CN103633182A - 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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- CN103633182A CN103633182A CN201310613803.XA CN201310613803A CN103633182A CN 103633182 A CN103633182 A CN 103633182A CN 201310613803 A CN201310613803 A CN 201310613803A CN 103633182 A CN103633182 A CN 103633182A
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- indium gallium
- copper indium
- gallium sulphur
- sulphur selenium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 11
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 128
- 229910052733 gallium Inorganic materials 0.000 claims description 128
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 claims description 126
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 120
- 239000012528 membrane Substances 0.000 claims description 47
- 239000010408 film Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 230000001235 sensitizing effect Effects 0.000 claims description 26
- 239000007791 liquid phase Substances 0.000 claims description 24
- 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 19
- 238000000137 annealing Methods 0.000 claims description 14
- 239000007772 electrode material Substances 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- 238000010345 tape casting Methods 0.000 claims description 8
- 239000000693 micelle Substances 0.000 claims description 7
- 229910052755 nonmetal Inorganic materials 0.000 claims description 7
- 150000002843 nonmetals Chemical class 0.000 claims description 7
- 238000005118 spray pyrolysis Methods 0.000 claims description 7
- 229910002367 SrTiO Inorganic materials 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 229910007709 ZnTe Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 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
- -1 sulfur halide Chemical class 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 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
- 238000001035 drying Methods 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
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-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
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
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- 238000013461 design Methods 0.000 description 8
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 8
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- 239000011701 zinc Substances 0.000 description 5
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- 206010070834 Sensitisation Diseases 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-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
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
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- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—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 potential barriers
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- 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 potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- 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]
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- 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
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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, be specifically related 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, and along with the development of human society, it is more and more important and urgent that the development and utilization of clean reproducible energy seems.Solar energy is a kind of clean, abundant, regenerative resource of not being subject to regional limits, the effective exploitation of solar energy and utilize tool to be of great significance.Solar cell is one of mankind's principal mode of effectively utilizing solar energy.
Sensitization type solar cell is low with its production cost, low equipment investment, energy resource consumption are few, simple without vacuum, technique, be expected to realize can be comparable with existing electricity price low cost generating, caused people's extensive concern.Yet traditional dye sensitization type solar cell, use be organic dyestuff and liquid electrolyte, cause device itself to have many latent defects that are difficult to overcome.Between long-term photostability, organic dyestuff and the semiconductive particles of organic dyestuff itself, the long-time stability of chemisorbed, organic dyestuff solidify at low temperatures and cause the various latent defects such as battery can not be used the burn into liquid electrolyte of encapsulating material at photoetch decomposition, the vaporization at high temperature of liquid electrolyte, the liquid electrolyte on semiconductive particles surface, are all difficult to overcome.
Summary of the invention
Problem in the face of prior art existence, the object of the present invention is to provide device architecture of a kind of all solid state inorganic dyestuff sensitized semiconductor anode solar cell and preparation method thereof, relate generally to all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell and preparation method thereof.
At this, on the one hand, the invention provides a kind of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, comprising: be formed at successively N-type nesa coating and N-type wide band gap semiconducter particulate perforated membrane on glass substrate; Thereby generate the copper indium gallium sulphur selenium sensitizing layer compound with it with surface in situ in the hole of described N-type wide band gap semiconducter particulate perforated membrane; And be formed at the back electrode on described copper indium gallium sulphur selenium sensitizing layer; Wherein, described all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is not containing organic dyestuff and liquid electrolyte.
Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of the present invention is compared with traditional organic dye sensitized solar cell, and copper indium gallium sulphur selenium has substituted organic dyestuff and liquid electrolyte, does not therefore have the encapsulation problem causing due to liquid electrolyte; Therefore between copper indium gallium sulphur selenium and semiconductor anode, form stable solid-solid interface, do not have organic dye and Anodic Desorption Study and the issue for battery life that causes; Copper indium gallium sulphur selenium is stable solid-state semiconductor, does not therefore have the photoetch problem that organic dye is caused by the light degradation of semiconductor anode; Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is all solid state solar cell, so the configuration design of battery is restricted hardly, can under utmost point low temperature, high temperature and intense radiation conditions, use, and can be prepared into flexible solar cell.Wherein the most important thing is, copper indium gallium sulphur selenium generates with surface in situ in the hole of porous semi-conductor anode, so can realize chemical bond closely between copper indium gallium sulphur selenium and porous semi-conductor anode, realizes photo-generated carrier effectively transmission on interface.
Preferably, described glass substrate is alkali metal glass substrate or ultrawhite solar energy glass substrate.
Preferably, described N-type nesa coating is made through magnetron sputtering, reactive sputtering, chemical vapour deposition (CVD), spray pyrolysis or sol-gel process by N-type transparent conductive film material, wherein said N-type transparent conductive film material is selected from FTO(fluorine-doped tin dioxide), ITO(tin indium oxide), AZO(Al-Doped ZnO), Cd
2snO
4, Zn
2snO
4, TiO
2: Nb and SrTiO
3: any one in Nb or two or more.
Preferably, the thickness of described N-type nesa coating is 100～1000nm.
Preferably, described N-type wide band gap semiconducter particulate perforated membrane is made through silk screen print method or the tape casting by wide bandgap N type semi-conducting material, wherein said wide bandgap N type semi-conducting material 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 any one or two or more.
Preferably, described wide bandgap N type oxide semiconductor material is selected from TiO
2, ZrO
2, Nb
2o
5, Ta
2o
5, ZnO, In
2o
3, SnO
2, and SrTiO
3in any one or two or more; Described wide bandgap N type sulfide semiconductor material is selected from ZnS, CdS, In
2s
3, SnS
2, and Sb
2s
3in any one or two or more; Described wide bandgap N type oxyhalogenation thing semi-conducting material is selected from BiOX and/or SbOX, and wherein X is selected from Cl, Br and/or I; Described wide bandgap N type sulfur halide semi-conducting material is BiSX, and wherein X is selected from Cl, Br and/or I.
Preferably, the thickness of described N-type wide band gap semiconducter particulate perforated membrane is 1～10 μ m.
Preferably, described copper indium gallium sulphur selenium sensitizing layer is copper indium gallium sulphur selenium semiconductive thin film, and its component is Cu
xin
1-yga
yse
2- zs
z, 0.6≤x≤0.9 wherein, 0≤y≤1,0≤z≤2.
Preferably, the thickness of described copper indium gallium sulphur selenium sensitizing layer is 50nm～5000nm.
Preferably, described back electrode is made through vacuum evaporation by back electrode material, and wherein said back electrode material is selected from high-work-function metal, high work function conductive non-metals or high work function P-type conduction compound.
Preferably, described high-work-function metal be selected from Cu, Ni, Mo, Au and Pt any one or two or more; Described high work function conductive non-metals be selected from C, Te and SiC any one or two or more; Described high work function P-type conduction compound is selected from ZnTe, ZnTe:Cu, CuTe and Sb
3te
2in any one or two or more.
Preferably, the thickness of described back electrode is 50～5000nm.
On the other hand, the present invention also provides a kind of preparation method of above-mentioned copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, comprising:
1) adopt N-type transparent conductive film material on glass substrate, to prepare N-type nesa coating through magnetron sputtering, reactive sputtering, chemical vapour deposition (CVD), spray pyrolysis or sol-gel process;
2) by containing particle diameter, be that the slurry of the wide bandgap N type semi-conducting material particulate of 1～1000nm is coated on described N-type nesa coating, forms N-type wide band gap semiconducter particulate perforated membrane after drying annealing through silk screen printing or the tape casting;
3) the copper indium gallium sulphur selenium liquid phase presoma that described N-type wide band gap semiconducter particulate perforated membrane is placed in to cupric, indium, gallium, sulphur and selenium element soaked after 0.1～5 hour, through 180～600 ℃ of annealing, after 5～120 minutes, in the hole of described N-type wide band gap semiconducter particulate perforated membrane, generated copper indium gallium sulphur selenium sensitizing layer with surface in situ;
4) back electrode material is formed to back electrode through vacuum vapour deposition on described copper indium gallium sulphur selenium sensitizing layer, make copper indium gallium sulphur selenium sensitized semiconductor anode solar cell.
Preferably, described 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 high-temperature cracking method preparation.
The present invention is by for example, preparing copper indium gallium sulphur selenium liquid phase presoma according to prior art (US2009145482A1 and CN101960610B) in advance, then prepared by early stage after semiconductor porous anode film is immersed in copper indium gallium sulphur selenium liquid phase presoma and anneal, obtain semiconductor anode perforated membrane-copper indium gallium sulphur selenium composite film.Because being adopts copper indium gallium sulphur selenium liquid phase precursor process that copper indium gallium sulphur selenium is introduced to anode perforated membrane, through annealing, in the hole of anode perforated membrane, generate copper indium gallium sulphur selenium with surface in situ, therefore between anode porous film surface and copper indium gallium sulphur selenium two-phase, form chemical bond closely, be conducive to the effective transmission of charge carrier between two-phase, therefore can greatly reduce the manufacturing cost of solar cell.
Preparation method's technique of the present invention is simple, with low cost, and equipment investment is few, and raw material availability is high, and controllability is strong, reproducible, is easy to realize large-scale production.
Accompanying drawing explanation
Fig. 1 is the device architecture schematic diagram of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of an example of the present invention;
Fig. 2 is the preparation flow schematic diagram of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of an example of the present invention.
Embodiment
Below in conjunction with accompanying drawing and following execution mode, further illustrate the present invention, should be understood that accompanying drawing and following execution mode are only for the present invention is described, and unrestricted the present invention.If not special instruction, the term in the present invention " N type semiconductor " is the semiconductor of depending on electron conduction.
Fig. 1 illustrates the device architecture figure of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of an example of the present invention.As shown in Figure 1, all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell can comprise: thus glass substrate 5, be formed at N-type nesa coating 4 on glass substrate 5 and N-type wide band gap semiconducter particulate perforated membrane 3 successively, in the hole of described N-type wide band gap semiconducter particulate perforated membrane 3 and surface in situ generate the copper indium gallium sulphur selenium sensitizing layer 2 compound with it and be formed at the back electrode 1 on copper indium gallium sulphur selenium sensitizing layer 2.
Glass substrate 5 as long as can see through sunlight, for example, can be selected from: the ultrawhite solar energy glass of alkali metal glass or high permeability.Wherein, alkali metal glass can be for example common soda-lime-silica glass.
N-type nesa coating 4 can be formed on glass substrate 5 through filming technology by N-type transparent conductive film material.Wherein N-type transparent conductive film material can be selected from: FTO, ITO, AZO, Cd
2snO
4, Zn
2snO
4, TiO
2: Nb and SrTiO
3: any one in Nb or two or more.Filming technology is not limit, as long as can form film, for example, can be magnetron sputtering, reactive sputtering, chemical vapour deposition (CVD), 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 perforated membrane 3 can be formed on N-type nesa coating 4 through filming technology by wide bandgap N type semi-conducting material.Wherein wide bandgap N type semi-conducting material can be selected from: any one in 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 or two or more.Filming technology is not limit, as long as can form perforated membrane, for example, can be silk screen print method or the tape casting.
Wide bandgap N type oxide semiconductor material can be selected from TiO
2, ZrO
2, Nb
2o
5, Ta
2o
5, ZnO, In
2o
3, SnO
2and SrTiO
3in any one or two or more.
Wide bandgap N type sulfide semiconductor material can be selected from ZnS, CdS, In
2s
3, SnS
2, and Sb
2s
3in any one or two or more.
Wide bandgap N type oxyhalogenation thing semi-conducting material can 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 and is selected from Cl, Br or I).
In one example, the thickness of N-type wide band gap semiconducter particulate perforated membrane 3 can be 1～10 μ m.
Copper indium gallium sulphur selenium sensitizing layer 2 is copper indium gallium sulphur selenium semiconductive thin film, and its component can be Cu
xin
1-yga
yse
2-zs
z(0.6≤x≤0.9,0≤y≤1,0≤z≤2).As shown in Figure 1, copper indium gallium sulphur selenium sensitizing layer 2 generates with surface in situ in the hole of N-type wide band gap semiconducter particulate perforated membrane 3, thereby forms copper indium gallium sulphur selenium sensitized semiconductor composite membrane.Can adopt copper indium gallium sulphur selenium liquid phase precursor process that copper indium gallium sulphur selenium is introduced in N-type wide band gap semiconducter particulate perforated membrane 3, through annealing, in its hole, generate copper indium gallium sulphur selenium with surface in situ.By means of this, between anode porous film surface and copper indium gallium sulphur selenium two-phase, form chemical bond closely, be conducive to the effective transmission of charge carrier between two-phase, therefore can greatly reduce the manufacturing cost of solar cell.
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 through filming technology by back electrode material.Wherein back electrode material can 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 can be for example to adopt vacuum evaporation.
High-work-function metal can be selected from Cu, Ni, Mo, Au and Pt any one or two or more.
High work function conductive non-metals can be selected from C, Te and SiC any one or two or more.
High work function P-type conduction compound can be selected from ZnTe, ZnTe:Cu, CuTe and Sb
3te
2in any one or two or more.
In one example, the thickness of back electrode 1 can be 50～5000nm.
Particularly, as example, with reference to Fig. 2, the preparation method of all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of the present invention is described.
1) adopt N-type transparent conductive film material through filming technology, on glass substrate, to prepare N-type nesa coating.
The N-type transparent conductive film material adopting as mentioned above.The filming technology adopting is not limit, as long as can form film, can be for example magnetron sputtering, reactive sputtering, chemical vapour deposition (CVD), spray pyrolysis or sol-gel filming technology, its concrete steps can be determined according to prior art by those skilled in the art.In one example, can adopt magnetron sputtering method, 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 is 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 as mentioned above.Preparation method can adopt known method, for example, can be selected from hydro thermal method, solvent-thermal method, sol-gel process, chemical precipitation method, microemulsion method, micelle assay, reverse micelle method or high-temperature cracking method.Those skilled in the art can determine according to prior art.In one example, can adopt hydro thermal method, its design parameter can be: hydrothermal temperature is 60～380 ℃, and the hydro-thermal time is 2～120 hours.Illustrate in the present embodiment and prepare wide bandgap N type semi-conducting material particulate, but should be understood that this step is not essential, for example also can select commercial particle diameter is the wide bandgap N type semi-conducting material particulate of 1～1000nm.
3) wide bandgap N type semi-conducting material microparticulate is made in solvent to slurry stable, that rheological property is good.For example the solid content of slurry can be 10～45%.
The solvent adopting can be selected as required, such as being ethanol, water etc.In order to make slurry there is better stability and rheological property, can also add the additives such as viscosity modifier.
4) will make slurry and through ceramic filming technology, on N-type nesa coating, prepare N-type wide band gap semiconducter precursor film, after drying annealing, on the glass substrate that is covered with N-type nesa coating, form N-type wide band gap semiconducter particulate perforated membrane.
Pottery filming technology can adopt known method, for example, can be silk screen print method or the tape casting.The temperature of drying and annealing can be for example 100～400 ℃, but also can carry out in other temperature range, as long as can form N-type wide band gap semiconducter particulate perforated membrane.The thickness of the N-type wide band gap semiconducter particulate perforated membrane making can be 1～10 μ m.
5) glass substrate that is covered with N-type nesa coating and N-type wide band gap semiconducter particulate perforated membrane making is placed in to copper indium gallium sulphur selenium liquid phase presoma and soaks after 0.1～5 hour, through 180～600 ℃ of annealing, after 5～120 minutes, in the hole of N-type wide band gap semiconducter particulate perforated membrane, generate copper indium gallium sulphur selenium sensitizing layer with surface in situ.
Wherein, the preparation method of indium gallium sulphur selenium liquid phase presoma does not limit, as long as it can original position generate copper indium gallium sulphur selenium.For example can adopt the method described in prior art (US Patent No. 2009145482A1 or Chinese patent CN101960610B) to be prepared.The chemical composition of the copper indium gallium sulphur selenium sensitizing layer making can be Cu
xin
1-yga
yse
2-zs
z, 0.6≤x≤0.9 wherein, 0≤y≤1,0≤z≤2, thickness can be 50nm～5000nm.
6) back electrode material is prepared to back electrode through filming technology on copper indium gallium sulphur selenium sensitizing layer, make all solid state inorganic dyestuff sensitized semiconductor anode solar cell.
The back electrode material adopting as mentioned above.The filming technology adopting can be for example vacuum evaporation, and 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 thickness is 50～5000nm.
Can also carry out performance test to all solid state inorganic dyestuff sensitized semiconductor anode solar cell of the present invention.For example, it is more than 2.3% under the analog light source of AM1.5, recording its photoelectric conversion efficiency.
All solid state inorganic dyestuff sensitized semiconductor anode solar cell of the present invention can be used as flexible solar cell.
The present invention goes out copper indium gallium sulphur selenium liquid phase presoma by previously prepared, then being prepared by early stage to semiconductor porous anode film is immersed in copper indium gallium sulphur selenium liquid phase presoma after 0.1～5h, after 180～600 ℃ of annealing 5～120min, obtain semiconductor anode perforated membrane-copper indium gallium sulphur selenium composite film.Because being adopts copper indium gallium sulphur selenium liquid phase precursor process that copper indium gallium sulphur selenium is introduced to anode perforated membrane, through annealing, in anode porous film surface original position, generate copper indium gallium sulphur selenium, therefore between anode porous film surface and copper indium gallium sulphur selenium two-phase, form chemical bond closely, be conducive to the effective transmission of charge carrier between two-phase, therefore can greatly reduce the manufacturing cost of solar cell.
Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of the present invention is compared with traditional organic dye sensitized solar cell, and copper indium gallium sulphur selenium has substituted organic dyestuff and liquid electrolyte, does not therefore have the encapsulation problem causing due to liquid electrolyte; Therefore between copper indium gallium sulphur selenium and semiconductor anode, form stable solid-solid interface, do not have organic dye and Anodic Desorption Study and the issue for battery life that causes; Copper indium gallium sulphur selenium is stable solid-state semiconductor, does not therefore have the photoetch problem that organic dye is caused by the light degradation of semiconductor anode; Copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is all solid state solar cell, so the configuration design of battery is restricted hardly, can under utmost point low temperature, high temperature and intense radiation conditions, use, and can be prepared into flexible solar cell.Wherein the most important thing is, copper indium gallium sulphur selenium is introduced porous semi-conductor anode by liquid phase precursor process, then anneal and generate in porous semi-conductor anode surface original position, therefore between copper indium gallium sulphur selenium and porous semi-conductor anode, can realize chemical bond closely, realize photo-generated carrier effectively transmission on interface; This battery preparation technique is simple, with low cost, and equipment investment is few, and raw material availability is high, and controllability is strong, reproducible, is easy to realize large-scale production.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameters such as the time that following example is concrete, concentration, temperature are only also examples in OK range, and those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
The all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of 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, 3 is N type semiconductor perforated membrane, 4 is N-type nesa coating, and 5 is glass substrate, and concrete preparation method is as follows:
1, the preparation of semiconductor anode perforated membrane
1) material of N-type nesa coating is selected and preparation
In the present embodiment, select AZO as N-type electrically conducting transparent membrane material, then take common soda-lime-silica glass as substrate, adopt magnetron sputtering method to prepare square resistance and be less than 10 Ω/, transmitance is used for all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell higher than 85% electrically conducting transparent AZO film.The design parameter of magnetron sputtering is: working gas is Ar, and operating air pressure is 0.5Pa, and power density is 6W cm
-2, power source is DC source;
2) selection of N-type wide bandgap semiconductor materials and the preparation of micro mist thereof
In the present embodiment, select ZnO as the anode material of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, the preparation method of its micro mist adopts hydro thermal method, concrete operation step and parameter are: the zinc sulfate solution 150ml of 0.1M is mixed with the urea liquid 50ml of 0.5M, add in hydrothermal reaction kettle, after 180 ℃ of hydro-thermal reaction 24h, obtain the ZnO micro mist of the about 50nm of particle diameter;
3) preparation of N-type wide band gap semiconducter perforated membrane
The present embodiment adopts silk screen print method to prepare porous ZnO film, concrete operation step and parameter are: 1g ZnO micro mist is distributed in 50ml ethanol, and add 1ml glycerol and 1ml terpinol, form ZnO slurry, then by silk screen, ZnO slurry is printed onto on AZO film, after 120 ℃ are dried, obtains ZnO perforated membrane.
2, the preparation of copper indium gallium sulphur selenium liquid phase presoma and copper indium gallium sulphur selenium sensitizing layer
1) preparation of copper indium gallium sulphur selenium liquid phase presoma: adopt method described in US Patent No. 2009145482A1 to be prepared, the concentration of prepared copper indium gallium sulphur selenium liquid phase presoma is 0.3M;
2) the ZnO perforated membrane making in step 1 is immersed in copper indium gallium sulphur selenium liquid phase presoma after 5h, after 500 ℃ of annealing 5min, obtains ZnO-copper indium gallium sulphur selenium composite film.
3, the selection of back electrode material and preparation thereof
In the present embodiment, select the noble metal Au of high work function as back electrode, its preparation method adopts vacuum vapour deposition, and its design parameter is: base vacuum is 6 * 10
-4pa, evaporation current is 200A, and the time is 3min, and film thickness is 600nm.
4, 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, record prepared all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, its photoelectric conversion efficiency is 4.6%.
Embodiment 2
1, the preparation of semiconductor anode perforated membrane
1) material of N-type nesa coating is selected and preparation
In the present embodiment, select FTO as N-type electrically conducting transparent membrane material, then take common soda-lime-silica glass as substrate, adopt sol-gel filming technology to prepare square resistance and be less than 10 Ω/, transmitance is used for all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell higher than 85% electrically conducting transparent FTO film;
2) selection of N-type wide bandgap semiconductor materials and the preparation of micro mist thereof
In the present embodiment, select ZnS as the anode material of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, the preparation method of its micro mist adopts sol-gel process, concrete operation step and parameter are: the zinc sulfate solution 100ml of 0.2M is mixed with the thiourea solution 100ml of 1.5M, add in hydrothermal reaction kettle, after 80 ℃ of hydro-thermal reaction 2h, obtain the ZnS micro mist of the about 50nm of particle diameter;
3) preparation of N-type wide band gap semiconducter perforated membrane
The present embodiment adopts the tape casting to prepare porous ZnS film, concrete operation step and parameter are: 0.5g ZnS micro mist is distributed in 20ml deionized water, and add 4ml acetylacetone,2,4-pentanedione and 4ml song to draw logical, form ZnS slurry, then by silk screen, ZnS slurry is printed onto on FTO film, after 200 ℃ are dried, obtains ZnS perforated membrane.
2, the preparation of copper indium gallium sulphur selenium liquid phase presoma and copper indium gallium sulphur selenium sensitizing layer
1) preparation of copper indium gallium sulphur selenium liquid phase presoma: adopt method described in Chinese patent CN101960610B to be prepared, the concentration of prepared copper indium gallium sulphur selenium liquid phase presoma is 0.2M;
2) the ZnS perforated membrane making in step 1 is immersed in copper indium gallium sulphur selenium liquid phase presoma after 5h, after 450 ℃ of annealing 5min, obtains ZnS-copper indium gallium sulphur selenium composite film.
3, the selection of back electrode material and preparation thereof
In the present embodiment, select high work function conductive non-metals SiC as back electrode, its preparation method adopts vacuum vapour deposition, and its design parameter is: base vacuum is 3 * 10
-4pa, evaporation current is 600A, and the time is 30min, and film thickness is 1000nm.
4, 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, record prepared all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, its photoelectric conversion efficiency is 2.3%.
Embodiment 3
1, the preparation of semiconductor anode perforated membrane
1) material of N-type nesa coating is selected and preparation
In the present embodiment, select Zn
2snO
4as N-type electrically conducting transparent membrane material, then take ultrawhite solar energy glass as substrate, adopt spray pyrolysis to prepare square resistance and be less than 10 Ω/, transmitance is higher than 85% electrically conducting transparent Zn
2snO
4film is for all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell;
2) selection of N-type wide bandgap semiconductor materials and the preparation of micro mist thereof
In the present embodiment, select BiOCl as the anode material of copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, the preparation method of its micro mist adopts micelle assay, and concrete operation step and parameter are: by 3.0g Bi (NO
3)
35H
2o joins in 60mL deionized water, after fully dissolving, adds the saturated NaCl solution of 5ml, then adds hydrothermal reaction kettle, at 120 ℃ of hydro-thermal reaction 24h, obtains the BiOCl micro mist of the about 150nm of particle diameter;
3) preparation of N-type wide band gap semiconducter perforated membrane
The present embodiment adopts the tape casting to prepare porous BiOCl film, concrete operation step and parameter are: 0.5g BiOCl micro mist is distributed in 20ml ethanol, and add 4ml acetylacetone,2,4-pentanedione and 0.01g ethyl cellulose, and form BiOCl slurry, then by silk screen, BiOCl slurry is printed onto to Zn
2snO
4on film, after 300 ℃ are dried, obtain BiOCl perforated membrane.
2, the preparation of copper indium gallium sulphur selenium liquid phase presoma and copper indium gallium sulphur selenium sensitizing layer
1) preparation of copper indium gallium sulphur selenium liquid phase presoma: adopt method described in Chinese patent CN101960610B to be prepared, the concentration of prepared copper indium gallium sulphur selenium liquid phase presoma is 0.8M;
2) the BiOCl perforated membrane making in step 1 is immersed in copper indium gallium sulphur selenium liquid phase presoma after 2h, after 480 ℃ of annealing 120min, obtains BiOCl-copper indium gallium sulphur selenium composite film.
3, the selection of back electrode material and preparation thereof
In the present embodiment, select high work function P-type conduction compound S b
3te
2as back electrode, its preparation method adopts vacuum vapour deposition, and its concrete preparation method is: base vacuum is 2 * 10
-4pa, evaporation current is 100A, and the time is 15min, and film thickness is 1500nm.
4, 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, record prepared all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, its photoelectric conversion efficiency is 8.4%.
Comparative example 1
In this comparative example, select FTO as N-type electrically conducting transparent membrane material; Select TiO
2anode material as copper indium gallium sulphur selenium sensitized semiconductor anode solar cell; Select copper indium gallium sulphur selenium nano-powder as sensitizing layer; Select Pt as back electrode.Due to copper indium gallium sulphur selenium nano-powder and porous TiO
2between anode, can not realize chemical bond closely, and just form limited mechanical bond.Therefore, prepared copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, under the analog light source of AM1.5, the photoelectric conversion efficiency recording is only 0.01%.
Industrial applicability: can realize chemical bond closely between copper indium gallium sulphur selenium and porous semi-conductor anode in copper indium gallium sulphur selenium sensitized semiconductor anode solar cell of the present invention, realize photo-generated carrier effectively transmission on interface, and preparation technology of the present invention is simple, with low cost, equipment investment is few, and raw material availability is high, controllability is strong, reproducible, be easy to realize large-scale production, can be applicable to solar cell energy field.
Claims (10)
1. an all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell, is characterized in that, comprising:
Be formed at successively N-type nesa coating and N-type wide band gap semiconducter particulate perforated membrane on glass substrate;
Thereby generate the copper indium gallium sulphur selenium sensitizing layer compound with it with surface in situ in the hole of described N-type wide band gap semiconducter particulate perforated membrane; And
Be formed at the back electrode on described copper indium gallium sulphur selenium sensitizing layer;
Wherein, described all solid state copper indium gallium sulphur selenium sensitized semiconductor anode solar cell is not containing organic dyestuff and liquid electrolyte.
2. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 1, is characterized in that, described 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 characterized in that, described N-type nesa coating is made through magnetron sputtering, reactive sputtering, chemical vapour deposition (CVD), spray pyrolysis or sol-gel process by N-type transparent conductive film material, wherein said N-type transparent conductive film material is selected from FTO, ITO, AZO, Cd
2snO
4, Zn
2snO
4, TiO
2: Nb and SrTiO
3: at least one in Nb; The thickness of described N-type nesa coating is 100～1000 nm.
4. according to the copper indium gallium sulphur selenium sensitized semiconductor anode solar cell described in any one in claims 1 to 3, it is characterized in that, described N-type wide band gap semiconducter particulate perforated membrane is made through silk screen print method or the tape casting by wide bandgap N type semi-conducting material, and wherein said wide bandgap N type semi-conducting material is selected from least one in 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; The thickness of described N-type wide band gap semiconducter particulate perforated membrane is 1～10 μ m.
5. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 4, is characterized in that, described wide bandgap N type oxide semiconductor material is selected from TiO
2, ZrO
2, Nb
2o
5, Ta
2o
5, ZnO, In
2o
3, SnO
2, and SrTiO
3in at least one; Described wide bandgap N type sulfide semiconductor material is selected from ZnS, CdS, In
2s
3, SnS
2, and Sb
2s
3in at least one; Described wide bandgap N type oxyhalogenation thing semi-conducting material is selected from BiOX and/or SbOX; Described wide bandgap N type sulfur halide semi-conducting material is BiSX; Wherein X is selected from Cl, Br and/or I.
6. according to the copper indium gallium sulphur selenium sensitized semiconductor anode solar cell described in any one in claim 1 to 5, it is characterized in that, described copper indium gallium sulphur selenium sensitizing layer is copper indium gallium sulphur selenium semiconductive thin film, and its component is Cu
xin
1-yga
yse
2-zs
z, 0.6≤x≤0.9 wherein, 0≤y≤1,0≤z≤2; The thickness of described copper indium gallium sulphur selenium sensitizing layer is 50 nm～5000 nm.
7. according to the copper indium gallium sulphur selenium sensitized semiconductor anode solar cell described in any one in claim 1 to 6, it is characterized in that, described back electrode is made through vacuum evaporation by back electrode material, and wherein said back electrode material is selected from high-work-function metal, high work function conductive non-metals or high work function P-type conduction compound; The thickness of described back electrode is 50～5000 nm.
8. copper indium gallium sulphur selenium sensitized semiconductor anode solar cell according to claim 7, is characterized in that, described high-work-function metal is selected from least one in Cu, Ni, Mo, Au and Pt; Described high work function conductive non-metals is selected from least one in C, Te and SiC; Described high work function P-type conduction compound is selected from ZnTe, ZnTe:Cu, CuTe and Sb
3te
2in at least one.
9. a preparation method for the copper indium gallium sulphur selenium sensitized semiconductor anode solar cell described in any one in claim 1 to 8, is characterized in that, comprising:
1) adopt N-type transparent conductive film material on glass substrate, to prepare N-type nesa coating through magnetron sputtering, reactive sputtering, chemical vapour deposition (CVD), spray pyrolysis or sol-gel process;
2) by containing particle diameter, be that the slurry of the wide bandgap N type semi-conducting material particulate of 1～1000nm is coated on described N-type nesa coating, forms N-type wide band gap semiconducter particulate perforated membrane after drying annealing through silk screen printing or the tape casting;
3) the copper indium gallium sulphur selenium liquid phase presoma that described N-type wide band gap semiconducter particulate perforated membrane is placed in to cupric, indium, gallium, sulphur and selenium element soaked after 0.1～5 hour, through 180～600 ℃ of annealing, after 5～120 minutes, in the hole of described N-type wide band gap semiconducter particulate perforated membrane, generated copper indium gallium sulphur selenium sensitizing layer with surface in situ; And
4) back electrode material is formed to back electrode through vacuum vapour deposition on described copper indium gallium sulphur selenium sensitizing layer, make copper indium gallium sulphur selenium sensitized semiconductor anode solar cell.
10. preparation method according to claim 9, is characterized in that, described 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 high-temperature cracking method preparation.
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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109103022A (en) * | 2018-07-31 | 2018-12-28 | 上海材料研究所 | Dye-sensitized solar cells and its working electrode and working electrode material |
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