CN105420780A - Preparation method of composite nano heterojunction thin film material and preparation method of composite heterojunction solar battery - Google Patents
Preparation method of composite nano heterojunction thin film material and preparation method of composite heterojunction solar battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000010409 thin film Substances 0.000 title claims abstract description 15
- 239000002073 nanorod Substances 0.000 claims abstract description 44
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 238000003491 array Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002120 nanofilm Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 3
- 239000007791 liquid phase Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 19
- 239000011701 zinc Substances 0.000 description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011165 3D composite Substances 0.000 description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a composite nano heterojunction thin film material and a preparation method of a composite heterojunction solar battery. The preparation method of the composite nano heterojunction thin film material is characterized in that the composite nano heterojunction thin film material comprises a base, an n-type ZnO nanorod array thin film growing on the base in a liquid-phase manner, and a ZnS thin film; gaps between ZnO nanorod arrays are filled with the ZnS thin film by adopting a continuous ionic deposition method; and the gaps are filled with the ZnS thin film, and then Cu2O is deposited on the surfaces of ZnO nanorods or ZnS nanorods by adopting an electrochemical deposition method. According to the invention, the gaps between the ZnO nanorod arrays are filled with ZnS, then Cu2O is deposited on the surfaces of the ZnO nanorods or the ZnS nanorods by adopting the electrochemical deposition method, and a ZnO/ZnS/Cu2O composite heterojunction thin film material is formed. With the adoption of the preparation method, the cost of the obtained composite heterojunction solar battery is low, the preparation is simple, and the composite heterojunction solar battery is good in performance.
Description
Technical field
The present invention relates to a kind of preparation method, particularly relate to a kind of composite Nano heterogenous junction film material and composite heterogenous junction solar cell preparation method.
Background technology
Current, energy environment issues is increasingly serious, and scientific circles are devoted to study the resourceful energy and material beyond silica removal always.Metal oxide materials has extraordinary optics and electric property, ZnO is the wide bandgap semiconductor materials of important N-shaped, under its room temperature, energy gap is: 3.37eV, exciton bind energy is 60meV, much larger than the hot ionization energy of room temperature (26meV), can produce exciton stimulated radiation under lower threshold, can realize exciton recombination luminescence at a room temperature and a high temperature, be a kind of ideal material preparing short-wave long light-emitting device.The energy gap of ZnS is 3.7eV, and can send short wavelength UV luminescence and laser that wavelength is about 330nm, exciton bind energy is 40meV.Can predict ZnO and ZnS is that two kinds of direct broad-band gaps of very important II-VI group partly lead not material, there is excellent photoelectric characteristic, have broad prospect of application in fields such as photodiode, sensor and photochemical catalysis, it is very meaningful for therefore studying p-n composite heterogenous junction material.
Cu
2o is a kind of semiconductor material be found very early, rare can by the semiconductor material of excited by visible light, its energy gap is about 2.17eV, can is the excited by visible light of 400 ~ 800nm, in addition Cu by wavelength
2o is nontoxic, rich reserves, and preparation cost is low, and theoretical utilising efficiency is high, and at electrode materials, catalytic field, the aspect such as electron device and gas sensor has important application.The Cu of research preparation low cost
2o based solar battery is to alternative high cost battery, and the extensive civil nature realizing solar cell is significant.By interface structure pectination, preparation three-dimensional structure compound film hetero-junction solar cell, can effectively increase heterojunction boundary area, the collection length of photo-generated carrier can be shortened like this while increasing multiple extinction, reduce the recombination probability of photo-generated carrier, be conducive to improving battery efficiency.The restriction being subject to the shade influence relevant with complex geometry due to solid inorganic semiconductor material in the filling process often cannot cover in nanostructured surface conformal or be difficult to realize its densification filling in nanoporous, therefore, explore a kind of technology of fully filling inoganic solids semi-conductor in orientation array and prepare the key that composite heterogenous junction battery is raising battery technology.
Not yet there is ZnO/ZnS/Cu at present
2the relevant report of O composite heterogenous junction thin-film material preparation method.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of composite Nano heterogenous junction film material and composite heterogenous junction solar cell preparation method, and it fills ZnS in ZnO nano-rod array space, then with electrochemical deposition technique by Cu
2o is deposited on ZnO or ZnS nanorod surfaces and forms ZnO/ZnS/Cu
2o composite heterogenous junction thin-film material and prepare the method for solar cell, the battery cost adopting present method obtained is low, and preparation is simple, and battery performance is good.
The present invention solves above-mentioned technical problem by following technical proposals: a kind of composite Nano heterogenous junction film material preparation method, it is characterized in that, composite Nano heterogenous junction film material in described composite Nano heterogenous junction film material preparation method comprises substrate, liquid growth is at suprabasil N-shaped ZnO nano-rod array film and adopt continuous ionic sedimentation to fill ZnS film in ZnO nano-rod array gap, be adopt ZnS film to be filled into space, then use electrochemical deposition method Cu
2o is deposited on ZnO or ZnS nanorod surfaces, and detailed process comprises the following steps:
Step one, puts into Zn (NO by the ZnO nano-rod array prepared
3)
2place deposition in solution, then use deionized water rinsing; Put into Na again
2place deposition in S solution, then use deionized water rinsing; Loop cycle is 15 times, and ZnS is fully filled into from bottom to top in the space of nanometer stick array and defines ZnO/ZnS composite nano film;
Step 2, with alkaline cupric salt solution for electrolytic solution, deposits 70-150s, by p-type Cu under the sedimentation potential of-0.4 ~ 0.6V
2o is electrochemically-deposited in ZnO or ZnS nanorod surfaces, realizes p-type Cu
2o semi-conductor covers the conformal of ZnO or ZnS nanometer rod, forms ZnO/ZnS/Cu
2o.
Preferably, the mode of deposition in described step one is: strength of solution is 0.1-0.2MpH is 12-13, depositing temperature 15-25 DEG C, depositing time 5-10min, and loop cycle is 15-25 time.
Preferably, the mode of deposition in described step 2 is: deposit solution pH11.0-13.0, depositing temperature 50-60 DEG C, and current potential is-0.4V, depositing time 100s.
Preferably, the alkaline cupric salt solution that described step 2 is used is the CuSO of 0.2 ~ 0.3M
4, add lactic acid in solution as complexing agent, lactic acid concn is 4M.
Preferably, described step one, when growing ZnO nanorod arrays film, adopts hydrothermal growing method, utilize sol-gel method making ZnO seed presoma, then in substrate, apply described ZnO seed presoma, form film, obtain one deck uniform nano level ZnO crystal seed layer through thermal treatment; In reaction vessel, substrate is immersed in ZnO growth solution with the unsettled back-off in face of crystal seed layer, under water bath condition, is obtained by reacting height-oriented ZnO nano-rod array.
Preferably, the preparation method of described N-shaped ZnO nano-rod array film comprises the following steps: adopt the method for spin coating plated film to prepare layer of ZnO colloidal film in cleaned substrate; In vacuum tube furnace, 350 DEG C ~ 550 DEG C annealing 10min ~ 30min, namely form the nano level ZnO crystal seed layer of one deck even compact at substrate surface; With KOH and Zn (NO
3)
21:8 compound concentration is the [Zn (OH) of 0.10 ~ 0.25M in molar ratio
4]
2-the aqueous solution, abundant magnetic agitation, obtains a settled solution, array growth liquid is poured in reaction vessel, then have facing down of crystal seed layer to be suspended in array growth liquid substrate preparation, good seal reaction vessel afterwards, is placed in electric heating constant temperature tank, under 20 ~ 50 DEG C of water bath condition, insulation 10min ~ 12h, takes out, uses rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature in vacuo is dried.
Preferably, described substrate is ITO or FTO conductive glass.
Preferably, described composite Nano heterogenous junction film material preparation method adopts alkali to reconcile pH, and conventional is potassium hydroxide.
The present invention also provides a kind of composite heterogenous junction solar cell preparation method, it is characterized in that, described composite heterogenous junction solar cell preparation method comprises the following steps: first, utilizes above-mentioned composite Nano heterogenous junction film material preparation method making ZnO/ZnS/Cu
2o composite Nano hetero-junction thin-film, then at the Cu of heterojunction
2o layer upper surface splash-proofing sputtering metal or conducting oxide electrode, obtain ZnO/ZnS/Cu
2o composite Nano heterojunction solar battery.
Preferably, the composite Nano heterojunction solar battery metal electrode used in described composite heterogenous junction solar cell preparation method is Au or Pt; Conducting oxide electrode used is ITO or FTO.
Positive progressive effect of the present invention is: the present invention fills ZnS in ZnO nano-rod array space, then with electrochemical deposition technique by Cu
2o is deposited on ZnO or ZnS nanorod surfaces and forms ZnO/ZnS/Cu
2o composite heterogenous junction thin-film material and prepare the method for solar cell, the battery cost adopting present method obtained is low, and preparation is simple, and battery performance is good.
Accompanying drawing explanation
Fig. 1 ZnO/ZnS/Cu
2the preparation were established figure of O composite Nano heterojunction solar battery.
Fig. 2 is transverse section field emission scanning electron microscope (SEM) photo of the ZnO nano-rod array of water heat transfer.
Fig. 3 is the scanning electron microscope of ZnO nano-rod array after successive sedimentation ZnS (SEM) photo.
Fig. 4 is ZnO/ZnS/Cu prepared by the invention process
2flied emission scanning electron (SEM) photo in the transverse section of O composite heterogenous junction material.
Fig. 5 is ZnO/ZnS/Cu of the present invention
2the schematic diagram of the three-dimensional composite heterogenous junction solar cell of O.
Embodiment
Present pre-ferred embodiments is provided, to describe technical scheme of the present invention in detail below in conjunction with accompanying drawing.
As shown in Figures 1 to 4, the present invention relates to making ZnO/ZnS/Cu
2the method of O composite Nano heterojunction material and prepare the method for solar cell with this material, relate to and adopt continuous ionic sedimentation in the semiconductor nanorods array of a kind of N-shaped ZnO of orientation, ZnS is filled in ZnO nano-rod array gap, then uses electrochemical deposition technique p-type Cu
2o semiconductor deposition at ZnO/ZnS on the surface, has just made ZnO/ZnS/Cu
2o composite heterogenous junction material and battery device, belong to semiconducter device and technical field of new energies.
Composite Nano heterogenous junction film material in composite Nano heterogenous junction film material preparation method of the present invention comprises substrate, liquid growth is at suprabasil N-shaped ZnO nano-rod array film and adopt continuous ionic sedimentation to fill ZnS film in ZnO nano-rod array gap, be adopt ZnS film to be filled into space, then use electrochemical deposition method Cu
2o is deposited on ZnO or ZnS nanorod surfaces, and detailed process comprises the following steps:
Step one, puts into Zn (NO by the ZnO nano-rod array prepared
3)
2place deposition in solution, then use deionized water rinsing; Put into Na again
2place deposition in S solution, then use deionized water rinsing; Loop cycle is 15 times, and ZnS is fully filled into from bottom to top in the space of nanometer stick array and defines ZnO/ZnS composite nano film;
Step 2, with alkaline cupric salt solution for electrolytic solution, deposits 70-150s, by p-type Cu under the sedimentation potential of-0.4 ~ 0.6V
2o is electrochemically-deposited in ZnO or ZnS nanorod surfaces, realizes p-type Cu
2o semi-conductor covers the conformal of ZnO or ZnS nanometer rod, forms ZnO/ZnS/Cu
2o.
Further, the mode of deposition in step one is: strength of solution is 0.1-0.2M, pH is 12-13, depositing temperature 15-25 DEG C, depositing time 5-10min, and loop cycle is 15-25 time.
Further, the mode of deposition in step 2 is: deposit solution pH11.0-13.0, depositing temperature 50-60 DEG C, and current potential is-0.4V, depositing time 100s.
Further, the alkaline cupric salt solution that step 2 is used is the CuSO of 0.2 ~ 0.3M
4, add lactic acid in solution as complexing agent, lactic acid concn is 4M.
Further, step one, when growing ZnO nanorod arrays film, adopts hydrothermal growing method, utilize sol-gel method making ZnO seed presoma, then in substrate, apply described ZnO seed presoma, form film, obtain one deck uniform nano level ZnO crystal seed layer through thermal treatment; In reaction vessel, substrate is immersed in ZnO growth solution with the unsettled back-off in face of crystal seed layer, under water bath condition, is obtained by reacting height-oriented ZnO nano-rod array.
The preparation method of N-shaped ZnO nano-rod array film comprises the following steps: adopt the method for spin coating plated film to prepare layer of ZnO colloidal film in cleaned substrate; In vacuum tube furnace, 350 DEG C ~ 550 DEG C annealing 10min ~ 30min, namely form the nano level ZnO crystal seed layer of one deck even compact at substrate surface; With KOH and Zn (NO
3)
21:8 compound concentration is the [Zn (OH) of 0.10 ~ 0.25M in molar ratio
4]
2-the aqueous solution, abundant magnetic agitation, obtains a settled solution, array growth liquid is poured in reaction vessel, then have facing down of crystal seed layer to be suspended in array growth liquid substrate preparation, good seal reaction vessel afterwards, is placed in electric heating constant temperature tank, under 20 ~ 50 DEG C of water bath condition, insulation 10min ~ 12h, takes out, uses rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature in vacuo is dried.The present invention's substrate used is ITO(IndiumTinOxide, tin-doped indium oxide) or FTO(Fluorine-dopedTinOxide, Fluorin doped tin-oxide) conductive glass.The present invention adopts alkali to reconcile pH, and conventional is potassium hydroxide.
Present invention also offers a kind of composite heterogenous junction solar cell preparation method, it comprises the following steps: first, utilizes above-mentioned composite Nano heterogenous junction film material preparation method making ZnO/ZnS/Cu
2o composite Nano hetero-junction thin-film, then at the Cu of heterojunction
2o layer upper surface splash-proofing sputtering metal or conducting oxide electrode, obtain ZnO/ZnS/Cu
2o composite Nano heterojunction solar battery.Composite Nano heterojunction solar battery metal electrode used in described composite heterogenous junction solar cell preparation method is Au or Pt; Conducting oxide electrode used is ITO or FTO.
The preparation process of ZnO crystal seed layer is as follows: with Zinc diacetate dihydrate Zn (Ac)
22H
2o is precursors, monoethanolamine NH
2cH
2cH
2oH is stablizer, ethylene glycol monomethyl ether CH
3oCH
2cH
2oH is solvent, polyoxyethylene glycol PEG4000 is the ZnO colloidal sol that 0.3M ~ 0.5M prepared by tensio-active agent.For the ZnO colloidal sol of 0.5M, concrete process for preparation is as follows: take 5.488g Zinc diacetate dihydrate, put into beaker, and adds the ethylene glycol monomethyl ether of 25ml wherein, magnetic agitation 15min; Measuring 1.5ml thanomin joins in the ethylene glycol monomethyl ether of 15ml, mechanical stirring ultrasonic disperse 5min; The ethylene glycol monomethyl ether dropwise of thanomin is added drop-wise in the ethylene glycol monomethyl ether solution of the zinc acetate that magnetic agitation, drip the deionized water of 0.9ml again, then add proper amount of glycol methyl ether adjustment liquor capacity and reach 50ml, sealed beaker, and stir 2h, still aging 24h at 60 DEG C of water-bath vigorous magnetic.Finally add 0.25g polyoxyethylene glycol [HO (CH
2cH
2o) nH] 4000,60 DEG C of stirring in water bath 30min, obtain faint yellow ZnO precursor sol.The method of spin coating plated film is adopted to prepare layer of ZnO colloidal film in cleaned substrate; In vacuum tube furnace, 350 DEG C ~ 550 DEG C annealing DEG C 10min ~ 30min, namely form the nano level ZnO crystal seed layer of one deck even compact at substrate surface.
The process of the growth of ZnO nano-rod array is as follows: with KOH and Zn (NO
3)
21:8 compound concentration is the [Zn (OH) of 0.10 ~ 0.25M in molar ratio
4]
2-the aqueous solution, abundant magnetic agitation, obtains a settled solution, is required array growth liquid.Array growth liquid is poured in reaction vessel, then facing down of crystal seed layer there is is to be suspended in array growth liquid substrate preparation, good seal reaction vessel afterwards, is placed in electric heating constant temperature tank, under 50 DEG C of water bath condition, insulation 10min ~ 12h, take out, use rinsed with deionized water successively, dehydrated alcohol rinses, room temperature in vacuo is dried, and namely obtains ZnO nano-rod array.
The preparation process of continuous ionic sedimentation making ZnO/ZnS composite nano film is as follows: the ZnO nano-rod array prepared being put into concentration is 0.2M, pH value be 13 Zn (NO
3)
2in solution place deposition, depositing temperature 25 DEG C, depositing time 10min, then uses deionized water rinsing, then puts into 0.2M, pH value be 13 Na
2place deposition in S solution, depositing temperature 25 DEG C, depositing time 10min, then uses deionized water rinsing.Loop cycle is 15 times.ZnS is fully filled into from bottom to top in the space of nanometer stick array and defines ZnO/ZnS composite nano film.
Electrochemical deposition making ZnO/ZnS/Cu
2the process of O composite Nano heterojunction is as follows: preparation p-type Cu
2the precursor solution of O semi-conductor, with CuSO
4solution, as precursor solution, adds lactic acid as stablizer, wherein CuSO
4concentration be 0.3M, the concentration of lactic acid is 4M, with KOH regulator solution pH=13.0; Using above-mentioned precursor solution as electrolytic solution, at ZnO or ZnS nanorod surfaces electrochemistry conformal deposit Cu
2o Seed Layer.The condition of deposition process is: temperature 50 C, sedimentation potential-0.5V, and depositing time 100s, realizes p-type Cu
2o semi-conductor covers the conformal of ZnO or ZnS nanometer rod.Then at the Cu of heterojunction
2o layer upper surface splash-proofing sputtering metal Au electrode, obtains ZnO/ZnS/Cu
2o composite Nano heterojunction solar battery.
As shown in Figure 5, ZnO/ZnS/Cu of the present invention
2the three-dimensional composite heterogenous junction solar cell of O comprises glass 1, FTO rete 2, ZnO crystal seed layer 3, ZnO nano-rod array 4, ZnO quantum dot 5, Cu from bottom to up successively
2o film 6, Au layer 7.
Above-described specific embodiment; the technical problem of solution of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a composite Nano heterogenous junction film material preparation method, it is characterized in that, composite Nano heterogenous junction film material in described composite Nano heterogenous junction film material preparation method comprises substrate, liquid growth is at suprabasil N-shaped ZnO nano-rod array film and adopt continuous ionic sedimentation to fill ZnS film in ZnO nano-rod array gap, be adopt ZnS film to be filled into space, then use electrochemical deposition method Cu
2o is deposited on ZnO or ZnS nanorod surfaces, and detailed process comprises the following steps:
Step one, puts into Zn (NO by the ZnO nano-rod array prepared
3)
2place deposition in solution, then use deionized water rinsing; Put into Na again
2place deposition in S solution, then use deionized water rinsing; Loop cycle is 15 times, and ZnS is fully filled into from bottom to top in the space of nanometer stick array and defines ZnO/ZnS composite nano film;
Step 2, with alkaline cupric salt solution for electrolytic solution, deposits 70-150s, by p-type Cu under the sedimentation potential of-0.4 ~ 0.6V
2o is electrochemically-deposited in ZnO or ZnS nanorod surfaces, realizes p-type Cu
2o semi-conductor covers the conformal of ZnO or ZnS nanometer rod, forms ZnO/ZnS/Cu
2o.
2. composite Nano heterogenous junction film material preparation method as claimed in claim 1, it is characterized in that, the mode of deposition in described step one is: strength of solution is 0.1-0.2MpH is 12-13, depositing temperature 15-25 DEG C, depositing time 5-10min, loop cycle is 15-25 time.
3. composite Nano heterogenous junction film material preparation method as claimed in claim 1, it is characterized in that, the mode of deposition in described step 2 is: deposit solution pH11.0-13.0, depositing temperature 50-60 DEG C, and current potential is-0.4V, depositing time 100s.
4. composite Nano heterogenous junction film material preparation method as claimed in claim 1, is characterized in that, described step 2 alkaline cupric salt solution used is the CuSO of 0.2 ~ 0.3M
4, add lactic acid in solution as complexing agent, lactic acid concn is 4M.
5. composite Nano heterogenous junction film material preparation method as claimed in claim 1, it is characterized in that, described step one is when growing ZnO nanorod arrays film, adopt hydrothermal growing method, utilize sol-gel method making ZnO seed presoma, then in substrate, apply described ZnO seed presoma, form film, obtain one deck uniform nano level ZnO crystal seed layer through thermal treatment; In reaction vessel, substrate is immersed in ZnO growth solution with the unsettled back-off in face of crystal seed layer, under water bath condition, is obtained by reacting height-oriented ZnO nano-rod array.
6. composite Nano heterogenous junction film material preparation method as claimed in claim 1, it is characterized in that, the preparation method of described N-shaped ZnO nano-rod array film comprises the following steps: adopt the method for spin coating plated film to prepare layer of ZnO colloidal film in cleaned substrate; In vacuum tube furnace, 350 DEG C ~ 550 DEG C annealing 10min ~ 30min, namely form the nano level ZnO crystal seed layer of one deck even compact at substrate surface; With KOH and Zn (NO
3)
21:8 compound concentration is the [Zn (OH) of 0.10 ~ 0.25M in molar ratio
4]
2-the aqueous solution, abundant magnetic agitation, obtains a settled solution, array growth liquid is poured in reaction vessel, then have facing down of crystal seed layer to be suspended in array growth liquid substrate preparation, good seal reaction vessel afterwards, is placed in electric heating constant temperature tank, under 20 ~ 50 DEG C of water bath condition, insulation 10min ~ 12h, takes out, uses rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature in vacuo is dried.
7. composite Nano heterogenous junction film material preparation method as claimed in claim 1, it is characterized in that, described substrate is ITO or FTO conductive glass.
8. composite Nano heterogenous junction film material preparation method as claimed in claim 1, is characterized in that, described composite Nano heterogenous junction film material preparation method adopts alkali to reconcile pH, and conventional is potassium hydroxide.
9. a composite heterogenous junction solar cell preparation method, is characterized in that, described composite heterogenous junction solar cell preparation method comprises the following steps: first, utilizes above-mentioned composite Nano heterogenous junction film material preparation method making ZnO/ZnS/Cu
2o composite Nano hetero-junction thin-film, then at the Cu of heterojunction
2o layer upper surface splash-proofing sputtering metal or conducting oxide electrode, obtain ZnO/ZnS/Cu
2o composite Nano heterojunction solar battery.
10. composite heterogenous junction solar cell preparation method as claimed in claim 9, it is characterized in that, the composite Nano heterojunction solar battery metal electrode used in described composite heterogenous junction solar cell preparation method is Au or Pt; Conducting oxide electrode used is ITO or FTO.
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