CN103633182B - Cu-Im-Ga-S-Se-sensitized semiconductor anode solar cell and preparation method thereof - Google Patents
Cu-Im-Ga-S-Se-sensitized semiconductor anode solar cell and preparation method thereof Download PDFInfo
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- CN103633182B CN103633182B CN201310613803.XA CN201310613803A CN103633182B CN 103633182 B CN103633182 B CN 103633182B CN 201310613803 A CN201310613803 A CN 201310613803A CN 103633182 B CN103633182 B CN 103633182B
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- indium gallium
- copper indium
- sulphur selenium
- solar cell
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 11
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 127
- 229910052733 gallium Inorganic materials 0.000 claims description 127
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 claims description 125
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 113
- 239000010408 film Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 36
- 230000001235 sensitizing effect Effects 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000000975 dye Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007772 electrode material Substances 0.000 claims description 13
- 238000011065 in-situ storage Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- -1 indium gallium compound Chemical class 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000693 micelle Substances 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 7
- 238000005118 spray pyrolysis Methods 0.000 claims description 7
- 238000010345 tape casting Methods 0.000 claims description 7
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910007709 ZnTe Inorganic materials 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- 150000002843 nonmetals Chemical class 0.000 claims description 6
- 238000005546 reactive sputtering Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 4
- 238000003556 assay Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910003465 moissanite Inorganic materials 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- 229910002531 CuTe Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910003107 Zn2SnO4 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000593 microemulsion method Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052959 stibnite Inorganic materials 0.000 claims description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 23
- 239000012528 membrane Substances 0.000 description 22
- 238000005516 engineering process Methods 0.000 description 16
- 230000006870 function Effects 0.000 description 11
- 238000013461 design Methods 0.000 description 8
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- H01L31/04—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
- H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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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- 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
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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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
- Y02E10/541—CuInSe2 material PV cells
-
- 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 relates to a Cu-Im-Ga-S-Se-sensitized semiconductor anode solar cell and a preparation method thereof. The solar cell comprises an N-type transparent conducting film and an N-type wide-band-gap semiconductor particle porous film which are formed on a glass substrate in sequence, a Cu-Im-Ga-S-Se-sensitized layer, and a back electrode; the Cu-Im-Ga-S-Se-sensitized layer is generated in holes and surface of the N-type wide-band-gap semiconductor particle porous film and is compounded with the N-type wide-band-gap semiconductor particle porous film; the back electrode is formed on the Cu-Im-Ga-S-Se-sensitized layer; the all-solid Cu-Im-Ga-S-Se-sensitized semiconductor anode solar cell does not contain organic dye and liquid electrolyte. Cu, Im, Ga, S and Se are generated in the holes and surface of the porous semiconductor anode, compact chemical combination between the porous semiconductor anode and the Cu, Im, Ga, S as well as Se can be realized, and effective transmission of photon-generated carriers in an interface is realized.
Description
Technical field
The invention belongs to solar cell energy field, and in particular to a kind of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode
Solar cell and preparation method thereof.
Background technology
The energy and environment are two great strategy problems of human social, with the continuous development of human society,
The development and utilization of clean reproducible energy seems more and more important and urgent.Solar energy is a kind of cleaning, enriches, does not receive region
The regenerative resource of restriction, the effective exploitation of solar energy and is of great significance using tool.Solar cell is that the mankind are effective
One of principal mode using solar energy.
Sensitization type solar cell with its low production cost, low equipment investment, energy resource consumption it is few, without the need for vacuum, process is simple,
It is expected to realize that low cost that can be comparable with existing electricity price generates electricity, causes the extensive concern of people.But traditional dyestuff is quick
Change type solar cell, uses organic dyestuff and liquid electrolyte, causes device itself to there is the inherence that many is difficult to overcome
Defect.The long-term photostability of organic dyestuff itself, long-time stability of chemisorbed between organic dyestuff and semiconductive particles,
Photoetch decomposition, the vaporization at high temperature of liquid electrolyte, liquid electrolyte confrontation package material of the organic dyestuff on semiconductive particles surface
The burn into liquid electrolyte of material solidifies at low temperature the various latent defects such as cause battery to use, and is all difficult to overcome.
The content of the invention
In the face of the problem that prior art is present, it is an object of the invention to provide a kind of all solid state inorganic dyestuff sensitization is partly led
Device architecture of body anode solar cell and preparation method thereof, relates generally to all solid state copper indium gallium sulphur selenium sensitized semiconductor anode too
Positive electricity pond and preparation method thereof.
Here, on the one hand, the present invention provides a kind of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, bag
Include：The N-type nesa coating being sequentially formed in glass substrate and N-type wide band gap semiconducter particulate porous film；In the N-type
Generate so as to the copper indium gallium sulphur selenium sensitizing layer compound with it with surface in situ in the hole of wide band gap semiconducter particulate porous film；With
And the back electrode being formed on the copper indium gallium sulphur selenium sensitizing layer；Wherein, all solid state copper indium gallium sulphur selenium sensitized semiconductor sun
Pole solar cell is without organic dyestuff and liquid electrolyte.
The copper indium gallium sulphur selenium sensitized semiconductor anode solar cell and traditional organic dye sensitized solar cell of the present invention
Compare, copper indium gallium sulphur selenium instead of organic dyestuff and liquid electrolyte, therefore there is no the caused envelope due to liquid electrolyte
Dress problem；Stable solid-solid interface is formed between copper indium gallium sulphur selenium and semiconductor anode side, therefore there is no organic dyestuff and anode
The issue for battery life for being desorbed and causing；Copper indium gallium sulphur selenium is stable solid-state semiconductor, therefore there is no organic dyestuff by half
The light degradation of conductor anode and the photoetch problem that causes；Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is all solid state sun
Battery, therefore the configuration design of battery is almost unrestricted, can use under extremely low temperature, high temperature and intense radiation conditions, can prepare
Into flexible solar cell.Most important of which is that, copper indium gallium sulphur selenium is given birth in the hole of porous semi-conductor anode with surface in situ
Into, therefore close chemical bond is capable of achieving between copper indium gallium sulphur selenium and porous semi-conductor anode, realize photo-generated carrier on boundary
Effectively transmit on face.
It is preferred that the glass substrate is alkali metal glass substrate or ultrawhite solar energy glass substrate.
It is preferred that the N-type nesa coating is by N-type transparent conductive film material Jing magnetron sputterings, reactive sputtering, chemistry
Vapour deposition, spray pyrolysis or sol-gel process are obtained, wherein the N-type transparent conductive film material is selected from FTO（Fluorine doped two
Tin oxide）, ITO（Tin indium oxide）, AZO（Al-Doped ZnO）, Cd2SnO4, Zn2SnO4, TiO2:Nb and SrTiO3:Appointing in Nb
Anticipate one or more.
It is preferred that the thickness of the N-type nesa coating is 100～1000nm.
It is preferred that the N-type wide band gap semiconducter particulate porous film is by wide bandgap N type semi-conducting material organizine net print process
Or the tape casting is obtained, wherein the wide bandgap N type semi-conducting material is selected from wide bandgap N type oxide semiconductor material, wide bandgap N
In type sulfide semiconductor material, wide bandgap N type oxyhalogenation thing semi-conducting material and wide bandgap N type sulfur halide semi-conducting material
Any one or it is two or more.
It is preferred that the wide bandgap N type oxide semiconductor material is selected from TiO2、ZrO2、Nb2O5、Ta2O5、ZnO、In2O3、
SnO2And SrTiO3In any one or it is two or more；The wide bandgap N type sulfide semiconductor material selected from ZnS, CdS,
In2S3、SnS2And Sb2S3In any one or it is two or more；The wide bandgap N type oxyhalogenation thing semi-conducting material is selected from
BiOX and/or SbOX, wherein X are selected from Cl, Br, and/or I；The wide bandgap N type sulfur halide semi-conducting material is BiSX, its
Middle X is selected from Cl, Br and/or I.
It is preferred that the thickness of the N-type wide band gap semiconducter particulate porous film is 1～10 μm.
It is preferred that the copper indium gallium sulphur selenium sensitizing layer is copper indium gallium sulphur selenium semiconductive thin film, its component is CuxIn1- yGaySe2-zSz, wherein 0.6≤x≤0.9,0≤y≤1,0≤z≤2.
It is preferred that the thickness of the copper indium gallium sulphur selenium sensitizing layer is 50nm～5000nm.
It is preferred that the back electrode is obtained by the vacuum evaporation of back electrode material Jing, wherein the back electrode material is selected from height
Workfunction metal, high work function conductive non-metals or high work function P-type conduction compound.
It is preferred that the high-work-function metal is selected from any one in Cu, Ni, Mo, Au and Pt or two or more；Institute
State high work function conductive non-metals in C, Te and SiC any one or it is two or more；The high work function P-type conduction
Compound is selected from ZnTe, ZnTe:Cu, CuTe and Sb3Te2In any one or it is two or more.
It is preferred that the thickness of the back electrode is 50～5000nm.
On the other hand, the present invention also provides a kind of preparation side of above-mentioned copper indium gallium sulphur selenium sensitized semiconductor anode solar cell
Method, including：
1）Using N-type transparent conductive film material Jing magnetron sputterings, reactive sputtering, chemical vapor deposition, spray pyrolysis or
Sol-gel process prepares on a glass substrate N-type nesa coating；
2）By the slurry organizine wire mark brush containing the wide bandgap N type semi-conducting material particulate that particle diameter is 1～1000nm or stream
N-type wide band gap semiconducter particulate porous film is formed after the method for prolonging is coated on the N-type nesa coating, drying is annealed；
3）The N-type wide band gap semiconducter particulate porous film is placed in into the copper indium gallium sulphur of cupric, indium, gallium, sulphur and selenium element
After soaking 0.1～5 hour in selenium liquid phase presoma, Jing after 180～600 DEG C are annealed 5～120 minutes in the N-type broad-band gap half
Copper indium gallium sulphur selenium sensitizing layer is generated in the hole of conductor particles perforated membrane with surface in situ；
4）Back electrode material Jing vacuum vapour deposition is formed into back electrode on the copper indium gallium sulphur selenium sensitizing layer, that is, copper is obtained
Indium gallium sulphur selenium sensitized semiconductor anode solar cell.
It is preferred that the wide bandgap N type semi-conducting material particulate is changed by hydro-thermal method, solvent-thermal method, sol-gel process
Learn the precipitation method, microemulsion method, micelle assay, reverse micelle method or high-temperature cracking method preparation.
The present invention is by previously according to prior art（Such as US2009145482A1 and CN101960610B）Prepare copper
Indium gallium sulphur selenium liquid phase presoma, then prepares early stage semiconductor porous anode film and is immersed in copper indium gallium sulphur selenium liquid phase presoma
After annealed, obtain semiconductor anode side perforated membrane-copper indium gallium sulphur selenium composite film.Due to being using copper indium gallium sulphur selenium liquid phase forerunner
Copper indium gallium sulphur selenium is introduced anodic porous film by body method, annealed to generate copper and indium gallium with surface in situ in the hole of anodic porous film
Close chemical bond is formed between sulphur selenium, therefore anodic porous film surface and copper indium gallium sulphur selenium two-phase, is conducive to carrier to exist
Effective transmission between two-phase, therefore the manufacturing cost of solar cell can be substantially reduced.
The preparation method process is simple of the present invention, with low cost, equipment investment is few, and raw material availability is high, and controllability is strong, weight
Renaturation is good, it is easy to accomplish large-scale production.
Description of the drawings
Fig. 1 is the device architecture of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of an example of the invention
Schematic diagram；
Fig. 2 is the preparation flow of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of an example of the invention
Schematic diagram.
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
It is merely to illustrate the present invention, and the unrestricted present invention.If not special instruction, the term " N-type semiconductor " in the present invention is referred to and leaned on
The semiconductor of electronic conduction.
Fig. 1 illustrates the device junction of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of an example of the invention
Composition.As shown in figure 1, all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell can include：Glass substrate 5, successively
The N-type nesa coating 4 being formed in glass substrate 5 and N-type wide band gap semiconducter particulate porous film 3, in the N-type broad-band gap
Generate so as to the copper indium gallium sulphur selenium sensitizing layer 2 and shape compound with it with surface in situ in the hole of semiconductive particles perforated membrane 3
Into the back electrode 1 on copper indium gallium sulphur selenium sensitizing layer 2.
As long as glass substrate 5 can pass through sunshine, for example, may be selected from：The ultrawhite of alkali metal glass or high permeability is too
Positive energy glass.Wherein, alkali metal glass for example can be common soda-lime-silica glass.
N-type nesa coating 4 can be formed in glass substrate 5 by N-type transparent conductive film material Jing filming technologies.Wherein
N-type transparent conductive film material may be selected from：FTO, ITO, AZO, Cd2SnO4, Zn2SnO4, TiO2:Nb and SrTiO3:Appointing in Nb
Anticipate one or more.Filming technology is not limited, as long as film can be formed, for example can be magnetron sputtering, reactive sputtering,
Chemical vapor deposition, spray pyrolysis or sol-gel filming technology.
In one example, the thickness of N-type nesa coating 4 can be 100～1000nm.
N-type wide band gap semiconducter particulate porous film 3 can be formed at N-type by wide bandgap N type semi-conducting material Jing filming technologies
On nesa coating 4.Wherein wide bandgap N type semi-conducting material may be selected from：Wide bandgap N type oxide semiconductor material, wide bandgap N
Type sulfide semiconductor material, wide bandgap N type oxyhalogenation thing semi-conducting material and wide bandgap N type sulfur halide semi-conducting material
In any one or it is two or more.Filming technology is not limited, as long as perforated membrane can be formed, for example, can be silk screen print method
Or the tape casting.
Wide bandgap N type oxide semiconductor material may be selected from TiO2、ZrO2、Nb2O5、Ta2O5、ZnO、In2O3、SnO2With
SrTiO3In any one or it is two or more.
Wide bandgap N type sulfide semiconductor material may be selected from ZnS, CdS, In2S3、SnS2And Sb2S3In any one or
It is two or more.
Wide bandgap N type oxyhalogenation thing semi-conducting material may be selected from BiOX and/or SbOX, and wherein X is selected from Cl, Br, and/or I.
Wide bandgap N type sulfur halide semi-conducting material can be BiSX（X is selected from Cl, Br or I）.
In one example, the thickness of N-type wide band gap semiconducter particulate porous film 3 can be 1～10 μm.
Copper indium gallium sulphur selenium sensitizing layer 2 is copper indium gallium sulphur selenium semiconductive thin film, and its component can be CuxIn1-yGaySe2-zSz（0.6
≤ x≤0.9,0≤y≤1,0≤z≤2）.As shown in figure 1, copper indium gallium sulphur selenium sensitizing layer 2 is more in N-type wide band gap semiconducter particulate
Generate with surface in situ in the hole of pore membrane 3, so as to form copper indium gallium sulphur selenium sensitized semiconductor composite membrane.Copper and indium gallium can be adopted
Sulphur selenium liquid phase precursor process is introduced into copper indium gallium sulphur selenium in N-type wide band gap semiconducter particulate porous film 3, annealed in its hole
Copper indium gallium sulphur selenium is generated with surface in situ.By means of this, formed between anodic porous film surface and copper indium gallium sulphur selenium two-phase tight
Chemical bond, be conducive to carrier effective transmission between the two phases, therefore being manufactured into for solar cell can be substantially reduced
This.
In one example, the thickness of copper indium gallium sulphur selenium sensitizing layer 2 can be 50nm～5000nm.
Back electrode 1 can be formed on copper indium gallium sulphur selenium sensitizing layer 2 by back electrode material Jing filming technology.Wherein back electrode material
Material may be selected from the compound of high-work-function metal, high work function conductive non-metals or high work function P-type conduction.Filming technology is for example
Can adopt vacuum evaporation.
High-work-function metal may be selected from any one in Cu, Ni, Mo, Au and Pt or two or more.
High work function conductive non-metals may be selected from any one in C, Te and SiC or two or more.
High work function P-type conduction compound may be selected from ZnTe, ZnTe:Cu, CuTe and Sb3Te2In any one or two
More than kind.
In one example, the thickness of back electrode 1 can be 50～5000nm.
Specifically, as an example, with reference to Fig. 2, all solid state copper indium gallium sulphur selenium sensitized semiconductor anode of the present invention is illustrated too
The preparation method in positive electricity pond.
1）N-type nesa coating is prepared on a glass substrate using N-type transparent conductive film material Jing filming technologies.
Using N-type transparent conductive film material it is as described above.Using filming technology do not limit, as long as film can be formed i.e.
Can, for example can be magnetron sputtering, reactive sputtering, chemical vapor deposition, spray pyrolysis or sol-gel filming technology, it has
Body step can be determined by those skilled in the art according to prior art.In one example, magnetron sputtering method can be adopted,
Its design parameter can be：Working gas is Ar, and operating air pressure is 0.2～1.0Pa, and power density is 1～10W cm-2, power source
For DC source or radio frequency source.The thickness of the N-type nesa coating of preparation can be 100～1000nm.
2）Prepare the wide bandgap N type semi-conducting material particulate that particle diameter is 1～1000nm.
Wherein wide bandgap N type semi-conducting material is as described above.Preparation method can adopt known method, for example, may be selected from water
Hot method, solvent-thermal method, sol-gel process, chemical precipitation method, microemulsion method, micelle assay, reverse micelle method or high-temperature cracking method.This
Art personnel can be determined according to prior art.In one example, hydro-thermal method can be adopted, its design parameter can
For：Hydrothermal temperature is 60～380 DEG C, and the hydro-thermal time is 2～120 hours.Illustrate in the present embodiment and prepare wide bandgap N type half
Conductor particles of material, it should be appreciated that the step is not required in that the particle diameter that can also for example select commercialization is 1～1000nm
Wide bandgap N type semi-conducting material particulate.
3）Wide bandgap N type semi-conducting material particulate is scattered in solvent and makes the good slurry of stable, rheological property.
The solid content of such as slurry can be 10～45%.
Using solvent can be selected as needed, for example can be ethanol, water etc..In order that slurry has preferably
Stability and rheological property, can also add the additives such as viscosity modifier.
4）Prepared slurry Jing ceramics filming technologies are prepared into N-type wide band gap semiconducter precursor film on N-type nesa coating,
Formation N-type wide band gap semiconducter particulate porous film in the glass substrate of N-type nesa coating is being covered with after drying annealing.
Ceramic filming technology can adopt known method, for example, can be silk screen print method or the tape casting.Drying and annealing
Temperature for example can be 100～400 DEG C, but it is also possible to carry out in other temperature ranges, as long as can form N-type broad-band gap partly leading
Body particulate porous film.The thickness of obtained N-type wide band gap semiconducter particulate porous film can be 1～10 μm.
5）The obtained glass substrate for being covered with N-type nesa coating and N-type wide band gap semiconducter particulate porous film is placed in
After soaking 0.1～5 hour in copper indium gallium sulphur selenium liquid phase presoma, Jing after 180～600 DEG C are annealed 5～120 minutes in N-type broadband
Copper indium gallium sulphur selenium sensitizing layer is generated in the hole of gap semiconductor particulate porous film with surface in situ.
Wherein, the preparation method of indium gallium sulphur selenium liquid phase presoma is not limited, if its can in-situ preparation copper indium gallium sulphur selenium be
Can.Prior art can for example be adopted（United States Patent (USP) US2009145482A1 or Chinese patent CN101960610B）Described in side
Method is prepared.The chemical composition of obtained copper indium gallium sulphur selenium sensitizing layer can be CuxIn1-yGaySe2-zSz, wherein 0.6≤x≤
0.9,0≤y≤1,0≤z≤2, thickness can be 50nm～5000nm.
6）Back electrode material Jing filming technology is prepared into back electrode on copper indium gallium sulphur selenium sensitizing layer, that is, all solid state nothing is obtained
Machine dye-sensitized semiconductor anode solar cell.
Using back electrode material it is as described above.Using filming technology for example can be vacuum evaporation, its design parameter
Can be：Base vacuum is 1 × 10-4～50 × 10-4Pa, evaporation current is 50～1000A, and the time is 1～60min, and film is thick
Spend for 50～5000nm.
Performance test can also be carried out to all solid state inorganic dyestuff sensitized semiconductor anode solar cell of the present invention.Example
Such as, its photoelectric transformation efficiency is measured under the analog light source of AM1.5 for more than 2.3%.
The all solid state inorganic dyestuff sensitized semiconductor anode solar cell of the present invention can be used as flexible solar cell.
The present invention by it is previously prepared go out copper indium gallium sulphur selenium liquid phase presoma, then early stage is prepared into semiconductor porous anode
Film is immersed in copper indium gallium sulphur selenium liquid phase presoma after 0.1～5h, Jing after 180～600 DEG C are annealed 5～120min, is partly led
Body anodic porous film-copper indium gallium sulphur selenium composite film.Due to being to be drawn copper indium gallium sulphur selenium using copper indium gallium sulphur selenium liquid phase precursor process
Enter anodic porous film, it is annealed to generate copper indium gallium sulphur selenium, therefore anodic porous film surface and copper in anodic porous film surface in situ
Close chemical bond is formed between indium gallium sulphur selenium two-phase, is conducive to carrier effective transmission between the two phases, therefore can be with
Substantially reduce the manufacturing cost of solar cell.
The copper indium gallium sulphur selenium sensitized semiconductor anode solar cell and traditional organic dye sensitized solar cell of the present invention
Compare, copper indium gallium sulphur selenium instead of organic dyestuff and liquid electrolyte, therefore there is no the caused envelope due to liquid electrolyte
Dress problem；Stable solid-solid interface is formed between copper indium gallium sulphur selenium and semiconductor anode side, therefore there is no organic dyestuff and anode
The issue for battery life for being desorbed and causing；Copper indium gallium sulphur selenium is stable solid-state semiconductor, therefore there is no organic dyestuff by half
The light degradation of conductor anode and the photoetch problem that causes；Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is all solid state sun
Battery, therefore the configuration design of battery is almost unrestricted, can use under extremely low temperature, high temperature and intense radiation conditions, can prepare
Into flexible solar cell.Most important of which is that, copper indium gallium sulphur selenium introduces porous semi-conductor anode by liquid phase precursor process, so
After annealing is capable of achieving tight in porous semi-conductor anode surface in-situ preparation between copper indium gallium sulphur selenium and porous semi-conductor anode
Close chemical bond, realizes that photo-generated carrier is effectively transmitted on interface；The battery preparation technique is simple, with low cost, equipment
Small investment, raw material availability is high, and controllability is strong, reproducible, it is easy to accomplish large-scale production.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
The technological parameters such as time, concentration, temperature are also only that an example in OK range, i.e. those skilled in the art can be by these
The explanation of text is done in suitable scope and is selected, and does not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
The all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell for preparing in the present embodiment as shown in Figure 1, wherein：
1 is back electrode, and 2 is copper indium gallium sulphur selenium sensitizing layer, and 3 is N-type semiconductor perforated membrane, and 4 is N-type nesa coating, and 5 is glass base
Piece, concrete preparation method is as follows：
1st, the preparation of semiconductor anode side perforated membrane
1）The material of N-type nesa coating is selected and its prepared
, then with common soda-lime-silica glass as substrate, adopted as N-type transparent conductive membrane material from AZO in the present embodiment
Square resistance is prepared less than 10 Ω/, electrically conducting transparent AZO film of the transmitance higher than 85% is used for all solid state with magnetron sputtering method
Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell.The design parameter of magnetron sputtering is：Working gas is Ar, and operating air pressure is
0.5Pa, power density is 6W cm-2, power source is DC source；
2）The selection of N-type wide bandgap semiconductor materials and its preparation of micro mist
Select ZnO as the anode material of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell in the present embodiment, its is micro-
The preparation method of powder adopts the hydro-thermal method, concrete operation step and parameter to be：By the zinc sulfate solution 150ml's of 0.1M and 0.5M
Urea liquid 50ml mixes, and in adding hydrothermal reaction kettle, Jing after 180 DEG C of hydro-thermal reactions 24h, the ZnO for obtaining particle diameter about 50nm is micro-
Powder；
3）The preparation of N-type wide band gap semiconducter perforated membrane
The present embodiment prepares porous ZnO film using silk screen print method, and concrete operation step and parameter are：By 1g ZnO micro mists
In being distributed to 50ml ethanol, and 1ml glycerine and 1ml terpinols are added, form ZnO slurries, then by silk screen by ZnO slurries
It is printed onto on AZO films, ZnO perforated membranes is obtained Jing after 120 DEG C of dryings.
2nd, the preparation of copper indium gallium sulphur selenium liquid phase presoma and copper indium gallium sulphur selenium sensitizing layer
1）The preparation of copper indium gallium sulphur selenium liquid phase presoma：Carried out using method described in United States Patent (USP) US2009145482A1
Prepare, the concentration of prepared copper indium gallium sulphur selenium liquid phase presoma is 0.3M；
2）Obtained ZnO perforated membranes in step 1 are immersed in copper indium gallium sulphur selenium liquid phase presoma after 5h, 500 DEG C of Jing is moved back
After fiery 5min, ZnO- copper indium gallium sulphur selenium composite films are obtained.
3rd, the selection and its preparation of back electrode material
Select the noble metal Au of high work function as back electrode in the present embodiment, its preparation method adopts vacuum vapour deposition,
Its design parameter is：Base vacuum is 6 × 10-4Pa, evaporation current is 200A, and the time is 3min, and film thickness is 600nm.
4th, the test of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell
By prepared copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, under the analog light source of AM1.5, institute is measured
The all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell for preparing, its photoelectric transformation efficiency is 4.6%.
Embodiment 2
1st, the preparation of semiconductor anode side perforated membrane
1）The material of N-type nesa coating is selected and its prepared
, then with common soda-lime-silica glass as substrate, adopted as N-type transparent conductive membrane material from FTO in the present embodiment
Square resistance is prepared less than 10 Ω/, electrically conducting transparent FTO film of the transmitance higher than 85% is used for sol-gel filming technology
All solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell；
2）The selection of N-type wide bandgap semiconductor materials and its preparation of micro mist
Select ZnS as the anode material of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell in the present embodiment, its is micro-
The preparation method of powder adopts the sol-gel process, concrete operation step and parameter to be：By the zinc sulfate solution 100ml of 0.2M with
The thiourea solution 100ml mixing of 1.5M, in adding hydrothermal reaction kettle, Jing after 80 DEG C of hydro-thermal reactions 2h, obtains particle diameter about 50nm's
ZnS micro mists；
3）The preparation of N-type wide band gap semiconducter perforated membrane
The present embodiment prepares porous ZnS film using the tape casting, and concrete operation step and parameter are：By 0.5g ZnS micro mists point
In being scattered to 20ml deionized waters, and add 4ml acetylacetone,2,4-pentanediones and 4ml Qulas logical, form ZnS slurries, then by silk screen by ZnS
Slurry is printed onto on FTO films, and ZnS perforated membranes are obtained Jing after 200 DEG C of dryings.
2nd, the preparation of copper indium gallium sulphur selenium liquid phase presoma and copper indium gallium sulphur selenium sensitizing layer
1）The preparation of copper indium gallium sulphur selenium liquid phase presoma：Using method system described in Chinese patent CN101960610B
Standby, the concentration of prepared copper indium gallium sulphur selenium liquid phase presoma is 0.2M；
2）Obtained ZnS perforated membranes in step 1 are immersed in copper indium gallium sulphur selenium liquid phase presoma after 5h, 450 DEG C of Jing is moved back
After fiery 5min, ZnS- copper indium gallium sulphur selenium composite films are obtained.
3rd, the selection and its preparation of back electrode material
From high work function conductive non-metals SiC as back electrode in the present embodiment, its preparation method adopts vacuum evaporation
Method, its design parameter is：Base vacuum is 3 × 10-4Pa, evaporation current is 600A, and the time is 30min, and film thickness is
1000nm。
4th, the test of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell
By prepared copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, under the analog light source of AM1.5, institute is measured
The all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell for preparing, its photoelectric transformation efficiency is 2.3%.
Embodiment 3
1st, the preparation of semiconductor anode side perforated membrane
1）The material of N-type nesa coating is selected and its prepared
Zn is selected in the present embodiment2SnO4As N-type transparent conductive membrane material, then with ultrawhite solar energy glass as substrate,
Using spray pyrolysis square resistance is prepared less than 10 Ω/, electrically conducting transparent Zn of the transmitance higher than 85%2SnO4Film is used for complete
Solid-state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell；
2）The selection of N-type wide bandgap semiconductor materials and its preparation of micro mist
BiOCl is selected in the present embodiment as the anode material of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, its
The preparation method of micro mist adopts the micelle assay, concrete operation step and parameter to be：By 3.0g Bi (NO3)3·5H2O is added to 60mL
In deionized water, fully after dissolving, 5ml saturation NaCl solutions are added, hydrothermal reaction kettle is subsequently adding, in 120 DEG C of hydro-thermal reactions
24h, obtains the BiOCl micro mists of particle diameter about 150nm；
3）The preparation of N-type wide band gap semiconducter perforated membrane
The present embodiment prepares porous BiOCl film using the tape casting, and concrete operation step and parameter are：0.5g BiOCl is micro-
Powder is distributed in 20ml ethanol, and adds 4ml acetylacetone,2,4-pentanediones and 0.01g ethyl celluloses, forms BiOCl slurries, is then passed through
BiOCl slurries are printed onto Zn by silk screen2SnO4On film, BiOCl perforated membranes are obtained Jing after 300 DEG C of dryings.
2nd, the preparation of copper indium gallium sulphur selenium liquid phase presoma and copper indium gallium sulphur selenium sensitizing layer
1）The preparation of copper indium gallium sulphur selenium liquid phase presoma：Using method system described in Chinese patent CN101960610B
Standby, the concentration of prepared copper indium gallium sulphur selenium liquid phase presoma is 0.8M；
2）Obtained BiOCl perforated membranes in step 1 are immersed in copper indium gallium sulphur selenium liquid phase presoma after 2h, 480 DEG C of Jing
After annealing 120min, BiOCl- copper indium gallium sulphur selenium composite films are obtained.
3rd, the selection and its preparation of back electrode material
High work function P-type conduction compound Sb is selected in the present embodiment3Te2Used as back electrode, its preparation method adopts vacuum
Vapour deposition method, its concrete preparation method is：Base vacuum is 2 × 10-4Pa, evaporation current is 100A, and the time is 15min, and film is thick
Spend for 1500nm.
4th, the test of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell
By prepared copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, under the analog light source of AM1.5, institute is measured
The all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell for preparing, its photoelectric transformation efficiency is 8.4%.
Comparative example 1
From FTO as N-type transparent conductive membrane material in this comparative example；From TiO2Partly lead as copper indium gallium sulphur selenium sensitization
The anode material of body anode solar cell；From copper indium gallium sulphur selenium nano-powder as sensitizing layer；From Pt as back electrode.By
In copper indium gallium sulphur selenium nano-powder and porous TiO2Close chemical bond can not be realized between anode, and simply forms limited
Mechanical bond.Therefore, prepared copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, under the analog light source of AM1.5, surveys
The photoelectric transformation efficiency for obtaining is only 0.01%.
Industrial applicability：Copper indium gallium sulphur selenium and porous in the copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of the present invention
Close chemical bond is capable of achieving between semiconductor anode side, realizes that photo-generated carrier is effectively transmitted on interface, and present invention system
Standby process is simple, with low cost, equipment investment is few, and raw material availability is high, and controllability is strong, reproducible, it is easy to accomplish extensive
Production, can be applicable to solar cell energy field.
Claims (10)
1. a kind of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, it is characterised in that include：
The N-type nesa coating being sequentially formed in glass substrate and N-type wide band gap semiconducter particulate porous film；
Generate so as to the copper and indium gallium compound with it with surface in situ in the hole of the N-type wide band gap semiconducter particulate porous film
Sulphur selenium sensitizing layer；And
The back electrode being formed on the copper indium gallium sulphur selenium sensitizing layer；
Wherein, all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is without organic dyestuff and liquid electrolyte.
2. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 1, it is characterised in that the glass
Substrate is alkali metal glass substrate or ultrawhite solar energy glass substrate.
3. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 1 and 2, it is characterised in that the N
Type nesa coating by N-type transparent conductive film material Jing magnetron sputterings, reactive sputtering, chemical vapor deposition, spray pyrolysis or
Sol-gel process is obtained, wherein the N-type transparent conductive film material is selected from FTO, ITO, AZO, Cd2SnO4, Zn2SnO4,
TiO2:Nb and SrTiO3:At least one in Nb；The thickness of the N-type nesa coating is 100～1000 nm.
4. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 1, it is characterised in that the N-type
Wide band gap semiconducter particulate porous film is obtained by wide bandgap N type semi-conducting material organizine net print process or the tape casting, wherein described
Wide bandgap N type semi-conducting material is selected from wide bandgap N type oxide semiconductor material, wide bandgap N type sulfide semiconductor material, width
At least one in band gap N-type oxyhalogenation thing semi-conducting material and wide bandgap N type sulfur halide semi-conducting material；The N-type width
The thickness of gap semiconductor particulate porous film is 1～10 μm.
5. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 4, it is characterised in that the broadband
Gap N-type oxide semiconductor material is selected from TiO2、ZrO2、Nb2O5、Ta2O5、ZnO、In2O3、SnO2And SrTiO3In at least one
Kind；The wide bandgap N type sulfide semiconductor material is selected from ZnS, CdS, In2S3、SnS2And Sb2S3In at least one；It is described
Wide bandgap N type oxyhalogenation thing semi-conducting material is selected from BiOX and/or SbOX；The wide bandgap N type sulfur halide semi-conducting material
For BiSX；Wherein X is selected from Cl, Br and/or I.
6. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 1, it is characterised in that the copper and indium
Gallium sulphur selenium sensitizing layer is copper indium gallium sulphur selenium semiconductive thin film, and its component is CuxIn1-yGaySe2-zSz, wherein 0.6≤x≤0.9,0
The ＜ z ＜ 2 of ＜ y ＜ 1,0；The thickness of the copper indium gallium sulphur selenium sensitizing layer is 50 nm～5000 nm.
7. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 1, it is characterised in that the back of the body electricity
Pole is obtained by the vacuum evaporation of back electrode material Jing, wherein the back electrode material is led selected from high-work-function metal or high work function
Electricity is nonmetallic；The thickness of the back electrode is 50～5000 nm.
8. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 7, it is characterised in that the Gao Gong
At least one of the function metal in Cu, Ni, Mo, Au and Pt；The high work function conductive non-metals are selected from C, Te and SiC
In at least one；The high work function P-type conduction compound is selected from ZnTe, ZnTe:Cu, CuTe and Sb3Te2In at least one
Kind.
9. the preparation side of the copper indium gallium sulphur selenium sensitized semiconductor anode solar cell any one of a kind of claim 1 to 8
Method, it is characterised in that include：
1）Using N-type transparent conductive film material Jing magnetron sputterings, reactive sputtering, chemical vapor deposition, spray pyrolysis or molten
Glue-gel method prepares on a glass substrate N-type nesa coating；
2）By the slurry organizine wire mark brush containing the wide bandgap N type semi-conducting material particulate that particle diameter is 1～1000nm or the tape casting
It is coated on the N-type nesa coating, drying forms N-type wide band gap semiconducter particulate porous film after annealing；
3）The N-type wide band gap semiconducter particulate porous film is placed in into the copper indium gallium sulphur selenium liquid of cupric, indium, gallium, sulphur and selenium element
After soaking 0.1～5 hour in phase precursor, Jing after 180～600 DEG C are annealed 5～120 minutes in the N-type wide band gap semiconducter
Copper indium gallium sulphur selenium sensitizing layer is generated in the hole of particulate porous film with surface in situ；And
4）Back electrode material Jing vacuum vapour deposition is formed into back electrode on the copper indium gallium sulphur selenium sensitizing layer, that is, copper and indium gallium is obtained
Sulphur selenium sensitized semiconductor anode solar cell.
10. preparation method according to claim 9, it is characterised in that the wide bandgap N type semi-conducting material particulate passes through
Hydro-thermal method, solvent-thermal method, sol-gel process, chemical precipitation method, microemulsion method, micelle assay, reverse micelle method or Pintsch process legal system
It is standby.
Priority Applications (1)
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| CN101471394A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院上海硅酸盐研究所 | Method for preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery |
| CN101789469A (en) * | 2010-03-05 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Method for preparing light absorption layer of Cu-In-Ga-Se-S thin film solar cell |
| CN102130202A (en) * | 2010-01-14 | 2011-07-20 | 正峰新能源股份有限公司 | Method and system for forming Cu-In-Ga-S-Se absorption layer and cadmium sulfide buffer layer in antivacuum way |
| CN102458832A (en) * | 2009-05-26 | 2012-05-16 | 珀杜研究基金会 | Thin films for photovoltaic cells |
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| US8613973B2 (en) * | 2007-12-06 | 2013-12-24 | International Business Machines Corporation | Photovoltaic device with solution-processed chalcogenide absorber layer |
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| CN101471394A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院上海硅酸盐研究所 | Method for preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery |
| CN102458832A (en) * | 2009-05-26 | 2012-05-16 | 珀杜研究基金会 | Thin films for photovoltaic cells |
| CN102130202A (en) * | 2010-01-14 | 2011-07-20 | 正峰新能源股份有限公司 | Method and system for forming Cu-In-Ga-S-Se absorption layer and cadmium sulfide buffer layer in antivacuum way |
| CN101789469A (en) * | 2010-03-05 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Method for preparing light absorption layer of Cu-In-Ga-Se-S thin film solar cell |
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