AU2013289503A1 - Use of microporous anionic inorganic framework structures containing dopant cations for producing thin film solar cells - Google Patents
Use of microporous anionic inorganic framework structures containing dopant cations for producing thin film solar cells Download PDFInfo
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- AU2013289503A1 AU2013289503A1 AU2013289503A AU2013289503A AU2013289503A1 AU 2013289503 A1 AU2013289503 A1 AU 2013289503A1 AU 2013289503 A AU2013289503 A AU 2013289503A AU 2013289503 A AU2013289503 A AU 2013289503A AU 2013289503 A1 AU2013289503 A1 AU 2013289503A1
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- Australia
- Prior art keywords
- layer
- framework
- film solar
- thin
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 111
- 150000001768 cations Chemical class 0.000 title claims abstract description 47
- 239000002019 doping agent Substances 0.000 title claims abstract description 47
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 38
- 239000013385 inorganic framework Substances 0.000 title claims abstract description 38
- 239000006096 absorbing agent Substances 0.000 claims abstract description 97
- 239000004065 semiconductor Substances 0.000 claims abstract description 94
- 229910052645 tectosilicate Inorganic materials 0.000 claims abstract description 55
- 150000002500 ions Chemical class 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- -1 alkali ions Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 229910001415 sodium ion Inorganic materials 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 27
- 230000004888 barrier function Effects 0.000 claims description 25
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims description 17
- 238000005240 physical vapour deposition Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 229910052665 sodalite Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
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- 239000011148 porous material Substances 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 150000002739 metals Chemical class 0.000 claims description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 claims description 2
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- 229940065287 selenium compound Drugs 0.000 claims description 2
- 150000003343 selenium compounds Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 claims 2
- 239000011734 sodium Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
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- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052907 leucite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
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- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 238000005496 tempering Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
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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
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- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System
- H01L31/0284—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System comprising porous silicon as part of the active layer(s)
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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
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- 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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- 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
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- 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
- H01L31/0323—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 characterised by the doping material
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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
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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
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- H01L31/0327—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4 characterised by the doping material
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- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0475—PV cell arrays made by cells in a planar, e.g. repetitive, configuration on a single semiconductor substrate; PV cell microarrays
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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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the use of microporous anionic inorganic framework structures, in particular framework silicates or framework germanates, in thin film solar cells or modules, in particular based on a glass substrate layer, for absorbing impurities from said thin film solar cells and/or modules, and for producing a semiconductor absorber layer of a thin film solar cell and/or module provided with monovalent dopant cations, in particular based on a glass substrate layer. The invention further relates to a photovoltaic thin film solar cell containing, in particular in at least one back electrode layer, in at least one contact layer, and/or in at least one semiconductor absorber layer, microporous anionic inorganic framework structures, in particular framework silicates or framework germanates. Preferably, the semiconductor absorber layer, in particular in exchange with metal ions of the semiconductor absorber layer, is doped using monovalent doping cations originating from the framework structures, in particular alkali ions. The invention further relates to a thin film solar module, having thin film solar cells according to the invention. Lastly, the invention relates to a method for producing thin film solar cells and modules according to the invention.
Description
Translation from German WO 2014/009061 A2 PCT/EP2013/061551 Use of Microporous Anionic Inorganic Framework Structures, in Particular Containing Dopant Cations, For Producing Thin Film Solar Cells and/or Modules, Photovoltaic Thin Film Solar Cells Containing Microporous Anionic Inorganic Framework Structures, and Method for Producing Such Photovoltaic Thin Film Solar Modules The present invention relates to: the use of microporous anionic inorganic framework structures, containing, in particular, dopant cations, for the production of thin-film solar cells and modules; thin-film photovoltaic solar cells and modules containing microporous anionic inorganic framework 5 structures; and methods for producing such thin-film photovoltaic solar modules. For a long time now, photovoltaic solar modules have been known in the art and have been available commercially. Suitable solar modules are crystalline silicon solar modules on the one hand, and so-called thin-film 10 solar modules on the other. Such thin-film solar modules are based on e.g. the use of what is called a chalcopyrite semiconductor absorber layer, such as the Cu(In, Ga)(Se,S) 2 system, and they constitute a complex multi-layer system. In these thin-film solar modules there is normally a molybdenum back electrode layer, on a glass substrate. In a variant of the is inventive method, this molybdenum back electrode layer is provided with a thin film of precursor metal, containing copper and indium, and possibly gallium, and is then converted, at elevated temperatures, in the presence of hydrogen sulphide and/or hydrogen selenide, to a so-called CIS or CIGS system. In another variant of the inventive method, elemental 20 selenium vapour and sulphur vapour can be used instead of hydrogen selenide and hydrogen sulphide. The production of these thin-film solar modules is thus a multi-stage process in which, due to numerous 2 WO 2014/009061 A2 PCT/EP2013/061551 interactions, each stage of the process must be carefully adapted to subsequent stages. Also, special attention needs to be paid to the selection, and purity, of the materials to be used in each layer. This is true even for the substrate layer. Any impurities in any of the steps of the 5 process can adversely affect the efficiency achieved. Normally, very pure starting substances are needed, along with considerable plant and equipment. This generally entails substantial costs. Also, with the temperatures and reaction-conditions employed to date in the individual stages of production, it has not been possible, up to now, to exclude the 10 possibility of contamination or interdiffusion of components, dopants, or impurities in individual layers of the multilayer system. Just the choice, and method of production, of the back electrode layer can be enough to affect the efficiency of a thin-film solar cell. For example, the back electrode layer needs to have high lateral conductivity, to ensure low-loss is series connection. Also, substances migrating from the substrate and/or the semiconductor absorber layer must have no effect on the quality and functioning of the back electrode layer or the semiconductor absorber layer. In addition, the material of the back electrode layer needs to be well adapted to the thermal expansion behaviour of the substrate and the 20 layers above it, so as to prevent microcracks. Furthermore, its adhesion to the substrate surface needs to meet all normal usage requirements. Finally, care should be taken to ensure the homogeneity of the composition of the respective layers of the thin-film system, particularly when an improvement in efficiency is to be brought about by using 25 suitable dopants. While it is possible to achieve good efficiency levels by using very pure back electrode material, this will usually entail unduly high production costs. Moreover, under normal production conditions, the above mentioned migration phenomena and, in particular, diffusion phenomena 30 can often lead to significant contamination of the back electrode material. For example, a dopant introduced into the semiconductor absorber layer 3 WO 2014/009061 A2 PCT/EP2013/061551 can diffuse, as mentioned, into the back electrode, thereby depleting the semiconductor absorber layer's dopant and leading to significant reductions in the efficiency of the finished solar module. Thus, even when all material and process optimisations have been attended to, one can still 5 be severely restricted in the final design of the thin-film solar modules destined for the market. According to DE 44 42 824 C1, it is possible to achieve a solar cell with a favourable absorber layer structure and good efficiency levels by doping the chalcopyrite semiconductor absorber layer with an element from the 10 group consisting of sodium, potassium, and lithium at a doping concentration of 1014 to 1016 atoms per cm 2 and providing, at the same time, a diffusion barrier layer between the substrate and the semiconductor absorber layer. Alternatively, if no diffusion barrier layer is to be provided, then it is proposed that an alkali-free substrate be used. 15 It is also possible to do without a barrier layer, by using instead the sodium ions that diffuse from the glass substrate at the temperatures prevailing during the production of the semiconductor absorber layer. However, this way of proceeding is very unreliable and hardly permits well-defined sodium doping of the semiconductor absorber layer. In 20 general it can be observed that, with this method, it is difficult, if not impossible, to predetermine the amount of sodium ions diffusing from the substrate glass. The diffusion of the sodium ions is affected not only by the glass itself, and its storage and pre-treatment, but also by the back electrode layer, and other layers, situated between the substrate layer and 25 the semiconductor absorber layer. For example, lateral inhomogeneities of the back electrode layer result in uneven diffusion of sodium ions into the semiconductor absorber layer. Introducing inorganic sodium compounds such as sodium fluoride, sodium sulphide, sodium selenide, or sodium phosphate, on the other hand, often 4 WO 2014/009061 A2 PCT/EP2013/061551 entails the risk that the anions also introduced with them will cause unwanted defects in the semiconductor absorber layer and/or will even be hygroscopic. For example, oxygen is known to produce electrical defects in the semiconductor absorber layer. 5 Furthermore, it has been found that the conventional way of introducing sodium ions into the semiconductor absorber layer can at times be very inefficient, because often only a very small proportion of the sodium ions introduced also actually become incorporated into, and electrically active in, the semiconductor absorber layer. 10 Moreover, it is important not to underestimate the fact that suitable sodium compounds, such as sodium fluoride, are critical in their handling, and entail high production costs. It would therefore be desirable to have access to thin-film photovoltaic solar modules that did not suffer from the drawbacks of the prior art. The is underlying objective of the invention was therefore, in particular, to introduce dopant cations, e.g. sodium ions, into a thin-film solar module, particularly the semiconductor absorber layer, in well defined and controlled amounts. A further objective of the invention was to minimise or eliminate the adverse effect of impurities on the efficiency of thin-film 20 solar cells. Another objective of the invention was to provide a method for producing thin-film solar modules that does not suffer from the drawbacks of the prior art. In this regard, it is desirable to have available a method whereby it is possible to introduce dopant cations, particularly sodium ions, reliably, efficiently, replicably, and uniformly into the semiconductor 25 absorber layer, in well-defined, settable, amounts, so that they are electrically active there. A further objective of the invention was to provide a method that would minimise or eliminate the detrimental effect of impurities on the efficiency of thin-film solar cells.
5 WO 2014/009061 A2 PCT/EP2013/061551 And so, the use of microporous anionic inorganic framework structures, in particular framework silicates or framework germanates, in thin-film solar cells or modules, particularly those based on a glass substrate layer (e.g. comprising or in the form of a sheet of glass), for the absorption of 5 impurities from those thin-film solar cells and modules, has been discovered. This may relate, inter alia, to the absorption of impurities from the thin-film solar cell, such as Fe 3 * and or Ni 2 +. In an advantageous form of the invention, the microporous anionic inorganic framework structures, in particular framework silicates or 10 framework germanates, are present in at least one back electrode layer, at least one contact layer, and/or at least one semiconductor absorber layer of the thin-film solar cell or module. With said microporous anionic inorganic framework structures, it is possible to efficaciously capture impurities, such as water molecules, and is iron and nickel ions and compounds, that have been introduced by the starting substances employed or during successive stages of the production process. These impurities can be stored away in the micropores of the framework structures, and remain there - no longer available to have a detrimental effect on efficiency. An advantage here is 20 that said framework structures are inert; meaning that, under the conditions in which thin-film solar modules are produced and used, said framework structures undergo no changes. For instance, they neither degrade nor do they react with other substances. A further advantage is that the framework structures are available with different micropore 25 diameter sizes, and the micropore diameter size used determines which impurity from the thin-film solar cell or intermediates is to be specifically captured. It is advantageous, in this regard, that even those microporous framework structures whose micropores have very small diameter sizes - e.g. in the region of 0.29 nm and below - may be used, as they are 30 often still able to absorb metal ions.
6 WO 2014/009061 A2 PCT/EP2013/061551 In another advantageous form of the invention, the thin-film solar cell or module - particularly the at least one semiconductor absorber layer thereof - has monovalent dopant cations, particularly alkali ions. Also discovered was the use of microporous anionic inorganic framework 5 structures, particularly framework silicates or framework germinates, whose micropores contain monovalent dopant cations, particularly alkali ions, for the production of a semiconductor absorber layer - provided with said monovalent dopant cations - for a thin-film solar cell or a module, particularly such a cell or module based on a glass substrate 10 layer comprising or in the form of e.g. a sheet of glass. In this regard, a further inventive feature may be that - in at least one back electrode layer, contact layer, and/or semiconductor absorber layer of the thin-film solar cell or module - there are microporous anionic inorganic framework structures, particularly framework silicates or is framework germanates, that are free of the monovalent dopant cations, particularly alkali ions, due to their emigration into at least one back electrode layer, contact layer, and/or semiconductor absorber layer of the thin-film solar cell or module. Also discovered was the use of microporous anionic inorganic framework 20 structures, particularly framework silicates or framework germanates, containing monovalent dopant cations, particularly alkali ions, in their micropores, for doping the semiconductor absorber layer of a thin-film solar cell or module with said monovalent dopant cations. The framework structures containing dopant ions (alkali ions) in their 25 micropores, and used in accordance with the invention, may also be referred to as intercalation compounds. In terms of the present invention, dopant cations may in particular be understood as referring to those cations that are suitable for improving the thin-film solar cell's electrical properties and its efficiency. This normally occurs through absorption of 7 WO 2014/009061 A2 PCT/EP2013/061551 these cations into the semiconductor absorber layer. In the present case, these dopant cations pass via the microporous anionic inorganic framework structures, as vehicle and dopant, into the thin-film solar cell (i.e. into the components thereof). There they are normally released by 5 the addition of energy, e.g. by heating, and/or by exchange for other substances, particularly cations, and can migrate into the semiconductor absorber layer. A feature of a preferred form of the invention may be that the microporous anionic inorganic framework structures, in particular framework silicates, 10 may contain, or be formed of, tetrahedral building blocks. Suitable framework silicates ("tectosilicates") are, inter alia, alumino-, titano-alumino-, boro-, gallo-, indium, and iron(II) tectosilicates. In a particularly useful form of the invention, the framework structure, in particular the framework silicate, contains, or is composed of, beta-cages, is especially condensed beta-cages. The cage structures in the framework structures used according to the present invention may, accordingly, be composed of e.g. A13*, Si 4 l, and 02- ions. The framework structures, particularly framework silicates, employed 20 according to the invention are preferably non-hygroscopic. In a particularly effective form of the invention, the micropores of the framework structure, particularly framework silicates, has a pore opening diameter enabling the replacement of the dopant cations, especially alkali ions, in the micropores with metal ions of the metals of the semiconductor 25 absorber layer, e.g. Cu', Ga 3 *, and/or In 3 *, and/or with impurities originally from the thin-film solar cell, such as Fe 3 * and/or Ni 2 +. Preferably, this exchange takes place at temperatures of 300'C or above, in particular 8 WO 2014/009061 A2 PCT/EP2013/061551 350C to 6000C and preferably 520C to 6000C. It is an advantage here that, in this replacement of alkali ions with ions from the semiconductor absorber layer, the framework structure is not decomposed, but generally remains fully intact. This exchange of said ions at elevated temperatures 5 is achieved not only when the framework structure containing the dopant cations, particularly alkali ions, is present in the semiconductor absorber layer itself, but also when it is present in a back electrode layer directly or indirectly adjacent to the semiconductor absorber layer. With the use according to the invention, it is even possible to replace all the dopant 10 cations, i.e. alkali ions, particularly sodium ions, that are present in the framework structure, with cations from the semiconductor absorber layer and/or with impurities in the thin-film solar cell, e.g. iron and/or nickel compounds or Fe 3 * and/or Ni 2 + ions. In this regard, forms of implementation are preferred in which the is framework structure, particularly framework silicate, has, in its micropores, sodium ions, potassium ions, lithium ions, rubidium ions, and/or caesium ions, but particularly sodium ions. Framework structures, in particular framework silicates, whose micropores have a pore opening diameter of less than about 0.29 nm have proved 20 particularly suitable for the present invention. Furthermore, in a suitable form of the invention, it can be specified that the framework structure is a framework silicate of Strunz Classes 09.F, e.g. cancrinite, or 09.G, e.g. leucite, or a framework germanate, particularly a framework silicate without zeolitic water and with additional 25 anions (as per the 9 th edition of the Strunz classification of minerals). Among the suitable framework structures, in particular framework silicates, those with a sodalite framework typology are particularly useful for the purposes of the invention. The mineral sodalite is especially preferred. Naturally-occurring sodalite has the composition 9 WO 2014/009061 A2 PCT/EP2013/061551 Na 8
[(CI,OH)
2 Al 6 Si 6
O
24 ] (= 6 Na[AISiO 4 ] . 2Na(CI,OH)). Here, the framework structure is normally composed of the aluminium silicate anions, which are present in the form of beta-cages. The beta cages generally have chloride, hydroxide, and part of the sodium ions, in them. 5 Of course, in other forms of suitable sodalite structures, NaCl and/or NaOH can substitute. Also preferred are those sodalite framework structures with sodium polysulphides, such as Na 2 Sn, e.g. Na 2
S
6 , in the beta cages, instead of NaCl and NaOH. Sodalite belongs to Strunz class 09.FB.10 (according to the 9 th edition of the Strunz classification of 10 minerals). Another provision of the invention, in this regard, may be that, in the framework silicate, up to 50% of the tetravalent silicon tetrahedral building blocks are replaced with tetrahedral building blocks that have a trivalent central atom, in particular aluminium. 15 It is particularly preferred that the framework silicate is a zeolite. The microporous anionic inorganic framework structures containing monovalent dopant cations, particularly alkali ions, and more particularly sodium ions, are preferred for use with those thin-film solar cells in which the semiconductor absorber layer is a kesterite or chalcopyrite 20 semiconductor absorber layer. Such kesterite and chalcopyrite semiconductor absorber layers suitable for thin-film solar cells, and how to produce them, are known to those skilled in the art. Furthermore, in one form of the inventive thin-film solar cell, it can be a feature of the invention that the semiconductor absorber layer is or comprises: a quaternary IB 25 lIlA-VIA chalcopyrite layer, in particular a Cu(In,Ga)Se 2 layer; a penternary IB-lIlA-VIA chalcopyrite layer, in particular a Cu(In,Ga)(Sel-x,Sx) 2 layer; or a kesterite layer, in particular a Cu 2 ZnSn(Sex,Sl,) 4 layer, e.g. a Cu 2 ZnSnSe 4 or Cu 2 ZnSnS 4 layer; where the value of x is from 0 to 1.
10 WO 2014/009061 A2 PCT/EP2013/061551 The objective of the invention is further achieved with a thin-film photovoltaic solar cell containing microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, particularly in at least one back electrode layer, contact layer, 5 and/or semiconductor absorber layer. In this way, it is possible, due to the inert nature of the framework structures used here, to capture impurities from the thin-film solar cell, for example Fe 3 * and or Ni 2 + A feature of a particularly advantageous form of the invention may be that, alternatively or in addition, the thin-film solar cell comprises microporous 10 anionic inorganic framework structures that have, in their micropores, metal ions from the semiconductor absorber layer, such as Cu*, Ga*, and/or In 3 *. Forms of the inventive thin-film solar cells whose semiconductor absorber layer is doped with monovalent dopant cations (especially alkali ions) is originally from the framework structures - particularly in exchange for metal ions of the semiconductor absorber layer - have proved to be particularly advantageous. In a form of the inventive thin-film solar cell that meets the objectives of the invention, thin-film solar cell comprises, in this order: 20 - at least one substrate layer, particularly one comprising, or in the form of, a sheet of glass, - if applicable, at least one first barrier layer, particularly one that is non-conductive, - at least one back electrode layer, 25 - if applicable, at least one second, conductive, barrier layer, and at least one contact layer, particularly an ohmic contact layer, - at least one semiconductor absorber layer, particularly a chalcopyrite or kesterite semiconductor absorber layer, and 11 WO 2014/009061 A2 PCT/EP2013/061551 particularly one that is immediately adjacent to the back electrode layer or the contact layer, - if applicable, at least one first buffer layer, - if applicable, at least one second buffer layer, and 5 - at least one front electrode layer. The general and specific statements made above with regard to the uses of the invention are, of course, likewise applicable to the thin-film solar cells and modules of the invention. The inventive thin-film solar cells have, in particular, microporous anionic 10 inorganic framework structures, in particular framework silicates (also called "tectosilicates"), that contain or are composed of tetrahedral building blocks. Suitable framework silicates (or "tectosilicates") used in the novel thin-film solar cells include alumino-, titano-alumino-, boro-, gallo-, indium, and iron(II) tectosilicates. 15 These particularly suitable framework structures, in particular framework silicates, are composed of, or contain, beta cages - in particular, condensed beta cages. Particularly suitable framework structures for the inventive thin-film solar cells, in particular framework silicates, are non-hygroscopic. 20 In the inventive thin-film solar cells, the framework structures, in particular framework silicates, preferably used have micropores whose pore opening diameter is such as to allow monovalent dopant cations, particularly alkali ions, that are present in the micropores to be replaced by metal ions of the metals of the absorber layer, such as Cu', Ga*, 25 and/or In 3 *, and/or by impurities originating from the thin-film solar cell, such as Fe 3 * and/or Ni 2
+.
12 WO 2014/009061 A2 PCT/EP2013/061551 The inventive thin-film solar cells have - in their semiconductor absorber layer - framework structures, particularly framework silicates, whose micropores contain sodium ions, potassium ions, lithium ions, rubidium ions, and/or caesium ions, but particularly sodium ions. In this regard - in 5 a particularly suitable form of the invention - suitable framework structures, particularly framework silicates, have micropores whose opening diameter is less than about 0.29 nm. By using framework structures with a pore opening diameter of less than about 0.29 nm, it is possible to operate particularly effectively without the disturbing effect of 10 water molecules. At the above-mentioned pore opening diameter, water molecules cannot get into or out of the micropores of said framework structures. Framework structures, particularly framework silicates, that have a sodalite framework topology - especially sodalite itself - have proven is particularly suitable for the inventive thin-film solar cells. Furthermore, particularly suitable embodiments of the inventive thin-film solar cell are achieved when framework silicates are used wherein up to 50% of the tetravalent silicon tetrahedral building blocks have been replaced with tetrahedral building blocks with a trivalent central atom, 20 particularly aluminium. According to the invention, crystalline framework silicates, particularly crystalline alkali tectosilicates, are preferably used. It may be a feature of another form of the invention that: the first buffer layer of the inventive thin-film solar cells contains, or substantially consists 25 of, CdS, or may be a CdS-free layer, particularly containing or essentially consisting of Zn(S,O), Zn(S,O,OH), and/or In 2
S
3 ; and/or the second buffer layer contains or essentially consists of intrinsic zinc oxide and/or high resistance zinc oxide.
13 WO 2014/009061 A2 PCT/EP2013/061551 Also suitable are thin-film solar cells, as per the invention, in which the contact layer comprises at least one metal layer and at least one metal chalcogenide layer, the former being adjacent to and contiguous with the back electrode, or adjacent to and contiguous with the barrier layer, and 5 the latter being adjacent to and contiguous with the semiconductor absorber layer. Another provision of the invention may be, inter alia, that the metal layer and the metal chalcogenide layer are based on the same metal, particularly molybdenum and/or tungsten. 10 It is particular preferable, among other things, for the contact layer to also be a metal chalcogenide layer. The objective of the invention is further achieved with a thin-film solar module containing series-connected, and in particular monolithically integrated, inventive solar cells as described above in general and in is particular. The objective of the invention is further achieved with methods for producing the inventive thin-film photovoltaic solar cells or modules, wherein microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, are applied onto and or 20 introduced into at least one back electrode layer, contact layer, and/or semiconductor absorber layer of: at least one thin-film solar cell, particularly one that is based on a glass substrate layer in the form of, or comprising, a sheet of glass, or at least one thin-film solar cell forming the thin-film solar module, 25 particularly such a thin-film solar cell that is based on a glass substrate layer. A particularly advantageous form of this method consists of the following steps: 14 WO 2014/009061 A2 PCT/EP2013/061551 - providing a substrate, particularly a flat one that comprises, or is in the form of, a sheet of glass; - applying, if appropriate, a first, and particularly a non-conductive, barrier layer to the substrate; 5 - applying at least one back electrode layer to the substrate or to the first barrier layer, by physical and/or chemical vapour deposition from at least one, first, source of material; - applying, if appropriate, at least one second, conductive, barrier layer to the at least 10 one back electrode layer, by physical and/or chemical vapour deposition from at least one, second, source of material and at least one contact layer, particularly an ohmic contact layer, to the second barrier layer, by physical and/or chemical vapour 15 deposition from at least one, third, source of material or at least one first metal layer (co-forming the contact layer), by physical and/or chemical vapour deposition on the second barrier layer from at least one, fourth, source of material; 20 - depositing at least one second metal layer, from at least one, fifth source of material, on the back electrode layer or the contact layer, by physical and/or chemical vapour deposition, said at least one, second, metal layer containing the metal components of the semiconductor absorber layer - particularly copper, indium, and 25 possibly gallium, for a chalcopyrite semiconductor absorber layer; and copper, zinc, and tin, for a kesterite semiconductor absorber layer; - depositing microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, on the 30 substrate layer and/or the back electrode layer and, as appropriate, on the first and/or second barrier layer and/or, as appropriate, on the 15 WO 2014/009061 A2 PCT/EP2013/061551 contact layer and/or, as appropriate, on the first metal layer, and/or on the second metal layer, and/or co-depositing these framework structures with the at least one back electrode layer and/or, as appropriate, with the at least one first 5 and/or second barrier layer and/or, as appropriate, with the at least one contact layer, and/or, as appropriate, with the at least one first metal layer, and/or with the at least one, second, metal layer, doing so from at least one, sixth, material-source, particularly by at least one wet-chemical deposition process and/or by physical 10 and/or chemical vapour deposition, - treating the second metal layer- when it is on the back electrode layer, or possibly on the contact layer or possibly on the first metal layer - with at least one sulphur and/or selenium compound and/or with gaseous elemental selenium and/or sulphur at temperatures 15 above 3000C but particularly from 350C to 6000C and preferably from 520C to 600C, thereby forming a semiconductor absorber layer, - applying, if appropriate, at least one first buffer layer to the semiconductor absorber layer, 20 - applying, if appropriate, at least one second buffer layer to the first buffer layer or the semiconductor absorber layer, - applying at least one transparent front electrode layer to the first or second buffer layer or the semiconductor absorber layer. Advantageously, a form of the inventive method that is particularly suitable 25 is one in which the microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, contain monovalent dopant cations, particularly alkali ions, in their micropores. The above-mentioned second tempering step serves, in a preferred form of the invention, not only to form the semiconductor absorber layer and/or 30 to form a back electrode layer containing or consisting of metal selenides, 16 WO 2014/009061 A2 PCT/EP2013/061551 but can also lead to the replacement of dopant cations (i.e. alkali ions, particularly sodium ions) from the micropores of the framework structure with metal ions from the semiconductor absorber layer, e.g. Cu', Ga*, and/or In 3 *, and/or with impurities in the thin-film solar cell, such as Fe 3 * 5 and/or Ni 2 + ions. Advantageously, this exchange of ions does not destroy the anion lattice of the framework structure, and nor is the latter's crystalline structure altered thereby. In accordance with a particularly advantageous form of the invention, physical vapour deposition (PVD) covers physical vapour deposition 10 coating, vapour deposition using an electron beam evaporator, vapour deposition using a resistance evaporator, induction evaporation, ARC evaporation, and/or cathode sputtering (sputter coating), in particular DC or RF-magnetron sputtering, in each case preferably in a high vacuum; and chemical vapour deposition (CVD) includes chemical vapour is deposition (CVD) coating, low pressure CVD, and/or atmospheric pressure CVD. Thus, the microporous anionic inorganic framework structures can be deposited, inter alia, by spray methods known to those versed in the art, or can be deposited from e.g. an emulsion or an aqueous system, e.g. an aqueous solution. 20 For the deposition of the microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, at least one wet-chemical deposition process is preferably employed, for instance: brush-coating, roller-coating, coating by sputtering or spraying, pouring on, blade-coating, and/or ink-jet or aerosol printing. 25 Also preferred are those process-variants in which: - the first and sixth material-sources constitute a first mixed target, and/or - the second and sixth material-sources constitute a second mixed target, and/or 17 WO 2014/009061 A2 PCT/EP2013/061551 - the third and sixth material-sources constitute a third mixed target, and/or - the fourth and sixth material-sources constitute a fourth mixed target, and/or 5 - the fifth and sixth material-sources constitute a fifth mixed target. A further feature may be that co-deposition is performed sequentially, or essentially at the same time, from the fifth, sixth, and first material sources; the fifth, sixth, and third material-sources; the fifth, sixth, and fourth material-sources; or from the fifth mixed target and the first 10 material-source; the fifth mixed target and the third material-source; or the fifth mixed target and the fourth material-source. It is also possible, in one form of the invention, for co-deposition to be performed sequentially or essentially at the same time from the fifth mixed target and the fifth material-source. 15 In another form of the inventive method suitable for the purposes of the invention, co-deposition is performed sequentially, or essentially at the same time, from the first, second, third, and/or fourth mixed target, particularly the first, third, or fourth mixed target, and the fifth material source. 20 A further provision may be that co-deposition is performed sequentially, or essentially at the same time, from the fifth mixed target and the first, second, third, and/or fourth mixed target, particularly the first or third or fourth mixed target. In another form of the inventive method, co-deposition is performed 25 sequentially, or essentially at the same time, from the first, second, or third mixed target, particularly the first or third mixed target, and the first, second, third, or fourth material-source, particularly the first or third or fourth material-source.
18 WO 2014/009061 A2 PCT/EP2013/061551 The following is preferably done in a single vacuum coating installation, preferably by the continuous sputtering method: application of the back electrode layer, and possibly the conductive barrier layer and first metal layer or the contact layer, and also the metals of the semiconductor 5 absorber layer (particularly Cu, In, and Ga layers for forming the chalcopyrite semiconductor absorber layer, or Cu, Zn, and Sn layers for forming the kesterite semiconductor absorber layer); and the microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, whose micropores contain monovalent dopant 10 cations, particularly alkali ions, preferably sodium ions. The present invention involves the surprising finding that semiconductor absorber layers of thin-film solar cells, especially those based on the use of a glass substrate and e.g. comprising, or being in the form of, a sheet of glass, are able to be doped, efficiently and reliably, to required levels in is various ranges of concentration, with monovalent dopant cations, particularly alkali ions, especially sodium ions. Accordingly, the amount of dopant cations, particularly alkali ions, especially sodium ions, to be introduced into the semiconductor absorber layer can be accurately dispensed, and a high level of utilisation of the electrically active dopant 20 cations, particularly alkali ions, especially sodium ions, can be achieved, relative to the amount of dopant cations, particularly alkali ions, actually introduced. The inventive thin-film solar cells doped in this way make it possible to achieve high efficiencies, and to do so replicably. With the thin film solar cells and modules of the invention, there is no risk of creating 25 electrical flaws or defects, nor is there any increased hygroscopicity, despite said doping with the monovalent dopant cations (alkali ions). Also, there is basically no longer any need to introduce foreign substances into the thin-film solar cell. In addition, the inventive doping with monovalent dopant cations (i.e. alkali ions, particularly sodium ions), can be done 30 without using any sensitive and/or toxic substances at all; and, with the substances used, no water or other oxygen-containing compounds are 19 WO 2014/009061 A2 PCT/EP2013/061551 introduced into the semiconductor absorber layer. For example, hydrolytic decomposition products are particularly effectively avoided in this way. Furthermore, it is particularly beneficial that it is possible to distribute the monovalent dopant cations (i.e. alkali ions, particularly sodium ions) 5 homogeneously and evenly over the entire width of the semiconductor absorber layer. Therefore, lateral inhomogeneities can be entirely - or almost entirely - prevented. In addition, for the first time, efficient exchange of monovalent dopant cations (alkali ions, particularly sodium ions) for cations of the semiconductor absorber layer, e.g. copper ions, is 10 ensured.
Claims (50)
1. The use of microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, in thin-film solar cells or modules, particularly those based on a glass 5 substrate layer, for the absorption of impurities from said thin-film solar cells or modules.
2. The use as claimed in claim 1, characterised in that the microporous anionic inorganic framework structures, particularly framework silicates or 10 framework germanates, are present in at least one back electrode layer, contact layer, and/or semiconductor absorber layer of the thin-film solar cell or module.
3. The use as claimed in claim 2, characterised in that the thin-film solar cell or module, particularly the at least one semiconductor absorber layer is of the thin-film solar cell or module, has monovalent dopant cations, particularly alkali ions, in it.
4. The use of microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, containing monovalent dopant cations, particularly alkali ions, in their micropores, 20 for the production of a semiconductor absorber layer of a thin-film solar cell or module, particularly one based on a glass substrate layer, said semiconductor absorber layer being provided with said monovalent dopant cations.
5. The use as claimed in claim 4, characterised in that, in at least one 25 back electrode layer, contact layer, and/or semiconductor absorber layer of the thin-film solar cell or module, there are microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, that are free of the monovalent dopant cations, 21 WO 2014/009061 A2 PCT/EP2013/061551 particularly alkali ions, as a result of emigration into at least one back electrode layer, contact layer, and/or semiconductor absorber layer of the thin-film solar cell or module.
6. The use of microporous anionic inorganic framework structures, in 5 particular framework silicates or framework germanates, containing monovalent dopant cations, particularly alkali ions, in their micropores, for doping the semiconductor absorber layer of a thin-film solar cell or module with said monovalent dopant cations.
7. The use as claimed in any of the above claims, characterised in that 10 the microporous anionic inorganic framework structures, particularly framework silicates, contain tetrahedral building blocks or are formed therefrom.
8. The use as claimed in any of the above claims, characterised in that the framework structure, in particular the framework silicates, is not 15 hygroscopic.
9. The use as claimed in any of claims 4 to 8, characterised in that the micropores of the framework structure, in particular the framework silicates or framework germanates, have a pore opening diameter enabling the monovalent dopant cations (particularly alkali ions) in the 20 micropores to be exchanged for metal ions of the metals of the absorber layer, for example Cu', Ga*, and/or In 3 *.
10. The use as claimed in any of the above claims, characterised in that the framework silicate, i.e. the "tectosilicate", is an alumino-, titano alumino-, boro-, gallo-, indium, or iron(Ill) tectosilicate. 25
11. The use as claimed in any of the above claims, characterised in that the framework structure, in particular the framework silicate, contains or is composed of beta-cages, in particular condensed beta-cages. 22 WO 2014/009061 A2 PCT/EP2013/061551
12. The use as claimed in any of the above claims, characterised in that the framework structure, particularly the framework silicate, has, in its micropores, sodium ions, potassium ions, lithium ions, rubidium ions, and/or caesium ions, particularly sodium ions. 5
13. The use as claimed in any of the above claims, characterised in that the framework structure, in particular the framework silicate, has micropores with a pore opening diameter of less than about 0.29 nm.
14. The use as claimed in any of the above claims, characterised in that the framework structure, in particular the framework silicate, has a 10 sodalite framework topology.
15. The use as claimed in any of the above claims, characterised in that, in the framework silicate, up to 50% of the tetravalent silicon tetrahedral building blocks are replaced by tetrahedral building blocks with a trivalent central atom, in particular aluminium. 15
16. The use as claimed in any of the above claims, characterised in that the framework structure is a framework silicate or framework germanate of Strunz class 09.F or Strunz class 09.G, particularly a framework silicate without zeolitic water and with additional anions.
17. The use as claimed in any of the above claims, characterised in that 20 the framework silicate is a zeolite.
18. The use as claimed in any of the above claims, characterised in that the semiconductor absorber layer is a kesterite or chalcopyrite semiconductor absorber layer.
19. A thin-film photovoltaic solar cell containing microporous anionic 25 inorganic framework structures, particularly framework silicates or 23 WO 2014/009061 A2 PCT/EP2013/061551 framework germanates, particularly in at least one back electrode layer, contact layer, and/or semiconductor absorber layer.
20. A thin-film solar cell as claimed in claim 19, characterised in that the microporous anionic inorganic framework structures have, in their 5 micropores: metal ions, such as Cu', Ga*, and/or In 3 *, originating from the semiconductor absorber layer; and/or impurities, such as Fe 3 * and/or Ni 2 +, originating from the thin-film solar cell.
21. A thin-film solar cell as claimed in claim 19 or 20, characterised in that the semiconductor absorber layer is doped with monovalent dopant 10 cations, particularly alkali ions, originally from the framework structures, particularly in exchange for metal ions of the semiconductor absorber layer.
22. A thin-film solar cell as claimed in any of claims 19 to 21, comprising, in this order: 15 - at least one substrate layer, particularly one comprising, or in the form of, a sheet of glass, - if applicable, at least one first barrier layer, particularly one that is non-conductive, - at least one back electrode layer, 20 - if applicable, at least one second, conductive, barrier layer, and at least one contact layer, particularly an ohmic contact layer, - at least one semiconductor absorber layer, particularly a chalcopyrite or kesterite semiconductor absorber layer, and particularly a semiconductor absorber layer that is immediately adjacent to the back 25 electrode layer or the contact layer, - if applicable, at least one first buffer layer, - if applicable, at least one second buffer layer, and - at least one front electrode layer. 24 WO 2014/009061 A2 PCT/EP2013/061551
23. A thin-film solar cell as claimed in any of claims 19 to 22, characterised in that the microporous anionic inorganic framework structures, particularly framework silicates, contain or are made up of tetrahedral building blocks. 5
24. A thin-film solar cell as claimed in any of claims 19 to 23, characterised in that the framework structure, particularly the framework silicates, is not hygroscopic.
25. A thin-film solar cell as claimed in any of claims 19 to 24, 10 characterised in that the micropores of the framework structure, particularly the framework silicates, have a pore opening diameter permitting the replacement of the dopant cations, particularly alkali ions, in the micropores with metal ions of the metals of the semiconductor absorber layer, for example Cu', Ga*, is and/or In 3 *, and/or with impurities originating from the thin-film solar cell, such as Fe 3 * and/or Ni 2 +.
26. A thin-film solar cell as claimed in any of claims 19 to 25, characterised in that the framework silicate (i.e. the "tectosilicate") is an alumino-, titano 20 alumino-, boro-, gallo-, indium, or iron(Ill) tectosilicate.
27. A thin-film solar cell as claimed in any of claims 19 to 26, characterised in that the framework structure, particularly the framework silicate, contains, or is composed of, beta-cages, especially condensed beta-cages. 25
28. A thin-film solar cell as claimed in any of claims 19 to 27, characterised in that 25 WO 2014/009061 A2 PCT/EP2013/061551 the framework structure, particularly the framework silicate, has, in its micropores, sodium ions, potassium ions, lithium ions, rubidium ions, and/or caesium ions, particularly sodium ions.
29. A thin-film solar cell as claimed in any of claims 19 to 28, 5 characterised in that the framework structure, particularly the framework silicate, has micropores with a pore opening diameter of less than about 0.29 nm.
30. A thin-film solar cell as claimed in any of claims 19 to 29, characterised in that 10 the framework structure, particularly the framework silicate, has a sodalite framework topology.
31. A thin-film solar cell as claimed in any of claims 19 to 30, characterised in that, in the framework silicate, up to 50% of the tetravalent silicon tetrahedral is building blocks are replaced with tetrahedral building blocks that have a trivalent central atom, particularly aluminium.
32. A thin-film solar cell as claimed in any of claims 19 to 31, characterised in that the framework structure is a framework silicate or framework germanate, 20 of Strunz Class 09.F or 09.G, particularly a framework silicate without zeolitic water and with additional anions.
33. A thin-film solar cell as claimed in any of claims 19 to 32, characterised in that the framework silicate is a zeolite. 25
34. A thin-film solar cell as claimed in any of claims 22 to 33, characterised in that 26 WO 2014/009061 A2 PCT/EP2013/061551 the first buffer layer contains or essentially consists of CdS, or is a CdS free layer, particularly containing or essentially consisting of Zn(S,OH), Zn(S,O,OH), and/or In 2 S 3 , and/or the second buffer layer contains, or essentially consists of, intrinsic zinc oxide and/or high-resistance zinc 5 oxide.
35. A thin-film solar cell as claimed in any of claims 19 to 34, characterised in that the semiconductor absorber layer is, or comprises, a quaternary IB-lIlA VIA chalcopyrite layer, particularly a Cu(In, Ga)Se 2 layer, a penternary IB 10 IllA-VIA chalcopyrite layer, particularly a Cu(In, Ga)(Se1 1 ., Sx)2 layer, or a kesterite layer, particularly a Cu 2 ZnSn(Sex, S1x)4 layer, e.g. a Cu 2 ZnSnSe 4 or Cu 2 ZnSnS 4 layer, where the value of x is from 0 to 1.
36. A thin-film solar cell as claimed in any of claims 19 to 35, characterised in that is the contact layer comprises at least one metal layer and at least one metal chalcogenide layer, the former being next to and contiguous with the back electrode, or next to and contiguous with the barrier layer, and the latter being next to and contiguous with the semiconductor absorber 20 layer.
37. A thin-film solar cell according to claim 36, characterised in that the metal layer and the metal chalcogenide are based on the same metal, particularly molybdenum and/or tungsten.
38. A thin-film solar cell as claimed in any of claims 19 to 37, 25 characterised in that the contact layer is, or comprises, a metal chalcogenide layer. 27 WO 2014/009061 A2 PCT/EP2013/061551
39. A thin-film solar module, containing series-connected - and in particular monolithically integrated - solar cells as claimed in any of claims 19 to 38.
40. A method for producing a thin-film photovoltaic solar cell as claimed 5 in any of claims 1 to 38 or for producing a thin-film photovoltaic solar module as claimed in claim 39, characterised in that microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, are applied onto and/or introduced into at least one back electrode layer, at least one contact 10 layer, and/or at least one semiconductor absorber layer of: at least one thin-film solar cell, particularly one that is based on a glass substrate layer, or at least one thin-film solar cell forming the thin-film solar module, particularly such a thin-film solar cell that is based on a glass substrate is layer.
41. A method as claimed in claim 40, comprising the steps of: - providing a substrate, particularly one that is flat, and that comprises, or is in the form of, a sheet of glass, - applying, if appropriate, a first, and particularly a non-conductive, 20 barrier layer to the substrate, - applying at least one back electrode layer to the substrate or the first barrier layer, by physical and/or chemical vapour deposition, from at least one, first, source of material, - applying, if appropriate, 25 at least one second, conductive, barrier layer to the at least one back electrode layer, by physical and/or chemical vapour deposition, from at least one, second, source of material and 28 WO 2014/009061 A2 PCT/EP2013/061551 at least one contact layer, particularly an ohmic contact layer, to the second barrier layer, by physical and/or chemical vapour deposition from at least one, third, source of material or 5 at least one first metal layer (co-forming the contact layer), by physical and/or chemical vapour deposition on the second barrier layer, from at least one, fourth, source of material, - depositing at least one second metal layer containing the metal components of the semiconductor absorber layer - particularly copper, 10 indium, and possibly gallium, for a chalcopyrite semiconductor absorber layer; and copper, zinc, and tin, for a kesterite semiconductor absorber layer - on the back electrode layer or the contact layer, by physical and/or chemical vapour deposition, from at least one, fifth, source of material, 15 - depositing microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, on the substrate layer and/or the back electrode layer, and, if appropriate, on the first and/or second barrier layer and/or, if appropriate, on the contact layer and/or, if appropriate, on the first metal layer, and/or on the second metal 20 layer, and/or co-depositing these framework structures with the at least one back electrode layer and/or, as appropriate, with the at least one first and/or second barrier layer and/or, as appropriate, with the at least one contact layer and/or, as appropriate, with the at least one first metal layer, and/or 25 with the at least one second metal layer, doing so from at least one sixth material-source, particularly by at least one wet-chemical deposition process and/or by physical and/or chemical vapour deposition, - treating the second metal layer- when it is on the back electrode 30 layer, or, as the case may be, on the contact layer or the first metal layer - with at least one sulphur and/or selenium compound and/or with gaseous elemental selenium and/or sulphur, at temperatures above 29 WO 2014/009061 A2 PCT/EP2013/061551 3000C, but particularly 3500C to 6000C, and preferably 5200C to 6000C, to form a semiconductor absorber layer, - applying, if appropriate, at least one first buffer layer to the semiconductor absorber layer, 5 - applying, if appropriate, at least one second buffer layer to the first buffer layer or the semiconductor absorber layer, - applying at least one transparent front electrode layer to the first or second buffer layer or the semiconductor absorber layer.
42. A method as claimed in claim 40 or 41, characterised in that 10 the microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, contain monovalent dopant cations, particularly alkali ions, in their micropores.
43. A method as claimed in any of claims 40 to 42, characterised in that physical vapour deposition (PVD) covers physical vapour deposition is (PVD) coating, vapour deposition using an electron beam evaporator, vapour deposition using a resistance evaporator, induction evaporation, ARC evaporation, and/or cathode sputtering (sputter coating), in particular DC- or RF-magnetron sputtering, in each case preferably in a high vacuum; and chemical vapour deposition (CVD) includes chemical vapour 20 deposition (CVD) coating, low pressure CVD, and/or atmospheric pressure CVD.
44. A method as claimed in any of claims 40 to 43, characterised in that: the first and sixth material-sources constitute a first mixed target, and/or the second and sixth material-sources constitute a second mixed target, 25 and/or the third and sixth material-sources constitute a third mixed target, and/or the fourth and sixth material-sources constitute a fourth mixed target, and/or the fifth and sixth material-sources constitute a fifth mixed target. 30 WO 2014/009061 A2 PCT/EP2013/061551
45. The method as claimed in any of claims 40 to 44, characterised in that co-deposition is performed - sequentially, or essentially at the same time - from the fifth, sixth, and first material-sources; the fifth, sixth, and third 5 material-sources; or the fifth, sixth, and fourth material-sources; or from the fifth mixed target and the first material-source; the fifth mixed target and the third material-source; or the fifth mixed target and the fourth material-source.
46. A method as claimed in any of claims 40 to 45, characterised in that 10 co-deposition is performed, sequentially or essentially at the same time, from the fifth mixed target and the fifth material-source.
47. A method as claimed in any of claims 40 to 46, characterised in that co-deposition is performed, sequentially or essentially at the same time, from the first, second, third, and/or fourth mixed target, particularly the is first, third, or fourth mixed target, and the fifth material-source.
48. A method as claimed in any of claims 40 to 47, characterised in that co-deposition is performed, sequentially or essentially at the same time, from the fifth mixed target and the first, second, third, and/or fourth mixed target, particularly the first or third or fourth mixed target. 20
49. A method as claimed in any of claims 40 to 48, characterised in that co-deposition is performed, sequentially or essentially at the same time, from the first, second, or third mixed target, particularly the first or third mixed target, and the first, second, third, or fourth material-source, particularly the first or third or fourth material-source. 25
50. A method as claimed in any of claims 40 to 49, characterised in that the application of the following is done in a single vacuum coating installation, preferably by the continuous sputtering method: the back electrode layer, possibly the conductive barrier layer and first metal layer 31 WO 2014/009061 A2 PCT/EP2013/061551 or the contact layer, and the metals of the semiconductor absorber layer (particularly Cu, In, and Ga layers in the case of the formation of the chalcopyrite semiconductor absorber layer, or Cu, Zn, and Sn layers in the case of the formation of the kesterite semiconductor absorber layer); 5 also, the microporous anionic inorganic framework structures, particularly framework silicates or framework germanates, containing alkali ions, particularly sodium ions, in their micropores.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012211894.2A DE102012211894A1 (en) | 2012-07-09 | 2012-07-09 | Use of microporous anionic inorganic framework structures, in particular containing dopant cations, for the production of thin-film solar cells or modules, photovoltaic thin-film solar cells containing microporous anionic inorganic framework structures, and methods for producing such thin-film solar photovoltaic modules |
| DE102012211894.2 | 2012-07-09 | ||
| PCT/EP2013/061551 WO2014009061A2 (en) | 2012-07-09 | 2013-06-05 | Use of microporous anionic inorganic framework structures, in particular containing dopant cations, for producing thin film solar cells and/or modules, photovoltaic thin film solar cells containing microporous anionic inorganic framework structures, and method for producing such photovoltaic thin film solar modules |
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| AU2013289503A1 true AU2013289503A1 (en) | 2015-02-26 |
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| AU2013289503A Abandoned AU2013289503A1 (en) | 2012-07-09 | 2013-06-05 | Use of microporous anionic inorganic framework structures containing dopant cations for producing thin film solar cells |
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| JP (1) | JP2015522216A (en) |
| KR (1) | KR20150032858A (en) |
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| AU (1) | AU2013289503A1 (en) |
| DE (1) | DE102012211894A1 (en) |
| IN (1) | IN2015DN00171A (en) |
| WO (1) | WO2014009061A2 (en) |
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| DE102014223485A1 (en) | 2014-11-18 | 2016-05-19 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg | Layer structure for a thin-film solar cell and manufacturing method |
| KR101975522B1 (en) * | 2017-09-29 | 2019-05-07 | 한국에너지기술연구원 | Transparent CIGS solar cell and method of manufacturing the same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5594263A (en) * | 1993-03-26 | 1997-01-14 | Uop | Semiconductor device containing a semiconducting crystalline nanoporous material |
| DE4442824C1 (en) * | 1994-12-01 | 1996-01-25 | Siemens Ag | Solar cell having higher degree of activity |
| US6346224B1 (en) * | 1999-10-22 | 2002-02-12 | Intevep, S.A. | Metaloalluminosilicate composition, preparation and use |
| SE0301350D0 (en) * | 2003-05-08 | 2003-05-08 | Forskarpatent I Uppsala Ab | A thin-film solar cell |
| DE102007063604A1 (en) * | 2007-05-24 | 2008-12-04 | Süd-Chemie AG | Metal-doped zeolite and process for its preparation |
| WO2010032802A1 (en) * | 2008-09-18 | 2010-03-25 | 富士フイルム株式会社 | Solar cell |
| JP4629151B2 (en) * | 2009-03-10 | 2011-02-09 | 富士フイルム株式会社 | Photoelectric conversion element, solar cell, and method for manufacturing photoelectric conversion element |
| JP5480782B2 (en) * | 2010-01-21 | 2014-04-23 | 富士フイルム株式会社 | Solar cell and method for manufacturing solar cell |
| US20110232761A1 (en) * | 2010-03-18 | 2011-09-29 | Lomasney Henry L | Solar photovoltaic devices having optional batteries |
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2012
- 2012-07-09 DE DE102012211894.2A patent/DE102012211894A1/en not_active Withdrawn
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2013
- 2013-06-05 AU AU2013289503A patent/AU2013289503A1/en not_active Abandoned
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- 2013-06-05 CN CN201380036606.4A patent/CN104584233A/en active Pending
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- 2013-06-05 IN IN171DEN2015 patent/IN2015DN00171A/en unknown
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| CN104584233A (en) | 2015-04-29 |
| KR20150032858A (en) | 2015-03-30 |
| WO2014009061A2 (en) | 2014-01-16 |
| DE102012211894A1 (en) | 2014-01-09 |
| EP2870634A2 (en) | 2015-05-13 |
| IN2015DN00171A (en) | 2015-06-12 |
| JP2015522216A (en) | 2015-08-03 |
| WO2014009061A3 (en) | 2014-07-31 |
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