WO2017195746A1 - Dispositif de conversion photoélectrique type stratifié, et procédé de fabrication de celui-ci - Google Patents

Dispositif de conversion photoélectrique type stratifié, et procédé de fabrication de celui-ci Download PDF

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WO2017195746A1
WO2017195746A1 PCT/JP2017/017432 JP2017017432W WO2017195746A1 WO 2017195746 A1 WO2017195746 A1 WO 2017195746A1 JP 2017017432 W JP2017017432 W JP 2017017432W WO 2017195746 A1 WO2017195746 A1 WO 2017195746A1
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photoelectric conversion
silicon substrate
crystalline silicon
conversion unit
thin film
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Japanese (ja)
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良太 三島
邦裕 中野
智巳 目黒
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Kaneka Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/164—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells
    • H10F10/165—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells
    • H10F10/166—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells the Group IV-IV heterojunctions being heterojunctions of crystalline and amorphous materials, e.g. silicon heterojunction [SHJ] photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/19—Photovoltaic cells having multiple potential barriers of different types, e.g. tandem cells having both PN and PIN junctions
    • 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
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a stacked photoelectric conversion device in which a crystalline silicon photoelectric conversion unit and a thin film photoelectric conversion unit are stacked, and a method for manufacturing the same.
  • a stacked photoelectric conversion device has been proposed in which a photoelectric conversion unit including a light absorption layer having a wider band gap than crystalline silicon is disposed on the light-receiving surface side of a crystalline silicon-based photoelectric conversion device.
  • Patent Document 1 discloses a stacked photoelectric conversion device in which a thin film photoelectric conversion unit is stacked on the light receiving surface side of a crystalline silicon-based photoelectric conversion unit.
  • Non-Patent Document 1 discloses a stacked photoelectric conversion device in which a perovskite photoelectric conversion unit is stacked on the light receiving surface side of a crystalline silicon photoelectric conversion unit. In this manner, by stacking photoelectric conversion units having light absorption layers having different band gaps, the optical wavelength range contributing to power generation can be expanded, so that high efficiency of the photoelectric conversion device can be realized.
  • a general single crystal silicon substrate is produced by slicing a silicon ingot formed by the Czochralski method using a diamond saw wire.
  • the silicon substrate sliced with saw wires has irregularities (sewing marks) on the surface, and the flatness is not sufficient.
  • a perovskite photoelectric conversion device is generally manufactured using a solution method. When a perovskite layer is formed on a crystalline silicon-based photoelectric conversion unit using a silicon substrate having a concavo-convex structure on the substrate surface, it is difficult to form a uniform film by the solution method due to the concavo-convexity of the silicon substrate. A short circuit occurs.
  • Non-Patent Document 1 it is possible to uniformly form a perovskite layer by a solution method by using a flatly polished crystalline silicon substrate, and by providing a texture structure on the surface of the silicon substrate where the perovskite layer is not formed. The light uptake effect is expressed.
  • a mirror-polished silicon substrate as proposed in Non-Patent Document 1 is very expensive and poor in mass production, so that it is difficult to put it to practical use industrially.
  • An object of the present invention is to provide a stacked photoelectric conversion device that can be manufactured industrially and has excellent conversion efficiency.
  • the present invention relates to a stacked photoelectric conversion device including a thin film photoelectric conversion unit on a light receiving surface side of a crystalline silicon photoelectric conversion unit including a crystalline silicon substrate.
  • the stacked photoelectric conversion device includes a first conductive silicon-based semiconductor layer, a thin film photoelectric conversion unit, and a light-receiving surface transparent electrode layer in this order on the first main surface side of the crystalline silicon substrate, and the second main surface of the crystalline silicon substrate.
  • a second conductivity type silicon-based semiconductor layer and a back electrode are sequentially provided on the side.
  • the thin film photoelectric conversion unit includes a back surface side semiconductor layer, a light absorption layer, and a light receiving surface side semiconductor layer from the crystalline silicon substrate side.
  • the crystalline silicon substrate is an epitaxial crystalline silicon substrate. The thickness of the epitaxial crystalline silicon substrate is preferably 100 to 300 ⁇ m.
  • Epitaxially crystalline silicon substrate is obtained by epitaxially forming silicon on the porous layer of the underlying crystalline silicon substrate having the porous layer and separating it from the porous layer.
  • the epitaxial crystal silicon substrate has high smoothness on the first main surface side which is a separation surface from the porous layer.
  • the epitaxial crystal silicon substrate may have a convex part locally on the second main surface which is an epitaxial growth surface. The height of the protrusion on the epitaxial growth surface may be equal to or greater than the thickness of the epitaxial crystal silicon substrate.
  • the thin film photoelectric conversion unit is preferably formed on the first main surface side which is a separation surface from the porous layer of the epitaxial crystal silicon substrate.
  • the light absorption layer of the thin film photoelectric conversion unit contains, for example, a perovskite crystal material. At least a part of the thin film photoelectric conversion unit may be formed by a solution method.
  • a texture structure may be formed on the entire second main surface of the epitaxial crystal silicon substrate by anisotropic etching or the like.
  • FIG. 1 is a schematic cross-sectional view of a stacked photoelectric conversion device according to an embodiment of the present invention, in which the upper side of the figure is the light receiving surface side and the lower side of the figure is the back side.
  • the photoelectric conversion device includes the thin film photoelectric conversion unit 1 on the first main surface (light receiving surface side) of the crystalline silicon-based photoelectric conversion unit 2.
  • a light receiving surface transparent electrode layer 41 and a patterned light receiving surface grid electrode 42 are provided on the first main surface of the thin film photoelectric conversion unit 1.
  • a back transparent electrode layer 51 and a back metal electrode 52 are provided on the second main surface (back side) of the crystalline silicon photoelectric conversion unit 2.
  • the crystalline silicon photoelectric conversion unit 2 includes a crystalline silicon substrate.
  • the crystalline silicon substrate 21 used in the crystalline silicon-based photoelectric conversion unit 2 is an epitaxial crystalline silicon substrate.
  • FIG. 2 is a conceptual diagram showing a procedure for producing an epitaxial crystal silicon substrate.
  • a crystalline silicon substrate 31 is prepared (FIG. 2A).
  • the surface of the crystalline silicon substrate 31 is oxidized by anodic oxidation or the like to form a porous silicon layer 32 (FIG. 2B), and silicon is epitaxially formed on the porous silicon layer 32, whereby the epitaxial crystalline silicon layer 21 is formed. Formed (FIG. 2C).
  • the thickness of the epitaxial crystalline silicon substrate is, for example, about 100 to 300 ⁇ m. By setting the thickness to 100 ⁇ m or more, in the crystalline silicon photoelectric conversion unit of the stacked photoelectric conversion device, the amount of absorption of long wavelength light can be increased and the conversion characteristics can be improved. If the thickness of the epitaxial crystal silicon substrate is 300 ⁇ m or less, the time for epitaxial film formation can be shortened.
  • the thickness of the epitaxial crystalline silicon substrate is more preferably 120 to 280 ⁇ m, and further preferably 150 to 250 ⁇ m.
  • pyramidal convex portions 215 are locally formed on the epitaxial growth surface of crystalline silicon.
  • the convex portion is equal to or greater than the thickness of the epitaxial crystalline silicon substrate. For example, when epitaxial crystal silicon is grown to a thickness of about 200 ⁇ m, a convex portion 205 having a height of about 200 to 800 ⁇ m is formed (see FIG. 6).
  • the porous layer 32 and the epitaxial crystalline silicon layer 21 are separated from the underlying crystalline silicon substrate 31 (FIG. 2D), and the porous silicon layer 32 is removed (FIG. 2E), so that it can be used as the epitaxial crystalline silicon substrate 21.
  • the conductivity type of the epitaxial crystalline silicon substrate 21 may be n-type or p-type.
  • the first main surface 21a which is a separation surface from the porous silicon layer 32, is excellent in flatness.
  • the crystalline silicon-based photoelectric conversion unit has conductive silicon-based semiconductor layers 24 and 25 on the light-receiving surface side and the back surface side on the epitaxial crystalline silicon substrate 21, respectively.
  • the first conductivity type silicon-based semiconductor layer 24 on the light receiving surface side has the first conductivity type
  • the second conductivity type silicon-based semiconductor layer 25 on the back surface side has the second conductivity type.
  • the first conductivity type and the second conductivity type are different conductivity types, one is p-type and the other is n-type.
  • Examples of the crystalline silicon photoelectric conversion unit having a p layer and an n layer on the surface of the epitaxial crystalline silicon substrate 21 include a diffusion type silicon photoelectric conversion unit and a heterojunction silicon photoelectric conversion unit.
  • conductive silicon semiconductor layers 24 and 25 are formed by diffusing doped impurities such as boron and phosphorus on the surface of the crystalline silicon substrate.
  • heterojunction silicon photoelectric conversion unit conductive silicon thin films such as amorphous silicon and microcrystalline silicon are provided as the conductive silicon semiconductor layers 24 and 25, and the epitaxial crystal silicon substrate 21 and the conductive silicon thin film 24 are provided. , 25 is formed as a heterojunction.
  • the heterojunction silicon photoelectric conversion unit preferably has intrinsic silicon thin films 22 and 23 between the epitaxial crystal silicon substrate 21 and the conductive silicon thin films 24 and 25. By providing an intrinsic silicon thin film on the surface of the epitaxial crystal silicon substrate, surface passivation can be effectively performed while suppressing diffusion of impurities into the epitaxial crystal silicon substrate.
  • a thin film photoelectric conversion unit 1 is provided on the light receiving surface side of the crystalline silicon-based photoelectric conversion unit 2.
  • the thin film photoelectric conversion unit 1 includes a back surface side semiconductor layer 11, a light absorption layer 12, and a light receiving surface side semiconductor layer 13 in this order from the epitaxial crystalline silicon substrate 12 side (the crystalline silicon photoelectric conversion unit 2 side).
  • the light absorption layer 12 is a layer that absorbs sunlight and generates photoexcited carriers, and is made of a material having a wider band gap than crystalline silicon.
  • Examples of thin film materials having a wider band gap than crystalline silicon include amorphous silicon-based materials such as amorphous silicon and amorphous silicon carbide, polymer materials, and perovskite crystal materials.
  • the first semiconductor layer 13 on the light receiving surface side of the thin film photoelectric conversion unit 1 has the same conductivity type as the first conductivity type silicon semiconductor layer 24 of the crystalline silicon photoelectric conversion unit 2.
  • the second semiconductor layer 11 on the back side of the thin film photoelectric conversion unit 1 has the same conductivity type as the second conductivity type silicon semiconductor layer 25 of the crystalline silicon photoelectric conversion unit 2.
  • the thin film photoelectric conversion unit 1 has a light-receiving surface side semiconductor layer 13 that is p-type and a back-side semiconductor. Layer 11 is n-type. Therefore, the thin film photoelectric conversion unit 1 and the crystalline silicon photoelectric conversion unit 2 are connected in series, and both have rectification in the same direction.
  • the light-receiving surface side semiconductor layer 13 and the back surface side semiconductor layer 11 are organic semiconductors or oxides, they are regarded as n-type if they have electron transport properties and p-type if they have hole transport properties.
  • the first conductive silicon-based semiconductor layer 24 of the crystalline silicon-based photoelectric conversion unit 2 is p-type
  • the second conductive silicon-based semiconductor layer 25 is n-type
  • the thin-film photoelectric conversion unit 1 is a perovskite as the light absorption layer 12.
  • the light receiving surface side semiconductor layer 13 may be p-type (hole transport layer) and the back surface side semiconductor layer 11 may be n type (electron transport layer).
  • the light-receiving surface grid electrode 42 and the light-receiving surface transparent electrode layer 41 are provided on the light-receiving surface side of the thin film photoelectric conversion unit 1, and from the back surface transparent electrode layer 51 and the back surface metal electrode 52 on the back surface side of the crystalline silicon-based photoelectric conversion unit 2.
  • a back electrode is provided.
  • the present invention will be described by taking, as an example, a stacked photoelectric conversion device using a heterojunction silicon photoelectric conversion unit 2 as a crystalline silicon photoelectric conversion unit and a perovskite photoelectric conversion unit 1 as a thin film photoelectric conversion unit thereon.
  • the embodiment will be described in more detail.
  • the first conductivity type silicon-based semiconductor layer is p-type
  • the second conductivity-type silicon-based semiconductor layer is n-type
  • the light-receiving surface side semiconductor layer is a hole transport layer
  • the back surface side semiconductor layer is an electron transport layer.
  • an n-type epitaxial crystal silicon substrate is used as the epitaxial crystal silicon substrate 21.
  • An intrinsic silicon-based thin film 22 and a p-type silicon-based thin film 24 as a first conductive silicon-based semiconductor layer are formed on the first main surface of the n-type epitaxial crystal silicon substrate 21.
  • an intrinsic silicon-based thin film 23 and an n-type silicon-based thin film 25 are formed as a second conductivity type silicon-based semiconductor layer.
  • an intrinsic amorphous silicon thin film as the intrinsic silicon thin films 22 and 23 on the surface of the epitaxial crystalline silicon substrate 21.
  • the film thickness of the intrinsic silicon thin films 23 and 24 is preferably about 2 to 15 nm.
  • the conductive silicon thin films 24 and 25 amorphous silicon, microcrystalline silicon (a material containing amorphous silicon and crystalline silicon), amorphous silicon alloy, microcrystalline silicon alloy, or the like is used.
  • the silicon alloy include silicon oxide, silicon carbide, silicon nitride, and silicon germanium.
  • the conductive silicon-based semi-thin film is preferably an amorphous silicon thin film.
  • the film thickness of the conductive silicon thin films 24 and 25 is preferably about 3 to 30 nm.
  • the silicon-based thin films 22, 23, 24, and 25 are preferably formed by plasma CVD (chemical vapor deposition). Even when the local convex portion 215 is formed on the second main surface of the epitaxial crystal silicon substrate 21 or when the texture is formed on the entire surface, the silicon-based thin films 23 and 25 are formed by a dry process such as plasma CVD. If the film is formed, the entire surface can be uniformly coated.
  • plasma CVD chemical vapor deposition
  • an electron transport layer 11 that is a back surface side semiconductor layer, a light absorption layer 12, and a hole transport layer 13 that is a light receiving surface side semiconductor layer are sequentially formed.
  • a thin film photoelectric conversion unit 1 is formed. Between the thin film photoelectric conversion unit 1 and the crystalline silicon photoelectric conversion unit 2, the electrical connection between the thin film photoelectric conversion unit and the crystalline silicon photoelectric conversion unit, adjustment of the amount of incident light for current matching, etc.
  • An intermediate layer (not shown) may be provided.
  • an inorganic material such as titanium oxide, zinc oxide, niobium oxide, zirconium oxide, aluminum oxide or the like is preferably used.
  • Organic materials such as fullerene-based materials such as PCBM and perylene-based materials can also be used as the material for the electron transport layer.
  • a donor may be added to the electron transport layer.
  • examples of the donor include yttrium, europium, and terbium.
  • the light absorption layer 12 contains a photosensitive material (perovskite crystal material) having a perovskite crystal structure.
  • the compound constituting the perovskite crystal material is represented by the general formula RNH 3 MX 3 or HC (NH 2 ) 2 MX 3 .
  • R is an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group.
  • M is a divalent metal ion, preferably Pb or Sn.
  • X is a halogen, and examples thereof include F, Cl, Br, and I. All three Xs may be the same halogen element, or a plurality of halogens may be mixed. By changing the type and ratio of the halogen X, the spectral sensitivity characteristic can be changed.
  • the wavelength range of light absorbed by the light absorption layer 12 is determined by the band gap of the perovskite crystal material.
  • the band gap of the perovskite light absorption layer 12 is preferably 1.55 to 1.75 eV, and preferably 1.6 to 1.65 eV. It is more preferable that
  • the perovskite crystal material is represented by the formula CH 3 NH 3 PbI 3-y Br y
  • y 0 to 0.85 is preferable in order to set the band gap to 1.55 to 1.75 eV.
  • y 0.15 to 0.55 is preferable.
  • an organic material is preferably used, and polythiophene derivatives such as poly-3-hexylthiophene (P3HT) and poly (3,4-ethylenedioxythiophene) (PEDOT), 2, 2 ′, 7 , 7'-tetrakis- (N, N-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Spiro-OMeTAD), carbazole derivatives such as polyvinylcarbazole, poly [bis (4 And triphenylamine derivatives such as (phenyl) (2,4,6-triphenylmethyl) amine] (PTAA), diphenylamine derivatives, polysilane derivatives, polyaniline derivatives, porphyrins, phthalocyanines, and the like.
  • Inorganic oxides such as MoO 3 , WO 3 , NiO, and CuO can also be used as the material for the hole transport layer, and may be laminated with an organic material.
  • the method for forming the electron transport layer 11, the light absorption layer 12 and the hole transport layer 13 of the perovskite photoelectric conversion unit is not particularly limited. Depending on the material specification, etc., a dry process such as a vacuum deposition method, a CVD method, or a sputtering method is used. Solution methods such as spin coating, spray coating, and bar coating can be used.
  • a highly uniform thin film can be formed thereon by a solution method.
  • the first main surface 21a (separation surface from the porous silicon layer) of the epitaxial crystal silicon substrate 21 has no protrusion due to the epitaxial growth of silicon and has excellent flatness.
  • the surface can be uniformly coated and a short circuit can be prevented.
  • CH 3 NH 3 PbI 3 when CH 3 NH 3 PbI 3 is formed as the light absorption layer 12, a solution in which lead iodide and methylammonium iodide are mixed in a solvent such as dimethyl sulfoxide or N, N-dimethylformamide is spin-coated. It is possible to grow CH 3 NH 3 PbI 3 crystals by applying the coating and heating the coating film. Crystallinity can also be improved by bringing a poor solvent into contact with the surface of the coating film.
  • the light absorption layer can also be produced by a combination of a dry method and a solution method.
  • a crystal of CH 3 NH 3 PbI 3 can be obtained by forming a lead iodide thin film by a vacuum deposition method and bringing the surface into contact with an isopropyl alcohol solution of methylammonium iodide.
  • a method of bringing the solution into contact with the surface of the deposited film a method of applying the solution by spin coating or the like, and a method of immersing the substrate in the solution can be mentioned.
  • a back surface transparent electrode layer 51 is formed on the back surface of the heterojunction silicon photoelectric conversion unit 2, and a light receiving surface transparent electrode layer 41 is formed on the light receiving surface of the perovskite photoelectric conversion unit 1.
  • a material for the transparent electrode layer an oxide such as zinc oxide (ZnO), tin oxide (SnO 2 ), indium oxide (In 2 O 3 ), a composite oxide such as indium tin oxide (ITO), or the like is used. Is preferred. Further, a material obtained by doping W 2 or Ti into In 2 O 3 or SnO 2 may be used. Since such a transparent conductive oxide has transparency and low resistance, photoexcited carriers can be collected efficiently.
  • the transparent electrode layer As a method for forming the transparent electrode layer, a sputtering method, an MOCVD method, or the like is preferable.
  • a sputtering method, an MOCVD method, or the like is preferable.
  • the transparent electrode layer in addition to oxides, fine metal wires such as Ag nanowires and organic materials such as PEDOT-PSS can also be used.
  • the light receiving surface grid electrode 42 is provided on the light receiving surface transparent electrode layer 41.
  • Examples of the pattern shape of the light-receiving surface grid electrode 42 include a grid shape including a plurality of finger electrodes arranged in parallel and a bus bar electrode extending in a direction orthogonal to the finger electrodes.
  • an antireflection film (not shown) on the outermost surface of the light receiving surface.
  • an antireflection film made of a low refractive index material such as MgF on the outermost surface, the difference in refractive index at the air interface can be reduced to reduce the reflected light and increase the amount of light taken into the photoelectric conversion unit.
  • the back metal electrode 52 is provided on the back transparent electrode layer 51.
  • the back metal electrode may be a solid film or a grid.
  • the back metal electrode can be formed by a printing method, various physical vapor deposition methods, a plating method, or the like.
  • the stacked photoelectric conversion device may have a texture structure on the back side of the crystalline silicon photoelectric conversion unit 2.
  • a texture structure on the back side By having a texture structure on the back side, a light capturing effect can be obtained, so that the conversion characteristics of the stacked photoelectric conversion device can be improved.
  • a texture structure on the second main surface of the epitaxial crystal silicon substrate 21 By providing a texture structure on the second main surface of the epitaxial crystal silicon substrate 21, a crystalline silicon photoelectric conversion unit having a texture structure can be produced.
  • the formation method of the texture on the second main surface of the epitaxial crystal silicon substrate is not particularly limited.
  • the texture can be formed on the surface by anisotropic etching using alkali or the like, similar to the formation of the texture on the surface of a general single crystal silicon substrate.
  • anisotropic etching is performed with the first main surface protected. Just do it.
  • a texture is formed before the epitaxial crystalline silicon substrate 21 is separated from the underlying crystalline silicon substrate 31 (FIG. 4D), and then the underlying crystalline silicon is formed on the second principal surface 21b from the first principal surface.
  • an epitaxial crystalline silicon substrate having a texture on the entire surface of the second main surface 21b and a flat first main surface 21a is obtained. Further, as shown in FIG.
  • a protective layer 61 is provided on the first main surface of the epitaxial crystal silicon substrate 21 separated from the underlying crystal silicon substrate (FIG. 5D), and only the second main surface is anisotropically etched. May be.
  • the method of forming a texture before separation from the base crystalline silicon substrate it is not necessary to form a protective film, so that the texture can be easily formed.
  • the method of providing the protective layer on the epitaxial crystalline silicon substrate separated from the underlying crystalline silicon can be performed without worrying about the residue of the porous layer.
  • the stacked photoelectric conversion device is preferably modularized for practical use.
  • modularization is performed by sealing cells between a substrate and a back sheet via a sealing material. Sealing may be performed after a plurality of cells are connected in series or in parallel via an interconnector.
  • Laminated Photoelectric Conversion Device 1 Thin Film Photoelectric Conversion Unit (Perovskite Photoelectric Conversion Unit) 11 Back side semiconductor layer (electron transport layer) 12 Light Absorption Layer 13 Light-Receiving Side Semiconductor Layer (Hole Transport Layer) 2 Crystalline silicon photoelectric conversion unit (heterojunction silicon photoelectric conversion unit) 21 Epitaxial crystalline silicon substrate 22, 23 Intrinsic silicon thin film 24 First conductivity type silicon semiconductor layer (p-type silicon thin film) 25 Second conductivity type silicon-based semiconductor layer (n-type silicon-based thin film) 31 Underlying crystalline silicon substrate 32 Porous layer 41 Light-receiving surface transparent electrode layer 42 Light-receiving surface grid electrode 51 Back surface transparent electrode layer 52 Back surface metal electrode 61 Protective film

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Abstract

Le dispositif de conversion photoélectrique type stratifié (100) de l'invention est équipé d'une unité de conversion photoélectrique à base de film mince (1) sur une unité de conversion photoélectrique à base de silicium cristallin (2) à son tour équipée d'un substrat de silicium cristallin épitaxial. Le substrat de silicium cristallin épitaxial (21) est obtenu par transformation d'un silicium en film épitaxial sur une couche poreuse d'un substrat de silicium cristallin de base possédant une couche poreuse, et par séparation du substrat de silicium cristallin de base. De préférence, l'unité de conversion photoélectrique à film mince (1) est formée au moins en partie par un procédé de dissolution.
PCT/JP2017/017432 2016-05-09 2017-05-08 Dispositif de conversion photoélectrique type stratifié, et procédé de fabrication de celui-ci Ceased WO2017195746A1 (fr)

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