WO2010063974A1 - Element en couches et dispositif photovoltaique comprenant un tel element - Google Patents
Element en couches et dispositif photovoltaique comprenant un tel element Download PDFInfo
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- WO2010063974A1 WO2010063974A1 PCT/FR2009/052405 FR2009052405W WO2010063974A1 WO 2010063974 A1 WO2010063974 A1 WO 2010063974A1 FR 2009052405 W FR2009052405 W FR 2009052405W WO 2010063974 A1 WO2010063974 A1 WO 2010063974A1
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- Prior art keywords
- layer
- protective coating
- moisture
- thin
- layers
- Prior art date
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- 239000011253 protective coating Substances 0.000 claims abstract description 74
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 230000004888 barrier function Effects 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 301
- 239000000758 substrate Substances 0.000 claims description 32
- 239000006096 absorbing agent Substances 0.000 claims description 30
- 239000011229 interlayer Substances 0.000 claims description 26
- 238000003475 lamination Methods 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 230000005540 biological transmission Effects 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 17
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 9
- 230000003247 decreasing effect Effects 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 229920006352 transparent thermoplastic Polymers 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 3
- 239000013047 polymeric layer Substances 0.000 claims description 3
- 230000003667 anti-reflective effect Effects 0.000 claims 1
- 238000000411 transmission spectrum Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000000151 deposition Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- -1 chalcopyrite compound Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229920000307 polymer substrate Polymers 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910010282 TiON Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- H01L31/02—Details
- H01L31/0216—Coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—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
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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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- 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
-
- 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
- Y02E10/52—PV systems with concentrators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E10/545—Microcrystalline silicon 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
- 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
- Y02E10/548—Amorphous silicon PV cells
Definitions
- the present invention relates to a layered element, in particular for a photovoltaic device.
- the invention also relates to a photovoltaic device comprising such a layered element, as well as to a method of manufacturing such a layered element.
- a photovoltaic device designates a photovoltaic cell or a photovoltaic module.
- a thin-film photovoltaic solar cell comprises a layer of an absorber material capable of ensuring the conversion of light energy into electrical energy, which is interposed between two electrically conductive layers respectively forming a front electrode intended to be disposed on the incident side of the light on the cell, and a rear electrode.
- the absorber layer may in particular be a thin layer of chalcopyrite compound comprising copper, indium and selenium, referred to as the CIS absorber layer, optionally supplemented with gallium (CIGS absorber layer), aluminum or aluminum oxide. sulfur.
- the absorber layer may be a thin layer based on silicon, amorphous or microcrystalline, or based on cadmium telluride.
- the front electrode of a thin-film photovoltaic cell may be formed based on a transparent conductive oxide (TCO) layer, for example a layer of doped zinc oxide, in particular with aluminum (AZO) or boron, or based on a transparent metal layer (Transparent Conductive Coating or TCC).
- TCO transparent conductive oxide
- AZO aluminum
- boron boron
- TCC Transparent Conductive Coating
- the front electrode of a thin-film photovoltaic cell is conventionally associated, on the incident side of the light on the cell, with a substrate with a glass function, or a front substrate, which can be constituted by a transparent glass or a transparent thermoplastic polymer, such as polyethylene, especially polytetrafluoroethylene (PTFE), polyimide, polycarbonate, polyurethane or polymethylmethacrylate.
- a transparent polymeric lamination interlayer is positioned between the front electrode and the front substrate to ensure good cohesion. of the cell during its assembly, in particular by rolling.
- a thin-film photovoltaic cell comprises a polymeric lamination interlayer or a polymer substrate positioned on a moisture-sensitive layer forming the front electrode of the cell, in particular a layer based on zinc oxide
- the cell has a significant degradation rate under the effect of moisture.
- the laminating interlayer which tends to store moisture
- the polymer substrate which is permeable to moisture, promotes the migration of moisture to the moisture sensitive layer forming the front electrode , and therefore the alteration of the properties of this layer.
- WO-A-97/36334 discloses a thin film photovoltaic cell in which a moisture barrier layer is interposed between a zinc oxide layer forming the front electrode of the cell and a polymeric lamination interlayer surmounting the electrode.
- a barrier layer makes it possible to limit the migration of moisture from the polymeric lamination interlayer to the front electrode-forming zinc oxide-based layer.
- the transmission of light at the interface between the polymeric lamination interlayer and the front electrode layer which is already limited due to a large difference in refractive indexes. between the lamination interlayer and the layer based on zinc oxide, is likely to be degraded. This results in a risk of a decrease in the luminous flux reaching the absorber layer of the photovoltaic cell, and therefore a risk of reducing the efficiency of the cell.
- the invention intends to remedy more particularly by proposing a layered element which, when integrated into a thin-film photovoltaic device gives this device improved resistance to humidity, without reducing the efficiency of the photovoltaic device, or even with an increase in this output.
- the subject of the invention is a layered element, in particular for a photovoltaic device, comprising a polymer layer, a moisture-sensitive layer and a moisture barrier protective coating sandwiched between the polymer layer and the moisture-sensitive layer, characterized in that the protective coating consists of an antireflection stack comprising at least two thin layers of different refractive indices with respect to each other.
- an antireflection stack is a stack which ensures transmission through the layered element of radiation, incident on the layered element on the side of the polymer layer, greater than or equal to the transmission of this radiation obtained in the absence of antireflection stacking.
- thin film is also understood to mean a layer of thickness less than 1 micrometer.
- each thin layer of the antireflection stack of the protective coating is adapted to maximize the transmission of radiation through the layered element;
- each thin layer of the antireflection stack of the protective coating is an oxide and / or nitride layer;
- the protective coating consists of an antireflection stack comprising at least three thin layers, the refractive index of a thin layer of each pair of successive thin layers of the antireflection stack being different from the refractive index of the another thin layer of the pair;
- the antireflection stack of the protective coating comprises a successive stacking, from the moisture-sensitive layer towards the polymer layer, of at least two thin layers of refractive indices which are alternatively lower and stronger with respect to each other; others;
- the antireflection stack of the protective coating comprises, successively, from the moisture-sensitive layer to the polymer layer:
- a first layer having a first refractive index of between 1.3 and 1.7 at 550 nm and a first geometric thickness of between 15 and 35 nm, preferably between 20 and 30 nm,
- a second layer having a second refractive index of between 1.8 and 2.3 at 550 nm and a second geometric thickness of between 20 and 35 nm, preferably between 25 and 30 nm,
- a third layer having a third refractive index of between 1.3 and 1.7 at 550 nm and a third geometric thickness of between 5 and 20 nm, preferably between 7 and 18 nm,
- the antireflection stack of the protective coating comprises the following sequence of thin layers, from the moisture-sensitive layer to the polymer layer:
- the antireflection stack of the protective coating comprises a successive stack of at least two thin layers of decreasing refractive indices from the layer closest to the moisture-sensitive layer to the layer closest to the polymer layer; ;
- the antireflection stack of the protective coating comprises successively at least two thin films of SiO x Ny of decreasing refractive indices from the layer closest to the moisture-sensitive layer to the layer closest to the polymer layer; .
- the invention also relates to a thin-film photovoltaic device comprising a layered element as described above and a layer of absorber material positioned on the side of the moisture-sensitive layer of the layered element.
- the geometric thickness of each thin layer of the protective coating is adapted to maximize the transmission, weighted on the solar spectrum and the absorption spectrum of the absorber material of the device, through the layered element and towards the layer of absorber material, a radiation incident on the device on the side of the polymer layer.
- the device comprises a transparent glass canopy substrate, the polymer layer being a transparent polymeric lamination interlayer with the substrate.
- the polymer layer is a glass function substrate transparent thermoplastic polymer of the photovoltaic device.
- transparent designates a transparency at least in the wavelength ranges that are useful for the photovoltaic device.
- the subject of the invention is a method for producing a layered element as described above, in which at least a portion of the thin layers of the antireflection stack of the sputter protective coating are deposited and / or or plasma enhanced chemical vapor deposition (PECVD).
- PECVD plasma enhanced chemical vapor deposition
- FIG. 1 is a schematic cross section of a photovoltaic solar cell according to a first embodiment of the invention
- FIG. 2 is a section similar to FIG. 1 of a variant of the photovoltaic solar cell of FIG. 1
- - Figure 3 is a section similar to Figure 1 for a photovoltaic solar cell according to a second embodiment of the invention.
- the photovoltaic solar cell 20 is a thin-film cell comprising a glass-fronted front substrate 1 and a back-up substrate 7, between which a stack of layers 2, 3 is arranged. , 4, 5, 6.
- the front substrate 1, intended to be arranged on the incident side of the light on the cell 20, is made of an extra-clear transparent glass with a very low content of iron oxides.
- extra-clear glasses include in particular the glasses marketed by Saint-Gobain Glass in the range
- the rear substrate 7 is made of any suitable material, transparent or not, in particular glass, and carries, on its face directed towards the interior of the cell 20, that is to say on the side of incidence of light on the cell 20, an electrically conductive layer 6 which forms a rear electrode of the cell 20.
- the layer 6 is based on molybdenum.
- the rear substrate 7 is made of glass and an alkaline barrier layer 8 is interposed between the rear substrate 7 and the rear electrode molybdenum layer 6.
- This alkaline barrier layer 8 is deposited, prior to the deposition of the layer 6, on all or part of the face of the rear substrate 7 which is directed towards the inside of the cell 20, for example by sputter-down magnetron sputtering or sputter up or by a process
- the alkaline barrier layer 8 comprises a dielectric material based on nitrides, oxides or oxynitrides of silicon or aluminum, or based on titanium or zirconium nitrides, used alone or as a mixture.
- the geometrical thickness of the layer 8 is between 3 and 200 nm, preferably between 20 and 150 nm.
- the alkali barrier layer 8 may be based on Si 3 N 4 .
- the back electrode layer 6 is conventionally surmounted by a layer of chalcopyrite compound absorber 5, in particular CIS or CIGS, suitable for converting solar energy into electrical energy.
- the absorber layer 5 is itself surmounted by a CdS cadmium sulphide layer, not shown in the figures and possibly associated with an undoped intrinsic ZnO layer, also not shown, and then by an electrically conductive layer 4 which forms a front electrode of the cell 20.
- the layer 4 is a layer based on zinc oxide doped with aluminum (AZO).
- the layer 4 may be a boron-doped zinc oxide layer, a layer based on another moisture-sensitive doped transparent conductive oxide, or a layer transparent metal sensitive to moisture such as a stack of silver.
- the cell 20 further comprises a moisture protection coating 3 arranged on the layer 4.
- a transparent polymeric lamination interlayer 2 is positioned between the protective coating 3 and the front substrate 1, so as to ensure the maintenance of the functional layers of the cell 20 between the substrates before 1 and back 7.
- the laminating interlayer 2 is a layer of thermosetting polymer, by example a polyvinyl butyral (PVB) layer.
- the lamination interlayer 2 may also be made of ethylene vinyl acetate (EVA).
- EVA ethylene vinyl acetate
- the protective coating 3 of the layered element 10 is a multilayer coating consisting of an antireflection stack of at least two thin transparent layers of refractive indices different from each other .
- the coating 3 is a four-ply coating comprising a stack of four thin transparent layers 31, 32, 33, 34 of refractive indices that are alternatively lower and stronger relative to each other. to others. More specifically, the stack of thin layers of the coating 3 comprises successively, from the AZO layer 4 forming the front electrode of the cell 20 to the laminating interlayer 2 made of PVB:
- a first layer 31 of SiO 2 having a refractive index n 3 i of 1.45-1.48 and a geometric thickness e 3 i of between 15 and 35 nm, preferably between 20 and 30 nm,
- a second layer 32 of Si 3 N 4 having a refractive index n 32 of 1.95-2.05 and a geometric thickness e 32 of between 20 and 35 nm, preferably between 25 and 30 nm,
- the third layer 33 of SiO 2 of the stack of thin layers of the coating 3 may have a geometric thickness of 33 between 35 and 55 nm, preferably between 40 and 50 nm.
- the coating 3 may be a bilayer coating consisting of a stack of two thin transparent layers, namely, from the AZO layer 4 to the laminar interlayer 2 made of PVB, a layer SiO 2 thin film, having a refractive index of 1.45-1.48 and a geometrical thickness of between 15 and 35 nm, preferably between 20 and 30 nm, and a thin layer of Si 3 N 4 having a refractive index. of refraction of 1.95-2.05 and a geometric thickness of between 10 and 30 nm, preferably between 15 and 25 nm.
- one or each thin layer with a higher refractive index of the coating 3 may be, instead of a layer of Si 3 N 4 , a layer based on SiN, SnZnSbO, SnO 2 , ZnO AlN, NbO, TiO 2 , TiZnO, SiTiO, TiON.
- one or each thin layer with a lower refractive index of the coating 3 may be, instead of a layer of SiO 2 , a layer based on Al 2 O 3 , MgF 2 , AlF 3. , Y 2 O 3 .
- An advantageous method of manufacturing a layered element according to the invention comprises depositing the multilayer protective coating by a vacuum technique, in particular by magnetic field assisted sputtering or corona discharge.
- the different layers of the protective coating are successively deposited cold, for example on the previously prepared AZO layer.
- the deposition of the 4-layer and two-layer protection coatings described above which comprise an alternating stack of layers of SiO 2 and Si 3 N 4 , can be produced by sputtering from a silicon target that it is lightly doped with a metal, such as aluminum, so as to make it sufficiently conductive.
- these layers may be deposited by reactive sputtering of the metal in question, respectively in the presence of nitrogen or in the presence of oxygen, under plasma argon.
- these layers may be deposited by a co-sputtering process targets zinc and tin, respectively, in the presence of oxygen, or by a method of spraying a target based on the desired mixture of tin and zinc, also in the presence of oxygen.
- Another advantageous method of manufacturing a layered element according to the invention comprises the deposition of the multilayer protective coating by plasma-enhanced chemical vapor deposition (PECVD).
- PECVD plasma-enhanced chemical vapor deposition
- This technique of deposition under reduced pressure implements the decomposition of precursors under the effect of a plasma, in particular under the effect of collisions between the excited or ionized species of the plasma and the molecules of the precursor.
- a deposit made by PECVD is consistent, that is to say that it marries the reliefs of the deposition surface, so that there is no shading effect in the case where the deposit is made on a surface having a rugged terrain.
- a PECVD deposit will therefore be preferred to spray deposition in cases where the deposition surface of the protective coating is irregular, in order to avoid any shading effect, and in particular when the protective coating is deposited after the etching steps of the solar cell.
- PECVD can be deposited with alternating refractive index multilayer coatings as well as multilayer graded index refractive coatings.
- the PECVD technique allows the deposition of successive thin layers of different chemical natures, in particular alternating, by modifying the nature of the precursors during the deposition.
- the introduction of different precursors during a deposition phase makes it possible to obtain a zone of different chemical nature within a layer, and thus to form multilayer coatings whose constituent thin layers are of different chemical compositions.
- the PECVD technique also makes it very easy to obtain a variation of the stoichiometry of a layer by modifying one or more quantities, especially the relative proportions of the precursors. It is therefore possible to form multilayer coatings whose constituent thin layers are of the same chemical nature but of different stoichiometries.
- Other deposition techniques are possible, but are less preferred, including evaporation techniques, or atmospheric pressure PECVD processes, particularly those using dielectric barrier discharge technologies.
- Table 1 shows the results of tests evaluating the performance, as a moisture barrier, of protective coatings 3 different compositions, comprising coatings 3 having a single layer of SiO 2 or Si 3 No. 4 , as well as the 3-layer and two-layer coatings described previously by way of examples.
- the quadric layer protective coating 3 of the layered element 10 shown in FIG. 1 provides effective protection of the aluminum support against moisture, in particular more effective than a monolayer protective coating in SisN. 4 and at least as effective as a monolayer protection layer SiO 2, for an overall geometric thickness ⁇ 3 of the protective coating less than 100 nm.
- a two-layer protection coating 3 as described above comprising a successive stack of a thin layer of SiO 2 , having a geometric thickness of 20 nm, and a thin layer of SisN 4 , having a geometrical thickness of 22 nm, is an effective barrier against moisture.
- this bilayer coating of overall ⁇ 3 geometrical thickness of 42 nm is at least as effective, as a moisture barrier, a monolayer protective coating in SiO 2 with an overall geometric thickness e 3 of 100 nm .
- a multilayer protection coating 3 in particular a four-layer coating or bilayer as described above, provides an effective barrier against moisture migration from the PVB lamination interlayer 2, which tends to store moisture, to the moisture sensitive layer 4.
- the effectiveness of such a multilayer coating 3 as a moisture barrier is even overall better than that obtained with a monolayer protective coating, for the same overall geometric thickness ⁇ 3 of the coating.
- the light transmission through the layered element 10 has been evaluated in a weighted manner on the solar spectrum, which can in particular be determined as an average of the solar spectra corresponding to the different incidences obtained, in one day, for a photovoltaic panel used at a given time. given latitude, and on the absorption spectrum of the absorber of the layer 5, which in this example is a CIS absorber layer, so as to allow an estimation of the luminous flux that is actually usable by the absorber layer 5 of cell 20 for photovoltaic conversion.
- TSQE CIS
- a multilayer protection coating 3 in particular four-layer or two-layer as described above by way of example, makes it possible to obtain a weighted transmission TSQE (CIS) through the layered element 10 greater than the weighted transmission TSQE (CIS) obtained in the absence of this protective coating.
- the stack of layers of the multilayer protective coating 3, in particular four-layer or two-layer, of an element 10 according to the invention is designed so that the refractive indices of the layers are alternatively lower and stronger each relative to the others from layer 4 to lamination interlayer 2.
- the multilayer protective coating 3 of an element 10 according to the invention constitutes an interference filter and ensures an antireflection function at the interface between the lamination interlayer 2 in PVB and the layer 4 in AZO.
- Suitable values of the geometrical thicknesses of the layers of the protective coating can in particular be selected by means of an optimization software.
- the useful light flux for the photovoltaic conversion reaching the absorber layer 5 of the cell 20 according to the invention is greater than the useful light flux reaching the absorber layer of a similar thin-film photovoltaic cell of the state of the art without a multilayer protective coating.
- a multilayer protective coating 3 interposed between the polymeric lamination interlayer 2 and the layer 4 of the layered element 10 according to the invention thus makes it possible to increase the efficiency of the cell 20 with respect to the yield obtained in FIG. the absence of multilayer protective coating.
- the photovoltaic cell 120 differs from the cell 20 of the first embodiment. embodiment in particular that it comprises a front substrate 102 made of a transparent thermoplastic polymer, and not glass.
- the cell 120 also comprises a rear substrate 107 which carries, on its face facing the inside of the cell 120, an electrically conductive layer 106 forming a rear electrode of the cell 120.
- the layer 106 is surmounted by a layer 105 of absorber material capable of ensuring the conversion of solar energy into electrical energy.
- the layer 105 may be, as desired, a CIS absorber thin film, a silicon-based thin film or a cadmium telluride thin film.
- the cell 120 is manufactured in substrate mode, that is to say by successive deposition of the constituent layers of the cell on the rear substrate 107
- the cell 120 is manufactured in superstrate mode, that is to say by successive deposition of constituent layers of the cell from the front substrate 102.
- the absorber layer 105 is surmounted by an electrically conductive and moisture-sensitive layer 104, based on aluminum-doped zinc oxide (AZO), which forms an electrode 120 of the cell 120.
- the cell 120 further comprises a protective coating 103, which is interposed between the moisture-sensitive layer 104 and the thermoplastic polymer front substrate 102.
- the transparent substrate 102 which may in particular be made of polyethylene, for example polytetrafluoroethylene (PTFE), polyimide, polycarbonate, polyurethane or polymethylmethacrylate, has, unlike a glass substrate, a permeability to moisture.
- the entire layer 104, the coating 103 and the superimposed substrate 102 form a layered element 110.
- the protective coating 103 of the layered element 110 is a multilayer coating consisting of an antireflection stack of at least two thin transparent layers.
- the coating 103 is a four-ply coating comprising a stack of four thin transparent layers 131, 132, 133, 134 of refractive indices that are alternatively lower and stronger with respect to each other. , namely successively, from the layer 104 to the polymer substrate 102:
- a third layer 133 of SiO 2 having a refractive index n 33 33 n 3 n of 1, 45-1, 48 and a geometric thickness ei 33 of between 5 and 20 nm, preferably between 7 and 18 nm, and
- the third layer 133 of SiO 2 of the thin film stack of the coating 103 may have a geometric thickness of 33 between 35 and 55 nm, preferably between 40 and 50 nm.
- the thin layers of the multilayer protective coating 103 interposed between the polymer substrate 102 and the moisture sensitive layer 104 of the layered element 110 have refractive indices which are alternatively lower and stronger than the others, from the layer 104 to the substrate 102.
- the multilayer coating 103 thus allows, compared with what is obtained with a protective coating of the state of the art, both of to improve the protection of the AZO layer 104 against the moisture that is likely to pass into the interior of the cell 120 through the permeable polymer substrate 102, thanks to the multiplicity of interfaces between the various layers constituting the coating 103, and to improve the transmission of useful light through the element 110 to the absorber layer 105, by an antireflection effect at the interface between the layer 104 of AZO and the polymer substrate 102. As in the first embodiment, this results in an increase in the efficiency of the photovoltaic cell 120 integrating the element 110 relative to photovoltaic cells of the state of the art without multilayer protective coating.
- a protective coating interposed between the moisture-sensitive layer and the polymer layer of a layered element according to the invention comprising an antireflection stack formed by at least two superimposed layers of different refractive indices.
- An antireflection stack of the protective coating interposed between the moisture-sensitive layer and the polymeric layer is a stack which provides transmission of radiation through the layered element greater than or equal to the transmission of said radiation obtained in the absence of antireflection stacking.
- the different layers of the antireflection stack of the protective coating of a layered element according to the invention can be arranged in such a way that the refractive indices of the layers are alternatively lower and stronger relative to each other. others, as in the examples described above.
- the different layers of the antireflection stack of the protective coating of a layered element according to the invention can also be arranged in such a way that the refractive indices of the layers are decreasing since the layer closest to the moisture-sensitive layer to the layer closest to the polymer layer.
- the multi-layered protective coating then creates a stepped gradient of refractive indices, which decreases from the moisture sensitive layer, whose refractive index is greater than that of the polymer layer, to the polymer layer.
- Such a multilayer coating with a graded gradient of refractive indices may notably be formed by a successive stack of layers of SiO x Ny of decreasing refractive indices from the moisture-sensitive layer to the polymer layer, the extreme layers being by for example, respectively, a layer of Si 3 N 4 in the vicinity of the moisture-sensitive layer and a layer of SiO 2 in the vicinity of the polymer layer.
- the different layers of SiO x Ny of decreasing refractive indices have relative proportions of nitrogen and oxygen which are different from one layer to another.
- These layers can be successively deposited cold on the moisture-sensitive layer by sputtering, under argon plasma, from a silicon target which is doped slightly with a metal, so as to make it sufficiently conductive, and in the presence of nitrogen and / or oxygen.
- the successive layers of SiO x Ny of decreasing refractive indices are then obtained by varying, in stages, the proportions of nitrogen and oxygen during the sputtering, in particular by reducing the proportion of nitrogen and increase the proportion of oxygen.
- these layers may be deposited successively by PECVD by modifying the stoichiometry between a thin layer and the following thin layer of the protective coating, in particular by varying, in steps, the relative proportions of the precursors.
- a multilayer coating with a graded refractive index gradient makes it possible, as well as a multilayer coating with alternating refractive indices, both to improve the protection of the moisture-sensitive layer, thanks to the multiplicity of interfaces between the different layers constituting the protective coating, and to improve the transmission of useful light through the layered element incorporating the protective coating, by an antireflection effect at the interface between the moisture-sensitive layer and the layer polymer.
- the invention provides a doubly advantageous layered element, in terms of protection against moisture. and in terms of light transmission.
- This double advantage has been obtained, on the one hand, by detecting the possibility of improving the moisture barrier effect of a protective coating due to the presence of a plurality of layers of different natures within the coating. and, on the other hand, taking advantage of the presence of this plurality of layers to set up, at the interface between the polymer layer and the moisture-sensitive layer, a multilayer antireflection stack.
- a layered element according to the invention can comprise a protective coating comprising any number, greater than or equal to two, of superimposed layers, the compositions and thicknesses of these layers may be different from those described above.
- the antireflection stack of the protective coating may equally well comprise an even or odd number of thin layers, the refractive index of a thin layer of each pair of successive thin layers of the antireflection stack being different from the refractive index of the other thin layer of the pair.
- the respective geometrical thicknesses of the layers are advantageously selected, for example by means of an optimization software, so as to maximize the light transmission weighted through the layered element.
- a three-layer or four-layer stack is advantageous because it provides a satisfactory number of interfaces for the function. moisture barrier.
- a four-layer stack as shown in FIGS. 1, 2 and 3 is particularly advantageous, in that it provides not only a satisfactory number of interfaces for the function moisture barrier, but also a satisfactory number of layers for the interference filter function of the protective coating.
- the polymer layer and the moisture-sensitive layer of a layered element according to the invention may be of different types and thicknesses than those described above.
- the moisture-sensitive layer may be formed at least partially by a metal layer.
- the moisture-sensitive layer may be formed in part by the rear-electrode molybdenum layer. , in the case where portions of this molybdenum layer are brought into direct contact with the polymeric lamination interlayer by etching certain parts of the cell.
- a layered element according to the invention can be used in a "tandem" type photovoltaic cell, in which the absorber layer is formed by a stack of several layers of different absorber materials.
- a layered element according to the invention can also be used in an organic absorber photovoltaic cell, the organic absorber layer then forming, at least in part, the moisture-sensitive layer.
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Abstract
Description
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Priority Applications (5)
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CN200980147725.0A CN102227815B (zh) | 2008-12-03 | 2009-12-03 | 层状元件和包含这种元件的光电装置 |
JP2011539082A JP2012510723A (ja) | 2008-12-03 | 2009-12-03 | 層状素子およびその層状素子を含む光起電力デバイス |
US13/132,045 US9196772B2 (en) | 2008-12-03 | 2009-12-03 | Layered element and photovoltaic device comprising such an element |
KR1020117012709A KR101739823B1 (ko) | 2008-12-03 | 2009-12-03 | 적층 요소 및 상기 적층 요소를 포함하는 광기전 장치 |
EP09801496A EP2374153A1 (fr) | 2008-12-03 | 2009-12-03 | Element en couches et dispositif photovoltaique comprenant un tel element |
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FR0858242A FR2939240B1 (fr) | 2008-12-03 | 2008-12-03 | Element en couches et dispositif photovoltaique comprenant un tel element |
FR0858242 | 2008-12-03 |
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EP (1) | EP2374153A1 (fr) |
JP (1) | JP2012510723A (fr) |
KR (1) | KR101739823B1 (fr) |
CN (1) | CN102227815B (fr) |
FR (1) | FR2939240B1 (fr) |
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US20080178922A1 (en) * | 2005-07-26 | 2008-07-31 | Solaria Corporation | Method and system for manufacturing solar panels using an integrated solar cell using a plurality of photovoltaic regions |
US20070178316A1 (en) * | 2006-01-30 | 2007-08-02 | Guardian Industries Corp. | First surface mirror with sol-gel applied protective coating for use in solar collector or the like |
US20080169021A1 (en) * | 2007-01-16 | 2008-07-17 | Guardian Industries Corp. | Method of making TCO front electrode for use in photovoltaic device or the like |
US20080308147A1 (en) * | 2007-06-12 | 2008-12-18 | Yiwei Lu | Rear electrode structure for use in photovoltaic device such as CIGS/CIS photovoltaic device and method of making same |
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2008
- 2008-12-03 FR FR0858242A patent/FR2939240B1/fr not_active Expired - Fee Related
-
2009
- 2009-12-03 EP EP09801496A patent/EP2374153A1/fr not_active Withdrawn
- 2009-12-03 US US13/132,045 patent/US9196772B2/en not_active Expired - Fee Related
- 2009-12-03 WO PCT/FR2009/052405 patent/WO2010063974A1/fr active Application Filing
- 2009-12-03 KR KR1020117012709A patent/KR101739823B1/ko active IP Right Grant
- 2009-12-03 JP JP2011539082A patent/JP2012510723A/ja active Pending
- 2009-12-03 CN CN200980147725.0A patent/CN102227815B/zh not_active Expired - Fee Related
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102347390A (zh) * | 2010-07-21 | 2012-02-08 | 杜邦太阳能有限公司 | 太阳能板与太阳能板的制作方法 |
CN104332505A (zh) * | 2014-12-01 | 2015-02-04 | 九州方园新能源股份有限公司 | 一种晶体硅太阳能电池氮化硅减反射膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2012510723A (ja) | 2012-05-10 |
FR2939240A1 (fr) | 2010-06-04 |
KR20110089865A (ko) | 2011-08-09 |
FR2939240B1 (fr) | 2011-02-18 |
KR101739823B1 (ko) | 2017-05-25 |
CN102227815A (zh) | 2011-10-26 |
EP2374153A1 (fr) | 2011-10-12 |
CN102227815B (zh) | 2017-10-31 |
US9196772B2 (en) | 2015-11-24 |
US20110232749A1 (en) | 2011-09-29 |
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