WO2014112053A1 - Cellule solaire et procédé de fabrication associé - Google Patents

Cellule solaire et procédé de fabrication associé Download PDF

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Publication number
WO2014112053A1
WO2014112053A1 PCT/JP2013/050676 JP2013050676W WO2014112053A1 WO 2014112053 A1 WO2014112053 A1 WO 2014112053A1 JP 2013050676 W JP2013050676 W JP 2013050676W WO 2014112053 A1 WO2014112053 A1 WO 2014112053A1
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Prior art keywords
semiconductor substrate
layer
surface side
electrode
back surface
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PCT/JP2013/050676
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English (en)
Japanese (ja)
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唐木田　昇市
濱本　哲
雅人 米澤
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三菱電機株式会社
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Priority to JP2014557227A priority Critical patent/JP6113196B2/ja
Priority to PCT/JP2013/050676 priority patent/WO2014112053A1/fr
Publication of WO2014112053A1 publication Critical patent/WO2014112053A1/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
    • H01L31/02—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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
    • 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
    • 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

Definitions

  • the present invention relates to a solar battery cell and a manufacturing method thereof.
  • solar cells Conventional bulk silicon solar cells (hereinafter sometimes referred to as solar cells) are generally manufactured by the following method.
  • a p-type silicon substrate is prepared as a first conductivity type substrate.
  • the damaged layer on the silicon surface generated when the silicon substrate is sliced from the cast ingot is removed with a thickness of 10 ⁇ m to 20 ⁇ m with an alkaline solution such as sodium hydroxide or potassium hydroxide of several wt% to 20 wt%, for example.
  • a surface uneven structure called texture is formed on the surface from which the damage layer has been removed.
  • a texture is usually formed in order to suppress light reflection and capture as much sunlight as possible onto the p-type silicon substrate.
  • an alkali texture method As a method for producing the texture, for example, there is a method called an alkali texture method.
  • anisotropic etching is performed with a solution in which an additive that promotes anisotropic etching such as IPA (isopropyl alcohol) is added to a low concentration alkali solution such as sodium hydroxide or potassium hydroxide of several wt%. Then, the texture is formed so that the silicon (111) surface appears.
  • IPA isopropyl alcohol
  • the p-type silicon substrate is treated for several tens of minutes at, for example, 800 ° C. to 900 ° C. in a mixed gas atmosphere of, for example, phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen, and the second surface is uniformly applied to the entire surface.
  • An n-type layer is formed as a conductive impurity layer.
  • the end face region of the p-type silicon substrate is etched by dry etching, for example.
  • end face separation of the p-type silicon substrate may be performed by a laser. Thereafter, the p-type silicon substrate is immersed in a hydrofluoric acid aqueous solution, and the glassy material (PSG) deposited on the surface during the diffusion treatment is removed by etching.
  • PSG glassy material
  • an insulating film such as a silicon oxide film, a silicon nitride film, or a titanium oxide film is formed with a uniform thickness on the surface of the n-type layer as an insulating film (antireflection film) for the purpose of preventing reflection.
  • an insulating film such as a silicon oxide film, a silicon nitride film, or a titanium oxide film is formed with a uniform thickness on the surface of the n-type layer as an insulating film (antireflection film) for the purpose of preventing reflection.
  • a silicon nitride film as the antireflection film, for example, it is formed by plasma CVD using silane (SiH 4 ) gas and ammonia (NH 3 ) gas as raw materials under conditions of 300 ° C. or higher and reduced pressure.
  • the refractive index of the antireflection film is about 2.0 to 2.2, and the optimum film thickness is about 70 nm to 90 nm. It should be noted that the antireflection film formed
  • a silver paste to be a surface side electrode is applied to the shape of the grid electrode and the bus electrode on the antireflection film by a screen printing method and dried.
  • the silver paste for the surface-side electrode is formed on an insulating film for the purpose of preventing reflection.
  • the back aluminum electrode paste containing aluminum, glass, etc., which becomes the back aluminum electrode, and the back silver paste which becomes the back silver bus electrode are screen-printed into the shape of the back aluminum electrode and the shape of the back silver bus electrode on the back surface of the substrate, respectively. Apply and dry.
  • the electrode paste applied to the front and back surfaces of the silicon substrate is simultaneously fired at about 600 ° C. to 900 ° C. for several minutes to several tens of seconds.
  • a grid electrode and a bus electrode are formed on the front surface side of the silicon substrate as surface side electrodes
  • a back aluminum electrode and a back silver bus electrode are formed on the back surface side of the silicon substrate as back surface side electrodes.
  • the silver material comes into contact with silicon and re-solidifies while the antireflection film is melted with the glass material contained in the silver paste. Thereby, electrical connection between the surface side electrode and the silicon substrate (n-type layer) is ensured.
  • Such a process is called a fire-through method.
  • the back aluminum electrode paste also reacts with the back surface of the silicon substrate to compensate for the n-type layer formed by diffusion immediately below the back aluminum electrode, thereby forming a P + layer.
  • the aluminum electrode formed using the aluminum paste has low light reflectance, and light incident on the light receiving surface side, transmitted through the solar cell, and reached the back surface of the solar cell. Low reflectivity.
  • the light reaching the back surface of the solar battery cell cannot be effectively used, and the photoelectric conversion efficiency cannot be improved by light reflection on the back surface.
  • the present invention has been made in view of the above, and is a solar cell in which the connection of a tab wire to an electrode is easy and the photoelectric conversion efficiency is improved by light reflection on the back surface, and a method for manufacturing the solar cell. The purpose is to obtain.
  • a solar battery cell includes a first conductivity type semiconductor substrate having an impurity diffusion layer in which a second conductivity type impurity element is diffused on one surface side.
  • a light receiving surface side electrode electrically connected to the impurity diffusion layer and formed on one surface side of the semiconductor substrate, and a light reflectance higher than that of an aluminum electrode formed of an aluminum paste, and the other surface of the semiconductor substrate
  • a light reflection layer that is formed in a partial region on the side and reflects light transmitted through the semiconductor substrate from one surface side of the semiconductor substrate; electrically connects the other surface side of the semiconductor substrate and other solar cells.
  • a conductive film that is a connection layer for connecting tab wires to be connected to each other and that is attached on a region excluding the light reflection layer on the other surface side of the semiconductor substrate.
  • the present invention there is an effect that it is possible to obtain a solar cell in which the tab wire can be easily connected to the electrode and the photoelectric conversion efficiency is improved by the light reflection on the back surface.
  • FIG. 1-1 is a diagram schematically showing the configuration of the solar battery cell according to the first embodiment of the present invention.
  • FIG. 1-2 is a diagram schematically showing the configuration of the solar battery cell according to the first embodiment of the present invention.
  • FIG. 1-3 is a diagram schematically showing a configuration of the solar battery cell according to the first embodiment of the present invention.
  • FIG. 1-4 is a diagram schematically showing the configuration of the solar battery cell according to the first embodiment of the present invention.
  • FIG. 1-5 is a diagram schematically illustrating the configuration of the solar battery cell according to the first embodiment of the present invention.
  • FIG. 2 is a flowchart for explaining an example of the manufacturing process of the solar battery cell according to the embodiment of the present invention and a method of connecting a tab to the back surface of the solar battery cell.
  • FIGS. 3-1 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-2 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-3 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-4 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-5 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-7 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-8 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-9 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-10 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-7 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-8 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIGS. 3-9 is process drawing which shows typically an example of the manufacturing process
  • FIGS. 3-11 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIG. 3-12 is a process diagram schematically showing an example of the manufacturing process of the solar battery cell according to the first embodiment of the present invention.
  • FIGS. 3-13 is process drawing which shows typically an example of the manufacturing process of the photovoltaic cell concerning Embodiment 1 of this invention.
  • FIGS. FIG. 4A is a process diagram schematically showing a process of connecting a tab to the back surface of the solar battery cell in the module process.
  • FIG. 4-2 is a process diagram schematically showing a process of connecting the tab to the back surface of the solar battery cell in the module process.
  • FIG. 4-3 is a process diagram schematically showing a process of connecting the tab to the back surface of the solar battery cell in the module process.
  • FIG. 4-4 is a process diagram schematically showing a process of connecting the tab to the back surface of the solar battery cell in the module process.
  • FIG. 4-5 is a process diagram schematically showing a process of connecting the tab to the back surface of the solar battery cell in the module process.
  • FIG. 5-1 is a top view schematically showing an aluminum foil with a conductive film according to the second embodiment of the present invention.
  • FIG. 5-2 is a cross-sectional view schematically showing the aluminum foil with a conductive film according to the second embodiment of the present invention, and is a cross-sectional view of the main part in the CC direction of FIG.
  • FIG. 5-1 is a top view schematically showing an aluminum foil with a conductive film according to the second embodiment of the present invention.
  • FIG. 5-2 is a cross-sectional view schematically showing the aluminum foil with a conductive film according to
  • FIG. 6-1 is a process diagram schematically illustrating a process of connecting a tab to the back surface of the solar battery cell when using the aluminum foil with a conductive film according to the second embodiment of the present invention.
  • FIG. 6-2 is a process diagram schematically showing a process of connecting a tab to the back surface of the solar battery cell when using the aluminum foil with a conductive film according to the second embodiment of the present invention.
  • FIG. 7-1 is a bottom view of the semiconductor substrate schematically showing the method for forming the high light reflection film according to the third embodiment of the present invention.
  • FIG. 7-2 is a bottom view of the semiconductor substrate schematically showing the method for forming the high light reflection film according to the third embodiment of the present invention.
  • FIGS. 7-3 is a bottom view of the semiconductor substrate schematically showing the method for forming the high light reflection film according to the third embodiment of the present invention.
  • FIG. 7-4 is a bottom view of the semiconductor substrate schematically showing the method for forming the high light reflection film according to the third embodiment of the present invention.
  • FIGS. 8-1 is sectional drawing which shows typically the manufacturing method of the photovoltaic cell concerning Embodiment 4 of this invention.
  • FIGS. FIGS. 8-2 is sectional drawing which shows typically the manufacturing method of the photovoltaic cell concerning Embodiment 4 of this invention.
  • FIG. FIGS. 1-1 to 1-5 are diagrams schematically showing the configuration of the solar battery cell 1 according to the first embodiment of the present invention.
  • FIG. 1-1 is a top view of the solar battery cell 1 viewed from the light receiving surface side.
  • FIG. 1-2 is a bottom view of the solar battery cell 1 as viewed from the side opposite to the light receiving surface (back surface).
  • 1-3 is a cross-sectional view of the main part of the solar battery cell 1, and is a cross-sectional view of the main part in the AA direction of FIGS. 1-1 and 1-2.
  • 1-4 is a cross-sectional view of the main part of the solar battery cell 1, and is a cross-sectional view of the main part in the BB direction of FIGS. 1-1 and 1-2.
  • FIG. 1-1 is a top view of the solar battery cell 1 viewed from the light receiving surface side.
  • FIG. 1-2 is a bottom view of the solar battery cell 1 as viewed from the side opposite to the light receiving surface (back surface).
  • FIG. 1-5 shows the sun as viewed from the side opposite to the light receiving surface (back surface) in a state where the conductive film 22 which is a connection layer for connecting tab wires for electrically connecting the solar cells is attached.
  • 2 is a bottom view of the battery cell 1.
  • FIG. The solar battery cell 1 is a silicon solar battery used for home use or the like.
  • an n-type impurity diffusion layer 3 is formed by phosphorous diffusion on the light receiving surface side of a semiconductor substrate 2 made of p-type single crystal silicon, and a semiconductor substrate 11 having a pn junction is formed.
  • an antireflection film 4 made of a silicon nitride film (SiN film) is formed on the n-type impurity diffusion layer 3.
  • the semiconductor substrate 2 is not limited to a p-type single crystal silicon substrate, and an n-type single crystal silicon substrate may be used.
  • a texture structure composed of minute irregularities 2a is formed on the light receiving surface side (n-type impurity diffusion layer 3) and the back surface side of the semiconductor substrate 11.
  • the texture structure increases the area for absorbing light from the outside on the light receiving surface, suppresses the light reflectance on the light receiving surface, and confines light.
  • the antireflection film 4 is made of an insulating film for the purpose of preventing reflection, such as a silicon nitride film (SiN film), a silicon oxide film (SiO 2 film), or a titanium oxide film (TiO 2 ) film.
  • a plurality of long and narrow surface silver grid electrodes 5 are provided side by side on the light receiving surface side of the semiconductor substrate 11, and a surface silver bus electrode 6 electrically connected to the surface silver grid electrode 5 is substantially the same as the surface silver grid electrode 5. They are provided so as to be orthogonal to each other, and are respectively electrically connected to the n-type impurity diffusion layer 3 at the bottom portion.
  • the front silver grid electrode 5 and the front silver bus electrode 6 are made of a silver material.
  • the front silver grid electrode 5 has a width of about 100 ⁇ m to 200 ⁇ m, for example, and is arranged substantially in parallel at intervals of about 2 mm, and collects electricity generated inside the semiconductor substrate 11. Further, the front silver bus electrodes 6 have a width of, for example, about 1 mm to 3 mm and are arranged in a number of 2 to 4 per solar battery cell, and the electricity collected by the front silver grid electrode 5 is taken out to the outside.
  • the front silver grid electrode 5 and the front silver bus electrode 6 constitute a light receiving surface side electrode 12 as a first electrode. Since the light receiving surface side electrode 12 blocks sunlight incident on the semiconductor substrate 11, it is desirable to reduce the area as much as possible from the viewpoint of improving the power generation efficiency, and a comb-shaped surface as shown in FIG. In general, the silver grid electrode 5 and the bar-shaped front silver bus electrode 6 are arranged.
  • a silver paste is usually used, for example, lead boron glass is added.
  • This glass has a frit shape and is composed of, for example, lead (Pb) 5-30 wt%, boron (B) 5-10 wt%, silicon (Si) 5-15 wt%, and oxygen (O) 30-60 wt%. Furthermore, zinc (Zn), cadmium (Cd), etc. may be mixed by several wt%.
  • lead boron glass has a property of melting by heating at several hundred degrees C. (for example, 800.degree. C.) and eroding silicon at that time.
  • a method of obtaining electrical contact between a silicon substrate and a silver paste by using the characteristics of the glass frit is used.
  • a back silver sputtering film 8 which is a reflective film is provided.
  • the back aluminum electrode 9 has a comb shape like the light receiving surface side of the semiconductor substrate 11 so that current collection from the back surface of the semiconductor substrate 11 can be efficiently performed.
  • the intersection part is formed in a substantially square shape.
  • the square portions are arranged in substantially the same direction as the front silver bus electrode 6. Since the back silver sputtering film 8 is disposed over the entire back surface of the semiconductor substrate 11, even when the electrode pattern of the back aluminum electrode 9 is broken, electricity can be collected and also has a role of assisting the electrode. . As shown in FIG. 1-5, tab wires 21 made of a conductive material for electrically connecting the solar cells 1 to each other are connected to the back aluminum electrode 9 in the module process.
  • a P + layer (BSF (Back Surface Field) layer) 10 containing a high concentration impurity is formed in a lower region of the back aluminum electrode 9 in the surface layer portion on the back surface (surface opposite to the light receiving surface) of the semiconductor substrate 11. Is formed.
  • the P + layer 10 is provided to obtain the BSF effect, and the electron concentration of the p-type layer (semiconductor substrate 2) is increased by an electric field having a band structure so that electrons in the p-type layer (semiconductor substrate 2) do not disappear. .
  • the solar cell 1 configured as described above, sunlight is applied to the pn junction surface (the junction surface between the semiconductor substrate 2 and the n-type impurity diffusion layer 3) of the semiconductor substrate 11 from the light receiving surface side of the solar cell 1. Then, holes and electrons are generated. The generated electrons move toward the n-type impurity diffusion layer 3 and the holes move toward the P + layer 10 due to the electric field at the pn junction. As a result, the number of electrons in the n-type impurity diffusion layer 3 becomes excessive and the number of holes in the P + layer 10 becomes excessive. As a result, 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 12 connected to the n-type impurity diffusion layer 3 becomes a negative pole, and the back aluminum electrode 9 connected to the P + layer 10 becomes a positive pole. Thus, a current flows through an external circuit (not shown).
  • FIG. 2 is a flowchart for explaining an example of the manufacturing process of solar cell 1 according to the embodiment of the present invention and a method of connecting tab wire 21 to the back surface of solar cell 1.
  • FIGS. 3-1 to 3-13 are process diagrams schematically showing an example of the manufacturing process of the solar battery cell 1 according to the first embodiment of the present invention.
  • FIGS. 3-1 to 3-6 are cross-sectional views of relevant parts corresponding to the AA and BB directions in FIGS. 1-1 and 1-2.
  • 3-7 and 3-10 are bottom views.
  • 3-8 and FIG. 3-11 are cross-sectional views of relevant parts corresponding to the direction AA in FIGS. 1-1 and 1-2.
  • FIGS. 4A to 4E are process diagrams schematically showing a process of connecting the tab wire 21 to the back surface of the solar battery cell 1.
  • FIGS. 4A to 4E are process diagrams schematically showing a process of connecting the tab wire 21 to the back surface of the solar battery cell 1.
  • a p-type single crystal silicon substrate having a thickness of several hundred ⁇ m is prepared as the semiconductor substrate 2 (FIG. 3A). Since the p-type single crystal silicon substrate 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 single crystal silicon substrate is etched near the surface of the p-type single crystal silicon substrate by etching the surface by immersing the surface in an acid or heated alkaline solution, for example, an aqueous sodium hydroxide solution. Remove the damage area that exists in the.
  • an acid or heated alkaline solution for example, an aqueous sodium hydroxide solution.
  • the surface is removed by a thickness of 10 ⁇ m to 20 ⁇ m with an alkali solution such as sodium hydroxide or potassium hydroxide of several wt% to 20 wt%.
  • an alkali solution such as sodium hydroxide or potassium hydroxide of several wt% to 20 wt%.
  • a p-type silicon substrate used for the semiconductor substrate 2 a p-type single crystal silicon substrate having a specific resistance of 0.1 ⁇ ⁇ cm to 5 ⁇ ⁇ cm and having a (100) plane orientation will be described as an example.
  • an additive that promotes anisotropic etching such as IPA (isopropyl alcohol) is added to the same alkaline low concentration solution, such as several wt% sodium hydroxide or potassium hydroxide.
  • Anisotropic etching is performed with the solution.
  • a micro-concave pattern 2a having a substantially quadrangular pyramid shape is formed on the light-receiving surface side and back surface side of the p-type single crystal silicon substrate so that the silicon (111) surface is exposed, thereby forming a texture structure. (Step S10, FIG. 3-2). That is, the texture structure is formed on the front and back surfaces of the p-type single crystal silicon substrate by wet etching (alkali texture method) using an alkaline solution.
  • a pn junction is formed in the semiconductor substrate 2 (step S20, FIG. 3-3). That is, a group V element such as phosphorus (P) is diffused into the semiconductor substrate 2 to form the n-type impurity diffusion layer 3 having a thickness of several hundred nm.
  • a pn junction is formed by diffusing phosphorus oxychloride (POCl 3 ) by thermal diffusion with respect to a p-type single crystal silicon substrate having a texture structure on the surface.
  • the p-type single crystal silicon substrate is placed in a mixed gas atmosphere of, for example, phosphorus oxychloride (POCl 3 ) gas nitrogen gas and oxygen gas at a high temperature of, for example, 800 ° C. to 900 ° C. for several tens of minutes.
  • the n-type impurity diffusion layer 3 in which phosphorus (P) is diffused is uniformly formed in the surface layer of the p-type single crystal silicon substrate by thermal diffusion.
  • Good electrical characteristics of the solar cell can be obtained when the sheet resistance range of the n-type impurity diffusion layer 3 formed on the surface of the semiconductor substrate 2 is about 30 ⁇ / ⁇ to 80 ⁇ / ⁇ .
  • the n-type impurity diffusion layer 3 is formed on the entire surface of the semiconductor substrate 2. For this reason, the front surface (light receiving surface) and the back surface of the semiconductor substrate 2 are in an electrically connected state. Therefore, in order to cut off this electrical connection, the end face region of the semiconductor substrate 2 is etched by dry etching, for example (FIG. 3-4). Further, a glassy (phosphosilicate glass, PSG: Phospho-Silicate Glass) layer deposited on the surface during the diffusion process is formed on the surface immediately after the formation of the n-type impurity diffusion layer 3. For this reason, the semiconductor substrate 2 is immersed in a hydrofluoric acid aqueous solution or the like to remove the PSG layer by etching.
  • PSG Phospho-Silicate Glass
  • an insulating film such as a silicon oxide film, a silicon nitride film, and a titanium oxide film is formed with a uniform thickness as an antireflection film 4 on one surface of the semiconductor substrate 11 on the light receiving surface side (Ste S30, FIG. 3-4).
  • the film thickness and refractive index of the antireflection film 4 are set to values that most suppress light reflection.
  • the antireflection film 4 is formed by using, for example, a plasma CVD method, using a mixed gas of silane (SiH 4 ) gas and ammonia (NH 3 ) gas as a raw material, and at 300 ° C. or higher and under reduced pressure. 4, a silicon nitride film is formed.
  • the refractive index is, for example, about 2.0 to 2.2, and the optimum antireflection film thickness is, for example, 70 nm to 90 nm.
  • the antireflection film 4 two or more films having different refractive indexes may be laminated.
  • the antireflection film 4 may be formed by vapor deposition, thermal CVD, or the like. It should be noted that the antireflection film 4 formed in this manner is an insulator, and simply forming the light receiving surface side electrode 12 on the surface does not act as a solar battery cell.
  • the n-type impurity diffusion layer 3 formed on the back surface of the semiconductor substrate 2 is removed by diffusion of phosphorus (P).
  • P phosphorus
  • the semiconductor substrate 2 made of p-type single crystal silicon which is the first conductivity type layer, and the n-type impurity diffusion layer 3 which is the second conductivity type layer formed on the light receiving surface side of the semiconductor substrate 2 A semiconductor substrate 11 having a pn junction is obtained (FIGS. 3-5).
  • the n-type impurity diffusion layer 3 is formed only on one surface of the semiconductor substrate 2, the above-described etching of the end surface region of the semiconductor substrate 2 and the removal of the n-type impurity diffusion layer 3 formed on the back surface of the semiconductor substrate 2 are performed. Is unnecessary.
  • a back surface passivation film 7 made of a silicon nitride film (SiN film) is formed on the back surface side of the semiconductor substrate 11 (step S40, FIGS. 3-6).
  • a back surface passivation film 7 made of a silicon nitride film (SiN film) having a refractive index of 1.9 to 2.2 and a thickness of 60 nm to 300 nm is formed on the silicon surface exposed on the back surface side of the semiconductor substrate 11 by, for example, plasma CVD. Form a film.
  • an opening 7a is formed in a region where a back aluminum paste for forming the back aluminum electrode 9 is applied (step S50, FIG. 3-7, FIG. 3-8, FIG. 3-9).
  • the opening 7a is formed using, for example, a laser or an etching paste. If the back aluminum paste to be used can fire through the back surface passivation film 7, this step is not necessary.
  • the opening 7a is formed in a comb-like pattern as shown in FIG. 3-7, for example.
  • 3-8 is a cross-sectional view of the main part in the AA direction in FIG. 3-7.
  • 3-9 is a cross-sectional view of the principal part in the BB direction in FIG. 3-7.
  • electrodes are formed by screen printing.
  • the light-receiving surface side electrode 12 is produced (before firing). That is, a silver paste, which is an electrode material paste containing glass frit, is applied to the shape of the front silver grid electrode 5 and the front silver bus electrode 6 on the antireflection film 4 that is the light receiving surface of the semiconductor substrate 11 by screen printing. Thereafter, the silver paste is dried (step S60).
  • a back aluminum paste as an electrode material paste is applied to the shape of the back aluminum electrode 9 by screen printing on the back side of the semiconductor substrate 11 and dried (step S70).
  • the back aluminum paste is printed by filling the openings 7 a provided in the back surface passivation film 7.
  • the electrode paste on the front and back surfaces of the semiconductor substrate 11 is simultaneously fired at, for example, 600 ° C. to 900 ° C., so that the antireflection film 4 is melted with the glass material contained in the silver paste on the front side of the semiconductor substrate 11.
  • the silver material comes into contact with the silicon and re-solidifies.
  • the surface silver grid electrode 5 and the surface silver bus electrode 6 as the light-receiving surface side electrode 12 are obtained, and conduction between the light-receiving surface side electrode 12 and the silicon of the semiconductor substrate 11 is ensured (step S80, FIG. 3).
  • -10, Fig. 3-11, Fig. 3-12 Such a process is called a fire-through method.
  • 3-11 is a cross-sectional view of the main part in the AA direction in FIG. 3-10.
  • 3-12 is a cross-sectional view of the principal part in the BB direction in FIG. 3-10.
  • the back aluminum paste reacts with the silicon of the semiconductor substrate 11 to obtain the back aluminum electrode 9, and the P + layer 10 is formed immediately below the back aluminum electrode 9. Further, the silver material of the silver paste comes into contact with silicon and re-solidifies to obtain the back silver electrode 8. In the figure, only the front silver grid electrode 5 and the back aluminum electrode 9 are shown.
  • a back silver sputtering film 8 is formed as a high light reflection film on the back surface passivation film 7 on the back surface of the semiconductor substrate 11 by sputtering (step S90, FIG. 3-13). Note that there is no particular problem even if silver is sputtered on the back aluminum electrode 9.
  • the solar battery cell 1 according to the present embodiment shown in FIGS. 1-1 to 1-4 is obtained.
  • the order of arrangement of the paste, which is an electrode material, on the semiconductor substrate 11 may be switched between the light receiving surface side and the back surface side.
  • FIG. 4A is a bottom view of the solar battery cell 1 viewed from the side opposite to the light receiving surface (back surface).
  • the conductive film 22 is stuck on the line where the square portions of the back aluminum electrode 9 on the back surface of the solar battery cell 1 are arranged (step S100, FIG. 4-2).
  • the conductive film 22 is a film-like anisotropic conductive adhesive, and is composed of an adhesive (binder) for fixing between conductive members and conductive particles uniformly dispersed in the binder. Both surfaces of the conductive film 22 have adhesiveness, and the other surface side of the conductive film 22 in a state where the tabbed separator 23 is attached to the one surface side is used as the back aluminum on the back surface of the solar battery cell 1. It sticks on the line in which the square part of the electrode 9 was located in a line.
  • step S110, FIG. 4-3, FIG. 4-4) the tab-attached separator 23 attached to one side of the conductive film 22 is peeled off.
  • the tab wire 21 is bonded to the one surface side of the conductive film 22 exposed by peeling off the tab attaching side separator 23 (step S120), and a temperature of 200 ° C. or lower and a predetermined pressing force are applied to the tab wire 21, for example. .
  • one end side of the tab wire 21 is electrically and mechanically connected to the back aluminum electrode 9 on the back surface of the solar battery cell 1 through the conductive film 22 (step S130, FIG. 4-5).
  • the other end side of the tab wire 21 is electrically connected to another solar battery cell or the like.
  • the back silver sputtering film 8 which is a high light reflection film having a higher light reflectivity than the aluminum electrode formed of aluminum paste is provided as the light reflection film on the back surface.
  • the tab wire 21 is electrically and mechanically connected to the back aluminum electrode 9 on the back surface of the solar battery cell 1 using the conductive film 22. Therefore, the back silver electrode on the back surface, the soldered tab wire and the flux, which are necessary for the tab line connection on the back surface side of the silicon substrate in the normal module process, are not required, and the connection of the tab wire 21 to the solar cell 1 is easy. become. And since silver is an expensive material, the photovoltaic cell 1 can be implement
  • the photoelectric conversion efficiency is improved by light reflection on the back surface, and the solar battery cell 1 in which the tab wire 21 can be easily connected to the back aluminum electrode 9 can be obtained at low cost. This makes it possible to easily tab the solar cell 1 with high photoelectric conversion efficiency.
  • FIG. Embodiment 2 demonstrates the other high light reflective film of the back surface of a photovoltaic cell.
  • International Publication No. 2010/150358 a technique using an aluminum foil as a conventional high light reflection film is proposed.
  • International Publication No. 2010/150358 does not specifically mention the tab line connection method.
  • a method for connecting tab wires when an aluminum foil is used as the high light reflection film will be described.
  • FIG. 5A is a top view schematically showing the aluminum foil 31 with a conductive film according to the second embodiment.
  • FIG. 5-2 is a cross-sectional view schematically showing the aluminum foil 31 with a conductive film according to the second embodiment, and is a main-portion cross-sectional view in the CC direction of FIG. 5-1.
  • the aluminum foil 31 with a conductive film according to the second embodiment is configured by holding the conductive film 22 on one side of an aluminum foil 32 having a surface shape equivalent to that of the semiconductor substrate 11.
  • the aluminum foil 32 there are two regions corresponding to the connection region of the tab wire 21 on the back surface of the solar battery cell 1, that is, the attachment region of the conductive film 22. It has an opening 32a that is generally smaller than the sticking area) and has an equivalent shape.
  • the two conductive films 22 are held on one side of the aluminum foil 32 so that the other side covers the opening 32a with the tab-attached separator 23 attached to the one side. Yes.
  • the conductive film 22 is temporarily bonded to the outer peripheral region of the opening 32a in the aluminum foil 32 by the adhesive force on the other surface side.
  • FIG. 6A and 6B are process diagrams schematically showing a process of connecting a tab to the back surface of the solar battery cell when using the aluminum foil 31 with the conductive film according to the second embodiment.
  • FIG. 6A is a bottom view showing the state of the semiconductor substrate 11 at the end of the baking process of step S80 in the first embodiment, and shows the same state as FIG. 3-10.
  • the aluminum foil 31 with a conductive film is attached to the back surface of the semiconductor substrate 11 with the surface on which the tab-attached separator 23 is attached facing outward (FIG. 6- 2).
  • the position of the opening 32a (the position of the conductive film 22) is aligned and adhered to the line where the square portions of the back aluminum electrode 9 are arranged on the back surface of the semiconductor substrate 11.
  • the aluminum foil 31 with a conductive film is temporarily bonded to the back surface of the semiconductor substrate 11 by the adhesive force of the other surface of the conductive film 22 exposed from the opening 32a.
  • the tab attaching side separator 23 is peeled off, and the tab wire 21 is adhered to one side of the conductive film 22 exposed by peeling off the tab attaching side separator 23, and heating and heating are performed in the same manner as in the first embodiment. Apply pressure. Thereby, the tab wire 21 is electrically and mechanically connected to the back aluminum electrode 9 on the back surface of the solar battery cell 1 through the conductive film 22.
  • the aluminum foil 32 part is brought into close contact with and adhered to the back surface passivation film 7 on the back surface of the solar battery cell 1.
  • the aluminum foil 32 which is a high light reflection film having a higher light reflectivity than the aluminum electrode formed of aluminum paste is provided as the light reflection film on the back surface.
  • the tab wire 21 is electrically and mechanically connected to the back aluminum electrode 9 on the back surface of the solar battery cell 1 using the conductive film 22. . Therefore, the back silver electrode on the back surface, the soldered tab wire and the flux, which are necessary for the tab line connection on the back surface side of the silicon substrate in the normal module process, are not required, and the connection of the tab wire 21 to the solar cell 1 is easy. become. And since silver is an expensive material, the photovoltaic cell 1 can be implement
  • the simplification of a manufacturing process is realizable by using the aluminum foil 31 with an electroconductive film in which the electroconductive film 22 and the aluminum foil 32 which is a high light reflection film were integrated.
  • the photoelectric conversion efficiency is improved by the light reflection on the back surface, and the solar battery cell in which the tab wire 21 can be easily connected to the back aluminum electrode 9. 1 is obtained at low cost. This makes it possible to easily tab the solar cell 1 with high photoelectric conversion efficiency.
  • Embodiment 3 demonstrates the other high light reflective film of the back surface of a photovoltaic cell.
  • Embodiment 3 an example will be described in which a high light reflection film having a higher light reflectivity than an aluminum electrode formed of an aluminum paste is formed using a liquid material.
  • 7A to 7D are bottom views of the semiconductor substrate 11 schematically showing the method for forming the high light reflection film according to the third embodiment.
  • FIG. 7-1 is a bottom view showing the state of the semiconductor substrate 11 at the end of the baking step of step S80 in the first embodiment, and shows the same state as FIG. 3-10.
  • the conductive film 22 is stuck on the line where the square portions of the back aluminum electrode 9 on the back surface of the solar battery cell 1 are arranged.
  • the other surface side of the conductive film 22 in a state where the liquid repellent tab-attached separator 41 having liquid repellency such as hydrophobicity is attached to the one surface side. It adheres on the line where the square portions of the back aluminum electrode 9 on the back surface of the solar battery cell 1 are arranged (FIG. 7-2).
  • the high light reflection film intermediate material 42 which is a chemical solution that functions as a high light reflection film by solidifying with heat or light without peeling off the liquid repellent tab-attached separator 41, is applied using a coating method such as spin coating. It is applied to the back surface of the solar battery cell 1 (FIG. 7-3). At this time, the surface of the liquid repellent tabbed side separator 41 is provided with a liquid repellent property that repels the high light reflective film intermediate material 42, so that the surface of the liquid repellent tabbed side separator 41 has a high light reflective film. The intermediate material 42 is not applied. Thereby, the high light reflection film intermediate material 42 can be selectively applied to a region other than the connection portion of the tab wire 21 on the back surface of the solar battery cell 1.
  • the liquid repellent tabbed side separator 41 is peeled off, and the liquid repellent tabbed side separator 41 is peeled off and exposed on the other surface side of the conductive film 22.
  • the tab wire 21 is bonded, and heating and pressing are performed in the same manner as in the first embodiment. Thereby, the tab wire 21 is electrically and mechanically connected to the back aluminum electrode 9 on the back surface of the solar battery cell 1 through the conductive film 22 (FIG. 7-4).
  • the high light reflection film intermediate material 42 that functions as a high light reflection film by solidifying with heat
  • the high light reflection film intermediate material 42 is solidified by heating at the time of tab connection, and the high light reflection film 43 is formed.
  • additional heating may be performed after the connection of the tab wire 21 to solidify the high light reflection film intermediate material 42.
  • the high light reflection film intermediate material 42 is solidified by irradiating ultraviolet rays. Is formed. The timing of ultraviolet irradiation may be before the tab wire 21 is bonded and after the tab wire 21 is bonded.
  • the high light reflection film which is a high light reflection film having a higher light reflectance than the aluminum electrode formed of aluminum paste as the light reflection film on the back surface. 43 is provided.
  • the light reflectance on the back surface can be improved, and the solar cell 1 is transmitted and reaches the back surface.
  • the light thus used can be effectively utilized, and the photoelectric conversion efficiency can be improved by light reflection on the back surface.
  • the tab wire 21 is electrically and mechanically connected to the back aluminum electrode 9 on the back surface of the solar battery cell 1 using the conductive film 22. . Therefore, the back silver electrode on the back surface, the soldered tab wire and the flux, which are necessary for the tab line connection on the back surface side of the silicon substrate in the normal module process, are not required, and the connection of the tab wire 21 to the solar cell 1 is easy. become. And since silver is an expensive material, the photovoltaic cell 1 can be implement
  • the back surface aluminum electrode of the back surface of the photovoltaic cell 1 is made into the electroconductive film 22 in the state by which the liquid-repellent tab attachment side separator 41 which has liquid repellency is stuck on the one surface side. 9 is stuck on the line in which the square portions are arranged, and the liquid high light reflection film intermediate material 42 is applied to the back surface of the solar battery cell 1.
  • a high light reflection film can be easily formed selectively with respect to a region other than the connection portion of the tab wire 21 on the back surface of the solar battery cell 1.
  • the photoelectric conversion efficiency is improved by light reflection on the back surface, and the solar battery cell in which the tab wire 21 can be easily connected to the back aluminum electrode 9. 1 is obtained at low cost. This makes it possible to easily tab the solar cell 1 with high photoelectric conversion efficiency.
  • Embodiment 4 In embodiment mentioned above, in order to suppress the recombination rate of the carrier in the back surface of the photovoltaic cell 1, the structure which uses the back surface passivation film 7 was demonstrated.
  • the back surface passivation film 7 is often an insulating film and cannot be electrically connected even if physically connected to the conductive film 22, and does not contribute to current collection on the back surface of the solar battery cell 1.
  • Embodiment 4 in order to suppress the recombination rate of the back surface of the solar battery cell, a case will be described in which the back surface BSF layer is formed by diffusion of impurities with respect to the back surface of the solar battery cell instead of the back surface passivation film.
  • FIGS. 8A and 8B are cross-sectional views schematically showing the method for manufacturing the solar battery cell according to the fourth embodiment.
  • FIG. 8-1 is a bottom view showing the state of the semiconductor substrate 11 at the end of removal of the n-type impurity diffusion layer 3 formed on the back surface of the semiconductor substrate 2 in the first embodiment, and is the same as FIG. 3-5 It is a figure which shows a state.
  • boron which is a p-type impurity
  • the boron diffusion layer 51 is p-type and has a higher impurity concentration than the semiconductor substrate 2. Is formed (FIG. 8-2).
  • the boron diffusion layer 51 becomes a P + layer to form a BSF layer, and reduces the recombination rate of carriers on the back surface of the solar battery cell.
  • a high light reflective film on the back surface is formed as the electrode layer, the light receiving surface side electrode 12 is formed, and the conductive film 22 is adhered.
  • the semiconductor substrate 11 is not formed without forming the back aluminum electrode.
  • the conductive film 22 is directly attached to the boron diffusion layer 51 on the back surface of the substrate.
  • a boron diffusion layer 51 for reducing the carrier recombination speed on the back surface of the solar battery cell is provided instead of the back surface passivation film, and a solar battery cell with the conductive film 22 having a high light reflection structure on the back surface is easily manufactured. can do.
  • the tab wire 21 can be easily connected to the solar battery cell 1 by connecting the tab wire 21 in the same manner as in the first to third embodiments.
  • the boron diffusion layer 51 on the back surface of the semiconductor substrate 11 and the conductive film 22 can be directly and physically connected.
  • the P + layer exists on the entire back surface of the solar battery cell and the resistance on the back surface side of the solar battery cell is low, the current cannot be collected efficiently with only the two tab wires 21. Is also possible.
  • the resistance on the back surface side is clearly lower than that of the conventional solar cell provided with the aluminum electrode for collecting current and the silver electrode for tab connection on the back surface. For this reason, even if the shape of the comb-shaped electrode pattern is adopted as the shape of the back surface side electrode as a countermeasure against the decrease in current collection, the number and width of the back surface side electrode can be greatly reduced. Thereby, it leads to the consumption cost reduction of aluminum and silver for electrodes, and an inexpensive solar cell can be realized.
  • a high light reflection film having a higher light reflectance than the aluminum electrode formed of aluminum paste is provided as the light reflection film on the back surface.
  • the tab wire 21 is electrically and mechanically connected to the boron diffusion layer 51 on the back surface of the semiconductor substrate 11 using the conductive film 22. Therefore, the back silver electrode on the back surface, the soldered tab wire and the flux, which are necessary for the tab line connection on the back surface side of the silicon substrate in the normal module process, are not required, and the connection of the tab wire 21 to the solar cell 1 is easy. become. Since silver is an expensive material, a solar battery cell can be realized at low cost by eliminating the need for a back silver electrode on the back surface.
  • the boron diffusion layer 51 which reduces the recombination rate of the carrier in the back surface of the photovoltaic cell 1 is provided instead of a back surface passivation film.
  • the back surface of the semiconductor substrate 11 can be physically and electrically directly connected to the conductive film 22, and good current collection can be realized.
  • the photovoltaic conversion efficiency is improved by light reflection on the back surface, and the solar cell in which the tab wire 21 is easily connected to the back surface of the solar battery cell.
  • a cell can be obtained at low cost. Thereby, it is possible to easily tab the solar cell having high photoelectric conversion efficiency.
  • the solar cell according to the present invention is useful for realizing a solar cell in which the tab line can be easily connected to the back surface and the photoelectric conversion efficiency is improved by the light reflection on the back surface. .
  • 1 solar cell 2 semiconductor substrate, 2a minute unevenness, 3 n-type impurity diffusion layer, 4 antireflection film, 5 surface silver grid electrode, 6 surface silver bus electrode, 7a opening, 7 back surface passivation film, 8 back silver sputtering Membrane, 9 back aluminum electrode, 10 P + layer, 11 semiconductor substrate, 12 light receiving surface side electrode, 13 back surface side electrode, 21 tab wire, 22 conductive film, 23 tabbed side separator, 31 aluminum foil with conductive film, 32 Aluminum foil, 32a opening, 41 liquid-repellent tabbed separator, 42 high light reflective film intermediate material, 43 high light reflective film, 51 boron diffusion layer.

Abstract

L'invention concerne une cellule solaire qui comprend : un substrat de semi-conducteur (2) d'un premier type de conductivité, qui possède, sur une surface, une couche de diffusion d'impuretés de type n (3) dans laquelle un élément d'impureté d'un second type de conductivité est diffusé ; une électrode côté surface de réception de lumière (12) qui est formée sur ledit un côté de surface de substrat de semi-conducteur (2) et qui est connectée électriquement à la couche de diffusion d'impuretés de type n (3) ; un film de pulvérisation d'argent côté arrière (8) qui est formé sur une région de l'autre surface du substrat de semi-conducteur (2), qui possède une réflectance de lumière supérieure à une électrode d'aluminium qui est formée à partir d'une pâte d'aluminium, et qui réfléchit la lumière émise à travers le substrat de semi-conducteur (2) à partir de ladite une surface du substrat de semi-conducteur (2) ; et un film conducteur (22) qui sert de couche de connexion pour connecter un fil de languette qui connecte électriquement l'autre surface du substrat de semi-conducteur (2) et une autre cellule solaire (1) l'une avec l'autre, et qui est collé à une région de l'autre surface du substrat de semi-conducteur (2), ladite région étant la région autre que le film de pulvérisation d'argent côté arrière (8).
PCT/JP2013/050676 2013-01-16 2013-01-16 Cellule solaire et procédé de fabrication associé WO2014112053A1 (fr)

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