WO2014162979A1 - Dispositif de conversion photoélectrique - Google Patents

Dispositif de conversion photoélectrique Download PDF

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Publication number
WO2014162979A1
WO2014162979A1 PCT/JP2014/058888 JP2014058888W WO2014162979A1 WO 2014162979 A1 WO2014162979 A1 WO 2014162979A1 JP 2014058888 W JP2014058888 W JP 2014058888W WO 2014162979 A1 WO2014162979 A1 WO 2014162979A1
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type
thin film
amorphous thin
silicon substrate
photoelectric conversion
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PCT/JP2014/058888
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English (en)
Japanese (ja)
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和也 辻埜
敏彦 酒井
直城 小出
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シャープ株式会社
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Priority to JP2015510045A priority Critical patent/JP6342386B2/ja
Publication of WO2014162979A1 publication Critical patent/WO2014162979A1/fr

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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
    • H01L31/072—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 PN heterojunction type
    • H01L31/0745—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 PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—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 PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
    • 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
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • 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

Definitions

  • the present invention relates to a photoelectric conversion device.
  • Patent Documents 1 and 2 Conventionally, a photoelectric conversion device in which two concavo-convex structures having different concavo-convex sizes are provided on the light incident side is known (Patent Documents 1 and 2).
  • a crystalline silicon substrate has a first uneven structure and a second uneven structure formed on the surface of the first uneven structure.
  • the second uneven structure has an uneven size smaller than that of the first uneven structure. Thereby, the reflectance at the light incident side is lowered.
  • a crystalline silicon solar cell is formed on a surface of a light incident side of a crystalline silicon substrate having a first concavo-convex structure on a surface on the light incident side, and a second concavo-convex structure.
  • the second uneven structure has an uneven size smaller than that of the first uneven structure.
  • Patent Document 1 since the crystalline silicon substrate has two uneven structures on the surface on the light incident side, there is a problem that the contact area between the crystalline silicon substrate and the electrode becomes large and carrier recombination is likely to occur. is there.
  • Patent Document 2 since the crystalline silicon substrate has a concavo-convex structure on the surface on the light incident side, there is a problem that the contact area between the crystalline silicon substrate and the transparent conductive film is large, and carrier recombination is likely to occur. .
  • the present invention has been made to solve such a problem, and an object thereof is to provide a photoelectric conversion device capable of reducing the reflectance on the light incident side and reducing the recombination of carriers. It is.
  • a photoelectric conversion device is a photoelectric conversion device that converts light into electricity, and includes a crystalline silicon substrate and an amorphous thin film.
  • a first uneven structure having a first uneven size is provided on the surface on the light incident side.
  • the amorphous thin film has a second concavo-convex structure having a second concavo-convex size different from the first concavo-convex size provided on the surface on the light incident side and is in contact with the light incident side surface of the crystal silicon substrate It is provided above and contains a group IV element.
  • the first uneven size is smaller than the second uneven size in the photoelectric conversion device according to the embodiment of the present invention.
  • the first uneven size is larger than the second uneven size in the photoelectric conversion device according to the embodiment of the present invention.
  • the photoelectric conversion device is the photoelectric conversion device according to any one of (1) to (3), wherein the amorphous thin film is the first amorphous It consists of either a thin film or a second amorphous thin film.
  • the first amorphous thin film is provided on the crystalline silicon substrate in contact with the surface on the light incident side of the crystalline silicon substrate and has a conductivity type opposite to that of the crystalline silicon substrate.
  • the structure is composed of a first amorphous layer provided on the surface on the light incident side.
  • the second amorphous thin film is provided on the crystalline silicon substrate in contact with the surface on the light incident side of the crystalline silicon substrate, and includes a second amorphous layer having an i-type conductivity type, A second conductive layer is provided on the second amorphous layer in contact with the amorphous layer and has a conductivity type opposite to that of the crystalline silicon substrate, and the second concavo-convex structure is provided on the light incident side surface. 3 amorphous layers.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to (4), wherein the crystalline silicon substrate has an n-type conductivity type, and the first amorphous layer Is made of p-type amorphous silicon, the second amorphous layer is made of i-type amorphous silicon, and the third amorphous layer is made of p-type amorphous silicon.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to (4), wherein the crystalline silicon substrate has a p-type conductivity type, and the first amorphous The layer is made of n-type amorphous silicon, the second amorphous layer is made of i-type amorphous silicon, and the third amorphous layer is made of n-type amorphous silicon.
  • the photoelectric conversion device according to the embodiment of the present invention further includes an electrode arranged on the light incident side in the photoelectric conversion device according to any one of (4) to (6), Of the surface on the light incident side of the crystalline silicon substrate, the portion facing the electrode is flat.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to any one of (1) to (3), wherein the crystalline silicon substrate includes a bulk region and a light incident side. And a diffusion region having a conductivity type opposite to that of the bulk region.
  • the photoelectric conversion device according to the embodiment of the present invention further includes an electrode provided in contact with a part of the diffusion region of the crystalline silicon substrate in the photoelectric conversion device according to (8), A part of the diffusion region is a flat plane.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to any one of (1) to (9), wherein the crystalline silicon substrate is a single crystal silicon substrate or a polycrystalline It consists of a silicon substrate.
  • the photoelectric conversion device in the photoelectric conversion device according to any one of (1) to (3), includes a plurality of first amorphous thin films and a plurality of first amorphous thin films. And a second amorphous thin film.
  • the plurality of first amorphous thin films are provided on the side opposite to the light incident side of the crystalline silicon substrate and have a conductivity type opposite to that of the crystalline silicon substrate.
  • the plurality of second amorphous thin films are provided on the opposite side to the light incident side of the crystalline silicon substrate and have the same conductivity type as that of the crystalline silicon substrate, and the plurality of second amorphous thin films are in the in-plane direction of the crystalline silicon substrate. Alternatingly arranged with one amorphous thin film.
  • the crystalline silicon substrate is a single crystal silicon substrate.
  • the photoelectric conversion device according to the embodiment of the present invention includes a plurality of first amorphous thin films and a plurality of second amorphous thin films, A third amorphous film having an i-type conductivity type and provided in contact with the plurality of first amorphous thin films, the plurality of second amorphous thin films, and the single crystal silicon substrate between the single crystal silicon substrate A thin film is further provided.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to (12), wherein the first amorphous thin film has a single-crystal silicon substrate having an n-type conductivity type.
  • the second amorphous thin film is made of an n-type single crystal silicon substrate.
  • the third amorphous thin film is made of i-type. Made of amorphous silicon.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to any one of (1) to (3), wherein the crystalline silicon substrate includes a plurality of first diffusion regions. And a plurality of second diffusion regions.
  • the plurality of first diffusion regions are provided in contact with a bulk region made of single crystal silicon and a back surface made of single crystal silicon and opposite to the light incident side of the crystal silicon substrate, opposite to the conductivity type of the bulk region. Has conductivity type.
  • the plurality of second diffusion regions are made of single crystal silicon and have the same conductivity type as that of the bulk region, and are in contact with the back surface alternately with the plurality of first diffusion regions in the in-plane direction of the crystalline silicon substrate. Be placed.
  • the amorphous thin film is the first amorphous It consists of a thin film, a second amorphous thin film, a third amorphous thin film, a fourth amorphous thin film, or a fifth amorphous thin film.
  • the first amorphous thin film is provided in contact with the surface on the light incident side of the crystalline silicon substrate, and the second concavo-convex structure is provided on the surface on the light incident side. It consists of a crystalline layer.
  • the second amorphous thin film is provided in contact with the surface on the light incident side of the crystalline silicon substrate, and the second uneven structure is provided on the surface on the light incident side. It consists of a crystalline layer.
  • the third amorphous thin film is provided in contact with the surface on the light incident side of the crystalline silicon substrate, the second uneven structure is provided on the surface on the light incident side, and has a p-type conductivity type. It consists of a crystalline layer.
  • the fourth amorphous thin film is provided in contact with the surface on the light incident side of the crystalline silicon substrate, and is formed on the fourth amorphous layer having the i-type conductivity type and the fourth amorphous layer.
  • the second concavo-convex structure is provided on the surface on the light incident side and is formed of a fifth amorphous layer having an n-type conductivity type.
  • the fifth amorphous thin film is provided in contact with the surface on the light incident side of the crystalline silicon substrate, and is formed on the sixth amorphous layer having the i-type conductivity type and the sixth amorphous layer.
  • the second uneven structure is provided on the surface on the light incident side, and is formed of a seventh amorphous layer having a p-type conductivity type.
  • the photoelectric conversion device according to the embodiment of the present invention is the photoelectric conversion device according to (15), wherein each of the first, fourth, and sixth amorphous layers is an i-type amorphous material.
  • Each of the second and fifth amorphous layers is made of n-type amorphous silicon, and each of the third and seventh amorphous layers is made of p-type amorphous silicon. .
  • two concavo-convex structures having different concavo-convex sizes are arranged on the light incident side, and the surface on the light incident side of the crystalline silicon substrate is formed by an amorphous thin film containing a group IV element. Covered. As a result, incident light is scattered by the two concavo-convex structures and enters the crystalline silicon substrate. The surface of the crystalline silicon substrate on the light incident side is passivated by an amorphous thin film.
  • the reflectance on the light incident side can be reduced, and the recombination of carriers at the interface between the amorphous thin film and the crystalline silicon substrate can be reduced.
  • FIG. 2 is an enlarged view in which a part of an n-type single crystal silicon substrate and an amorphous thin film shown in FIG. 1 are enlarged. It is the schematic which shows the structure of the amorphous thin film shown in FIG. It is a 1st process drawing which shows the manufacturing method of the photoelectric conversion apparatus shown in FIG.
  • FIG. 4 is a second process diagram illustrating a method for manufacturing the photoelectric conversion device illustrated in FIG. 1.
  • FIG. 4 is a third process diagram illustrating a method for manufacturing the photoelectric conversion device illustrated in FIG. 1.
  • FIG. 3 is a schematic diagram illustrating a configuration of another photoelectric conversion device according to Embodiment 1.
  • FIG. 8 is a first process diagram illustrating a method for manufacturing the photoelectric conversion device illustrated in FIG. 7.
  • FIG. 8 is a second process diagram illustrating a method for manufacturing the photoelectric conversion device illustrated in FIG. 7.
  • FIG. 8 is a third process diagram illustrating the method for manufacturing the photoelectric conversion device illustrated in FIG. 7.
  • FIG. 5 is a schematic diagram illustrating a configuration of still another photoelectric conversion device according to Embodiment 1.
  • FIG. 5 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to a second embodiment. It is the schematic which shows the structure of the amorphous thin film shown in FIG. FIG.
  • FIG. 14 is a first process diagram showing a method of manufacturing the photoelectric conversion device shown in FIG. 13.
  • FIG. 14 is a second process diagram illustrating a method of manufacturing the photoelectric conversion device illustrated in FIG. 13.
  • FIG. 14 is a third process diagram illustrating a method for manufacturing the photoelectric conversion device illustrated in FIG. 13.
  • 6 is a schematic diagram illustrating a configuration of another photoelectric conversion device according to Embodiment 2.
  • FIG. FIG. 6 is a schematic diagram illustrating a configuration of a photoelectric conversion device according to a third embodiment. It is the schematic which shows the structure of the amorphous thin film shown in FIG.
  • FIG. 20 is a schematic view showing a configuration of another amorphous thin film shown in FIG. 19.
  • FIG. 20 is a schematic view showing a configuration of another amorphous thin film shown in FIG. 19.
  • FIG. 20 is a first process diagram illustrating a method of manufacturing the photoelectric conversion device illustrated in FIG. 19.
  • FIG. 20 is a second process diagram illustrating the method of manufacturing the photoelectric conversion device illustrated in FIG. 19.
  • FIG. 20 is a third process diagram illustrating the method of manufacturing the photoelectric conversion device illustrated in FIG. 19.
  • FIG. 20 is a fourth process diagram illustrating the method of manufacturing the photoelectric conversion device illustrated in FIG. 19.
  • FIG. 6 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to a fourth embodiment.
  • FIG. 27 is a first process diagram illustrating a method of manufacturing the photoelectric conversion device illustrated in FIG. 26.
  • FIG. 27 is a second process diagram illustrating the method of manufacturing the photoelectric conversion device illustrated in FIG. 26.
  • FIG. 27 is a third process diagram illustrating the method of manufacturing the photoelectric conversion device illustrated in FIG. 26.
  • FIG. 27 is a fourth process diagram illustrating the method of manufacturing the photoelectric conversion device illustrated in FIG. 26.
  • FIG. 6 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to a fifth embodiment.
  • FIG. 10 is a schematic diagram illustrating a configuration of another photoelectric conversion device according to Embodiment 5.
  • FIG. 10 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to a sixth embodiment.
  • FIG. 10 is a schematic diagram illustrating a configuration of another photoelectric conversion device according to Embodiment 6.
  • FIG. 10 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to a seventh embodiment.
  • FIG. 10 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to a seventh embodiment.
  • FIG. 10 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to an eighth embodiment. It is the schematic which shows the structure of a photoelectric conversion module provided with the photoelectric conversion apparatus by this embodiment. It is the schematic which shows the structure of a solar energy power generation system provided with the photoelectric conversion apparatus by this embodiment. It is the schematic which shows the structure of the photoelectric conversion module array shown in FIG. It is the schematic which shows the structure of another photovoltaic power generation system provided with the photoelectric conversion apparatus by this embodiment. It is the schematic which shows the structure of another photovoltaic power generation system provided with the photoelectric conversion apparatus by this embodiment. It is the schematic which shows the structure of another solar power generation system provided with the photoelectric conversion apparatus by this embodiment.
  • amorphous means that the ratio of the peak intensity based on crystals to the peak intensity based on amorphous in Raman scattering is 0.1 or less.
  • amorphous silicon is expressed as “a-Si”, this notation actually means that a hydrogen (H) atom is included.
  • FIG. 1 is a schematic diagram showing a configuration of a photoelectric conversion apparatus according to Embodiment 1 of the present invention.
  • a photoelectric conversion device 10 according to Embodiment 1 of the present invention includes an n-type single crystal silicon substrate 1, an amorphous thin film 2, a transparent conductive film 3, electrodes 4 and 6, and passivation. And a membrane 5.
  • the n-type single crystal silicon substrate 1 has a specific resistance of 0.1 to 10 ⁇ cm and a thickness of 100 to 300 ⁇ m.
  • the n-type single crystal silicon substrate 1 has a (100) plane orientation.
  • the n-type single crystal silicon substrate 1 has a concavo-convex structure TX1 on the surface on the light incident side.
  • the amorphous thin film 2 is disposed on the n-type single crystal silicon substrate 1 in contact with the light incident side surface of the n-type single crystal silicon substrate 1.
  • the amorphous thin film 2 has a concavo-convex structure TX2 on the light incident side surface.
  • the transparent conductive film 3 is disposed on the amorphous thin film 2 in contact with the amorphous thin film 2.
  • the transparent conductive film 3 is made of ITO (Indium Tin Oxide), SnO 2 , ZnO, or the like.
  • the electrodes 4 are in contact with the transparent conductive film 3 and are arranged on the transparent conductive film 3 at a desired interval.
  • the electrode 4 is made of, for example, silver (Ag).
  • the passivation film 5 is made of, for example, silicon oxide (SiO 2 ) and has a thickness of 100 nm to 200 nm.
  • the electrode 6 is disposed in contact with the back surface of the n-type single crystal silicon substrate 1 and the passivation film 5.
  • the electrode 6 is made of, for example, aluminum (Al).
  • FIG. 2 is an enlarged view of a part of the n-type single crystal silicon substrate 1 and the amorphous thin film 2 shown in FIG.
  • the height H1 is defined as the distance between the valley and the mountain
  • the width W1 is defined as the distance between two adjacent valleys or the distance between two adjacent mountains.
  • the height H2 and the width W2 are defined.
  • the height H1 is, for example, 1 ⁇ m to 10 ⁇ m, and the width W1 is 1 ⁇ m to 10 ⁇ m.
  • the height H2 is, for example, 1 nm to 200 nm, and the width W2 is 1 nm to 200 nm.
  • the uneven size of the uneven structure TX1 is defined by the height H1 and / or the width W1. The same applies to the uneven structure TX2.
  • the concavo-convex structure TX1 has a larger concavo-convex size than the concavo-convex structure TX2.
  • the photoelectric conversion device 10 is provided with the concavo-convex structure TX1 on the light incident side surface of the n-type single crystal silicon substrate 1, and the concavo-convex structure TX2 having a concavo-convex size smaller than the concavo-convex structure TX1 is more incident than the concavo-convex structure TX1 It is provided on the side.
  • the incident light is scattered by the concavo-convex structure TX2, and the scattered light is further scattered by the concavo-convex structure TX1. Therefore, the reflectance of incident light can be reduced as compared with the case where only one uneven structure is provided on the light incident side of the photoelectric conversion device 10.
  • FIG. 3 is a schematic view showing the configuration of the amorphous thin film 2 shown in FIG.
  • amorphous thin film 2 includes an i-type amorphous thin film 21 and a p-type amorphous thin film 22 (see (a)).
  • the i-type amorphous thin film 21 is arranged along the uneven structure TX1 on the light incident side of the n-type single crystal silicon substrate 1.
  • the p-type amorphous thin film 22 is disposed on the i-type amorphous thin film 21 in contact with the i-type amorphous thin film 21, and has a concavo-convex structure TX2 on the light incident side surface.
  • the i-type amorphous thin film 21 includes i-type amorphous silicon (i-type a-Si), i-type amorphous silicon germanium (i-type a-SiGe), i-type amorphous germanium (i-type a-Ge).
  • I-type amorphous silicon carbide i-type a-SiC
  • i-type amorphous silicon nitride i-type a-SiN
  • i-type amorphous silicon oxide i-type a-SiO
  • It is made of any one of amorphous silicon carbon oxide (i-type a-SiCO) or the like, and is generally made of an i-type amorphous thin film containing a group IV element.
  • the i-type amorphous thin film 21 has a thickness of 10 to 20 nm.
  • the p-type amorphous thin film 22 includes p-type amorphous silicon (p-type a-Si), p-type amorphous silicon germanium (p-type a-SiGe), and p-type amorphous germanium (p-type a-Ge).
  • p-type amorphous silicon carbide p-type a-SiC
  • p-type amorphous silicon nitride p-type a-SiN
  • p-type amorphous silicon oxide p-type a-SiO
  • It is made of any one of amorphous silicon carbon oxide (p-type a-SiCO) or the like, and is generally made of a p-type amorphous thin film containing a group IV element.
  • the p-type amorphous thin film 22 has a thickness of 1 to 200 nm.
  • the p-type amorphous thin film 22 includes, for example, boron (B) as a p-type dopant, and the concentration of B is, for example, 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 .
  • the combination of the material of the i-type amorphous thin film 21 and the material of the p-type amorphous thin film 22 is arbitrary, but the i-type amorphous thin film 21 is made of i-type a-Si, and the p-type amorphous A combination in which the thin film 22 is made of p-type a-Si is preferable.
  • the amorphous thin film 2 may be composed of a p-type amorphous thin film 23 (see FIG. 3B).
  • the p-type amorphous thin film 23 is disposed along the light incident side concavo-convex structure TX1 of the n-type single crystal silicon substrate 1, and has a concavo-convex structure TX2 on the light incident side surface.
  • the p-type amorphous thin film 23 is made of the same material as the p-type amorphous thin film 22 described above, and contains B having a concentration of 1 ⁇ 10 17 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 as a p-type dopant. .
  • the p-type amorphous thin film 23 has a thickness of 1 to 200 nm.
  • the B concentration may gradually increase from the interface between the n-type single crystal silicon substrate 1 and the p-type amorphous thin film 23 toward the transparent conductive film 3.
  • the passivation effect of the surface of the n-type single crystal silicon substrate 1 by the p-type amorphous thin film 23 is further increased, and carriers (electrons) at the interface between the n-type single crystal silicon substrate 1 and the p-type amorphous thin film 23 are increased. And hole) recombination can be further reduced.
  • the amorphous thin film 2 includes at least a p-type amorphous thin film (p-type amorphous thin film 22 or p-type amorphous thin film 23).
  • the photoelectric conversion device 10 has a structure in which the amorphous thin film 2 is provided in contact with the surface of the n-type single crystal silicon substrate 1 on which the concavo-convex structure TX1 is formed, the concavo-convex structure of the n-type single crystal silicon substrate 1 is provided.
  • the surface on which TX1 is formed is passivated by the amorphous thin film 2.
  • the i-type amorphous thin film 21 has a greater passivation effect on the surface of the n-type single crystal silicon substrate 1 than the p-type amorphous thin films 22 and 23.
  • the amorphous thin film 2 with the i-type amorphous thin film 21 and the p-type amorphous thin film 22, carriers (electrons and electrons) at the interface between the n-type single crystal silicon substrate 1 and the amorphous thin film 2 are formed. Hole recombination can be further reduced.
  • the photoelectric conversion device 10 When the amorphous thin film 2 includes the i-type amorphous thin film 21 and the p-type amorphous thin film 22, the photoelectric conversion device 10 has a pin junction, and the amorphous thin film 2 is a p-type amorphous thin film 23. When it consists of, the photoelectric conversion apparatus 10 has a pn junction.
  • the photoelectric conversion device 10 generates power.
  • the i-type amorphous thin film 21 is made of an i-type amorphous thin film containing a group IV element
  • each of the p-type amorphous thin films 22 and 23 is a p-type amorphous film containing a group IV element.
  • the amorphous thin film 2 is made of an amorphous thin film containing a group IV element.
  • the amorphous thin film 2 has a passivation effect on the surface of the n-type single crystal silicon substrate 1 and forms a pn junction or a pin junction with the n-type single crystal silicon substrate 1.
  • the amorphous thin film 2 reduces the light reflectance on the light incident side of the photoelectric conversion device 10 together with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1.
  • 4 to 6 are first to third process diagrams showing a method for manufacturing the photoelectric conversion device 10 shown in FIG. 1, respectively.
  • the amorphous thin film 2 is made of i-type amorphous silicon (i-type a-Si) and p-type amorphous silicon (p-type a-Si).
  • i-type a-Si i-type amorphous silicon
  • p-type a-Si p-type amorphous silicon
  • n-type single crystal silicon substrate 30 is ultrasonically cleaned using alcohol, and then cleaned with pure water. Then, the n-type single crystal silicon substrate 30 is washed with hydrofluoric acid (HF) to remove the natural oxide film, and the surface of the n-type single crystal silicon substrate 30 is terminated with hydrogen (step (a)).
  • HF hydrofluoric acid
  • the n-type single crystal silicon substrate 30 has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 to 300 ⁇ m.
  • a passivation film 20 made of SiO2 is formed on the back surface of the n-type single crystal silicon substrate 30 by sputtering (step (b)).
  • the surface of the n-type single crystal silicon substrate 30 is chemically anisotropically etched using alkali to form the concavo-convex structure TX1 on the surface of the n-type single crystal silicon 30 (step (c)). Thereby, n-type single crystal silicon substrate 1 is formed. Thereafter, as described above, the natural oxide film is removed using HF, and the surface of the n-type single crystal silicon substrate 1 is terminated with hydrogen.
  • i-type amorphous silicon (i-type a-Si) and p-type amorphous silicon (p-type a-Si) are removed by plasma CVD (Chemical Vapor Deposition).
  • the n-type single crystal silicon substrate 1 is sequentially deposited on the uneven structure TX1.
  • the i-type amorphous thin film 21 and the p-type amorphous thin film 24 are sequentially deposited on the n-type single crystal silicon substrate 1 (step (d)).
  • i-type amorphous silicon is formed using, for example, silane (SiH 4 ) gas and hydrogen (H 2 ) gas
  • p-type amorphous silicon is formed using, for example, SiH 4 gas, H 2 gas, and It is formed using diborane (B 2 H 6 ) gas.
  • [H 2 gas flow rate] / [H 2 gas flow rate + SiH 4 gas flow rate + B 2 H 6 gas flow rate] is 0.2 or less.
  • the flow rate of SiH 4 gas, the flow rate of H 2 gas, and the flow rate of B 2 H 6 gas are determined.
  • the i-type amorphous silicon and the p-type amorphous silicon cover the concavo-convex structure TX1. It is uniformly formed on the concavo-convex structure TX1.
  • the temperature of the sample is raised to a temperature not lower than the boiling point of the etching gas, and the etching gas is sprayed on the surface of the p-type amorphous thin film 24 under a pressure of 300 KPa or lower. Then, the surface of the p-type amorphous thin film 24 is etched (step (e)).
  • the etching gas is made of a gas containing fluorine atoms such as ClF 3 , XeF 2 , BrF 3 , BrF 5 and NF 3 .
  • a gas containing fluorine atoms By using a gas containing fluorine atoms, a fluoride of silicon is formed on the surface of the p-type amorphous thin film 24, and the surface of the p-type amorphous thin film 24 can be etched.
  • the etching gas may contain a gas containing oxygen atoms in the molecule.
  • the gas containing oxygen atoms in the molecule includes, for example, O 2 , carbon dioxide (CO 2 ), nitrogen dioxide (NO 2 ), and the like.
  • a gas containing oxygen atoms By using a gas containing oxygen atoms, a region that is easily etched (Si—Si) and a region that is difficult to etch (Si—O) can be formed, and a concavo-convex structure can be formed by a difference in etching rate between the regions.
  • the etching gas may contain an inert gas.
  • the inert gas includes, for example, nitrogen (N 2 ) gas, argon (Ar) gas, helium (He) gas, and the like, and generally includes a gas that does not react with silicon.
  • N 2 nitrogen
  • Ar argon
  • He helium
  • an inert gas is used.
  • step (e) After step (e) is completed, a p-type amorphous thin film 22 (p-type a-Si) having a concavo-convex structure TX2 formed on the surface on the light incident side is formed (step (f)). Thereby, the amorphous thin film 2 is formed along the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1.
  • the transparent conductive film 3 made of ITO is deposited on the p-type amorphous thin film 22 by sputtering (step (g)).
  • step (g) an Ag paste is applied by screen printing, and the applied Ag paste is baked to form electrode 4 on transparent conductive film 3 (step (h)).
  • the passivation film 20 is patterned by photolithography and etching to form a through hole in the passivation film 20. Thereby, the passivation film 5 is formed (step (i)).
  • step (j) Al is deposited so as to cover the passivation film 5 to form an electrode 6. Thereby, the photoelectric conversion device 10 is completed (step (j)).
  • the photoelectric conversion device 10 is manufactured using a low temperature process such as a plasma CVD method and sputtering, it is possible to suppress the occurrence of thermal strain in the n-type single crystal silicon substrate 1. As a result, the lifetime of carriers in the n-type single crystal silicon substrate 1 can be extended.
  • the method for manufacturing the photoelectric conversion device 10 will be described by taking the case where the amorphous thin film 2 is composed of the i-type amorphous thin film 21 and the p-type amorphous thin film 22 as an example.
  • the photoelectric conversion device 10 performs the step (d) shown in FIG.
  • the process (e) shown in FIG. 5 is manufactured according to a process diagram in which a process of etching p-type amorphous silicon with an etching gas is replaced.
  • the photoelectric conversion device 10 is It is manufactured according to the process chart shown in FIGS.
  • the i-type amorphous thin film 21 is made of i-type a-SiGe, SiH 4 gas, germane (GeH 4 ) gas, and H 2 gas are used, and the i-type amorphous thin film 21 is i-type a-Ge.
  • GeH 4 gas and H 2 gas are used, and when the i-type amorphous thin film 21 is made of i-type a-SiC, SiH 4 gas, methane (CH 4 ) gas and H 2 gas are used, When the i-type amorphous thin film 21 is made of i-type a-SiN, SiH 4 gas, ammonia (NH 3 ) gas, and H 2 gas are used, and the i-type amorphous thin film 21 is made of i-type a-SiO.
  • i-type amorphous thin film 21 is made of i-type a-SiCO, SiH 4 gas, CH 4 gas, O 2 gas and H 2 gas are Used.
  • the p-type amorphous thin films 22 and 23 are made of p-type a-SiGe, SiH 4 gas, GeH 4 gas, B 2 H 6 gas, and H 2 gas are used.
  • 23 is made of p-type a-Ge, GeH 4 gas, B 2 H 6 gas and H 2 gas are used.
  • SiH 4 gas is used.
  • CH 4 gas, B 2 H 6 gas and H 2 gas are used, and when the p-type amorphous thin films 22 and 23 are made of p-type a-SiN, SiH 4 gas, NH 3 gas, B 2 H 6 gas are used.
  • p-type amorphous thin films 22 and 23 are made of p-type a-SiO, SiH 4 gas, O 2 gas, B 2 H 6 gas and H 2 gas are used. If the amorphous thin film 22 is made of p-type a-SiCO, SiH Gas, CH 4 gas, O 2 gas, B 2 H 6 gas and H 2 gas is used.
  • FIG. 7 is a schematic diagram showing a configuration of another photoelectric conversion device according to the first embodiment.
  • the photoelectric conversion device according to Embodiment 1 may be a photoelectric conversion device 10A illustrated in FIG.
  • photoelectric conversion device 10 ⁇ / b> A is obtained by replacing passivation film 5 and electrode 6 of photoelectric conversion device 10 shown in FIG. 1 with amorphous thin film 7 and electrode 8, and the others are photoelectric conversion devices. 10 is the same.
  • the amorphous thin film 7 is disposed in contact with the back surface of the n-type single crystal silicon substrate 1.
  • the electrode 8 is disposed in contact with the amorphous thin film 7.
  • the electrode 8 is made of, for example, Al.
  • FIG. 8 is a schematic diagram showing the configuration of the amorphous thin film 7 shown in FIG.
  • amorphous thin film 7 includes an i-type amorphous thin film 71 and an n-type amorphous thin film 72 (see (a)).
  • the i-type amorphous thin film 71 is made of the same material as the i-type amorphous thin film 21 described above.
  • the i-type amorphous thin film 71 has a thickness of 10 to 20 nm.
  • the n-type amorphous thin film 72 is disposed in contact with the i-type amorphous thin film 71.
  • the n-type amorphous thin film 72 is one of n-type a-SiGe, n-type a-Ge, n-type a-SiC, n-type a-SiN, n-type a-SiO, and n-type a-SiCO. Generally, it consists of an n-type amorphous thin film containing a group IV element.
  • the n-type amorphous thin film 72 has a thickness of 10 to 20 nm. Further, the n-type amorphous thin film 72 contains phosphorus (P) as an n-type dopant, and the P concentration is, for example, 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 .
  • the combination of the material of the i-type amorphous thin film 71 and the material of the n-type amorphous thin film 72 is arbitrary, but the i-type amorphous thin film 71 is made of i-type a-Si, and the n-type amorphous thin film 71 A combination in which the thin film 72 is made of n-type a-Si is preferable.
  • the amorphous thin film 7 may be composed of an n-type amorphous thin film 73 (see FIG. 8B).
  • N-type amorphous thin film 73 is disposed in contact with the back surface of n-type single crystal silicon substrate 1.
  • the n-type amorphous thin film 73 is made of the same material as that of the n-type amorphous thin film 72, and has a concentration of 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 as an n-type dopant. Including.
  • the n-type amorphous thin film 73 has a thickness of 20 to 40 nm.
  • the amorphous thin film 7 includes at least an n-type amorphous thin film (n-type amorphous thin film 72 or n-type amorphous thin film 73).
  • the photoelectric conversion device 10A is provided with an amorphous thin film 2 in contact with the surface of the n-type single crystal silicon substrate 1 on which the concavo-convex structure TX1 is formed, and is in contact with the back surface of the n-type single crystal silicon substrate 1 to be amorphous. Since the thin film 7 is provided, the surface of the n-type single crystal silicon substrate 1 on which the concavo-convex structure TX1 is formed is passivated by the amorphous thin film 2, and the back surface of the n-type single crystal silicon substrate 1 is amorphous. Passivated by the thin film 7.
  • the i-type amorphous thin film 71 has a greater passivation effect on the back surface of the n-type single crystal silicon substrate 1 than the n-type amorphous thin films 72 and 73.
  • amorphous thin film 7 by forming the amorphous thin film 7 by the i-type amorphous thin film 71 and the n-type amorphous thin film 72, carriers (electrons and electrons) at the interface between the n-type single crystal silicon substrate 1 and the amorphous thin film 7 are formed. Hole recombination can be further reduced.
  • the photoelectric conversion device 10A has a structure in which the amorphous thin films 2 and 7 are arranged on the light incident side and the back surface side of the n-type single crystal silicon substrate 1, respectively, when the photoelectric conversion device 10A is manufactured, the n-type Thermal strain applied to the single crystal silicon substrate 1 becomes uniform in the thickness direction, and warpage of the n-type single crystal silicon substrate 1 can be suppressed.
  • the same effect as that in the photoelectric conversion device 10 can be obtained.
  • 9 to 11 are first to third process diagrams showing a method for manufacturing the photoelectric conversion device 10A shown in FIG. 7, respectively.
  • the amorphous thin film 2 is made of i-type amorphous silicon and p-type amorphous silicon
  • the amorphous thin film 7 is made of i-type amorphous silicon and n.
  • a method for manufacturing the photoelectric conversion device 10A will be described by taking as an example the case of a type amorphous silicon.
  • process (a) shown in FIG. 4 when manufacturing of photoelectric conversion device 10A is started, the same process as process (a) shown in FIG. 4 is performed, and n-type single crystal silicon substrate 30 is cleaned (process (a)). ).
  • Step (c) Thereafter, the same process as the process (d) shown in FIG. 4 is performed, and the i-type amorphous thin film 21 and the p-type amorphous thin film 24 are sequentially laminated along the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1. (Step (c)).
  • i-type amorphous silicon and n-type amorphous silicon are sequentially stacked on the back surface of the n-type single crystal silicon substrate 1 by plasma CVD.
  • the i-type amorphous thin film 71 and the n-type amorphous thin film 72 are sequentially deposited on the back surface of the n-type single crystal silicon substrate 1 (step (d)).
  • i-type amorphous silicon is formed using, for example, SiH 4 gas and H 2 gas
  • n-type amorphous silicon is formed using, for example, SiH 4 gas, H 2 gas, and phosphine (PH 3 ) gas. It is formed using.
  • step (d) the same step as step (e) shown in FIG. 5 is performed to etch the surface of p-type amorphous thin film 24 to form concavo-convex structure TX2 (step) (E)).
  • step (f) the amorphous thin film 2 composed of the i-type amorphous thin film 21 and the p-type amorphous thin film 22 is formed (step (f)).
  • the transparent conductive film 3 made of ITO is formed on the p-type amorphous thin film 22 in contact with the p-type amorphous thin film 22 by sputtering (step (g)).
  • step (g) an Ag paste is applied by screen printing, and the applied Ag paste is baked to form electrode 4 on transparent conductive film 3. Further, Al is vapor-deposited on the n-type amorphous thin film 72 to form the electrode 8. Thus, the photoelectric conversion device 10A is completed (step (h)).
  • the photoelectric conversion device 10A is manufactured by forming the amorphous thin films 2 and 7 on both surfaces of the n-type single crystal silicon substrate 1 by the plasma CVD method, respectively.
  • the thermal strain applied to the n-type single crystal silicon substrate 1 from the thickness direction becomes uniform, and the warpage of the n-type single crystal silicon substrate 1 can be suppressed.
  • the amorphous thin film 2 is composed of an i-type amorphous thin film 21 and a p-type amorphous thin film 22, and the amorphous thin film 7 is an i-type amorphous thin film 71.
  • the method for manufacturing the photoelectric conversion device 10A has been described by taking the case of the n-type amorphous thin film 72 as an example.
  • the amorphous thin film 2 is made of the p-type amorphous thin film 23 and the amorphous thin film 7 is n 9A, the photoelectric conversion device 10A performs the step (c) shown in FIG.
  • step (d) shown in FIG. 9 is replaced with the step of depositing the n-type amorphous thin film 73 on the back surface of the n-type single crystal silicon substrate 1 by plasma CVD.
  • step (e) the p-type amorphous thin film 23 is etched with an etching gas. It is prepared according to process diagram instead etching to process.
  • the photoelectric conversion device 10A is It is manufactured according to the process chart shown in FIGS.
  • the i-type amorphous thin film 71 is made of any of i-type a-SiGe, i-type a-Ge, i-type a-SiC, i-type a-SiN, i-type a-SiO, and i-type a-SiCO.
  • the material gas is as described above.
  • n-type amorphous thin films 72 and 73 are made of n-type a-SiGe, SiH 4 gas, GeH 4 gas, PH 3 gas and H 2 gas are used, and the n-type amorphous thin films 72 and 73 are When n-type a-Ge is used, GeH 4 gas, PH 3 gas and H 2 gas are used. When the n-type amorphous thin films 72 and 73 are made of n-type a-SiC, SiH 4 gas and CH 4 gas are used.
  • n-type amorphous thin films 72 and 73 are made of n-type a-SiN, SiH 4 gas, NH 3 gas, PH 3 gas and H 2 gas are used, and when the n-type amorphous thin films 72 and 73 are made of n-type a-SiO, SiH 4 gas, O 2 gas, PH 3 gas, and H 2 gas are used, and the n-type amorphous thin films 72 and 73 are n-type. If it made of a-SiCO, SiH 4 gas, CH 4 gas , O 2 gas, PH 3 gas and H 2 gas is used.
  • FIG. 12 is a schematic diagram showing a configuration of still another photoelectric conversion device according to the first embodiment.
  • the photoelectric conversion device according to Embodiment 1 may be a photoelectric conversion device 10B illustrated in FIG.
  • photoelectric conversion device 10 ⁇ / b> B is obtained by replacing n-type single crystal silicon substrate 1 with n-type single crystal silicon substrate 11 and replacing electrode 4 with electrode 9 in photoelectric conversion device 10 shown in FIG. 1. Others are the same as the photoelectric conversion device 10.
  • the n-type single crystal silicon substrate 11 has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 ⁇ m to 300 ⁇ m.
  • the n-type single crystal silicon substrate 11 has a concavo-convex structure TX3 provided on the surface on the light incident side and a flat surface FT1 provided on a portion facing the electrode 9 on the surface on the light incident side.
  • the uneven structure TX3 has the same uneven size as the uneven structure TX1 shown in FIG.
  • the electrode 9 is disposed in contact with the flat surface FT2 of the transparent conductive film 3 facing the flat surface FT1.
  • the amorphous thin film 2 is disposed in contact with the concavo-convex structure TX3 and the flat surface FT1 of the n-type single crystal silicon substrate 11, and has the concavo-convex structure TX2 on the surface on the light incident side.
  • the transparent conductive film 3 is disposed along the uneven structure TX3 and the flat surface FT1 of the n-type single crystal silicon substrate 11, and faces the flat surface FT1 among the surfaces on the light incident side.
  • a part has a flat surface FT2.
  • the amorphous thin film 2 is in contact with the n-type single crystal silicon substrate 11 on the flat surface FT1 below the electrode 9.
  • the contact area between the amorphous thin film 2 and the n-type single crystal silicon substrate 11 decreases below the electrode 9. Therefore, recombination of carriers (electrons and holes) at the interface between the amorphous thin film 2 and the n-type single crystal silicon substrate 11 can be further reduced as compared with the case where the n-type single crystal silicon substrate 1 is used.
  • the same effects as the photoelectric conversion device 10 can be obtained.
  • the photoelectric conversion device 10B performs the step (c) shown in FIG. 4 in the process diagrams shown in FIGS. 4 to 6 with the n-type facing the electrode 9 on the light incident surface of the n-type single crystal silicon substrate 11.
  • a portion of the single crystal silicon substrate 11 is covered with a resist, and the light incident side surface not covered with the resist is manufactured according to a process diagram in place of etching with alkali.
  • the photoelectric conversion device according to Embodiment 1 may be the one in which the same change as the change from the photoelectric conversion device 10 to the photoelectric conversion device 10B is applied to the photoelectric conversion device 10A.
  • the photoelectric conversion device performs step (b) shown in FIG. 9 in the process diagrams shown in FIGS. 9 to 11 to face the electrode 9 on the light incident side surface of the n-type single crystal silicon substrate 11.
  • a part of n-type single crystal silicon substrate 11 is covered with a resist, and the light incident side surface not covered with the resist is manufactured according to a process diagram in place of etching with alkali.
  • this photoelectric conversion device similarly to the photoelectric conversion device 10B, carriers (electrons and electrons) at the interface between the amorphous thin film 2 and the n-type single crystal silicon substrate 11 are used as compared with the case where the n-type single crystal silicon substrate 1 is used. Hole recombination can be further reduced.
  • the photoelectric conversion device according to Embodiment 1 may be one in which n-type single crystal silicon substrates 1 and 11 are replaced with n-type polycrystalline silicon substrates.
  • the surface on the light incident side of the n-type polycrystalline silicon substrate is roughened by dry etching.
  • a photoelectric conversion apparatus provided with an n-type polycrystalline silicon substrate is manufactured according to the same manufacturing method as any manufacturing method of the photoelectric conversion apparatuses 10, 10A, and 10B mentioned above.
  • the photoelectric conversion device according to Embodiment 1 is obtained by replacing the n-type single crystal silicon substrates 1 and 11 of the photoelectric conversion devices 10, 10A, and 10B with a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate. May be.
  • the p-type single crystal silicon substrate has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 ⁇ m to 300 ⁇ m.
  • the p-type polycrystalline silicon substrate has a specific resistance of 0.1 to 10 ⁇ cm and a thickness of 100 ⁇ m to 300 ⁇ m, and the surface on the light incident side is roughened by dry etching.
  • the amorphous thin film 2 is made of an i-type amorphous thin film and an n-type amorphous thin film, or an n-type amorphous thin film. Specific examples of the i-type amorphous thin film and the n-type amorphous thin film are as described above.
  • the amorphous thin film 7 is composed of an i-type amorphous thin film and a p-type amorphous thin film, or a p-type amorphous thin film. Specific examples of the i-type amorphous thin film and the p-type amorphous thin film are as described above.
  • a photoelectric conversion device including a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate is obtained by converting an n-type amorphous thin film into a p-type amorphous film in any of the manufacturing methods of the photoelectric conversion devices 10, 10A, and 10B described above. It is manufactured according to a manufacturing method in which a p-type amorphous thin film is replaced with an n-type amorphous thin film.
  • the photoelectric conversion device is disposed in contact with the first concavo-convex structure, the crystalline silicon substrate provided with the first concavo-convex structure having the first concavo-convex size on the surface on the light incident side,
  • a second concavo-convex structure having a second concavo-convex size smaller than the first concavo-convex size is provided with an amorphous thin film provided on the light incident side surface, and a pn junction is formed by the amorphous thin film and the crystalline silicon substrate. Or what is necessary is just to form a pin junction.
  • FIG. 13 is a schematic diagram illustrating the configuration of the photoelectric conversion apparatus according to the second embodiment.
  • photoelectric conversion device 100 according to Embodiment 2 replaces n-type single crystal silicon substrate 1 of photoelectric conversion device 10 shown in FIG. Is replaced with the amorphous thin film 102, the electrode 4 is replaced with the electrode 104, and the rest is the same as the photoelectric conversion device 10.
  • the n-type single crystal silicon substrate 101 has a p-type diffusion region 101p on the light incident side.
  • the p-type diffusion region 101p has a diffusion depth of 0.01 ⁇ m to 0.1 ⁇ m, for example, and is disposed in contact with the concavo-convex structure TX1.
  • the p-type diffusion region 101p contains B as a p-type dopant, and the concentration of B is, for example, 10 17 cm ⁇ 3 to 10 18 cm ⁇ 3 .
  • the n-type single crystal silicon substrate 101 includes the bulk region 101b having the n-type conductivity and the p-type diffusion region 101p having the p-type conductivity, and has a built-in pn junction on the light incident side. .
  • n-type single crystal silicon substrate 101 The other description of the n-type single crystal silicon substrate 101 is the same as the description of the n-type single crystal silicon substrate 1.
  • the amorphous thin film 102 is disposed on the p-type diffusion region 101p in contact with the p-type diffusion region 101p of the n-type single crystal silicon substrate 101.
  • the amorphous thin film 102 has a concavo-convex structure TX2 on the light incident side surface.
  • the electrode 104 is made of Ag, for example.
  • the electrode 104 penetrates the transparent conductive film 3 and the amorphous thin film 102 and is disposed in contact with a part of the p-type diffusion region 101 p of the n-type single crystal silicon substrate 101.
  • the transparent conductive film 3 is disposed on the amorphous thin film 102 in contact with the amorphous thin film 102.
  • FIG. 14 is a schematic diagram showing the configuration of the amorphous thin film 102 shown in FIG. Referring to FIG. 14, amorphous thin film 102 is composed of any one of amorphous thin films 102A to 102E.
  • the amorphous thin film 102A includes an i-type amorphous thin film 102i and a p-type amorphous thin film 102p (see (a)).
  • the i-type amorphous thin film 102i is disposed in contact with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 101.
  • the i-type amorphous thin film 102i has a thickness of 10 to 20 nm, for example.
  • the p-type amorphous thin film 102p is disposed on the i-type amorphous thin film 102i in contact with the i-type amorphous thin film 102i, and has a concavo-convex structure TX2 on the surface on the light incident side.
  • the p-type amorphous thin film 102p has a thickness of 1 to 200 nm.
  • the p-type amorphous thin film 102p has an arbitrary B concentration.
  • the i-type amorphous thin film 102i is made of the same material as the i-type amorphous thin film 21 described above.
  • the p-type amorphous thin film 102p is made of the same material as the p-type amorphous thin film 22 described above.
  • the material combination of the i-type amorphous thin film 102i and the p-type amorphous thin film 102p is arbitrary, but the i-type amorphous thin film 102i is made of i-type a-Si, and the p-type amorphous A combination in which the thin film 102p is made of p-type a-Si is preferable.
  • the amorphous thin film 102B is made of an i-type amorphous thin film 103i (see FIG. 14B).
  • the i-type amorphous thin film 103i is disposed in contact with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 101, and has the concavo-convex structure TX2 on the light incident side surface.
  • the i-type amorphous thin film 103i has a thickness of 1 to 200 nm, for example.
  • the i-type amorphous thin film 103i is made of the same material as the i-type amorphous thin film 21 described above.
  • the amorphous thin film 102C is composed of a p-type amorphous thin film 103p (see FIG. 14C).
  • the p-type amorphous thin film 103p is disposed in contact with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 101, and has the concavo-convex structure TX2 on the light incident side surface.
  • the p-type amorphous thin film 103p has a thickness of 1 to 200 nm, for example.
  • the p-type amorphous thin film 103p is made of the same material as the p-type amorphous thin film 22 described above.
  • the amorphous thin film 102D includes an i-type amorphous thin film 102i and an n-type amorphous thin film 102n (see FIG. 14D).
  • the n-type amorphous thin film 102n is disposed on the i-type amorphous thin film 102i in contact with the i-type amorphous thin film 102i, and has a concavo-convex structure TX2 on the light incident side surface.
  • the n-type amorphous thin film 102n has a thickness of 1 to 200 nm and an arbitrary P concentration, for example.
  • the n-type amorphous thin film 102n is made of the same material as the n-type amorphous thin film 72 described above.
  • the material combination of the i-type amorphous thin film 102i and the n-type amorphous thin film 102n is arbitrary, but the i-type amorphous thin film 102i is made of i-type a-Si, and the n-type amorphous thin film 102i A combination in which the thin film 102n is made of n-type a-Si is preferable.
  • the amorphous thin film 102E is composed of an n-type amorphous thin film 103n (see (e) of FIG. 14).
  • the n-type amorphous thin film 103n is disposed in contact with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 101, and has the concavo-convex structure TX2 on the light incident side surface.
  • the n-type amorphous thin film 103n has a thickness of 1 to 200 nm, for example.
  • the n-type amorphous thin film 103n is made of the same material as the n-type amorphous thin film 72 described above.
  • the amorphous thin film 102 does not form a junction, the reflectance of the light is reduced on the light incident side, and the passivation effect on the surface of the n-type single crystal silicon substrate 101 on the light incident side. Therefore, it is made of the various materials described above.
  • 15 to 17 are first to third process diagrams showing a method for manufacturing the photoelectric conversion device 100 shown in FIG. 13, respectively.
  • the amorphous thin film 102 is composed of an i-type amorphous thin film 102i (i-type a-Si) and a p-type amorphous thin film 102p (p-type a-Si).
  • i-type a-Si i-type a-Si
  • p-type amorphous thin film 102p p-type a-Si
  • step (a) to step (c) when manufacturing of photoelectric conversion device 100 is started, the same steps as steps (a) to (c) shown in FIG. 4 are performed, and an n-type single crystal having passivation film 20 on the back surface.
  • the silicon substrate 1 is manufactured (step (a) to step (c)).
  • step (c) B is diffused from the surface side of the n-type single crystal silicon substrate 1 where the concavo-convex structure TX1 is formed, so that the p-type diffusion region 101p becomes the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1.
  • step (d) Form in contact (step (d)). Thereby, an n-type single crystal silicon substrate 101 is manufactured.
  • the diffusion of B in the step (d) is performed, for example, by depositing a BSG (B-doped Silicate Glass) film on the n-type single crystal silicon substrate 1 by an APCVD (Atmospheric Chemical Vapor Deposition) method as a B source.
  • the deposited BSG film is heat-treated at a temperature of about 800 ° C. in a nitrogen gas atmosphere, and then the BSG film is removed.
  • the material gas is as described above.
  • step (e) the same step as step (e) shown in FIG. 5 is performed to etch the light incident side surface of p-type amorphous thin film 104p (step (f)).
  • step (f) the same step as step (e) shown in FIG. 5 is performed to etch the light incident side surface of p-type amorphous thin film 104p (step (f)).
  • step (g) the same step as step (e) shown in FIG. 5 is performed to etch the light incident side surface of p-type amorphous thin film 104p (step (f)).
  • step (g) the same step as step (e) shown in FIG. 5 is performed to etch the light incident side surface of p-type amorphous thin film 104p (step (f)).
  • step (g) the same step as step (e) shown in FIG. 5 is performed to etch the light incident side surface of p-type amorphous thin film 104p (step (f)).
  • step (g) the same step as step
  • the transparent conductive film 3 is deposited on the amorphous thin film 102 by a sputtering method (step (h)).
  • a part of the transparent conductive film 3 and the amorphous thin film 102 is etched at a desired interval using photolithography and etching to expose a part of the n-type single crystal silicon substrate 101 (step (i)).
  • step (i) Ag paste is applied to the exposed portion of n-type single crystal silicon substrate 101, and the applied Ag paste is baked. As a result, the electrode 104 is formed (step (j)).
  • steps (i) and (j) shown in FIG. 6 are sequentially performed to complete the photoelectric conversion device 100 (steps (k) and (l)).
  • the photoelectric conversion device 100 is shown in FIG. It is manufactured according to the process diagram shown in FIG.
  • the i-type amorphous thin films 102i and 103i are made of a material other than i-type a-Si, and the p-type amorphous thin films 102p and 103p are made of a material other than p-type a-Si. Even when 102n and 103n are made of a material other than n-type a-Si, the photoelectric conversion device 100 is manufactured according to the process diagrams shown in FIGS.
  • the material gases for depositing the i-type amorphous thin films 102i and 103i, the p-type amorphous thin films 102p and 103p, and the n-type amorphous thin films 102n and 103n are as described above.
  • the photoelectric conversion device 100 is disposed in contact with the light incident side surface of the n type single crystal silicon substrate 101, the n type single crystal silicon substrate 101 having the concavo-convex structure TX1 on the light incident side surface, and the light incident side surface. Is provided with the amorphous thin film 102 having the concavo-convex structure TX2, so that the reflectance of light on the surface on the light incident side can be lowered and the surface on the light incident side of the n-type single crystal silicon substrate 101 is passivated to form an n-type. Recombination of carriers (electrons and holes) at the interface between the single crystal silicon substrate 101 and the amorphous thin film 102 can be reduced.
  • the photoexcited holes reach the electrode 104 through the p-type diffusion region 101p, so that the amorphous thin film 102 is more conductive than conducting the photoexcited holes to the electrode 104. This also contributes to a reduction in hole recombination and a reduction in light reflectance at the interface with the p-type diffusion region 101p.
  • the amorphous thin film 102 is composed of any one of the amorphous thin films 102A, 102B, and 102D. This is because the i-type amorphous thin films 102i and 103i have a greater passivation effect on the surface of the n-type single crystal silicon substrate 101 than the p-type amorphous thin film 103p and the n-type amorphous thin film 103n containing the dopant. In view of the passivation effect, the simplification of the manufacturing process, and the reduction of the material cost, it is most preferable that the amorphous thin film 102 is constituted only by the i-type amorphous thin film 103i.
  • the dopant concentration is relatively 10 16 cm ⁇ 3 to 10 17 cm ⁇ 3. It is preferable to set it low. By reducing the dopant concentration, the defect density at the interface between the amorphous thin film 102 and the p-type diffusion region 101p of the n-type single crystal silicon substrate 101 can be reduced, and at the interface between the amorphous thin film 102 and the p-type diffusion region 101p. This is because recombination can be reduced.
  • the dopant concentration in the amorphous thin film 102 is gradually increased from the n-type single crystal silicon substrate 101 toward the transparent conductive film 3. May be.
  • FIG. 18 is a schematic diagram showing a configuration of another photoelectric conversion apparatus according to the second embodiment.
  • the photoelectric conversion device according to Embodiment 2 may be a photoelectric conversion device 100A illustrated in FIG.
  • a photoelectric conversion device 100A is obtained by replacing n-type single crystal silicon substrate 101 with n-type single crystal silicon substrate 111 and replacing electrode 104 with electrode 114 in photoelectric conversion device 100 shown in FIG. 13. Others are the same as those of the photoelectric conversion device 100.
  • the n-type single crystal silicon substrate 111 has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 ⁇ m to 300 ⁇ m.
  • the n-type single crystal silicon substrate 111 has a concavo-convex structure TX3 provided on the surface on the light incident side and a flat surface FT3 provided on a portion in contact with the electrode 114 on the surface on the light incident side.
  • the uneven structure TX3 has the same uneven size as the uneven structure TX1 shown in FIG.
  • the n-type single crystal silicon substrate 111 has a p-type diffusion region 111p on the light incident surface side.
  • the p-type diffusion region 111p is disposed in contact with the concavo-convex structure TX3 on the light incident side of the n-type single crystal silicon substrate 111.
  • the p-type diffusion region 111p has the same diffusion depth and B concentration as the p-type diffusion region 101p (see FIG. 13) of the photoelectric conversion device 100.
  • the n-type single crystal silicon substrate 111 includes a bulk region 111b having an n-type conductivity type and a p-type diffusion region 111p having a p-type conductivity type, and incorporates a pn junction on the light incident side.
  • the electrode 114 is made of Ag, for example. Electrode 114 penetrates transparent conductive film 3 and amorphous thin film 102, and is disposed in contact with flat surface FT3 of p-type diffusion region 111p of n-type single crystal silicon substrate 111.
  • the electrode 114 is in contact with the flat surface FT3 of the n-type single crystal silicon substrate 111, so that the contact area between the n-type single crystal silicon substrate 111 and the electrode 114 is smaller than that of the photoelectric conversion device 100. Therefore, recombination of minority carriers (holes) at the interface between the n-type single crystal silicon substrate 111 and the electrode 114 can be further reduced as compared with the photoelectric conversion device 100. In the photoelectric conversion device 100A, the same effects as the photoelectric conversion device 100 can be obtained.
  • the photoelectric conversion device 100A performs the step (c) shown in FIG. 15 in the process diagrams shown in FIGS. 15 to 17 in the n-type single crystal silicon substrate 111 on the light incident side surface n in contact with the electrode 114.
  • a portion of the single crystal silicon substrate 111 is covered with a resist, and the light incident side surface not covered with the resist is manufactured according to a process diagram in place of etching with alkali.
  • the photoelectric conversion devices 100 and 100A using the n-type single crystal silicon substrates 101 and 111 have been described.
  • the photoelectric conversion device according to the second embodiment is not limited to this.
  • the type single crystal silicon substrates 101 and 111 may be replaced with n-type polycrystalline silicon substrates.
  • the surface on the light incident side of the n-type polycrystalline silicon substrate is roughened by dry etching.
  • a photoelectric conversion apparatus provided with an n-type polycrystalline silicon substrate is manufactured according to the same manufacturing method as the manufacturing method of any of the photoelectric conversion apparatuses 100 and 100A described above.
  • the photoelectric conversion device according to the second embodiment may be one in which the n-type single crystal silicon substrates 101 and 111 of the photoelectric conversion devices 100 and 100A are replaced with a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate. Good.
  • the p-type single crystal silicon substrate has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 ⁇ m to 300 ⁇ m.
  • the p-type polycrystalline silicon substrate has a specific resistance of 0.1 to 10 ⁇ cm and a thickness of 100 ⁇ m to 300 ⁇ m, and the surface on the light incident side is roughened by dry etching.
  • a photoelectric conversion device including a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate is obtained by replacing the p-type diffusion region with an n-type diffusion region in any one of the manufacturing methods of the photoelectric conversion devices 100 and 100A described above. Manufactured according to.
  • the photoelectric conversion device includes various photoelectric conversion devices. Therefore, in the photoelectric conversion device according to the second embodiment, the first concavo-convex structure having the first concavo-convex size is provided on the surface on the light incident side, is provided in contact with the surface on the light incident side, and is a bulk region.
  • a crystalline silicon substrate including a diffusion region having a conductivity type opposite to that of the first conductive layer, a bulk region, and a first concavo-convex structure, and a second concavo-convex size smaller than the first concavo-convex size. What is necessary is just to provide the 2nd uneven structure with the amorphous thin film provided in the surface by the side of light incidence.
  • FIG. 19 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to the third embodiment.
  • photoelectric conversion device 200 according to Embodiment 3 deletes electrode 4 of photoelectric conversion device 10 shown in FIG. 1, replaces amorphous thin film 2 with amorphous thin film 102, and forms passivation film 5.
  • the electrode 6 is replaced with amorphous thin films 201 to 20n (n is an integer of 2 or more), 211 to 21n-1, electrodes 221 to 22n, 231 to 23n-1, and the others are the photoelectric conversion device 10 Is the same.
  • the amorphous thin film 102 is disposed in contact with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1, and has a concavo-convex structure TX2 on the surface on the light incident side.
  • the amorphous thin film 102 is composed of any one of the amorphous thin films 102A to 102E (see FIGS. 14A to 14E).
  • the amorphous thin film 102 has a thickness of 1 to 200 nm, for example.
  • the amorphous thin films 201 to 20n are in contact with the back surface of the n-type single crystal silicon substrate 1, and are alternately arranged with the amorphous thin films 211 to 21n-1 in the in-plane direction DR1 of the n-type single crystal silicon substrate 1. .
  • the amorphous thin films 211 to 21n-1 are in contact with the back surface of the n-type single crystal silicon substrate 1, and are alternately arranged with the amorphous thin films 201 to 20n in the in-plane direction DR1.
  • the electrodes 221 to 22n are disposed in contact with the amorphous thin films 201 to 20n, respectively.
  • the electrodes 231 to 23n-1 are disposed in contact with the amorphous thin films 211 to 21n-1, respectively.
  • Each of the electrodes 221 to 22n and 231 to 23n-1 is made of, for example, Al.
  • FIG. 20 is a schematic diagram showing the configuration of the amorphous thin film 201 shown in FIG. Referring to FIG. 20, the amorphous thin film 201 is composed of an amorphous thin film 201A or an amorphous thin film 201B.
  • the amorphous thin film 201A includes an i-type amorphous thin film 201i and an n-type amorphous thin film 201n (see FIG. 20A).
  • the i-type amorphous thin film 201 i is disposed in contact with the back surface of the n-type single crystal silicon substrate 1.
  • the i-type amorphous thin film 201i has a thickness of 10 to 20 nm, for example.
  • the i-type amorphous thin film 201i is made of the same material as the i-type amorphous thin film 21 described above.
  • the n-type amorphous thin film 201n is disposed in contact with the i-type amorphous thin film 201i.
  • the n-type amorphous thin film 201n has a thickness of 10 to 20 nm, for example.
  • the n-type amorphous thin film 201n has a P concentration of, for example, 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 .
  • the n-type amorphous thin film 201n is made of the same material as the n-type amorphous thin film 72 described above.
  • the combination of the material of the i-type amorphous thin film 201i and the material of the n-type amorphous thin film 201n is arbitrary, but the i-type amorphous thin film 201i is made of i-type a-Si, and the n-type amorphous thin film 201i A combination in which the thin film 201n is made of n-type a-Si is preferable.
  • the amorphous thin film 201B is composed of an n-type amorphous thin film 201n ′ (see FIG. 20B).
  • N-type amorphous thin film 201 n ′ is disposed in contact with the back surface of n-type single crystal silicon substrate 1.
  • the n-type amorphous thin film 201n ′ has a thickness of 20 to 40 nm, for example.
  • the n-type amorphous thin film 201n ′ has a P concentration of 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 , for example.
  • the n-type amorphous thin film 201n ′ is made of the same material as the n-type amorphous thin film 72 described above.
  • the amorphous thin film 201 includes at least an n-type amorphous thin film.
  • each of the amorphous thin films 202 to 20n shown in FIG. 19 is composed of either of the amorphous thin films 201A and 201B shown in FIG.
  • FIG. 21 is a schematic diagram showing a configuration of another amorphous thin film 211 shown in FIG. Referring to FIG. 21, amorphous thin film 211 includes amorphous thin film 211A or amorphous thin film 211B.
  • the amorphous thin film 211A includes an i-type amorphous thin film 211i and a p-type amorphous thin film 211p (see FIG. 21A).
  • the i-type amorphous thin film 211 i is disposed in contact with the back surface of the n-type single crystal silicon substrate 1.
  • the i-type amorphous thin film 211i has a thickness of 10 to 20 nm, for example.
  • the i-type amorphous thin film 211i is made of the same material as the i-type amorphous thin film 21 described above.
  • the p-type amorphous thin film 211p is disposed in contact with the i-type amorphous thin film 211i.
  • the p-type amorphous thin film 211p has a thickness of 10 to 20 nm, for example.
  • the p-type amorphous thin film 211p has a B concentration of, for example, 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 .
  • the p-type amorphous thin film 211p is made of the same material as the p-type amorphous thin film 22 described above.
  • the combination of the material of the i-type amorphous thin film 211i and the material of the p-type amorphous thin film 211p is arbitrary, but the i-type amorphous thin film 211i is made of i-type a-Si, and the p-type amorphous A combination in which the thin film 211p is made of p-type a-Si is preferable.
  • the amorphous thin film 211B is made of a p-type amorphous thin film 211p ′ (see FIG. 21B).
  • the p-type amorphous thin film 211p ′ is disposed in contact with the back surface of the n-type single crystal silicon substrate 1.
  • the p-type amorphous thin film 211p ′ has a thickness of 20 to 40 nm, for example.
  • the p-type amorphous thin film 211p ′ has a B concentration of, for example, 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 .
  • the p-type amorphous thin film 211p ′ is made of the same material as the p-type amorphous thin film 22 described above.
  • the amorphous thin film 211 includes at least a p-type amorphous thin film.
  • each of the amorphous thin films 212 to 21n-1 shown in FIG. 19 is composed of either of the amorphous thin films 211A and 211B shown in FIG.
  • the area occupancy ratio which is the ratio of the total area of the amorphous thin films 211 to 21n-1 to the area of the n-type single crystal silicon substrate 1 is 60 to 93%.
  • the area occupation ratio which is the ratio of the total area of the thin films 201 to 20n to the area of the n-type single crystal silicon substrate 1, is 5 to 20%.
  • the reason why the area occupancy of the amorphous thin films 211 to 21n-1 is larger than the area occupancy of the amorphous thin films 201 to 20n is that the photo-excited electrons in the n-type single crystal silicon substrate 1 and Holes are easily separated by a pn junction (amorphous thin film 211 to 21n-1 / n-type single crystal silicon substrate 1 including at least a p-type amorphous thin film), and power generation of photoexcited electrons and holes is facilitated. This is to increase the contribution rate.
  • incident light enters the n-type single crystal silicon substrate 1 from the transparent conductive film 3 side.
  • there is no electrode on the light incident side and there are two concavo-convex structures TX1 and TX2 having different concavo-convex sizes, so that the reflectance of light is reduced, and more incident light is n-type single crystal silicon. Incident on the substrate 1.
  • the photoexcited electrons reach the amorphous thin films 201 to 20n by diffusion, and reach the electrodes 221 to 22n through the amorphous thin films 201 to 20n.
  • the photoexcited electrons in the vicinity of the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1 cause the amorphous thin film 102 and the n-type single crystal silicon substrate 1 to pass through the surface of the n-type single crystal silicon substrate 1 by the passivation effect. It becomes difficult to recombine at the interface with the type single crystal silicon substrate 1, and it becomes easy to diffuse into the amorphous thin films 201 to 20n.
  • photoexcited holes reach the amorphous thin films 211 to 21n-1 by diffusion, and reach the electrodes 231 to 23n-1 through the amorphous thin films 211 to 21n-1.
  • holes photoexcited in the vicinity of the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1 are separated from the amorphous thin film 102 by the passivation effect of the surface of the n-type single crystal silicon substrate 1 by the amorphous thin film 102. It becomes difficult to recombine at the interface with the n-type single crystal silicon substrate 1, and it becomes easy to diffuse into the amorphous thin films 211 to 21n-1.
  • the photoelectric conversion device 200 is a back contact type photoelectric conversion device that extracts photoexcited carriers (electrons and holes) from the back surface.
  • the photoelectric conversion device 200 is arranged in contact with the n-type single crystal silicon substrate 1 on which the concavo-convex structure TX1 is formed, and the concavo-convex structure TX1, and has a non-convex structure TX2 formed on the surface on the light incident side. Since the crystalline thin film 102 is provided, the reflectivity for incident light can be reduced on the light incident side surface, and carriers at the interface between the amorphous thin film 102 and the concavo-convex structure TX1 of the n-type single crystal silicon substrate 1 can be reduced. Recombination of (electrons and holes) can be reduced.
  • 22 to 25 are first to fourth process diagrams showing a method for manufacturing the photoelectric conversion device 200 shown in FIG. 19, respectively.
  • the amorphous thin film 102 includes an i-type amorphous thin film 102i and an n-type amorphous thin film 102n (see FIG. 14D), and the amorphous thin films 201 to 20n.
  • a method for manufacturing the photoelectric conversion device 200 will be described by taking the case of the p-type amorphous thin film 211p (see FIG. 21A) as an example.
  • n-type single crystal silicon substrate 30 is cleaned (step (a)).
  • n-type single crystal silicon substrate 30 is anisotropically etched with alkali to form the concavo-convex structure TX1 (step (b)). Thereby, n-type single crystal silicon substrate 1 is formed.
  • a resist is applied to the entire surface of p-type amorphous thin film 240p, and the applied resist is patterned by photolithography to form a resist pattern 250 (step (step (2)). e)).
  • the p-type amorphous thin film 240p is etched using the resist pattern 250 as a mask to form n ⁇ 1 p-type amorphous thin films 201p (step (f)).
  • step (g) resist pattern 250 is removed. Then, the n-type amorphous thin film 260 is removed by lift-off. As a result, amorphous thin films 201 to 20n and amorphous thin films 211 to 21n-1 are formed on the back surface of n-type single crystal silicon substrate 1.
  • the transparent conductive film 3 is formed on the amorphous thin film 102 by a sputtering method (step (j)).
  • step (j) Al paste is applied onto amorphous thin films 201 to 20n and amorphous thin films 211 to 21n-1, and the applied Al paste is baked to form electrode 221. To 22n and 231 to 23n-1. Thereby, the photoelectric conversion device 200 is completed (step (k)).
  • the photoelectric conversion device 200 is shown in FIG. It is manufactured according to the process diagram shown in FIG.
  • the amorphous thin film 102 is made of the i-type amorphous thin film 103i shown in FIG. 14B, only the i-type amorphous thin film is deposited in step (c) shown in FIG.
  • the surface of the light incident side of the i-type amorphous thin film thus etched is etched in the step (h) shown in FIG.
  • the amorphous thin film 102 is composed of the p-type amorphous thin film 103p shown in FIG. 14C, only the p-type amorphous thin film is deposited in the step (c) shown in FIG. In the step (h) shown in FIG. 24, the surface on the light incident side of the p-type amorphous thin film thus etched is etched.
  • the amorphous thin film 102 is composed of the i-type amorphous thin film 102i / p-type amorphous thin film 102p shown in FIG. 14A
  • the step (c) shown in FIG. The thin film 102i and the p-type amorphous thin film are sequentially deposited, and the surface on the light incident side of the deposited p-type amorphous thin film is etched in step (h) shown in FIG.
  • the amorphous thin film 102 is composed of the n-type amorphous thin film 103n shown in FIG. 14E, only the n-type amorphous thin film is deposited in the step (c) shown in FIG. The surface of the light incident side of the n-type amorphous thin film thus etched is etched in the step (h) shown in FIG.
  • the photoelectric conversion device 200 is shown in FIGS. Manufactured according to the process diagram shown. In this case, the deposition of the i-type amorphous thin film is omitted in step (d) of FIG.
  • the amorphous thin films 201 to 20n are i-type amorphous thin films 201i / n-type amorphous thin films 201n, and the amorphous thin films 211 to 21n-1 are p-type amorphous thin films.
  • the thin film 211p ′ may consist of only the amorphous thin film 201-20n, which consists of only the n-type amorphous thin film 201n ′, and the amorphous thin film 211-21n-1 includes the i-type amorphous thin film 211i / p. It may consist of a type amorphous thin film 211p.
  • the photoelectric conversion device 200 is manufactured according to the process diagrams shown in FIGS.
  • both the i-type amorphous thin film 102i and the p-type amorphous thin film 104p are etched using the resist pattern 250 as a mask.
  • the amorphous thin films 201 to 20n are made of the i-type amorphous thin film 201i / n-type amorphous thin film 201n, and the amorphous thin films 211 to 21n-1 are made of only the p-type amorphous thin film 211p ′.
  • the i-type amorphous thin film 102 i and the n-type amorphous thin film 104 n are sequentially stacked.
  • the i-type amorphous film is formed using the resist pattern 250 as a mask. Both the thin film 102i and the n-type amorphous thin film 104n are etched, and a p-type amorphous thin film is deposited in step (g) of FIG.
  • the photoelectric conversion device 200 is shown in FIGS. Manufactured according to the process diagram.
  • the photoelectric conversion device 200 includes an amorphous thin film 102 on the light incident side of the n-type single crystal silicon substrate 1, and amorphous thin films 201 to 20n and an amorphous thin film 211 on the back side of the n-type single crystal silicon substrate 1. ⁇ 21n ⁇ 1, the strain applied to the n-type single crystal silicon substrate 1 in the manufacturing process is uniform in the thickness direction. Accordingly, warpage of the n-type single crystal silicon substrate 1 can be suppressed.
  • the photoelectric conversion device 200 is described as including the n-type single crystal silicon substrate 1, in Embodiment 3, the photoelectric conversion device 200 is not limited to this and includes the p-type single crystal silicon substrate. Also good.
  • the amorphous thin films 201 to 20n are i-type amorphous thin film / p-type amorphous thin film or p-type amorphous thin film
  • the amorphous thin films 211 to 21n-1 are i-type non-crystalline thin films. It consists of a crystalline thin film / n-type amorphous thin film or an n-type amorphous thin film.
  • the photoelectric conversion apparatus 200 is manufactured according to the process diagrams shown in FIGS. 22 to 25 even when the p-type single crystal silicon substrate is provided.
  • the amorphous thin film 102 is disposed in contact with the concavo-convex structure TX1 formed on the light incident side surface of the n-type single crystal silicon substrate or the p-type single crystal silicon substrate, and the light of the amorphous thin film 102 is Photoelectric conversion in which a concavo-convex structure TX2 is arranged on the surface on the incident side, and amorphous thin films 201 to 20n and 211 to 21n-1 for back contact are formed on the back surface of an n-type single crystal silicon substrate or a p-type single crystal silicon substrate The apparatus has been described.
  • the photoelectric conversion device is arranged in contact with the concavo-convex structure TX1 and the single crystal silicon substrate having the concavo-convex structure TX1 on the surface on the light incident side, and has a non-convex structure TX2 on the surface on the light incident side.
  • a crystalline thin film 102 and amorphous thin films 201 to 20n and 211 to 21n-1 for forming a back contact may be provided.
  • FIG. 26 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to the fourth embodiment.
  • photoelectric conversion device 300 according to Embodiment 4 deletes amorphous thin films 201 to 20n and 211 to 21n-1 of photoelectric conversion device 200 shown in FIG. 1 is replaced with the n-type single crystal silicon substrate 301, and the electrodes 221 to 22n and 231 to 23n-1 are replaced with the electrodes 331 to 33n and 341 to 34n-1, and the others are the same as the photoelectric conversion device 200. is there.
  • the n-type single crystal silicon substrate 301 has a concavo-convex structure TX1 on the light incident side surface, and n-type diffusion regions 311 to 31n and p-type diffusion regions 321 to 32n-1 on the back surface side.
  • the n-type single crystal silicon substrate 301 includes a bulk region 301b, n-type diffusion regions 311 to 31n and p-type diffusion regions 321 to 32n-1, and a pn junction (p-type diffusion regions 321 to 32n-1).
  • N-type single crystal silicon substrate 301) is built in the back side.
  • n-type single crystal silicon substrate 301 is the same as that of the n-type single crystal silicon substrate 1.
  • n-type diffusion regions 311 to 31n and the p-type diffusion regions 321 to 32n-1 are alternately arranged in the in-plane direction DR1 of the n-type single crystal silicon substrate 301 in contact with the back surface of the n-type single crystal silicon substrate 301. .
  • the n-type diffusion regions 311 to 31n have, for example, a P concentration of 1 ⁇ 10 17 cm ⁇ 3 to 1 ⁇ 10 18 cm ⁇ 3
  • the p-type diffusion regions 321 to 32n ⁇ 1 have, for example, 1 ⁇ 10 17 B concentration of cm ⁇ 3 to 1 ⁇ 10 18 cm ⁇ 3 .
  • the n-type diffusion regions 311 to 31n and the p-type diffusion regions 321 to 32n-1 have a diffusion depth of 0.01 ⁇ m to 0.1 ⁇ m.
  • the n-type diffusion regions 311 to 31n have the same length as the p-type diffusion regions 321 to 32n-1. Have.
  • the area occupancy ratio which is the ratio of the total area of the p-type diffusion regions 321 to 32n-1 to the area of the n-type single crystal silicon substrate 301, is 60 to 93%, and the n-type diffusion regions 311 to 31n
  • the area occupation ratio which is the ratio of the entire area to the area of the n-type single crystal silicon substrate 301, is 5 to 20%.
  • the reason why the area occupancy of the p-type diffusion regions 321 to 32n-1 is larger than the area occupancy of the n-type diffusion regions 311 to 31n is that the electrons excited in the n-type single crystal silicon substrate 301 and This is because holes are easily separated by the pn junction (p-type diffusion regions 321 to 32n-1 / n-type single crystal silicon substrate 301), and the contribution ratio of photoexcited electrons and holes to power generation is increased.
  • the electrodes 331 to 33n are disposed in contact with the n-type diffusion regions 311 to 31n, respectively.
  • the electrodes 341 to 34n-1 are disposed in contact with the p-type diffusion regions 341 to 34n-1, respectively.
  • the electrodes 331 to 33n and 341 to 34n-1 are made of, for example, Al.
  • the power generation principle of the photoelectric conversion device 300 is the same as the power generation principle of the photoelectric conversion device 200 described above. Therefore, the photoelectric conversion device 300 is also a back-contact type photoelectric conversion device that extracts photoexcited carriers (electrons and holes) from the back surface.
  • the photoelectric conversion device 300 includes an n-type single crystal silicon substrate 301 on which a concavo-convex structure TX1 is formed, an amorphous thin film 102 that is disposed in contact with the concavo-convex structure TX1, and has a concavo-convex structure TX2 formed on the light incident side surface. Therefore, it is possible to reduce the reflectance with respect to incident light on the surface on the light incident side, and at the same time carriers (electrons and holes) at the interface between the amorphous thin film 102 and the concavo-convex structure TX1 of the n-type single crystal silicon substrate 301. ) Recombination can be reduced.
  • 27 to 30 are first to fourth process diagrams showing a method for manufacturing the photoelectric conversion device 300 shown in FIG. 26, respectively.
  • a method for manufacturing the photoelectric conversion device 300 will be described by taking as an example the case where the amorphous thin film 102 includes an i-type amorphous thin film 102 i and an n-type amorphous thin film 102 n.
  • n-type single crystal silicon substrate 30 is cleaned (step (a)).
  • a BSG film 350B and an NSG (Non-doped Silicate Glass) film 350N are sequentially stacked on the back surface of the n-type single crystal silicon substrate 30 by the APCVD method (step (b)).
  • a resist is applied to the entire surface of the NSG film 350N, and the applied resist is patterned by photolithography and etching to form a resist pattern 360 (step (c)).
  • step (d) the NSG film 350N and the BSG film 350B are etched using the resist pattern 360 as a mask, and then the resist pattern 360 is removed.
  • BSG films 350B-1 to 350Bn-1 and NSG films 350N-1 to 350Nn-1 are formed (step (d)).
  • a PSG (Phosphorus Silicate Glass) film 350P is formed by APCVD so as to cover the back surface of n-type single crystal silicon substrate 30 and NSG films 350N-1 to 350Nn-1. (Step (e)).
  • the n-type single crystal silicon substrate 30, the BSG films 350B-1 to 350Bn-1, the NSG films 350N-1 to 350Nn-1 and the PSG film 350P are heat-treated at a temperature of 800 ° C. in a nitrogen gas atmosphere. (Step (f)).
  • B diffuses from the BSG films 350B-1 to 350B-n-1 into the n-type single crystal silicon substrate 30, and P of the PSG film 350P comes into the n-type from the portion in contact with the n-type single crystal silicon substrate 30. It diffuses into the single crystal silicon substrate 30.
  • the NSG film 350N-1 is interposed between the BSG films 350B-1 to 350B-n-1 and the PSG film 350P. Since ⁇ 350Nn-1 exists, P does not diffuse into the n-type single crystal silicon substrate 30 from the PSG film 350P.
  • the BSG films 350B-1 to 350B-n-1, the NSG films 350N-1 to 350N-n-1 and the PSG film 350P are removed.
  • n-type diffusion regions 311 to 31n and p-type diffusion regions 321 to 32n-1 are formed on the back surface side of the n-type single crystal silicon substrate 30 (step (g)).
  • the surface on the light incident side of the n-type single crystal silicon substrate 30 is anisotropically etched with alkali to form the concavo-convex structure TX1 (step (h). Thereby, the n-type single crystal silicon substrate 301 is manufactured. .
  • process (j) the same process as the process (e) of FIG. 5 is performed to etch the light incident side surface of the n-type amorphous thin film 104n (process (j)).
  • process (j) an n-type amorphous thin film 102n having a concavo-convex structure TX2 is formed on the light incident side surface, and the amorphous thin film 102 is disposed in contact with the concavo-convex structure TX1 of the n-type single crystal silicon substrate 301 (step). (K)).
  • transparent conductive film 3 is deposited on amorphous thin film 102 by a sputtering method (step (l)).
  • step (m) an Al paste is applied on the n-type diffusion regions 311 to 31n and the p-type diffusion regions 321 to 32n-1, and the applied Al paste is baked. As a result, electrodes 331 to 33n and 341 to 34n-1 are formed, and the photoelectric conversion device 300 is completed (step (m)).
  • the photoelectric conversion device 300 is shown in FIG. Manufactured according to the process diagram shown in FIG.
  • the amorphous thin film 102 is made of the i-type amorphous thin film 103i shown in FIG. 14B, only the i-type amorphous thin film is deposited in step (i) shown in FIG.
  • the surface of the light incident side of the i-type amorphous thin film thus etched is etched in the step (j) shown in FIG.
  • the amorphous thin film 102 is composed of the p-type amorphous thin film 103p shown in FIG. 14C, only the p-type amorphous thin film is deposited in step (i) shown in FIG. The surface on the light incident side of the p-type amorphous thin film thus etched is etched in the step (j) shown in FIG.
  • the amorphous thin film 102 is composed of the i-type amorphous thin film 102i / p-type amorphous thin film 102p shown in FIG. 14A
  • the step (i) shown in FIG. The thin film 102i and the p-type amorphous thin film are sequentially deposited, and the surface on the light incident side of the deposited p-type amorphous thin film is etched in the step (j) shown in FIG.
  • amorphous thin film 102 is composed of the n-type amorphous thin film 103n shown in FIG. 14E, only the n-type amorphous thin film is deposited in the step (i) shown in FIG. The surface of the light incident side of the n-type amorphous thin film thus etched is etched in step (j) shown in FIG.
  • the photoelectric conversion device 300 includes the n-type single crystal silicon substrate 301, the photoelectric conversion device 300 includes a p-type single crystal silicon substrate in Embodiment 4 without being limited thereto. Also good.
  • the photoelectric conversion apparatus 300 is manufactured according to the process diagrams shown in FIGS. 27 to 30 even when the p-type single crystal silicon substrate is provided.
  • the amorphous thin film 102 is disposed in contact with the concavo-convex structure TX1 formed on the light incident side surface of the n-type single crystal silicon substrate or the p-type single crystal silicon substrate, and the light of the amorphous thin film 102 is
  • An uneven structure TX2 is disposed on the surface on the incident side, and n-type diffusion regions 311 to 31n and p-type diffusion regions 321 to 32n-1 for back contact are provided on the back side of the n-type single crystal silicon substrate or the p-type single crystal silicon substrate.
  • the photoelectric conversion device is arranged in contact with the concavo-convex structure TX1 and the single crystal silicon substrate having the concavo-convex structure TX1 on the surface on the light incident side, and has the non-convex structure TX2 on the surface on the light incident side. What is necessary is just to provide the crystalline thin film 102 and the diffusion area
  • FIG. 31 is a schematic diagram illustrating a configuration of a photoelectric conversion apparatus according to the fifth embodiment.
  • photoelectric conversion device 400 according to Embodiment 5 replaces n-type single crystal silicon substrate 1 of photoelectric conversion device 10 shown in FIG. Is the same as the photoelectric conversion device 10 except that the amorphous thin film 402 is used.
  • the n-type single crystal silicon substrate 401 has a concavo-convex structure TX5 on the light incident side surface.
  • the height H3 and the width W3 are defined in the same manner as the height H2 and the width W2 shown in FIG.
  • the height H3 is, for example, 1 nm to 40 nm, and the width W3 is 1 nm to 40 nm.
  • the other description of the n-type single crystal silicon substrate 401 is the same as that of the n-type single crystal silicon substrate 1.
  • the amorphous thin film 402 is disposed in contact with the concavo-convex structure TX5 of the n-type single crystal silicon substrate 401, and has a concavo-convex structure TX4 on the surface on the light incident side.
  • the height H4 and the width W4 are defined in the same manner as the height H1 and the width W1 shown in FIG.
  • the height H4 is, for example, 50 nm to 1 ⁇ m
  • the width W4 is 50 nm to 1 ⁇ m.
  • the concavo-convex structure TX4 has a larger concavo-convex size than the concavo-convex structure TX5.
  • the amorphous thin film 402 has a configuration shown in FIG.
  • the amorphous thin film 402 has the structure shown in FIG. 3A (i-type amorphous thin film 21 / p-type amorphous thin film 22)
  • the i-type amorphous thin film 21 is formed of n-type single crystal silicon.
  • the p-type amorphous thin film 22 is disposed in contact with the concavo-convex structure TX5 of the substrate 401, and is disposed in contact with the i-type amorphous thin film 21, and has a concavo-convex structure TX4 on the surface on the light incident side.
  • the p-type amorphous thin film 23 has a concavo-convex structure TX5 of the n-type single crystal silicon substrate 401. And has a concavo-convex structure TX4 on the surface on the light incident side.
  • the transparent conductive film 3 is disposed along the concavo-convex structure TX4 of the amorphous thin film 402, and has the concavo-convex structure TX4 on the surface on the light incident side.
  • the passivation film 5 is disposed in contact with the back surface of the n-type single crystal silicon substrate 401, and the electrode 6 is disposed in contact with the back surface of the passivation film 5 and the n-type single crystal silicon substrate 401.
  • the two concavo-convex structures TX4 and TX5 are arranged so as to change from a large concavo-convex size to a small concavo-convex size in the light incident direction.
  • the two concavo-convex structures TX4 and TX5 are arranged so as to change from a large concavo-convex size to a small concavo-convex size with respect to the light incident direction, the light reflectance on the light incident side of the photoelectric conversion device 400 is increased. Can be reduced.
  • i-type a-Si or the like is disposed in contact with the concavo-convex structure TX5 of the n-type single crystal silicon substrate 401. . Since i-type a-Si and the like are formed by the plasma CVD method, they are uniformly formed on the concavo-convex structure TX5 so as to cover the concavo-convex structure TX5 having the concavo-convex size described above. As a result, the surface of the n-type single crystal silicon substrate 401 on which the concavo-convex structure TX5 is formed is passivated by the amorphous thin film 402.
  • the photoelectric conversion device 400 is manufactured according to the process chart shown in FIGS.
  • the n-type single crystal silicon substrate 401 has the concavo-convex structure TX5 formed on the surface on the light incident side in the step (c) of FIG.
  • the concavo-convex structure TX5 having a small concavo-convex size is formed by shortening the time of anisotropic etching with alkali.
  • the concavo-convex structure TX5 may be formed using dry etching.
  • the concavo-convex structure TX4 is formed on the surface of the amorphous thin film 402 on the light incident side.
  • the concavo-convex structure TX4 having a large concavo-convex size is formed by lengthening the etching time with the gas containing fluorine atoms.
  • photoelectric conversion device 400 is the same as the description of the photoelectric conversion device 10 in the first embodiment.
  • FIG. 32 is a schematic diagram showing a configuration of another photoelectric conversion apparatus according to the fifth embodiment.
  • the photoelectric conversion device according to Embodiment 5 may be the photoelectric conversion devices 400A and 400B shown in FIGS. 32 (a) and 32 (b).
  • the photoelectric conversion device 400A is obtained by replacing the n-type single crystal silicon substrate 1 of the photoelectric conversion device 10A shown in FIG. 7 with an n-type single crystal silicon substrate 401 and replacing the amorphous thin film 2 with an amorphous thin film 402. The others are the same as those of the photoelectric conversion device 10A (see FIG. 32A).
  • n-type single crystal silicon substrate 401 and the amorphous thin film 402 are as described in FIG.
  • the transparent conductive film 3 is disposed along the concavo-convex structure TX4 of the amorphous thin film 402, and has the concavo-convex structure TX4 on the light incident side surface.
  • the amorphous thin film 7 is disposed in contact with the back surface of the n-type single crystal silicon substrate 401.
  • the photoelectric conversion device 400A is manufactured according to the manufacturing method shown in FIGS.
  • the n-type single crystal silicon substrate 401 has the concavo-convex structure TX5 formed on the surface on the light incident side in the step (b) of FIG.
  • the concavo-convex structure TX5 having a small concavo-convex size is formed by shortening the anisotropic etching time with alkali.
  • the concavo-convex structure TX5 may be formed using dry etching.
  • the uneven structure TX4 is formed on the surface of the amorphous thin film 402 on the light incident side. Also in this case, the concavo-convex structure TX4 having a large concavo-convex size is formed by extending the etching time using the gas containing fluorine atoms.
  • the photoelectric conversion device 400A has the same structure as the photoelectric conversion device 400 on the light incident side, as described above, the reflectance of incident light can be reduced, and the n-type single crystal silicon substrate 401 and the amorphous thin film 402 can be reduced. The recombination of carriers (electrons and holes) at the interface with can be reduced.
  • photoelectric conversion device 400A is the same as the description of the photoelectric conversion device 10A in the first embodiment.
  • the photoelectric conversion device 400B is obtained by replacing the n-type single crystal silicon substrate 11 of the photoelectric conversion device 10B shown in FIG. 12 with an n-type single crystal silicon substrate 411 and replacing the amorphous thin film 2 with an amorphous thin film 412. The others are the same as those of the photoelectric conversion device 10B (see FIG. 32B).
  • the n-type single crystal silicon substrate 411 has a concavo-convex structure TX7 and a flat surface FT4 on the surface on the light incident side.
  • the uneven structure TX7 has the same uneven size as the uneven structure TX5.
  • the other description of the n-type single crystal silicon substrate 411 is the same as the description of the n-type single crystal silicon substrate 1.
  • the amorphous thin film 412 is disposed in contact with the concavo-convex structure TX7 and the flat surface FT4 of the n-type single crystal silicon substrate 411, and has a concavo-convex structure TX6 and a flat surface FT5 on the surface on the light incident side.
  • the uneven structure TX6 has the same uneven size as the uneven structure TX4, and the flat surface FT5 is disposed to face the flat surface FT4.
  • the amorphous thin film 412 has a configuration shown in FIG. 3 (a) or (b).
  • the amorphous thin film 412 has the configuration shown in FIG. 3A (i-type amorphous thin film 21 / p-type amorphous thin film 22)
  • the i-type amorphous thin film 21 is formed of n-type single crystal silicon.
  • the concavo-convex structure TX7 and the flat surface FT4 of the substrate 411 are arranged in contact with the flat surface FT4.
  • the p-type amorphous thin film 22 is arranged in contact with the i-type amorphous thin film 21, and the concavo-convex structure TX6 and flat surface are arranged on the light incident side surface.
  • the p-type amorphous thin film 23 has the concavo-convex structure TX7 of the n-type single crystal silicon substrate 411. Further, it is disposed in contact with the flat surface FT4, and has a concavo-convex structure TX6 and a flat surface FT5 on the surface on the light incident side.
  • the transparent conductive film 3 is disposed along the uneven structure TX6 and the flat surface FT5 of the amorphous thin film 412, and has the uneven structure TX6 and the flat surface FT6 on the light incident side surface.
  • the flat surface FT6 faces the flat surface FT5.
  • the electrode 9 is disposed in contact with the flat surface FT6 of the transparent conductive film 3.
  • the photoelectric conversion device 400B performs the process (c) shown in FIG. 4 in the process diagrams shown in FIGS. 4 to 6 with the n-type facing the electrode 9 on the light incident surface of the n-type single crystal silicon substrate 411.
  • a portion of the single crystal silicon substrate 411 is covered with a resist, and the light incident side surface not covered with the resist is manufactured according to a process diagram in place of etching with an alkali.
  • the amorphous thin film 412 is in contact with the n-type single crystal silicon substrate 411 at the flat surface FT4.
  • the contact area between the amorphous thin film 412 and the n-type single crystal silicon substrate 411 is reduced below the electrode 9. Therefore, recombination of carriers (electrons and holes) at the interface between the amorphous thin film 412 and the n-type single crystal silicon substrate 411 can be reduced as compared with the case where the n-type single crystal silicon substrate 401 is used.
  • the same effects as the photoelectric conversion device 400 can be obtained.
  • the photoelectric conversion device according to Embodiment 5 may be the one in which the same change as the change from the photoelectric conversion device 400 to the photoelectric conversion device 400B is applied to the photoelectric conversion device 400A.
  • the photoelectric conversion device performs step (b) shown in FIG. 9 in the process diagrams shown in FIGS. 9 to 11 to face the electrode 9 on the light incident side surface of the n-type single crystal silicon substrate 411.
  • a part of n-type single crystal silicon substrate 411 is covered with a resist, and the light-incident side surface not covered with the resist is manufactured according to a process diagram in place of etching with alkali.
  • this photoelectric conversion device similarly to the photoelectric conversion device 400B, carriers (electrons and electrons) at the interface between the amorphous thin film 412 and the n-type single crystal silicon substrate 411 are used, compared with the case where the n-type single crystal silicon substrate 401 is used. Hole recombination can be reduced.
  • the photoelectric conversion device may be one in which n-type single crystal silicon substrates 401 and 411 are replaced with n-type polycrystalline silicon substrates.
  • the surface on the light incident side of the n-type polycrystalline silicon substrate is roughened by dry etching.
  • a photoelectric conversion apparatus provided with an n-type polycrystalline silicon substrate is manufactured according to the same manufacturing method as the manufacturing method of any of the photoelectric conversion apparatuses 400, 400A, and 400B described above.
  • the photoelectric conversion device according to the fifth embodiment is obtained by replacing the n-type single crystal silicon substrates 401 and 411 of the photoelectric conversion devices 400, 400A, and 400B with a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate. May be.
  • the p-type single crystal silicon substrate has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 ⁇ m to 300 ⁇ m.
  • the p-type polycrystalline silicon substrate has a specific resistance of 0.1 to 10 ⁇ cm and a thickness of 100 ⁇ m to 300 ⁇ m, and the surface on the light incident side is roughened by dry etching.
  • the amorphous thin film 412 is made of an i-type amorphous thin film and an n-type amorphous thin film, or is made of an n-type amorphous thin film. Specific examples of the i-type amorphous thin film and the n-type amorphous thin film are as described above.
  • the amorphous thin film 7 is composed of an i-type amorphous thin film and a p-type amorphous thin film, or a p-type amorphous thin film. Specific examples of the i-type amorphous thin film and the p-type amorphous thin film are as described above.
  • a photoelectric conversion device including a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate is obtained by converting an n-type amorphous thin film into a p-type amorphous film in any of the manufacturing methods of the photoelectric conversion devices 400, 400A, and 400B. It is manufactured according to a manufacturing method in which a p-type amorphous thin film is replaced with an n-type amorphous thin film.
  • the photoelectric conversion device includes a crystalline silicon substrate in which the third uneven structure having the third uneven size is provided on the surface on the light incident side, and the crystalline silicon substrate in contact with the third uneven structure. And an amorphous thin film having a fourth uneven structure having a fourth uneven size larger than the third uneven size provided on the surface on the light incident side. Any pn junction or pin junction may be formed by the substrate.
  • the amorphous thin film contains a group IV element.
  • FIG. 33 is a schematic diagram showing the configuration of the photoelectric conversion apparatus according to the sixth embodiment.
  • photoelectric conversion device 500 according to Embodiment 6 replaces n-type single crystal silicon substrate 101 of photoelectric conversion device 100 shown in FIG. Is replaced with the amorphous thin film 502, and the rest is the same as the photoelectric conversion device 100.
  • the n-type single crystal silicon substrate 501 has a concavo-convex structure TX5 on the light incident side surface.
  • the n-type single crystal silicon substrate 501 has a p-type diffusion region 501p on the light incident side.
  • the p-type diffusion region 501p has a diffusion depth of 0.01 ⁇ m to 0.1 ⁇ m, for example, and is disposed in contact with the concavo-convex structure TX5.
  • the p-type diffusion region 501p contains B as a p-type dopant, and the concentration of B is, for example, 10 17 cm ⁇ 3 to 10 18 cm ⁇ 3 .
  • the n-type single crystal silicon substrate 501 includes the bulk region 501b having the n-type conductivity and the p-type diffusion region 501p having the p-type conductivity, and has a built-in pn junction on the light incident side. .
  • the n-type single crystal silicon substrate 501 is otherwise the same as the n-type single crystal silicon substrate 1.
  • the amorphous thin film 502 is disposed on the p-type diffusion region 501p in contact with the p-type diffusion region 501p of the n-type single crystal silicon substrate 501.
  • the amorphous thin film 502 has a concavo-convex structure TX4 on the light incident side surface.
  • the amorphous thin film 502 is made of any of the amorphous thin films 102A to 102E (see (a) to (e) of FIG. 14).
  • the i-type amorphous thin film 102i is formed on the n-type single crystal silicon substrate 501.
  • the p-type amorphous thin film 102p is disposed in contact with the concavo-convex structure TX5, and is disposed in contact with the i-type amorphous thin film 102i, and has a concavo-convex structure TX4 on the surface on the light incident side.
  • the i-type amorphous thin film 103i is in contact with the concavo-convex structure TX5 of the n-type single crystal silicon substrate 501. It is arranged and has a concavo-convex structure TX4 on the surface on the light incident side.
  • the p-type amorphous thin film 103p is in contact with the concavo-convex structure TX5 of the n-type single crystal silicon substrate 501. It is arranged and has a concavo-convex structure TX4 on the surface on the light incident side.
  • the i-type amorphous thin film 102i is an n-type single crystal silicon substrate.
  • the n-type amorphous thin film 102n is disposed in contact with the i-type amorphous thin film 102i, and has a concavo-convex structure TX4 on the light incident side surface.
  • the n-type amorphous thin film 103n is in contact with the concavo-convex structure TX5 of the n-type single crystal silicon substrate 501. It is arranged and has a concavo-convex structure TX4 on the surface on the light incident side.
  • the electrode 104 is disposed in contact with part of the p-type diffusion region 501p of the n-type single crystal silicon substrate 501.
  • the photoelectric conversion device 500 is manufactured according to the process chart shown in FIGS.
  • the n-type single crystal silicon substrate 501 is provided with the concavo-convex structure TX5 on the surface on the light incident side in the step (c) of FIG.
  • the concavo-convex structure TX5 having a small concavo-convex size is formed by shortening the time of anisotropic etching with alkali.
  • the concavo-convex structure TX5 may be formed using dry etching.
  • the uneven structure TX4 is formed on the surface of the amorphous thin film 502 on the light incident side. More specifically, the concavo-convex structure TX4 having a large concavo-convex size is formed by increasing the etching time using a gas containing fluorine atoms.
  • the photoelectric conversion device 500 is disposed in contact with the light incident side surface of the n-type single crystal silicon substrate 501 and the n-type single crystal silicon substrate 501 having the concavo-convex structure TX5 on the light incident side surface. Is provided with the amorphous thin film 502 having the concavo-convex structure TX4, so that the reflectance of light on the surface on the light incident side can be reduced, and the surface on the light incident side of the n-type single crystal silicon substrate 501 is passivated to form an n-type. Recombination of carriers (electrons and holes) at the interface between the single crystal silicon substrate 501 and the amorphous thin film 502 can be reduced.
  • the same effects as the photoelectric conversion device 100 can be obtained.
  • FIG. 34 is a schematic diagram showing the configuration of another photoelectric conversion apparatus according to the sixth embodiment.
  • the photoelectric conversion device according to Embodiment 6 may be a photoelectric conversion device 500A shown in FIG.
  • photoelectric conversion device 500A is obtained by replacing n-type single crystal silicon substrate 501 with n-type single crystal silicon substrate 511 and replacing electrode 104 with electrode 114 in photoelectric conversion device 500 shown in FIG. Others are the same as those of the photoelectric conversion device 500.
  • the n-type single crystal silicon substrate 511 has a concavo-convex structure TX7 and a flat surface FT7 on the surface on the light incident side.
  • the uneven structure TX7 has the same uneven size as the uneven structure TX5.
  • the n-type single crystal silicon substrate 511 has a p-type diffusion region 511p.
  • the p-type diffusion region 511p is disposed in contact with the uneven structure TX7 and the flat surface FT7.
  • the p-type diffusion region 511p has the same diffusion depth and B concentration as the p-type diffusion region 501p.
  • the n-type single crystal silicon substrate 511 includes the bulk region 511b having the n-type conductivity type and the p-type diffusion region 511p having the p-type conductivity type, and has a built-in pn junction on the light incident side. .
  • n-type single crystal silicon substrate 511 The other description of the n-type single crystal silicon substrate 511 is the same as the description of the n-type single crystal silicon substrate 1.
  • the electrode 114 is disposed in contact with the flat surface FT7 of the p-type diffusion region 511p of the n-type single crystal silicon substrate 511.
  • the photoelectric conversion device 500A performs the step (c) shown in FIG. 15 by performing n-type single contact with the electrode 114 on the light incident side surface of the n-type single crystal silicon substrate 511.
  • a part of the crystalline silicon substrate 511 is covered with a resist, and the light incident side surface that is not covered with the resist is manufactured according to a process diagram in place of etching with an alkali.
  • the contact area between the n-type single crystal silicon substrate 511 and the electrode 114 is smaller than that of the photoelectric conversion device 500. Accordingly, recombination of minority carriers (holes) at the interface between the n-type single crystal silicon substrate 511 and the electrode 114 can be further reduced as compared with the photoelectric conversion device 500. In the photoelectric conversion device 500A, the same effects as the photoelectric conversion device 100 can be obtained.
  • the photoelectric conversion devices 500 and 500A using the n-type single crystal silicon substrates 501 and 511 have been described.
  • the photoelectric conversion device according to the sixth embodiment is not limited to this, and the n The type single crystal silicon substrates 501 and 511 may be replaced with n-type polycrystalline silicon substrates.
  • the surface on the light incident side of the n-type polycrystalline silicon substrate is roughened by dry etching.
  • a photoelectric conversion apparatus provided with an n-type polycrystalline silicon substrate is manufactured according to the same manufacturing method as the manufacturing method of any of the photoelectric conversion apparatuses 500 and 500A mentioned above.
  • the photoelectric conversion device according to the sixth embodiment may be one in which the n-type single crystal silicon substrates 501 and 511 of the photoelectric conversion devices 500 and 500A are replaced with p-type single crystal silicon substrates or p-type polycrystalline silicon substrates. Good.
  • the p-type single crystal silicon substrate has a (100) plane orientation, a specific resistance of 0.1 to 10 ⁇ cm, and a thickness of 100 ⁇ m to 300 ⁇ m.
  • the p-type polycrystalline silicon substrate has a specific resistance of 0.1 to 10 ⁇ cm and a thickness of 100 ⁇ m to 300 ⁇ m, and the surface on the light incident side is roughened by dry etching.
  • a photoelectric conversion device including a p-type single crystal silicon substrate or a p-type polycrystalline silicon substrate is obtained by replacing the p-type diffusion region with an n-type diffusion region in any of the manufacturing methods of the photoelectric conversion devices 500 and 500A described above. Manufactured according to.
  • the photoelectric conversion device includes various photoelectric conversion devices. Therefore, in the photoelectric conversion device according to the sixth embodiment, the third concavo-convex structure having the third concavo-convex size is provided on the surface on the light incident side, is provided in contact with the surface on the light incident side, and is a bulk region.
  • a crystalline silicon substrate including a diffusion region having a conductivity type opposite to that of the first conductive type and a bulk region; a fourth silicon crystal disposed on the crystalline silicon substrate in contact with the third concavo-convex structure and having a size larger than the third concavo-convex size; As long as the fourth uneven structure having the uneven size is provided with an amorphous thin film provided on the surface on the light incident side.
  • the amorphous thin film contains a group IV element.
  • FIG. 35 is a schematic diagram showing the configuration of the photoelectric conversion apparatus according to the seventh embodiment.
  • photoelectric conversion apparatus 600 according to Embodiment 7 replaces n-type single crystal silicon substrate 1 of photoelectric conversion apparatus 200 shown in FIG. Is the same as the photoelectric conversion device 200.
  • the n-type single crystal silicon substrate 401 is as described in FIG.
  • the amorphous thin film 502 is as described in FIG. In the photoelectric conversion device 600, the amorphous thin film 502 is disposed in contact with the uneven structure TX5 of the n-type single crystal silicon substrate 401.
  • the photoelectric conversion device 600 is manufactured according to the process chart shown in FIGS.
  • the n-type single crystal silicon substrate 401 has the concavo-convex structure TX5 formed on the surface on the light incident side in the step (b) of FIG.
  • the concavo-convex structure TX5 having a small concavo-convex size is formed by shortening the time of anisotropic etching with alkali.
  • the concavo-convex structure TX5 may be formed using dry etching.
  • the uneven structure TX4 is formed on the light incident side surface of the amorphous thin film 502. More specifically, the concavo-convex structure TX4 having a large concavo-convex size is formed by increasing the etching time using a gas containing fluorine atoms.
  • the photoelectric conversion device 600 is disposed in contact with the light incident side surface of the n type single crystal silicon substrate 401 and the n type single crystal silicon substrate 401 having the concavo-convex structure TX5 on the light incident side surface. Is provided with the amorphous thin film 502 having the concavo-convex structure TX4, so that the reflectance of light on the surface on the light incident side can be lowered and the surface on the light incident side of the n-type single crystal silicon substrate 401 is passivated to form an n-type. Recombination of carriers (electrons and holes) at the interface between the single crystal silicon substrate 401 and the amorphous thin film 502 can be reduced.
  • the photoelectric conversion device 600 includes an amorphous thin film 502 on the light incident side of the n-type single crystal silicon substrate 401, and the amorphous thin films 201 to 20n and amorphous on the back side of the n-type single crystal silicon substrate 401. Since the thin films 211 to 21n-1 are provided, the thermal strain applied to the n-type single crystal silicon substrate 401 in the manufacturing process is uniform in the thickness direction. Accordingly, warpage of the n-type single crystal silicon substrate 401 can be suppressed.
  • the photoelectric conversion device 600 includes the n-type single crystal silicon substrate 401, in Embodiment 7, the photoelectric conversion device 600 includes a p-type single crystal silicon substrate without being limited thereto. Also good.
  • the amorphous thin films 201 to 20n are i-type amorphous thin film / p-type amorphous thin film or p-type amorphous thin film
  • the amorphous thin films 211 to 21n-1 are i-type non-crystalline thin films. It consists of a crystalline thin film / n-type amorphous thin film or an n-type amorphous thin film.
  • the photoelectric conversion apparatus 600 is manufactured according to the process diagrams shown in FIGS. 22 to 25 even when the p-type single crystal silicon substrate is provided.
  • the amorphous thin film 502 is disposed in contact with the concavo-convex structure TX5 formed on the light incident side surface of the n-type single crystal silicon substrate or the p-type single crystal silicon substrate, and the light of the amorphous thin film 502 is Photoelectric conversion in which a concavo-convex structure TX4 is disposed on the incident-side surface, and amorphous thin films 201 to 20n and 211 to 21n-1 for back contact are formed on the back surface of an n-type single crystal silicon substrate or a p-type single crystal silicon substrate The apparatus has been described.
  • the photoelectric conversion device is disposed on the single crystal silicon substrate having the concavo-convex structure TX5 on the surface on the light incident side, and on the single crystal silicon substrate in contact with the concavo-convex structure TX5, and on the surface on the light incident side. It is only necessary to include the amorphous thin film 502 having the concavo-convex structure TX4 and the amorphous thin films 201 to 20n and 211 to 21n-1 for forming the back contact.
  • FIG. 36 is a schematic diagram showing the configuration of the photoelectric conversion apparatus according to the eighth embodiment.
  • photoelectric conversion device 700 according to Embodiment 8 replaces n-type single crystal silicon substrate 301 of photoelectric conversion device 300 shown in FIG. Is the same as the photoelectric conversion device 300.
  • n-type single crystal silicon substrate 601 has a concavo-convex structure TX5 on the light incident side surface.
  • the other description of the n-type single crystal silicon substrate 601 is the same as the description of the n-type single crystal silicon substrate 301.
  • n-type single crystal silicon substrate 601 includes bulk region 601b, n-type diffusion regions 311 to 31n, and p-type diffusion regions 321 to 32n-1.
  • the configuration of the amorphous thin film 502 is as described in FIG. In the photoelectric conversion device 700, the amorphous thin film 502 is disposed in contact with the uneven structure TX5 of the n-type single crystal silicon substrate 601.
  • the photoelectric conversion device 700 is manufactured according to the process chart shown in FIGS.
  • the concavo-convex structure TX 5 is formed on the surface on the light incident side in the step (h) of FIG.
  • the concavo-convex structure TX4 is formed on the light incident side surface in the step (j) of FIG.
  • the photoelectric conversion device 700 includes an n-type single crystal silicon substrate 601 having a concavo-convex structure TX5 on the light incident side surface, and an n-type single crystal silicon substrate 601 in contact with the light incident side surface of the n-type single crystal silicon substrate 601. And the amorphous thin film 502 having the concavo-convex structure TX4 on the light incident side surface, the light reflectance on the light incident side surface can be reduced and the light incident on the n-type single crystal silicon substrate 601 can be reduced.
  • the surface on the side can be passivated to reduce recombination of carriers (electrons and holes) at the interface between the n-type single crystal silicon substrate 601 and the amorphous thin film 502.
  • the photoelectric conversion device 700 includes the n-type single crystal silicon substrate 601, in Embodiment 8, the present invention is not limited to this, and the photoelectric conversion device 700 includes a p-type single crystal silicon substrate. Also good.
  • the photoelectric conversion apparatus 700 is manufactured according to the process diagrams shown in FIGS. 27 to 30 even when the p-type single crystal silicon substrate is provided.
  • the amorphous thin film 502 is disposed in contact with the concavo-convex structure TX5 formed on the light incident side surface of the n-type single crystal silicon substrate or the p-type single crystal silicon substrate, and the light of the amorphous thin film 502 is
  • An uneven structure TX4 is arranged on the incident-side surface, and n-type diffusion regions 311 to 31n and p-type diffusion regions 321 to 32n-1 for back contact are formed on the back side of the n-type single crystal silicon substrate or the p-type single crystal silicon substrate.
  • the photoelectric conversion device is arranged on the single crystal silicon substrate having the concavo-convex structure TX5 on the surface on the light incident side, the single crystal silicon substrate in contact with the concavo-convex structure TX5, and on the surface on the light incident side. It suffices to include an amorphous thin film 502 having a concavo-convex structure TX4 and a diffusion region for forming a back contact.
  • FIG. 37 is a schematic diagram showing a configuration of a photoelectric conversion module including the photoelectric conversion device according to this embodiment.
  • photoelectric conversion module 1000 includes a plurality of photoelectric conversion devices 1001, a cover 1002, and output terminals 1003 and 1004.
  • a plurality of photoelectric conversion devices 1001 are arranged in an array and connected in series. Note that the plurality of photoelectric conversion devices 1001 may be connected in parallel instead of being connected in series, or may be connected in combination of series and parallel.
  • Each of the plurality of photoelectric conversion devices 1001 includes any of the photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, 500A, 600, 700.
  • the cover 1002 is made of a weather resistant cover and covers the plurality of photoelectric conversion devices 1001.
  • the output terminal 1003 is connected to a photoelectric conversion device 1001 disposed at one end of a plurality of photoelectric conversion devices 1001 connected in series.
  • the output terminal 1004 is connected to the photoelectric conversion device 1001 arranged at the other end of the plurality of photoelectric conversion devices 1001 connected in series.
  • the photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, 500A, 600, 700 reduce the reflectance on the light incident side, and The recombination is reduced and the conversion efficiency is high.
  • the conversion efficiency of the photoelectric conversion module 1000 can be improved.
  • the photoelectric conversion module according to Embodiment 9 is not limited to the configuration shown in FIG. 37, and the photoelectric conversion elements 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, 500A, 600, Any configuration may be used as long as at least one of 700 is used.
  • FIG. 38 is a schematic diagram showing a configuration of a photovoltaic power generation system including the photoelectric conversion device according to this embodiment.
  • the photovoltaic power generation system 1100 includes a photoelectric conversion module array 1101, a connection box 1102, a power conditioner 1103, a distribution board 1104, and a power meter 1105.
  • connection box 1102 is connected to the photoelectric conversion module array 1101.
  • the power conditioner 1103 is connected to the connection box 1102.
  • Distribution board 1104 is connected to power conditioner 1103 and electrical equipment 1110.
  • the power meter 1105 is connected to the distribution board 1104 and the commercial power system.
  • the photoelectric conversion module array 1101 converts sunlight into electricity to generate DC power, and supplies the generated DC power to the connection box 1102.
  • connection box 1102 receives the DC power generated by the photoelectric conversion module array 1101 and supplies the received DC power to the power conditioner 1103.
  • the power conditioner 1103 converts the DC power received from the connection box 1102 into AC power, and supplies the converted AC power to the distribution board 1104. Further, the power conditioner 1103 may supply a part of the DC power received from the connection box 1102 to the distribution board 1104 as it is without converting the DC power into AC power.
  • Distribution board 1104 supplies AC power received from power conditioner 1103 and / or commercial power received via power meter 1105 to electrical equipment 1110. Moreover, when the AC power received from the power conditioner 1103 is larger than the power consumption of the electrical equipment 1110, the distribution board 1104 supplies the surplus AC power to the commercial power system via the power meter 1105.
  • the power meter 1105 measures the power in the direction from the commercial power system to the distribution board 1104 and measures the power in the direction from the distribution board 1104 to the commercial power system.
  • FIG. 39 is a schematic diagram showing the configuration of the photoelectric conversion module array 1101 shown in FIG.
  • the photoelectric conversion module array 1101 includes a plurality of photoelectric conversion modules 1120 and output terminals 1121 and 1122.
  • the plurality of photoelectric conversion modules 1120 are arranged in an array and connected in series. Note that the plurality of photoelectric conversion modules 1120 may be connected in parallel instead of being connected in series, or may be connected in combination of series and parallel. Each of the plurality of photoelectric conversion modules 1120 includes a photoelectric conversion module 1000 shown in FIG.
  • the output terminal 1121 is connected to a photoelectric conversion module 1120 located at one end of a plurality of photoelectric conversion modules 1120 connected in series.
  • the output terminal 1122 is connected to the photoelectric conversion module 1120 located at the other end of the plurality of photoelectric conversion modules 1120 connected in series.
  • the photoelectric conversion module array 1101 generates sunlight by converting sunlight into electricity, and supplies the generated DC power to the power conditioner 1103 via the connection box 1102.
  • the power conditioner 1103 converts the DC power received from the photoelectric conversion module array 1101 into AC power, and supplies the converted AC power to the distribution board 1104.
  • Distribution board 1104 supplies AC power received from power conditioner 1103 to electrical equipment 1110 when the AC power received from power conditioner 1103 is greater than or equal to the power consumption of electrical equipment 1110. Then, the distribution board 1104 supplies the surplus AC power to the commercial power system via the power meter 1105.
  • distribution board 1104 receives AC power received from the commercial power system and AC power received from power conditioner 1103 when the AC power received from power conditioner 1103 is less than the power consumption of electrical equipment 1110. 1110 is supplied.
  • the photovoltaic power generation system 1100 is at least one of the photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, 500A, 600, 700 having high conversion efficiency. Has one.
  • the conversion efficiency of the photovoltaic power generation system 1100 can be improved.
  • FIG. 40 is a schematic diagram showing the configuration of another photovoltaic power generation system including the photoelectric conversion device according to this embodiment.
  • solar power generation system 1100A is obtained by adding storage battery 1106 to solar power generation system 1100 shown in FIG. 38, and is otherwise the same as solar power generation system 1100.
  • the storage battery 1106 is connected to the power conditioner 1103.
  • the storage battery 1106 accumulates the DC power supplied from the power conditioner 1103 and outputs the DC power to the power conditioner 1103.
  • the photoelectric conversion module array 1101 generates sunlight by converting sunlight into electricity, and supplies the generated DC power to the power conditioner 1103 via the connection box 1102.
  • the power conditioner 1103 appropriately converts a part or all of the DC power received from the photoelectric conversion module array 1101 and stores it in the storage battery 1106.
  • the storage battery 1106 supplies DC power to the power conditioner 1103 as appropriate according to the power generation amount of the photoelectric conversion module array 1101 and the power consumption amount of the electrical equipment 1110.
  • the power conditioner 1103 converts the DC power received from the photoelectric conversion module array 1101 and / or the storage battery 1106 into AC power, and supplies the converted AC power to the distribution board 1104.
  • the distribution board 1104 supplies AC power received from the power conditioner 1103 and / or the commercial power system to the electrical equipment 1110, or receives AC power received from the power conditioner 1103 as the electrical equipment 1110. And / or to the commercial power system.
  • the storage battery 1106 may be built in the power conditioner 1103. Thereby, output fluctuations from the power conditioner 1103 due to fluctuations in the amount of sunlight can be suppressed, and electric power stored in the storage battery 1106 can be supplied to the electrical equipment 1110 even in a time zone without sunlight.
  • the photovoltaic power generation systems 1100 and 1100A include “Home Energy Management System (HEMS)”, “Building Energy Management System (BEMS)”, and the like. A function to be called may be added.
  • HEMS Home Energy Management System
  • BEMS Building Energy Management System
  • the photovoltaic power generation system according to the tenth embodiment is not limited to the configuration shown in FIGS. 38 to 40, and the photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, Any configuration may be used as long as at least one of 500A, 600, and 700 is used.
  • FIG. 41 is a schematic diagram showing a configuration of still another photovoltaic power generation system including the photoelectric conversion device according to this embodiment.
  • photovoltaic power generation system 1200 includes subsystems 1201 to 120n (n is an integer of 2 or more), power conditioners 1211 to 121n, and a transformer 1221.
  • the photovoltaic power generation system 1200 is a photovoltaic power generation system having a larger scale than the photovoltaic power generation system 1100 shown in FIG. 38 and the photovoltaic power generation system 1100A shown in FIG.
  • the power conditioners 1211 to 121n are connected to the subsystems 1201 to 120n, respectively.
  • the transformer 1221 is connected to the power conditioners 1211 to 121n and the commercial power system.
  • Each of the subsystems 1201 to 120n includes module systems 1231 to 123j (j is an integer of 2 or more).
  • Each of the module systems 1231 to 123j includes photoelectric conversion module arrays 1301 to 130i (i is an integer of 2 or more), connection boxes 1311 to 131i, and a current collection box 1321.
  • Each of the photoelectric conversion module arrays 1301 to 130i has the same configuration as the photoelectric conversion module array 1101 shown in FIG.
  • connection boxes 1311 to 131i are connected to the photoelectric conversion module arrays 1301 to 130i, respectively.
  • the current collection box 1321 is connected to the connection boxes 1311 to 131i. Also, j current collection boxes 1321 of the subsystem 1201 are connected to the power conditioner 1211. The j current collection boxes 1321 of the subsystem 1202 are connected to the power conditioner 1212. Hereinafter, similarly, j current collection boxes 1321 of the subsystem 120n are connected to the power conditioner 121n.
  • the i photoelectric conversion module arrays 1301 to 130i of the module system 1231 convert sunlight into electricity to generate DC power, and the generated DC power is supplied to the current collecting box 1321 through the connection boxes 1311 to 131i, respectively.
  • the i photoelectric conversion module arrays 1301 to 130i of the module system 1232 convert sunlight into electricity to generate DC power, and the generated DC power is supplied to the current collecting box 1321 through the connection boxes 1311 to 131i, respectively.
  • the i photoelectric conversion module arrays 1301 to 130i of the module system 123j convert sunlight into electricity to generate DC power, and the generated DC power is connected to the connection boxes 1311 to 131i, respectively. To supply box 1321.
  • the j current collection boxes 1321 of the subsystem 1201 supply DC power to the power conditioner 1211.
  • the j current collection boxes 1321 of the subsystem 1202 supply DC power to the power conditioner 1212 in the same manner.
  • the j current collecting boxes 1321 of the subsystem 120n supply DC power to the power conditioner 121n.
  • the power conditioners 1211 to 121n convert the DC power received from the subsystems 1201 to 120n into AC power, and supply the converted AC power to the transformer 1221.
  • the transformer 1221 receives AC power from the power conditioners 1211 to 121n, converts the voltage level of the received AC power, and supplies it to the commercial power system.
  • the photovoltaic power generation system 1200 is one of the photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, 500A, 600, 700 having high conversion efficiency. It has.
  • the conversion efficiency of the photovoltaic power generation system 1200 can be improved.
  • FIG. 42 is a schematic diagram showing a configuration of still another photovoltaic power generation system including the photoelectric conversion device according to this embodiment.
  • the storage batteries 1311 to 131n are connected to the power conditioners 1211 to 121n, respectively.
  • the power conditioners 1211 to 121n appropriately convert part or all of the DC power received from the subsystems 1201 to 120n and store them in the storage batteries 1311 to 131n, respectively.
  • the storage batteries 1311 to 131n supply the stored power to the power conditioners 1211 to 121n as appropriate according to the power generation amounts of the subsystems 1201 to 120n, respectively.
  • the power conditioners 1211 to 121n convert the DC power received from the storage batteries 1311 to 131n into AC power, and supply the converted AC power to the transformer 1221.
  • the transformer 1221 converts the voltage level of the AC power received from the power conditioners 1211 to 121n and supplies it to the commercial power system.
  • the storage batteries 1311 to 131n may be incorporated in the power conditioners 1211 to 121n, respectively.
  • fluctuations in output from the power conditioners 1211 to 121n due to fluctuations in the amount of sunlight can be suppressed, and power stored in the storage batteries 1311 to 131n can be supplied to the commercial power system even in a time zone without sunlight. it can.
  • the photovoltaic power generation system according to Embodiment 11 is not limited to the configuration shown in FIG. 41 or 42, and photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, Any configuration may be used as long as at least one of 500A, 600, and 700 is used.
  • the photovoltaic power generation systems 1200 and 1200A have the photoelectric conversion devices 10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, and 500A having high conversion efficiency as described above. , 600, 700.
  • the conversion efficiency of the photovoltaic power generation systems 1200 and 1200A can be improved.
  • a photoelectric conversion device including an amorphous thin film having a smaller uneven structure TX2 on the light incident side surface has been described.
  • the amorphous thin film contains a group IV element.
  • the crystal silicon substrate having the concavo-convex structure TX5 on the surface on the light incident side and the concavo-convex structure TX5 are disposed on the crystal silicon substrate so as to have a concavo-convex size.
  • the photoelectric conversion device including the amorphous thin film having the concavo-convex structure TX4 larger than the structure TX5 on the light incident side surface has been described.
  • the amorphous thin film contains a group IV element.
  • the photoelectric conversion device includes a crystalline silicon substrate in which the first uneven structure having the first uneven size is provided on the surface on the light incident side, and the second different from the first uneven size.
  • a second concavo-convex structure having the concavo-convex size is provided on the surface of the light incident side and is in contact with the surface of the crystal silicon substrate on the light incident side; As long as it has.
  • the photoelectric conversion device is a crystal in which the first concavo-convex structure having the first concavo-convex size is provided on the surface on the light incident side.
  • a silicon substrate and a second concavo-convex structure having a second concavo-convex size smaller than the first concavo-convex size are provided on the surface on the light incident side and in contact with the surface on the light incident side of the crystal silicon substrate.
  • an amorphous thin film containing a group IV element is provided on the surface on the light incident side.
  • the photoelectric conversion device is a crystal in which the first concavo-convex structure having the first concavo-convex size is provided on the surface on the light incident side.
  • a silicon substrate and a second concavo-convex structure having a second concavo-convex size larger than the first concavo-convex size are provided on the surface on the light incident side and in contact with the surface on the light incident side of the crystal silicon substrate.
  • an amorphous thin film containing a group IV element is provided on the surface on the light incident side.
  • the photoelectric conversion device is a photoelectric conversion device in which a pn junction or a pin junction is formed on the light incident side.
  • a crystal silicon substrate provided with a first concavo-convex structure having a concavo-convex size on the surface on the light incident side, and a second concavo-convex structure having a second concavo-convex size different from the first concavo-convex size on the surface on the light incident side
  • an amorphous thin film containing a group IV element provided on the crystalline silicon substrate in contact with the surface on the light incident side of the crystalline silicon substrate.
  • the photoelectric conversion device is a photoelectric conversion device in which a pn junction or a pin junction is formed on the back surface side opposite to the light incident side.
  • Is provided on the surface of the light incident side is in contact with the surface of the single crystal silicon substrate on the light incident side, is provided on the single crystal silicon substrate, and includes an amorphous thin film containing a group IV element.
  • the present invention has the following configuration.
  • a photoelectric conversion device (10, 10A, 10B, 100, 100A, 200, 300, 400, 400A, 400B, 500, 500A, 600, 700) that converts light into electricity,
  • a crystalline silicon substrate (1, 11, 101, 111, 401, 411, 501, 511) having a first uneven structure (TX1, TX3, TX5, TX7) having a first uneven size provided on the surface on the light incident side.
  • a second concavo-convex structure (TX2, TX4, TX6) having a second concavo-convex size different from the first concavo-convex size is provided on the surface on the light incident side and the crystalline silicon substrate (1, 11, 101, 111, 401, 411, 501, 511, 601) are provided on the crystalline silicon substrate (1, 11, 101, 111, 401, 411, 501, 511, 601) in contact with the light incident surface of the group IV element. And an amorphous thin film (2, 7, 102, 402, 412 and 502).
  • incident light is scattered by two concavo-convex structures having different concavo-convex sizes arranged in the traveling direction of the incident light and is incident on the crystalline silicon substrate.
  • the surface of the crystalline silicon substrate on which the first uneven structure is formed is passivated by an amorphous thin film containing a group IV element. Therefore, the reflectance of incident light can be reduced on the light incident side of the photoelectric conversion device, and carrier recombination can be reduced at the interface between the amorphous thin film and the crystalline silicon substrate.
  • incident light is scattered by the second concavo-convex structure, and the scattered light is scattered by the first concavo-convex structure in which the concavo-convex size is smaller than that of the second concavo-convex structure.
  • the surface of the crystalline silicon substrate on which the first uneven structure is formed is passivated by an amorphous thin film containing a group IV element.
  • the reflectance of incident light can be reduced on the light incident side of the photoelectric conversion device, and an amorphous thin film and a crystal Carrier recombination can be reduced at the interface with the silicon substrate.
  • incident light is scattered by the second concavo-convex structure, and the scattered light is scattered by the first concavo-convex structure having a concavo-convex size larger than that of the second concavo-convex structure.
  • the surface of the crystalline silicon substrate on which the first uneven structure is formed is passivated by an amorphous thin film containing a group IV element.
  • the reflectance of incident light can be reduced on the light incident side of the photoelectric conversion device, and an amorphous thin film and a crystal Carrier recombination can be reduced at the interface with the silicon substrate.
  • the amorphous thin film (2, 402, 412) is composed of either the first amorphous thin film or the second amorphous thin film,
  • the first amorphous thin film is provided on the crystalline silicon substrate (1, 11, 401, 411) in contact with the light incident side surface of the crystalline silicon substrate (1, 11, 401, 411).
  • the second silicon substrate has a conductivity type opposite to that of the crystalline silicon substrate (1, 11, 401, 411), and the second uneven structure (TX2, TX4, TX6) is provided on the light incident side surface.
  • the second amorphous thin film is A second electrode having an i-type conductivity type is provided on the crystalline silicon substrate (1, 11, 401, 411) in contact with the light incident surface of the crystalline silicon substrate (1, 11, 401, 411).
  • TX2, TX4, TX6 provided on the light incident side surface (1) to (3)
  • the photoelectric conversion apparatus as described in any one of these.
  • the amorphous thin film forms a pn junction or a pin junction with the crystalline silicon substrate, and passivates the surface of the crystalline silicon substrate on which the first concavo-convex structure is formed, so that the incident light Are scattered by the second concavo-convex structure and guided to the first concavo-convex structure of the crystalline silicon substrate. Further, the first uneven structure of the crystalline silicon substrate further scatters the light scattered by the second uneven structure of the amorphous thin film and guides it into the crystalline silicon substrate.
  • the reflectance of incident light can be reduced and carriers can be recombined at the interface between the amorphous thin film and the crystalline silicon substrate. Can be reduced.
  • the crystalline silicon substrate (1, 11, 401, 411) has an n-type conductivity type
  • the first amorphous layer (23) is made of p-type amorphous silicon
  • the second amorphous layer (21) is made of i-type amorphous silicon
  • the amorphous thin film is made of amorphous silicon, and forms a pn junction or a pin junction with a crystalline silicon substrate having an n-type conductivity.
  • the reflectance of incident light can be reduced and an amorphous thin film and a crystal Carrier recombination can be reduced at the interface with the silicon substrate.
  • the crystalline silicon substrate (1, 11, 401, 411) has a p-type conductivity
  • the first amorphous layer (23) is made of n-type amorphous silicon
  • the second amorphous layer (21) is made of i-type amorphous silicon
  • the amorphous thin film is made of amorphous silicon, and forms a pn junction or a pin junction with a crystalline silicon substrate having a p-type conductivity.
  • the reflectance of incident light can be reduced and an amorphous thin film and a crystal Carrier recombination can be reduced at the interface with the silicon substrate.
  • the amorphous thin film is in contact with the flat plane of the crystalline silicon substrate below the electrodes. As a result, the contact area between the amorphous thin film and the crystalline silicon substrate is reduced below the electrode.
  • the crystalline silicon substrate (101, 111, 501, 511) is provided in contact with the bulk region (101b, 111b, 501b, 511b) and the surface on the light incident side, and the bulk region (101b , 111b, 501b, 511b), and a diffusion region (101p, 111p, 501p, 511p) having a conductivity type opposite to that of the photoelectric conversion device according to any one of (1) to (3) .
  • the crystalline silicon substrate incorporates a pn junction on the light incident side, and the amorphous thin film is disposed in contact with the diffusion region of the crystalline silicon substrate.
  • the reflectance of incident light can be reduced and the recombination of carriers can be reduced at the interface between the amorphous thin film and the crystalline silicon substrate.
  • An electrode (114) provided in contact with a part of the diffusion region (111p, 511p) of the crystalline silicon substrate (111, 511) is further provided.
  • the electrode is in contact with the flat plane of the diffusion region of the crystalline silicon substrate. As a result, the contact area between the electrode and the diffusion region of the crystalline silicon substrate is reduced.
  • the reflectance of incident light can be reduced and carrier recombination can be reduced at the interface between the amorphous thin film and the crystalline silicon substrate.
  • a plurality of first amorphous elements provided on the opposite side of the crystalline silicon substrate (1,401) from the light incident side and having a conductivity type opposite to that of the crystalline silicon substrate (1,401).
  • a thin film (211 to 21n-1), The crystalline silicon substrate (1,401) is provided on the opposite side of the light incident side and has the same conductivity type as the crystalline silicon substrate (1,401).
  • the said crystalline silicon substrate (1,401) is a photoelectric conversion apparatus as described in any one of (1) to (3) which consists of a single crystal silicon substrate.
  • the plurality of first amorphous thin films and the plurality of second amorphous thin films form a pn junction with the single crystal silicon substrate on the back side of the single crystal silicon substrate.
  • the reflectance of incident light can be reduced, and carriers can be regenerated at the interface between the amorphous thin film and the single crystal silicon substrate. Bonding can be reduced.
  • the plurality of first amorphous thin films, the plurality of second amorphous thin films, and the third amorphous thin film are connected to the single crystal silicon substrate on the back surface side of the single crystal silicon substrate. A pin junction is formed between them.
  • the reflectance of incident light can be reduced, and carriers can be regenerated at the interface between the amorphous thin film and the single crystal silicon substrate. Bonding can be reduced.
  • the first amorphous thin film (211 to 21n-1) is made of p-type amorphous silicon when the single crystal silicon substrate (1,401) has n-type conductivity
  • the single crystal silicon substrate (1,401) has p-type conductivity
  • it is made of n-type amorphous silicon
  • the second amorphous thin film (201 to 20n) is made of n-type amorphous silicon when the single-crystal silicon substrate (1,401) has an n-type conductivity type, and the single-crystal silicon substrate ( 1, 401) has a p-type conductivity, is made of p-type amorphous silicon
  • the photoelectric conversion device according to (12) wherein the third amorphous thin film (201i, 211i) is made of i-type amorphous silicon.
  • a pin junction is formed on the back surface side of the single crystal silicon substrate so that the i-type amorphous silicon contacts the back surface of the single crystal silicon substrate.
  • carrier recombination on the back surface of the single crystal silicon substrate can be further reduced as compared with the case where the p-type amorphous silicon and the n-type amorphous silicon are in contact with the back surface of the single crystal silicon substrate.
  • the crystalline silicon substrate (301, 601) A bulk region (301b, 601b) made of single crystal silicon; A plurality of the single-crystal silicon and provided in contact with the back surface opposite to the light incident side of the crystalline silicon substrate (301, 601) and having a conductivity type opposite to that of the bulk region (301b, 601b).
  • First diffusion regions (321 to 32n-1) of It is made of the single crystal silicon and has the same conductivity type as that of the bulk regions (301b, 601b), and a plurality of first diffusion regions (321 ⁇ ) in the in-plane direction of the crystalline silicon substrate (301, 601).
  • the photoelectric conversion device according to any one of (1) to (3).
  • the plurality of first diffusion regions and the plurality of second diffusion regions form a pn junction on the back surface side of the single crystal silicon substrate.
  • the reflectance of incident light can be reduced and the recombination of carriers can be reduced at the interface between the amorphous thin film and the single crystal silicon substrate.
  • the amorphous thin films (102, 502) include a first amorphous thin film (102B), a second amorphous thin film (102E), a third amorphous thin film (102C), and a fourth Of the amorphous thin film (102D) and the fifth amorphous thin film (102A),
  • the first amorphous thin film (102B) is provided in contact with the light incident side surface of the crystalline silicon substrate (101, 111, 301, 501, 511, 601) and the second concavo-convex structure (TX2).
  • TX4 is provided on the surface on the light incident side and includes a first amorphous layer (103i) having an i-type conductivity type
  • the second amorphous thin film (102E) is provided in contact with the light incident side surface of the crystalline silicon substrate (101, 111, 301, 501, 511, 601) and the second uneven structure (TX2).
  • TX4 is provided on the light incident side surface and includes a second amorphous layer (103n) having an n-type conductivity type
  • the third amorphous thin film (102C) is provided in contact with the light incident side surface of the crystalline silicon substrate (101, 111, 301, 501, 511, 601) and the second concavo-convex structure (TX2).
  • TX4 is provided on the surface on the light incident side and includes a third amorphous layer (103p) having a p-type conductivity type
  • the fourth amorphous thin film (102D) is provided in contact with the light incident side surface of the crystalline silicon substrate (101, 111, 301, 501, 511, 601) and has an i-type conductivity type.
  • the fourth amorphous layer (102i) and the fourth amorphous layer (102i), and the second concavo-convex structure (TX2, TX4) is provided on the light incident side surface.
  • a fifth amorphous layer (102n) having an n-type conductivity type The fifth amorphous thin film (102A) is provided in contact with the light incident side surface of the crystalline silicon substrate (101, 111, 301, 501, 511, 601) and has an i-type conductivity type.
  • the sixth amorphous layer (102i) and the sixth amorphous layer (102i), and the second uneven structure (TX2, TX4) is provided on the surface on the light incident side.
  • the photoelectric conversion device according to any one of (8) to (14), comprising a seventh amorphous layer (102p) having a p-type conductivity type.
  • the pn junction or the pin junction is built in the crystalline silicon substrate or disposed on the back side of the single crystal silicon substrate.
  • the amorphous thin film formed on the surface on the light incident side of the crystalline silicon substrate or the single crystalline silicon substrate does not constitute a pn junction or a pin junction.
  • the amorphous thin film formed on the light incident side surface of the crystalline silicon substrate or the single crystalline silicon substrate can be constituted by various amorphous thin films.
  • Each of the first, fourth and sixth amorphous layers (102i, 103i) is made of i-type amorphous silicon
  • Each of the second and fifth amorphous layers (102n, 103n) is made of n-type amorphous silicon
  • the amorphous thin film formed on the surface of the light incident side of the crystalline silicon substrate or the single crystalline silicon substrate is i-type amorphous silicon, p-type amorphous silicon, and n-type amorphous. Any of the crystalline silicon is disposed in contact with the first uneven structure of the crystalline silicon substrate or the single crystalline silicon substrate.
  • the light incident side surface of the crystalline silicon substrate or single crystal silicon substrate can be passivated.
  • This invention is applied to a photoelectric conversion device.

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Abstract

La présente invention se rapporte à un dispositif de conversion photoélectrique (10) qui comprend un substrat de silicium monocristallin de type n (1), un film mince amorphe (2), un film conducteur transparent (3) et des électrodes (4). Le substrat de silicium monocristallin de type n (1) présente une structure évidée et projetée (TX1) sur la surface côté incident de la lumière. Le film mince amorphe (2) est agencé sur le substrat de silicium monocristallin de type n (1) en contact avec la structure évidée et projetée (TX1) du substrat de silicium monocristallin de type n (1) et comprend une structure évidée et projetée (TX2) sur la surface côté incident de la lumière. Les dimensions des évidements et des projections de la structure évidée et projetée (TX2) sont plus petites que celles de la structure évidée et projetée (TX1). Le film mince amorphe (2) est formé d'un film mince amorphe de type i/film mince amorphe de type p ou d'un film mince amorphe de type p. Le film conducteur transparent (3) est agencé sur le film mince amorphe (2) en contact avec le film mince amorphe (2). Les électrodes (4) sont agencées à une distance souhaitée les unes des autres sur le film conducteur transparent (3) en contact avec le film conducteur transparent (3).
PCT/JP2014/058888 2013-04-01 2014-03-27 Dispositif de conversion photoélectrique WO2014162979A1 (fr)

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JP2019009402A (ja) * 2017-06-28 2019-01-17 国立研究開発法人物質・材料研究機構 太陽電池およびその製造方法
US11791426B1 (en) 2022-09-08 2023-10-17 Zhejiang Jinko Solar Co., Ltd. Photovoltaic cell and photovoltaic module
JP7381687B1 (ja) 2022-09-08 2023-11-15 ジョジアン ジンコ ソーラー カンパニー リミテッド 太陽電池および光起電力モジュール
US11923468B1 (en) 2022-09-08 2024-03-05 Zhejiang Jinko Solar Co., Ltd. Photovoltaic cell and photovoltaic module
JP2024038961A (ja) * 2022-09-08 2024-03-21 ジョジアン ジンコ ソーラー カンパニー リミテッド 太陽電池および光起電力モジュール
JP7525718B2 (ja) 2022-09-08 2024-07-30 ジョジアン ジンコ ソーラー カンパニー リミテッド 太陽電池および光起電力モジュール

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