WO2010050189A1 - 太陽電池の製造方法、エッチング装置及びcvd装置 - Google Patents
太陽電池の製造方法、エッチング装置及びcvd装置 Download PDFInfo
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- WO2010050189A1 WO2010050189A1 PCT/JP2009/005675 JP2009005675W WO2010050189A1 WO 2010050189 A1 WO2010050189 A1 WO 2010050189A1 JP 2009005675 W JP2009005675 W JP 2009005675W WO 2010050189 A1 WO2010050189 A1 WO 2010050189A1
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- transparent conductive
- conductive film
- solar cell
- power generation
- forming
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000005530 etching Methods 0.000 title claims description 43
- 239000000758 substrate Substances 0.000 claims abstract description 47
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 27
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- 238000010248 power generation Methods 0.000 claims description 49
- 238000004544 sputter deposition Methods 0.000 claims description 48
- 238000004140 cleaning Methods 0.000 claims description 37
- 238000001039 wet etching Methods 0.000 claims description 23
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
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- 238000000151 deposition Methods 0.000 claims description 2
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- 238000011144 upstream manufacturing Methods 0.000 claims description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 62
- 238000011109 contamination Methods 0.000 description 32
- 239000011787 zinc oxide Substances 0.000 description 31
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
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- 230000006866 deterioration Effects 0.000 description 6
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
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- 238000000137 annealing Methods 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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Images
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
- H01L31/04—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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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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
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
- H01L31/076—Multiple junction or tandem solar cells
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Definitions
- the present invention relates to a method for manufacturing a solar cell, and more particularly, a solar cell capable of removing a contamination when etching is performed on a transparent conductive film constituting the solar cell and capable of producing a solar cell having excellent power generation characteristics. It relates to a manufacturing method.
- the present invention also relates to an etching apparatus and a CVD apparatus that are preferably used in this manufacturing method.
- FIG. 11 is a schematic cross-sectional view of an amorphous silicon solar cell.
- the solar cell 100 is composed of a glass substrate 101 constituting the surface, an upper electrode 103 made of a zinc oxide-based transparent conductive film provided on the glass substrate 101, and amorphous silicon in order from the top to the bottom of the drawing.
- a top cell 105 configured, an intermediate electrode 107 made of a transparent conductive film, a bottom cell 109 made of microcrystalline silicon, a buffer layer 110 made of a transparent conductive film, and a back electrode 111 made of a metal film are laminated.
- the intermediate electrode 107 is provided between the top cell 105 and the bottom cell 109.
- the top cell 105 has a three-layer structure of a p layer 105p, an i layer 105i, and an n layer 105n. Among them, the i layer 105i is formed of amorphous silicon. Similarly to the top cell 105, the bottom cell 109 has a three-layer structure of a p layer 109p, an i layer 109i, and an n layer 109n. Among them, the i layer 109i is made of microcrystalline silicon.
- a solar cell 100 sunlight incident from the glass substrate 101 side is reflected by the back electrode 111 through the upper electrode 103, the top cell 105 (p-i-n layer), and the buffer layer 110.
- a contrivance has been made such as reflecting sunlight at the back electrode 111 or providing a texture structure on the upper electrode 101.
- the texture structure has a prism effect for extending the optical path of incident sunlight and an effect for confining light.
- the buffer layer 110 is intended to prevent diffusion of the metal film used for the back electrode 111 (see, for example, Patent Document 2).
- the wavelength band used for the photovoltaic effect varies depending on the device structure of the solar cell.
- the transparent conductive film constituting the upper electrode is required to have the property of transmitting light for absorption by the i layer and the electrical conductivity for extracting electrons generated by the photovoltaic power.
- an FTO or ZnO-based oxide thin film in which fluorine is added as an impurity to SnO 2 is used.
- the buffer layer is also required to have the property of transmitting the light reflected by the back electrode and the light reflected by the back electrode in order to absorb the i layer and the electrical conductivity for transferring holes to the back electrode.
- the characteristics required for the transparent conductive film used for solar cells are roughly divided into three elements: (1) conductivity, (2) optical characteristics, and (3) texture structure. Among them, (1) Regarding electrical conductivity, low electrical resistance is required to extract generated electricity.
- FTO fluorine-doped tin oxide
- FTO fluorine-doped tin oxide
- a ZnO-based material that is attracting attention as post-ITO titanium-doped indium oxide
- post-ITO titanium-doped indium oxide
- conductivity is obtained by adding a material containing oxygen deficiency and Al or Ga to ZnO.
- the transparent conductive film for solar cells since the transparent conductive film for solar cells is mainly used on the incident light side, optical characteristics that transmit the wavelength band absorbed by the power generation layer are required.
- the texture structure a texture structure that scatters light is necessary to efficiently absorb sunlight in the power generation layer.
- a texture forming process such as wet etching is required.
- etching with a general oxalic acid-based etching solution as an amorphous ITO etching solution results in a carbon-based material. Contamination will occur. This contamination degrades the series resistance of the solar cell and reduces the conversion efficiency of the solar cell.
- the present invention has been devised in view of such a conventional situation.
- a transparent conductive film made of a ZnO-based material is formed by sputtering and then a texture is formed by wet etching, the transparent conductive film is formed.
- Method for producing solar cell capable of removing a contamination during film etching and preventing a decrease in series resistance due to the contamination, and thus a decrease in photoelectric conversion efficiency, and producing a solar cell having excellent power generation characteristics
- the primary purpose is to provide Further, the present invention is an etching apparatus for performing wet etching on a transparent conductive film for a solar cell, which can remove contamination during etching of the transparent conductive film, and has characteristics caused by this contamination.
- a method for manufacturing a solar cell according to an embodiment of the present invention is a method for manufacturing a solar cell in which a ZnO transparent conductive film is formed as a light-extraction-side power extraction electrode, and a sputtering voltage is applied to the transparent conductive film.
- Sputtering a target made of a film forming material to form the transparent conductive film on a substrate Step B forming a texture on the surface of the transparent conductive film, and the texture formed
- the process C which cleans the surface of a transparent conductive film using UV / ozone, and the process D which forms an electric power generation layer on the said transparent conductive film are provided at least in order.
- the method for manufacturing a solar cell according to an embodiment of the present invention may employ a configuration in which the sputtering voltage is applied, a horizontal magnetic field is generated on the surface of the target, and the target is sputtered.
- the method for manufacturing a solar cell according to an embodiment of the present invention may employ a configuration in which an upper electrode serving as a power extraction electrode on the light incident side is formed by the transparent conductive film.
- the manufacturing method of the solar cell according to the embodiment of the present invention may employ a configuration using a wet etching method in order to form the texture in the step B.
- the method for manufacturing a solar cell according to an embodiment of the present invention may employ a configuration in which, in the step A, a material obtained by adding a substance containing Al or Ga to ZnO is used as a film forming material for the transparent conductive film.
- An etching apparatus according to an embodiment of the present invention is an etching apparatus that performs wet etching on a transparent conductive film for a solar cell, and cleaning the surface of the transparent conductive film using UV / ozone after wet etching. You may employ
- the etching apparatus further includes a wet etching unit that performs wet etching on the transparent conductive film, and the cleaning unit is provided downstream of the wet etching unit. Also good.
- the etching apparatus which concerns on the form of this invention may further be equipped with the electric power generation layer formation part which forms an electric power generation layer, and the said electric power generation layer formation part may employ
- a CVD apparatus according to an embodiment of the present invention is a CVD apparatus for forming a power generation layer for a solar cell by a CVD method, and before forming the power generation layer, a substrate surface on which the power generation layer is formed is subjected to UV / ozone. You may employ
- the CVD apparatus may further include a film forming unit that forms the power generation layer, and the cleaning unit may be provided upstream of the film forming unit.
- the present invention provides a method for manufacturing a solar cell that can prevent a decrease in series resistance due to the contamination, and thus a decrease in photoelectric conversion efficiency, and that can produce a solar cell having excellent characteristics. can do.
- the transparent conductive film surface for the solar cell is wet-etched and then has a cleaning unit for cleaning the surface of the transparent conductive film using UV / ozone, the transparent conductive film is etched. In this case, contamination can be removed.
- the present invention provides an etching apparatus that can prevent deterioration of characteristics due to the contamination and can produce a transparent conductive film (upper electrode) for solar cells having excellent characteristics. Can do.
- the substrate surface on which the power generation layer is formed is cleaned using UV / ozone. Contamination can be removed.
- a CVD apparatus that can prevent deterioration of characteristics due to the contamination and can produce a power generation layer for solar cells having excellent characteristics.
- FIG. 1 It is a schematic diagram which shows another example of the CVD apparatus which concerns on this invention. It is a figure which shows the SEM image of the transparent conductive film before an etching. It is a figure which shows the SEM image of the transparent conductive film after an etching. It is a figure which shows a XRD measurement result about the transparent conductive film of an Example and a comparative example. It is sectional drawing which shows an example of the conventional solar cell.
- FIG. 1 is a cross-sectional view showing an example of the configuration of a solar cell.
- the solar cell 50 includes, in order from the top to the bottom of the drawing, a glass substrate 51 constituting the surface thereof, an upper electrode 53 made of a zinc oxide-based transparent conductive film 54 provided on the glass substrate 51, and amorphous silicon.
- a back electrode 63 made of a metal film is laminated.
- the intermediate electrode 57 is provided between the top cell 55 and the bottom cell 59.
- the solar cell 50 is an a-Si / microcrystalline Si tandem solar cell.
- the short-wavelength light is absorbed by the top cell 55 and the long-wavelength light is absorbed by the bottom cell 59, so that the power generation efficiency can be improved.
- the upper electrode 53 has a thickness of 2000 to 10,000 mm.
- the top cell 55 has a three-layer structure of a p layer 55p, an i layer 55i, and an n layer 55n. Among them, the i layer 55i is formed of amorphous silicon.
- the bottom cell 59 has a three-layer structure of a p layer 59p, an i layer 59i, and an n layer 59n. Among them, the i layer 59i is made of microcrystalline silicon.
- the solar cell 50 having such a configuration, when energetic particles called photons contained in sunlight hit the i layer, electrons and holes are generated by the photovoltaic effect, and the electrons move toward the n layer. Then, the holes move toward the p layer. Electrons generated by the photovoltaic effect can be taken out by the upper electrode 53 and the back electrode 63, and light energy can be converted into electric energy.
- the sunlight incident from the glass substrate 51 side passes through each layer and is reflected by the back electrode 63.
- a texture structure is formed on the upper electrode 53 in order to improve the conversion efficiency of light energy.
- This texture structure has a prism effect for extending the optical path of sunlight incident on the upper electrode 53 and a light confinement effect.
- the method for manufacturing a solar cell according to the present embodiment includes a process A (upper electrode forming process, transparent conductive film forming process), a process B (texture forming process), and a process C (cleaning process) that are executed at least in order.
- Step D power generation layer forming step.
- step A while applying a sputtering voltage to a target made of a material (film forming material) for forming the transparent conductive film 54, a sputtering process is performed by generating a horizontal magnetic field on the surface of the target. 51) By forming the transparent conductive film 54 on the upper electrode 53, the upper electrode 53 is formed.
- step B a texture is formed on the surface of the transparent conductive film 54.
- step C the surface of the transparent conductive film 54 on which the texture is formed is cleaned using UV / ozone.
- step D a power generation layer (top cell 55) is formed on the upper electrode 53.
- the transparent conductive film 54 is cleaned using UV / ozone before forming the power generation layer. Therefore, contamination during the etching of the transparent conductive film 54 can be removed. As a result, in this embodiment, it is possible to prevent a decrease in series resistance due to the contamination, and thus a decrease in photoelectric conversion efficiency of the solar cell, and a solar cell having excellent characteristics can be manufactured.
- FIG. 2 is a schematic configuration diagram illustrating an example of a sputtering apparatus (film forming apparatus) used in the method for manufacturing a solar cell according to the present embodiment.
- 3 is a cross-sectional view showing the main part of the film forming chamber of the sputtering apparatus according to FIG.
- the sputtering apparatus 1 is an inter-back type sputtering apparatus.
- a loading / unloading chamber 2 for loading / unloading a substrate such as an alkali-free glass substrate (not shown), and a zinc oxide-based transparent conductive film on the substrate.
- a film forming chamber (vacuum container) 3 for forming the film.
- the preparation / removal chamber 2 is provided with a roughing exhaust unit 4 such as a rotary pump for roughly evacuating the chamber, and a substrate tray 5 for holding and transporting the substrate is movably disposed in the chamber. ing.
- a roughing exhaust unit 4 such as a rotary pump for roughly evacuating the chamber
- a substrate tray 5 for holding and transporting the substrate is movably disposed in the chamber. ing.
- a heater 11 for heating the substrate 6 is provided in a vertical shape on one side surface 3a of the film forming chamber 3, and a zinc oxide-based material is provided on the other side surface 3b.
- a sputtering cathode mechanism (target holding unit) 12 for holding a target 7 of material and applying a desired sputtering voltage is provided in a vertical type.
- a high vacuum exhaust unit 13 such as a turbo molecular pump that draws a high vacuum in the film forming chamber 3
- a gas introduction unit 15 for introducing the gas is provided.
- the sputter cathode mechanism 12 is made of a plate-like metal plate, and the target 7 is fixed to the sputter cathode mechanism 12 by bonding (fixing) with a mouth material or the like.
- the power source 14 is for applying a sputtering voltage in which a high-frequency voltage is superimposed on a DC voltage to the target 7, and includes a DC power source and a high-frequency power source (not shown).
- the gas introduction unit 15 introduces a sputtering gas such as Ar.
- FIG. 4 is a cross-sectional view showing an example of another sputtering apparatus used in the solar cell manufacturing method of the present embodiment. That is, FIG. 4 shows the main part of the film forming chamber of the inter-back magnetron sputtering apparatus.
- the magnetron sputtering apparatus 21 shown in FIG. 4 is different from the sputtering apparatus 1 shown in FIGS. 2 and 3 in that a target 7 made of zinc oxide material is held on the side surface 3a of the film forming chamber 3, and a desired
- the sputtering cathode mechanism (target holding unit) 22 for generating a magnetic field is provided in a vertical shape.
- the sputter cathode mechanism 22 includes a back plate 23 in which the target 7 is bonded (fixed) with a brazing material or the like, and a magnetic circuit 24 disposed along the back surface of the back plate 23.
- the magnetic circuit 24 generates a horizontal magnetic field on the surface of the target 7, and a plurality of magnetic circuit units (two in FIG. 4) 24 a and 24 b are connected and integrated by a bracket 25.
- the magnetic circuit units 24 a and 24 b include a first magnet 26, a second magnet 27, and a yoke 28 on which the first magnet 26 and the second magnet 27 are mounted. Among them, the first magnet 26 and the second magnet 27 have different polarities on the surface on the back plate 23 side.
- a magnetic field represented by a magnetic force line 29 is generated by the first magnet 26 and the second magnet 27 having different polarities on the back plate 23 side.
- a position 30 where the vertical magnetic field is 0 (the horizontal magnetic field is maximum) is generated on the surface of the target 7 between the first magnet 26 and the second magnet 27.
- the high-density plasma is generated at the position 30, so that the film forming speed can be improved.
- the sputtering cathode mechanism 22 that generates a desired magnetic field is provided vertically on one side surface 3a of the film forming chamber 3, so that the sputtering voltage is 340 V or less,
- the maximum value of the horizontal magnetic field strength on the surface of the target 7 is 600 gauss or more.
- the zinc oxide-based transparent conductive film formed in this manner is hardly oxidized even when annealing is performed at a high temperature after film formation, and an increase in specific resistance can be suppressed.
- the upper electrode of a solar cell is comprised with such a zinc oxide type transparent conductive film, the upper electrode of the solar cell excellent in heat resistance can be obtained.
- a zinc oxide-based transparent conductive film constituting the upper electrode of the solar cell is formed on the substrate using the sputtering apparatus 1 shown in FIGS.
- An example of the method is described.
- the target 7 is fixed to the sputter cathode mechanism 12 by bonding with a brazing material or the like.
- a zinc oxide-based material for example, aluminum-added zinc oxide (AZO) to which 0.1 to 10% by mass of aluminum (Al) is added, or 0.1 to 10% by mass of gallium (Ga) is added.
- AZO aluminum-added zinc oxide
- Ga gallium-doped zinc oxide
- GZO gallium-doped zinc oxide
- aluminum-added zinc oxide (AZO) is preferable because a thin film having a low specific resistance can be formed.
- the preparation / removal chamber 2 and the film formation chamber 3 are roughened by the roughing exhaust unit 4.
- the substrate 6 is carried into the film formation chamber 3 from the preparation / removal chamber 2. Is placed in front of the heater 11 with the setting turned off, the substrate 6 is opposed to the target 7, and the substrate 6 is heated by the heater 11 to be in a temperature range of 100 ° C. to 600 ° C. .
- the film forming chamber 3 is evacuated by the high vacuum exhaust unit 13 so that the film forming chamber 3 has a predetermined high vacuum, for example, 2.7 ⁇ 10 ⁇ 4 Pa (2.0 ⁇ 10 ⁇ 3 mTorr).
- a sputtering gas such as Ar is introduced into the film forming chamber 3 by the sputtering gas introducing unit 15, and the inside of the film forming chamber 3 is set to a predetermined pressure (sputtering pressure).
- a sputtering voltage for example, a sputtering voltage in which a high frequency voltage is superimposed on a DC voltage is applied to the target 7 by the power source 14.
- a sputtering voltage is applied, plasma is generated on the substrate 6, and ions of sputtering gas such as Ar excited by the plasma collide with the target 7.
- Atoms constituting a zinc oxide-based material such as (GZO) are ejected, and a transparent conductive film 54 made of a zinc oxide-based material is formed on the substrate 6.
- the substrate 6 (glass substrate 51) is transferred from the film formation chamber 3 to the preparation / removal chamber 2, the vacuum of the preparation / removal chamber 2 is broken, and the substrate on which the zinc oxide-based transparent conductive film 54 is formed. 6 (glass substrate 51) is taken out.
- step B a texture is formed on the surface of the transparent conductive film 54 (step B).
- a wet etching method is used to form the texture.
- a wet etching process is performed on the transparent conductive film 54 using an oxalic acid-based etching solution or the like. Thereby, a fine texture is formed on the surface of the transparent conductive film 54.
- carbon-based contamination occurs in the transparent conductive film 54 due to the etching process. This contamination degrades the series resistance of the resulting solar cell and reduces the conversion efficiency.
- the surface of the transparent conductive film 54 on which the texture is formed is cleaned using UV / ozone (Step C).
- UV / ozone By cleaning with UV / ozone, carbon-based contamination generated during etching of the transparent conductive film can be removed.
- FIG. 5 is a diagram schematically showing an etching apparatus of the present invention.
- the etching apparatus 70 includes a load chamber 71 (L chamber), a buffer chamber 72, an etching chamber 73, a cleaning chamber 74, a UV / ozone cleaning chamber 75 (UV / O3), and an unload chamber 76 (UL chamber). ).
- the etching apparatus 70 of the present embodiment includes the cleaning unit (UV / ozone cleaning chamber 75) for cleaning the surface of the transparent conductive film using UV / ozone after wet etching (etching chamber 73). It is characterized by.
- the etching apparatus 70 of the present embodiment includes a cleaning unit that cleans the surface of the transparent conductive film 54 using UV / ozone after performing wet etching on the transparent conductive film 54 for solar cells.
- the contamination during the etching of the transparent conductive film 54 can be cleaned and removed.
- the substrate 6 (glass substrate 51) on which the zinc oxide-based transparent conductive film 54 is formed is obtained.
- a power generation layer is formed on the upper electrode 53 (step D).
- the material for forming the power generation layer (here, the top cell 55 including the p layer 55p, the i layer 55i, and the n layer 55n as the power generation layer) is plasmatized on the upper electrode, and this material is formed on the upper electrode.
- a power generation layer is formed by vapor deposition and lamination.
- the CVD apparatus 80 includes a UV / ozone cleaning chamber (UV / O 3) 81, a load chamber (L chamber) 82, film formation chambers 83, 84, 85 for forming a p layer, an i layer, and an n layer, and A UL chamber 86 is provided.
- UV / O 3 UV / ozone cleaning chamber
- L chamber load chamber
- film formation chambers 83, 84, 85 for forming a p layer, an i layer, and an n layer
- a UL chamber 86 is provided.
- the CVD apparatus 80 includes a cleaning unit (UV / ozone cleaning chamber 81) that cleans the surface of the substrate on which the power generation layer is formed using UV / ozone before forming the power generation layer. It is characterized by having.
- a cleaning unit UV / ozone cleaning chamber 81
- the CVD apparatus 80 of the present embodiment has a cleaning unit that cleans the surface of the substrate on which the power generation layer is formed using UV / ozone before forming the power generation layer for solar cells by the CVD method. Therefore, the contamination of the substrate can be removed. As a result, according to this embodiment, since the deterioration of the characteristic resulting from the said contamination is suppressed, the electric power generation layer for solar cells which has the outstanding solar cell characteristic can be produced.
- the CVD apparatus 80A (80) shown in FIG. 6 is an inline type apparatus, and the CVD apparatuses 80B and 80C (80) shown in FIGS. 7A and 7B are cluster type apparatuses. Since the UV / ozone cleaning that is a feature of the present embodiment does not need to be performed under reduced pressure, the UV / ozone cleaning is provided in front of the load chamber 82 as shown in FIG. 7A. As shown in FIG. 7B, it is conceivable to provide one chamber of a cluster type CVD apparatus.
- the solar cell obtained through at least the above steps is washed with UV / ozone after forming the texture on the surface of the transparent conductive film and before forming the power generation layer, the transparent conductive film Contamination during film etching can be removed. As a result, the solar cell thus obtained can prevent a decrease in series resistance due to the contamination, and thus a decrease in photoelectric conversion efficiency, and has excellent characteristics.
- the etching apparatus and the CVD apparatus according to this embodiment having the above-described cleaning unit using UV / ozone may be used in combination. Only one side may be used.
- a transparent conductive film was formed on the substrate by using a sputtering apparatus (film forming apparatus) 1 as shown in FIGS.
- a sputtering apparatus film forming apparatus 1
- the target 7 of 5 inches ⁇ 16 inches was attached to the sputter cathode mechanism 12.
- a film forming material in which 2% by weight of Al 2 O 3 was added as an impurity to ZnO was used.
- the setting of the heater 11 was adjusted so that the substrate temperature was 250 ° C., and the film formation chamber 3 was heated.
- a non-alkali glass substrate (substrate 6) was placed in the charging / unloading chamber 2, exhausted by the roughing exhaust unit 4, and then transferred to the film forming chamber 3.
- the film forming chamber 3 is maintained at a predetermined degree of vacuum by the high vacuum exhaust unit 13.
- Ar gas as a process gas from the sputtering gas introduction unit 15 at a pressure of 5 mTorr
- a ZnO-based target attached to the sputtering cathode mechanism 12 was sputtered by applying 1 kW of power to the sputtering cathode mechanism 12 from a DC power source.
- a ZnO-based transparent conductive film was formed to a thickness of 500 nm on an alkali-free glass substrate. Thereafter, the substrate was taken out from the preparation / removal chamber 2. Then, wet etching is performed by immersing the transparent conductive film in an oxalic acid-based etching solution kept at 40 ° C. for 2 minutes. Thereby, a texture was formed on the surface of the transparent conductive film.
- FIG. 8 shows a surface SEM image of the transparent conductive film before the etching treatment.
- FIG. 9 shows a surface SEM image of the transparent conductive film after the etching treatment.
- FIG. 10 shows the results of XPS analysis of a transparent conductive film (Example) subjected to UV / ozone cleaning and a transparent conductive film (Comparative Example) not subjected to UV / ozone cleaning.
- a transparent conductive film Example
- Comparative Example a transparent conductive film not subjected to UV / ozone cleaning.
- peaks are observed in the vicinity of binding energy of 285 eV and in the vicinity of 289 eV, which is considered to be caused by contamination derived from carbon that occurs during the etching process. It is done.
- this peak disappears, and it can be seen that the contamination is removed by the UV / ozone cleaning.
- a minicell solar cell was produced using the obtained transparent conductive film as an upper electrode, and the solar cell performance was evaluated by a solar simulator. did.
- the transparent conductive film of an Example and a comparative example it is a solar cell characteristic (it is also called "power generation characteristic") [conversion efficiency (Eff), short circuit current density (Jsc), open circuit voltage (Voc), fill factor (FF). , Parallel resistance (Rsh), series resistance (Rs)] are summarized in Table 1.
- the present invention can be widely applied to a method of manufacturing a solar cell in which the upper electrode functioning as a power extraction electrode on the light incident side is made of a transparent conductive film having ZnO as a basic constituent element.
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Abstract
Description
本願は、2008年10月29日に、日本に出願された特願2008-278725号に基づき優先権を主張し、その内容をここに援用する。
(3)テクスチャー構造に関して、太陽光を効率的に発電層で吸収するために光を散乱させるテクスチャー構造が必要となる。通常、スパッタプロセスで作製されたZnO系薄膜は平坦な表面状態となるため、ウェットエッチング等によるテクスチャーの形成処理が必要となる。
また、本発明は、太陽電池用の透明導電膜に対してウェットエッチングを行うエッチング装置であって、前記透明導電膜のエッチングの際の汚染を除去することができ、この汚染に起因する特性の低下を防止し、優れた発電特性を有する太陽電池用の透明導電膜を作製することができるエッチング装置を提供することを第二の目的とする。
また、本発明は、太陽電池用の発電層をCVDにより形成するCVD装置であって、この発電層が形成される基体の汚染を除去することができ、この汚染に起因する特性の低下を防止し、優れた発電特性を有する太陽電池用の発電層を作製することができるCVD装置を提供することを第三の目的とする。
本発明の形態に係る太陽電池の製造方法は、前記スパッタ電圧を印加して、前記ターゲットの表面に水平磁界を発生させて、前記ターゲットをスパッタさせる、構成を採用してもよい。
本発明の形態に係る太陽電池の製造方法は、前記透明導電膜により、光入射側の電力取り出し電極とする上部電極を形成する、構成を採用してもよい。
本発明の形態に係る太陽電池の製造方法は、前記工程Bにおいて、前記テクスチャーを形成するために、ウェットエッチング法を用いる、構成を採用してもよい。
本発明の形態に係る太陽電池の製造方法は、前記工程Aにおいて、前記透明導電膜の成膜材料として、Al又はGaを含む物質をZnOに添加した材料を用いる、構成を採用してもよい。
本発明の形態に係るエッチング装置は、太陽電池用の透明導電膜に対してウェットエッチングを行うエッチング装置であって、ウェットエッチングの後に、前記透明導電膜表面をUV/オゾンを用いて洗浄する洗浄ユニットを備える、構成を採用してもよい。
本発明の形態に係るエッチング装置は、前記透明導電膜に対してウェットエッチングを行うウェットエッチング部をさらに備え、前記洗浄ユニットは、前記ウェットエッチング部の下流に設けられている、構成を採用してもよい。
本発明の形態に係るエッチング装置は、発電層を形成する発電層形成部をさらに備え、前記発電層形成部は、前記洗浄ユニットの下流に設けられている、構成を採用してもよい。
本発明の形態に係るCVD装置は、太陽電池用の発電層をCVD法により形成するCVD装置であって、前記発電層を形成する前に、前記発電層が形成される基体表面をUV/オゾンを用いて洗浄する洗浄ユニットを備える、構成を採用してもよい。
本発明の形態に係るCVD装置は、前記発電層を成膜する成膜部をさらに備え、前記洗浄ユニットは、前記成膜部の上流に設けられている、構成を採用してもよい。
まず、本実施形態で製造される太陽電池について、図1に基づいて説明する。図1は太陽電池の構成の一例を示す断面図である。
太陽電池50は、図面の上から下への順で、その表面を構成するガラス基板51と、ガラス基板51上に設けられた酸化亜鉛系の透明導電膜54からなる上部電極53と、アモルファスシリコン(a-Si)で構成されたトップセル55と、透明導電膜からなる中間電極57と、微結晶シリコン(微結晶Si)で構成されたボトムセル59と、透明導電膜からなるバッファ層61と、金属膜からなる裏面電極63とが積層されている。その中、中間電極57は、トップセル55とボトムセル59との間に設けられている。
次に、このような太陽電池の製造方法について説明する。
本実施形態に係る太陽電池の製造方法は、少なくとも順に実行される工程A(上部電極形成工程、透明導電膜成膜工程)と、工程B(テクスチャー形成工程)と、工程C(洗浄工程)と、工程D(発電層形成工程)とを備えている。その中、工程Aにおいて、前記透明導電膜54の形成材料(成膜材料)からなるターゲットにスパッタ電圧を印加しつつ、このターゲットの表面に水平磁界を発生させてスパッタを行い、基板(ガラス基板51)上に前記透明導電膜54を成膜することにより、前記上部電極53を形成する。工程Bにおいて、前記透明導電膜54の表面にテクスチャーを形成する。工程Cにおいて、前記テクスチャーが形成された前記透明導電膜54の表面を、UV/オゾンを用いて洗浄する。工程Dにおいて、前記上部電極53上に、発電層(トップセル55)を形成する。
(スパッタ装置1)
図2は、本実施形態の太陽電池の製造方法に用いられるスパッタ装置(成膜装置)の一例を示す概略構成図である。図3は、図2に係るスパッタ装置の成膜室の主要部を示す断面図である。スパッタ装置1は、インターバック式のスパッタ装置であり、例えば、無アルカリガラス基板(図示せず)等の基板を搬入/搬出する仕込み/取出し室2と、基板上に酸化亜鉛系の透明導電膜を成膜する成膜室(真空容器)3とを備えている。
電源14は、ターゲット7に、直流電圧に高周波電圧が重畳されたスパッタ電圧を印加するためのもので、直流電源と高周波電源(図示略)とを備えている。
ガス導入ユニット15は、Ar等のスパッタガスを導入する。
図4は、本実施形態の太陽電池の製造方法に用いられる別なスパッタ装置の一例を示す断面図である。即ち図4は、インターバック式のマグネトロンスパッタ装置の成膜室の主要部を示す。図4に示すマグネトロンスパッタ装置21が、図2、図3に示すスパッタ装置1と異なる点は、成膜室3の―方の側面3aに酸化亜鉛系材料のターゲット7を保持し、且つ所望の磁界を発生するスパッタカソード機構(ターゲット保持ユニット)22を縦型に設けた点である。
(1)初めに、前記透明導電膜54の形成材料(成膜材料)からなるターゲット7にスパッタ電圧を印加しつつ、このターゲット7の表面に水平磁界を発生させてスパッタを行い、基板(ガラス基板51)上に前記透明導電膜54を成膜することにより前記上部電極53を形成する(工程A)。
次いで、前記透明導電膜54に対してシュウ酸系エッチング液等を用いてウェットエッチング処理を行う。これにより、透明導電膜54の表面に微細テクスチャーが形成される。
この際、エッチング処理により透明導電膜54にカーボン系の汚染が生じてしまう。この汚染は、得られる太陽電池の直列抵抗を劣化させ、変換効率を低下させてしまう。
UV/オゾンを用いて洗浄することで、透明導電膜のエッチングの際に生じたカーボン系の汚染を除去することができる。その結果、本実施形態では、前記汚染に起因する直列抵抗の低下、ひいては光電変換効率の低下を防止することができ、優れた特性を有する太陽電池を作製することができる。
このエッチング装置70は、ロードチャンバー71(Lチャンバー)と、バッファチャンバー72と、エッチングチャンバー73と、洗浄チャンバー74と、UV/オゾン洗浄チャンバー75(UV/O3)と、アンロードチャンバー76(ULチャンバー)とを備えている。このように本実施形態のエッチング装置70は、ウェットエッチング(エッチングチャンバー73)の後に、UV/オゾンを用いて前記透明導電膜表面を洗浄する洗浄ユニット(UV/オゾン洗浄チャンバー75)を備えたことを特徴とする。
本実施形態のエッチング装置70では、太陽電池用の透明導電膜54に対してウェットエッチングを行った後に、UV/オゾンを用いて前記透明導電膜54の表面を洗浄する洗浄ユニットを備えているので、透明導電膜54のエッチングの際の汚染を洗浄、除去することができる。その結果、本実施形態では、前記汚染に起因する特性の低下を防止することができ、優れた特性を有する太陽電池用の透明導電膜54(上部電極53)を作製することができる。
上部電極上に発電層(ここでは発電層として、p層55p、i層55i、n層55nからなるトップセル55のことをいう。)の形成材料をプラズマ化させ、この材料を上部電極上に蒸着、積層することにより、発電層を形成する。
このCVD装置80は、UV/オゾン洗浄チャンバー(UV/O3)81、ロードチャンバー(Lチャンバー)82、p層、i層、n層をそれぞれ形成するための成膜チャンバー83、84、85、及びULチャンバー86を備える。
このように本実施形態のCVD装置80は、前記発電層を形成する前に、この発電層が形成される基体表面をUV/オゾンを用いて洗浄する洗浄ユニット(UV/オゾン洗浄チャンバー81)を有することを特徴とする。
本実施形態の特徴であるUV/オゾン洗浄は、減圧下で処理する必要がないため、図7Aに示すようにロードチャンバー82の前に設けるが、UV/オゾン処理の有無の条件が混在する場合、図7Bに示すように、クラスター型のCVD装置の1つのチャンバーとして設けることも考えられる。
(実施例)
図2及び図3に示したようなスパッタ装置(成膜装置)1を用いて、基板上に透明導電膜を成膜した。
まず、スパッタカソード機構12に、5インチ×16インチのターゲット7を取り付けた。ターゲット7には、ZnOに不純物としてAl2O3を2重量%添加した成膜材料を用いた。また、基板温度が250℃になるようにヒータ11の設定を調整し、成膜室3を加熱した。
スパッタガス導入ユニット15からArガスをプロセスガスとして、圧力5mTorrで導入後、スパッタカソード機構12にDC電源により1kWの電力を印加することにより、スパッタカソード機構12に取り付けたZnO系ターゲットをスパッタした。
その後、仕込み/取り出し室2から基板を取り出した。
その後、前記透明導電膜を、40℃に保温したシュウ酸系エッチング液に2分間浸漬することにより、ウェットエッチングを行う。これにより、透明導電膜の表面にテクスチャーを形成した。
UV/オゾン洗浄を実施した透明導電膜(実施例)と、UV/オゾン洗浄を実施していない透明導電膜(比較例)について、XPSにより分析した結果を図10に示す。図10から明らかなように、比較例においては、結合エネルギー(binding energy)285eV付近、及び289eV近辺にピークが見られ、これは、エッチング処理の際に生じる、カーボンに由来する汚染によるものと考えられる。一方、UV/オゾン洗浄を実施した実施例では、このピークが消えており、前記汚染がUV/オゾン洗浄により除去されていることがわかる。
実施例及び比較例の透明導電膜について、太陽電池特性(「発電特性」とも呼ぶ)[変換効率(Eff)、短絡電流密度(Jsc)、開放電圧(Voc)、曲線因子(F.F.)、並列抵抗(Rsh)、直列抵抗(Rs)]について表1に纏めて示す。
51 ガラス基板(基板)
53 上部電極
54 透明導電膜
55 トップセル
59 ボトムセル
57 中間電極
61 バッファ層
63 裏面電極
Claims (10)
- 光入射側の電力取り出し電極として、ZnOの透明導電膜を成膜する太陽電池の製造方法であって、
スパッタ電圧を印加して、前記透明導電膜の成膜材料からなるターゲットをスパッタさせて、基板上に前記透明導電膜を成膜する工程Aと、
前記透明導電膜の表面にテクスチャーを形成する工程Bと、
前記テクスチャーが形成された前記透明導電膜の表面を、UV/オゾンを用いて洗浄する工程Cと、
前記透明導電膜上に、発電層を形成する工程Dと、
を少なくとも順に備えたことを特徴とする太陽電池の製造方法。 - 前記スパッタ電圧を印加して、前記ターゲットの表面に水平磁界を発生させて、前記ターゲットをスパッタさせる、ことを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記透明導電膜により、前記光入射側の電力取り出し電極とする上部電極を形成する、ことを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記工程Bにおいて、ウェットエッチングにより前記テクスチャーを形成することを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記工程Aにおいて、前記透明導電膜の成膜材料として、Al又はGaを含む物質をZnOに添加した材料を用いることを特徴とする請求項1又は請求項4に記載の太陽電池の製造方法。
- 太陽電池用の透明導電膜に対してウェットエッチングを行うエッチング装置であって、
ウェットエッチングの後に、UV/オゾンを用いて、前記透明導電膜表面を洗浄する洗浄ユニットを備えたことを特徴とするエッチング装置。 - 前記透明導電膜に対してウェットエッチングを行うウェットエッチング部をさらに備え、
前記洗浄ユニットは、前記ウェットエッチング部の下流に設けられている、ことを特徴とする請求項6に記載のエッチング装置。 - 発電層を形成する発電層形成部をさらに備え、
前記発電層形成部は、前記洗浄ユニットの下流に設けられている、ことを特徴とする請求項7に記載のエッチング装置。 - 太陽電池用の発電層をCVD法により形成するCVD装置であって、
前記発電層を形成する前に、UV/オゾンを用いて、前記発電層が形成される基体の表面を洗浄する洗浄ユニットを備えたことを特徴とするCVD装置。 - 前記発電層を成膜する発電層成膜部をさらに備え、
前記洗浄ユニットは、前記発電層成膜部の上流に設けられている、ことを特徴とする請求項9に記載のCVD装置。
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JP2010535663A JPWO2010050189A1 (ja) | 2008-10-29 | 2009-10-27 | 太陽電池の製造方法、エッチング装置及びcvd装置 |
CN2009801429346A CN102203962A (zh) | 2008-10-29 | 2009-10-27 | 太阳能电池的制造方法、蚀刻装置和cvd装置 |
US13/126,108 US8420436B2 (en) | 2008-10-29 | 2009-10-27 | Method for manufacturing solar cell, etching device, and CVD device |
KR1020117009392A KR101243995B1 (ko) | 2008-10-29 | 2009-10-27 | 태양 전지의 제조 방법, 에칭 장치 및 cvd장치 |
EP09823302A EP2357675A4 (en) | 2008-10-29 | 2009-10-27 | METHOD FOR PRODUCING A SOLAR CELL, DEVICE AND CVD DEVICE |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60175465A (ja) | 1984-02-21 | 1985-09-09 | Nippon Sheet Glass Co Ltd | 太陽電池基板 |
JPH02503615A (ja) | 1987-05-22 | 1990-10-25 | グラステツク・ソーラー・インコーポレーテツド | 太陽電池用基板 |
JP2002025350A (ja) * | 2000-07-11 | 2002-01-25 | Sanyo Electric Co Ltd | 透明導電膜付き基板及びその作製方法,それを用いたエッチング方法並びに光起電力装置 |
WO2005081324A1 (ja) * | 2004-02-20 | 2005-09-01 | Sharp Kabushiki Kaisha | 光電変換装置用基板、光電変換装置、積層型光電変換装置 |
WO2007126102A1 (ja) * | 2006-05-02 | 2007-11-08 | Mitsubishi Chemical Corporation | 有機光電変換素子の製造方法及び有機光電変換素子 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2503615B2 (ja) | 1988-12-28 | 1996-06-05 | カシオ計算機株式会社 | 薄膜トランジスタ及びその製造方法 |
JP2984595B2 (ja) * | 1996-03-01 | 1999-11-29 | キヤノン株式会社 | 光起電力素子 |
JPH10261484A (ja) * | 1997-03-19 | 1998-09-29 | Minolta Co Ltd | 有機エレクトロルミネセンス素子およびその製造方法 |
DE19713215A1 (de) * | 1997-03-27 | 1998-10-08 | Forschungszentrum Juelich Gmbh | Solarzelle mit texturierter TCO-Schicht sowie Verfahren zur Herstellung einer solchen TCO-Schicht für eine solche Solarzelle |
US6015759A (en) * | 1997-12-08 | 2000-01-18 | Quester Technology, Inc. | Surface modification of semiconductors using electromagnetic radiation |
KR20030064028A (ko) * | 2002-01-25 | 2003-07-31 | 한국전자통신연구원 | 전계 발광 소자 및 그 제조 방법 |
JP2003264058A (ja) * | 2002-03-07 | 2003-09-19 | Konica Corp | 基板及び該基板を用いた有機エレクトロルミネッセンス表示装置 |
DE102004003760B4 (de) * | 2004-01-23 | 2014-05-22 | Forschungszentrum Jülich GmbH | Verfahren zur Herstellung einer leitfähigen und transparenten Zinkoxidschicht und Verwendung derselben in einer Dünnschichtsolarzelle |
WO2008045423A1 (en) * | 2006-10-10 | 2008-04-17 | Structured Materials Inc. | Self assembled controlled luminescent transparent conductive photonic crystals for light emitting devices |
US9184317B2 (en) | 2007-04-02 | 2015-11-10 | Merck Patent Gmbh | Electrode containing a polymer and an additive |
US8022291B2 (en) * | 2008-10-15 | 2011-09-20 | Guardian Industries Corp. | Method of making front electrode of photovoltaic device having etched surface and corresponding photovoltaic device |
US8263427B2 (en) * | 2009-06-02 | 2012-09-11 | Intermolecular, Inc. | Combinatorial screening of transparent conductive oxide materials for solar applications |
WO2011007603A1 (ja) * | 2009-07-14 | 2011-01-20 | 三菱電機株式会社 | 基板の粗面化方法、光起電力装置の製造方法、光起電力装置 |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60175465A (ja) | 1984-02-21 | 1985-09-09 | Nippon Sheet Glass Co Ltd | 太陽電池基板 |
JPH02503615A (ja) | 1987-05-22 | 1990-10-25 | グラステツク・ソーラー・インコーポレーテツド | 太陽電池用基板 |
JP2002025350A (ja) * | 2000-07-11 | 2002-01-25 | Sanyo Electric Co Ltd | 透明導電膜付き基板及びその作製方法,それを用いたエッチング方法並びに光起電力装置 |
WO2005081324A1 (ja) * | 2004-02-20 | 2005-09-01 | Sharp Kabushiki Kaisha | 光電変換装置用基板、光電変換装置、積層型光電変換装置 |
WO2007126102A1 (ja) * | 2006-05-02 | 2007-11-08 | Mitsubishi Chemical Corporation | 有機光電変換素子の製造方法及び有機光電変換素子 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2357675A4 * |
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KR101243995B1 (ko) | 2013-03-15 |
EP2357675A4 (en) | 2012-07-11 |
JPWO2010050189A1 (ja) | 2012-03-29 |
CN102203962A (zh) | 2011-09-28 |
US8420436B2 (en) | 2013-04-16 |
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