WO2011001735A1 - 薄膜太陽電池およびその製造方法 - Google Patents
薄膜太陽電池およびその製造方法 Download PDFInfo
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- WO2011001735A1 WO2011001735A1 PCT/JP2010/057288 JP2010057288W WO2011001735A1 WO 2011001735 A1 WO2011001735 A1 WO 2011001735A1 JP 2010057288 W JP2010057288 W JP 2010057288W WO 2011001735 A1 WO2011001735 A1 WO 2011001735A1
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- conductive film
- transparent conductive
- film
- solar cell
- insulating substrate
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- 239000010409 thin film Substances 0.000 title claims abstract description 79
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
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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
- 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
-
- 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
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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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
- H01L31/035281—Shape of the body
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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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0543—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the refractive type, e.g. lenses
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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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
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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
- Y02E10/52—PV systems with concentrators
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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 thin film solar cell and a manufacturing method thereof, and particularly to a thin film solar cell excellent in light confinement technology and a manufacturing method thereof.
- a light confinement technique As this light confinement technique, a method of forming a concavo-convex structure on the surface of a transparent conductive film on a light-transmitting insulating substrate when light is incident from the light-transmitting insulating substrate side is used.
- the photoelectric conversion efficiency of the thin-film solar cell is improved by the light reflectance reduction effect and the light scattering effect.
- the light incident from the translucent insulating substrate side is scattered at the interface between the transparent conductive film having a concavo-convex structure and the power generation layer and then enters the power generation layer, so that the light enters the power generation layer substantially obliquely.
- a substantial optical path of light in the power generation layer is extended and light absorption is increased, so that an output current of the solar cell is increased.
- tin oxide (SnO 2 ) is well known as a transparent conductive film having such an uneven structure.
- the concavo-convex structure on the surface of tin oxide (SnO 2 ) is formed by growing crystal grains having a diameter of several tens of nanometers to several ⁇ m on the film surface by a thermal CVD (Chemical Vapor Deposition) method.
- zinc oxide (ZnO) is spreading as a transparent conductive film material replacing tin oxide (SnO 2 ) from the viewpoint of excellent plasma resistance and abundant resources.
- ZnO zinc oxide
- a transparent conductive film is formed on a glass substrate by a sputtering method, and then the transparent conductive film is etched using an acid so that an uneven structure is formed on the film surface.
- a forming technique has been reported (see, for example, Patent Document 1). By forming a concavo-convex structure simply by this method, cost reduction of a thin film solar cell is expected.
- the present invention has been made in view of the above, and an object of the present invention is to obtain a thin film solar cell having high light scattering performance in a wide wavelength range of sunlight and excellent in photoelectric conversion efficiency, and a method for producing the same.
- a thin-film solar cell according to the present invention is formed on the translucent insulating substrate by a translucent insulating substrate and a crystalline transparent conductive film, and is formed on the surface.
- a structure having high light scattering performance in a wide wavelength range of sunlight is realized without increasing the number of irregularities on the surface of the transparent conductive film of the transparent electrode layer, and the wide wavelength range of sunlight is effectively utilized.
- the thin film solar cell excellent in the photoelectric conversion efficiency obtained is produced.
- FIGS. 2-1 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 1 of this invention.
- FIGS. FIGS. 2-2 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 1 of this invention.
- FIGS. FIGS. 2-3 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 1 of this invention.
- FIGS. FIGS. 2-4 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 1 of this invention.
- FIGS. 2-5 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 1 of this invention.
- FIGS. FIG. 3 is a top view showing the cavity region on the translucent insulating substrate in the manufacturing process of the thin-film solar cell according to the first embodiment of the present invention.
- FIGS. 4-1 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 2 of this invention.
- FIGS. FIGS. 4-2 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 2 of this invention.
- FIGS. FIGS. 4-3 is sectional drawing for demonstrating an example of the manufacturing process of the thin film solar cell concerning Embodiment 2 of this invention.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a thin-film solar cell 10 according to a first embodiment of the present invention.
- the thin-film solar cell 10 is formed on the light-transmitting insulating substrate 1, the first transparent conductive film 2 formed on the light-transmitting insulating substrate 1, the first transparent conductive film 2, and has a concavo-convex structure on the surface. 2 a transparent conductive film 3, a power generation layer 5 formed on the second transparent conductive film 3, and a back electrode layer 6 formed on the power generation layer 5.
- the first transparent conductive film 2 and the second transparent conductive film 3 constitute a transparent electrode layer that is a first electrode layer.
- a cavity 4 is provided between adjacent convex portions in the first transparent conductive film 2.
- an insulating substrate having translucency is used.
- a material having a high transmittance is usually used, and for example, a glass substrate having a small absorption from the visible to the near infrared region is used.
- a glass substrate having a small absorption from the visible to the near infrared region is used.
- an alkali-free glass substrate may be used, or an inexpensive blue plate glass substrate may be used.
- the first transparent conductive film 2 is made of a transparent conductive film and has an uneven structure.
- the first transparent conductive film 2 uses, for example, a crystallized zinc oxide (ZnO) film, and at least one element selected from Al, Ga, In, B, Y, Si, Zr, and Ti as a dopant. Or a transparent conductive film formed by laminating these films.
- ZnO crystallized zinc oxide
- a transparent conductive film formed by laminating these films In the above, a crystallized ZnO film or the like is shown as the first transparent conductive film 2, but the first transparent conductive film 2 is not limited to this, and the transparent conductive film that is crystallized and has high light transmittance. Any film may be used.
- Examples of such a transparent conductive film include SnO 2 , In 2 O 3 , ZnO, CdO, CdIn 2 O 4 , CdSnO 3 , MgIn 2 O 4 , CdGa 2 O 4 , GaInO 3 , InGaZnO 4 , Cd 2 Sb 2.
- a crystallized film of O 7 , Cd 2 GeO 4 , CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , TiO 2 , Al 2 O 3 , or a transparent conductive film configured by stacking these films may be used.
- a film using at least one element selected from Al, Ga, In, B, Y, Si, Zr, and Ti as a dopant for these films, or a transparent conductive film formed by stacking these elements may be used. .
- the first transparent conductive film 2 for example, a physical method such as a DC sputtering method, a vacuum deposition method, or an ion plating method, or a chemical method such as a spray method, a dip method, or a CVD method can be used.
- a physical method such as a DC sputtering method, a vacuum deposition method, or an ion plating method
- a chemical method such as a spray method, a dip method, or a CVD method.
- the first transparent conductive film 2 includes cavities 4 between the adjacent convex portions 2 a in the first transparent conductive film 2.
- the cavity 4 is provided substantially in parallel in the depth direction of the paper.
- the shape of the hollow portion 4 between the convex portions 2a protrudes from the translucent insulating substrate 1 in the direction of the power generation layer 5, and the cross-sectional shape is a substantially triangular shape (convex shape) with the surface of the translucent insulating substrate 1 as the bottom surface.
- the height is about 0.2 ⁇ m
- the bottom width is about 0.15 ⁇ m on the short side
- the long side in the depth direction on the paper
- the distance from the center of the cavity 4 to the center of the adjacent cavity 4 across the protrusion 2a of the first transparent conductive film 2 is about 0.3 ⁇ m.
- the second transparent conductive film 3 is made of a transparent conductive film, and has a concavo-convex structure on the surface that is gentler than the concavo-convex structure of the first transparent conductive film 2.
- the second transparent conductive film 3 uses, for example, a tin oxide (SnO 2 ) film, and at least one element selected from Al, Ga, In, B, Y, Si, Zr, Ti, and F as a dopant. Or a transparent conductive film formed by laminating these films.
- the second transparent conductive film 3 is not limited to this, a transparent conductive film having a Mitsutaka permeability If it is.
- a transparent conductive film In 2 O 3 , ZnO, CdO, CdIn 2 O 4 , CdSnO 3 , MgIn 2 O 4 , CdGa 2 O 4 , GaInO 3 , InGaZnO 4 , Cd 2 Sb 2 O 7 , Cd It may be a 2 GeO 4 , CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , TiO 2 , Al 2 O 3 film, or a transparent conductive film formed by laminating these films. Further, a transparent conductive film formed by laminating these films, or a film using at least one element selected from Al, Ga, In, B, Y, Si, Zr, Ti, and F as a
- the second transparent conductive film 3 for example, a physical method such as a DC sputtering method, a vacuum deposition method, or an ion plating method, or a chemical method such as a spray method, a dip method, or a CVD method can be used.
- a physical method such as a DC sputtering method, a vacuum deposition method, or an ion plating method
- a chemical method such as a spray method, a dip method, or a CVD method.
- the second transparent conductive film 3 has a convex portion 3 a having a film thickness of about 0.7 ⁇ m from the surface of the translucent insulating substrate 1, and the convex portion 3 a and the concave portion 3 b of the second transparent conductive film 3.
- the height difference of the top surface is about 0.4 ⁇ m
- the interval between the apexes of the convex portions 3 a is about 0.6 ⁇ m
- the width of the bottom surface of the convex portions 3 a is about 0.5 ⁇ m. Therefore, the width of the recess 3b is about 0.1 ⁇ m.
- the power generation layer 5 has a pn junction or a pin junction, and is configured by laminating at least two thin film semiconductor layers that generate power by incident light.
- the power generation layer 5 is, for example, a p-type amorphous silicon carbide film (a-SiC film) that is a first conductivity type semiconductor layer, a buffer layer, and a second conductivity type semiconductor layer i from the second transparent conductive film 3 side.
- a-SiC film p-type amorphous silicon carbide film
- a first power generation layer (not shown) composed of an n-type amorphous silicon film (a-Si film), an n-type amorphous silicon film (a-Si film) as a third conductivity type semiconductor layer, and a first conductivity type
- a second power generation layer (not shown) composed of a p-type microcrystalline silicon film that is a p-type semiconductor layer, an i-type microcrystalline silicon film that is a second conductive semiconductor layer, and an n-type microcrystalline silicon film that is a third conductive semiconductor layer
- the power generation layer 5 has a crystalline layer in any one of the layers.
- an amorphous silicon-based film or a crystalline silicon-based film such as amorphous silicon germanium or microcrystalline silicon germanium may be used.
- the power generation layer 5 may have a single structure with a single pin structure or a triple structure with three pin structures stacked.
- An intermediate layer made of a transparent conductive film may be formed between the first power generation layer and the second power generation layer.
- middle layer is comprised with the film
- a film of zinc oxide (ZnO), indium tin oxide (ITO), tin oxide (SnO 2 ), silicon monoxide (SiO), or the like can be used.
- the back electrode layer 6 is a second electrode layer made of a conductive film that reflects light.
- a conductive film that reflects light.
- Al aluminum
- Al silver
- a transparent conductive film such as
- the back electrode layer 6 is formed by a known means such as a sputtering method, a CVD method, or a spray method.
- a translucent insulating substrate is provided by providing the hollow portions 4 between the adjacent convex portions 2 a in the first transparent conductive film 2.
- a sufficient light scattering effect can be obtained with respect to sunlight incident from one side. That is, part of the sunlight incident from the translucent insulating substrate 1 side is incident on each convex portion 2 a in the first transparent conductive film 2 and scattered at the interface between the convex portion 2 a and the second transparent conductive film 3. Then, the light enters the second transparent conductive film 3.
- the other part of the sunlight incident from the translucent insulating substrate 1 side is incident on the cavity 4 and scattered at the interface between the cavity 4 and the second transparent conductive film 3 to be second transparent conductive.
- the light enters the film 3. Therefore, by providing the convex portions 2a and the hollow portions 4, a sufficient light scattering effect can be obtained with respect to sunlight incident from the translucent insulating substrate 1 side without increasing the number of the convex portions 2a. In addition, since the bottom of the hollow portion 4 is formed by the translucent insulating substrate 1, a large amount of sunlight is directly incident from the translucent insulating substrate 1 side, and sufficient light scattering performance can be obtained. .
- corrugations on the surface of the 1st transparent conductive film 2 can be reduced, and 1st transparent Generation of defects in the power generation layer 5 due to the unevenness of the surface of the conductive film 2 can be suppressed.
- the fall of the output voltage resulting from the defect in the electric power generation layer 5 can be prevented, and high photoelectric conversion efficiency can be obtained. That is, a high photoelectric property can be obtained without causing the problem that the number of irregularities on the surface of the transparent conductive film increases as in the prior art, resulting in an increase in defects in the power generation layer and a decrease in output voltage. Conversion efficiency can be realized.
- the second transparent conductive film 3 is formed on the first transparent conductive film 2, and the power generation layer 5 is formed thereon. For this reason, the unevenness of the steep slope of the transparent conductive film at the interface between the transparent conductive film of the transparent electrode layer and the power generation layer 5 is alleviated, and the generation of defects in the power generation layer 5 due to the unevenness of the steep slope is suppressed. This improves the yield and reliability.
- the thin-film solar cell 10 according to the present embodiment, a structure having high light scattering performance in a wide wavelength range of sunlight is realized without increasing the number of irregularities on the surface of the transparent conductive film of the transparent electrode layer.
- a thin film solar cell excellent in photoelectric conversion efficiency that effectively utilizes a wide wavelength range of sunlight can be obtained.
- the shape of the cavity 4 is a substantially triangular shape (convex shape) with the surface of the translucent insulating substrate 1 as the bottom surface has been described.
- the surface of the translucent insulating substrate 1 is the bottom surface.
- the first transparent conductive film 2 is present in the region between the convex portions 2 a on the translucent insulating substrate 1, and the cavity 4 having a shape protruding in the direction of the power generation layer 5 on the first transparent conductive film 2. May be provided.
- FIGS. 2-1 to 2-5 are cross-sectional views for explaining an example of the manufacturing process of the thin-film solar cell 10 according to the present embodiment.
- the translucent insulating substrate 1 is prepared.
- a non-alkali glass substrate is used as the translucent insulating substrate 1 and will be described below.
- an inexpensive soda lime glass substrate may be used as the light-transmitting insulating substrate 1, but in this case, in order to prevent the diffusion of alkali components from the light-transmitting insulating substrate 1, an SiO 2 film is formed by a PCVD method or the like. It is preferable to form about 50 nm.
- a translucent insulating substrate is formed by sputtering a zinc oxide (ZnO) film having a film thickness of 0.35% containing aluminum (Al) dopant. 1 is formed to form a crystallized transparent conductive film 21 having crystal grains 2c (FIG. 2-1).
- the width of the crystal grain 2c is about 0.3 ⁇ m.
- a physical method such as a vacuum deposition method or an ion plating method, or a chemical method such as a spray method, a dip method, or a CVD method may be used.
- heat treatment may be performed to control the size of the crystal grains 2c and improve the mobility of the film.
- etching proceeds until the surface of the light-transmitting insulating substrate 1 is exposed at the crystal grain boundaries that are easily etched, a depression is formed, and a first transparent conductive film 2 in which a large number of convex portions 2a are arranged is formed. (Fig. 2-2).
- hydrochloric acid 0.3% by weight of hydrochloric acid is used as a liquid used for etching, but is not limited thereto.
- hydrochloric acid one kind or a mixture of two or more kinds of sulfuric acid, nitric acid, hydrofluoric acid, acetic acid, formic acid, etc. Is mentioned.
- FIG. 3 is a top view showing a region of the cavity 4 on the translucent insulating substrate 1.
- the second transparent conductive film 3 is formed using atmospheric pressure CVD (FIG. 2-3).
- the surface of the transparent conductive film 21 and the film forming chamber is heated to, for example, 540 ° C., and tin tetrachloride, water, and hydrogen chloride gas are simultaneously blown at a hydrogen chloride flow rate / tin tetrachloride flow rate ratio of 2.0, thereby forming irregularities on the surface.
- the second transparent conductive film 3 is not formed on the bottom of the hollow of the first transparent conductive film 2, and has an overhang shape, and a cavity 4 with the translucent insulating substrate 1 as the bottom is formed there. .
- the formation of the hollow portion 4 occurs because the reactive species are less likely to reach the concave portion than the convex portion, and the convex portion is preferentially formed. If the aspect ratio, the short side length of the bottom of the recess, and the side surface angle of the recess, any of the protrusions 2a on the diagonal line of the first transparent conductive film 2 and between the adjacent protrusions 2a The cavity 4 is also formed in the recess.
- the transparent conductive film 21 is etched until the surface of the transparent insulating substrate 1 is exposed is described as an example.
- the transparent insulating substrate is formed at the bottom of the recess of the transparent conductive film 21. Even when the surface of 1 is not completely exposed, the cavity 4 is formed between the adjacent convex portions 2a.
- the surface shape of the second transparent conductive film 3 is hardly affected by the unevenness of the base. That is, the surface shape of the second transparent conductive film 3 is hardly affected by the convex portion 2 a of the first transparent conductive film 2. This is because the film formation of the second transparent conductive film 3 proceeds in an overhang shape in the underlying depression, so that even if there is a depression in the foundation, the deposition immediately reaches the height of the convex portion. .
- the film thickness of the convex portion 3a of the second transparent conductive film 3 is about 0.7 ⁇ m, and the height difference between the upper surface of the convex portion 3a and the upper surface of the concave portion 3b of the second transparent conductive film 3 is about 0.4 ⁇ m.
- the interval between the apexes of the convex portions 3a is about 0.6 ⁇ m
- the width of the bottom surface of the convex portions 3a is about 0.5 ⁇ m
- the width of the concave portions 3b is about 0.1 ⁇ m.
- the shape of the cavity 4 projects from the translucent insulating substrate 1 toward the power generation layer 5, and the cross-sectional shape is a substantially triangular shape (convex shape) with the surface of the translucent insulating substrate 1 as the bottom surface.
- the width of the bottom surface is about 0.2 ⁇ m
- the short side is about 0.15 ⁇ m
- the long side is the length of the translucent insulating substrate 1.
- the distance from the center of the cavity 4 to the center of the adjacent cavity 4 across the convex part 2a of the first transparent conductive film 2 is about 0.3 ⁇ m.
- the area occupied by the cavity 4 in the plane of the first transparent conductive film 2 is approximately 75% when viewed from above.
- the thermal CVD method is used as a method of forming the second transparent conductive film 3, but the method of forming the second transparent conductive film 3 is not limited to this, and other methods such as a plasma CVD method are used. But you can.
- the power generation layer 5 is formed on the second transparent conductive film 3 by a plasma CVD method.
- a plasma CVD method As the power generation layer 5, from the second transparent conductive film 3 side, a p-type amorphous silicon carbide film (a-SiC film), which is a first conductive type semiconductor layer, a buffer layer, and a second conductive type semiconductor.
- a-SiC film p-type amorphous silicon carbide film
- a first power generation layer comprising an i-type amorphous silicon film (a-Si film) as a layer and an n-type amorphous silicon film (a-Si film) as a third conductivity type semiconductor layer;
- a second power generation comprising a p-type microcrystalline silicon film as a first conductive type semiconductor layer, an i-type microcrystalline silicon film as a second conductive type semiconductor layer, and an n-type microcrystalline silicon film as a third conductive type semiconductor layer.
- Layers are sequentially stacked (FIGS. 2-4).
- An intermediate layer made of a transparent conductive film may be formed between the first power generation layer and the second power generation layer.
- middle layer is comprised with the film
- a film of zinc oxide (ZnO), indium tin oxide (ITO), tin oxide (SnO 2 ), silicon monoxide (SiO), or the like can be used.
- the back electrode layer 6 is formed on the power generation layer 5 by sputtering (FIG. 2-5).
- an aluminum (Al) film having a thickness of 200 nm is formed.
- a silver (Ag) film having a high light reflectance may be used, and in order to prevent metal diffusion into silicon, A transparent conductive film such as zinc oxide (ZnO), indium tin oxide (ITO), or tin oxide (SnO 2 ) may be formed between the back electrode layer 6 and the back electrode layer 6.
- ZnO zinc oxide
- ITO indium tin oxide
- SnO 2 tin oxide
- the thin film solar cell produced by the method for manufacturing a thin film solar cell according to the present embodiment described above was used as the thin film solar cell of Example 1.
- a thin film solar cell produced by forming tin oxide (SnO 2 ) having a macro uneven structure on the surface as a transparent electrode layer on a glass substrate by a room temperature thermal CVD method is referred to as a thin film solar cell of Conventional Example 1.
- a transparent electrode layer is provided in which a zinc oxide (ZnO) film, which is a transparent conductive film, is formed on a glass substrate, and the zinc oxide (ZnO) film is etched with an acid to form an uneven structure on the surface.
- ZnO zinc oxide
- a thin film solar cell was produced and used as the thin film solar cell of Conventional Example 2.
- the thin film solar cell of the comparative example 1 and the comparative example 2 is the same as the thin film solar cell of Example 1 except the structure of a transparent electrode layer.
- the haze ratio (%) of the transparent conductive film (transparent electrode layer) after the formation of the texture structure (concave / convex structure): ((diffuse transmittance / total light transmittance) ⁇ 100) was evaluated.
- the haze ratio is a numerical value representing the degree of light diffusion.
- the transparent conductive film (transparent electrode layer) of the thin film solar cell of Example 1 has a haze ratio of 10% or more in the wavelength range of 300 nm to 900 nm, and the transparent conductive film (transparent) of the thin film solar cell of Conventional Example 1 It was confirmed that the light scattering effect was improved.
- the short circuit current was able to be improved by increasing the light confinement effect in the transparent conductive film (transparent electrode layer).
- the transparent conductive film (transparent electrode layer) of the thin film solar cell of Conventional Example 2 steep irregularities on the surface are formed by etching, whereas the transparent conductive film (transparent of the thin film solar cell of Example 1 is transparent).
- the transparent conductive film is further formed from above after the etching, it is possible to prevent the formation of irregularities on the surface with steep slopes. Thereby, generation
- Table 2 shows the yield of the thin film solar cells of Example 1 and Conventional Example 2.
- the yield shown here shows the yield of 20 thin-film solar cells of Example 1 and Conventional Example 2 each having a size of 10 mm square.
- Table 2 shows that the thin film solar cell of Example 1 has a higher yield than the thin film solar cell of Conventional Example 2. Therefore, in the thin film solar cell of Example 1, it was confirmed that the thin film solar cell which has a favorable yield was implement
- the light-transmitting insulating substrate is formed by forming the hollow portions 4 between the adjacent convex portions 2 a in the first transparent conductive film 2.
- a sufficient light scattering effect can be obtained with respect to sunlight incident from one side.
- the cavity 4 has a bottom surface formed by etching along the grain boundary of the transparent conductive film up to the translucent insulating substrate, so that sufficient light scattering performance can be obtained.
- the number of irregularities on the surface of the first transparent conductive film 2 can be reduced, and the first Generation
- the fall of the output voltage resulting from the defect in the electric power generation layer 5 can be prevented, and high photoelectric conversion efficiency can be obtained. That is, a high photoelectric property can be obtained without causing the problem that the number of irregularities on the surface of the transparent conductive film increases as in the prior art, resulting in an increase in defects in the power generation layer and a decrease in output voltage. Conversion efficiency can be realized.
- the second transparent conductive film 3 is formed on the first transparent conductive film 2, and the power generation layer 5 is formed thereon. For this reason, the unevenness of the steep slope of the transparent conductive film at the interface between the transparent conductive film of the transparent electrode layer and the power generation layer 5 is alleviated, and the generation of defects in the power generation layer 5 due to the unevenness of the steep slope is suppressed. And yield and reliability can be improved.
- a structure having high light scattering performance in a wide wavelength region of sunlight without increasing the number of irregularities on the surface of the transparent conductive film of the transparent electrode layer is possible to produce a thin-film solar cell that is excellent in photoelectric conversion efficiency by effectively utilizing a wide wavelength range of sunlight.
- the thin film solar cell having a tandem structure in which the pin structure of the power generation layer has two stages has been described as an example.
- the pin structure has The present invention can also be applied to a single-stage single structure or a structure in which three or more pin structures are stacked, and the above-described effects of the present invention can be obtained.
- FIG. 1 another method for manufacturing a transparent conductive film in the method for manufacturing a thin-film solar cell according to the present invention will be described with reference to FIGS. 4-1 to 4-3.
- FIGS. 4-1 to 4-3 are cross-sectional views for explaining an example of the manufacturing process of the thin-film solar cell according to the second embodiment.
- the manufacturing method of the thin film solar cell concerning Embodiment 2 is the same as the manufacturing method of the thin film solar cell concerning Embodiment 2 mentioned above except the manufacturing process of a transparent conductive film. Therefore, below, the manufacturing method of a transparent conductive film is demonstrated.
- a zinc oxide (ZnO) film containing 0.3% by weight of an aluminum (Al) dopant is formed at a film formation temperature of 200 ° C. and a film thickness of 0.23 ⁇ m, and the same dopant amount is formed thereon.
- a zinc oxide (ZnO) film having a thickness of 0.22 ⁇ m is formed by sputtering at a film forming temperature of 400 ° C.
- This lower layer film becomes a crystallized transparent conductive film 210a having crystal grains 2d
- the upper layer film becomes a crystallized transparent conductive film 210b having crystal grains 2e larger than the crystal grains 2d.
- a transparent conductive film 210 having a two-layer structure in which the transparent conductive film 210a and the transparent conductive film 210b are laminated is formed (FIG. 4-1).
- the width of each crystal grain 2d is about 0.2 ⁇ m, and the width of each crystal grain 2e is about 0.3 ⁇ m.
- the transparent conductive film 210 is immersed in an aqueous solution of 0.3 wt% hydrochloric acid and 30 ° C. for 60 seconds, and then washed with pure water and dried for 1 minute or more.
- the etching progresses in the crystal grain boundary, the amorphous-like region, or the defective region lacking oxygen or the like in the upper transparent conductive film 210b, and the upper transparent conductive film 210b and the lower transparent conductive film 210a. Reach the interface.
- the lower transparent conductive film 210a a film that is more easily etched is formed.
- the etching rate of the lower transparent conductive film 210a is faster than the etching rate of the upper transparent conductive film 210b. For this reason, when etching proceeds until the surface of the translucent insulating substrate 1 is exposed, a recess is formed, and a first transparent conductive film 20 in which a number of convex portions 2f having an overhang shape are arranged is formed (FIG. 4-2).
- the film thickness m of the lower layer of the convex portion 2f of the first transparent conductive film 20 from the translucent insulating substrate 1 is 0.23 ⁇ m
- the film thickness n of the upper layer of the convex portion 2f is 0.12 ⁇ m.
- the length k in the lateral direction of the substrate at the bottom of the upper layer of the protrusion 2f is 0.25 ⁇ m.
- the length j in the substrate lateral direction at the bottom of the upper layer between the adjacent convex portions 2f is 0.05 ⁇ m, and the length in the substrate diagonal direction is 0.07 ⁇ m.
- the angle of the upper side taper of the convex portion 2f is 85 degrees with the angle in the in-plane direction of the bottom surface being 0 degrees.
- the length l in the substrate lateral direction of the cavity at the height of the boundary between the upper layer of the convex part 2f and the lower layer of the convex part 2f is 0.2 ⁇ m.
- the second transparent conductive film 3 is formed using atmospheric pressure CVD (FIG. 4-3).
- the surface of the transparent conductive film 20 and the film forming chamber is heated to, for example, 540 ° C., and tin tetrachloride, water, and hydrogen chloride gas are simultaneously blown at a hydrogen chloride flow rate / tin tetrachloride flow rate ratio of 2.0, thereby forming irregularities on the surface.
- the second transparent conductive film 3 is not formed on the bottom of the hollow of the first transparent conductive film 20, and a cavity 40 with the translucent insulating substrate 1 as the bottom is formed there.
- the formation of the cavity 40 makes it difficult for the reactive species to reach the recess compared to the protrusion, and furthermore, since the protrusion 2f of the first transparent conductive film 20 has an overhang shape, it reaches the recess further. This occurs because the projections are preferentially formed.
- the cavity 40 can be formed between the convex portions 2f, and sufficient light can be obtained with respect to the sunlight incident from the translucent insulating substrate 1 side by the formed cavity 40. A scattering effect is obtained.
- a thin-film solar cell was manufactured according to the method for manufacturing a thin-film solar cell according to the second embodiment described above, and the characteristics and yield of the solar cell were evaluated in the same manner as in the first embodiment. As a result, it was confirmed that a thin film solar cell excellent in yield and photoelectric conversion efficiency was realized as in the case of Embodiment 1.
- the thin film solar cell according to the present invention is useful for effective use of a wide wavelength range of sunlight.
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Abstract
Description
図1は、本発明の実施の形態1にかかる薄膜太陽電池10の概略構成を示す断面図である。薄膜太陽電池10は、透光性絶縁基板1、透光性絶縁基板1上に形成された第1透明導電膜2、第1透明導電膜2上に形成されるとともに表面に凹凸構造を有する第2透明導電膜3、第2透明導電膜3上に形成された発電層5、発電層5上に形成された裏面電極層6を備える。ここでは、第1透明導電膜2と第2透明導電膜3とにより第1電極層である透明電極層が構成される。また、第1透明導電膜2における隣接する凸部間には、空洞部4を備える。
実施の形態2では、本発明にかかる薄膜太陽電池の製造方法における透明導電膜の他の製造方法について図4-1~図4-3を参照して説明する。図4-1~図4-3は、実施の形態2にかかる薄膜太陽電池の製造工程の一例を説明するための断面図である。なお、実施の形態2にかかる薄膜太陽電池の製造方法は、透明導電膜の製造工程以外は、上述した実施の形態2にかかる薄膜太陽電池の製造方法と同様である。したがって、以下では、透明導電膜の製造方法について説明する。
2 第1透明導電膜
2a 凸部
2c 結晶粒
2d 結晶粒
2e 結晶粒
2f 凸部
3 第2透明導電膜
3a 凸部
3b 凹部
4 空洞部
5 発電層
6 裏面電極層
10 薄膜太陽電池
20 透明導電膜
21 透明導電膜
40 空洞部
210 透明導電膜
210a 透明導電膜
210b 透明導電膜
Claims (7)
- 透光性絶縁基板と、
結晶質の透明導電膜により前記透光性絶縁基板上に形成され、表面に凹凸構造を有する第1透明導電膜と、
透明導電膜により前記第1透明導電膜上に形成され、前記第1透明導電膜の凹凸構造よりも緩やかな凹凸構造を表面に有する第2透明導電膜と、
前記第2透明導電膜上に形成され、少なくとも結晶質層を一層有して発電を行う発電層と、
光を反射する導電膜により前記発電層上に形成された裏面電極層と、
を備え、
前記第1透明導電膜の凹凸構造における隣接する凸部間に、前記透光性絶縁基板から前記発電層方向に突出した略凸状の空洞部を有すること、
を特徴とする薄膜太陽電池。 - 前記空洞部は、底面が前記透光性絶縁基板の表面であり、該透光性絶縁基板の表面と前記第2透明導電膜とにより囲まれて構成されていること、
を特徴とする請求項1に記載の薄膜太陽電池。 - 前記第1透明導電膜の凸部は、オーバーハング形状を有すること、
を特徴とする請求項1に記載の薄膜太陽電池。 - 透光性絶縁基板の一面上に結晶質の透明導電膜を形成する第1工程と、
前記透明導電膜の一部を、酸を含む溶液を用いて前記透明導電膜のエッチングを行って、前記透光性絶縁基板上に凹凸構造が配列されてなる第1透明導電膜を形成する第2工程と、
前記第1透明導電膜上および露出した前記透光性絶縁基板上に透明導電膜を堆積して、前記第1透明導電膜の凹凸構造における隣接する凸部間に空洞部を有するとともに前記第1透明導電膜の凹凸構造よりも緩やかな凹凸構造を表面に有する第2透明導電膜を形成する第3工程と、
前記第2透明導電膜上に、少なくとも一層の結晶質層を含む半導体層からなる発電層を形成する第4工程と、
前記発電層上に光を反射する導電膜により裏面電極層を形成する第5工程と、
を含むことを特徴とする薄膜太陽電池の製造方法。 - 前記第1工程では、後の製膜ほど高温で行う2段階以上の製膜条件で前記透明導電膜を形成すること、
を特徴とする請求項4に記載の薄膜太陽電池の製造方法。 - 前記第1工程では、ドーパントとしてアルミニウムを含む結晶化した酸化亜鉛膜をスパッタリング法により製膜して前記第1透明導電膜を形成し、
前記第2工程では、前記酸を含む溶液として塩酸を使用して前記エッチングを行い、
前記第3工程では、前記第2透明導電膜として常圧熱CVD法により酸化錫を形成すること、
を特徴とする請求項4に記載の薄膜太陽電池の製造方法。 - 前記第2工程では、前記透光性絶縁基板の表面が露出するまで前記透明導電膜のエッチングを行うこと、
を特徴とする請求項4に記載の薄膜太陽電池の製造方法。
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JP2021009958A (ja) * | 2019-07-02 | 2021-01-28 | 株式会社東芝 | 太陽電池、積層体、多接合型太陽電池、太陽電池モジュール及び太陽光発電システム |
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Also Published As
Publication number | Publication date |
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CN102473748A (zh) | 2012-05-23 |
JPWO2011001735A1 (ja) | 2012-12-13 |
CN102473748B (zh) | 2014-08-20 |
JP5174966B2 (ja) | 2013-04-03 |
US20120138146A1 (en) | 2012-06-07 |
US9117957B2 (en) | 2015-08-25 |
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