WO2013105600A1 - Procédé de production destiné à un substrat de cellule solaire et procédé de production destiné à un élément de cellule solaire - Google Patents

Procédé de production destiné à un substrat de cellule solaire et procédé de production destiné à un élément de cellule solaire Download PDF

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WO2013105600A1
WO2013105600A1 PCT/JP2013/050301 JP2013050301W WO2013105600A1 WO 2013105600 A1 WO2013105600 A1 WO 2013105600A1 JP 2013050301 W JP2013050301 W JP 2013050301W WO 2013105600 A1 WO2013105600 A1 WO 2013105600A1
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solar cell
forming
mask layer
substrate
semiconductor substrate
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PCT/JP2013/050301
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English (en)
Japanese (ja)
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明博 織田
吉田　誠人
野尻　剛
倉田　靖
岩室　光則
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日立化成株式会社
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Priority to CN201380004639.0A priority Critical patent/CN104025306A/zh
Priority to JP2013553306A priority patent/JP5842931B2/ja
Publication of WO2013105600A1 publication Critical patent/WO2013105600A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—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
    • H01L31/04—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
    • H01L31/0682—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 back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction 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
    • H01L31/18—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
    • 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 method for manufacturing a solar cell substrate and a method for manufacturing a solar cell element.
  • a p-type silicon substrate having a textured structure is prepared so as to promote the light confinement effect and achieve high efficiency.
  • a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen is used at 800 ° C. to 900 ° C.
  • An n-type diffusion layer is uniformly formed by performing several tens of minutes at a temperature.
  • an electrode paste such as Ag was applied to the light receiving surface, and an electrode paste such as aluminum was applied to the back surface, and then fired to obtain a solar cell element.
  • a back electrode type solar cell has been developed that has no electrode on the light receiving surface, an n type diffusion layer and a p + type diffusion layer on the back surface, and an n electrode and a p electrode on each diffusion layer (for example, JP, 2011-507246, A).
  • a method of forming such a back electrode type solar cell will be described.
  • a mask is formed on the entire light receiving surface and back surface of the n-type silicon substrate.
  • the mask has a function of suppressing the diffusion of the dopant into the silicon substrate.
  • a part of the mask on the back surface of the silicon substrate is removed to form an opening.
  • the p + -type diffusion layer is formed only in the region corresponding to the opening.
  • a mask is formed again on the entire back surface of the silicon substrate.
  • n + and type diffusion layer formed areas by removing part of the mask of different regions to form an opening portion, an n-type dopant is diffused into the back surface of the silicon substrate from the opening, n + A mold diffusion layer is formed. Subsequently, by removing all the masks on the back surface of the silicon substrate, a p + -type diffusion layer and an n + -type diffusion layer are formed on the back surface. Furthermore, a back electrode type solar cell is completed by forming a texture structure, an antireflection film, a passivation film, an electrode, and the like.
  • the method of generating an oxide film on the substrate surface by the thermal oxidation method described in the above-mentioned Japanese Patent Application Laid-Open No. 2002-329880 has a problem that the manufacturing cost is high because the throughput is long. Further, in the method using a masking paste containing a SiO 2 precursor described in JP-A-2007-49079, it is intended to physically prevent diffusion of a donor element or an acceptor element, and further a mask made of SiO 2. Since it is difficult to form a dense film, it is easy to form pinholes, so that it is difficult to sufficiently prevent diffusion of the dopant into the substrate.
  • the present invention has been made in view of the above-described conventional problems, and a method for manufacturing a solar cell substrate and a method for manufacturing a solar cell element that can easily and selectively form a doping region. It is an issue to provide.
  • Means for solving the problems are as follows. ⁇ 1> forming a mask layer containing a metal compound containing an alkaline earth metal or an alkali metal on the surface of the semiconductor substrate; Forming a diffusion layer in a region of the semiconductor substrate where the mask layer is not formed; The manufacturing method of the board
  • the solar cell substrate is a double-sided electrode type solar cell substrate having electrodes on a light receiving surface of a semiconductor substrate and a back surface opposite to the light receiving surface, Forming the mask layer on the back surface of the semiconductor substrate; Forming an n-type diffusion layer on the light receiving surface; Removing the mask layer on the back surface; The manufacturing method of the board
  • the solar cell substrate is a back electrode type solar cell substrate having an electrode only on the back surface opposite to the light receiving surface of the semiconductor substrate, Forming the first mask layer on the entire light-receiving surface and part of the back surface of the semiconductor substrate; Forming a p-type diffusion layer in a region where the first mask layer is not formed on the back surface; Removing the first mask layer on the light receiving surface and the back surface; Forming a second mask layer in a region different from a region where the p-type diffusion layer is formed on the back surface; Forming an n-type diffusion layer in a region where the second mask layer is not formed on the back surface; Removing the second mask layer on the light receiving surface and the back surface;
  • the solar cell substrate is a double-sided solar cell substrate capable of receiving light on both sides of a semiconductor substrate, Forming the first mask layer on the entire surface of the first surface which is one surface of the semiconductor substrate; Forming a p-type diffusion layer on the second surface which is the other surface of the semiconductor substrate; Removing the first mask layer on the first surface; Forming a second mask layer on the entire second surface of the semiconductor substrate; Forming an n-type diffusion layer on the first surface of the semiconductor substrate; Removing the second mask layer on the second surface;
  • ⁇ 5> The method for manufacturing a solar cell substrate according to any one of ⁇ 2> to ⁇ 4>, wherein in the step of removing the mask layer, the mask layer is removed with an acid aqueous solution.
  • the metal compound containing an alkaline earth metal or alkali metal is selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium, and radium as a metal element.
  • a mask forming composition containing the alkaline earth metal or the metal compound containing an alkali metal, a dispersion medium, and an organic binder is applied to a semiconductor substrate and heat-treated.
  • ⁇ 8> The sun according to ⁇ 7>, wherein a content ratio of the alkaline earth metal or the metal compound containing the alkali metal is 5% by mass or more and less than 100% by mass in the nonvolatile component of the mask forming composition.
  • ⁇ 9> The solar cell according to ⁇ 7> or ⁇ 8>, wherein the mask layer is formed by applying the mask forming composition to a semiconductor substrate by any one of inkjet, dispenser, or screen printing. A method for manufacturing a substrate.
  • n-type diffusion layer is formed using a gas containing phosphorus oxychloride.
  • n-type diffusion layer is formed by applying a composition containing a phosphorus compound to a semiconductor substrate and performing heat treatment. Manufacturing method.
  • ⁇ 12> The method for producing a solar cell substrate according to ⁇ 11>, wherein the phosphorus compound is a glass powder containing a phosphorus atom.
  • ⁇ 13> The method for producing a solar cell substrate according to any one of ⁇ 3> to ⁇ 12>, wherein the p-type diffusion layer is formed using a gas containing boron bromide.
  • ⁇ 14> The solar cell substrate according to any one of ⁇ 3> to ⁇ 12>, wherein the p-type diffusion layer is formed by applying a composition containing a boron compound to a semiconductor substrate and performing a heat treatment. Manufacturing method.
  • boron compound is a glass powder containing a boron atom.
  • a method for producing a solar cell element comprising a step of forming an electrode on a diffusion layer of a solar cell substrate obtained by the production method according to any one of ⁇ 1> to ⁇ 15>.
  • the present invention it is possible to provide a method for manufacturing a solar cell substrate that makes it possible to easily and selectively form a doping region, and a method for manufacturing a solar cell element using the same.
  • the conceptual schematic diagram which shows an example of the manufacturing process of a single-sided light reception and a back electrode type solar cell.
  • the conceptual schematic diagram which shows an example of the manufacturing process of a single-sided light reception and a double-sided electrode type solar cell.
  • the conceptual schematic diagram which shows an example of the manufacturing process of double-sided light reception and a double-sided electrode type solar cell.
  • the manufacturing method of the solar cell substrate of the present invention will be described, and then the mask forming composition used in the manufacturing method of the solar cell substrate will be described.
  • the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended action of the process is achieved. included.
  • “to” indicates a range including the numerical values described before and after the minimum and maximum values, respectively.
  • the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
  • the donor element or the acceptor element may be referred to as a dopant.
  • the solar cell substrate refers to a general solar cell substrate, and refers to a substrate in which an n-type diffusion layer or a p-type diffusion layer is formed on a semiconductor substrate.
  • a solar cell element refers to the element which has an electrode on the diffusion layer of the board
  • the method for producing a substrate for a solar cell of the present invention includes a step of forming a mask layer containing an alkaline earth metal or a metal compound containing an alkali metal (hereinafter also referred to as “specific compound”) on the surface of a semiconductor substrate.
  • the manufacturing method of the solar cell element of this invention includes the process of forming an electrode on the diffusion layer of the board
  • a mask layer containing an alkaline earth metal or a metal compound containing an alkali metal in a region where a donor element or an acceptor element is not desired to be diffused in a semiconductor substrate, diffusion of the donor element and the acceptor element in the region is performed. Can be sufficiently prevented. Therefore, it is possible to selectively form a doping region in the semiconductor substrate. The reason for this can be considered as follows.
  • the specific compound is preferably a basic compound.
  • the specific compound of the basic compound undergoes an acid-base reaction with the doping compound, and this acid-base reaction has high reactivity, and thus more effectively inhibits the donor element or the acceptor element from diffusing into the semiconductor substrate.
  • an alkaline earth metal or a metal compound containing an alkali metal is stable even at a high temperature (for example, 500 ° C. or higher), the effect of the present invention is sufficiently obtained when the donor element or the acceptor element is thermally diffused into the semiconductor substrate. Can be demonstrated. Moreover, since the alkaline earth metal or the metal compound containing the alkali metal does not act as a carrier recombination center in the semiconductor substrate when dissolved in the semiconductor substrate, the conversion efficiency of the solar cell substrate is reduced. Can be suppressed.
  • FIG. 1 is a schematic cross-sectional view conceptually showing an example of a manufacturing process of a single-sided light receiving, back electrode type solar cell substrate and solar cell element.
  • FIG. 2 is a schematic cross-sectional view conceptually showing an example of a manufacturing process of a single-sided light receiving, double-sided electrode type solar cell substrate and a solar cell element.
  • FIG. 3 is a schematic cross-sectional view conceptually showing an example of the manufacturing process of the double-sided light receiving, double-sided electrode type solar cell substrate and solar cell element.
  • the back electrode type solar cell substrate manufacturing method includes the following steps. (1-1) forming a first mask layer on the entire light-receiving surface and part of the back surface of the semiconductor substrate; (1-2) forming a p-type diffusion layer in a region of the back surface where the first mask layer is not formed; (1-3) removing the first mask layer on the light receiving surface and the back surface; (1-4) forming a second mask layer in a region different from a region where the p-type diffusion layer is formed on the back surface; (1-5) forming an n-type diffusion layer in a region where the second mask layer is not formed on the light receiving surface and the back surface; and (1-6) the second mask layer on the back surface. Removing.
  • FIG. 1A an alkaline solution is applied to a silicon substrate that is an n-type semiconductor substrate 101 to remove a damaged layer, and then a texture structure is obtained by an etching step or the like. Specifically, for example, a damaged layer on the surface of the silicon substrate generated when slicing from an ingot is removed with 20% by mass caustic soda. Next, a texture structure is formed on the light receiving surface side by dry etching using plasma (the description of the texture structure is omitted in the figure). In the solar cell element, by forming a texture structure on the light receiving surface (surface) side, a light confinement effect is promoted, and high efficiency is achieved. In addition, carrier recombination can be suppressed by making the back surface a mirror shape.
  • a first mask layer is formed on the entire surface of the n-type semiconductor substrate 101 (that is, the light receiving surface) and a part of the back surface that is the opposite surface.
  • a mask layer 11 is formed. The opening where the first mask layer 11 is not formed corresponds to the electrode formation scheduled region.
  • the formation method of the mask layer is not particularly limited as long as a mask layer containing an alkaline earth metal or a metal compound containing an alkali metal is formed.
  • Examples of the method for forming the mask layer include a method in which a mask-forming composition containing a later-described alkaline earth metal or a metal compound containing an alkali metal is applied to the entire light-receiving surface and a part of the back surface. . Details of the mask forming composition will be described later.
  • Examples of the method for applying the mask forming composition to the n-type semiconductor substrate 101 include a printing method, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, an ink jet method, a dispenser method, and the like.
  • a printing method a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, an ink jet method, a dispenser method, and the like.
  • the ink jet method, the dispenser method, or the screen printing method is preferable from the viewpoint that the mask forming composition can be easily applied in a pattern.
  • Specific examples of such an application method include a method using a screen printer, an offset printer, a gravure printer, a flexographic printer, an inkjet machine, and the like.
  • a part thereof may be removed by etching or the like to form a patterned mask layer.
  • the method for applying the mask forming composition to the entire light receiving surface is not particularly limited, and the above method can be appropriately selected.
  • the amount of the mask forming composition applied is not particularly limited.
  • the solid content after the heat treatment is 0.001 mg / cm 2 to 10 mg / cm 2.
  • it is 0.01 mg / cm 2 to 5 mg / cm 2 , more preferably 0.05 mg / cm 2 to 1 mg / cm 2 .
  • the applied amount is 0.001 mg / cm 2 or more, sufficient diffusion inhibiting ability tends to be obtained, and by setting it to 10 mg / cm 2 or less, the amount of the mask forming composition can be reduced.
  • a solar cell element can be manufactured at low cost.
  • the thickness of the coating film of the mask forming composition is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m, and more preferably 1 ⁇ m to 30 ⁇ m.
  • the mask forming composition applied to the n-type semiconductor substrate 101 can be dried as necessary to obtain a mask layer.
  • the drying temperature can be appropriately adjusted depending on components such as a dispersion medium contained in the mask forming composition, and is not particularly limited. For example, it is preferably 50 ° C. to 800 ° C., and preferably 100 ° C. to 500 ° C.
  • FIGS. 1 (3) and 1 (4) p-type diffusion layer is formed on the back surface of the n-type semiconductor substrate 101 where the first mask layer 11 is not applied.
  • a + type diffusion layer 17 is formed.
  • a known method can be used as a method of forming the p + -type diffusion layer 17.
  • boron atoms as p-type dopants are diffused into the n-type semiconductor substrate 10 by a method of forming using a gas containing boron bromide or a method of applying a heat treatment by applying a composition containing a boron compound.
  • a + -type diffusion layer 17 can be formed.
  • the heat treatment temperature is not particularly limited, but is preferably a heat treatment at a temperature of 750 ° C. to 1050 ° C. for 1 minute to 300 minutes.
  • the first mask layer 11 contains an alkaline earth metal or a metal compound containing an alkali metal, the diffusion of the p-type dopant is sufficiently inhibited in the region where the first mask layer 11 is formed.
  • heat treatment (about 800 ° C. to 1200 ° C.) is performed while flowing a gas containing boron such as boron bromide. Then, a borosilicate glass layer 18 is formed, and thermal diffusion (about 800 ° C. to 1200 ° C.) is performed to form a p + -type diffusion layer 17.
  • the composition containing a boron compound is preferably a composition in which the boron compound is a glass powder containing boron atoms, as described in JP 2011-181901 A.
  • the method for applying the composition include an inkjet method, a dispenser method, and a screen printing method.
  • FIG. 1 (5) Step of Removing First Mask Layer
  • the first mask layer 11 on the light receiving surface and the back surface is removed.
  • the borosilicate glass layer 18 or the like is generated in the step of forming the p + -type diffusion layer
  • the borosilicate glass layer 18 is also removed.
  • the removal of the mask layer 11 and the removal of the borosilicate glass layer 18 carried out as necessary are preferably performed using an aqueous acid solution.
  • the acid aqueous solution include hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, acetic acid aqueous solution, and the like. Among these, it is preferable to use a hydrofluoric acid aqueous solution.
  • hydrofluoric acid aqueous solution after using hydrochloric acid (for example, a 10% by mass HCl aqueous solution).
  • concentration of hydrofluoric acid in the aqueous hydrofluoric acid solution is preferably 0.1% by mass to 40% by mass. Further, following this step, it is preferable to perform pn junction isolation by side etching or the like.
  • the second mask layer is formed so as to have an opening in a region different from the region where the p + -type diffusion layer 17 is formed on the back surface.
  • a mask layer 111 is formed.
  • the method for forming the second mask layer 111 may be the same method as the method for forming the first mask layer 11 on the back surface.
  • n + -type diffusion is applied to regions where the second mask layer 111 on the light receiving surface and the back surface is not formed.
  • Layer 13 is formed.
  • a known method can be used as a method of forming the n + -type diffusion layer 13.
  • phosphorus which is an n-type dopant, is diffused into the n-type semiconductor substrate 10 by a method of forming using a gas containing phosphorus oxychloride or a method of applying a heat treatment by applying a composition containing a phosphorus compound, and n + The mold diffusion layer 13 can be formed.
  • the second mask layer 111 contains an alkaline earth metal or a metal compound containing an alkali metal, the diffusion of the n-type dopant is sufficiently inhibited in the region where the second mask layer 111 is formed.
  • n + -type diffusion layer 13 using a gas containing phosphorus oxychloride
  • heat treatment about 800 ° C. to 1000 ° C.
  • a gas containing phosphorus oxychloride is flowing while flowing a gas containing phosphorus oxychloride, and a phosphosilicate glass layer is formed on the semiconductor substrate. 12 and thermal diffusion (about 800 ° C. to 1000 ° C.) forms an n + -type diffusion layer 13.
  • the composition containing a phosphorus compound is a composition whose phosphorus compound is a glass powder containing a phosphorus atom as described in WO2011 / 090216.
  • the method for applying the composition include an inkjet method, a dispenser method, and a screen printing method.
  • a back electrode type solar cell substrate in which both regions of the n + type diffusion layer and the p + type diffusion layer are formed on one surface of the semiconductor substrate is obtained.
  • an electrode is formed on the diffusion layer to produce a back electrode type solar cell element.
  • the passivation film 14 is formed on part of the light receiving surface and the back surface of the semiconductor substrate 101.
  • the passivation film is preferably a SiN film, a SiO 2 film, an amorphous-Si film, or a film containing Al 2 O 3 as a main component, and more preferably a SiN film.
  • the thickness of the passivation film is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm.
  • the method for forming the passivation film 14 on a part of the back surface is not particularly limited.
  • an etching solution a solution containing hydrofluoric acid, ammonium fluoride, phosphoric acid, or the like
  • heat treatment is performed.
  • the step of opening the passivation film 14 can be omitted.
  • a composition for forming an electrode containing glass frit is applied onto the passivation film 14 and baked at a temperature in the range of 600 ° C. to 900 ° C. for a few seconds to a few minutes, the glass frit melts the passivation film 14 and the metal particles (for example, silver particles) form a contact portion with the semiconductor substrate 101 and solidify.
  • the formed n-electrode 15 and p-electrode 16 are electrically connected to the semiconductor substrate 101. This is called fire-through.
  • an n electrode 15 is formed on the n + type diffusion layer 13 and a p electrode 16 is formed on the p + type diffusion layer 17.
  • the material and formation method of the n electrode 15 and the p electrode 16 are not particularly limited.
  • a back electrode may be formed by applying an electrode-forming composition containing a metal such as aluminum, silver, or copper and drying the composition. Further, the n electrode and the p electrode may be made of the same material. Next, the electrode is fired to produce a solar cell.
  • Double-sided electrode type solar cell substrate and method for manufacturing solar cell element The double-sided electrode type solar cell substrate manufacturing method includes the following steps. (2-1) forming a mask layer on the back surface of the semiconductor substrate; (2-2) forming an n-type diffusion layer on the light receiving surface; and (2-3) removing the mask layer on the back surface.
  • FIG. 2A an alkaline solution is applied to a silicon substrate that is a p-type semiconductor substrate 10 to remove a damaged layer, and then a texture structure is obtained by an etching step or the like. Specifically, for example, a damaged layer on the surface of the silicon substrate generated when slicing from an ingot is removed with 20% by mass caustic soda. Next, a texture structure is formed on the light receiving surface side by dry etching using plasma (the description of the texture structure is omitted in the figure). In the solar cell element, by forming a texture structure on the light receiving surface (surface) side, a light confinement effect is promoted, and high efficiency is achieved. In addition, carrier recombination can be suppressed by making the back surface a mirror shape.
  • the mask layer 11 is formed on the back surface of the semiconductor substrate 10 which is the opposite surface to the light receiving surface (front surface).
  • the method for forming the mask layer 11 can be the same method as the method for forming the first mask layer in the method for manufacturing the back electrode type solar cell.
  • the n + -type diffusion layer 13 is formed on the light receiving surface of the semiconductor substrate 10.
  • the method for forming the n + -type diffusion layer 13 can be the same as the method for forming the n-type diffusion layer in the method for manufacturing the back electrode type solar cell.
  • a double-sided electrode type solar cell substrate in which an n + -type diffusion layer is formed on the light-receiving surface (front surface) of the semiconductor substrate is obtained. And when forming the back surface electrode mentioned later, a p ⁇ +> type
  • the passivation film 14 is formed on the light receiving surface of the semiconductor substrate.
  • the material and the formation method of the passivation film 14 are the same as the material and the formation method described for the passivation film in the method for manufacturing the back electrode type solar cell.
  • FIGS. 2 (7) and 2 (8) an n electrode 15 and a p electrode 16 are formed.
  • a p + -type diffusion layer 17 is also formed during firing when the p-electrode 16 is formed (FIG. 2 (8)).
  • the same method as the method for forming the passivation film and the electrode in the method for manufacturing the back electrode type solar cell can be used.
  • the composition for forming an n electrode includes a glass frit, and the n electrode 15 and the semiconductor substrate are formed by fire-through without passing through the opening process of the passivation film 14. 10 is conducted.
  • the double-sided light-receiving solar cell substrate manufacturing method includes the following steps. (3-1) forming a first mask layer over the entire first surface, which is one surface of the semiconductor substrate; (3-2) forming a p-type diffusion layer on the second surface which is the other surface of the semiconductor substrate; (3-3) removing the first mask layer on the first surface; (3-4) forming a second mask layer over the entire second surface of the semiconductor substrate; (3-5) forming an n-type diffusion layer on the first surface of the semiconductor substrate; and (3-6) removing the second mask layer on the second surface.
  • FIG. 3A Step of Preparing a Semiconductor Substrate
  • an alkaline solution is applied to an n-type silicon substrate which is an n-type semiconductor substrate 101 to remove a damaged layer, and then a texture structure is formed by an etching step or the like. obtain. Specifically, for example, a damaged layer on the surface of the silicon substrate generated when slicing from an ingot is removed with 20% by mass caustic soda.
  • a texture structure is formed on both sides by alkali etching using an aqueous caustic soda solution of about 5% by mass (the description of the texture structure is omitted in the figure).
  • the solar cell element by forming a texture structure on the light receiving surface (both sides) side, a light confinement effect is promoted, and high efficiency is achieved.
  • the first mask layer 11 is formed on the entire first surface which is one surface of the semiconductor substrate 101.
  • the method for forming the mask layer 11 can be the same method as the method for forming the first mask layer in the method for manufacturing the back electrode type solar cell.
  • FIGS. 3 (3) and 3 (4) Formation of p-type diffusion layer
  • p + is formed on the surface (second surface) on the semiconductor substrate 101 where the first mask layer 11 is not formed.
  • a mold diffusion layer 17 is formed.
  • the method for forming the p + -type diffusion layer 17 can be the same method as the method for forming the p-type diffusion layer in the method for manufacturing the back electrode type solar cell.
  • the first mask layer 11 on the first surface is removed.
  • the borosilicate glass layer 18 or the like is generated in the step of forming the p + type diffusion layer, the borosilicate glass layer 18 is also removed.
  • the method for removing the mask layer 11 and the borosilicate glass layer 18 and the like can be the same method as the method for removing the first mask layer in the method for producing the back electrode type solar cell.
  • the second mask is formed on the entire surface (second surface) on the semiconductor substrate 10 on which the p + -type diffusion layer is formed.
  • Layer 111 is formed.
  • the method of forming the mask layer 111 includes the same method as the step of forming the first mask layer in the method for manufacturing the back electrode type solar cell.
  • N + -type diffusion layer 13 is formed.
  • the method for forming the n + -type diffusion layer 13 can be the same as the method for forming the n-type diffusion layer in the method for manufacturing the back electrode type solar cell.
  • the second mask layer 111 on the second surface is removed.
  • the phosphosilicate glass layer 12 or the like is formed in the n-type diffusion layer forming step, the phosphosilicate glass layer 12 is also removed.
  • the method for removing the mask layer 111, the phosphosilicate glass layer 12, and the like can be the same method as the method for removing the first mask layer in the method for manufacturing the back electrode type solar cell.
  • n + -type diffusion layer on one surface of the light-receiving surface of the semiconductor substrate p + -type diffusion layer is formed bifacial solar cell substrate is obtained on the other side.
  • an electrode is formed on the diffusion layer to produce a double-sided light receiving solar cell element.
  • FIG. 3 (10) the passivation film 14 is formed on both surfaces of the semiconductor substrate.
  • the n electrode 15 is formed on the surface side where the n + type diffusion layer 13 is formed
  • the p electrode 16 is formed on the surface side where the p + type diffusion layer 17 is formed.
  • the method of forming a passivation film and an electrode can use the method similar to the method of forming the said passivation film and electrode in the manufacturing method of the said back surface electrode type solar cell.
  • both an n electrode forming composition for forming the n electrode 15 and a p electrode forming composition for forming the p electrode 16 include glass frit.
  • the n-electrode 15 and the p-electrode 16 and the semiconductor substrate 101 are electrically connected by fire-through without using the step of opening the passivation film 14.
  • the mask layer according to the present invention is preferably formed by applying and heat-treating a mask-forming composition containing an alkaline earth metal or a metal compound containing an alkali metal.
  • the mask-forming composition preferably further contains a dispersion medium and an organic binder from the viewpoint of applicability.
  • the alkaline earth metal or the metal compound containing the alkali metal may be liquid or solid at room temperature (about 20 ° C.). From the viewpoint that it is necessary to be chemically stable even at a high temperature in order to maintain sufficient mask performance even at a high temperature, it is preferably a solid at a high temperature (for example, 500 ° C. or higher) at which heat diffusion is performed.
  • the alkaline earth metal or the metal compound containing an alkali metal includes an alkaline earth metal or a metal oxide containing an alkali metal, an alkaline earth metal or a metal salt containing an alkali metal.
  • the alkaline earth metal or the metal compound containing an alkali metal is not particularly limited, and is preferably a material that changes to a basic compound at a high temperature of 700 ° C. or higher at which a donor element or an acceptor element is thermally diffused.
  • the metal compound contains at least one selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and radium as a metal element. It is more preferable that it contains at least one selected from the group consisting of magnesium, calcium, barium, potassium, and sodium, and that it contains at least one selected from the group consisting of magnesium, calcium, and potassium.
  • the viewpoint of low toxicity and availability it is more preferable to contain one or more selected from the group consisting of magnesium and calcium.
  • from the viewpoint of chemical stability from the group consisting of metal oxides, metal carbonates, metal nitrates, metal sulfates and metal hydroxides containing one or more selected from the group consisting of these metal elements It is preferably one or more selected, more preferably one or more selected from the group consisting of metal oxides, metal carbonates and metal hydroxides.
  • metal oxides such as sodium oxide, potassium oxide, lithium oxide, calcium oxide, magnesium oxide, rubidium oxide, cesium oxide, beryllium oxide, strontium oxide, barium oxide, radium oxide, and complex oxides thereof; sodium hydroxide, Metal hydroxides such as potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide; sodium carbonate, carbonic acid Metal carbonates such as potassium, lithium carbonate, calcium carbonate, magnesium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, strontium carbonate, barium carbonate, radium carbonate; sodium nitrate, potassium nitrate, lithium nitrate, calcium nitrate Metal nitrates such as magnesium nitrate, rubidium nitrate, cesium nitrate, beryllium nitrate, strontium oxide,
  • the particle diameter of the particles is preferably 30 ⁇ m or less, preferably 0.01 ⁇ m to 30 ⁇ m. More preferably, it is more preferably 0.02 ⁇ m to 10 ⁇ m, and particularly preferably 0.03 ⁇ m to 5 ⁇ m.
  • the particle diameter is 30 ⁇ m or less, a donor element or an acceptor element can be uniformly diffused (doped) into a desired region of the semiconductor substrate.
  • the alkaline earth metal or the metal compound containing an alkali metal may be dissolved in the dispersion medium.
  • the particle diameter represents a volume average particle diameter, and can be measured with a laser scattering diffraction particle size distribution measuring apparatus or the like.
  • the volume average particle diameter can be calculated based on the Mie scattering theory by detecting the relationship between the scattered light intensity and the angle of the laser light applied to the particles.
  • the method for obtaining particles of the specific compound having a particle size of 30 ⁇ m or less is not particularly limited, and can be obtained by, for example, pulverization.
  • a grinding method a dry grinding method and a wet grinding method can be employed.
  • a jet mill, a vibration mill, a ball mill, or the like can be employed.
  • a wet pulverization method a bead mill, a ball mill or the like can be used.
  • the lifetime of the carrier in the semiconductor substrate may be reduced, so the materials such as the pulverization container, beads, and balls have an effect on the semiconductor substrate. It is preferable to select a material having a small amount.
  • the material of the container and the like that are preferably used during pulverization include alumina and partially stabilized zirconia.
  • a gas phase oxidation method, a hydrolysis method, or the like can be used in addition to the pulverization method.
  • the particles of the specific compound are particles made of a compound other than an alkaline earth metal or a metal compound containing an alkali metal (for example, silicon oxide particles) as a carrier, and the surface of the carrier is an alkaline earth metal or an alkali metal.
  • a material in which a metal compound containing is coated or dispersedly supported may be used.
  • it is possible to increase the effective surface area of the alkaline earth metal or the metal compound containing the alkali metal it is possible to increase the effective surface area of the alkaline earth metal or the metal compound containing the alkali metal, and there is a possibility that the property of inhibiting the diffusion of the donor element or the acceptor element into the semiconductor substrate may be improved. .
  • the carrier is preferably a material having a BET specific surface area of 10 m 2 / g or more, and examples thereof include particles of inorganic materials such as SiO 2 , activated carbon, carbon fiber, and zinc oxide.
  • the shape of the particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a scale shape, a block shape, an oval shape, a plate shape, and a rod shape.
  • the shape of the particles can be confirmed by electrophotography or the like.
  • the content of the alkaline earth metal or the metal compound containing the alkali metal in the mask forming composition is determined in consideration of the coating property, the diffusibility of the donor element or the acceptor element, and the like.
  • the content ratio of the alkaline earth metal or the metal compound containing an alkali metal in the mask forming composition is preferably 0.1% by mass or more and 95% by mass or less in the mask forming composition. More preferably 0.1% by weight or more and 80% by weight or less, further preferably 0.1% by weight or more and 50% by weight or less, particularly preferably 2% by weight or more and 50% by weight or less, Most preferably, it is 5 mass% or more and 20 mass% or less.
  • the content of the alkaline earth metal or the metal compound containing the alkali metal is 0.1% by mass or more, the diffusion of the donor element or the acceptor element into the semiconductor substrate can be sufficiently suppressed.
  • the content is 95% by mass or less, the dispersibility of the alkaline earth metal or the metal compound containing the alkali metal in the mask forming composition is improved, and the coating property to the substrate is improved.
  • the total mass ratio of the alkaline earth metal and the metal compound containing the alkali metal in the total nonvolatile components of the mask forming composition is preferably 5% by mass or more and less than 100% by mass, and 20 or more and 99% by mass. The following is more preferable. By being within the above range, a sufficient mask control effect tends to be obtained.
  • the non-volatile component refers to a component that does not volatilize when heat-treated at 600 ° C. or higher.
  • the non-volatile component can be obtained by a thermogravimetric analyzer TG, and the total content of the alkaline earth metal and the metal compound containing the alkali metal in the non-volatile component is determined by ICP emission spectroscopy / mass spectrometry (ICP-MS). Method) and atomic absorption method.
  • ICP-MS ICP emission spectroscopy / mass spectrometry
  • the composition for forming a mask according to the present invention contains a dispersion medium.
  • the dispersion medium is a medium in which the alkaline earth metal or the metal compound containing the alkali metal is dispersed or dissolved in the composition.
  • Examples of the dispersion medium include a solvent and water.
  • Examples of the solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-i-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, and methyl-n-hexyl ketone.
  • Ketone solvents such as diethyl ketone, dipropyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone; diethyl ether, methyl ethyl ether, Methyl-n-propyl ether, di-i-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethyl Glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glyco
  • Ester solvents acetonitrile, N-methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, Aprotic polar solvents such as dimethyl sulfoxide; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2- Methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethy
  • the dispersion medium is preferably water, an alcohol solvent, a glycol monoether solvent, or a terpene solvent.
  • Water, alcohol, cellosolve, ⁇ -terpineol, diethylene glycol mono N-Butyl ether or diethylene glycol acetate mono-n-butyl ether is more preferable, and water, alcohol, ⁇ -terpineol or cellosolve is more preferable.
  • the content of the dispersion medium in the mask forming composition is determined in consideration of the coating property and the dopant concentration, and is, for example, 5% by mass or more and 99% by mass or less with respect to 100% by mass of the mask forming composition. Is more preferable, 20 mass% or more and 95 mass% or less is more preferable, and 40 mass% or more and 90 mass% or less is further more preferable.
  • the mask forming composition according to the present invention preferably contains an organic binder.
  • the organic binder By containing the organic binder, the alkaline earth metal or the metal compound containing the alkali metal is bound to each other at a high temperature, and the alkaline earth metal or the metal compound containing the alkali metal is bound to the semiconductor substrate. It becomes easy to make.
  • organic binder examples include polyvinyl alcohol; polyacrylamide resin; polyvinyl amide resin; polyvinyl pyrrolidone resin; polyethylene oxide resin; polysulfone resin; acrylamide alkyl sulfone resin; cellulose derivatives such as cellulose ether, carboxymethyl cellulose, hydroxyethyl cellulose, and ethyl cellulose; Starch, starch derivative; sodium alginate; xanthan; guar, gua derivative; scleroglucan, scleroglucan derivative; tragacanth, tragacanth derivative; dextrin, dextrin derivative; (meth) acrylic acid resin; alkyl (meth) (Meth) acrylic acid ester resins such as acrylate resins and dimethylaminoethyl (meth) acrylate resins; Tajien resins; styrene resins; and can select these copolymers as appropriate.
  • the molecular weight of the organic binder is not particularly limited, and it is desirable to adjust appropriately in view of the desired viscosity as the composition.
  • the content rate in the case of containing an organic binder is 0.5 mass% or more and 30 mass% or less, and it is more preferable that it is 3 mass% or more and 25 mass% or less. Preferably, it is 3 mass% or more and 20 mass% or less.
  • the mass ratio of the total content of the alkaline earth metal and the metal compound containing the alkali metal to the total content of the organic binder (alkaline earth metal and alkali metal metal compound) / (organic binder) is 99.9. /0.1 to 0.1 / 99.9 is preferable, and 99/1 to 20/80 is more preferable.
  • a dispersion medium in which an organic binder is dissolved may be used as the dispersion medium and the organic binder.
  • the mask forming composition may include a thickener, a wetting agent, a surfactant, You may contain various additives, such as inorganic powder, resin containing a silicon atom, and a thixotropic agent.
  • the surfactant examples include nonionic surfactants, cationic surfactants, and anionic surfactants.
  • nonionic surfactants or cationic surfactants are preferable because impurities such as heavy metals are not brought into the semiconductor device.
  • silicon surfactants, fluorine surfactants, and hydrocarbon surfactants are exemplified as nonionic surfactants, and since they are rapidly baked during heating such as diffusion, hydrocarbon surfactants are preferable.
  • hydrocarbon surfactants include ethylene oxide-propylene oxide block copolymers, acetylene glycol compounds, and the like, and acetylene glycol compounds are more preferred because they reduce the variation in resistance of the semiconductor substrate.
  • Examples of the inorganic powder include silicon oxide, titanium oxide, silicon nitride, silicon oxide, silicon carbide and the like.
  • the mask forming composition may contain a thixotropic agent containing a solid content. This makes it possible to easily control the thixotropy, and constitute a mask forming composition for screen printing having a viscosity suitable for screen printing, and a composition for forming a mask for ink jet having a viscosity suitable for ink jet printing. can do. Furthermore, since thixotropy is controlled, bleeding and sagging from the print pattern of the mask forming composition during printing can be suppressed.
  • the organic binder described above may also serve as a thixotropic agent. Examples of such a material include ethyl cellulose.
  • the composition for forming a mask according to the present invention does not contaminate the semiconductor substrate, that is, from the viewpoint of suppressing the recombination of carriers in the semiconductor substrate, the content of iron, tungsten, gold, nickel, chromium, manganese, etc.
  • the content is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
  • the viscosity of the mask forming composition is not particularly limited. Specifically, it is preferably 0.5 Pa ⁇ s to 400 Pa ⁇ s at 25 ° C., more preferably 10 Pa ⁇ s to 100 Pa ⁇ s.
  • the viscosity of the mask forming composition can be determined by a rotation method, a stress control method, or a strain control method using a B-type viscometer, an E-type viscometer, a viscoelasticity measuring device, or the like.
  • the composition for forming a mask according to the present invention uses a blender, a mixer, a mortar, or a rotor containing an alkaline earth metal or a metal compound containing an alkali metal, a dispersion medium, an organic binder, and components added as necessary. Can be obtained by mixing. Moreover, when mixing, you may add a heat
  • the heating temperature at this time can be, for example, 30 ° C. to 100 ° C.
  • the solar cell includes one or more of the solar cell elements, and is configured by arranging a wiring material on the electrode of the solar cell element. If necessary, the solar cell may be constituted by connecting a plurality of solar cell elements via a wiring material and further sealing with a sealing material.
  • the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in the industry.
  • % Means “% by mass” unless otherwise specified.
  • the volume average particle size of the alkaline earth metal or the metal compound containing the alkali metal in the examples is measured using a laser diffraction scattering method particle size distribution analyzer (LS 13 320 manufactured by Beckman Coulter), and the particle size in a dispersed state. Was measured.
  • composition 1 for mask formation 10 g of calcium carbonate (rare metallic, purity 99.99%, volume average particle size 1.8 ⁇ m), 20 g of ⁇ -terpineol (manufactured by Dow Chemical Co., STD200) dissolved in 15% by mass, ⁇ -terpineol (manufactured by Terpene Chemical), ⁇ -
  • the composition 1 for mask formation was prepared by mixing 25 g of terpineol.
  • the mask forming composition 1 was applied to the back surface by screen printing. This was heat-treated at 150 ° C. and 500 ° C. for 1 minute to form a mask layer.
  • the mask layer was formed at 0.11 mg / cm 2 .
  • the tube was placed in a tube type diffusion furnace, and a heat treatment was performed at 850 ° C. for 30 minutes by flowing a N 2 —O 2 mixed gas containing phosphorus oxychloride.
  • the substrate was washed with a 10% HNO 3 aqueous solution and then with a 5% HF aqueous solution to remove the phosphosilicate glass and the mask layer.
  • a SiNx film was formed on the light-receiving surface side by a plasma-enhanced chemical vapor deposition method using silane gas and ammonia as raw materials.
  • the thickness of the SiNx film was 80 nm.
  • an Ag electrode paste (made by DuPont) was applied to the light-receiving surface side, and an Al electrode paste (made by PVGS) was applied to the back surface by screen printing, dried at 150 ° C., and then fired at 800 ° C. to produce a solar cell element. .
  • the power generation characteristics were evaluated using a solar cell evaluation system (NF circuit design block, As-510-PV). The conversion efficiency was 16.0%.
  • Example 2 In the mask forming composition 1 described in Example 1, the sun was formed in the same manner as in Example 1 except that calcium oxide (manufactured by High Purity Chemical Laboratory, volume average particle size 2.5 ⁇ m) was used instead of calcium carbonate. A battery element was produced. The conversion efficiency was 15.8%.
  • Example 3 A solution of 4 g of calcium carbonate (rare metallic, purity 99.99%, volume average particle size 1.8 ⁇ m) and 6 g of ⁇ -terpineol was prepared and pulverized with a planetary ball mill. This solution was mixed with 10 g of ⁇ -lupineol in which 12% by mass of ethylcellulose was dissolved to prepare a composition 3 for forming a mask.
  • a solar cell element was prepared and evaluated in the same manner as in Example 1 except that the mask forming composition 3 was used.
  • the conversion efficiency was 15.8%.
  • Example 4 (Back electrode type solar cell) 2 g of B 2 O 3 (manufactured by High Purity Chemical Laboratory, volume average particle size 3.0 ⁇ m) and 8 g of ⁇ -terpineol solution containing 8% by mass of ethyl cellulose were mixed in an agate mortar, Prepared.
  • An as-sliced n-type silicon substrate (manufactured by Advantech) was immersed in a 20% aqueous NaOH solution and treated at 50 ° C. for 30 minutes to remove the damaged layer.
  • an alkaline etching solution SUN-X600 (manufactured by Wako Pure Chemical Industries) and treated at 60 ° C. for 30 minutes to form a texture structure on the light receiving surface side.
  • SUN-X600 manufactured by Wako Pure Chemical Industries
  • only the back surface side was sequentially immersed in a 10% HF, 20% HNO 3 , 10% CH 3 COOH aqueous solution to form a mirror structure.
  • the composition 1 for mask formation was apply
  • the p-type diffusion layer forming composition was screen-printed on the portion of the back surface where the mask layer was not formed, and heat-treated at 150 ° C. for 1 minute and at 500 ° C. for 1 minute. This was put in a tube type diffusion furnace and heat-treated at 950 ° C. for 30 minutes while flowing N 2 gas to form a p-type diffusion layer.
  • the substrate was washed with a 10% HNO 3 aqueous solution and then with a 5% HF aqueous solution to remove the borosilicate glass and the mask layer.
  • the mask-forming composition 1 was applied to the portion where the p-type diffusion layer was formed by screen printing, and this was heat-treated at 150 ° C. and 500 ° C. for 1 minute to form a mask layer. This was put in a tube type diffusion furnace and heat-treated at 850 ° C. for 30 minutes while flowing an O 2 —N 2 gas containing phosphorus oxychloride gas to form an n-type diffusion layer. Next, the substrate was washed with a 10% HNO 3 aqueous solution and then with a 5% HF aqueous solution to remove the phosphosilicate glass and the mask layer.
  • a SiNx film was formed on the light-receiving surface side by a plasma-enhanced chemical vapor deposition method using silane gas and ammonia as raw materials.
  • the thickness of the SiNx film was 80 nm.
  • an Ag electrode paste (manufactured by DuPont) was applied to the silicon substrate surface on which the p-type diffusion layer and the n-type diffusion layer on the back surface were formed by screen printing, dried at 150 ° C., and then fired at 800 ° C. Finally, solder dipping was performed to complete the solar cell. The conversion efficiency was 16.4%.
  • Example 5 Double-sided solar cell
  • An as-sliced n-type silicon substrate manufactured by Advantech
  • a 20% aqueous NaOH solution was immersed in a 20% aqueous NaOH solution and treated at 50 ° C. for 30 minutes to remove the damaged layer.
  • an alkaline etching solution SUN-X600 manufactured by Wako Pure Chemical Industries, Ltd.
  • SUN-X600 manufactured by Wako Pure Chemical Industries, Ltd.
  • the mask-forming composition 1 was applied to the light-receiving surface by screen printing. This was heat-treated at 150 ° C. and 500 ° C. for 1 minute to form a mask layer. The mask layer was formed at 0.11 mg / cm 2 .
  • the p-type diffusion layer forming composition prepared in Example 4 was screen-printed on the back surface, and heat-treated at 150 ° C. for 1 minute and at 500 ° C. for 1 minute. This was put into a tube type diffusion furnace and heat-treated at 950 ° C. for 30 minutes while flowing N 2 gas. Next, the substrate was washed with a 10% HNO 3 aqueous solution and then with a 5% HF aqueous solution to remove the borosilicate glass and the mask layer.
  • the mask-forming composition 1 was applied to the back surface by screen printing, and this was heat-treated at 150 ° C. and 500 ° C. for 1 minute to form a mask layer. This was put in a tube type diffusion furnace and heat-treated at 850 ° C. for 30 minutes while flowing O 2 —N 2 gas containing phosphorus oxychloride gas. Next, the substrate was washed with a 10% HNO 3 aqueous solution and then with a 5% HF aqueous solution to remove the phosphosilicate glass and the mask layer.
  • the silicon substrate was placed in a tube type diffusion furnace, and heat treatment was performed at 1000 ° C. for 1 hour while flowing N 2 —O 2 gas bubbling ultrapure water to form thermal oxide films on both sides.
  • Example 1 A solar cell was produced in the same manner as in Example 1 except that silicon oxide (manufactured by High-Purity Chemical, volume average particle size 1.0 ⁇ m, substantially granular) was used instead of calcium carbonate in Example 1. The conversion efficiency was 13.5%.
  • the conversion efficiency of the solar cell elements of Examples 1 to 5 manufactured by the manufacturing method of the present invention is 0.9% or more higher than the conversion efficiency of the solar cell element of Comparative Example 1. Showed efficiency.

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Abstract

La présente invention a trait à un procédé de production destiné à un substrat de cellule solaire, lequel procédé inclut : une étape au cours de laquelle une couche de masque est formée sur la surface d'un substrat semi-conducteur, ladite couche de masque incluant un composé métallique qui inclut un métal alcalino-terreux ou un métal alcalin ; et une étape au cours de laquelle une couche de diffusion est formée sur une zone située sur le substrat semi-conducteur sur laquelle la couche de masque n'est pas formée.
PCT/JP2013/050301 2012-01-10 2013-01-10 Procédé de production destiné à un substrat de cellule solaire et procédé de production destiné à un élément de cellule solaire WO2013105600A1 (fr)

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JP2013553306A JP5842931B2 (ja) 2012-01-10 2013-01-10 太陽電池用基板の製造方法

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WO2016165810A1 (fr) * 2015-04-15 2016-10-20 Merck Patent Gmbh Milieux dopants, formant barrière à une diffusion parasitaire et imprimables, à base de sol-gel et destinés au dopage local de tranches de silicium
WO2016165812A1 (fr) * 2015-04-15 2016-10-20 Merck Patent Gmbh Pâte dopée au bore utilisable en sérigraphie, inhibant simultanément la diffusion de phosphore lors de processus de co-diffusion

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CN107359112B (zh) * 2017-08-02 2021-06-01 巨力新能源股份有限公司 一种p型双面晶硅电池的制作方法

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