CN108389727B - Semiconductors coupling heterojunction photovoltaic pole and preparation method thereof - Google Patents
Semiconductors coupling heterojunction photovoltaic pole and preparation method thereof Download PDFInfo
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- CN108389727B CN108389727B CN201810220254.2A CN201810220254A CN108389727B CN 108389727 B CN108389727 B CN 108389727B CN 201810220254 A CN201810220254 A CN 201810220254A CN 108389727 B CN108389727 B CN 108389727B
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000008878 coupling Effects 0.000 title claims abstract description 22
- 238000010168 coupling process Methods 0.000 title claims abstract description 22
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 37
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010408 film Substances 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- 229960001296 zinc oxide Drugs 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 12
- 238000000231 atomic layer deposition Methods 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 7
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- MDHJNKFLHDPGRI-UHFFFAOYSA-N tetramethylazanium titanium(4+) Chemical compound [Ti+4].C[N+](C)(C)C MDHJNKFLHDPGRI-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003426 co-catalyst Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- -1 wherein Substances 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 description 14
- 229910002915 BiVO4 Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000001782 photodegradation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 208000007578 phototoxic dermatitis Diseases 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910014312 BVO4 Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to a kind of preparation methods of semiconductors coupling heterojunction photovoltaic pole: deposition thickness is the zinc-oxide film of 10-60nm in the conductive substrates of load pucherite nano thin-film, wherein, zinc-oxide film is reacted at 150 DEG C -200 DEG C by zinc source and oxygen source and is got；By treated, conductive substrates are put into copper salt solution, and displacement reaction occurs at 60 DEG C -100 DEG C, so that zinc oxide is transformed into copper oxide, then anneals at 350 DEG C -550 DEG C, forms the conductive substrates for loading and having pucherite and copper oxide hetero-junctions；Then there is the surface deposition of titanium oxide film of the conductive substrates of pucherite and copper oxide hetero-junctions in load, wherein titanium deoxid film is reacted at 80 DEG C -150 DEG C by titanium source and oxygen source to be got.Hetero-junctions of the invention has petal-shaped pattern, increases the specific surface area of electrode, the TiO of load2As co-catalyst, promotes hole and react with electrolyte, effectively raise photocatalytic water efficiency.
Description
Technical field
The present invention relates to photovoltaic electrodes technical field more particularly to a kind of semiconductors coupling heterojunction photovoltaic pole and its preparations
Method.
Background technique
Since 21 century, with the continuous development of society, energy shortage and environmental degradation two large problems gradually cause people
Attention, the two have become restrict human progress and social development biggest crisis.Wherein problem of energy crisis is more and more tighter
Weight, such as coal, petroleum, natural gas non-renewable energy resources are just increasingly depleted.And it is big caused by various fossil fuels to burn
The let us mankind are also fallen into the predicament that can not be extricated oneself by the global environmental degradation problem such as gas and water pollution, greenhouse effects.The world
Various countries in order to solve this problem all greatly develop it is novel using clean energy resource.In numerous renewable energy, the sun
Can be very rich with water energy, the energy of received solar radiation consumed the one of energy summation by the current mankind 1 year on the earth
Wan Bei, but since solar energy metric density is low, restricted by unstable factors such as time, place and weathers, so solar energy
Utilization rate it is not high.Water is also the most abundant a kind of compound on the earth, the whole world there are about 3/4ths area covering dampening,
The traditional approach such as power station are limited to more to the utilization of water energy at present.Therefore finding new ideal clean energy resource carrier becomes solution energy
One of source crisis most efficient method.
Hydrogen energy source is exactly the advantageous competitor of future source of energy carrier as up-and-coming youngster, and hydrogen can be generated by decomposition water,
And since the product after burning is water to generate any pollution.Therefore, photolysis water hydrogen system can be very good
This problem is solved, because the water decomposition of compound state can be generated free state using solar energy as energy source by this system
Hydrogen both improved the utilization rate of solar energy and water energy so that unstable solar energy be stored in the form of Hydrogen Energy,
It can produce the reproducible hydrogen resource of cleaning again, be to kill two birds with one stone.Using the photocatalysis of semiconductor material, will partly lead
System is extremely decomposed water generation hydrogen at the photoelectricity of photochemical cell using sunlight and provides new way.Preferably use light
Solution aqueous systems, which prepare hydrogen, becomes the ideal chose for solving energy energy shortage and the big crisis of environmental degradation two.
The photoelectric material of the aquatic hydrogen producing of effective photodegradation should have following advantages: 1, stronger light absorpting ability；
2, presence that can be stable under any system；3, suitable band edge position is conducive to the oxidation and reduction reaction of water
It carries out；4, efficient carrier transport in body phase in the semiconductors；5, the global voltage transformation in redox reaction is lower；6,
Low cost；7, environmentally friendly.But there's almost no a kind of semiconductor material at present can meet above-mentioned all advantages simultaneously,
Thus improve remaining aspect after meeting certain advantages is particularly important for improving the efficiency of photocatalytic water.
Existing research work is directed generally to improve the light absorption of optoelectronic pole and efficient carrier transmission.It is utilizable
Means have: 1, element doping usually can be enhanced wide bandgap semiconductor materials to the absorption of visible light or promote narrow band gap light sun
The transmission of pole carrier, so as to improve the PEC performance of optoelectronic pole；2, the shape characteristic of photo-anode film is to photoelectrochemical cell point
The efficiency of Xie Shui also functions to very important effect.Especially monodimension nano stick, nanotube, nano wire and mesoporous and multistage knot
Structure, these structures can shorten the length of carrier transport, increase the specific surface area and enhancing light absorption of optoelectronic pole.3, surface
Processing includes cladding passivation layer and supports total, co-catalyst, and can not only increase quantum efficiency can also improve photoelectrochemical behaviour.
4, hetero-junctions is constructed to enhance light absorption, is inhibited the compound of electron hole pair, is accelerated the separation and electron-transport of carrier.But
The preparation method of current optoelectronic pole is more complex, higher cost, and prepared optoelectronic pole is not high to the utilization efficiency of light, makes significantly
The about development in photocatalytic water field.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of semiconductors coupling heterojunction photovoltaic pole and its systems
Preparation Method, method and process of the invention is simple, at low cost, and environmental protection, prepared optoelectronic pole has petal-shaped hetero-junctions, electrode ratio
It is larger compared with area, and load cocatalyst, effectively increase the utilization efficiency to light.
The present invention provides a kind of preparation methods of semiconductors coupling heterojunction photovoltaic pole, comprising the following steps:
(1) pucherite (BiVO with a thickness of 70nm-200nm is prepared in conductive substrates4) nano thin-film, form load vanadium
The conductive substrates of sour bismuth；
(2) atomic layer deposition (ALD) method is used, is 10nm- in the surface deposition thickness of the conductive substrates of load pucherite
Zinc oxide (ZnO) film of 60nm, wherein zinc-oxide film is reacted at 150 DEG C -200 DEG C by zinc source and oxygen source to be got；
(3) will through step (2), treated, and conductive substrates are put into copper salt solution, replaced at 60 DEG C -100 DEG C
React (preferably 80 DEG C), reaction time 15min-60min makes zinc oxide be transformed into copper oxide (CuO), then 350 DEG C-
It anneals 0.5h-5h (preferably 1h) under 550 DEG C (preferably 450 DEG C), forming load has leading for pucherite and copper oxide hetero-junctions
Electric substrate；The crystallinity of sample can be improved in annealing；
(4) atomic layer deposition method is used, has the surface of the conductive substrates of pucherite and copper oxide hetero-junctions to deposit in load
With a thickness of the titanium dioxide (TiO of 0.5nm-10nm2) film, obtain semiconductors coupling heterojunction photovoltaic pole, wherein titanium dioxide
Film is reacted at 80 DEG C -150 DEG C by titanium source and oxygen source to be got.
Further, in step (1), conductive substrates are fluorine-doped tin oxide electro-conductive glass (FTO), monocrystal silicon substrate
(Si) or indium doping fin oxide condutire glass (ITO).
Further, in step (1), load the preparation method of the conductive substrates of pucherite the following steps are included:
1g-2g bismuth nitrate and 1g-3.8g citric acid are dissolved in 5ml-20mL nitric acid, 0.1g-0.8g metavanadic acid is then added
Ammonium is reacted, and after 0.2g-2g polyvinyl alcohol is added, is stirred 1h-24h, is obtained blue solution, be then coated to blue solution
Conductive substrates surface forms the conductive substrates of load pucherite after 300 DEG C of -550 DEG C of calcining 2h-24h.
Further, it is coated using spin coating method, spin speed is 1000-5000 revs/min, spin coating number of repetition
It is 2-6 times, changes the thickness of rotation speed and the controllable pucherite nano thin-film of number.
Further, in step (2), zinc source be one of diethyl zinc (DEZ), zinc methide and a zinc ethyl or
It is several.Preferably, zinc source is diethyl zinc.
Further, in step (2) and step (4), oxygen source is water or air.Preferably, oxygen source is deionized water.
In step (2), the thickness of ZnO film can be controlled by controlling the cycle-index of ALD method.
Further, in step (3), the mantoquita in copper salt solution is one in copper nitrate, copper sulphate and copper chloride
Kind is several.Preferably, mantoquita is copper nitrate.
Further, in step (3), the concentration of copper salt solution is 2 × 10-3mol/L-1×10-2mol/L.It is preferred that
Ground, the concentration of copper salt solution are 3.2 × 10-3mol/L。
It in step (3), using ZnO as sacrifice agent template, is reacted by displacement, the copper ion in copper salt solution is by ZnO
In zinc atom cement out, CuO and zinc ion are formed, so that BVO be formed on the substrate4/ CuO hetero-junctions, between being due to CuO
It connects in BVO4It is formed on film, so being formed by hetero-junctions with petal-shaped pattern, increases the specific surface of final electrode
Product, enhances the sunken photosensitiveness of the electrode material of electrode material, increases optoelectronic pole of the invention and connects in application with electrolyte
Contacting surface product.Simultaneously compared with traditional single material electrodes, the formation of hetero-junctions effectively promotes photohole and light induced electron
Separating capacity.
Further, in step (4), titanium source is isopropyl titanate or tetramethylammonium titanium.
Preferably, in step (4), TiO2Film with a thickness of 0.5nm-1nm.
Co-catalyst TiO is introduced by step (4)2, hole can be effectively promoted and reacted with electrolyte, be conducive to
It improves electron hole pair to separate in electrode surface, by a series of enhancing, effectively raises photocatalytic water efficiency.
The present invention also provides semiconductors coupling heterojunction photovoltaic poles prepared by a kind of above-mentioned preparation method, including conduction
Substrate, load has pucherite and copper oxide hetero-junctions and titanium dioxide co-catalyst, pucherite and copper oxide in conductive substrates
Hetero-junctions is in petal-shaped.
Semiconductors coupling heterojunction photovoltaic pole of the invention mentions significantly compared to traditional unitary electrode, the efficiency of photocatalytic water
Height, 8-40 times before photoelectric current is increased under the voltage of 1.23V.Therefore electrode prepared by method of the invention is to improve
The practicable means of photodegradation water efficiency.
According to the above aspect of the present invention, the present invention has at least the following advantages:
The semiconductor photoelectrode of method preparation of the invention, which has, promotes optoelectronic pole surface chemical reaction, is conducive to improve half
The advantages that conducting electrons hole is to separation.Simultaneously because the raising of photosensitiveness is fallen into caused by pattern and narrow bandgap semiconductor material,
The utilization efficiency of light is also greatly improved.Compared with the single semi-conducting electrode of tradition, the composite heterogenous junction prepared in the present invention is electric
Pole also overcomes the disadvantages of electron-hole recombinations existing for single semi-conducting electrode are serious, carrier mobility ability is poor, effectively
Improve photocatalytic water efficiency, and this method preparation process has fairly simple, the advantages such as raw material are sufficient, price is low.Favorably
In large-scale production, there is huge potential using value.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the SEM (scanning electron microscope) of semiconductors coupling heterojunction photovoltaic pole prepared by the embodiment of the present invention 1
Figure；
Fig. 2 is the performance diagram of photodegradation water of the Different electrodes under different voltages prepared by the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
The present invention provides a kind of technology of preparing of semiconductors coupling heterojunction photovoltaic pole, by by two kinds of semiconductor materials
The method for constituting hetero-junctions and composite catalyst is prepared.Specific method is to first pass through spin-coating method in FTO electro-conductive glass
On obtain vanadic acid bismuth thin film, by annealing process improve sample crystallinity.Then by the method for atomic layer deposition in vanadic acid
Zinc oxide is then converted to copper oxide by ion-exchange, obtains BiVO by developing zinc oxide on bismuth thin film4/ CuO compound electric
Combination electrode is finally obtained BiVO by the method for atomic layer deposition by pole4/CuO/TiO2Optoelectronic pole.Implement below the present invention
In example, using the electrode material of preparation as the working electrode of photoelectrochemical cell, platinum electrode is used as to electrode, with the sulfuric acid of 0.5M
Sodium (Na2SO4) aqueous solution as electrolyte, carries out the experiment of photodegradation water.
Embodiment 1
(1) using FTO as conductive substrates, by conductive substrates according to acetone, the sequence of dehydrated alcohol and deionized water is super
Respectively it is cleaned by ultrasonic in sound machine 30 minutes.
By five nitric hydrate bismuth of 1.6169g, 1.2808g anhydrous citric acid is dissolved in 10mL nitric acid (concentration 23.3%),
Continue stirring until uniform mixing.0.39g ammonium metavanadate is dissolved in the above solution and stirred, is completely dissolved to solution, is added
It is stirred 5 hours after 0.4g polyvinyl alcohol (PVA), obtains transparent blue solution.
Cleaned conductive substrates are placed on spin coating instrument, take appropriate transparent blue solution drop in conductive substrates with liquid-transfering gun
On, vanadic acid bismuth thin film is obtained by way of spin coating, spin speed is 4000 revs/min, which recycles 5 times.Spin coating is good
Conductive substrates in the lehr 400 DEG C calcine 5 hours, heating rate be two degrees per minute.It is born after Temperature fall is cooling
Carry vanadic acid bismuth thin film conductive substrates, vanadic acid bismuth thin film with a thickness of 120nm or so.
(2) the step of obtaining (1) processed conductive substrates are put into the cavity of atomic layer deposition, use DEZ as
Zinc source, deionized water is as oxygen source, and controlling reaction cavity temperature is 200 DEG C, in BiVO4Film surface prepares zinc-oxide film,
Form BiVO4/ ZnO sample.The zinc oxide of preparation is with a thickness of 40nm.
0.302g Gerhardite is dissolved in 500ml deionized water and obtains copper nitrate solution.By BiVO4/ ZnO sample
Product are put into the copper nitrate solution just prepared, then react 45min in 80 DEG C of water-bath, and ZnO is converted into CuO.For
The crystallinity for improving sample is finally needed for the sample of drying to be put into annealing furnace and be calcined 1 hour at 450 DEG C, and heating rate is
Five degree per minute.BiVO is obtained after Temperature fall4/ CuO sample.
(3) by BiVO4/ CuO sample is put into the cavity of atomic layer deposition, use isopropyl titanate or tetramethylammonium titanium as
Titanium source, for deionized water as oxygen source, controlling reaction cavity temperature is 150 DEG C, prepares the TiO of 0.5nm thickness2Film finally obtains
BiVO4/CuO/TiO2Combination electrode, as semiconductors coupling heterojunction photovoltaic pole.
BiVO4/CuO/TiO2The pattern of combination electrode is as shown in Figure 1.As can be seen from Figure 1 it is grown on vanadic acid bismuth thin film
A large amount of petal-like copper oxide.The pattern makes the specific surface area of electrode become larger, and is conducive to the promotion of photocatalytic water efficiency.
The optoelectronic pole of above-mentioned preparation is assembled into photoelectrochemical cell, then the photodegradation water under different voltages.In order to
As control, while to load BiVO4The FTO of the film and BiVO prepared according to the method described above4/ CuO sample is respectively as work
Make electrode, platinum guaze as to electrode, photodegradation water, is as a result shown in Fig. 2 under identical condition.As can be seen from Figure 2,1.23V's
Under voltage, dark current (dotted line in figure) can be ignored substantially, and the photoelectric current of optoelectronic pole prepared by the method for the present embodiment can be with
Reach 0.479mA/cm2；And BiVO4Film and BiVO4The photoelectric current of/CuO only has 0.013mA/cm2And 0.299mA/cm2。
Embodiment 2
BiVO is prepared according to 1 step of embodiment (1)-(3) method4/CuO/TiO2Combination electrode, difference are, in step
(3) in, the TiO of different recurring numbers is deposited by controlling ALD technique2Program, to obtain the TiO of different-thickness2, so that step
(3) TiO in2With a thickness of 1nm.
The optoelectronic pole of above-mentioned preparation is assembled into photoelectrochemical cell, then the photodegradation water under different voltages.?
Under the voltage of 1.23V, the photoelectric current of optoelectronic pole prepared by the method for the present embodiment can achieve 0.412mA/cm2；And with
BiVO4/ CuO sample only has 0.299mA/cm as the photoelectric current of working electrode2。
Embodiment 3
BiVO is prepared according to 1 step of embodiment (1)-(3) method4/CuO/TiO2Combination electrode, difference be, step
(2) water-bath time in is 15min, so that ZnO is converted into the reaction time difference of this step of CuO, is obtained and real
Apply the CuO petal-shaped pattern that example 1 has different densities.
The optoelectronic pole of above-mentioned preparation is assembled into photoelectrochemical cell, then the photodegradation water under different voltages.?
Under the voltage of 1.23V, the photoelectric current of optoelectronic pole prepared by the method for the present embodiment can achieve 0.38mA/cm2；And with
BiVO4/ CuO sample only has 0.2mA/cm as the photoelectric current of working electrode2。
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of semiconductors coupling heterojunction photovoltaic pole, which comprises the following steps:
(1) the pucherite nano thin-film with a thickness of 70-200nm is prepared in conductive substrates, forms the conductive base of load pucherite
Bottom；
(2) atomic layer deposition method is used, is 10nm-60nm's in the surface deposition thickness of the conductive substrates of the load pucherite
Zinc-oxide film, wherein the zinc-oxide film is reacted at 150 DEG C -200 DEG C by zinc source and oxygen source to be got；The zinc source is
One or more of diethyl zinc, zinc methide and a zinc ethyl；
(3) will through step (2), treated, and conductive substrates are put into copper salt solution, it is anti-that displacement occurs at 60 DEG C -100 DEG C
It answers, zinc oxide is made to be transformed into copper oxide, then anneal at 350 DEG C -550 DEG C, forming load has pucherite and copper oxide heterogeneous
The conductive substrates of knot；
(4) atomic layer deposition method is used, has the surface of the conductive substrates of pucherite and copper oxide hetero-junctions to deposit in the load
With a thickness of the titanium deoxid film of 0.5-10nm, semiconductors coupling heterojunction photovoltaic pole is obtained, wherein the titanium dioxide
Film is reacted at 80 DEG C -150 DEG C by titanium source and oxygen source to be got.
2. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 1 pole, it is characterised in that: in step
(1) in, the conductive substrates are fluorine-doped tin oxide electro-conductive glass, monocrystal silicon substrate or indium doping fin oxide condutire glass.
3. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 1 pole, which is characterized in that in step
(1) in, it is described load pucherite conductive substrates preparation method the following steps are included:
Bismuth nitrate and citric acid are dissolved in nitric acid, ammonium metavanadate is then added and is reacted, after polyvinyl alcohol is added, obtains blue
Then the blue solution is coated to conductive substrates surface by solution, form the load vanadic acid after 300 DEG C of -550 DEG C of calcinings
The conductive substrates of bismuth.
4. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 3 pole, it is characterised in that: respectively with body
The ratio of long-pending and quality meter, the nitric acid and polyvinyl alcohol is 5ml-20mL:0.2g-2g.
5. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 1 pole, it is characterised in that: in step
(2) and in step (4), the oxygen source is water or air.
6. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 1 pole, it is characterised in that: in step
(3) in, the mantoquita in the copper salt solution is one or more of copper nitrate, copper sulphate and copper chloride.
7. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 1 pole, it is characterised in that: in step
(3) in, the concentration of the copper salt solution is 2 × 10-3mol/L-1×10-2mol/L。
8. the preparation method of semiconductors coupling heterojunction photovoltaic according to claim 1 pole, it is characterised in that: in step
(4) in, the titanium source is isopropyl titanate or tetramethylammonium titanium.
9. semiconductors coupling heterojunction photovoltaic pole prepared by a kind of preparation method of any of claims 1-8,
Be characterized in that: including conductive substrates, load has pucherite and copper oxide hetero-junctions and titanium dioxide to help in the conductive substrates
Catalyst, the pucherite and copper oxide hetero-junctions are in petal-shaped.
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