CN108695137A - A kind of crosslinked nano-particles film and preparation method and film light electronic device - Google Patents
A kind of crosslinked nano-particles film and preparation method and film light electronic device Download PDFInfo
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- CN108695137A CN108695137A CN201710233270.0A CN201710233270A CN108695137A CN 108695137 A CN108695137 A CN 108695137A CN 201710233270 A CN201710233270 A CN 201710233270A CN 108695137 A CN108695137 A CN 108695137A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 154
- 239000007789 gas Substances 0.000 claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229960004424 carbon dioxide Drugs 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 235000013339 cereals Nutrition 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 150000001298 alcohols Chemical group 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 150000003346 selenoethers Chemical class 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000004033 diameter control Methods 0.000 claims 1
- 238000005036 potential barrier Methods 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 34
- 239000011787 zinc oxide Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910015711 MoOx Inorganic materials 0.000 description 4
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910003087 TiOx Inorganic materials 0.000 description 2
- 229910007667 ZnOx Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 2
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical group Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02557—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/0256—Selenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02601—Nanoparticles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention discloses a kind of crosslinked nano-particles film and preparation method and film light electronic device, wherein including:In a solvent by nano particle dispersion, it and stirs evenly, obtains nanoparticles solution;Nanometer particle film is made in nanoparticles solution by solwution method, and is passed through combination gas, promotes cross-linking reaction, obtains crosslinked nano-particles film.The present invention is used when nano particle forms a film, and is passed through combination gas, is promoted to be cross-linked with each other between particle, and thus being electrically coupled between increase particle, reduces the potential barrier of carrier transport, increase carrier mobility, to significantly promote electric property.
Description
Technical field
The present invention relates to device field of film preparation more particularly to a kind of crosslinked nano-particles film and preparation method with it is thin
Film opto-electronic device.
Background technology
Oxide nano particles(Or spherical oxide is nanocrystalline)With good crystallization degree, it ensure that itself and body material
Material(Low-dimensional materials)Similar optics, electrical properties;On the other hand, since the effect of nano-particles self assemble film forming is fine, make
The coating preparation process of low cost can be applied.During opto-electronic device prepared by solwution method, nano particle is to be formed
One of the important solutions of corresponding oxide film.Common example includes zinc oxide(ZnOx)Nano particle, titanium oxide
(TiOx)Semiconductor of the film of particle in light emitting diode, thin-film solar cells, thin film transistor (TFT) as transmission electronics
Material;Nickel oxide(NiOx)As the semi-conducting material of transporting holes in same device.
Nevertheless, the film of formation is mutually accumulated between nano particle and body material film still has difference, this master
It is embodied in the transmission characteristic of carrier.Although having good crystallinity, such structure office inside nano particle
Limit, even if in the case of solid matter, is often filled out by the surface ligand to insulate in the range of Nano grade between nano particle
It fills and is filled even without any substance.In this way, there are quite high carrier transport potential barriers, carrier to receive between nano particle
Transmission inside rice grain film can only follow the rule of great-jump-forward transmission, this leads to the load that material is shown under film scale
It flows transport factor and is much smaller than corresponding body material film.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of crosslinked nano-particles film and preparations
Method and film light electronic device, it is intended to the carrier transport potential barrier for solving existing device film is higher, carrier mobility compared with
Low problem.
Technical scheme is as follows:
A kind of preparation method of crosslinked nano-particles film, wherein including:
Step A, in a solvent by nano particle dispersion, it and stirs evenly, obtains nanoparticles solution;
Step B, nanoparticles solution is made by nanometer particle film by solwution method, and is passed through combination gas, promote crosslinking anti-
It should occur, obtain crosslinked nano-particles film.
The preparation method of the crosslinked nano-particles film, wherein the combination gas includes reducibility gas, oxygen
Gas and water vapour and carbon dioxide.
The preparation method of the crosslinked nano-particles film, wherein reducibility gas bias voltage control 1 ~ 100Pa it
Between, oxygen partial is controlled 0 ~ 2 × 104Between Pa, steam bias voltage control is 0 ~ 2 × 103Between Pa, carbon dioxide bias voltage control
Between 0 ~ 100Pa.
The preparation method of the crosslinked nano-particles film, wherein in the step A, the nanoparticles solution
Mass concentration is 1 ~ 100mg/ml.
The preparation method of the crosslinked nano-particles film, wherein the nano particle is oxide nano particles, sulphur
It is one or more in compound nano particle, selenides nano particle, nitride nano particle, fluoride nano granule.
The preparation method of the crosslinked nano-particles film, wherein the average diameter of the nano particle is controlled in 5nm
Within.
The preparation method of the crosslinked nano-particles film, wherein the solvent is alcohols solvent.
The preparation method of the crosslinked nano-particles film, wherein the step B is specifically included:
Step B1, nanoparticles solution is placed in closed environment first, nanoparticles solution is made up of solwution method and is received
Rice grain film;
Step B2, and then into closed environment it is passed through combination gas, promotes cross-linking reaction, it is thin to obtain crosslinked nano-particles
Film.
The preparation method of the crosslinked nano-particles film, wherein the step B is specifically included:
Step B1 ', nanoparticles solution is placed in inert gas environment first, nanoparticles solution is made up of solwution method
Nanometer particle film;
Step B2 ' and then nanometer particle film is placed in closed environment, combination gas is passed through into closed environment, promoted
Make cross-linking reaction, obtains crosslinked nano-particles film.
The preparation method of the crosslinked nano-particles film, wherein the reducibility gas be carbon monoxide, hydrogen and
One kind in ammonia.
The preparation method of the crosslinked nano-particles film, wherein in the step B, the crosslinked nano-particles are thin
The thickness of film is 15 ~ 60nm.
A kind of crosslinked nano-particles film, wherein using the preparation of any one of them crosslinked nano-particles film as above
Method is prepared.
A kind of film light electronic device, wherein including crosslinked nano-particles film as described above.
The film light electronic device, wherein the film light electronic device be electroluminescent device, film photovoltaic,
Any one in thin-film photodetector, thin film transistor (TFT).
Advantageous effect:The present invention makes to be cross-linked with each other between particle when nano particle forms a film, to increase the electricity between particle
Coupling is learned, the potential barrier of carrier transport is reduced, increases carrier mobility, to significantly promote electric property, is prepared
The nanometer particle film gone out can be obviously improved the performance of film light electronic device.
Description of the drawings
Fig. 1 is the structural schematic diagram of existing uncrosslinked Zinc oxide nanoparticle film.
Fig. 2 is the structural schematic diagram of crosslinking-oxidization zinc nanoparticles film prepared by the method for the present invention.
Fig. 3 is different films to ITO/NPB/MoOxThe current -voltage curve schematic diagram of/Al devices.
Specific implementation mode
A kind of crosslinked nano-particles film of present invention offer and preparation method and film light electronic device, to make the present invention's
Purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that this place is retouched
The specific embodiment stated is only used to explain the present invention, is not intended to limit the present invention.
A kind of preparation method preferred embodiment of crosslinked nano-particles film of the present invention, wherein including:
Step A, in a solvent by nano particle dispersion, it and stirs evenly, obtains nanoparticles solution;
The step A in a solvent by nano particle dispersion, and is stirred specifically, by the proportioning that mass concentration is 1 ~ 100mg/ml
Mix the nanoparticles solution prepared to being uniformly mixed and obtain using for solwution method film forming.Wherein, the nano particle can be
Oxide nano particles, sulfide nanoparticle, selenides nano particle, nitride nano particle, the fluoride of broad-band gap are received
One or more in rice grain, the oxide nano particles can be but be not limited to ZnOx(Such as ZnO),TiOx(Such as TiO2)
One kind in;One kind that the sulfide nanoparticle can be but be not limited in zinc sulphide, molybdenum sulfide;The selenides is received
One kind that rice grain can be but be not limited in zinc selenide, lead selenide;The nitride nano particle can be but be not limited to nitrogen
One kind in SiClx, aluminium nitride;One kind that the fluoride nano granule can be but be not limited in lanthanum fluoride, sodium fluoride.This
The size of invention control nano particle, preferably by the control of the average diameter of spherical nanoparticles within 5nm, to ensure having foot
Amount surface state metallic atom can participate in reacting.The solvent can be alcohols solvent, such as methanol, ethyl alcohol.
Step B, nanoparticles solution is made by nanometer particle film by solwution method, and is passed through combination gas, promote to hand over
Join reaction, obtains crosslinked nano-particles film.For the present invention by solwution method deposition film, the solwution method can be rotation
Painting, inkjet printing, spraying, blade coating etc..
Specifically, the combination gas includes reducibility gas, oxygen, steam and carbon dioxide.Preferably, reproducibility gas
Body(Such as carbon monoxide, hydrogen or ammonia)Between 1 ~ 100Pa, oxygen partial is controlled 0 ~ 2 × 10 bias voltage control4Pa it
Between, steam bias voltage control is 0 ~ 2 × 103Between Pa, carbon dioxide bias voltage control is between 0 ~ 100Pa.The present invention controls and film
The combination gas of contact, preferably by the combination gas contacted with film control in above-mentioned bias range, this is because inclined at this
Manufactured film consistency can be higher in pressure range, and carrier electrons mobility also can be higher in film.
The condition for crosslinking reaction to above-mentioned all types of nano particles below is described in detail.
1, oxide nano particles
When nano particle is Zinc oxide nanoparticle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias voltage control
Between 1 ~ 100Pa, oxygen partial is controlled 0 ~ 1 × 103Between Pa, steam bias voltage control is 0 ~ 1 × 103Between Pa, titanium dioxide
Carbon bias voltage control is between 0 ~ 100Pa.Manufactured film consistency can be higher in the bias range, carrier electrons in film
Mobility also can be higher.
When nano particle is Titanium dioxide nanoparticle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias
Between 1 ~ 100Pa, oxygen partial is controlled 0 ~ 1 × 10 for control4Between Pa, steam bias voltage control is 0 ~ 2 × 103Between Pa, two
Carbonoxide bias voltage control is between 0 ~ 100Pa.Manufactured film consistency can be higher in the bias range, carrier in film
Electron mobility also can be higher.
When nano particle is nickel oxide nanoparticle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias
Between 1 ~ 100Pa, oxygen partial is controlled 0 ~ 5 × 10 for control3Between Pa, steam bias voltage control is 0 ~ 2 × 103Between Pa, two
Carbonoxide bias voltage control is between 0 ~ 100Pa.Manufactured film consistency can be higher in the bias range, carrier in film
Electron mobility also can be higher.
2, sulfide nanoparticle
When nano particle is zine sulfide nano particles, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias voltage control
Between 1 ~ 100Pa, oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is 0 ~ 2 × 103Between Pa, carbon dioxide it is inclined
Voltage-controlled system is between 0 ~ 100Pa.Manufactured film consistency can be higher in the bias range, and carrier electrons migrate in film
Rate also can be higher.
When nano particle is molybdenum sulfide nanoparticles, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias
Control is between 1 ~ 100Pa, and oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is 0 ~ 2 × 103Between Pa, titanium dioxide
Carbon bias voltage control is between 0 ~ 100Pa.Manufactured film consistency can be higher in the bias range, carrier electrons in film
Mobility also can be higher.
3, selenides nano particle
When nano particle is selenizing zinc nanoparticles, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias voltage control
Between 1 ~ 100Pa, oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is 0 ~ 1 × 102Between Pa, carbon dioxide it is inclined
Voltage-controlled system is between 0 ~ 10Pa.Manufactured film consistency can be higher in the bias range, and carrier electrons migrate in film
Rate also can be higher.
When nano particle is lead selenide nano particle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias
Control is between 1 ~ 100Pa, and oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is inclined less than 0.1Pa, carbon dioxide
Voltage-controlled system is between 0 ~ 100Pa.Manufactured film consistency can be higher in the bias range, and carrier electrons migrate in film
Rate also can be higher.
4, nitride nano particle
When nano particle is silicon nitride nano particles, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias voltage control
Between 1 ~ 100Pa, oxygen partial is controlled in 0.1 ~ 1Pa, and steam bias voltage control is 0 ~ 2 × 103Between Pa, carbon dioxide bias
Control is between 0 ~ 100Pa.In addition, nitrogen is maintained at 1 × 105Pa or so.The manufactured film consistency in the bias range
Can be higher, carrier electrons mobility also can be higher in film.
When nano particle is aluminum nitride nanometer particle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias
Control is between 1 ~ 100Pa, and oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is 0 ~ 2 × 103Between Pa, titanium dioxide
Carbon bias voltage control is between 10 ~ 100Pa.In addition, nitrogen is maintained at 1 × 105Pa or so.The manufactured film in the bias range
Consistency can be higher, and carrier electrons mobility also can be higher in film.
5, fluoride nano granule
When nano particle is lanthanum fluoride nano particle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias voltage control
Between 1 ~ 100Pa, oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is 0 ~ 1 × 102Between Pa, carbon dioxide it is inclined
Voltage-controlled system is between 0 ~ 10Pa.Manufactured film consistency can be higher in the bias range, and carrier electrons migrate in film
Rate also can be higher.
When nano particle is sodium fluoride nano particle, by reducibility gas(Such as carbon monoxide, hydrogen or ammonia)Bias
Control is between 1 ~ 100Pa, and oxygen partial is controlled less than 0.1Pa, and steam bias voltage control is 0 ~ 2 × 103Between Pa, titanium dioxide
Carbon bias voltage control is between 10 ~ 100Pa.Manufactured film consistency can be higher in the bias range, carrier electricity in film
Transport factor also can be higher.
The present invention makes nano particle be cross-linked with each other in film forming, and crosslinking refers to having substance to fill and pass through between nano particle
Chemical bond makes nano particle connect.Correspondingly, the object connected not over chemical bond between uncrosslinked nano particle
Matter.The consistency and carrier mobility of respective films can be improved by above-mentioned cross-linking method in the present invention.
Nanoparticles solution can be directly prepared into nanometer particle film by the present invention under non-vacuum condition, specifically, described
Step B is specifically included:
Step B1, nanoparticles solution is placed in closed environment first, nanoparticles solution is made up of solwution method and is received
Rice grain film;
Step B2, and then into closed environment it is passed through combination gas, promotes cross-linking reaction, it is thin to obtain crosslinked nano-particles
Film.
Above-mentioned steps are nanometer particle film to be made in nanoparticles solution under closed non-vacuum condition, then
It is passed through said combination gas in the environment closed toward this, promotes cross-linking reaction, obtains crosslinked nano-particles film.
It, can also first under inert gas conditions the present invention is not limited to which crosslinked nano-particles film is made under above-mentioned gas environment
After nanometer particle film is made, obtained nanometer particle film is placed in closed environment, then passes to combination gas and promote
Cross-linking reaction occurs, and obtains crosslinked nano-particles film.Specifically, the step B is specifically included:
Step B1 ', nanoparticles solution is placed in inert gas environment first, nanoparticles solution is made up of solwution method
Nanometer particle film;
Step B2 ' and then nanometer particle film is placed in closed environment, combination gas is passed through into closed environment, promoted
Make cross-linking reaction, obtains crosslinked nano-particles film.
After the above-mentioned cross-linking reaction of the present invention, processing also is dried to crosslinked nano-particles film, finally obtains thickness
Degree is the crosslinked nano-particles film of 15 ~ 60nm.Wherein boiling point of the drying temperature higher than solvent in nanoparticles solution;According to film
Thickness, drying time are more than every 50 nanometers of 15 minutes.
The present invention also provides a kind of crosslinked nano-particles films, wherein uses any one of them crosslinking nano as above
The preparation method of grain film is prepared.
Common nanometer particle film is formed by mutually not crosslinked nano-particles self assemble, and the present invention is used in nanometer
When grain film forming, it is passed through combination gas, promotes to be cross-linked with each other between particle, thus being electrically coupled between increase particle, reduces and carry
The potential barrier of stream transmission, increases carrier mobility, to significantly promote electric property.The crosslinking nano that will so obtain
Grain film is applied in light emitting diode prepared by such as solwution method, thin-film solar cells, optical detector, thin film transistor (TFT),
The performance of above-mentioned device can be obviously improved.
It is to existing uncrosslinked Zinc oxide nanoparticle film and square through the invention below by taking Zinc oxide nanoparticle as an example
The performance of crosslinking-oxidization zinc nanoparticles film prepared by method is tested.In conjunction with Fig. 1-3, Fig. 1 is existing uncrosslinked zinc oxide
The structural schematic diagram of nanometer particle film, Fig. 2 are that the structure of crosslinking-oxidization zinc nanoparticles film prepared by the method for the present invention is shown
It is intended to, Fig. 3 is different films to ITO/NPB/MoOxThe current -voltage curve schematic diagram of/Al devices.It will be seen from figure 1 that not
The substance connected not over chemical bond between crosslinked nano particle 1;Figure it is seen that having between nano particle 2
Substance 3 fills and so that nano particle 2 is connected by chemical bond.Since the zinc oxide of addition is to ITO/NPB/MoOxThis knot of/Al
The electric current of structure has very effective inhibiting effect, can judge that ZnO nano particle is thin by observing the whether increased mode of electric current
Film is detached from either with or without in soaking process.From figure 3, it can be seen that crosslinking ZnO nano particle film is whether molten by alcohols
Agent(Such as ethyl alcohol)It impregnates, electric current is held at relatively low numerical value, this illustrates to be crosslinked ZnO nano particle film not in soaking process
It is detached from so that ZnO is to ITO/NPB/MoOxThe electric current of this structure of/Al plays apparent inhibiting effect;And uncrosslinked ZnO
Nanometer particle film passes through alcohols solvent(Such as ethyl alcohol)After immersion, electric current significantly increases, this illustrates uncrosslinked ZnO nano particle
Film falls off in soaking process, and the electric current of response device is made significantly to increase, and close proximity to not adding, ZnO nano particle is thin
The device of film.Therefore, the crosslinking-oxidization zinc nanoparticles film obtained after Zinc oxide nanoparticle crosslinking is in former solvent(Refer to dispersion
The solvent used when Zinc oxide nanoparticle, typically alcohols solvent)It is detached from without obviously dissolving or substance after middle immersion;Phase
Instead, non-crosslinked nanometer particle film is easy to fall off after immersion.
The present invention also provides a kind of film light electronic devices, wherein including crosslinked nano-particles film as described above.Tool
Body, the film light electronic device is appointing in electroluminescent device, film photovoltaic, thin-film photodetector, thin film transistor (TFT)
Meaning is a kind of.
The present invention makes nano particle crosslinking that can increase the consistency of film and increases mobility of the carrier in film.
Crosslinked nanometer particle film is applied can improve load in electroluminescent device prepared by solwution method as electron transfer layer
Quantum balancing is flowed, luminous efficiency and device lifetime are improved;It is applied and is used as electron-transport in film photovoltaic prepared by solwution method
Layer can significantly reduce the linear resistance of device, improve parallel resistance, improve the energy conversion efficiency of device;It is applied molten
Electric current can be reduced as electronics abstraction, layer and hole blocking layer in thin-film photodetector prepared by liquid method, improves detectivity;It will
It applies the carrier mobility that semiconductor layer can be improved in thin film transistor (TFT) prepared by solwution method, increases source drain
Electric current improves response frequency.
In conclusion a kind of crosslinked nano-particles film provided by the invention and preparation method and film light electronic device,
The present invention is used when nano particle forms a film, and is passed through combination gas, is promoted to be cross-linked with each other between particle, thus between increase particle
Be electrically coupled, reduce the potential barrier of carrier transport, increase carrier mobility, to significantly promote electric property.It will be as
This crosslinked nano-particles film obtained is applied in film light electronic device prepared by solwution method, and device can be significantly improved
Performance.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (14)
1. a kind of preparation method of crosslinked nano-particles film, which is characterized in that including:
Step A, in a solvent by nano particle dispersion, it and stirs evenly, obtains nanoparticles solution;
Step B, nanoparticles solution is made by nanometer particle film by solwution method, and is passed through combination gas, promote crosslinking anti-
It should occur, obtain crosslinked nano-particles film.
2. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that
The combination gas includes reducibility gas, oxygen, steam and carbon dioxide.
3. the preparation method of crosslinked nano-particles film according to claim 2, which is characterized in that reducibility gas bias
Between 1 ~ 100Pa, oxygen partial is controlled 0 ~ 2 × 10 for control4Between Pa, steam bias voltage control is 0 ~ 2 × 103Between Pa, two
Carbonoxide bias voltage control is between 0 ~ 100Pa.
4. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that in the step A, institute
The mass concentration for stating nanoparticles solution is 1 ~ 100mg/ml.
5. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that the nano particle is
In oxide nano particles, sulfide nanoparticle, selenides nano particle, nitride nano particle, fluoride nano granule
It is one or more.
6. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that the nano particle
Average diameter controls within 5nm.
7. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that the solvent is alcohols
Solvent.
8. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that the step B is specific
Including:
Step B1, nanoparticles solution is placed in closed environment first, nanoparticles solution is made up of solwution method and is received
Rice grain film;
Step B2, and then into closed environment it is passed through combination gas, promotes cross-linking reaction, it is thin to obtain crosslinked nano-particles
Film.
9. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that the step B is specific
Including:
Step B1 ', nanoparticles solution is placed in inert gas environment first, nanoparticles solution is made up of solwution method
Nanometer particle film;
Step B2 ' and then nanometer particle film is placed in closed environment, combination gas is passed through into closed environment, promoted
Make cross-linking reaction, obtains crosslinked nano-particles film.
10. the preparation method of crosslinked nano-particles film according to claim 2, which is characterized in that the reproducibility gas
Body is one kind in carbon monoxide, hydrogen and ammonia.
11. the preparation method of crosslinked nano-particles film according to claim 1, which is characterized in that in the step B,
The thickness of the crosslinked nano-particles film is 15 ~ 60nm.
12. a kind of crosslinked nano-particles film, which is characterized in that using such as claim 1 ~ 11 any one of them crosslinking nano
The preparation method of particle film is prepared.
13. a kind of film light electronic device, which is characterized in that including crosslinked nano-particles film as claimed in claim 12.
14. film light electronic device according to claim 13, which is characterized in that the film light electronic device is electroluminescent
Any one in luminescent device, film photovoltaic, thin-film photodetector, thin film transistor (TFT).
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| CN201710233270.0A CN108695137B (en) | 2017-04-11 | 2017-04-11 | Cross-linked nano-particle film, preparation method thereof and film optoelectronic device |
| EP18784835.3A EP3611756A4 (en) | 2017-04-11 | 2018-03-14 | Crosslinked nanoparticle thin film and preparation method therefor, and thin film optoelectronic device |
| KR1020197028863A KR102260236B1 (en) | 2017-04-11 | 2018-03-14 | Cross-linked nanoparticle thin film and manufacturing method and thin film optoelectronic device |
| PCT/CN2018/079025 WO2018188448A1 (en) | 2017-04-11 | 2018-03-14 | Crosslinked nanoparticle thin film and preparation method therefor, and thin film optoelectronic device |
| JP2020502747A JP7075476B2 (en) | 2017-04-11 | 2018-03-14 | Cross-linked nanoparticle thin film and manufacturing method, and thin film optoelectronic device |
| US16/603,772 US20200313089A1 (en) | 2017-04-11 | 2018-03-14 | Crosslinked nanoparticle thin film, preparation method thereof, and thin film optoelectronic device having the same |
| US17/874,934 US11778891B2 (en) | 2017-04-11 | 2022-07-27 | Crosslinked nanoparticle thin film, preparation method thereof, and thin film optoelectronic device having the same |
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| CN112397671A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Modified zinc sulfide, preparation method thereof and quantum dot light-emitting diode |
| CN112397657A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Modified zinc sulfide, preparation method thereof and quantum dot light-emitting diode |
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