CN108269934A - A kind of nano material, preparation method and semiconductor devices - Google Patents
A kind of nano material, preparation method and semiconductor devices Download PDFInfo
- Publication number
- CN108269934A CN108269934A CN201611260234.5A CN201611260234A CN108269934A CN 108269934 A CN108269934 A CN 108269934A CN 201611260234 A CN201611260234 A CN 201611260234A CN 108269934 A CN108269934 A CN 108269934A
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- China
- Prior art keywords
- nano material
- presoma
- nano
- zinc
- cadmium
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 79
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 79
- 239000002096 quantum dot Substances 0.000 claims description 123
- 239000011701 zinc Substances 0.000 claims description 101
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 150000001875 compounds Chemical class 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 47
- 150000001450 anions Chemical class 0.000 claims description 41
- 125000002091 cationic group Chemical group 0.000 claims description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229910052793 cadmium Inorganic materials 0.000 claims description 23
- 238000005341 cation exchange Methods 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 15
- -1 caddy Chemical compound 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 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
- 239000000126 substance Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 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
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000331 cadmium sulfate Inorganic materials 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 compound 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-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
- 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 4
- 229910000011 cadmium carbonate 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
- 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
- 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
- 238000000926 separation method Methods 0.000 claims description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims 1
- 239000010410 layer Substances 0.000 description 184
- 239000011669 selenium Substances 0.000 description 44
- 150000001768 cations Chemical class 0.000 description 29
- 230000005012 migration Effects 0.000 description 24
- 238000013508 migration Methods 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 18
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 230000005540 biological transmission Effects 0.000 description 16
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 14
- 239000005642 Oleic acid Substances 0.000 description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 14
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 14
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 230000027756 respiratory electron transport chain Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
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- 238000006862 quantum yield reaction Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005424 photoluminescence Methods 0.000 description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 229910052711 selenium Inorganic materials 0.000 description 8
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical class [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ZJGSVSYBKAZJGP-KVVVOXFISA-N (z)-octadec-9-enoic acid;zinc Chemical compound [Zn].CCCCCCCC\C=C/CCCCCCCC(O)=O ZJGSVSYBKAZJGP-KVVVOXFISA-N 0.000 description 7
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 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
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- GOBNDSNLXZYUHQ-UHFFFAOYSA-N selenium;tributylphosphane Chemical compound [Se].CCCCP(CCCC)CCCC GOBNDSNLXZYUHQ-UHFFFAOYSA-N 0.000 description 1
- SCTHSTKLCPJKPF-UHFFFAOYSA-N selenium;triphenylphosphane Chemical compound [Se].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SCTHSTKLCPJKPF-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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Classifications
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention discloses a kind of nano material, preparation method and semiconductor devices, wherein, the nano material includes N number of nano structured unit arranged successively in radial directions, wherein N >=2；The nano structured unit includes A1 and A2 types, and the A1 types are the consistent homogeneous components structure of level width in the radial direction；The A2 types are the wider graded alloy component structure of more outside level width in the radial direction；The inside of the nano material is made of the nano structured unit of at least one layer of A1 types, and the outside of the nano material is made of the nano structured unit of at least one layer of A2 types；In radial directions in adjacent nano structured unit, it is not more than the level width of the nano structured unit far from nano material center close to the level width of the nano structured unit at nano material center, and the energy level of the nano structured unit of adjacent graded alloy component structure is continuous.
Description
Technical field
The present invention relates to a kind of quantum dot field more particularly to nano 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 and the search time as Application of micron in QLED devices and corresponding display technology
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 CdS quantum dots
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.
The quanta point material that can be applied to the exploitation of high-performance QLED devices is mainly the quantum dot of nucleocapsid, core and shell
Fixed and nucleocapsid has clear and definite boundary, such as quantum dot (the J. Phys. with CdSe/ZnS nucleocapsids to ingredient respectively
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 material, preparation method and half
Conductor device, it is intended to solve that existing nano material its luminescent properties are to be improved, can not meet semiconductor devices for nanometer
The problem of requirement of material.
Technical scheme is as follows：
A kind of nano material, wherein, the nano material includes N number of nano structured unit arranged successively in radial directions,
Wherein N >=2；
The nano structured unit includes A1 and A2 types, uniform group consistent for level width in the radial direction of the A1 types
Separation structure；The A2 types are the wider graded alloy component structure of more outside level width in the radial direction；
The inside of the nano material is made of the nano structured unit of at least one layer of A1 types, the outside of the nano material by
The nano structured unit composition of at least one layer of A2 types；
In radial directions in adjacent nano structured unit, close to the level width of the nano structured unit at nano material center
No more than the level width of the nano structured unit far from nano material center, and the nanometer of adjacent graded alloy component structure
The energy level of structural unit is continuous.
The nano material, wherein, the quantum-dot structure unit of the A1 types is comprising II races and VI races element
Uniform alloy compositions structure, the quantum-dot structure unit of the A2 types is the graded alloy component comprising II races and VI races element
Structure.It should be noted that the above situation is preferable case, for the quantum-dot structure unit of graded alloy component structure,
Component is alloy compositions；And for the quantum-dot structure unit of homogeneous components structure, component can be alloy compositions,
Can also be alloy compositions, but currently preferred is alloy compositions, i.e., described homogeneous components structure is uniform alloy compositions knot
Structure, it is further preferred that comprising II races and VI races element, subsequent embodiment of the present invention is carried out by taking uniform alloy compositions structure as an example
Illustrate, it will be clear that can equally implement for unalloyed homogeneous components structure.
The nano material, wherein, the alloy compositions of the nano structured unit of the A1 types are Cdx0Zn1- x0Sey0S1-y0, wherein 0≤x0≤1,0≤y0≤1, and it is 0 during x0 with y0 differences and is asynchronously 1, and x0 and y0 are corresponding
It is fixed value in the nano structured unit of A1 types.
The nano material, wherein, the alloy compositions composition of the nano structured unit of the A2 types is Cdx1Zn1- x1Sey1S1-y1, wherein 0≤x1≤1,0≤y1≤1, and it is 0 during x1 with y1 differences and is asynchronously 1.
The nano material, wherein, in the nano structured unit of the A2 types, the alloy compositions of A points are respectively
Cd x1 AZn1- x1 ASe y1 AS1- y1 A, the alloy compositions of B points are Cd x1 BZn1- x1 BSe y1 BS1- y1 B, wherein A points relative to B points more
Close to nano material center, and the composition of A points and B points meets：x1 A> x1 B,y1 A> y1 B。
The nano material, wherein, the nano structured unit includes 2-20 layers of monoatomic layer or the nanometer
Structural unit includes 1-10 layers of structure cell layer.
The nano material, wherein, two of adjacent nano structured unit intersection are monatomic in radial directions
Two structure cells of continuous alloy compositions structure or nano structured unit intersection adjacent in radial directions are formed between layer
Continuous alloy compositions structure is formed between layer.
The nano material, wherein, the glow peak wave-length coverage of the nano material is 400 nanometers to 700 nanometers.
The nano material, wherein, the peak width at half height of the glow peak of the nano material is 12 nanometers to 80 nanometers.
A kind of preparation method of nano 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 material, the nanometer occur between the first compound and second of chemical combination object
The glow peak wavelength of material is first constant, blue shift then occurs.
The preparation method of the nano material, wherein, the first described compound and/or second of compound
Cationic presoma includes the presoma of Zn, and the presoma of the Zn is zinc methide, diethyl zinc, zinc acetate, acetylacetone,2,4-pentanedione
Zinc, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate,
At least one of zinc sulfate, zinc oleate or zinc stearate.
The preparation method of the nano material, wherein, the first described compound and/or second of compound
Cationic presoma includes the presoma of Cd, and 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, cadmium perchlorate, cadmium phosphate, cadmium sulfate, oil
At least one of sour cadmium or cadmium stearate.
The preparation method of the nano material, wherein, the first described compound and/or second of compound
Anion presoma includes the presoma of Se, the presoma of the Se is Se-TOP, Se-TBP, Se-TPP, Se-ODE, Se-OA,
At least one of Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
The preparation method of the nano material, wherein, the first described compound and/or second of compound
Anion presoma includes the presoma of S, the presoma of the S is S-TOP, S-TBP, S-TPP, S-ODE, S-OA, S-ODA,
At least one of S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide.
The preparation method of the nano material, wherein, the first described compound and/or second of compound
Anion presoma includes the presoma of Te, the presoma of the Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA,
At least one of Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
The preparation method of the nano material, wherein, make the first compound and second of chemical combination in a heated condition
Cation exchange reaction occurs between object.
The preparation method of the nano material, wherein, heating temperature is between 100 DEG C to 400 DEG C.
The preparation method of the nano material, wherein, heating time is in 2s between for 24 hours.
The preparation method of the nano material, wherein, when synthesizing the first compound, cationic presoma with it is cloudy from
The molar ratio of sub- presoma is 100:1 to 1:Between 50.
The preparation method of the nano material, wherein, when synthesizing second of compound, cationic presoma with it is cloudy from
The molar ratio of sub- presoma is 100:1 to 1:Between 50.
A kind of semiconductor devices, wherein, including as above any one of them nano 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 nanometers with full graded alloy component from inside to outside radially
Material not only realizes more efficient luminous efficiency, while also can more meet semiconductor devices and corresponding display technology to receiving
The comprehensive performance requirement of rice material is the preferable nano material of a kind of suitable semiconductor devices and display technology.
Description of the drawings
Fig. 1 is a kind of level structure curve of nano material preferred embodiment of the present invention.
Fig. 2 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 13.
Fig. 3 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 14.
Fig. 4 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 15.
Fig. 5 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 16.
Fig. 6 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 17.
Fig. 7 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 18.
Specific embodiment
The present invention provides a kind of nano material, preparation method and semiconductor devices, to make the purpose of the present invention, technical solution
And effect is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
A kind of nano material provided by the present invention, wherein, the nano material is arranged successively in radial directions including N number of
The nano structured unit of cloth, wherein N >=2；
The nano structured unit includes A1 and A2 types, the A1 types uniform conjunction consistent for level width in the radial direction
Golden component structure；The A2 types are the wider graded alloy component structure of more outside level width in the radial direction；Herein
Radial direction refers to the center outwardly direction from nano material, it is assumed for example that nano material of the invention is spherical or similar ball
Shape structure, then the radial direction refers to the direction along radius, and the center of nano material refers to the center of its physical arrangement, nanometer
The surface of material refers to the surface of its physical arrangement.
The inside of the nano material is made of the nano structured unit of at least one layer of A1 types, outside the nano material
Portion is made of the nano structured unit of at least one layer of A2 types；
In radial directions in adjacent nano structured unit, close to the level width of the nano structured unit at nano material center
No more than the level width of the nano structured unit far from nano material center, and the nanometer of adjacent graded alloy component structure
The energy level of structural unit is continuous；That is when the outside of the luminescent material includes the nano junction of at least two layers A2 type
During structure unit, then the energy level of the nano structured unit of the adjacent A2 types is continuous；It is i.e. each adjacent in the present invention
The level width of the nano structured unit of graded alloy component structure has the characteristics that consecutive variations rather than mutation structure, also
It is to say that the external synthesis component of nano material has continuity, this characteristic is more advantageous to realizing high luminous efficiency.
Nano material in the present invention, belongs to Quantum Well, and level structure is as shown in Figure 1.I.e. described receives
In rice material, nano structured unit is distributed as A1 ... A1A2 ... A2, i.e., the inside of described nano material is by A1 types
Nano structured unit forms, the outside of the nano material is made of the nano structured unit of A2 types, and A1 types are received
The quantity of rice structural unit and the quantity of the nano structured unit of A2 types are all higher than being equal to 1；
In the nano structured unit of A1 types, level width is uniform；In the nano structured unit of A2 types, energy
Level width is more more outside wider；In radial directions in adjacent nano structured unit, by paracentral nano structured unit
Level width is not more than the level width of deep nano structured unit；And the level width tool of adjacent nanostructures unit
There is continuous structure.The level structure of Fig. 1 is referred to as Quantum Well in a particular embodiment.
Further, the alloy nanostructures unit includes II races and VI races element, i.e., the nanostructured of described A1 types
Unit is the uniform alloy compositions structure comprising II races and VI races element；The nano structured unit of the A2 types is includes II races
With the graded alloy component structure of VI races elements.II races element includes but not limited to Zn, Cd, Hg, Cn etc..The VI races member
Element includes but not limited to O, S, Se, Te, Po, Lv etc..
Further, the alloy compositions of the nano structured unit of the A1 types are Cdx0Zn1-x0Sey0S1-y0, wherein 0≤x0
≤ 1,0≤y0≤1, and be 0 during x0 with y0 differences and be asynchronously 1, and x0 and y0 is in the nanostructured list of corresponding A1 types
It is fixed value in first.Such as the alloy compositions of certain point are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point also should be
Cd0.5Zn0.5Se0.5S0.5。
Further, the alloy compositions composition of the nano structured unit of the A2 types is Cdx1Zn1-x1Sey1S1-y1, wherein 0
≤ x1≤1,0≤y1≤1, and be 0 during x1 with y1 differences and be asynchronously 1.Such as the alloy compositions of certain point are
Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point are Cd0.3Zn0.7Se0.4S0.6。
Specifically, in the nano structured unit of the A2 types, the alloy compositions of A points are Cd x1 AZn1- x1 ASey1 AS1- y1 A, the alloy compositions of B points are Cd x1 BZn1- x1 BSe y1 BS1- y1 B, wherein A points are relative to B points closer to nano material
Center, and the composition of A points and B points meets：x1 A> x1 B,y1 A> y1 B.That is, for appointing in A2 type nano structured units
Anticipate 2 point A points and B points, and A points relative to B points closer to the center of nano material, thenx1 A> x1 B,y1 A > y1 B, i.e. the Cd of A points
Content is more than the Cd contents of B points, and 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, A points
S contents be less than B points S contents.In this way, in A2 type nano structured units, graded junction is just formd in radial directions
Structure, and due in radial directions, it is more outside（That is the center far from nano material）Then Cd and Se contents are lower, and Zn and S contain
Amount is higher, then according to the characteristic of these types of element, level width will be wider.
Further, the nano structured unit includes 2-20 layers of monoatomic layer.That is, each nano structured unit wraps
Containing 2-20 layers of monoatomic layer.Preferably 2 monoatomic layers to 5 monoatomic layers, the preferred number of plies can ensure quantum dot
Realize good photoluminescence quantum yield and efficient charge injection efficiency.
Further, each monoatomic layer in A1 types and A2 type nano structured units is minimum structural unit,
Its alloy compositions of i.e. each layer of single atomic layer are fixed, and may be formed gradually between two adjacent monoatomic layers
Become alloy compositions structure, for example, in the nano structured unit of A2 types, the monoatomic layer far from nano material center, Cd
Low with Se contents, Zn and S contents are high, and the monoatomic layer close to nano material center, Cd and Se contents are low, Zn and S contents are high,
So as to form graded alloy component structure.But in the nano structured unit of A1 types, its alloy group of each layer of monoatomic layer
Split-phase is same, to form uniform alloy compositions structure.
Alternatively, the A1 types and A2 types nano structured unit include 1-10 layers of structure cell layer, i.e., each nano junction
Structure unit includes 1-10 layers of structure cell layer, such as includes 2-5 layers of structure cell layer.Structure cell layer is minimum structural unit, i.e., each
The structure cell layer of layer, alloy compositions are fixed, i.e., have identical lattice parameter and element in each structure cell layer.Each nanometer
Structural unit be structure cell layer it is continuously coupled and form closed unit cell curved surface.
Further, two lists of the nano structured unit intersection of adjacent graded alloy component structure in radial directions
Continuous alloy compositions structure is formed between atomic layer.That is, the nano structured unit intersection of two graded alloy component structures
Between two monoatomic layers be continuous alloy compositions structure namely its level width be also gradual change rather than mutation.Or
Person, in radial directions shape between two structure cell layers of the quantum-dot structure unit intersection of adjacent graded alloy component structure
Into continuous alloy compositions structure.The nano structured unit of adjacent graded alloy component structure mentioned above is adjacent A2 classes
The nano structured unit of type.
That is, the nano material of the present invention, has from inside to outside between adjacent A2 type nano structured units
Continuous alloy compositions radially.This quantum-dot structure has in constituent radially to be connected from inside to outside
The characteristics of continuous variation, relative to the quantum dot core on clear and definite boundary and the relationship of shell, nano material of the invention is not only advantageous
In the more efficient luminous efficiency of realization, while it also can more meet the synthesis of semiconductor devices and corresponding display technology to nano material
Performance requirement is a kind of suitable semiconductor devices and the preferable CdS quantum dots of display technology.
The nano material of the present invention using the above structure, the photoluminescence quantum yield that can be realized ranging from 1% to 100% are excellent
The photoluminescence quantum yield of choosing ranging from 30% to 100% can ensure the good of quantum dot in the range of preferred photoluminescence quantum yield
Application.
The nano material of the present invention using the above structure, the glow peak wave-length coverage that can be realized are 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 material realizes the photoluminescence quantum yield more than 30% within this range.
In the present invention, the peak width at half height of the glow peak of the nano material is 12 nanometers to 80 nanometers.
Nano material provided by the present invention has the advantages that：First, help to reduce difference to the full extent
Lattice tension between the quantum dot crystal of alloy compositions simultaneously alleviates lattice mismatch, so as to reduce the formation of boundary defect, improves
The luminous efficiency of quantum dot.Second, the level structure that nano material provided by the present invention is formed is more advantageous to quantum
Effective constraint of electron cloud in point greatly reduces diffusion probability of the electron cloud to quantum dot surface, thus the greatly amount of inhibiting
The auger recombination loss of son point radiationless transition, reduces quantum dot and flickers and improve quantum dot light emitting efficiency.Third, institute of the present invention
The level structure that the nano material of offer is formed is more advantageous to improving the injection of quantum dot light emitting layer charge in semiconductor devices
Efficiency and efficiency of transmission；It can effectively avoid the aggregation of charge and resulting Exciton quenching simultaneously.4th, institute of the present invention
The easily controllable diversity level structure that the quanta point material of offer is formed can fully meet and other in coordination device
The level structure of functional layer, to realize the matching of device entirety level structure, so as to help to realize efficient semiconductor devices.
A kind of preparation method of nano 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 material, the nanometer occur between the first compound and second of chemical combination object
The glow peak wavelength of material is first constant, blue shift then occurs.
Quantum dot SILAR synthetic methods incorporating quantum point one-step synthesis is generated nano material by the preparation method of the present invention,
It is specially successively grown using quantum dot and forms graded component transitional crust using quantum dot one-step synthesis.It is being pre-positioned
Putting place and successively being formed two layers has identical or different-alloy component compound thin film, is occurred between two layers of compound by making
Cation exchange reaction is distributed so as to fulfill in the alloy compositions of pre-position.Repeating above procedure can constantly realize
The alloy compositions distribution of radial direction pre-position.
Described the first compound and second of compound can be binary or binary more than compound.
Further, blue shift after the glow peak wavelength of the nano material is first constant, energy is represented if glow peak wavelength is constant
Level width is constant, and glow peak is represented if there is blue shift and is moved to shortwave direction, i.e., level width broadens, as shown in Figure 1, measuring
In the radial direction, constant in first interval level width, level width broadens son point in second interval（Blue shift）.
The cationic presoma of the first described compound and/or second of compound includes：The presoma of Zn, institute
The presoma for stating Zn is zinc methide（dimethyl Zinc）, diethyl zinc（diethyl Zinc）, zinc acetate（Zinc
acetate）, zinc acetylacetonate（Zinc acetylacetonate）, zinc iodide（Zinc iodide）, zinc bromide（Zinc
bromide）, zinc chloride（Zinc chloride）, zinc fluoride（Zinc fluoride）, zinc carbonate（Zinc carbonate）、
Zinc cyanide（Zinc cyanide）, zinc nitrate（Zinc nitrate）, zinc oxide（Zinc oxide）, zinc peroxide（Zinc
peroxide）, zinc perchlorate（Zinc perchlorate）, zinc sulfate（Zinc sulfate）, zinc oleate（Zinc oleate）
Or zinc stearate（Zinc stearate）At least one of Deng, but not limited to this.
The cationic presoma of the first described compound and/or second of compound includes the presoma of Cd, institute
The presoma for stating Cd is dimethyl cadmium（dimethyl cadmium）, diethyl cadmium（diethyl cadmium）, cadmium acetate
（cadmium acetate）, acetylacetone,2,4-pentanedione cadmium（cadmium acetylacetonate）, cadmium iodide（cadmium iodide）、
Cadmium bromide（cadmium bromide）, caddy（cadmium chloride）, cadmium fluoride（cadmium fluoride）, carbon
Sour cadmium（cadmium carbonate）, cadmium nitrate（cadmium nitrate）, cadmium oxide（cadmium oxide）, perchloric acid
Cadmium（cadmium perchlorate）, cadmium phosphate（cadmium phosphide）, cadmium sulfate（cadmium sulfate）, oil
Sour cadmium（cadmium oleate）Or cadmium stearate（cadmium stearate）At least one of Deng, but not limited to this.
The anion presoma of the first described compound and/or second of compound includes the presoma of Se, example
As Se with some organic matters arbitrarily combines formed compound, 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 can be with alkyl hydrosulfide (alkyl thiol), institute
State alkyl hydrosulfide can be hexyl mercaptan (hexanethiol), spicy thioalcohol (octanethiol), decyl mercaptan (decanethiol),
Lauryl 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 includes the presoma of Te, institute
The presoma for stating Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA
At least one of.
Above-mentioned cation precursor and anion presoma can form to determine to select it according to final nano material
One or more of：Such as when needing to synthesize the nano material of CdxZn1-xSeyS1-y, then the presoma of Cd, Zn are needed
Presoma, the presoma of Se, S presoma；If desired for synthesis CdxZn1-xS nano material when, then need Cd presoma,
The presoma of Zn, the presoma of S；If desired for synthesis CdxZn1-xSe nano material when, then before needing the presoma of Cd, Zn
Drive the presoma of body, Se.
In the preparation process in accordance with the present invention, the condition that cation exchange reaction occurs preferably carries out heating reaction, such as
Heating temperature is between 100 DEG C to 400 DEG C, between preferred heating temperature is 150 DEG C to 380 DEG C.Heating time is in 2s to for 24 hours
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 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 material prepared by above-mentioned preparation method, glow peak wave-length coverage is 400 nanometers to 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 quantum
Point realizes the photoluminescence quantum yield more than 30% within this range.
Nano material prepared by method made above, photoluminescence quantum yield ranging from 1% to 100%, preferred luminous quantity
Sub- yield ranging from 30% to 100% can ensure the applications well of quantum dot in the range of preferred photoluminescence quantum yield.
Other than the nano material of the present invention is prepared according to above-mentioned preparation method, the present invention also provides another as above
The preparation method of the nano material, 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 nanometer material with anion presoma
Material, and the glow peak wavelength of the nano material during the reaction first it is constant after there is blue shift, so as to fulfill in specific bit
Put the graded alloy component distribution at place.
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 graded alloy component, and later approach is directly controlled in pre-position
The synthesis cationic presoma of alloy compositions and anion presoma needed for adding in carry out reaction and form nano material, so as to real
Existing graded alloy component distribution of the present invention.For later approach, reaction principle be the high cationic presoma of reactivity and
Anion presoma first reacts, and reacts after the low cationic presoma of reactivity and anion presoma, and
During the reaction, cation exchange reaction occurs for different cations, is distributed so as to fulfill graded alloy component of the present invention.Extremely
It has been described in detail in preceding method in the type of cationic presoma and anion presoma.As for reaction temperature, reaction time
With proportioning etc. can the nano material of synthesis according to needed for specific it is different and different, with aforementioned former approach substantially phase
Together, it is subsequently illustrated with specific embodiment.
The present invention also provides a kind of semiconductor devices, including as above any one of them nano 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, the electroluminescent hair of quantum dot using nano material of the present invention as emitting layer material
Optical 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 material of the present invention, have easily controllable and various
The characteristics of performance level structure, can fully meet the level structure of other functional layers in simultaneously coordination device, to realize device entirety
The matching of 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 material can be as the luminescent material of photo luminescent devices.
The solar cell is also referred to as photovoltaic device, and nano material of the invention can be as the light absorption material of solar cell
Material 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, quanta point material is applied in photodetector, there is following advantage：To vertical incidence light
Sensitive, photoconductive response degree height, specific detecivity are high, detection wavelength is continuously adjusted and can low temperature preparation.The photoelectricity of this structure is visited
Survey device in the process of running, quantum dot light photosensitive layer（Nano material i.e. using the present invention）Absorb the photoproduction electricity generated after photon
To can be detached under the action of built in field, this causes the structure photodetector to have lower driving in son-hole
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 material is coated, and so as to form fluorescence probe, is applied in cell imaging or substance detection field, relative to
Traditional organic fluorescent dye probe, bioprobe prepared by nano material using the present invention have fluorescence intensity height, chemistry
The characteristics of 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 nanocrystal occurs（I.e. above-mentioned two layers of compound）Middle Cd and Zn
The exchange of ion；The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller,
It can be in CdyZn1-ySebS1-bLayer and CdzZn1-zSecS1-cThe near interface of layer forms the graded alloy component of Cd contents and Zn contents
Distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1,0≤a≤1.
Embodiment 2：Preparation based on CdZnS/CdZnS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion S is injected into reaction system,
It is initially formed CdyZn1-yS layers（Wherein 0≤y≤1）；Continue by the presoma of cationic Cd, cation Zn presoma and it is cloudy from
The presoma of sub- S is injected into reaction system, can be in above-mentioned CdyZn1-yS layer surfaces form CdzZn1-zS layers（Wherein 0≤z≤1,
And z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, ectonexine nanocrystal occurs（It is i.e. above-mentioned
Two layers of compound）The exchange of middle Cd and Zn ions；Since the limited and more remote migration distance of the migration distance of cation is moved
The probability of shifting, therefore can be in Cd with regard to smalleryZn1-yS layers and CdzZn1-zS layers of near interface forms Cd contents and Zn contents gradually
Become alloy compositions distribution, i.e. CdxZn1-xS, wherein 0≤x≤1.
Embodiment 3：Preparation based on CdZnSe/CdZnSe quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion Se is injected into reaction system
It is initially formed CdyZn1-ySe layers（Wherein 0≤y≤1）；Continue the presoma and the moon of the presoma of cationic Cd, cation Zn
The presoma of ion Se is injected into reaction system, can be in above-mentioned CdyZn1-ySe layer surfaces form CdzZn1-zSe layers（Wherein 0≤z
≤ 1, and z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, Cd in ectonexine nanocrystal occurs
With the exchange of Zn ions；The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller,
It therefore can be in CdyZn1-ySe layers and CdzZn1-zSe layers of near interface forms the graded alloy component point of Cd contents and Zn contents
Cloth, i.e. CdxZn1-xSe, wherein 0≤x≤1.
Embodiment 4：Preparation based on CdS/ZnS quantum dots
First the presoma of the presoma of cationic Cd and anion S is injected into reaction system, is initially formed CdS layer；Continuing will
The presoma of cationic Zn and the presoma of anion S are injected into reaction system, can form ZnS layers on above-mentioned CdS layer surface；
Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd
Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation
The probability that migrates of the limited and 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 Quantum Well
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 11：The preparation of green quantum dot with Quantum Well
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 12：The preparation of red quantum dot with Quantum Well
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 13
The present embodiment light emitting diode with quantum dots, as shown in Fig. 2, 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 material of luminescent layer 15 is nano material as described in Example 10.
Embodiment 14
Light emitting diode with quantum dots in the present embodiment, as shown in figure 3, 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 material is nano material as described in Example 11.
Embodiment 15
The present embodiment light emitting diode with quantum dots, as shown in figure 4, including 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 material of the quantum dot light emitting layer 35 is nano material as described in Example 12.
Embodiment 16
The present embodiment light emitting diode with quantum dots, as shown in figure 5, including 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 material of the quantum dot light emitting layer 44
Expect for nano material as described in Example 10.
Embodiment 17
The present embodiment light emitting diode with quantum dots, as shown in fig. 6, including 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
Material is nano material as described in Example 11.
Embodiment 18
The present embodiment light emitting diode with quantum dots, as shown in fig. 7, including 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 material of son point luminescent layer is nano material as described in Example 12.
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 (22)
1. a kind of nano material, which is characterized in that the nano material includes N number of nano junction arranged successively in radial directions
Structure unit, wherein N >=2；
The nano structured unit includes A1 and A2 types, uniform group consistent for level width in the radial direction of the A1 types
Separation structure；The A2 types are the wider graded alloy component structure of more outside level width in the radial direction；
The inside of the nano material is made of the nano structured unit of at least one layer of A1 types, the outside of the nano material by
The nano structured unit composition of at least one layer of A2 types；
In radial directions in adjacent nano structured unit, close to the level width of the nano structured unit at nano material center
No more than the level width of the nano structured unit far from nano material center, and the quantum of adjacent graded alloy component structure
The energy level of point structural unit is continuous.
2. nano material according to claim 1, which is characterized in that the quantum-dot structure unit of the A1 types be comprising
II races and the uniform alloy compositions structure of VI races element, the quantum-dot structure unit of the A2 types is comprising II races and VI races member
The graded alloy component structure of element.
3. nano material according to claim 2, which is characterized in that the alloy group of the nano structured unit of the A1 types
It is divided into Cdx0Zn1-x0Sey0S1-y0, wherein 0≤x0≤1,0≤y0≤1, and it is 0 during x0 with y0 differences and is asynchronously 1, and x0
With y0 in the nano structured unit of corresponding A1 types be fixed value.
4. nano material according to claim 2, which is characterized in that the alloy group of the nano structured unit of the A2 types
It is grouped into Cdx1Zn1-x1Sey1S1-y1, wherein 0≤x1≤1,0≤y1≤1, and it is 0 during x1 with y1 differences and is asynchronously 1.
5. nano material according to claim 4, which is characterized in that in the nano structured unit of the A2 types, A points
Alloy compositions are respectively Cd x1 AZn1- x1 ASe y1 AS1- y1 A, the alloy compositions of B points are Cd x1 BZn1- x1 BSe y1 BS1- y1 B, wherein A
It puts relative to B points closer to nano material center, and the composition of A points and B points meets：x1 A> x1 B,y1 A> y1 B。
6. nano material according to claim 1, which is characterized in that the nano structured unit includes 2-20 layers of single original
Sublayer or the nano structured unit include 1-10 layers of structure cell layer.
7. nano material according to claim 6, which is characterized in that adjacent nano structured unit is handed in radial directions
Continuous alloy compositions structure or nano structured unit adjacent in radial directions are formed between two monoatomic layers at boundary
Continuous alloy compositions structure is formed between two structure cell layers of intersection.
8. nano material according to claim 1, which is characterized in that the glow peak wave-length coverage of the nano material is
400 nanometers to 700 nanometers.
9. nano material according to claim 1, which is characterized in that the peak width at half height of the glow peak of the nano material is
12 nanometers to 80 nanometers.
10. a kind of preparation method of nano 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 material, the nanometer occur between the first compound and second of chemical combination object
The glow peak wavelength of material is first constant, blue shift then occurs.
11. the preparation method of nano material according to claim 8, which is characterized in that the first described compound and/or
The cationic presoma of second of compound includes the presoma of Zn, and the presoma of the Zn is zinc methide, diethyl
Zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide,
At least one of zinc peroxide, zinc perchlorate, zinc sulfate, zinc oleate or zinc stearate.
12. the preparation method of nano material according to claim 8, which is characterized in that the first described compound and/or
The cationic presoma of second of compound includes the presoma of Cd, and 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, perchloric acid
At least one of cadmium, cadmium phosphate, cadmium sulfate, cadmium oleate or cadmium stearate.
13. the preparation method of nano material according to claim 10, 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-TBP,
At least one of Se-TPP, Se-ODE, Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
14. the preparation method of nano material according to claim 10, which is characterized in that the first described compound and/
Or the anion presoma of second of compound includes the presoma of S, the presoma of the S is S-TOP, S-TBP, S-
At least one of TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide.
15. the preparation method of nano material according to claim 10, which is characterized in that the first described compound and/
Or the anion presoma of second of compound includes the presoma of Te, the presoma of the Te is Te-TOP, Te-TBP,
At least one of Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
16. the preparation method of nano material according to claim 10, which is characterized in that make the first in a heated condition
Cation exchange reaction occurs between compound and second of chemical combination object.
17. the preparation method of nano material according to claim 16, which is characterized in that heating temperature is at 100 DEG C to 400
Between DEG C.
18. the preparation method of nano material according to claim 16, which is characterized in that heating time 2s to for 24 hours it
Between.
19. the preparation method of nano material according to claim 10, which is characterized in that synthesizing the first compound
When, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:Between 50.
20. the preparation method of nano material according to claim 10, which is characterized in that synthesizing second of compound
When, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:Between 50.
21. a kind of semiconductor devices, which is characterized in that including such as claim 1 ~ 9 any one of them nano material.
22. semiconductor devices according to claim 21, 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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| CN201611260234.5A CN108269934A (en) | 2016-12-30 | 2016-12-30 | A kind of nano material, preparation method and semiconductor devices |
| PCT/CN2017/080621 WO2018120516A1 (en) | 2016-12-30 | 2017-04-14 | Nanomaterial, manufacturing method, and semiconductor device |
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| US20110311453A1 (en) * | 2003-05-07 | 2011-12-22 | Indiana University Research And Technology Corporation | Alloyed semiconductor quantum dots and concentration-gradient alloyed quantum dots, series comprising the same and methods related thereto |
| WO2008038970A1 (en) * | 2006-09-25 | 2008-04-03 | Seoul National University Industry Foundation | Quantum dots having composition gradient shell structure and manufacturing method thereof |
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