WO2012005253A1 - Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque - Google Patents

Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque Download PDF

Info

Publication number
WO2012005253A1
WO2012005253A1 PCT/JP2011/065386 JP2011065386W WO2012005253A1 WO 2012005253 A1 WO2012005253 A1 WO 2012005253A1 JP 2011065386 W JP2011065386 W JP 2011065386W WO 2012005253 A1 WO2012005253 A1 WO 2012005253A1
Authority
WO
WIPO (PCT)
Prior art keywords
diffusion layer
type diffusion
forming composition
layer forming
glass powder
Prior art date
Application number
PCT/JP2011/065386
Other languages
English (en)
Japanese (ja)
Inventor
修一郎 足立
吉田　誠人
野尻　剛
香 岡庭
洋一 町井
岩室　光則
鉄也 佐藤
木沢　桂子
Original Assignee
日立化成工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2010155173A external-priority patent/JP5691268B2/ja
Priority claimed from JP2010155174A external-priority patent/JP5691269B2/ja
Application filed by 日立化成工業株式会社 filed Critical 日立化成工業株式会社
Priority to CN2011800271169A priority Critical patent/CN102934205A/zh
Priority to KR1020127031636A priority patent/KR20130086146A/ko
Publication of WO2012005253A1 publication Critical patent/WO2012005253A1/fr

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • H01L21/2225—Diffusion sources
    • 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
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—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 an impurity diffusion layer forming composition, a method for manufacturing an impurity diffusion layer, and a method for manufacturing a solar cell element, and more specifically, forming an impurity diffusion layer in a specific portion of a silicon substrate which is a semiconductor substrate. More particularly, the present invention relates to a technology capable of reducing the internal stress of a silicon substrate, which is a semiconductor substrate, and to an impurity diffusion layer forming technology capable of suppressing damage at crystal grain boundaries, suppressing crystal defect growth, and suppressing warpage.
  • a p-type silicon substrate having a textured structure formed on the light receiving surface is prepared so as to promote the light confinement effect, and then a donor element-containing compound such as phosphorus oxychloride (POCl 3 ), nitrogen, oxygen
  • a donor element-containing compound such as phosphorus oxychloride (POCl 3 ), nitrogen, oxygen
  • POCl 3 phosphorus oxychloride
  • the n-type diffusion layer is uniformly formed on the substrate by performing several tens of minutes at 800 ° C. to 900 ° C. in the mixed gas atmosphere.
  • phosphorus is diffused using a mixed gas
  • n-type diffusion layers are formed not only on the surface but also on the side surface and the back surface. Therefore, side etching is performed to remove the n-type diffusion layer on the side surface.
  • the n-type diffusion layer on the back surface needs to be converted into a p + -type diffusion layer, and an aluminum paste is applied on the n-type diffusion layer on the back surface, and this is baked. It was converted to a p + type diffusion layer.
  • the aluminum layer formed from the aluminum paste has a low conductivity, and in order to reduce the sheet resistance, it is The aluminum layer formed on the entire surface must have a thickness of about 10 ⁇ m to 20 ⁇ m after firing. Furthermore, when a thick aluminum layer is formed in this way, the thermal expansion coefficient differs greatly between silicon and aluminum, so that a large internal stress is generated in the silicon substrate during the firing and cooling process, resulting in damage to the grain boundaries, In some cases, defects increased and warped.
  • n-type diffusion layer in the gas phase reaction using phosphorus oxychloride, not only one side (usually the light receiving surface or the surface) that originally requires the n-type diffusion layer but also the other side An n-type diffusion layer is also formed on the surface (non-light-receiving surface or back surface) and side surfaces. Further, even in the method of applying a solution containing phosphate and thermally diffusing, an n-type diffusion layer is formed on the surface other than the surface as in the gas phase reaction method. Therefore, in order to have a pn junction structure as an element, it is necessary to perform etching on the side surface and convert the n-type diffusion layer to the p-type diffusion layer on the back surface. In general, an aluminum paste which is a Group 13 element is applied to the back surface and fired to convert the n-type diffusion layer into a p-type diffusion layer.
  • the present invention has been made in view of the above-described conventional problems, and an n-type diffusion layer is formed in a specific portion without forming an unnecessary n-type diffusion layer in a manufacturing process of a solar cell element using a silicon substrate. It is an object of the present invention to provide an n-type diffusion layer-forming composition, a method for producing an n-type diffusion layer, and a method for producing a solar cell element.
  • the present invention provides a p-type diffusion layer formation capable of forming a p-type diffusion layer while suppressing the occurrence of internal stress in the silicon substrate and warping of the substrate in a manufacturing process of a solar cell using a silicon substrate.
  • An object is to provide a p-type diffusion layer forming composition that is a composition and excellent in dispersion stability, a method for producing a p-type diffusion layer, and a method for producing a solar cell element.
  • An impurity diffusion layer forming composition comprising a glass powder containing a donor element or an acceptor element, a binder having a weight average molecular weight of 5,000 to 500,000, and a solvent.
  • the glass powder includes a glass component substance and a donor element-containing substance, and the content ratio of the donor element-containing substance is 1% by mass to 75% by mass with respect to the glass powder.
  • n-type diffusion layer forming composition according to any one of ⁇ 2> to ⁇ 4>, wherein the donor element is at least one selected from P (phosphorus) and Sb (antimony).
  • the glass powder containing the donor element includes at least one donor element-containing material selected from P 2 O 3 , P 2 O 5, and Sb 2 O 3 , and SiO 2 , K 2 O, and Na 2 O. And at least one glass component material selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , and MoO 3.
  • the n-type diffusion layer forming composition according to any one of the above.
  • n-type diffusion layer forming composition according to any one of ⁇ 2> to ⁇ 6>, further including at least one metal selected from Ag, Si, Cu, Fe, Zn, and Mn. .
  • An n-type diffusion comprising a step of applying the n-type diffusion layer forming composition according to any one of ⁇ 2> to ⁇ 8> on a semiconductor substrate and a step of performing a thermal diffusion treatment.
  • Layer manufacturing method
  • n-type diffusion layer forming composition according to any one of ⁇ 2> to ⁇ 8> above on a semiconductor substrate and a thermal diffusion treatment to form an n-type diffusion layer
  • the manufacturing method of the solar cell element which has a process and the process of forming an electrode on the formed n type diffused layer.
  • the glass powder includes a glass component substance and an acceptor element-containing substance, and a content ratio of the acceptor element-containing substance in the glass powder is 1% by mass or more and 90% by mass or less.
  • a p-type diffusion layer forming composition is a p-type diffusion layer forming composition.
  • ⁇ 14> The p-type according to any one of ⁇ 11> to ⁇ 13>, wherein the acceptor element is at least one selected from B (boron), Al (aluminum), and Ga (gallium). Diffusion layer forming composition.
  • the glass powder containing the acceptor element is at least one acceptor element-containing material selected from B 2 O 3 , Al 2 O 3, and Ga 2 O 3 , and SiO 2 , K 2 O, and Na 2 O. And at least one glass component material selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, SnO, ZrO 2 , and MoO 3.
  • the p-type diffusion layer forming composition according to any one of ⁇ 11> to ⁇ 14>.
  • a p-type diffusion having a step of applying the p-type diffusion layer forming composition according to any one of ⁇ 11> to ⁇ 15> on a semiconductor substrate and a step of performing a thermal diffusion treatment.
  • Layer manufacturing method
  • a step of applying the p-type diffusion layer forming composition according to any one of the above ⁇ 11> to ⁇ 15> on the semiconductor substrate and a thermal diffusion treatment to form a p-type diffusion layer The manufacturing method of the solar cell element which has a process and the process of forming an electrode on the formed p-type diffused layer.
  • n-type diffusion layer in the manufacturing process of a solar cell element using a silicon substrate, it is possible to form an n-type diffusion layer in a specific portion without forming an unnecessary n-type diffusion layer, thereby improving dispersion stability.
  • An excellent n-type diffusion layer forming composition can be provided.
  • the manufacturing method of the n type diffused layer using this n type diffused layer formation composition and the manufacturing method of a photovoltaic cell can be provided.
  • a p-type diffusion layer in the manufacturing process of a solar cell element using a silicon substrate, a p-type diffusion layer can be formed while suppressing internal stress in the silicon substrate and warping of the substrate.
  • a p-type diffusion layer forming composition that is a diffusion layer forming composition and excellent in dispersion stability, a method for producing a p-type diffusion layer, and a method for producing a solar battery cell can be provided.
  • FIG. 2A It is sectional drawing which shows notionally an example of the manufacturing process of the solar cell element of this invention. It is the top view which looked at the solar cell element from the surface. It is a perspective view which expands and shows a part of FIG. 2A.
  • the present invention is an impurity diffusion layer forming composition containing a glass powder containing a donor element or an acceptor element, a binder having a weight average molecular weight of 5,000 or more and 500,000 or less, and a solvent.
  • the impurity diffusion layer forming composition is an n-type diffusion layer forming composition
  • the glass powder contains a donor element
  • the impurity diffusion layer forming composition is a p-type diffusion layer forming composition
  • the glass powder contains an acceptor element.
  • the n-type diffusion layer forming composition and the p-type diffusion layer forming composition are The viscosity can be adjusted so that it can be uniformly applied on the silicon substrate. Further, the binder can be completely burned in the thermal diffusion treatment, and the diffusion of the donor element or the acceptor element becomes easy. Further, the dispersion stability of the n-type diffusion layer forming composition and the p-type diffusion layer forming composition is improved. Therefore, the n-type diffusion layer forming composition and the p-type diffusion layer forming composition of the present invention are excellent in dispersion stability, and an n-type diffusion layer or a p-type diffusion layer can be formed in a specific portion.
  • an n-type diffusion layer forming composition and a p-type diffusion layer forming composition of the present invention will be described, and then an n-type diffusion layer manufacturing method using the n-type diffusion layer forming composition, p-type diffusion layer forming composition
  • a method for manufacturing a p-type diffusion layer using a solar cell and a method for manufacturing a solar cell element 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 as long as the intended action of the process is achieved. included.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition in the present specification when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.
  • the composition for forming an n-type diffusion layer of the present invention includes at least one kind of glass powder containing at least a donor element (hereinafter sometimes simply referred to as “glass powder”) and a binder having a weight average molecular weight of 5,000 to 500,000. And at least one solvent, and may further contain other additives as required in consideration of coating properties and the like.
  • the n-type diffusion layer forming composition contains a glass powder containing a donor element, and is a material capable of forming an n-type diffusion layer by thermally diffusing this donor element after being applied to a silicon substrate.
  • an n-type diffusion layer is formed at a desired site, and an unnecessary n-type diffusion layer is not formed on the back surface or side surface.
  • the composition for forming an n-type diffusion layer of the present invention is applied, the side etching step that is essential in the gas phase reaction method that has been widely employed is not necessary, and the process is simplified.
  • the step of converting the n-type diffusion layer formed on the back surface into the p + -type diffusion layer is not necessary. Therefore, the method for forming the p + -type diffusion layer on the back surface and the material, shape, and thickness of the back electrode are not limited, and the choice of manufacturing method, material, and shape to be applied is widened. Although details will be described later, generation of internal stress in the silicon substrate due to the thickness of the back electrode is suppressed, and warpage of the silicon substrate is also suppressed.
  • the glass powder contained in the n-type diffusion layer forming composition of the present invention is melted by firing to form a glass layer on the n-type diffusion layer.
  • a glass layer is formed on the n-type diffusion layer in the conventional gas phase reaction method and the method of applying a phosphate-containing solution, and thus the glass layer produced in the present invention is the same as the conventional method. Further, it can be removed by etching. Therefore, the n-type diffusion layer forming composition of the present invention does not generate unnecessary products and does not increase the number of steps as compared with the conventional method.
  • the donor component of the glass powder is difficult to volatilize even during firing, the formation of an n-type diffusion layer not only on the surface but also on the back surface and side surfaces due to the generation of the volatilizing gas is suppressed.
  • the reason for this is considered that the donor component is bonded to an element in the glass powder or is taken into the glass, so that it is difficult to volatilize.
  • the n-type diffusion layer forming composition of the present invention can form an n-type diffusion layer having a desired concentration at a desired site, a selective region having a high n-type dopant concentration is formed. It becomes possible to form. On the other hand, it is generally difficult to form a selective region having a high n-type dopant concentration by a gas phase reaction method, which is a general method of an n-type diffusion layer, or a method using a phosphate-containing solution. .
  • a donor element is an element that can form an n-type diffusion layer by doping into a silicon substrate.
  • a Group 15 element can be used, and examples thereof include P (phosphorus), Sb (antimony), Bi (bismuth), As (arsenic), and the like. From the viewpoints of safety, ease of vitrification, etc., P or Sb is preferred.
  • Examples of the donor element-containing material used for introducing the donor element into the glass powder include P 2 O 3 , P 2 O 5 , Sb 2 O 3 , Bi 2 O 3 and As 2 O 3 , and P 2 O 3 It is preferable to use at least one selected from P 2 O 5 and Sb 2 O 3 .
  • the glass powder containing a donor element can control a melting temperature, a softening temperature, a glass transition temperature, chemical durability, etc. by adjusting a component ratio as needed. Furthermore, it is preferable to contain the glass component substance described below.
  • glass component materials include SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , MoO 3 , La 2 O 3 , Examples include Nb 2 O 5 , Ta 2 O 5 , Y 2 O 3 , TiO 2 , ZrO 2 , GeO 2 , TeO 2, and Lu 2 O 3, and include SiO 2 , K 2 O, Na 2 O, Li 2 O. It is preferable to use at least one selected from BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , and MoO 3
  • the glass powder containing a donor element include a system containing both the donor element-containing substance and the glass component substance, and a P 2 O 5 -SiO 2 system (in order of donor element-containing substance-glass component substance). in described, the same applies hereinafter), P 2 O 5 -K 2 O based, P 2 O 5 -Na 2 O-based, P 2 O 5 -Li 2 O system, P 2 O 5 -BaO-based, P 2 O 5 - SrO-based, P 2 O 5 -CaO-based, P 2 O 5 -MgO-based, P 2 O 5 -BeO based, P 2 O 5 -ZnO-based, P 2 O 5 -CdO based, P 2 O 5 -PbO system , including P 2 O 5 -V 2 O 5 system, P 2 O 5 -SnO-based, P 2 O 5 -GeO 2 system, a P 2 O 5 as a donor element-containing material of P 2
  • a donor element-containing material is used instead of P 2 O 5 in a system containing P 2 O 5 .
  • glass powder of a system containing Sb 2 O 3 instead of P 2 O 5 in a system containing P 2 O 5 , a donor element-containing material is used.
  • glass powder of a system containing Sb 2 O 3 a glass powder containing two or more kinds of donor element-containing substances, such as a P 2 O 5 —Sb 2 O 3 system and a P 2 O 5 —As 2 O 3 system, may be used.
  • a composite glass containing two components is exemplified, but glass powder containing three or more components such as P 2 O 5 —SiO 2 —V 2 O 5 and P 2 O 5 —SiO 2 —CaO may be used.
  • the content ratio of the glass component substance in the glass powder is preferably set as appropriate in consideration of the doping concentration of the donor element into the silicon substrate, the melting temperature of the glass powder, the softening temperature, the glass transition temperature, and the chemical durability. In general, the content is preferably 1% by mass or more and 75% by mass or less.
  • the content ratio of the donor element-containing substance in the glass powder is 1% by mass or more, the doping concentration of the donor element into the silicon substrate does not become too low, and the n-type diffusion layer is sufficiently formed.
  • the content ratio of the donor element-containing material such as P 2 O 5 is 75% by mass or less, the donor element-containing material absorbs moisture in the glass powder.
  • the donor element-containing material is P 2 O 5 Can suppress the formation of phosphoric acid (H 3 PO 4 ).
  • H 3 PO 4 phosphoric acid
  • moisture-absorbing substances such as H 3 PO 4 are suppressed from being volatilized during the thermal diffusion treatment, and the diffusion of the donor element such as P (phosphorus) extends to the side surface and the back surface as well as the surface. It is possible to prevent the n-type diffusion layer from being formed on the side surface and the back surface other than the part.
  • the content of the donor element-containing material in the glass powder is 2% by mass or more and 75% by mass. % Or less, and more preferably 10% by mass or more and 70% by mass or less.
  • the content ratio of the donor element-containing material is more preferably 30% by mass or more and 70% by mass or less.
  • the content ratio of the glass component substance in the glass powder is preferably set as appropriate in consideration of the melting temperature, the softening temperature, the glass transition temperature, and the chemical durability, and generally 0.1% by mass or more and 95% by mass. % Or less, more preferably 0.5% by mass or more and 90% by mass or less.
  • the content ratio of SiO 2 is preferably 1% by mass or more and 90% by mass or less, and more preferably 3% by mass or more and 80% by mass or less. It is more preferable.
  • the softening point of the glass powder is preferably 200 ° C. to 1000 ° C., more preferably 300 ° C. to 900 ° C., from the viewpoints of diffusibility during the diffusion treatment and dripping.
  • the shape of the glass powder examples include a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of the application property to the substrate and the uniform diffusibility when it is an n-type diffusion layer forming composition, It is desirable to have a substantially spherical shape, a flat shape or a plate shape.
  • the particle size of the glass powder is desirably 100 ⁇ m or less. When glass powder having a particle size of 100 ⁇ m or less is used, a smooth coating film is easily obtained. Furthermore, the particle size of the glass powder is more desirably 50 ⁇ m or less. The lower limit is not particularly limited, but is preferably 0.01 ⁇ m or more.
  • the particle diameter of glass represents an average particle diameter, and can be measured by a laser scattering diffraction particle size distribution measuring apparatus or the like.
  • the glass powder containing a donor element is produced by the following procedure.
  • raw materials for example, the donor element-containing material and the glass component material are weighed and filled in a crucible.
  • the material for the crucible include platinum, platinum-rhodium, iridium, alumina, quartz, carbon, and the like, and are appropriately selected in consideration of the melting temperature, atmosphere, reactivity with the molten material, and the like.
  • it heats with the temperature according to a glass composition with an electric furnace, and is set as a melt. At this time, it is desirable to stir the melt uniformly.
  • the obtained melt is poured onto a zirconia substrate, a carbon substrate or the like to vitrify the melt.
  • the glass is crushed into powder.
  • a known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
  • the content ratio of the glass powder containing the donor element in the n-type diffusion layer forming composition is determined in consideration of the coating property, the diffusibility of the donor element, and the like. Generally, the content ratio of the glass powder in the n-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less, and more preferably 1% by mass or more and 90% by mass or less.
  • the n-type diffusion layer forming composition of the present invention contains at least one binder having a weight average molecular weight of 5000 to 500,000 and at least one solvent. These serve as a dispersion medium for the glass powder.
  • binder examples include polyvinyl alcohol, polyacrylamides, polyvinylamides, polyvinylpyrrolidone, polyethylene oxides, polysulfonic acid, acrylamide alkylsulfonic acid, cellulose ethers, cellulose derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch And starch derivatives, sodium alginates, xanthan, gua and gua derivatives, scleroglucan and scleroglucan derivatives, tragacanth and tragacanth derivatives, dextrin and dextrin derivatives, (meth) acrylic acid resins, (meth) acrylic acid ester resins (e.g.
  • Alkyl (meth) acrylate resins Alkyl (meth) acrylate resins, dimethylaminoethyl (meth) acrylate resins, etc.), butadiene Fat, styrene resins and copolymers thereof, as well as appropriately selected and siloxane resin. These are used singly or in combination of two or more.
  • the n-type diffusion layer forming composition of the present invention has a weight average molecular weight of 5,000 or more and 500,000 or less of the binder contained therein. Thereby, it is possible to adjust the viscosity so that the n-type diffusion layer forming composition can be uniformly applied on the silicon substrate. If the molecular weight of the binder is less than 5000, the viscosity of the n-type diffusion layer forming composition may increase. This can be considered, for example, because the three-dimensional repulsion when adsorbed on glass particles is insufficient and the particles aggregate.
  • the weight average molecular weight of the binder when the weight average molecular weight of the binder is larger than 500,000, the binders aggregate in the solvent, and as a result, the viscosity of the n-type diffusion layer forming composition may increase.
  • the burning temperature of the binder increases, the binder is not completely burned in the thermal diffusion treatment, and the diffusion of the donor element is difficult to proceed. There is a possibility of diffusing to the substrate.
  • the molecular weight of the binder is preferably 6000 or more and 450,000 or less, and more preferably 6500 or more and 400,000 or less.
  • the weight average molecular weight of a binder is measured by the normal method using GPC.
  • the solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, Ketone solvents such as diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl -N-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane,
  • n-type diffusion layer forming composition ⁇ -terpineol, diethylene glycol mono-n-butyl ether, and 2- (2-butoxyethoxy) ethyl acetate are preferable from the viewpoint of applicability to the substrate.
  • the content ratio of the binder and the solvent in the n-type diffusion layer forming composition is appropriately selected in consideration of coating properties, donor element-containing substance concentration, and the like.
  • the content ratio of the binder can be, for example, 0.01% by mass to 5% by mass with respect to the n-type diffusion layer forming composition, and from the viewpoint of dispersion stability, 0.1% by mass to 3%. It is preferable that it is mass%.
  • the content ratio of the solvent can be 1% by mass to 60% by mass with respect to the n-type diffusion layer forming composition, and is preferably 5% by mass to 40% by mass from the viewpoint of dispersion stability. .
  • the viscosity of the n-type diffusion layer forming composition is preferably 10 mPa ⁇ s or more and 1000000 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or more and 500000 mPa ⁇ s or less in consideration of applicability.
  • pH adjuster examples include dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, tartaric acid, citric acid, fumaric acid, malic acid, phytic acid, succinic acid, gluconic acid, lactic acid, sodium hydroxide, potassium carbonate, sodium bicarbonate, carbonate Sodium etc. are mentioned. These are used singly or in combination of two or more.
  • the pH of the n-type diffusion layer forming composition is appropriately set in consideration of the equipotential point of the glass composition (the pH at which the zeta potential becomes 0 and the particles easily aggregate), acid resistance, and alkali resistance.
  • the pH (25 ° C.) is preferably 2.0 or more and 13.0 or less, and more preferably 3.0 or more and 12.0 or less.
  • the pH is measured at 25 ° C. using a normal pH measuring device.
  • the pH (25 ° C.) of the n-type diffusion layer forming composition is preferably 3.0 or more and 11.0 or less. More preferably, it is 0 or more and 10.0 or less.
  • the n-type diffusion layer forming composition may contain other additives.
  • other additives include metals that easily react with the glass powder.
  • the n-type diffusion layer forming composition is applied on a semiconductor substrate and heat-treated at a high temperature to form an n-type diffusion layer. At that time, glass is formed on the surface. This glass is removed by dipping in an acid such as hydrofluoric acid, but some glass is difficult to remove depending on the type of glass. In that case, the glass can be easily removed after the acid cleaning by adding a metal such as Ag, Mn, Cu, Fe, Zn, or Si. Among these, it is preferable to use at least one selected from Ag, Si, Cu, Fe, Zn and Mn, more preferable to use at least one selected from Ag, Si and Zn. It is particularly preferred.
  • the content ratio of the metal is desirably adjusted as appropriate depending on the type of glass and the type of the metal, and is generally 0.01% by mass or more and 10% by mass or less with respect to the glass powder.
  • the said metal can be used with forms, such as a metal simple substance and a metal oxide.
  • the p-type diffusion layer forming composition of the present invention includes at least one kind of glass powder containing at least an acceptor element (hereinafter sometimes simply referred to as “glass powder”) and a binder having a weight average molecular weight of 5,000 to 500,000. And at least one solvent, and may further contain other additives as required in consideration of coating properties and the like.
  • the p-type diffusion layer forming composition contains an acceptor element.
  • the p-type diffusion layer is formed by thermally diffusing the acceptor element by applying thermal diffusion treatment (baking) after being applied to a silicon substrate. A material that can be used.
  • the p + -type diffusion layer forming step and the ohmic contact forming step can be separated, and the choice of electrode material for forming the ohmic contact is widened.
  • the options also expand. For example, if a low resistance material such as silver is used for the electrode, a low resistance can be achieved with a thin film thickness.
  • the electrodes need not be formed on the entire surface, and may be partially formed like a comb shape. As described above, by forming a partial shape such as a thin film or a comb shape, it is possible to form a p-type diffusion layer while suppressing the occurrence of internal stress in the silicon substrate and warping of the substrate.
  • the p-type diffusion layer forming composition of the present invention is applied, a conventionally widely employed method, that is, printing an aluminum paste and firing it to turn the n-type diffusion layer into a p + -type diffusion layer.
  • a conventionally widely employed method that is, printing an aluminum paste and firing it to turn the n-type diffusion layer into a p + -type diffusion layer.
  • the internal stress in the substrate and the warpage of the substrate that are generated by the method of obtaining the ohmic contact are suppressed.
  • the acceptor component in the glass powder is not easily volatilized even during firing, the formation of a p-type diffusion layer other than the desired region due to the generation of the volatilizing gas is suppressed. The reason for this is considered that the acceptor component is bonded to an element in the glass powder or is taken into the glass, so that it is difficult to volatilize.
  • the content ratio of the acceptor element-containing substance in the glass powder contained therein is preferably 1% by mass or more and 90% by mass or less. Thereby, a surface resistance value falls and the performance as a photovoltaic cell can be improved. Details of the acceptor element-containing material will be described later.
  • An acceptor element is an element that can form a p-type diffusion layer by doping into a silicon substrate.
  • a Group 13 element can be used, and examples thereof include B (boron), Al (aluminum), and Ga (gallium).
  • acceptor element-containing material used for introducing the acceptor element into the glass powder examples include B 2 O 3 , Al 2 O 3 , and Ga 2 O 3 , and B 2 O 3 , Al 2 O 3, and Ga 2 O. It is preferable to use at least one selected from 3 .
  • the glass powder containing an acceptor element can control a melting temperature, a softening temperature, a glass transition temperature, chemical durability, etc. by adjusting a component ratio as needed. Furthermore, it is preferable to contain the components described below.
  • glass component materials include SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, SnO, ZrO 2 , MoO 3 , La 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , Y 2 O 3 , TiO 2 , GeO 2 , TeO 2, and Lu 2 O 3, and the like can be mentioned.
  • SiO 2 , K 2 O, Na 2 O, Li 2 It is preferable to use at least one selected from O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, SnO, ZrO 2 , and MoO 3 .
  • the glass powder containing an acceptor element include a system containing both the acceptor element-containing substance and the glass component substance, and a B 2 O 3 —SiO 2 system (in order of acceptor element-containing substance—glass component substance). And the same applies hereinafter), B 2 O 3 —ZnO system, B 2 O 3 —PbO system, B 2 O 3 single system, etc., a system containing B 2 O 3 as an acceptor element-containing substance, Al 2 O 3 —SiO Glasses such as a system containing Al 2 O 3 as the acceptor element-containing material such as a 2 system and a system containing Ga 2 O 3 as the acceptor element containing material such as a Ga 2 O 3 —SiO 2 system can be given.
  • a glass powder containing two or more kinds of acceptor element-containing materials such as Al 2 O 3 —B 2 O 3 series, Ga 2 O 3 —B 2 O 3 series, etc. may be used.
  • acceptor element-containing materials such as Al 2 O 3 —B 2 O 3 series, Ga 2 O 3 —B 2 O 3 series, etc.
  • a single component glass or a composite glass containing two components is exemplified, but three or more types of composite glasses such as B 2 O 3 —SiO 2 —Na 2 O may be used as necessary.
  • the content ratio of the glass component substance in the glass powder is preferably set as appropriate in consideration of the melting temperature, the softening temperature, the glass transition temperature, and the chemical durability, and is generally 0.1% by mass to 95% by mass. It is preferable that it is 0.5 mass% or more and 90 mass% or less.
  • the softening temperature of the glass powder is preferably 200 ° C. to 1000 ° C., more preferably 300 ° C. to 900 ° C., from the viewpoints of diffusibility during the diffusion treatment and dripping.
  • the shape of the glass powder examples include a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of applicability to a substrate and uniform diffusibility when a p-type diffusion layer forming composition is used. It is desirable to have a substantially spherical shape, flat shape, or plate shape.
  • the particle size of the glass powder is desirably 50 ⁇ m or less. When glass powder having a particle size of 50 ⁇ m or less is used, a smooth coating film is easily obtained. Further, the particle size of the glass powder is more preferably 10 ⁇ m or less. The lower limit is not particularly limited, but is preferably 0.01 ⁇ m or more.
  • the particle diameter of glass represents an average particle diameter, and can be measured by a laser scattering diffraction particle size distribution measuring apparatus or the like.
  • the glass powder containing an acceptor element is produced by the following procedure. First, weigh the ingredients and fill the crucible. Examples of the material for the crucible include platinum, platinum-rhodium, iridium, alumina, quartz, carbon, and the like, and are appropriately selected in consideration of the melting temperature, atmosphere, reactivity with the molten material, and the like. Next, it heats with the temperature according to a glass composition with an electric furnace, and is set as a melt. At this time, it is desirable to stir the melt uniformly. Subsequently, the obtained melt is poured onto a zirconia substrate, a carbon substrate or the like to vitrify the melt. Finally, the glass is crushed into powder. A known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
  • the content ratio of the glass powder containing the acceptor element in the p-type diffusion layer forming composition is determined in consideration of applicability, acceptor element diffusibility, and the like. Generally, the content ratio of the glass powder in the p-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less, and more preferably 1% by mass or more and 90% by mass or less.
  • the p-type diffusion layer forming composition of the present invention contains at least one binder having a weight average molecular weight of 5000 to 500,000 and at least one solvent. These serve as a dispersion medium for the glass powder.
  • binder examples include polyvinyl alcohol, polyacrylamides, polyvinylamides, polyvinylpyrrolidone, polyethylene oxides, polysulfonic acid, acrylamide alkylsulfonic acid, cellulose ethers, cellulose derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch And starch derivatives, sodium alginates, xanthan, gua and gua derivatives, scleroglucan and scleroglucan derivatives, tragacanth and tragacanth derivatives, dextrin and dextrin derivatives, (meth) acrylic acid resins, (meth) acrylic acid ester resins (e.g.
  • Alkyl (meth) acrylate resins Alkyl (meth) acrylate resins, dimethylaminoethyl (meth) acrylate resins, etc.), butadiene Fat, styrene resins and copolymers thereof, as well as appropriately selected and siloxane resin. These are used singly or in combination of two or more.
  • the binder contained therein has a weight average molecular weight of 5,000 to 500,000.
  • coat a p-type diffused layer formation composition on a silicon substrate uniformly can be adjusted.
  • the molecular weight of the binder is less than 5000, the viscosity of the p-type diffusion layer forming composition may increase. This can be considered, for example, because the three-dimensional repulsion when adsorbed on glass particles is insufficient and the particles aggregate.
  • the weight average molecular weight of the binder when the weight average molecular weight of the binder is larger than 500,000, the binders aggregate in the solvent, and as a result, the viscosity of the p-type diffusion layer forming composition may increase.
  • the burning temperature of the binder increases, the binder is not completely burned in the thermal diffusion treatment, and the diffusion of the donor element is difficult to proceed. There is a possibility of diffusing to the substrate.
  • the molecular weight of the binder is preferably 6000 or more and 450,000 or less, and more preferably 6500 or more and 400,000 or less.
  • the weight average molecular weight of a binder is measured by the normal method using GPC.
  • the same solvent as the solvent in the n-type diffusion layer forming composition can be used, and the preferred range is also the same.
  • the content ratio of the binder and the solvent in the p-type diffusion layer forming composition is appropriately selected in consideration of coating properties, donor element-containing substance concentration, and the like.
  • the content ratio of the binder can be, for example, 0.01% by mass to 5% by mass with respect to the n-type diffusion layer forming composition. It is preferable that it is mass%.
  • the content ratio of the solvent can be 1% by mass to 60% by mass with respect to the n-type diffusion layer forming composition, and is preferably 5% by mass to 40% by mass from the viewpoint of dispersion stability. .
  • the viscosity of the p-type diffusion layer forming composition is preferably 10 mPa ⁇ s or more and 1000000 mPa ⁇ s or less, and more preferably 50 mPa ⁇ s or more and 500000 mPa ⁇ s or less in consideration of applicability.
  • pH adjuster examples include dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, tartaric acid, citric acid, fumaric acid, malic acid, phytic acid, succinic acid, gluconic acid, lactic acid, sodium hydroxide, potassium carbonate, sodium bicarbonate, carbonate Sodium etc. are mentioned. These are used singly or in combination of two or more.
  • the pH of the p-type diffusion layer forming composition is appropriately set in consideration of the equipotential point of the glass composition (the pH at which the zeta potential becomes 0 and the particles easily aggregate), acid resistance, and alkali resistance.
  • the pH (25 ° C.) is preferably 2.0 or more and 13.0 or less, and more preferably 3.0 or more and 12.0 or less.
  • the pH is measured at 25 ° C. using a normal pH measuring device.
  • the pH (25 ° C.) of the p-type diffusion layer forming composition is preferably 3.0 or more and 11.0 or less. More preferably, it is 0 or more and 10.0 or less.
  • FIG. 1 is a schematic cross-sectional view conceptually showing an example of the manufacturing process of the solar cell element of the present invention.
  • common constituent elements are denoted by the same reference numerals.
  • an alkaline solution is applied to a silicon substrate which is a p-type semiconductor substrate 10 to remove a damaged layer, and a texture structure is obtained by etching.
  • a texture structure is obtained by etching.
  • the damaged layer on the silicon surface generated when slicing from the ingot is removed with 20% by mass caustic soda.
  • etching is performed with a mixed solution of 1% by mass caustic soda and 10% by mass isopropyl alcohol to form a texture structure (the description of the texture structure is omitted in the figure).
  • a texture structure on the light receiving surface (surface) side, a light confinement effect is promoted, and high efficiency is achieved.
  • the n-type diffusion layer forming composition layer 11 is formed by applying the n-type diffusion layer forming composition to the surface of the p-type semiconductor substrate 10, that is, the surface that becomes the light receiving surface.
  • the coating method is not limited, and examples thereof include a printing method, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
  • the coating amount of the n-type diffusion layer forming composition is not particularly limited.
  • the coating amount of the glass powder can be 10 g / m 2 to 250 g / m 2, and 20 g / m 2 to 150 g / m 2. 2 is preferable.
  • a drying step for volatilizing the solvent contained in the composition may be necessary after coating.
  • drying is performed at a temperature of about 80 ° C. to 300 ° C. for about 1 to 10 minutes when using a hot plate, and about 10 to 30 minutes when using a dryer or the like.
  • the drying conditions depend on the solvent composition of the n-type diffusion layer forming composition, and are not particularly limited to the above conditions in the present invention.
  • the manufacturing method of the p + -type diffusion layer (high concentration electric field layer) 14 on the back surface is limited to a method by conversion from an n-type diffusion layer to a p-type diffusion layer with aluminum paste.
  • any conventionally known method can be adopted, and the options of the manufacturing method are expanded. Therefore, for example, the high-concentration electric field layer 14 can be formed by applying the composition 13 containing a Group 13 element such as B (boron).
  • the composition 13 containing a Group 13 element such as B (boron) for example, the aforementioned p-type diffusion layer forming composition of the present invention can be used.
  • the high-concentration electric field layer 14 can be formed on the back surface by subjecting the p-type diffusion layer forming composition applied to the back surface to a thermal diffusion treatment similar to the thermal diffusion treatment in the n-type diffusion layer forming composition described later. .
  • the thermal diffusion treatment of the p-type diffusion layer forming composition is preferably performed simultaneously with the thermal diffusion treatment of the n-type diffusion layer forming composition.
  • the semiconductor substrate 10 on which the n-type diffusion layer forming composition layer 11 is formed is subjected to thermal diffusion treatment at 600 ° C. to 1200 ° C.
  • thermal diffusion treatment As shown in FIG. 1C, the donor element diffuses into the semiconductor substrate, and the n-type diffusion layer 12 is formed.
  • a known continuous furnace, batch furnace, or the like can be applied to the thermal diffusion treatment. Further, the furnace atmosphere during the thermal diffusion treatment can be appropriately adjusted to air, oxygen, nitrogen or the like.
  • the thermal diffusion treatment time can be appropriately selected according to the content of the donor element contained in the n-type diffusion layer forming composition. For example, it can be 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes.
  • a glass layer such as phosphate glass is formed on the surface of the formed n-type diffusion layer 12, this phosphate glass is removed by etching.
  • etching a known method such as a method of immersing in an acid such as hydrofluoric acid or a method of immersing in an alkali such as caustic soda can be applied.
  • n-type diffusion layer 12 In the method for forming an n-type diffusion layer of the present invention in which the n-type diffusion layer 12 is formed using the n-type diffusion layer forming composition 11 of the present invention shown in FIGS. Only the n-type diffusion layer 12 is formed, and unnecessary n-type diffusion layers are not formed on the back surface and side surfaces. Therefore, in the conventional method of forming an n-type diffusion layer by a gas phase reaction method, a side etching process for removing an unnecessary n-type diffusion layer formed on a side surface is essential. According to the manufacturing method of the invention, the side etching process is not required, and the process is simplified.
  • n-type diffusion layer formed on the back surface it is necessary to convert an unnecessary n-type diffusion layer formed on the back surface into a p-type diffusion layer.
  • a group 13 element is added to the n-type diffusion layer on the back surface.
  • a method is adopted in which an aluminum paste is applied and baked to diffuse aluminum into the n-type diffusion layer and convert it into a p-type diffusion layer.
  • an aluminum amount of a certain amount or more is required in order to sufficiently convert to the p-type diffusion layer and to form a high concentration electric field layer of p + layer. Therefore, the aluminum layer is formed thick. There was a need.
  • n-type diffusion layer since an unnecessary n-type diffusion layer is not formed on the back surface, it is not necessary to perform conversion from the n-type diffusion layer to the p-type diffusion layer, and the necessity of increasing the thickness of the aluminum layer is eliminated. . As a result, generation of internal stress and warpage in the silicon substrate can be suppressed. As a result, it is possible to suppress an increase in power loss and damage to the element.
  • the manufacturing method of the p + -type diffusion layer (high concentration electric field layer) 14 on the back surface is limited to a method by conversion from an n-type diffusion layer to a p-type diffusion layer with aluminum. Therefore, any conventionally known method can be adopted, and the options of the manufacturing method are expanded.
  • a p + -type diffusion layer may be formed using the p-type diffusion layer forming composition of the present invention.
  • the material used for the back surface electrode 20 is not limited to Group 13 aluminum, and for example, Ag (silver), Cu (copper), or the like can be applied. In addition, it can be formed thinner than the conventional one.
  • an antireflection film 16 is formed on the n-type diffusion layer 12.
  • the antireflection film 16 is formed by applying a known technique.
  • the antireflection film 16 is a silicon nitride film, it is formed by a plasma CVD method using a mixed gas of SiH 4 and NH 3 as a raw material. At this time, hydrogen diffuses into the crystal, and orbits that do not contribute to the bonding of silicon atoms, that is, dangling bonds and hydrogen are combined to inactivate defects (hydrogen passivation).
  • the mixed gas flow ratio NH 3 / SiH 4 is 0.05 to 1.0
  • the reaction chamber pressure is 13.3 Pa (0.1 Torr) to 266.6 Pa (2 Torr)
  • the temperature is 300 ° C. to 550 ° C. and the frequency for plasma discharge is 100 kHz or more.
  • a surface electrode metal paste is printed, applied and dried by a screen printing method on the antireflection film 16 on the surface (light receiving surface) to form the surface electrode 18.
  • the metal paste for a surface electrode contains (1) metal particles and (2) glass particles as essential components, and includes (3) a resin binder and (4) other additives as necessary.
  • the back electrode 20 is also formed on the high-concentration electric field layer 14 on the back surface.
  • the material and forming method of the back electrode 20 are not particularly limited.
  • the back electrode 20 may be formed by applying and drying a back electrode paste containing a metal such as aluminum, silver, or copper.
  • a silver paste for forming a silver electrode may be partially provided on the back surface for connection between elements in the module process.
  • the electrode is fired to complete the solar cell element.
  • the antireflection film 16 as an insulating film is melted by the glass particles contained in the electrode metal paste on the surface side, and the silicon 10 surface is also partially melted.
  • the metal particles (for example, silver particles) in the paste form a contact portion with the silicon substrate 10 and solidify. Thereby, the formed surface electrode 18 and the silicon substrate 10 are electrically connected. This is called fire-through.
  • FIG. 2A is a plan view of a solar cell element in which the surface electrode 18 includes a bus bar electrode 30 and a finger electrode 32 intersecting with the bus bar electrode 30 as viewed from the surface.
  • FIG. 2B is an enlarged perspective view illustrating a part of FIG.
  • Such a surface electrode 18 can be formed, for example, by means such as screen printing of the above-described metal paste, plating of the electrode material, or vapor deposition of the electrode material by electron beam heating in a high vacuum.
  • the surface electrode 18 composed of the bus bar electrode 30 and the finger electrode 32 is generally used as an electrode on the light receiving surface side and is well known, and it is possible to apply known forming means for the bus bar electrode and finger electrode on the light receiving surface side. it can.
  • tens of minutes of treatment is performed at 800 ° C. to 900 ° C. in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen to uniformly form an n-type diffusion layer.
  • a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen to uniformly form an n-type diffusion layer.
  • the diffusion of phosphorus extends to the side surface and the back surface, and the n-type diffusion layer is formed not only on the surface but also on the side surface and the back surface. Therefore, side etching is performed to remove the n-type diffusion layer on the side surface.
  • the p-type diffusion layer forming composition is applied onto the n-type diffusion layer on the back surface of the p-type semiconductor substrate, that is, the surface that is not the light receiving surface.
  • the coating method is not limited, and examples thereof include a printing method, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
  • the coating amount of the p-type diffusion layer forming composition is not particularly limited.
  • the coating amount of the glass powder can be 10 g / m 2 to 250 g / m 2, and 20 g / m 2 to 150 g / m 2. 2 is preferable.
  • a drying step for volatilizing the solvent contained in the composition may be necessary after coating.
  • drying is performed at a temperature of about 80 ° C. to 300 ° C. for about 1 to 10 minutes when using a hot plate, and about 10 to 30 minutes when using a dryer or the like.
  • the drying conditions depend on the solvent composition of the n-type diffusion layer forming composition, and are not particularly limited to the above conditions in the present invention.
  • the semiconductor substrate coated with the p-type diffusion layer forming composition is heat-treated at 600 ° C. to 1200 ° C. By this heat treatment, the acceptor element diffuses into the semiconductor substrate, and a p + -type diffusion layer is formed.
  • a known continuous furnace, batch furnace, or the like can be applied to the heat treatment. Further, the furnace atmosphere during the thermal diffusion treatment can be appropriately adjusted to air, oxygen, nitrogen or the like.
  • the thermal diffusion treatment time can be appropriately selected according to the content of the acceptor element contained in the p-type diffusion layer forming composition. For example, it can be 1 minute to 60 minutes, and more preferably 2 minutes to 30 minutes.
  • the glass is removed by etching.
  • etching a known method such as a method of immersing in an acid such as hydrofluoric acid or a method of immersing in an alkali such as caustic soda can be applied.
  • an aluminum paste is printed on the back surface, and this is baked to change the n-type diffusion layer into a p + -type diffusion layer, and at the same time, an ohmic contact is obtained.
  • the electrical conductivity of the aluminum layer formed from the aluminum paste is low, and in order to reduce the sheet resistance, the aluminum layer generally formed on the entire back surface must have a thickness of about 10 ⁇ m to 20 ⁇ m after firing.
  • the thermal expansion coefficient differs greatly between silicon and aluminum, so that a large internal stress is generated in the silicon substrate during the firing and cooling process, causing warpage. This internal stress has a problem that the crystal grain boundary is damaged and the power loss increases.
  • the warp easily damages the element in the transportation of the solar cell element in the module process and the connection with a copper wire called a tab wire.
  • the thickness of the silicon substrate has been reduced due to the improvement of the slice processing technique, and the elements tend to be easily broken.
  • the material used for the back electrode is not limited to aluminum.
  • Ag (silver) or Cu (copper) can be applied, and the thickness of the back electrode can be made thinner than the conventional one. Further, it is not necessary to form the entire surface. Therefore, it is possible to reduce internal stress and warpage in the silicon substrate that occur during the firing and cooling processes.
  • an antireflection film is formed on the n-type diffusion layer formed above. This step is the same as that described with reference to FIG. 1 (4) in the formation of the n-type diffusion layer.
  • the surface electrode is formed by applying a surface electrode metal paste on the surface (light receiving surface) of the antireflection film by screen printing and drying. This step is the same as that described with reference to FIG. 1 (5) in the formation of the n-type diffusion layer.
  • a back electrode is also formed on the p + -type diffusion layer on the back surface.
  • the back electrode formation process is also the same as that described for the n-type diffusion layer.
  • the above electrode is fired to complete the solar cell element. This process is the same as that described with reference to FIG. 1 (6) in the formation of the n-type diffusion layer.
  • a mixed gas of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen is used to form an n-type diffusion layer on a silicon substrate which is a p-type semiconductor substrate.
  • the n-type diffusion layer may be formed using the above-described n-type diffusion layer forming composition.
  • the n-type diffusion layer forming composition is applied to the light-receiving surface which is the surface of the p-type semiconductor substrate, and the back surface of the p-type semiconductor substrate according to the present invention is applied.
  • the mold diffusion layer forming composition is applied and subjected to thermal diffusion treatment at 600 ° C. to 1200 ° C.
  • the donor element diffuses into the p-type semiconductor substrate on the front surface to form an n-type diffusion layer
  • the acceptor element diffuses on the back surface to form a p + -type diffusion layer.
  • a solar cell element is produced by the same steps as those described above.
  • the solar cell element in which the n-type diffusion layer is formed on the front surface, the p + -type diffusion layer is formed on the back surface, and the front surface electrode and the back surface electrode are provided on the respective layers has been described. If the diffusion layer forming composition and the p-type diffusion layer forming composition are used, a back contact type solar cell element can also be produced.
  • the back contact type solar cell element has all electrodes provided on the back surface to increase the area of the light receiving surface. That is, in the back contact type solar cell element, it is necessary to form both the n-type diffusion region and the p + -type diffusion region on the back surface to form a pn junction structure.
  • the n-type diffusion layer forming composition and the p-type diffusion layer forming composition of the present invention can form an n-type diffusion site and a p-type diffusion site only at a specific site, and thus a back contact solar cell. It can be suitably applied to the manufacture of elements.
  • Example 1A 20 g of P 2 O 5 —SiO 2 glass (P 2 O 5 content: 10%) powder, 0.3 g of ethyl cellulose (weight average molecular weight 140000) as a binder, and 7 g of 2- (2-butoxyethoxy) ethyl acetate Then, using an automatic mortar kneading apparatus, the mixture was made into a paste to prepare an n-type diffusion layer forming composition 1. When the pH of the obtained n-type diffusion layer forming composition was measured at 25 ° C. using a pH measuring device, the pH (25 ° C.) was 5.6.
  • Example 2A In Example 1A, an n-type diffusion layer forming composition 2 was prepared in the same manner as in Example 1A, except that the binder was changed to ethyl cellulose having a weight average molecular weight of 300,000. The pH (25 ° C.) was 5.6.
  • Example 3A In Example 1A, except that the glass powder was replaced with P 2 O 5 —ZnO-based glass powder (P 2 O 5 content: 10%), an n-type diffusion layer forming composition 3 was prepared in the same manner as in Example 1A. Prepared. The pH (25 ° C.) was 5.6.
  • Example 4A In Example 1A, an n-type diffusion layer forming composition 4 was prepared in the same manner as in Example 1A, except that the binder was changed to polyvinyl alcohol (weight average molecular weight 250,000). The pH (25 ° C.) was 5.6.
  • Example 5A 19.7 g of P 2 O 5 —SiO 2 glass (P 2 O 5 content: 10%) powder, 0.3 g of Ag, 0.3 g of ethyl cellulose (molecular weight 140000), and 2- (2-butoxyethoxy) acetate Ethyl 7g was mixed and pasted using an automatic mortar kneader to prepare n-type diffusion layer forming composition 5.
  • the pH (25 ° C.) was 5.6.
  • Example 6A In Example 1A, an n-type diffusion layer forming composition 6 was prepared in the same manner as in Example 1A, except that the pH was adjusted to 3.8 using citric acid.
  • Example 7A In Example 1A, an n-type diffusion layer forming composition 7 was prepared in the same manner as in Example 1A, except that the pH was adjusted to 9.8 using sodium hydrogen carbonate.
  • Example 8A In Example 1A, an n-type diffusion layer forming composition 8 was prepared in the same manner as in Example 1A, except that the binder was changed to ethyl cellulose having a weight average molecular weight of 7000. The pH (25 ° C.) was 5.6.
  • Example 9A In Example 1A, an n-type diffusion layer forming composition 9 was prepared in the same manner as in Example 1A, except that the binder was changed to ethyl cellulose having a weight average molecular weight of 450,000. The pH (25 ° C.) was 5.6.
  • Example 1A an n-type diffusion layer forming composition C1 was prepared in the same manner as in Example 1A, except that the binder was changed to ethyl cellulose having a weight average molecular weight of 4500.
  • the pH (25 ° C.) was 5.6.
  • Example 1A an n-type diffusion layer forming composition C2 was prepared in the same manner as in Example 1A, except that the binder was changed to ethyl cellulose having a weight average molecular weight of 750000.
  • the pH (25 ° C.) was 5.6.
  • Viscosity change rate was less than 0.05, and neither gelation nor aggregation of glass particles was observed.
  • B Viscosity change rate was 0.05 or more and less than 0.10, and neither gelation nor aggregation of glass particles was observed.
  • C Viscosity change rate was 0.10 or more and less than 0.15, and neither gelation nor aggregation of glass particles was observed.
  • D Viscosity change rate was less than 0.15, but glass particles were gelled or aggregated.
  • E Viscosity change rate was 0.15 or more, and glass particles were gelled or aggregated.
  • the n-type diffusion layer forming composition prepared in Example 1A to Example 9A was applied to the surface of the p-type silicon substrate by screen printing so that the application amount was 70 g / m 2 (as the glass powder application amount). And dried on a hot plate at 150 ° C. for 5 minutes. Subsequently, a thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C., and then the substrate was immersed in hydrofluoric acid for 5 minutes to remove the glass layer, washed with running water, and then dried.
  • the n-type diffusion layer forming compositions prepared in Comparative Example 1 and Comparative Example 2 had low dispersion stability and could not be screen printed.
  • the sheet resistance of the surface is 100 ⁇ / ⁇ or less, P (phosphorus) is diffused, and an n-type diffusion layer is formed. It was.
  • the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
  • Example 1B Using an automatic mortar kneading apparatus, 20 g of B 2 O 3 —SiO 2 glass (B 2 O 3 : 10%) powder, 3 g of ethyl cellulose (weight average molecular weight 140000), and 77 g of 2- (2-butoxyethoxy) ethyl acetate are used. And mixed to paste to prepare p-type diffusion layer forming composition 1. When the pH of the obtained p-type diffusion layer forming composition was measured at 25 ° C. using a pH measuring device, the pH (25 ° C.) was 5.6.
  • Example 2B In Example 1B, p-type diffusion layer forming composition 2 was prepared in the same manner as in Example 1B, except that the binder was changed to ethyl cellulose having a weight average molecular weight of 300,000. The pH (25 ° C.) was 5.6.
  • Example 3B A p-type diffusion layer forming composition 3 was prepared in the same manner as in Example 1B, except that the glass powder was replaced with a B 2 O 3 —ZnO-based (B 2 O 3 content: 60%) in Example 1B. .
  • the pH (25 ° C.) was 5.6.
  • Example 4B In Example 1B, a p-type diffusion layer forming composition 4 was prepared in the same manner as in Example 1B, except that the binder was changed to polyvinyl alcohol (molecular weight 250,000). The pH (25 ° C.) was 5.6.
  • Example 5B In Example 1B, p-type diffusion layer forming composition 5 was prepared in the same manner as in Example 1B, except that the pH was adjusted to 3.8 using citric acid.
  • Example 6B In Example 1B, p-type diffusion layer forming composition 6 was prepared in the same manner as in Example 1B, except that the pH was adjusted to 10.6 using sodium hydrogen carbonate.
  • Example 7B A p-type diffusion layer forming composition 7 was prepared in the same manner as in Example 1B, except that in Example 1B, the binder was changed to ethyl cellulose having a weight average molecular weight of 8000. The pH (25 ° C.) was 5.6.
  • Example 8B A p-type diffusion layer forming composition 8 was prepared in the same manner as in Example 1B, except that in Example 1B, the binder was replaced with ethyl cellulose having a weight average molecular weight of 450,000. The pH (25 ° C.) was 5.6.
  • Example 1B A p-type diffusion layer forming composition C1 was prepared in the same manner as in Example 1B, except that in Example 1B, the binder was replaced with ethyl cellulose having a weight average molecular weight of 4500.
  • the pH (25 ° C.) was 5.6.
  • Example 2B A p-type diffusion layer forming composition C2 was prepared in the same manner as in Example 1B, except that in Example 1B, the binder was changed to ethyl cellulose having a weight average molecular weight of 750,000. The pH (25 ° C.) was 5.6.
  • the p-type diffusion layer forming composition prepared in Example 1B to Example 8B was applied to the surface of the p-type silicon substrate by screen printing so that the application amount was 70 g / m 2, and a hot plate at 150 ° C. Dry for 5 minutes above. Subsequently, a thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C., and then the substrate was immersed in hydrofluoric acid for 5 minutes to remove the glass layer, washed with running water, and then dried.
  • the surface sheet resistance is 100 ⁇ / ⁇ or less, and B (boron) is diffused to form a p-type diffusion layer. It was.
  • the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more and could not be measured, and no p-type diffusion layer was formed. Further, the substrate was not warped.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Sustainable Development (AREA)
  • Photovoltaic Devices (AREA)
  • Glass Compositions (AREA)

Abstract

Composition permettant de former une couche de diffusion d'impuretés, laquelle composition comprend une poudre de verre contenant elle-même soit un élément donneur, soit un élément accepteur, un liant ayant une masse moléculaire moyenne de 5 000-500 000, et un solvant. Lorsque la composition sert à former une couche de diffusion de type n, la poudre de verre contient un élément donneur. Lorsque la composition sert à former une couche de diffusion de type p, la couche de verre contient un élément accepteur. Lorsque la composition est appliquée en vue de la formation d'une couche de diffusion d'impuretés et est soumise à un traitement de diffusion thermique, une couche de diffusion de type n ou une couche de diffusion de type p sont formées. De cette manière sont produits des éléments de cellule photovoltaïque à couche de diffusion de type n ou à couche de diffusion de type p.
PCT/JP2011/065386 2010-07-07 2011-07-05 Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque WO2012005253A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2011800271169A CN102934205A (zh) 2010-07-07 2011-07-05 杂质扩散层形成组合物、杂质扩散层的制造方法、以及太阳能电池元件的制造方法
KR1020127031636A KR20130086146A (ko) 2010-07-07 2011-07-05 불순물 확산층 형성 조성물, 불순물 확산층의 제조 방법, 및 태양 전지 소자의 제조 방법

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010155173A JP5691268B2 (ja) 2010-07-07 2010-07-07 ｐ型拡散層形成組成物、ｐ型拡散層の製造方法、及び太陽電池セルの製造方法
JP2010155174A JP5691269B2 (ja) 2010-07-07 2010-07-07 ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法
JP2010-155173 2010-07-07
JP2010-155174 2010-07-07

Publications (1)

Publication Number Publication Date
WO2012005253A1 true WO2012005253A1 (fr) 2012-01-12

Family

ID=45441231

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/065386 WO2012005253A1 (fr) 2010-07-07 2011-07-05 Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque

Country Status (4)

Country Link
KR (1) KR20130086146A (fr)
CN (1) CN102934205A (fr)
TW (1) TW201212107A (fr)
WO (1) WO2012005253A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105602A1 (fr) * 2012-01-10 2013-07-18 日立化成株式会社 COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, ENSEMBLE DE COMPOSITIONS DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION DESTINÉ À UN SUBSTRAT SEMI-CONDUCTEUR DOTÉ D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION DESTINÉ À UN ÉLÉMENT DE CELLULE SOLAIRE
WO2013129002A1 (fr) * 2012-02-29 2013-09-06 日立化成株式会社 COMPOSITION POUR LA FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n, ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE
JP2016027661A (ja) * 2012-02-23 2016-02-18 日立化成株式会社 不純物拡散層形成組成物、不純物拡散層付き半導体基板の製造方法及び太陽電池素子の製造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104392899A (zh) * 2014-10-08 2015-03-04 程德明 整流单晶硅片免喷砂扩散镀镍工艺
JP6195597B2 (ja) * 2015-09-29 2017-09-13 東洋アルミニウム株式会社 ペースト組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02162720A (ja) * 1988-12-15 1990-06-22 Sharp Corp 半導体装置の製造方法
JPH04158514A (ja) * 1990-10-22 1992-06-01 Sumitomo Chem Co Ltd 半導体基板への不純物拡散方法
JPH04174517A (ja) * 1990-11-07 1992-06-22 Canon Inc ダイヤモンド半導体の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5026008B2 (ja) * 2006-07-14 2012-09-12 東京応化工業株式会社 膜形成組成物
US20090092745A1 (en) * 2007-10-05 2009-04-09 Luca Pavani Dopant material for manufacturing solar cells
JP5522900B2 (ja) * 2008-02-22 2014-06-18 東京応化工業株式会社 電極形成用導電性組成物及び太陽電池の形成方法
US8053867B2 (en) * 2008-08-20 2011-11-08 Honeywell International Inc. Phosphorous-comprising dopants and methods for forming phosphorous-doped regions in semiconductor substrates using phosphorous-comprising dopants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02162720A (ja) * 1988-12-15 1990-06-22 Sharp Corp 半導体装置の製造方法
JPH04158514A (ja) * 1990-10-22 1992-06-01 Sumitomo Chem Co Ltd 半導体基板への不純物拡散方法
JPH04174517A (ja) * 1990-11-07 1992-06-22 Canon Inc ダイヤモンド半導体の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105602A1 (fr) * 2012-01-10 2013-07-18 日立化成株式会社 COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, ENSEMBLE DE COMPOSITIONS DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION DESTINÉ À UN SUBSTRAT SEMI-CONDUCTEUR DOTÉ D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION DESTINÉ À UN ÉLÉMENT DE CELLULE SOLAIRE
JP2016027661A (ja) * 2012-02-23 2016-02-18 日立化成株式会社 不純物拡散層形成組成物、不純物拡散層付き半導体基板の製造方法及び太陽電池素子の製造方法
WO2013129002A1 (fr) * 2012-02-29 2013-09-06 日立化成株式会社 COMPOSITION POUR LA FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n, ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE
JP5610100B2 (ja) * 2012-02-29 2014-10-22 日立化成株式会社 ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法

Also Published As

Publication number Publication date
TW201212107A (en) 2012-03-16
CN102934205A (zh) 2013-02-13
KR20130086146A (ko) 2013-07-31

Similar Documents

Publication Publication Date Title
JP4868079B1 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法
JP5573945B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
JP5447397B2 (ja) ｐ型拡散層形成組成物、ｐ型拡散層の製造方法、及び太陽電池セルの製造方法
JP5958485B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
WO2011162394A1 (fr) COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION D'IMPURETÉS, COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE FABRICATION DE COUCHE DE DIFFUSION DE TYPE n, COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE p, PROCÉDÉ DE FABRICATION DE COUCHE DE DIFFUSION DE TYPE p, ET PROCÉDÉ DE FABRICATION D'ÉLÉMENTS DE CELLULE SOLAIRE
WO2012005253A1 (fr) Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque
JP5176159B1 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
JP5541358B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
WO2013005738A1 (fr) COMPOSITION POUR LA FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ POUR LA PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION D'ÉLÉMENTS DE CELLULE SOLAIRE
JP2013026578A (ja) ｎ型拡散層の製造方法及び太陽電池素子の製造方法
JP5625537B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法
JP5842431B2 (ja) ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
JP5703673B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法
JP5834578B2 (ja) ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
JP5691269B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法
JP5626340B2 (ja) ｐ型拡散層形成組成物、ｐ型拡散層の製造方法、及び太陽電池素子の製造方法
JP5333564B2 (ja) 太陽電池セルの製造方法
JP5691268B2 (ja) ｐ型拡散層形成組成物、ｐ型拡散層の製造方法、及び太陽電池セルの製造方法
WO2011132782A1 (fr) COMPOSITION FORMANT UNE COUCHE DE DIFFUSION DE TYPE p, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE p ET PROCÉDÉ DE PRODUCTION D'UN ÉLÉMENT DE CELLULE SOLAIRE
JP2016006893A (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
JP2016021589A (ja) ｐ型拡散層形成組成物、ｐ型拡散層の製造方法、及び太陽電池素子の製造方法
JP2012231013A (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
JP2012231012A (ja) ｐ型拡散層形成組成物、ｐ型拡散層の製造方法、及び太陽電池素子の製造方法
JP2013026477A (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180027116.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11803587

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20127031636

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11803587

Country of ref document: EP

Kind code of ref document: A1