WO2015033864A1 - Procédé permettant de fabriquer une cellule solaire - Google Patents

Procédé permettant de fabriquer une cellule solaire Download PDF

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Publication number
WO2015033864A1
WO2015033864A1 PCT/JP2014/072695 JP2014072695W WO2015033864A1 WO 2015033864 A1 WO2015033864 A1 WO 2015033864A1 JP 2014072695 W JP2014072695 W JP 2014072695W WO 2015033864 A1 WO2015033864 A1 WO 2015033864A1
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WO
WIPO (PCT)
Prior art keywords
silicon substrate
metal ions
aqueous solution
solar cell
porous layer
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PCT/JP2014/072695
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English (en)
Japanese (ja)
Inventor
熊谷　晃
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株式会社ジェイ・イー・ティ
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Publication date
Application filed by 株式会社ジェイ・イー・ティ filed Critical 株式会社ジェイ・イー・ティ
Priority to TW103130074A priority Critical patent/TW201523898A/zh
Publication of WO2015033864A1 publication Critical patent/WO2015033864A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • 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 method for manufacturing a solar cell, and more particularly to a method for forming a porous layer on the surface of a silicon substrate.
  • Textures An infinite number of fine irregularities (hereinafter referred to as “textures”) having a role of effectively taking in sunlight are formed on the surface of the solar cell.
  • the texture of the pyramid structure can be easily obtained by etching the Si (100) surface using an alkaline solution.
  • polycrystalline silicon since various crystal orientations appear on the surface of the silicon substrate, it is difficult to form a uniform texture on the entire surface of the silicon substrate like single crystal silicon.
  • a porous layer is formed on the surface of the silicon substrate by immersing the silicon substrate in a mixed aqueous solution of an oxidant and hydrofluoric acid containing metal ions.
  • a forming method (for example, Patent Document 1) is disclosed.
  • a second step of forming a texture by dipping in a mixed acid mainly composed of hydrofluoric acid and nitric acid to form a texture (for example, Patent Document 2) is disclosed.
  • the silicon substrate having a texture formed by the method of Patent Document 1 has a problem that the surface of the silicon substrate is discolored although the reflectance is low, and as a result, the characteristics of the solar cell are greatly deteriorated.
  • the surface of the silicon substrate that has undergone the same process as in Patent Document 1 is immersed in a mixed acid mainly composed of hydrofluoric acid and nitric acid to form a texture.
  • a clean silicon surface can be obtained while maintaining the effect of reducing the reflectance, and the metal at the bottom of the hole can be removed. It is described in Document 2.
  • Patent Documents 1 and 2 have a problem that it is difficult to form a texture having a uniform size and density on the surface of the silicon substrate.
  • an object of the present invention is to provide a method for manufacturing a solar cell capable of more uniformly forming a texture on the surface of a silicon substrate.
  • the method for manufacturing a solar cell according to the present invention is the method for manufacturing a solar cell in which a porous layer is formed on the surface of a silicon substrate by etching using metal ions, wherein the silicon is added to the first aqueous solution containing a strong acid and metal ions.
  • the dispersibility of metal ions is improved by immersing a silicon substrate in a first aqueous solution containing a strong acid and metal ions, and attaching the metal ions to the surface of the silicon substrate. Can be more uniformly attached to the surface of the silicon substrate.
  • FIG. 3A is a cross-sectional view showing a method for manufacturing a solar cell according to the present embodiment step by step
  • FIG. 3A is a state in which metal ions are attached
  • FIG. 3B is a state in which a porous layer is formed
  • FIG. 3D is a diagram illustrating a state where metal ions are removed.
  • 4A and 4B are SEM images of the surface of a silicon substrate manufactured by the manufacturing method according to the present embodiment, in which FIG. 4A shows a state in which a porous layer is formed, and FIG. 4B shows a state in which the porous layer is etched with a mixed acid mainly containing hydrofluoric acid.
  • FIG. 4A shows a state in which a porous layer is formed
  • FIG. 4B shows a state in which the porous layer is etched with a mixed acid mainly containing hydrofluoric acid.
  • a solar cell 1 shown in FIG. 1 includes a silicon substrate 2 that performs photoelectric conversion and a porous layer 3 in which the surface of the silicon substrate 2 is processed into a textured shape, and is incident from a light receiving surface on which the porous layer 3 is formed. Light is converted into electrical energy in the silicon substrate 2.
  • the porous layer 3 light incident on the surface of the silicon substrate 2 is repeatedly transmitted and reflected, and as a result, more light is guided into the silicon substrate 2 than on the flat silicon substrate surface. It is generally known that the fine texture formed in the porous layer 3 can efficiently confine incident light when the height and density are uniform rather than nonuniform.
  • the solar cell 1 according to the present embodiment is characterized in that a fine texture is uniformly formed in the porous layer 3 as compared with the conventional one, and the other configuration is the same as the conventional one.
  • the solar cell 1 has a diffusion layer, an antireflection film, and a grid electrode sequentially formed on the light receiving surface side where the porous layer 3 is formed with respect to the p-type silicon substrate. An electric field layer and a back electrode are formed in this order.
  • the antireflection film is formed on the surface of the porous layer 3 in order to suppress light reflection.
  • the antireflection film is composed of, for example, a single layer structure of a titanium oxide (TiO 2 ) film or a silicon nitride (SiN) film formed by a chemical vapor deposition (CVD) method or the like.
  • the concentration is mass%.
  • step SP1 the silicon substrate 2 is immersed in a first aqueous solution in which a strong acid and a metal are mixed, and the metal ions 5 are adhered to the surface of the silicon substrate 2 by electroless plating (FIG. 3A). Since the first aqueous solution contains a strong acid and is acidic, the metal easily becomes the metal ion 5. The metal ions 5 do not aggregate due to the repulsive force of the potential, and the dispersibility is improved.
  • the strong acid for example, hydrofluoric acid, hydrochloric acid, sulfuric acid and the like can be used.
  • Ag can be applied as the metal.
  • the first aqueous solution can be generated using AgNO 3 as the metal-containing agent.
  • the electroless plating conditions can be, for example, an immersion time of 300 seconds and a temperature of the first aqueous solution of 26 degrees.
  • the silicon substrate 2 has a natural oxide film removed beforehand.
  • the method for removing the natural oxide film on the silicon substrate 2 is not particularly limited, and for example, a sputtering method, a plasma method, or the like can be used.
  • the silicon substrate 2 is immersed in the first aqueous solution containing metal ions, and the silicon substrate 2 Metal ions were allowed to adhere to the surface.
  • the metal ions can be uniformly attached to the surface of the silicon substrate 2 as compared with the conventional case where the metal ions are attached and etched simultaneously.
  • the silicon substrate 2 is immersed in a first aqueous solution containing a strong acid and metal ions, and the metal ions 5 are attached to the surface of the silicon substrate 2. did. Thereby, the dispersibility of the metal ions 5 can be improved, and the metal ions 5 can be more uniformly attached to the surface of the silicon substrate 2.
  • the metal ions 5 are well dispersed in the first aqueous solution, the metal ions 5 adhere more reliably to the surface of the silicon substrate 2. Therefore, the metal ions 5 have a large bonding force with the surface of the silicon substrate 2 and can be prevented from being lost due to water washing or the like.
  • the amount of metal ions 5 attached can be controlled. Therefore, by managing the concentration of the metal ions 5 to be introduced into the first aqueous solution, the metal ions 5 can be uniformly attached within the surface of one silicon substrate 2.
  • step SP2 water washing is performed in step SP2, and in step SP3, the silicon substrate 2 is immersed in a second aqueous solution containing hydrofluoric acid and hydrogen peroxide water.
  • the hydrogen reduction reaction of the hydrogen peroxide solution by the catalytic action of the metal ions 5 attached to the surface proceeds.
  • electrons are extracted from the surface of the silicon substrate 2 in contact with the metal ions 5 in order to compensate for the increase in the amount of electron consumption.
  • holes are generated in the silicon substrate 2 and cause oxidative dissolution of the silicon substrate 2.
  • the porous layer 3 is formed by the holes 6 and portions where the holes 6 are not formed (convex) (FIG. 3B).
  • the second aqueous solution is only intended to form the porous layer 3 on the surface of the silicon substrate 2 by etching, and is not intended to attach the metal ions 5 to the surface of the silicon substrate 2. Does not contain.
  • the concentration of the hydrogen peroxide solution in the second aqueous solution is preferably suppressed to a concentration that does not suppress the etching of the metal ions 5 in order to form the porous layer 3 more reliably.
  • the concentration of the hydrogen peroxide solution is preferably 25 to 50% with respect to the concentration of hydrofluoric acid. Since the hydrogen peroxide solution has a stronger ability to take electrons from the silicon substrate than the metal ions, if the concentration of the hydrogen peroxide solution is higher than 50%, the etching rate by the hydrogen peroxide solution is higher than the etching rate by the catalytic action of the metal ions. As a result, the entire surface of the silicon substrate is oxidized and becomes a mirror surface, and the porous layer is not formed. Further, when the concentration with respect to hydrofluoric acid is outside the above range, that is, when the concentration with respect to hydrofluoric acid is higher than 50%, and when the concentration with respect to hydrofluoric acid is less than 25%, The reflectance cannot be reduced.
  • the silicon substrate 2 is immersed in a second aqueous solution containing hydrofluoric acid and hydrogen peroxide solution, and the catalytic reaction of the metal ions 5 is performed.
  • the porous layer 3 was formed on the surface of the silicon substrate 2.
  • the silicon substrate 2 is immersed in a second aqueous solution in which the concentrations of hydrofluoric acid and hydrogen peroxide water are controlled for a predetermined time, and porous on the surface of the silicon substrate 2. Since the layer 3 is formed, the texture can be more uniformly formed on the surface of the silicon substrate 2.
  • the second aqueous solution that forms the porous layer 3 deteriorates in proportion to the number of processed silicon substrates 2 and needs to be replaced.
  • the second aqueous solution contains metal ions 5. Since it is a separate body from the first aqueous solution, it is not necessary to discard the metal ions 5 as in the prior art, so that the management of the aqueous solution can be simplified.
  • step SP4 water washing is performed, and in step SP5, the silicon substrate 2 is immersed in a third aqueous solution containing hydrofluoric acid and nitric acid and etched (FIG. 3C).
  • a third aqueous solution containing hydrofluoric acid and nitric acid and etched FIGG. 3C
  • the silicon substrate 2 which has the porous membrane 3A which has a bigger hole can be obtained (FIG. 3D).
  • the immersion time can be 240 seconds to 360 seconds.
  • step SP6 the substrate is washed with water, and then the silicon substrate 2 is immersed in an alkaline chemical solution to remove the stain film (step SP7).
  • the stain film is a black-brown film formed on the surface of the silicon substrate 2 by etching.
  • the silicon substrate 2 provided with the porous layer 3A according to the present embodiment can be obtained by washing with water (step SP8).
  • the present invention is not limited to the above-described embodiment, and can be appropriately changed within the scope of the gist of the present invention.
  • an acid capable of removing the natural oxide film as the strong acid for example, hydrofluoric acid
  • the metal ions 5 can be attached while removing the natural oxide film.
  • a p-type silicon substrate is used as the silicon substrate 2.
  • Hydrofluoric acid as a strong acid and AgNO 3 as a metal-containing agent were mixed to prepare a first aqueous solution.
  • the silicon substrate 2 was immersed in a first aqueous solution, and the metal ions 5 were attached to the surface of the silicon substrate 2 by electroless plating.
  • the plating conditions in this case were an immersion time of 300 seconds and a temperature of the second aqueous solution of 26 degrees. Further, the second aqueous solution was allowed to flow around the silicon substrate 2 by the pump circulator.
  • FIG. 4A shows an SEM image (Scanning Electron Microscope) of the surface of the silicon substrate 2 on which the porous layer 3 is thus formed.
  • the porous layer 3 can be more uniformly formed on the surface of the silicon substrate 2.
  • the formed silicon substrate 2 was immersed and etched. An SEM image of the surface of the silicon substrate 2 etched in this manner is shown in FIG. 4B.
  • the porous layer 3A having larger pores on the surface of the silicon substrate 2 can be formed more uniformly.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electromagnetism (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Weting (AREA)
  • Photovoltaic Devices (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

L'invention concerne un procédé permettant de fabriquer une cellule solaire, ledit procédé pouvant fournir la surface d'un substrat de silicium avec une texture plus uniforme. Un procédé permettant de fabriquer une cellule solaire (1), selon lequel une couche poreuse (3) est formée sur la surface d'un substrat de silicium (2) par gravure à l'aide d'ions métalliques (5), est caractérisé par le fait qu'il comprend : une étape au cours de laquelle le substrat de silicium (2) est immergé dans une première solution aqueuse contenant un acide fort et les ions métalliques (5) et les ions métalliques (5) sont amenés à adhérer à la surface du substrat de silicium (2) au moyen d'un placage anélectrolytique ; et une étape au cours de laquelle le substrat de silicium (2), à la surface duquel les ions métalliques (5) ont été amenés à adhérer, est immergé dans une seconde solution aqueuse contenant de l'acide fluorhydrique et une solution de peroxyde d'hydrogène, et la couche poreuse (3) est formée sur la surface du substrat de silicium (2) au moyen d'une réaction catalytique des ions métalliques (5).
PCT/JP2014/072695 2013-09-06 2014-08-29 Procédé permettant de fabriquer une cellule solaire WO2015033864A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW103130074A TW201523898A (zh) 2013-09-06 2014-09-01 太陽電池之製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013185543A JP2015053398A (ja) 2013-09-06 2013-09-06 太陽電池の製造方法
JP2013-185543 2013-09-06

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Publication number Priority date Publication date Assignee Title
CN107431100B (zh) 2015-03-31 2019-05-10 松下知识产权经营株式会社 太阳能电池元件、太阳能电池组件、以及制造方法
CN104993019A (zh) * 2015-07-09 2015-10-21 苏州阿特斯阳光电力科技有限公司 一种局部背接触太阳能电池的制备方法
TWI596788B (zh) * 2015-11-10 2017-08-21 財團法人工業技術研究院 雙面光電轉換元件

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003105209A1 (fr) * 2002-06-06 2003-12-18 関西ティー・エル・オー株式会社 Procede de production de substrat de silicium polycristallin pour cellule solaire
JP2013093537A (ja) * 2011-10-07 2013-05-16 Jet Co Ltd 太陽電池の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003105209A1 (fr) * 2002-06-06 2003-12-18 関西ティー・エル・オー株式会社 Procede de production de substrat de silicium polycristallin pour cellule solaire
JP2013093537A (ja) * 2011-10-07 2013-05-16 Jet Co Ltd 太陽電池の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAZUYA TSUJINO: "Wet Etching for Fabricating Low Reflective Textured Surface on Crystalline Silicon Wafers for Solar Cells", THE JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, vol. 56, no. 12, 2005, pages 843 - 846 *
S.K.SRIVASTAVA, SOLAR ENERGY MATERIALS AND SOLAR CELLS, vol. 100, 20 May 2011 (2011-05-20), pages 33 - 38 *

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JP2015053398A (ja) 2015-03-19

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