain
Corresponding device performance result.
But the photoelectric device system of QLED devices and corresponding display technology as a set of complexity, there is all various factors
It can influence the performance of device.List is from the quanta point material as core emitting layer material, the quantum dot performance of required tradeoff
Index will be much more complex.
First, quantum dot is existing in the form of quantum dot light emitting layer solid film in QLED devices, therefore quantum
Originally obtained every luminescent properties parameter can show apparent difference to point material after solid film is formed in the solution:
Such as glow peak wavelength has different degrees of red shift in solid film(It is moved to long wavelength), shine peak width can become larger,
Quantum yield has different degrees of reduction, that is to say, that the superior luminescence performance of quanta point material in the solution can not be complete
It is inherited into the quantum dot solid film of QLED devices.Therefore in the structure and synthesizing formula for designing and optimizing quanta point material
When, the hair of the luminescent properties optimization and quanta point material of quanta point material itself under solid film state need to be considered simultaneously
Optical property, which is inherited, to be maximized.
Secondly, the luminous of quanta point material is realized by electroexcitation in QLED devices, i.e., respectively from QLED
Anode and cathodal closing the injection hole of device and electronics, hole and electronics are existed by the transmission of corresponding function layer in QLED devices
After quantum dot light emitting layer is compound, emitted by way of radiation transistion photon realize shine.From above procedure as can be seen that amount
It is to influence the efficiency of radiation transistion in the above process that son, which puts the luminescent properties of itself such as luminous efficiency, and QLED devices is whole
Body luminous efficiency can also simultaneously by hole in the above process and electronics in quanta point material charge injection and efficiency of transmission,
Relative charge balance in quanta point material of hole and electronics, the recombination region of hole and electronics in quanta point material etc.
It influences.Therefore when designing and optimizing the fine nanometer nuclear shell nano-structure of structure especially quantum dot of quanta point material, weight is also needed
Point considers that quantum dot forms the later electric property of solid film:Such as the charge of quantum dot injects and conductive performance, quantum dot
Fine band structure, quantum dot exciton lifetime etc..
Finally, it is contemplated that QLED devices and corresponding display technology future will pass through the solution rule of great production cost advantage
If prepared by ink-jet printing, therefore the design of material of quantum dot and exploitation need to consider the processing performance of quantum dot solution,
Such as the dispersible dissolubility of quantum dot solution or marking ink, colloidal stability, it is printed as film property etc..Meanwhile quantum dot material
The exploitation of material will also be cooperateed with the whole preparation process flow and requirement of other functional layer materials of QLED devices and device.
In short, traditional only being designed from the quantum-dot structure for promoting quantum dot itself luminescent properties consideration is can not to expire
Sufficient QLED devices and corresponding display technology are various in optical property, electric property, processing performance etc. for quanta point material
Composite request.The requirement for QLED devices and corresponding display technology is needed, to the fine nucleocapsid knot of quantum dot light emitting material
Structure, component, energy level etc. carry out customized.
Due to the high surface atom ratio of quantum dot, not with surface ligand(Ligand)Form non-covalent bond(Dangling
bond)Atom will exist with surface defect state, this surface defect state will cause the transition of non-radiative pathway so that
The photoluminescence quantum yield of quantum dot is substantially lowered.To solve this problem, it can grow and include in former quantum dot superficies
The semiconductor shell of another semi-conducting material forms the nucleocapsid of quantum dot(core-shell)Structure, can the amount of significantly improving
The luminescent properties of son point, while increase the stability of quantum dot.
It can be applied to the quanta point material predominantly quantum dot with nucleocapsid of high-performance QLED devices exploitation, core
Fixed and nucleocapsid has clear and definite boundary, such as quantum dot (the J. Phys. with CdSe/ZnS nucleocapsids respectively with shell component
Chem., 1996,100 (2), 468-471), there is quantum dot (the J. Am. Chem. of CdSe/CdS nucleocapsids
Soc. 1997,119, (30), 7019-7029), the quantum dot with CdS/ZnS nucleocapsids, with CdS/CdSe/CdS
The quantum dot (7,919,012 B2 of Patent US) of core+multilayer shell structurre has CdSe/CdS/ZnS cores+multilayer shell
Quantum dot (J. Phys. Chem. B, 2004,108 (49), 18826-18831) of structure etc..In these nucleocapsids
Quantum dot in, usually the constituent of core and shell is fixed and different, and is usually by a kind of cation and one
The binary compound system of kind anion composition.In this configuration, since the growth of core and shell is independently to carry out respectively, because
Boundary between this core and shell is clear and definite, i.e., core and shell can be distinguished.The exploitation of this nuclear shell structure quantum point improves original
Luminous quantum efficiency, monodispersity and the quantum dot stability of first single component quantum dot.
Although the quantum dot part of nucleocapsid described above improves quantum dot performance, from mentality of designing or
From prioritization scheme or from the aspect of the luminous efficiency based on promotion quantum dot itself, luminescent properties need to be improved,
In addition other aspect particular/special requirements of semiconductor devices for quanta point material are not considered yet.
Therefore, above-mentioned technology has yet 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 nano luminescent material, preparation methods
And semiconductor devices, it is intended to solve that existing nano luminescent material its luminescent properties are to be improved, can not meet semiconductor devices
The problem of requirement for nano luminescent material.
Technical scheme is as follows:
A kind of nano luminescent material, wherein, the monoatomic layer arranged successively in radial directions including at least two layers, adjacent list
The graded alloy component structure of level width variation or in the radial direction level width in the radial direction are formed between atomic layer
Consistent homogeneous components structure.
The nano luminescent material, wherein, graded alloy component structure, composition are formed between adjacent monoatomic layer
More outside level width is wider in radial directions for the corresponding level width of ingredient, and constituent in radial directions corresponds to
Energy level be continuous.
The nano luminescent material, wherein, in the nano luminescent material, positioned at the adjacent monatomic of center and surface
The wider graded alloy component structure of more outside level width in the radial direction is formed between layer, between center and surface
Adjacent monoatomic layer between form the consistent homogeneous components structure of level width;And adjacent monoatomic layer in radial directions
Energy level be continuous.
The nano luminescent material, wherein, the nano luminescent material includes two kinds of graded alloy component structures, wherein
A kind of wider graded alloy component structure of level width more outside in the radial direction formed between adjacent monoatomic layer, separately
A kind of narrower graded alloy component structure of level width more outside in the radial direction formed between adjacent monoatomic layer, institute
Two kinds of graded alloy component structures are stated radially to be alternately distributed successively;And the energy of adjacent monoatomic layer in radial directions
Grade is continuous.
The nano luminescent material, wherein, more outside energy level in the radial direction is formed between the adjacent monoatomic layer
The wider graded alloy component structure of width, and the energy level of adjacent monoatomic layer is discontinuous.
The nano luminescent material, wherein, more outside energy level in the radial direction is formed between the adjacent monoatomic layer
The narrower graded alloy component structure of width, and the energy level of adjacent monoatomic layer is discontinuous.
The nano luminescent material, wherein, the nano luminescent material includes graded alloy component structure and uniform group
Separation structure, wherein, it is wide that the graded alloy component structure forms more outside energy level in the radial direction between adjacent monoatomic layer
The wider graded alloy component structure of degree, the level width that the homogeneous components structure is formed between adjacent monoatomic layer are consistent
Homogeneous components structure, the inside of the nano luminescent material includes at least one layer of graded alloy component structure, the nanometer hair
The outside of luminescent material includes at least one layer of homogeneous components structure, and the energy level of monoatomic layer adjacent in radial directions is continuous
's.
The nano luminescent material, wherein, the nano luminescent material includes homogeneous components structure and graded alloy group
Separation structure, wherein, the consistent homogeneous components knot of level width that the homogeneous components structure is formed between adjacent monoatomic layer
Structure, the level width more outside in the radial direction that the graded alloy component structure is formed between adjacent monoatomic layer are wider
Graded alloy component structure, the inside of the nano luminescent material include at least one layer of homogeneous components structure, the nano luminescent
The outside of material includes at least one layer of graded alloy component structure, and the energy level of monoatomic layer adjacent in radial directions is to connect
Continuous.
The nano luminescent material, wherein, the nano luminescent material includes 2-20 layers of monoatomic layer or described receives
Rice luminescent material includes 1-10 layers of structure cell layer.
The nano luminescent material, wherein, the graded alloy component structure includes II races and VI races element;It is described equal
One component structure is the uniform alloy compositions structure comprising II races and VI races element.
The nano luminescent material, wherein, the glow peak wave-length coverage of the nano luminescent material for 400 nanometers extremely
700 nanometers.
The nano luminescent material, wherein, the peak width at half height of the glow peak of the nano luminescent material for 12 nanometers extremely
80 nanometers.
A kind of preparation method of nano luminescent 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 cation exchange reaction formation nano luminescent material occurs between the first compound and second of chemical combination object, it is described
The glow peak wavelength of nano luminescent material occur blue shift, red shift and it is constant in it is one or more.
The preparation method of the nano luminescent material, wherein, the first described compound and/or second of the chemical combination
The cationic presoma of object includes the presoma of Zn, and the presoma of the Zn is zinc methide, diethyl zinc, zinc acetate, acetyl
Acetone zinc, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, high chlorine
At least one of sour zinc, zinc sulfate, zinc oleate or zinc stearate.
The preparation method of the nano luminescent material, wherein, the first described compound and/or second of the chemical combination
The cationic presoma of object further includes the presoma of Cd, and the presoma of the Cd is dimethyl cadmium, diethyl cadmium, cadmium acetate, second
Acyl acetone cadmium, cadmium iodide, cadmium bromide, caddy, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium perchlorate, cadmium phosphate, sulphur
At least one of sour cadmium, cadmium oleate or cadmium stearate.
The preparation method of the nano luminescent material, wherein, the first described compound and/or second of the chemical combination
The anion presoma of object includes the presoma of Se, the presoma of the Se is Se-TOP, Se-TBP, Se-TPP, Se-ODE,
At least one of Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
The preparation method of the nano luminescent material, wherein, the first described compound and/or second of the chemical combination
The anion presoma of object further includes the presoma of S, the presoma of the S is S-TOP, S-TBP, S-TPP, S-ODE, S-OA,
At least one of S-ODA, S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide.
The preparation method of the nano luminescent material, wherein, the first described compound and/or second of the chemical combination
The anion presoma of object further includes the presoma of Te, the presoma of the Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE,
At least one of Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
The preparation method of the nano luminescent material, wherein, make the first compound and second in a heated condition
Cation exchange reaction occurs between chemical combination object.
The preparation method of the nano luminescent material, wherein, heating temperature is between 100 DEG C to 400 DEG C.
The preparation method of the nano luminescent material, wherein, heating time is in 2s between for 24 hours.
The preparation method of the nano luminescent material, wherein, when synthesizing the first compound, cationic predecessor with
The molar feed ratio of anion predecessor is 100:1 to 1:Between 50.
The preparation method of the nano luminescent material, wherein, when synthesizing second of compound, cationic presoma with
The molar ratio of anion presoma is 100:1 to 1:Between 50.
A kind of semiconductor devices, wherein, including as above any one of them nano luminescent material.
The semiconductor devices, wherein, the semiconductor devices is electroluminescent device, photo luminescent devices, the sun
Can be in battery, display device, photodetector, bioprobe and device for non-linear optical any one.
Advantageous effect:The present invention provides a kind of nano luminescent materials with graded alloy component from inside to outside radially
Material, not only realizes more efficient nano luminescent material luminous efficiency, while also can more meet semiconductor devices and accordingly show
Show comprehensive performance requirement of the technology to nano luminescent material, be a kind of suitable semiconductor devices and the preferable nanometer hair of display technology
Luminescent material.
Description of the drawings
Fig. 1 is a kind of level structure curve of nano luminescent material concrete structure 1 of the present invention.
Fig. 2 is a kind of level structure curve of nano luminescent material concrete structure 2 of the present invention.
Fig. 3 is a kind of level structure curve of nano luminescent material concrete structure 3 of the present invention.
Fig. 4 is a kind of level structure curve of nano luminescent material concrete structure 4 of the present invention.
Fig. 5 is a kind of level structure curve of nano luminescent material concrete structure 5 of the present invention.
Fig. 6 is a kind of level structure curve of nano luminescent material concrete structure 6 of the present invention.
Fig. 7 is a kind of level structure curve of nano luminescent material concrete structure 7 of the present invention.
Fig. 8 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 33.
Fig. 9 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 34.
Figure 10 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 35.
Figure 11 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 36.
Figure 12 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 37.
Figure 13 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 38.
Specific embodiment
The present invention provides a kind of nano luminescent material, preparation method and semiconductor devices, to make the purpose of the present invention, technology
Scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It is it should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
Nano luminescent material provided by the present invention is arranged monatomic successively in radial directions including at least two layers
Layer, level width changes in the radial direction graded alloy component structure or radial direction are formed between adjacent monoatomic layer
The consistent homogeneous components structure of upper level width.
That is nano luminescent material provided by the invention is made of multilayer monoatomic layer, and adjacent monoatomic layer it
Between may make up the wider graded alloy component structure of more outside level width in the radial direction, can also be configured in the radial direction
The narrower graded alloy component structure of more outside level width forms the consistent homogeneous components of level width in the radial direction
Structure.
Further, in nano luminescent material provided by the invention, in radial directions, the energy of adjacent monoatomic layer
Grade is continuous or discontinuous.
Radial direction herein refers to the center outwardly direction from nano luminescent material, it is assumed for example that nanometer of the invention
Luminescent material is spherical or similar spherical structure, then the radial direction refers to the direction along radius, in nano luminescent material
The heart(It is or internal)Refer to the center of its physical arrangement, the surface of nano luminescent material(It is or external)Refer to the table of its physical arrangement
Face.
Should be noted the above situation is preferable case, for the quantum-dot structure unit of graded alloy component structure,
Its component is alloy compositions;And for the quantum-dot structure unit of homogeneous components structure, component can be alloy group
Point or non-alloyed component, but currently preferred is alloy compositions, i.e., described homogeneous components structure is uniform alloy group
Separation structure, it is further preferred that comprising II races and VI races element, subsequent embodiment of the present invention is by taking uniform alloy compositions structure as an example
It illustrates, it will be clear that can equally implement for unalloyed homogeneous components structure.
Structure existing for nano luminescent material of the present invention is described in detail below:
Specifically, as shown in Figure 1, the present invention provides a kind of nano luminescent material with funnel type level structure, positioned at institute
It states the monoatomic layer alloy constituent inside nano luminescent material and corresponds to level width less than positioned at the monatomic laminated of outside
Golden constituent corresponds to level width, that is to say, that the nano luminescent material that Fig. 1 of the present invention is provided includes at least two layers radially
It is wider to form more outside level width in the radial direction between adjacent monoatomic layer for the monoatomic layer arranged successively on direction
Graded alloy component structure, and the energy level of monoatomic layer adjacent in radial directions is continuous;By Fig. 1 in subsequent embodiment
The structure of shown nano luminescent material is known as concrete structure 1.Nano luminescent material in Fig. 1, each adjacent monoatomic layer
Level width has continuous structure, i.e., the level width of each adjacent quantum-dot structure unit has the characteristics that consecutive variations,
Rather than mutation structure, that is to say, that the alloy compositions of nano luminescent material are also the subsequent continuous structure principle with continuity
It is identical.
Further, in radial directions in adjacent monoatomic layer, the monoatomic layer close to nano luminescent material center
Level width is less than the level width of the monoatomic layer far from nano luminescent material center;That is, the nano luminescent
In material, gradually broaden from the level width of center to face, so as to form the funnel type structure that opening becomes larger,
In opening become larger and refer in level structure as shown in Figure 1, from nano luminescent material center to nano luminescent material table
The energy level in face is continuous.Meanwhile the nano luminescent material in the present invention, the energy level of each adjacent monoatomic layer is continuous
, that is to say, that the synthesis component of nano luminescent material also has the characteristic of consecutive variations, and this characteristic is more advantageous to realizing high
Luminous efficiency.
That is, the concrete structure 1 of the nano luminescent material is with radially continuous from inside to outside
The quantum-dot structure of graded alloy component;This quantum-dot structure has radially continuous from inside to outside in constituent
The characteristics of variation;Correspondingly, energy level distribution on also on there are from inside to outside radially consecutive variations;This amount
Son point structure in constituent and the characteristics of consecutive variations in energy level distribution, relative to the quantum dot core with clear and definite boundary and
The relationship of shell, nano luminescent material of the invention not only contribute to realize more efficient luminous efficiency, while also can more meet half
The comprehensive performance requirement of conductor device and corresponding display technology to nano luminescent material, is a kind of suitable semiconductor devices and display
The preferable nano luminescent material of technology.
Further, in the nano luminescent material provided such as Fig. 1, the alloy compositions of A points are 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 closer to nano luminescent material center, and A
The composition of point and B points meets:x0 A>x0 B,y0 A >y0 B.That is, for any two points A points and B points in nano luminescent material,
And A points relative to B points closer to nano luminescent material center, thenx0 A>x0 B,y0 A >y0 B, i.e. the Cd contents of A points are more than B points
Cd contents, the Zn contents of A points 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 are less than B
The S contents of point.In this way, in the nano luminescent material, grading structure is just formd in radial directions, and due to radially
It is more outside on direction(I.e. far from nano luminescent material center)Then Cd and Se contents are lower, Zn and S contents are higher, then according to
The characteristic of these types of element, level width will be wider.
In the nano luminescent material of follow-up difference concrete structure, if graded alloy component structure is between adjacent monoatomic layer
The wider graded alloy component structure of level width more outside in the radial direction formed, then its alloy compositions be both preferably
Cdx0Zn1-x0Sey0S1-y0, wherein, the alloy compositions of A points are Cdx0 AZn1-x0 ASey0 AS1-y0 A, the alloy compositions of B points are
Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points expire relative to B points closer to nano luminescent material center, and the composition of A points and B points
Foot:x0 A>x0 B,y0 A >y0 B.What if graded alloy component structure was formed between adjacent monoatomic layer gets in the radial direction to external enwergy
The narrower graded alloy component structure of level width, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0, wherein, the conjunction of C points
Golden component is Cdx0 CZn1-x0 CSey0 CS1-y0 C, the alloy compositions of D points are Cdx0 DZn1-x0 DSey0 DS1-y0 D, wherein C points are relative to D points
Closer to nano luminescent material center, and the composition of C points and D points meets:x0 C<x0 D,y0 C<y0 D.If uniform alloy compositions structure
The consistent uniform alloy compositions structure of the level width that is formed between adjacent monoatomic layer, 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 expire relative to F points closer to nano luminescent material center, and the composition of E points and F points
Foot:x0 E=x0 F,y0 E=y0 F。
Further, as shown in Fig. 2, the present invention also provides a kind of nano luminescent material, wherein, it is described to be located at center and surface
Adjacent monoatomic layer between form the wider graded alloy component structure of more outside level width in the radial direction, in being located at
The consistent uniform alloy compositions structure of level width is formed between adjacent monoatomic layer between the heart and surface;And in radial direction
The energy level of upper adjacent monoatomic layer is continuous;The structure of nano luminescent material shown in Fig. 2 is known as having in subsequent embodiment
Body structure 2.
Specifically, as Fig. 2 provide nano luminescent material in, the adjacent monoatomic layer between center and surface
Between in the consistent uniform alloy compositions structure of the level width that forms, the alloy compositions of any point are Cdx1Zn1-x1Sey1S1-y1,
Wherein 0≤x1≤1,0≤y1≤1, and be 0 during x1 with y1 differences and be asynchronously 1, and x1 and y1 is fixed value.Such as certain
The alloy compositions of any 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 the homogeneous components of certain point are Cd in a certain uniform alloy compositions structure0.7Zn0.3S, it is another
The alloy compositions of point also should be Cd0.7Zn0.3S;In another example the homogeneous components of certain point are in a certain uniform alloy compositions structure
CdSe, and the alloy compositions of another point also should be CdSe in the uniform alloy compositions structure.
And the alloy compositions composition formed between center and the adjacent monoatomic layer on surface is Cdx2Zn1- x2Sey2S1-y2, wherein 0≤x2≤1,0≤y2≤1, and it is 0 during x2 with y2 differences and is asynchronously 1.Such as the conjunction of certain point
Golden component is Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point are Cd0.3Zn0.7Se0.4S0.6。
That is, in the nano luminescent material provided in Fig. 2, other sections in addition to containing uniform alloy compositions section
It is interior, along the corresponding level width of alloy constituent of quantum dot any point in the radial direction be greater than it is adjacent and closer to
The corresponding level width of alloy constituent of other points of nano luminescent material center.
Further, as shown in figure 3, the present invention also provides a kind of nanometers of the full graded alloy component with quantum well structure
Luminescent material;That is, nano luminescent material provided by the invention includes two kinds of two kinds of graded alloy component structures(A1 types
With A2 types), the graded alloy component structures of wherein A1 types formed between adjacent monoatomic layer in the radial direction more to
The wider graded alloy component structure of outer level width, the graded alloy component structures of the A2 types structure between adjacent monoatomic layer
Into the narrower graded alloy component structure of level width more outside in the radial direction, described two graded alloy component structure edges
Radial direction is alternately distributed successively, and the energy level of monoatomic layer adjacent in radial directions is continuous.It is that is, described
The monoatomic layer of nano luminescent material is distributed:A1, A2, A1, A2, A1 ... or A2, A1, A2, A1, A2 ..., i.e.,
The graded alloy component structure of starting can be A1 types or A2 types.In the graded alloy component structure of A1 types
In, level width is more more outside wider, in the graded alloy component structure of A2 types, level width be it is more outside more
Narrow, both level structures extend in radial directions like the form of wave, by nanometer shown in Fig. 3 in subsequent embodiment
The structure of luminescent material is known as concrete structure 3.
Further, as shown in figure 4, the present invention also provides a kind of full graded alloys of the quantum well structure with energy level mutation
The nano luminescent material of component specifically, it is wider to form more outside level width in the radial direction between adjacent monoatomic layer
Graded alloy component structure, and the energy level of adjacent monoatomic layer is discontinuous, i.e., the energy level of each adjacent monoatomic layer
Width has the characteristics that discontinuous variation, that is, has the characteristics that mutation, that is to say, that the alloy compositions of nano luminescent material are also tool
There is mutability, subsequent mutation structure principle is identical.The structure of nano luminescent material shown in Fig. 4 is known as having in subsequent embodiment
Body structure 4.
Specifically, the nano luminescent material described in Fig. 4 is arranged successively by way of mutation structure by multiple monoatomic layers
Into forming the graded alloy component structure that more outside level width is wider in the radial direction between these adjacent monoatomic layers.Into
One step, in the nano luminescent material, the level width close to the monoatomic layer at nano luminescent material center is less than far from nanometer
The level width of the monoatomic layer at luminescent material center.That is, in the nano luminescent material, from center to face
Level width gradually broadens, and so as to the funnel type structure that the opening for forming interruption becomes larger, opening therein gradually becomes
Refer to greatly in level structure as shown in Figure 4, from nano luminescent material center to the energy level in the direction on nano luminescent material surface
The variation tendency of width certainly, in the nano luminescent material, is also not limited to aforesaid way, i.e., deep single former
The level width of sublayer might be less that the level width by paracentral monoatomic layer, and in this structure, adjacent is monatomic
The level width of layer has the place being overlapping.
Further, as shown in figure 5, the full gradual change the present invention also provides another quantum well structure that there is energy level to be mutated is closed
The nano luminescent material of golden component specifically, it is narrower to form more outside level width in the radial direction between adjacent monoatomic layer
Graded alloy component structure, and the energy level of adjacent monoatomic layer is discontinuous;By nanometer shown in Fig. 5 in subsequent embodiment
The structure of luminescent material is known as concrete structure 5.
Specifically, the nano luminescent material described in Fig. 5 is arranged successively by way of mutation structure by multiple monoatomic layers
Into forming the graded alloy component structure that more outside level width is narrower in the radial direction between these adjacent monoatomic layers.Into
One step in the nano luminescent material, is more than deep monoatomic layer by the level width of paracentral monoatomic layer
Level width.That is, in the nano luminescent material, become narrow gradually from the level width of center to face, from
And the gradually smaller funnel type structure of opening of interruption is formed, opening narrows therein refer to energy level knot as shown in Figure 5
It is certainly, described from nano luminescent material center to the variation tendency of the level width in the direction on nano luminescent material surface in structure
Nano luminescent material in, be also not limited to aforesaid way, i.e., the level width of deep monoatomic layer can also be more than
By the level width of paracentral monoatomic layer, in this structure, the level width of adjacent monoatomic layer has what is be overlapping
Place.
Further, as shown in fig. 6, the present invention also provides a kind of nano luminescent material, specifically, the nano luminescent material
Including graded alloy component structure and uniform alloy compositions structure(A3 types and A4 types), wherein, the graded alloy of A3 types
The wider graded alloy component knot of level width more outside in the radial direction that component structure is formed between adjacent monoatomic layer
Structure, the consistent uniform alloy compositions of level width that the uniform alloy compositions structures of A4 types is formed between adjacent monoatomic layer
Structure, the inside of the nano luminescent material include at least one layer of graded alloy component structure, the nano luminescent material it is outer
Portion includes at least one layer of uniform alloy compositions structure, and the energy level of monoatomic layer adjacent in radial directions is continuous.Afterwards
The structure of nano luminescent material shown in Fig. 6 is known as concrete structure 6 in continuous embodiment.
Specifically, in nano luminescent material as shown in Figure 6, monoatomic layer is distributed as A3 ... A3A4 ... A4, i.e. institute
The inside for stating nano luminescent material is made of the graded alloy component structure of A3 types, the outside of the quanta point material be by
The uniform alloy compositions structure composition of A4 types, and the quantity of monoatomic layer and A4 classes in A3 type graded alloy component structures
The quantity of monoatomic layer in the uniform alloy compositions structure of type is all higher than being equal to 1.
Further, as shown in fig. 7, the present invention also provides a kind of level widths of inner alloy constituent to be uniform,
And the level width of outermost alloy constituent is by center to the external nano luminescent material to become larger;Specifically,
The nano luminescent material includes uniform alloy compositions structure and graded alloy component structure(Respectively A5 types and A6 types),
Wherein, the uniform alloy group of the level width that the uniform alloy compositions structure of A5 types is formed between adjacent monoatomic layer unanimously
Separation structure, the energy level more outside in the radial direction that the graded alloy component structure of A6 types is formed between adjacent monoatomic layer are wide
The wider graded alloy component structure of degree, the inside of the nano luminescent material include at least one layer of uniform alloy compositions structure,
The outside of the nano luminescent material includes at least one layer of graded alloy component structure, and adjacent monatomic in radial directions
The energy level of layer is continuous;The structure of nano luminescent material shown in Fig. 7 is known as concrete structure 7 in subsequent embodiment.
Specifically, in nano luminescent material as shown in Figure 7, monoatomic layer is distributed as A5 ... A5A6 ... A6, i.e. institute
The inside for stating nano luminescent material is made of the monoatomic layer in the uniform alloy compositions structure of A5 types, the nano luminescent material
The outside of material is made of the monoatomic layer in A6 type graded alloy component structures, and in the uniform alloy compositions structure of A5 types
The quantity of monoatomic layer and the quantity of the monoatomic layer in A6 type graded alloy component structures be all higher than be equal to 1.
Further, in the present invention, the graded alloy component structure includes II races and VI races element;The homogeneous components
Structure is the uniform alloy compositions structure comprising II races and VI races element.II races element include but not limited to Zn, Cd, Hg,
Cn etc.;VI races element includes but not limited to O, S, Se, Te, Po, Lv etc..
Further, nano luminescent material provided by the present invention includes 2-20 layers of monoatomic layer.Preferably, nano luminescent
Material 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 nano luminescent material can also be at least two layers structure cell layer arranged successively in radial directions,
It may make up graded alloy component structure or uniform alloy compositions structure between adjacent structure cell layer.
Further, the nano luminescent material 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 is
Minimum structural unit, i.e., its alloy compositions of each layer of structure cell layer are fixed, i.e., have identical lattice in each structure cell layer
Parameter and element.The nano luminescent material is the closed unit cell curved surface that forms of structure cell layer connection, between adjacent cell layer
Energy level is continuous or discontinuous.
Present invention nano luminescent material 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% can ensure quantum dot in the range of preferred photoluminescence quantum yield
Applications well.
Present invention nano luminescent material using the above structure, the glow peak wave-length coverage that can be realized for 400 nanometers extremely
700 nanometers, preferred glow peak wave-length coverage is 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can
Ensure that 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 nano luminescent material is 12 nanometers to 80 nanometers.
Nano luminescent material provided by the present invention has the advantages that:First, help to reduce to the full extent
Lattice tension between the quantum dot crystal of different-alloy component simultaneously alleviates lattice mismatch, so as to reduce the formation of boundary defect,
Improve the luminous efficiency of quantum dot.Second, the level structure that quanta point material provided by the present invention is formed is more advantageous to
Effective constraint to electron cloud in quantum dot greatly reduces diffusion probability of the electron cloud to quantum dot surface, so as to greatly press down
The auger recombination loss of quantum dot radiationless transition has been made, quantum dot has been reduced and flickers and improve quantum dot light emitting efficiency.Third, this
The level structure that the provided quanta point material of invention is formed is more advantageous to improving quantum dot light emitting layer electricity in semiconductor devices
The injection efficiency and efficiency of transmission of lotus;It can effectively avoid the aggregation of charge and resulting Exciton quenching simultaneously.4th,
The easily controllable diversity level structure that quanta point material provided by the present invention is formed can fully meet and dispenser
The level structure of other functional layers in part, to realize the matching of device entirety level structure, so as to help to realize efficient half
Conductor device.
The present invention also provides a kind of preparation method of nano luminescent 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 cation exchange reaction formation nano luminescent material occurs between the first compound and second of chemical combination object, it is described
The glow peak wavelength of nano luminescent material 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 nano luminescent material by the preparation method of the present invention
Material is specially successively grown using quantum dot and forms graded component transitional crust using quantum dot one-step synthesis.I.e. pre-
It positions the place of putting and successively forms two layers with identical or different-alloy component compound thin film, by making between two layers of compound
Cation exchange reaction occurs, is distributed so as to fulfill in the alloy compositions of pre-position.Repeating above procedure can be constantly real
The alloy compositions distribution of present radial direction pre-position.
Described the first compound and second of compound can be binary or binary more than compound.
Further, when blue shift occurs in the glow peak wavelength of the nano luminescent material, illustrate that glow peak is rectangular to shortwave
To movement, level width broadens;When red shift occurs in the glow peak wavelength of the nano luminescent material, glow peak is represented to long wave
Direction is moved, and level width narrows;When the glow peak wavelength of the nano luminescent material 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 may include the presoma of Se,
Such as Se arbitrarily combines formed compound with some organic matters, can be 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 arbitrarily combines formed compound, specifically S-TOP (sulfur-trioctylphosphine), S- with some organic matters
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
(sulfur-oleylamine) etc., but not limited to this;The presoma of the S be alkyl hydrosulfide (alkyl thiol), the alkane
Base mercaptan is hexyl mercaptan (hexanethiol), spicy thioalcohol (octanethiol), decyl mercaptan (decanethiol), dodecyl
Mercaptan (dodecanethiol), hexadecyl mercaptan (hexadecanethiol) or mercapto propyl silanes
At least one of (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.
Above-mentioned cation precursor and anion presoma can form to determine choosing according to final nano luminescent material
Select one or more therein:Such as it needs to synthesize CdxZn1-xSeyS1-yNano luminescent material when, then need Cd presoma,
The presoma of Zn, the presoma of Se, S presoma;If desired for synthesis CdxZn1-xDuring the nano luminescent material of S, then need Cd's
Presoma, the presoma of Zn, S presoma;If desired for synthesis CdxZn1-xDuring the nano luminescent material of Se, then before needing Cd
Drive the presoma of body, the presoma of Zn, Se.
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.
Heating temperature is higher, and the rate of cation exchange reaction is faster, the thickness range of cation exchange and exchange degree
Also it is 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 directly determine formed graded alloy component distribution.Cation exchange is formed gradually
Become alloy compositions distribution also to be determined by the binary or the thickness of multi-element compounds nano luminescent material that are respectively formed simultaneously.
When forming each layer compound, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:50(Tool
Molar feed ratio of the body for 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 nano luminescent material prepared by above-mentioned preparation method, glow peak wave-length coverage is received for 400 nanometers to 700
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
Nano luminescent material realizes the photoluminescence quantum yield more than 30% within this range.
Nano luminescent material prepared by method made above, photoluminescence quantum yield ranging from 1% to 100% are preferred to send out
Quantum yield ranging from 30% to 100% can ensure the applications well of quantum dot in the range of preferred photoluminescence quantum yield.
Further, in the present invention, the peak width at half height of the glow peak of the nano luminescent material is 12 nanometers to 80 nanometers.
Other than the nano luminescent material of the present invention is prepared according to above-mentioned preparation method, the present invention also provides another
The preparation method of nano luminescent material as described above, including step:
Pre-position adds in one or more kinds of cationic presomas in radial directions;It adds in simultaneously under certain condition
One or more kinds of anion presomas, makes cationic presoma react forming nano luminescent with anion presoma
Material, and there is blue shift and constant during the reaction in the glow peak wavelength of the nano luminescent material, so as to fulfill pre-
The graded alloy component distribution at place is put in positioning.
The difference of such method and former approach is, former is successively to form two layers of compound, Ran Houfa
Raw cation exchange reaction, is distributed so as to fulfill alloy compositions needed for the present invention, and later approach is directly controlled predetermined
The synthesis cationic presoma of alloy compositions and anion presoma needed for being added at position carry out reaction and form nano luminescent material
Material, is distributed so as to fulfill alloy compositions needed for the present invention.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-
Should, and during the reaction, cation exchange reaction occurs for different cations, so as to fulfill 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 the nano luminescent material of synthesis according to needed for specific it is different and different, with aforementioned former
Method is substantially the same, and is subsequently illustrated with specific embodiment.
The present invention also provides a kind of semiconductor devices, including as above any one of them nano luminescent material.
The semiconductor devices is electroluminescent device, photo luminescent devices, solar cell, display device, photoelectricity are visited
Survey any one in device, bioprobe and device for non-linear optical.
By taking electroluminescent device as an example, using nano luminescent material of the present invention as the quantum dot of emitting layer material electricity
Electroluminescence device.This quanta point electroluminescent device can be realized:1) high efficiency charge injection, 2) high brightness, 3) low
Driving voltage, 4) the excellent devices performance such as high device efficiency.Meanwhile nano luminescent material of the present invention, have and be easy to control
The characteristics of system and diversity level structure, can fully meet the level structure of other functional layers in simultaneously coordination device, to realize
The matching of device entirety level structure, so as to help to realize the semiconductor devices of efficient stable.
The photo luminescent devices refer to that relying on external light source is irradiated, and so as to obtain energy, generating excitation causes to send out
The device of light, ultraviolet radioactive, visible ray and infra-red radiation can cause luminescence generated by light, such as phosphorescence and fluorescence.The present invention's receives
Rice luminescent material can be as the luminescent material of photo luminescent devices.
The solar cell is also referred to as photovoltaic device, and nano luminescent material of the invention can be inhaled as the light of solar cell
Material is received, effectively improves the properties of photovoltaic device.
The display device refers to the display panel of backlight module or the application backlight module, and the display panel can be with
It applies in various products, such as display, tablet computer, mobile phone, laptop, flat panel TV, wearable display
Equipment or other include the products of different size display panels.
The photodetector refers to optical signal can be converted to the device of electric signal, and principle is to be caused to be shone by radiation
It penetrates material electric conductivity to change, nano luminescent material is applied in photodetector, there is following advantage:To vertical incidence
Photaesthesia, photoconductive response degree are high, specific detecivity is high, detection wavelength is continuously adjusted and can low temperature preparation.The photoelectricity of this structure
Detector in the process of running, quantum dot light photosensitive layer(Nano luminescent material i.e. using the present invention)Absorb the light generated after photon
Raw electron-hole pair can detach under the action of built in field, and it is lower that this so that the structure photodetector has
Driving voltage can just work, and easily controllable under low applying bias even 0 applying bias.
The bioprobe refers to modify certain class material, makes it have the device of mark function, such as to this hair
Bright nano luminescent material is coated, and so as to form fluorescence probe, is applied in cell imaging or substance detection field, phase
For traditional organic fluorescent dye probe, the bioprobe of nano luminescent material preparation using the present invention is strong with fluorescence
The characteristics of degree is high, chemical stability is good, anti-light bleaching power is strong, tool has been widely used.
The device for non-linear optical belongs to optical lasers technical field, using wide, such as opens the light for electric light
And Laser Modulation, the tuning of conversion, laser frequency for laser frequency;Carry out optical Information Processing, improve image quality and
Beam quality;As nonlinear etalon and bistable device;The highly excited level and high-resolution spectroscopy and object of research substance
Transfer process and other relaxation processes of matter internal energy and excitation etc..
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, form 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 nano luminescent material occurs(I.e. above-mentioned two layers of compound)Middle Cd
With the exchange of Zn ions;The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller,
It therefore can be in CdyZn1-ySebS1-bLayer and CdzZn1-zSecS1-cThe near interface of layer forms the graded alloy of Cd contents and Zn contents
Component is distributed, 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 nano luminescent material occurs(I.e.
Above-mentioned two layers of compound)The exchange of middle Cd and Zn ions;Due to the migration distance hair that the migration distance of cation is limited and more remote
The probability of migration is given birth to regard to smaller, therefore can be in CdyZn1-yS layers and CdzZn1-zS layers of near interface forms Cd contents and Zn contents
Graded alloy component 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, ectonexine nano luminescent material occurs
The exchange of middle Cd and Zn ions;The probability migrated due to the limited and more remote migration distance of migration distance of cation is more
It is small, therefore can be in CdyZn1-ySe layers and CdzZn1-zSe layers of near interface forms the graded alloy component of Cd contents and Zn contents
Distribution, 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 more remote 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 point of Zn contents
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 more remote migration distance of migration distance of son migrates, therefore can be in CdSe layers and ZnSe layer with regard to smaller
Near interface formed 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 more remote migration distance of migration distance with regard to smaller, therefore can be in CdSebS1-bLayer with
ZnSecS1-cThe near interface of layer formed 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 more remote 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 near formed Zn contents it is radially outward gradually decrease, the radially outward graded alloy component point gradually increased of Cd contents
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 more remote migration distance of migration distance of son migrates, therefore can be in ZnSe layer and CdSe layers with regard to smaller
Near interface formed 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 more remote migration distance of migration distance of son migrates, therefore can be in ZnSe with regard to smallerbS1-bLayer with
CdSecS1-cThe near interface of layer formed 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, 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 group 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 group 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:The influence that cadmium oleate charge velocity synthesizes the blue quantum dot with concrete structure 1
On the basis of embodiment 10, the graded of quantum dot component can be regulated and controled by the charge velocity for adjusting cadmium oleate
Slope, so as 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 generate 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 is 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 concrete 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:The influence that cadmium oleate injection rate synthesizes the blue quantum dot 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, so as 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 generate CdxZn1-xTemperature of reaction system after reacting 10 min, is down to 280 DEG C, then by 2mL by S
Trioctylphosphine sulfide presoma and 6mL cadmium oleates presoma reaction is injected into the rate of 3 mL/h and 10mL/h simultaneously respectively
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 group 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 group 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, treat 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 after reacting 10 min, is down to 280 DEG C, then by Se
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, 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 generate 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, 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 group 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, 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 presoma
It is continuously injected into 20 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 the rate of 0.4 mmol/h and 6 mmol/h in 1h to reaction system respectively.
After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification,
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 generate 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 group 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 generate 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 group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, 3 mL are vulcanized three
Octyl group phosphine presoma is continuously injected into the rate of 3 mL/h in 1h to reaction system, injects 20 in trioctylphosphine sulfide presoma
During min, 2 mL cadmium oleates presomas are injected into 6 mL/h in reaction system, inject 40 in trioctylphosphine sulfide presoma
During min, 4 mL cadmium oleates presomas are injected into 12 mL/h in reaction system.After reaction, treat that reaction solution is cooled to room
Product with toluene and absolute methanol is dissolved, 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, it is 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 generate 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 group 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 group 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 after reacting 10 min, is down to 280 DEG C, by selenium by Se
Change tri octyl phosphine-trioctylphosphine sulfide presoma to be added dropwise in reaction system with the rate of 4 mL/h.After reaction, it treats
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
Into under nitrogen atmosphere, and in preservation 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 is heated to reflux preserving 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, CdS is quickly generated, 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 simultaneously with the rate of 3 mL/h and 10 mL/h 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, CdSe is quickly generated, 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 sunk
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, CdSe is quickly generated, 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
The present embodiment light emitting diode with quantum dots, as shown in figure 8, including successively from bottom to top:ITO substrates 11, hearth electrode 12,
PEDOT:PSS hole injection layers 13, poly-TPD hole transmission layers 14, quantum dot light emitting layer 15, ZnO electron transfer layers 16 and Al
Top electrode 17.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows:
Hearth electrode 12,30 nm PEDOT are sequentially prepared on ITO substrates 11:13 and 30 nm poly-TPD of PSS hole injection layers
After hole transmission layer 14, one layer of quantum dot light emitting layer 15 is prepared on poly-TPD hole transmission layers 14, thickness is 20 nm, with
Prepare 40 nm ZnO electron transfer layers 16 and 100 nm Al top electrodes 17 on quantum dot light emitting layer 15 again afterwards.The quantum dot
The nano luminescent material of luminescent layer 15 is nano luminescent material as described in Example 1.
Embodiment 34
Light emitting diode with quantum dots in the present embodiment, as shown in figure 9, including successively from bottom to top:ITO substrates 21, hearth electrode 22,
PEDOT:PSS hole injection layers 23, Poly (9-vinylcarbazole) (PVK) hole transmission layer 24, quantum dot light emitting layer
25th, ZnO electron transfer layers 26 and Al top electrodes 27.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows:
Hearth electrode 22,30 nm PEDOT are sequentially prepared on ITO substrates 21:23 and 30 nm PVK holes of PSS hole injection layers
After transport layer 24, one layer of quantum dot light emitting layer 25 is prepared on PVK hole transmission layers 24, thickness is 20 nm, then again in quantum
40 nm ZnO electron transfer layers 26 and 100 nm Al top electrodes 27 are prepared on point luminescent layer 25.The quantum dot light emitting layer 25
Nano luminescent material is nano luminescent material as described embodiments.
Embodiment 35
The present embodiment light emitting diode with quantum dots as shown in Figure 10, includes successively from bottom to top:ITO substrates 31, hearth electrode 32,
PEDOT:PSS hole injection layers 33, poly-TPD hole transmission layers 34, quantum dot light emitting layer 35, TPBi electron transfer layers 36 and
Al top electrodes 37.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows:
Hearth electrode 32,30 nm PEDOT are sequentially prepared on ITO substrates 31:33 and 30 nm poly-TPD of PSS hole injection layers
After hole transmission layer 34, one layer of quantum dot light emitting layer 35 is prepared on poly-TPD hole transmission layers 34, thickness is 20 nm, with
30 nm TPBi electron transfer layers 36 are prepared by vacuum deposition method on quantum dot light emitting layer 35 again afterwards and 100 nm Al are pushed up
Electrode 37.The nano luminescent material of the quantum dot light emitting layer 35 is nano luminescent material as described embodiments.
Embodiment 36
The present embodiment light emitting diode with quantum dots as shown in figure 11, includes successively from bottom to top:ITO substrates 41, hearth electrode 42,
ZnO electron transfer layers 43, quantum dot light emitting layer 44, NPB hole transmission layers 45, MoO3Hole injection layer 46 and Al top electrodes 47.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows:
42,40 nm ZnO electron transfer layers 43 of hearth electrode are sequentially prepared on ITO substrates 41, on ZnO electron transfer layers 43
One layer of quantum dot light emitting layer 44 is prepared, thickness is 20 nm, then prepares 30 nm NPB holes by vacuum deposition method again
45,5 nm MoO of transport layer346 and 100 nm Al top electrodes 47 of hole injection layer.The nanometer hair of the quantum dot light emitting layer 44
Luminescent material is nano luminescent material as described embodiments.
Embodiment 37
The present embodiment light emitting diode with quantum dots as shown in figure 12, includes successively from bottom to top:Glass substrate 51, Al electrodes 52,
PEDOT:PSS hole injection layers 53, poly-TPD hole transmission layers 54, quantum dot light emitting layer 55, ZnO electron transfer layers 56 and
ITO top electrodes 57.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows:
100 nm Al electrodes 52 are prepared by vacuum deposition method in glass substrate 51, are then sequentially prepared 30 nm
PEDOT:After 53 and 30 nm poly-TPD hole transmission layers 54 of PSS hole injection layers, on poly-TPD hole transmission layers 54
One layer of quantum dot light emitting layer 55 is prepared, thickness is 20 nm, then prepares 40 nm ZnO electronics on quantum dot light emitting layer 55 again
Transport layer 56 prepares 120 nm ITO as top electrode 57 finally by sputtering method.The nanometer of the quantum dot light emitting layer 55
Luminescent material is nano luminescent material as described embodiments.
Embodiment 38
The present embodiment light emitting diode with quantum dots as shown in figure 13, includes successively from bottom to top:Glass substrate 61, Al electrodes 62,
ZnO electron transfer layers 63, quantum dot light emitting layer 64, NPB hole transmission layers 65, MoO3Hole injection layer 66 and ITO top electrodes 67.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows:
100 nm Al electrodes 62 are prepared by vacuum deposition method in glass substrate 61, are then sequentially prepared 40 nm ZnO
63,20 nm quantum dot light emitting layers 64 of electron transfer layer then prepare 30 nm NPB hole transports by vacuum deposition method again
65,5 nm MoO of layer3Hole injection layer 66 prepares 120 nm ITO as top electrode 67 finally by sputtering method.The amount
The nano luminescent material of son point luminescent layer is nano luminescent material as described embodiments.
It should be understood that the application of the present invention is not limited to the above, it for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (25)
1. a kind of nano luminescent material, which is characterized in that the monoatomic layer arranged successively in radial directions including at least two layers,
The graded alloy component structure or in the radial direction of the variation of level width in the radial direction is formed between adjacent monoatomic layer
The consistent homogeneous components structure of level width.
2. nano luminescent material according to claim 1, which is characterized in that gradual change is formed between adjacent monoatomic layer and is closed
Golden component structure, more outside level width is wider in radial directions, and in radial direction side for the corresponding level width of constituent
The corresponding energy level of upward constituent is continuous.
3. nano luminescent material according to claim 1, which is characterized in that in the nano luminescent material, positioned at center
The graded alloy component structure that more outside level width is wider in the radial direction is formed between the adjacent monoatomic layer on surface,
The consistent homogeneous components structure of level width is formed between adjacent monoatomic layer between center and surface;And in radial direction side
The energy level of adjacent monoatomic layer is continuous upwards.
4. nano luminescent material according to claim 1, which is characterized in that the nano luminescent material includes two kinds of gradual changes
Alloy compositions structure, the level width more outside in the radial direction that one of which is formed between adjacent monoatomic layer are wider gradually
Become alloy compositions structure, the level width more outside in the radial direction that another kind is formed between adjacent monoatomic layer is narrower gradually
Become alloy compositions structure, described two graded alloy component structures are radially alternately distributed successively;And in radial directions
The energy level of adjacent monoatomic layer is continuous.
5. nano luminescent material according to claim 1, which is characterized in that formed radially between the adjacent monoatomic layer
The wider graded alloy component structure of more outside level width on direction, and the energy level of adjacent monoatomic layer is discontinuous.
6. nano luminescent material according to claim 1, which is characterized in that formed radially between the adjacent monoatomic layer
The narrower graded alloy component structure of more outside level width on direction, and the energy level of adjacent monoatomic layer is discontinuous.
7. nano luminescent material according to claim 1, which is characterized in that the nano luminescent material includes graded alloy
Component structure and homogeneous components structure, wherein, the graded alloy component structure forms radial direction side between adjacent monoatomic layer
The wider graded alloy component structure of upward more outside level width, homogeneous components structure structure between adjacent monoatomic layer
Into the consistent homogeneous components structure of level width, the inside of the nano luminescent material includes at least one layer of graded alloy component
Structure, the outside of the nano luminescent material include at least one layer of homogeneous components structure, and single original adjacent in radial directions
The energy level of sublayer is continuous.
8. nano luminescent material according to claim 1, which is characterized in that the nano luminescent material includes homogeneous components
Structure and graded alloy component structure, wherein, the level width that the homogeneous components structure is formed between adjacent monoatomic layer
Consistent homogeneous components structure, the graded alloy component structure formed between adjacent monoatomic layer in the radial direction more to
The wider graded alloy component structure of outer level width, the inside of the nano luminescent material include at least one layer of homogeneous components knot
Structure, the outside of the nano luminescent material include at least one layer of graded alloy component structure, and list adjacent in radial directions
The energy level of atomic layer is continuous.
9. nano luminescent material according to claim 1, which is characterized in that the nano luminescent material includes 2-20 layers of list
Atomic layer or the nano luminescent material include 1-10 layers of structure cell layer.
10. nano luminescent material according to claim 1, which is characterized in that the graded alloy component structure includes II
Race and VI races element;The homogeneous components structure is the uniform alloy compositions structure comprising II races and VI races element.
11. nano luminescent material according to claim 1, which is characterized in that the luminous spike of the nano luminescent material
It is ranging from 400 nanometers to 700 nanometers long.
12. nano luminescent material according to claim 1, which is characterized in that the glow peak of the nano luminescent material
Peak width at half height is 12 nanometers to 80 nanometers.
13. a kind of preparation method of nano luminescent material as described in claim 1, which is characterized in that 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 cation exchange reaction formation nano luminescent material occurs between the first compound and second of chemical combination object, it is described
The glow peak wavelength of nano luminescent material occur blue shift, red shift and it is constant in it is one or more.
14. the preparation method of nano luminescent material according to claim 13, which is characterized in that the first described compound
And/or the cationic presoma of second of compound includes the presoma of Zn, the presoma of the Zn is zinc methide, two
Zinc ethyl, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, oxygen
Change at least one of zinc, zinc peroxide, zinc perchlorate, zinc sulfate, zinc oleate or zinc stearate.
15. the preparation method of nano luminescent material according to claim 13, which is characterized in that the first described compound
And/or the cationic presoma of second of compound further includes the presoma of Cd, the presoma of the Cd is dimethyl cadmium,
Diethyl cadmium, cadmium acetate, acetylacetone,2,4-pentanedione cadmium, cadmium iodide, cadmium bromide, caddy, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide,
At least one of cadmium perchlorate, cadmium phosphate, cadmium sulfate, cadmium oleate or cadmium stearate.
16. the preparation method of nano luminescent material according to claim 13, which is characterized in that the first described compound
And/or the anion presoma of second of compound includes the presoma of Se, the presoma of the Se is Se-TOP, Se-
At least one of TBP, Se-TPP, Se-ODE, Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
17. the preparation method of nano luminescent material according to claim 13, which is characterized in that the first described compound
And/or the anion presoma of second of compound further includes the presoma of S, the presoma of the S is S-TOP, S-
At least one of TBP, S-TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide.
18. the preparation method of nano luminescent material according to claim 13, which is characterized in that the first described compound
And/or the anion presoma of second of compound further includes the presoma of Te, the presoma of the Te is Te-TOP,
At least one of Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
19. the preparation method of nano luminescent material according to claim 13, which is characterized in that make in a heated condition
Cation exchange reaction occurs between a kind of compound and second of chemical combination object.
20. according to the preparation method of the nano luminescent material described in claim 19, which is characterized in that heating temperature at 100 DEG C extremely
Between 400 DEG C.
21. according to the preparation method of the nano luminescent material described in claim 19, which is characterized in that heating time is in 2s to for 24 hours
Between.
22. the preparation method of nano luminescent material according to claim 13, which is characterized in that synthesizing the first chemical combination
During object, the molar feed ratio of cationic predecessor and anion predecessor is 100:1 to 1:Between 50.
23. the preparation method of nano luminescent material according to claim 13, which is characterized in that synthesizing second of chemical combination
During object, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:Between 50.
24. a kind of semiconductor devices, which is characterized in that including such as claim 1 ~ 12 any one of them nano luminescent material.
25. semiconductor devices according to claim 24, which is characterized in that the semiconductor devices is electroluminescent cell
In part, photo luminescent devices, solar cell, display device, photodetector, bioprobe and device for non-linear optical
Any one.
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