WO2011074280A1 - Dispositif photovoltaïque et son procédé de préparation - Google Patents

Dispositif photovoltaïque et son procédé de préparation Download PDF

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Publication number
WO2011074280A1
WO2011074280A1 PCT/JP2010/058288 JP2010058288W WO2011074280A1 WO 2011074280 A1 WO2011074280 A1 WO 2011074280A1 JP 2010058288 W JP2010058288 W JP 2010058288W WO 2011074280 A1 WO2011074280 A1 WO 2011074280A1
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electrode
back surface
semiconductor substrate
opening
film
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PCT/JP2010/058288
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English (en)
Japanese (ja)
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剛彦 佐藤
秀一 檜座
雅 酒井
松野　繁
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三菱電機株式会社
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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
    • H01L31/068—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photovoltaic device and a method for manufacturing the same, and more particularly to a photovoltaic device having a back surface passivation structure capable of improving efficiency in a crystalline silicon-based photovoltaic device and a method for manufacturing the same. is there.
  • a currently manufactured solar cell using a polycrystalline silicon substrate has a p-type polycrystalline silicon substrate formed with a p-type polycrystalline silicon substrate having a surface texture, an n-type diffusion layer, and an antireflection film that increase the light absorption rate.
  • a comb-shaped silver (Ag) electrode (light-receiving surface-side electrode) is formed on the light-receiving surface side of the polycrystalline silicon substrate, and an aluminum (Al) electrode (back-surface electrode) is formed on the non-light-receiving surface side using screen printing, followed by firing. It is manufactured by the manufacturing process of.
  • baking has the effect of volatilizing and baking the electrode paste components of the silver (Ag) electrode and aluminum (Al) electrode printed by screen printing.
  • firing is a process in which a comb-shaped silver (Ag) electrode breaks through the antireflection film on the light-receiving surface side and connects to the n-type impurity diffusion layer, and an aluminum (Al) electrode on the non-light-receiving surface side A part of the p-type polycrystalline silicon substrate side diffuses into the p-type polycrystalline silicon substrate to form a back surface field layer (BSF).
  • a comb-shaped silver (Ag) electrode breaks through the antireflection film on the light-receiving surface side and connects to the n-type impurity diffusion layer
  • Al aluminum
  • This BFS layer applies an electric field to the back surface of the p-type polycrystalline silicon substrate to provide a barrier against minority carriers, thereby driving off minority carriers from the vicinity of the aluminum (Al) electrode and recombining carriers near the aluminum (Al) electrode. It is provided for the purpose of obtaining a high open circuit voltage by suppressing.
  • a contact portion between the back electrode and the substrate is formed as a point for the purpose of further suppressing carrier recombination on the back surface side of the substrate, and a region other than the contact portion on the back surface of the substrate is formed.
  • a substrate back surface is passivated by covering with an insulating film (back surface passivation film) having a function (passivation effect) for repairing defects on the substrate surface (see, for example, Patent Document 1, Patent Document 2, and Non-Patent Document 1). ).
  • Patent Document 1 and Non-Patent Document 1 after forming a diffusion bonding layer and an antireflection film on the light receiving surface side of the substrate, a back surface passivation film is formed, and a part of the back surface passivation film is used as an electrode contact portion. Is opened by laser, etc., electrodes such as aluminum (Al) are formed on the back surface by screen printing, etc., electrodes are formed on the light-receiving surface side, and finally the electrodes on the front and back are baked collectively. The method of doing is described.
  • Al aluminum
  • the passivation effect may be reduced.
  • the aluminum (Al) electrode formed on the passivation film is in the form of particles, and there is a problem that long wavelength light reaching the back surface cannot be effectively reflected and is absorbed there.
  • the present invention has been made in view of the above, and an object thereof is to obtain a photovoltaic device having good solar cell characteristics and a method for manufacturing the photovoltaic device.
  • a photovoltaic device includes a first conductivity type semiconductor substrate having an impurity diffusion layer in which a second conductivity type impurity element is diffused on one side.
  • the openings have a substantially rectangular shape in the in-plane direction of the back surface of the semiconductor substrate, and a plurality of the openings are arranged in substantially parallel rows in the short direction of the openings.
  • the second electrode is embedded in the opening. Rarely presenting a substantially rectangular shape substantially equal to the opening, a plurality of the second electrodes are arranged in a substantially parallel row in the short direction of the second electrode, and the second in one row in the short direction of the second electrode.
  • the inter-electrode pitch which is the distance between the center position of the electrode and the center position of the second electrode in the adjacent row, is in the range of 1.5 mm to 3.0 mm, and the width of the second electrode in the short direction is 20 ⁇ m to It is characterized by being in the range of 200 ⁇ m.
  • FIG. 1-1 is a cross-sectional view of relevant parts for explaining the cross-sectional structure of the solar battery cell according to the first embodiment of the present invention.
  • FIG. 1-2 is a top view of the solar cell according to the first embodiment of the present invention as viewed from the light receiving surface side.
  • FIG. 1-3 is a bottom view of the solar battery cell according to Embodiment 1 of the present invention as viewed from the side opposite to the light receiving surface (back surface side).
  • 1-4 is an essential part cross-sectional view showing an enlarged back surface structure of the solar battery cell according to the first embodiment of the present invention.
  • FIG. FIG. 2 is a flowchart for explaining the manufacturing process of the solar battery cell according to the first embodiment of the present invention.
  • FIGS. 3-1 is a cross-sectional view for explaining a manufacturing step for the solar battery cell according to the first embodiment of the present invention.
  • FIG. 3-2 is a cross-sectional view for explaining a manufacturing step for the solar battery cell according to the first embodiment of the present invention.
  • FIGS. 3-3 is sectional drawing for demonstrating the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-4 is sectional drawing for demonstrating the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-5 is sectional drawing for demonstrating the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIG. 4 is a characteristic diagram showing voltage-current characteristics of the solar battery cell according to the example of the present invention.
  • FIG. 5 is a characteristic diagram showing the relationship between the laser irradiation position and the extraction current in the solar cell of the example having an interelectrode pitch of 2 mm.
  • FIG. 6 is a characteristic diagram showing the relationship between the laser irradiation position and the extraction current in the solar battery cell of the example having an interelectrode pitch of 1 mm.
  • the inventors opened the back surface passivation film on the back surface of the solar cell by forming and firing the electrodes by local screen printing with a size that covers the openings on the back surface in various shapes and patterns.
  • the solar cell provided was formed and the solar cell characteristics were examined.
  • the pattern of the opening and the electrode shape by screen printing on the opening greatly affect the solar cell characteristics.
  • a small point contact portion having an outer diameter of about several tens of nanometers is formed and screen printing and firing of the back electrode are performed, the electrode formed during firing Part of the alloy layer is pulled out with the thermal contraction of the electrode when the temperature is lowered after firing, voids are generated, and the electrical connection of the opening is broken.
  • a solar battery cell that has both a suppression of increase in series resistance and a passivation effect in forming a passivation structure by screen printing and firing through an opening, and has better solar battery characteristics than a conventional structure.
  • FIG. FIGS. 1-1 to 1-4 are diagrams showing a configuration of a solar cell that is a photovoltaic device according to the present embodiment
  • FIG. 1-1 is a diagram for explaining a cross-sectional structure of the solar cell.
  • 1-2 is a top view of the solar cell viewed from the light receiving surface side
  • FIG. 1-3 is a bottom view of the solar cell viewed from the side opposite to the light receiving surface (back side)
  • FIG. 1-1 is a cross-sectional view of an essential part taken along line AA in FIG. 1-2.
  • the solar cell according to the present embodiment is a solar cell substrate having a photoelectric conversion function and having a pn junction, and An antireflection film 4 made of a silicon nitride film (SiN film) which is an insulating film formed on the light receiving surface side (surface) and prevents reflection of incident light on the light receiving surface, and a light receiving surface side of the semiconductor substrate 1 On the surface (front surface), the light receiving surface side electrode 5 which is the first electrode formed in conduction with the semiconductor substrate 1 and the silicon nitride film (SiN) formed on the surface (back surface) opposite to the light receiving surface of the semiconductor substrate 1.
  • SiN film silicon nitride film
  • the semiconductor substrate 1 is a first conductivity type layer, and a p-type polycrystalline silicon substrate 2 and an impurity diffusion layer (n-type impurity) which is a second conductivity type layer formed by phosphorous diffusion on the light receiving surface side of the semiconductor substrate 1.
  • a pn junction is constituted by the diffusion layer 3.
  • the p-type polycrystalline silicon substrate 2 has a size of 150 mm ⁇ 150 mm and a resistivity of 0.5 ⁇ cm to 3 ⁇ cm.
  • the light-receiving surface side electrode 5 includes a grid electrode 6 and a bus electrode 7 of the solar battery cell, and is electrically connected to the n-type impurity diffusion layer 3.
  • the grid electrode 6 is locally provided on the light receiving surface to collect electricity generated by the semiconductor substrate 1.
  • the bus electrode 7 is provided substantially orthogonal to the grid electrode 6 in order to take out the electricity collected by the grid electrode 6.
  • the back surface side electrode 9 is formed in a stripe shape in a state surrounded by a plurality of back surface insulating films (back surface passivation films) 8 provided over the entire back surface of the semiconductor substrate 1 and is electrically connected to the semiconductor substrate 1.
  • the back insulating film (back passivation film) 8 is provided with a substantially rectangular opening 8 a reaching the back surface of the semiconductor substrate 1. Then, in the plane of the back surface insulating film (back surface passivation film) 8, filling the opening 8 a and in the width direction of the opening 8 a (the dimension in the short direction of the line-shaped back surface insulating film (back surface passivation film) 8).
  • a plurality of rectangular (striped) back-side electrodes 9 made of an electrode material containing aluminum, glass or the like are provided so as to slightly overlap the back-side insulating film (back-side passivation film) 8.
  • the back surface side electrode 9 should just be provided in the area
  • the inter-electrode pitch P in the short side direction (width direction of the opening 8a) of the back-side electrode 9 formed in a stripe shape is set to 1.5 mm to 3.0 mm.
  • the inter-electrode pitch P is the distance between the center position in the short direction of the back surface side electrode 9 and the center position in the short direction of the adjacent back surface side electrode 9. That is, the distance between the center position in the short direction of the opening 8a and the center position in the short direction of the opening 8a of the adjacent row.
  • the opening width W of the opening 8a is 20 ⁇ m to 200 ⁇ m.
  • the width of the back-side electrode 9 is approximately 20 ⁇ m to 200 ⁇ m although it slightly overlaps with the back-side insulating film (back-side passivation film) 8. Further, the electrode length (length in the longitudinal direction) L of the back-side electrode 9 is set to a dimension close to the length of one side of the semiconductor substrate 1.
  • the back surface insulating film (back surface passivation film) 8 is made of a silicon nitride film (SiN film), and is formed on almost the entire back surface of the semiconductor substrate 1 by a plasma CVD (Chemical Vapor Deposition) method.
  • the back surface reflection film 10 is provided so as to cover at least the back surface insulating film (back surface passivation film) 8.
  • the back surface reflecting film 10 is provided on the back surface of the semiconductor substrate 1 so as to cover the back surface side electrode 9 and the back surface insulating film (back surface passivation film) 8.
  • the material of the back surface reflection film 10 for example, a material having a high reflectivity with respect to long wavelength light is used. Thereby, long wavelength light can be efficiently taken into the semiconductor substrate 1, a high generated current (Jsc) can be realized, and output characteristics can be improved.
  • a material for example, silver (Ag) or aluminum (Al) can be used.
  • an aluminum-silicon (Al—Si) alloy portion 11 is formed in a region on the back surface side of the semiconductor substrate 1 and in contact with the back surface side electrode 9 and in the vicinity thereof.
  • a BSF (Back Surface Filed layer) 12 which is a high-concentration diffusion layer having the same conductivity type as the p-type polycrystalline silicon substrate 2, surrounds the aluminum-silicon (Al—Si) alloy part 11 on the outer periphery. Is formed.
  • the solar cell configured as described above, sunlight is applied from the light receiving surface side of the solar cell to the pn junction surface of the semiconductor substrate 1 (the junction surface between the p-type polycrystalline silicon substrate 2 and the n-type impurity diffusion layer 3).
  • the generated electrons move toward the n-type impurity diffusion layer 3, and the holes move toward the p-type polycrystalline silicon substrate 2.
  • the number of electrons in the n-type impurity diffusion layer 3 becomes excessive, and the number of holes in the p-type polycrystalline silicon substrate 2 becomes excessive.
  • photovoltaic power is generated.
  • This photovoltaic power is generated in the direction of biasing the pn junction in the forward direction, the light receiving surface side electrode 5 connected to the n-type impurity diffusion layer 3 becomes a negative electrode, and the back surface side electrode 9 connected to the p-type polycrystalline silicon substrate 2. Becomes a positive pole, and current flows in an external circuit (not shown).
  • FIG. 2 is a flowchart for explaining a manufacturing process of the solar battery cell according to the present embodiment.
  • FIGS. 3-1 to 3-9 are cross-sectional views for explaining the manufacturing process of the solar battery cell according to the present embodiment.
  • a p-type polycrystalline silicon substrate most frequently used for consumer solar cells is prepared (hereinafter referred to as a p-type polycrystalline silicon substrate 1a).
  • a polycrystalline silicon substrate having dimensions of, for example, 150 mm ⁇ 150 mm and a resistivity of about 0.5 ⁇ cm to 3 ⁇ cm is used.
  • the p-type polycrystalline silicon substrate 1a is manufactured by slicing an ingot formed by cooling and solidifying molten silicon with a wire saw, damage at the time of slicing remains on the surface. Therefore, the p-type polycrystalline silicon substrate 1a is first removed by immersing the surface of the p-type polycrystalline silicon substrate 1a in an acid or a heated alkaline solution, for example, in an aqueous solution of sodium hydroxide so as to remove the damaged layer. Thus, the damaged region existing near the surface of the p-type polycrystalline silicon substrate 1a is removed.
  • minute unevenness is formed as a texture structure on the light receiving surface side surface of the p-type polycrystalline silicon substrate 1a (FIG. 3-1, step S10).
  • a texture structure By forming such a texture structure on the light receiving surface side of the semiconductor substrate 1, multiple reflection of light is caused on the surface of the solar battery cell, and light incident on the solar battery cell is efficiently transmitted to the p-type polycrystalline silicon substrate. 1a can be absorbed, and the reflectance can be effectively reduced and the conversion efficiency can be improved.
  • FIG. 3A the illustration of the texture structure is omitted.
  • this invention is invention concerning the back surface structure of a photovoltaic apparatus, it does not restrict
  • an alkaline aqueous solution containing isopropyl alcohol, a method using acid etching mainly composed of a mixed solution of hydrofluoric acid and nitric acid, or a mask material partially provided with an opening is formed on the surface of the p-type polycrystalline silicon substrate 1a.
  • Any method such as a method of obtaining a honeycomb structure or an inverted pyramid structure on the surface of the p-type polycrystalline silicon substrate 1a by etching through the mask material, or a method using reactive gas etching (RIE) Can be used.
  • RIE reactive gas etching
  • this p-type polycrystalline silicon substrate 1a is put into a thermal oxidation furnace and heated in an atmosphere of phosphorus (P) which is an n-type impurity.
  • phosphorus (P) is diffused on the surface of the p-type polycrystalline silicon substrate 1a, and an n-type impurity diffusion layer 3 is formed as a bonding layer having a conductivity type opposite to that of the p-type polycrystalline silicon substrate 1a.
  • a bond is formed (FIG. 3-2, step S20).
  • the n-type impurity diffusion layer 3 is formed by heating the p-type polycrystalline silicon substrate 1a in a phosphorus oxychloride (POCl3) gas atmosphere at a temperature of 800 ° C. to 850 ° C., for example.
  • POCl3 phosphorus oxychloride
  • a phosphorus glass layer mainly composed of glass is formed on the surface immediately after the formation of the n-type impurity diffusion layer 3, it is removed using a hydrofluoric acid solution or the like.
  • a silicon nitride film (SiN film) is formed as the antireflection film 4 on the light receiving surface side of the p-type polycrystalline silicon substrate 1a on which the n-type impurity diffusion layer 3 is formed in order to improve the photoelectric conversion efficiency (FIG. 3-3, Step S30).
  • a plasma CVD method is used, and a silicon nitride film is formed as the antireflection film 4 using a mixed gas of silane and ammonia.
  • the film thickness and refractive index of the antireflection film 4 are set to values that most suppress light reflection. Note that two or more films having different refractive indexes may be laminated as the antireflection film 4. Further, a different film forming method such as a sputtering method may be used for forming the antireflection film 4. Further, a silicon oxide film may be formed as the antireflection film 4.
  • the n-type impurity diffusion layer 3 formed on the back surface of the p-type polycrystalline silicon substrate 1a is removed by diffusion of phosphorus (P) (FIG. 3-4, step S40).
  • P phosphorus
  • the removal of the n-type impurity diffusion layer 3 formed on the back surface of the p-type polycrystalline silicon substrate 1a is performed using, for example, a single-sided etching apparatus.
  • a method of using the antireflection film 4 as a mask material and immersing the entire p-type polycrystalline silicon substrate 1a in an etching solution may be used.
  • an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide heated to room temperature to 95 ° C., preferably 50 ° C. to 70 ° C., or a mixed aqueous solution of nitric acid and hydrofluoric acid can be used.
  • the silicon surface exposed on the back surface of the semiconductor substrate 1 is washed in order to keep the recombination rate low in film formation described later. Cleaning is performed, for example, by RCA cleaning (step S50).
  • a back surface insulating film (back surface passivation film) 8 made of a silicon nitride film (SiN film) is formed on the back surface side (opposite to the light receiving surface) of the semiconductor substrate 1 (FIG. 3-5, step S60).
  • a back surface insulating film (back surface passivation film) 8 made of a silicon nitride film (SiN film) having a thickness of about 100 nm to 200 nm is formed by plasma CVD.
  • a stripe-shaped opening 8a for formation is formed (FIG. 3-6, step S70).
  • the stripe-shaped openings 8a are formed by, for example, direct patterning by laser irradiation on the back surface insulating film (back surface passivation film) 8. Laser irradiation is performed, for example, with a spot diameter (opening width W of the opening 8a) of 60 nm and an interval of 0.5 mm to 3.0 mm. Further, the length of the opening 8 a is set to a dimension close to the length of one side of the semiconductor substrate 1.
  • the film is applied in a limited manner by screen printing so as not to contact the backside electrode material paste 9a that covers a region that is slightly larger than the diameter and fills the adjacent opening 8a (FIG. 3-7, step S80).
  • the application shape, the application amount, and the like of the back surface side electrode material paste 9a are set such that, for example, the opening width W of the opening 8a: the electrode thickness T after firing is 1.5: 1.
  • the electrode thickness T after baking is the height from the back surface insulating film (back surface passivation film) 8 of the back electrode 9 after baking.
  • a light receiving surface electrode material paste 5 a which is an electrode material of the light receiving surface side electrode 5 and contains silver (Ag), glass or the like is formed into the shape of the light receiving surface side electrode 5. It is selectively applied by screen printing and dried (FIG. 3-7, step S80).
  • the light-receiving surface electrode material paste 5a for example, prints a pattern of long grid electrodes 6 and a pattern of strip-shaped bus electrodes 7 in a direction substantially orthogonal to the pattern.
  • step S90 firing is performed at, for example, a peak temperature of 760 ° C. to 900 ° C. using an infrared heating furnace (FIG. 3-8, step S90).
  • the light receiving surface side electrode 5 and the back surface side electrode 9 are formed, and the Al—Si alloy portion 11 is formed in the region on the back surface side of the semiconductor substrate 1 and in contact with the back surface side electrode 9 and its vicinity. Is done.
  • a BSF 12 that is a p + region in which aluminum is diffused in a high concentration from the back surface side electrode 9 is formed on the outer periphery of the Al—Si alloy portion 11, and the BSF layer 12 and the back surface side electrode 9 are electrically connected to each other. Connect.
  • a forming gas annealing process is performed at 300 ° C. to 400 ° C. for 10 minutes in an atmosphere of a forming gas (for example, an inert gas containing 5% hydrogen) (step S100).
  • a forming gas for example, an inert gas containing 5% hydrogen
  • the region where the back electrode material paste 9a is not applied on the back surface of the semiconductor substrate 1 is protected by the back surface insulating film (passivation film) 8 made of a silicon nitride film (SiN film).
  • the adherence and fixation of contaminants do not proceed to the back surface of the semiconductor substrate 1, and a good state is maintained without degrading the recombination speed.
  • a highly reflective structure is formed on the back side of the semiconductor substrate 1. That is, a silver (Ag) film (silver sputtering film) is formed on the entire back surface of the semiconductor substrate 1 by vapor deposition so as to cover the back surface side electrode 9 and the back surface insulating film (passivation film) 8 ( FIG. 3-9, step S110). In addition, you may form the back surface reflecting film 10 by adhesion
  • Ag silver sputtering film
  • the solar battery cell according to Embodiment 1 shown in FIGS. 1-1 to 1-4 is manufactured.
  • the order of application of the paste as the electrode material may be switched between the light receiving surface side and the back surface side.
  • a solar battery cell was produced according to the method for manufacturing a solar battery cell according to this embodiment described above, and this was used as a solar battery cell of the example. Further, for comparison of solar cell characteristics, an aluminum electrode as a back electrode 9 is formed on the entire back surface of the semiconductor substrate 1 without forming a back insulating film (passivation film) 8 on the back surface of the semiconductor substrate 1. Except having formed, the photovoltaic cell was formed like the manufacturing method of the photovoltaic cell concerning this Embodiment mentioned above, and this was made into the photovoltaic cell of the comparative example A.
  • the manufacture of the solar battery cell according to this embodiment described above is performed. Then, the solar cell is formed by filling the opening 8a and forming an aluminum electrode as the back side electrode 9 on the entire back side of the semiconductor substrate 1 and then forming the solar cell. A solar battery cell was obtained.
  • a back surface insulating film (passivation film) 8 on the back surface side of the semiconductor substrate 1, circular (dot-shaped) openings having a diameter of 0.1 mm to 0.3 mm are formed at intervals of 0.5 mm to 2.5 mm. And further fills the circular (dot-shaped) opening and covers an area somewhat wider than the diameter of the circular (dot-shaped) opening in the in-plane direction of the back surface insulating film (back surface passivation film) 8
  • a solar cell was formed by forming an aluminum electrode so as not to come into contact with the back-side electrode material paste 9a filling the circular (dot-shaped) opening to be made, and this was used as the solar cell of Comparative Example C.
  • FIG. 4 is a characteristic diagram showing voltage-current characteristics of the solar battery cell according to the example.
  • each of the product of the open circuit voltage and the short circuit current (Voc ⁇ Jsc), the fill factor (FF), and the conversion efficiency (Eff) with respect to the interelectrode pitch P of the back-side electrode 9 is used as a parameter of the voltage-current characteristic.
  • the values normalized by taking the value obtained from the IV measurement of Comparative Example A as 1 were plotted.
  • the pitch P between the backside electrodes 9 increased, the product of the open circuit voltage and the short circuit current (Voc ⁇ Jsc) increased, but the fill factor (FF) tended to decrease.
  • the conversion efficiency (Eff) when the inter-electrode pitch P of the back surface side electrodes 9 is 1.5 mm to 3.0 mm, aluminum (Al) as the back surface side electrode 9 is formed on the entire back surface side of the semiconductor substrate 1. It exceeded the conversion efficiency (Eff) of the solar battery cell of Comparative Example A in which the electrodes were formed, and the conversion efficiency (Eff) was maximized when the interelectrode pitch P was around 2 mm.
  • the extracted currents were compared by the LBIC (laser beam induced current) method.
  • this examination was performed before formation of the back surface reflection film 10 by the high reflectance material in the cell formation process.
  • a laser having a wavelength of 653 nm is applied from the back side of the semiconductor substrate 1 across several back side electrodes 9 in a direction substantially perpendicular to the extending direction of the striped back side electrodes 9.
  • the semiconductor substrate 1 was irradiated, and the amount of current flowing between the front and back electrodes was measured with respect to the laser irradiation position.
  • FIG. 5 is a characteristic diagram showing the relationship between the laser irradiation position and the extraction current (A) in the solar cell of the example having an interelectrode pitch P of 2 mm.
  • FIG. 6 is a characteristic diagram showing the relationship between the laser irradiation position and the extraction current (A) in the solar battery cell of the example having an interelectrode pitch P of 1 mm. 5 and 6 indicate that the larger the area surrounded by the mountain-shaped plot, the larger the extracted current amount. 5 and 6, it can be seen that the laser extraction current decreases in the range of about 0.5 mm from the back electrode 9 in the laser irradiation direction.
  • the above-described book is formed until the stripe-shaped openings 8a are formed at intervals of 2 mm after the back surface insulating film (passivation film) 8 is formed on the back surface side of the semiconductor substrate 1.
  • the solar cell is manufactured in the same manner as the method for manufacturing the solar cell according to the embodiment, and then the aluminum electrode as the back side electrode 9 is formed on the entire back side of the semiconductor substrate 1 while filling the opening 8a.
  • the conversion efficiency exceeded that of the sample in which the metal thin film was formed as the back surface reflecting film as in this embodiment. could not get.
  • Comparative Example B the entire back surface is covered with Al by screen printing, but Al by this screen printing is in the form of particles and has a low light reflectance.
  • the long wavelength light that passed through the substrate and reached the back surface was absorbed by the electrode, and the reflection efficiency was lowered, so the light absorption efficiency in the substrate was lowered, and the short circuit current depending on the amount of generated carriers was reduced. Conceivable.
  • the short circuit current increase by the effect of back surface reflection was able to be confirmed.
  • a back surface insulating film (passivation film) 8 on the back surface side of the semiconductor substrate 1, circular (dot-shaped) openings having a diameter of 0.1 mm to 0.3 mm are formed at intervals of 0.5 mm to 2.5 mm.
  • the fill factor (FF) was as small as 0.7 or less.
  • FF fill factor
  • voids are less likely to occur by increasing the opening area by making the opening 8a reaching the back surface of the semiconductor substrate 1 into a rectangular shape (linear shape). Further, even when a void is generated, a portion where a void is formed and a portion where a void is not formed in the rectangular (linear) opening 8a are alternately arranged in the longitudinal direction of the opening 8a in the same opening 8a. As a result, disconnection due to voids and increase in contact resistance are less likely to occur, and a decrease in fill factor (FF) can be suppressed.
  • FF fill factor
  • the inter-electrode pitch P between the back-side electrodes 9 formed in a stripe shape is 1.5 mm or less, a sufficient passivation effect cannot be obtained due to deterioration of the back-side insulating film (passivation film) 8 or the like.
  • the inter-electrode pitch P of the back-side electrodes 9 formed in a stripe shape is 3.0 mm or more, the resistance when the generated carriers move to the back-side electrodes 9 increases.
  • the inter-electrode pitch P of the back-side electrodes 9 formed in a stripe shape is 1.5 mm to 3.0 mm, it is possible to achieve both a good passivation effect that exceeds the conventional structure and a suppression of an increase in series resistance. it can.
  • the length of the striped back electrode 9 is not limited to this, and the opening 8a is rectangular, and the back electrode 9 adjacent in the direction perpendicular to the longitudinal direction of the opening 8a in the back surface. If the inter-electrode pitch P is in the range of 1.5 mm to 3.0 mm, the same effect can be obtained even if the rectangular backside electrodes 9 having an electrode length L that is at least twice the electrode width are arranged. It is done. That is, the plurality of back surface side electrodes 9 may be discontinuously arranged in the direction of the electrode length L.
  • the printing pattern of the back surface side electrode 9 formed on the opening part 8a was made into the stripe form which covers the opening part 8a, and the opening width W of the opening part 8a was 60 micrometers. .
  • the opening width W of the opening 8a is less than 20 ⁇ m with respect to the inter-electrode pitch P of 1.5 mm or more, the contact resistance increases.
  • the opening width W of the opening 8a is 200 ⁇ m or more with respect to the inter-electrode pitch P of 1.5 mm or more
  • the area occupied by the back-side electrode 9 increases with respect to the electrode interval, thereby reducing the passivation effect. Therefore, it is possible to achieve both a low contact resistance and a passivation effect by setting the opening width W of the opening 8a to 20 ⁇ m to 200 ⁇ m.
  • the opening width W of the opening 8a is set to 20 ⁇ m to 200 ⁇ m, and has a shape similar to that of the opening 8a and slightly overlaps with the back surface insulating film (passivation film) 8 around the opening 8a.
  • the back surface side electrode 9 Is covered with an aluminum (Al) electrode (back surface side electrode 9), thereby reducing the ratio of the aluminum (Al) electrode (back surface side electrode 9) to be formed on the back surface insulating film (passivation film) 8 and increasing the passivation effect. Can be improved. Note that the overlap between the back surface insulating film (passivation film) 8 and the aluminum (Al) electrode (back surface side electrode 9) around the opening 8a is necessary because of the alignment during printing. 9, the width of the back electrode 9 may be 20 ⁇ m to 200 ⁇ m, which is the same as the opening width W of the opening 8a.
  • the electrode thickness T after firing affects the volume due to the heat shrinkage of the electrode.
  • the opening width W of the opening 8a: the electrode thickness T after firing is 1.5: 1, but the opening width W of the opening 8a: the electrode thickness after firing.
  • T is larger than “2: 1”, that is, when the electrode thickness T after firing is less than 50% of the opening width W of the opening 8a, the thickness of the BSF layer 12 is not sufficient, and the solar cell characteristics Leading to a decline.
  • the electrode thickness T after baking is smaller than “1: 1”, that is, the electrode thickness T after baking is larger than 100% of the opening width W of the opening 8a.
  • the electrode volume is large, the suction and void of the electrode are easily formed due to the thermal contraction of the electrode after firing. Therefore, when the opening width W of the opening 8a is in the range of the electrode thickness T after firing of “1: 1 to 2: 1”, that is, the electrode thickness T after firing is 50% or more of the opening width W of the opening 8a.
  • a high fill factor (FF) is obtained when it is in the range of 100% or less.
  • the back surface reflecting film 10 is formed of a highly reflective metal thin film after the electrodes are fired.
  • the aluminum (Al) electrode formed by screen printing on the back surface insulating film (passivation film) 8 becomes particulate, and long wavelength light reaching the back surface cannot be effectively reflected and absorbed there. Therefore, the printing area of the aluminum (Al) electrode is limited only to the opening 8a and its peripheral area, and the other area is covered with a metal thin film having a high reflectance to form the back surface reflecting film 10, thereby forming the back surface on the back surface. The light on the long wavelength side that reaches can be reflected, and the light can be effectively absorbed by the semiconductor substrate 1.
  • a solar battery cell having good solar battery characteristics can be obtained.
  • a p-type polycrystalline silicon substrate is used as the semiconductor substrate 1, but p-type single crystal silicon may be used instead of p-type polycrystalline silicon.
  • FIG. 2 a modification of the method for manufacturing the solar battery cell described in the first embodiment will be described with reference to FIG.
  • the structure of the solar battery cell manufactured according to Embodiment 2 is the same as that of Embodiment 1, and is the structure shown in FIGS. 1-1 to 1-2.
  • steps S10 to S80 in FIG. 2 are performed, and the light receiving surface side electrode 5 and the back surface side electrode 9 are formed by screen printing in the same manner as in the first embodiment (before firing).
  • Step S90 firing is performed at a peak temperature of 760 ° C. to 900 ° C. using, for example, an infrared heating furnace.
  • the light receiving surface side electrode 5 and the back surface side electrode 9 are formed, and the Al—Si alloy portion 11 is formed in the region on the back surface side of the semiconductor substrate 1 and in contact with the back surface side electrode 9 and its vicinity. Is done.
  • the silver in the light receiving surface side electrode 5 penetrates the antireflection film 4, and the n-type impurity diffusion layer 3 and the light receiving surface side electrode 5 are electrically connected.
  • the cooling rate in the vicinity of 600 ° C. to 700 ° C. in the cooling process after firing is set to 10 to 30 ° C./sec.
  • an infrared heating furnace in which a heating chamber and a cooling chamber are separated, and cooling is performed by transporting the semiconductor substrate 1 to the cooling chamber after heating.
  • nitrogen for example, is introduced into the cooling chamber as an inert gas and cooled in a non-oxidizing atmosphere so as not to oxidize as much as possible when aluminum (Al) solidifies during the cooling process.
  • a forming gas annealing process is performed at 300 ° C. to 400 ° C. for 10 minutes in an atmosphere of a forming gas (for example, an inert gas containing 5% hydrogen).
  • a highly reflective structure is formed on the back side of the semiconductor substrate 1. That is, a silver (Ag) film (silver sputtering film) is formed on the entire back surface of the semiconductor substrate 1 by a sputtering method so as to cover the back surface side electrode 9 and the back surface insulating film (passivation film) 8.
  • Ag silver sputtering film
  • the rate of temperature decrease in the vicinity of 600 ° C. to 700 ° C. at which aluminum (Al) solidifies after firing is set to 10 to 30 ° C./sec. Suction of the alloy part 11 can be suppressed.
  • the series resistance can be reduced as compared with the solar cell of Comparative Example D, whereas the fill factor of the solar cell of Comparative Example D was 0.75.
  • the solar cell characteristics were improved by 0.77.
  • the case where a p-type silicon substrate is used as the semiconductor substrate has been described.
  • a reverse conductivity type solar cell in which a p-type diffusion layer is formed using an n-type silicon substrate.
  • a polycrystalline silicon substrate is used as the semiconductor substrate, a single crystal silicon substrate may be used.
  • the size of the semiconductor substrate is 150 mm ⁇ 150 mm, but the size of the semiconductor substrate is not limited to this.
  • the photovoltaic device according to the present invention is useful for the production of a photovoltaic device having good solar cell characteristics.
  • SYMBOLS 1 Semiconductor substrate 1a p-type polycrystalline silicon substrate 2 p-type polycrystalline silicon substrate 3 n-type impurity diffusion layer 4 Antireflection film 5 Light-receiving surface side electrode 5a Light-receiving surface electrode material paste 6 Grid electrode 7 Bus electrode 8 Back surface insulating film 8a Opening Part 9 Back side electrode 9a Back side electrode material paste 10 Back reflective film 11 Aluminum-silicon (Al-Si) alloy part 12 BSF layer P Pitch between electrodes L Back side electrode length (length in longitudinal direction) T Electrode thickness after firing W Opening width of opening

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Abstract

L'invention concerne un dispositif photovoltaïque qui comporte un substrat semi-conducteur (1), d'un premier type de conductivité, possédant une couche de diffusion d'impuretés (3), un film anti-réflexion (4) formé sur la couche de diffusion d'impuretés (3), de premières électrodes (5) connectées électriquement à la couche de diffusion d'impuretés (3), un film d'isolation de face inverse (8) possédant des ouvertures (8a) pénétrant jusqu'à l'autre face du substrat semi-conducteur (1) et formées sur l'autre face du substrat semi-conducteur (1), de secondes électrodes (9) connectées électriquement à l'autre face du substrat semi-conducteur (1) et un film de réflexion de face inverse (10) formé de manière à recouvrir au moins le film d'isolation de face inverse (8). Les ouvertures (8a) sont respectivement presque d'une forme rectangulaire dans la direction du plan de la face inverse du substrat semi-conducteur (1), et une pluralité de celles-ci est disposée selon des droites presque parallèles dans la direction du petit côté de l'ouverture (8a). Les secondes électrodes (9) sont respectivement presque de la même forme des ouvertures (8a) et une pluralité de celles-ci est disposée selon des droites presque parallèles, à un pas entre électrodes compris entre 1,5 et 3,0 mm dans la direction du petit côté de la seconde électrode. La largeur de la seconde électrode (9) dans la direction du petit côté est comprise entre 20 et 200 µm.
PCT/JP2010/058288 2009-12-14 2010-05-17 Dispositif photovoltaïque et son procédé de préparation WO2011074280A1 (fr)

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JP2015073065A (ja) * 2013-10-02 2015-04-16 台湾茂▲し▼電子股▲ふん▼有限公司Ｍｏｓｅｌ Ｖｉｔｅｌｉｃ Ｉｎｃ． 太陽電池の製造方法
US20220310865A1 (en) * 2020-09-23 2022-09-29 Suzhou Talesun Solar Technologies Co., Ltd. Laminated cell structure and preparation method thereof

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JPS6262229A (ja) * 1985-09-13 1987-03-18 Minolta Camera Co Ltd 多分割測光装置を有するカメラ
CN103489934B (zh) * 2013-09-25 2016-03-02 晶澳（扬州）太阳能科技有限公司 一种双面透光的局部铝背场太阳能电池及其制备方法
CN107078177A (zh) * 2014-09-22 2017-08-18 京瓷株式会社 太阳能电池元件
TWI590473B (zh) * 2014-10-24 2017-07-01 昱晶能源科技股份有限公司 太陽能電池及其製造方法
JP6502651B2 (ja) 2014-11-13 2019-04-17 信越化学工業株式会社 太陽電池の製造方法及び太陽電池モジュールの製造方法
JP6486219B2 (ja) * 2015-06-24 2019-03-20 三菱電機株式会社 太陽電池の製造方法

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JP2004006565A (ja) * 2002-04-16 2004-01-08 Sharp Corp 太陽電池とその製造方法

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JP2004006565A (ja) * 2002-04-16 2004-01-08 Sharp Corp 太陽電池とその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015073065A (ja) * 2013-10-02 2015-04-16 台湾茂▲し▼電子股▲ふん▼有限公司Ｍｏｓｅｌ Ｖｉｔｅｌｉｃ Ｉｎｃ． 太陽電池の製造方法
US20220310865A1 (en) * 2020-09-23 2022-09-29 Suzhou Talesun Solar Technologies Co., Ltd. Laminated cell structure and preparation method thereof

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