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WO2011132781A1 - COMPOSITION FORMANT UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION D'UN ÉLÉMENT DE CELLULE SOLAIRE - Google Patents

COMPOSITION FORMANT UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION D'UN ÉLÉMENT DE CELLULE SOLAIRE Download PDF

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Publication number
WO2011132781A1
WO2011132781A1 PCT/JP2011/059973 JP2011059973W WO2011132781A1 WO 2011132781 A1 WO2011132781 A1 WO 2011132781A1 JP 2011059973 W JP2011059973 W JP 2011059973W WO 2011132781 A1 WO2011132781 A1 WO 2011132781A1
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Prior art keywords
diffusion layer
type diffusion
forming composition
layer forming
glass powder
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Ceased
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PCT/JP2011/059973
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English (en)
Japanese (ja)
Inventor
野尻　剛
吉田　誠人
香 岡庭
洋一 町井
岩室　光則
修一郎 足立
鉄也 佐藤
木沢　桂子
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to JP2012511723A priority Critical patent/JP5541358B2/ja
Priority to CN201180018428.3A priority patent/CN102834898B/zh
Priority to KR1020127030146A priority patent/KR20130066613A/ko
Publication of WO2011132781A1 publication Critical patent/WO2011132781A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions 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
    • C03C8/02—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
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • 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 n-type diffusion layer forming composition for a solar cell element, a method for producing an n-type diffusion layer, and a method for producing a solar cell element, and more specifically, a specific portion of a silicon substrate that is a semiconductor substrate.
  • the present invention relates to a technique that makes it possible to form an n-type diffusion layer.
  • 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 to 900 ° C.
  • the n-type diffusion layer is uniformly formed by performing several tens of minutes.
  • n-type diffusion layers are formed not only on the surface but also on the side surface and the back surface. Therefore, a side etching process for removing the side n-type diffusion layer is necessary.
  • the n-type diffusion layer on the back surface needs to be converted into a p + -type diffusion layer.
  • An aluminum paste is applied on the n-type diffusion layer on the back surface, and the p + -type diffusion is performed from the n-type diffusion layer by the diffusion of aluminum. Was converted into a layer.
  • phosphorus such as phosphorus pentoxide (P 2 O 5 ) or ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) is used.
  • a method for forming an n-type diffusion layer by applying a solution containing an acid salt has been proposed.
  • this method uses a solution, as in the gas phase reaction method using the above mixed gas, the diffusion of phosphorus extends to the side surface and back surface, and n-type diffusion layers are formed not only on the surface but also on the side surface and back surface. Is done.
  • n-type diffusion layer in the gas phase reaction using phosphorus oxychloride, not only one surface (usually the light receiving surface, the surface) that originally requires the n-type diffusion layer but also the other surface ( An n-type diffusion layer is also formed on the non-light-receiving surface, 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 in a manufacturing process of a solar cell element using a silicon substrate, a specific part can be more efficiently performed without forming an unnecessary n-type diffusion layer. It is an object to provide an n-type diffusion layer forming composition capable of forming an n-type diffusion layer, a method for producing an n-type diffusion layer, and a method for producing a solar cell element.
  • n-type diffusion layer forming composition comprising a glass powder containing a donor element and having a softening temperature of 300 ° C. to 950 ° C., and a dispersion medium.
  • 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.
  • n-type diffusion layer forming composition At least one glass component material selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , CeO 2 and MoO 3 ⁇ 1 > Or ⁇ 2> The n-type diffusion layer forming composition. ⁇ 4> The n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 3>, wherein the crystallization temperature of the glass powder is 1050 ° C. or higher.
  • ⁇ 5> A method for producing an n-type diffusion layer, comprising a step of applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 4> and a step of performing a thermal diffusion treatment.
  • ⁇ 6> A step of applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 4> 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 the process to form and the process of forming an electrode on the formed said n type diffused layer.
  • n-type diffusion layer 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.
  • 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 n-type diffusion layer forming composition of the present invention will be described, and then the n-type diffusion layer and solar cell element manufacturing method using the n-type diffusion layer forming composition 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 numerical values described before and after that as a minimum value and a 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 comprises a glass powder containing at least a donor element and a softening temperature of 300 ° C. to 950 ° C. (hereinafter sometimes simply referred to as “glass powder”), a dispersion medium And may further contain other additives as required in consideration of applicability and the like.
  • the n-type diffusion layer forming composition contains a donor element.
  • the n-type diffusion layer is formed by thermally diffusing the donor element by thermal diffusion treatment (firing). A material that can be formed.
  • an n-type diffusion layer is formed only at a desired site to which the n-type diffusion layer forming composition is applied, and the n-type diffusion layer forming composition is applied. Unnecessary n-type diffusion layers are not formed on the back and side surfaces.
  • 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 required, 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.
  • 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.
  • production of the internal stress in the silicon substrate resulting from the thickness of a back surface electrode is suppressed, and the curvature of a 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 also in the conventional gas phase reaction method and the method of applying a phosphate-containing solution. Therefore, the glass layer produced
  • the donor component in the glass powder is difficult to volatilize even during firing, it is suppressed that the n-type diffusion layer is formed not only on the surface but also on the back surface and side surfaces due to the generation of the volatilizing gas. 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), and As (arsenic). 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 , CeO 2, 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 the like, SiO 2, K 2 O, Na 2 O, It is preferable to use at least one selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , CeO 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
  • a system containing P 2 O 5 as a donor element-containing substance such as a P 2 O 5 —CeO 2 system, a P 2 O 5 —SnO system, a P 2 O 5 —Ge
  • 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 has been exemplified, but glass powder containing three or more components such as P 2 O 5 —SiO 2 —CeO 2 or 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 appropriately in consideration of the melting temperature, softening temperature, glass transition temperature, crystallization temperature, chemical durability, and generally 0.1% by mass or more. It is preferably 95% by mass or less, and more preferably 0.5% by mass or more and 90% by mass or less.
  • the content ratio of CeO 2 is preferably 1% by mass or more and 50% by mass or less, and more preferably 3% by mass or more and 40% by mass or less. It is more preferable. With such a content ratio, the n-type diffusion layer can be formed more uniformly.
  • the softening temperature of the glass powder is important from the viewpoint of obtaining a more uniform n-type diffusion layer by more effectively diffusing the donor element into the silicon substrate during the thermal diffusion treatment described later.
  • the softening temperature is 300 ° C. to 950 ° C., preferably 350 ° C. to 900 ° C., more preferably 370 ° C. to 850 ° C., and further preferably 390 ° C. to 800 ° C.
  • the softening temperature of the glass powder is less than 300 ° C., the glass component tends to crystallize during the thermal diffusion treatment at a high temperature, and the etching removability tends to decrease in the etching removal step of the glass component after the thermal diffusion treatment.
  • the donor element since the melting point is lowered, the donor element is likely to volatilize and the n-type diffusion layer tends to be easily formed in an unnecessary portion during the thermal diffusion treatment.
  • the softening temperature of glass powder exceeds 950 degreeC, it becomes difficult to soften glass at the time of a thermal-diffusion process, and the glass powder remains with the granular shape. Therefore, the diffusion of the donor element proceeds without the glass component being microscopically uniformly covered on the silicon substrate, and as a result, the formability of the n-type diffusion layer tends to be non-uniform, and the sheet resistance value May rise.
  • the softening temperature of the glass powder can be easily measured from its endothermic peak using a known differential thermal analyzer (DTA).
  • the crystallization temperature of glass powder is 1050 degreeC or more, It is more preferable that it is 1100 degreeC or more, It is further more preferable that it is 1200 degreeC or more.
  • the crystallization temperature is 1050 ° C. or higher, crystallization of the glass component during the thermal diffusion treatment is suppressed. Thereby, the residual of the crystallized substance in the glass component etching removal step after the thermal diffusion treatment is suppressed, and the etching removability of the glass component is improved.
  • the crystallization temperature of glass powder can be easily measured from the exothermic peak with a well-known differential thermal analyzer (DTA).
  • DTA differential thermal analyzer
  • 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. 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 graphite plate, a platinum plate, a platinum-rhodium alloy plate, a zirconia plate 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 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.
  • 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, more preferably 1% by mass or more and 90% by mass or less, The content is more preferably 1.5% by mass or more and 85% by mass or less, and particularly preferably 2% by mass or more and 80% by mass or less.
  • the dispersion medium is a medium in which the glass powder is dispersed in the composition. Specifically, a binder, a solvent, or the like is employed as the dispersion medium.
  • 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, copolymers thereof, Additional be appropriately selected siloxane resin. These are used singly or in combination of two or more.
  • the molecular weight of the binder is not particularly limited, and it is desirable to adjust appropriately in view of the desired viscosity as the composition.
  • 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 preferred from the viewpoint of applicability to the substrate.
  • the content ratio of the dispersion medium in the n-type diffusion layer forming composition is determined in consideration of applicability and donor concentration.
  • the viscosity of the n-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.
  • 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 glass powder amount can be 0.01 g / m 2 to 100 g / m 2, and preferably 0.1 g / m 2 to 10 g / m 2 .
  • a drying step for volatilizing the solvent contained in the composition may be provided 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. Therefore, any conventionally known method can be adopted, and the options of the manufacturing method are expanded. Therefore, for example, the composition layer 13 can be formed by applying a composition containing a Group 13 element such as B (boron), and the high concentration electric field layer 14 can be formed.
  • composition 13 containing a Group 13 element such as B (boron) for example, a glass powder containing an acceptor element is used instead of a glass powder containing a donor element, and the same as the composition for forming an n-type diffusion layer.
  • a p-type diffusion layer forming composition constituted as described above can be given.
  • the acceptor element may be an element belonging to Group 13, and examples thereof include B (boron), Al (aluminum), and Ga (gallium).
  • the glass powder containing acceptor element preferably comprises at least one selected from B 2 O 3, Al 2 O 3 and Ga 2 O 3.
  • the method for applying the p-type diffusion layer forming composition to the back surface of the silicon substrate is the same as the method for applying the n-type diffusion layer forming composition described above on the silicon substrate.
  • 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 as necessary.
  • the thermal diffusion treatment time can be appropriately selected according to the donor element content contained in the n-type diffusion layer forming composition, the softening temperature of the glass powder, and the like. For example, it can be 1 minute to 60 minutes, and 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 glass layer 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.
  • the n-type diffusion layer 12 is formed using the n-type diffusion layer forming composition layer 11 of the present invention.
  • the n-type diffusion layer 12 is formed only at the site, and an unnecessary n-type diffusion layer is not formed on the back surface or the side surface. 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.
  • conversion to the p-type diffusion layer is sufficient, and in order to form a high-concentration electric field layer of the p + -type diffusion layer, a certain amount of aluminum is required. There was a need to form.
  • the manufacturing method of the present invention 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 solar cell 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 forming composition configured in the same manner as the n-type diffusion layer forming composition is formed on the back surface (n).
  • the p + -type diffusion layer (high-concentration electric field layer) 14 is preferably formed on the back surface by applying to the surface opposite to the surface on which the mold diffusion layer forming composition is applied and baking.
  • 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.
  • 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 0.1 Torr to 2 Torr
  • the temperature during film formation is 300 ° C. to 550 ° C.
  • 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 solar cell 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 a perspective view showing 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.
  • 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 further provided on the respective layers has been described.
  • a layer formation composition it is also possible to produce a back contact type solar cell element.
  • 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 of the present invention can form an n-type diffusion site only at a specific site, and therefore can be suitably applied to the production of a back contact type solar cell element.
  • Example 1 P 2 O 5 —CeO 2 -based glass (P 2 O 5 : 39.6%, CeO 2 : 10%, BaO: 10.4%, MoO 3 having a substantially spherical particle shape and an average particle diameter of 3.5 ⁇ m) : 10%, ZnO: 30%) 20 g of powder, 0.3 g of ethyl cellulose and 7 g of 2- (2-butoxyethoxy) ethyl acetate were mixed using an automatic mortar kneader to form a paste, forming an n-type diffusion layer A composition was prepared.
  • the above P 2 O 5 -CeO 2 glass powder was subjected to thermal analysis with a thermal analyzer manufactured by Shimadzu Corporation (TG-DTA, DTG60H type, measurement conditions: heating rate 20 ° C./min, air flow rate 100 ml / min).
  • a thermal analyzer manufactured by Shimadzu Corporation (TG-DTA, DTG60H type, measurement conditions: heating rate 20 ° C./min, air flow rate 100 ml / min).
  • the softening temperature was 520 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the glass particle shape was determined by observation using a TM-1000 scanning electron microscope manufactured by Hitachi High-Technologies Corporation.
  • the average particle size of the glass was calculated using a LS 13 320 type laser scattering diffraction particle size distribution analyzer (measurement wavelength: 632 nm) manufactured by Beckman Coulter, Inc.
  • the prepared paste (n-type diffusion layer forming composition) was applied to the surface of the p-type silicon substrate by screen printing and dried on a hot plate at 150 ° C. for 5 minutes. Subsequently, thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C., and then the substrate was immersed in 10% hydrofluoric acid for 5 minutes to remove the glass layer, and washed with running water. Thereafter, drying was performed.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 45 ⁇ / ⁇ , P (phosphorus) diffused, and an n-type diffusion layer was formed.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the evaluation results are shown in Table 1.
  • the sheet resistance was measured by a four-probe method using a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation.
  • Example 2 An n-type diffusion layer was formed in the same manner as in Example 1 except that the thermal diffusion treatment time was 15 minutes.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 30 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • Example 3 An n-type diffusion layer was formed in the same manner as in Example 1 except that the thermal diffusion treatment time was 30 minutes.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 17 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • Example 4 A glass powder having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m P 2 O 5 —ZnO-based glass (P 2 O 5 : 40%, ZnO: 40%, CeO 2 : 10%, MgO: 5) %, CaO: 5%).
  • An n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 480 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 41 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder is made of P 2 O 5 —SiO 2 glass (P 2 O 5 : 30%, SiO 2 : 50%, CeO 2 : 10%, ZnO) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. : 10%), an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 610 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 48 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • Example 6 An n-type diffusion layer was formed in the same manner as in Example 5 except that the thermal diffusion treatment time was 30 minutes.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 30 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • Example 7 Except that the glass powder was made into P 2 O 5 —PbO glass (P 2 O 5 : 30%, PbO: 50%, ZnO: 20%) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. Then, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 330 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 15 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer. On the other hand, it was judged that the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured and was not substantially formed.
  • the glass powder is a P 2 O 5 —SiO 2 glass (P 2 O 5 : 40%, SiO 2 : 10%, PbO: 30%, ZnO: having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m). 10%, CaO: 10%)
  • An n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 360 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 21 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder is made of P 2 O 5 —SiO 2 glass (P 2 O 5 : 40%, SiO 2 : 10%, PbO: 20%, ZnO: having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m).
  • An n-type diffusion layer forming composition was prepared in the same manner as in Example 1 except that 20% and NaO: 10%), and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 385 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 25 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder is made of P 2 O 5 —ZnO-based glass (P 2 O 5 : 30%, ZnO: 40%, CaO: 20%, Al 2 O 3) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. : 10%), an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 450 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 36 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder is a P 2 O 5 —SiO 2 glass (P 2 O 5 : 50%, SiO 2 : 10%, ZnO: 30%, CaO: having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m). 10), except that the thermal diffusion treatment time was 20 minutes, an n-type diffusion layer forming composition was prepared as Example 1, and an n-type diffusion layer was similarly formed using this composition.
  • the softening temperature of the glass powder was 610 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 40 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder was P 2 O 5 —SiO 2 glass (P 2 O 5 : 27%, SiO 2 : 58%, CaO: 15%) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. Except for the above, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 830 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 69 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder was P 2 O 5 —SiO 2 glass (P 2 O 5 : 30%, SiO 2 60%, CaO 10%) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. Except for the above, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 875 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 71 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer. On the other hand, the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the glass powder is made of P 2 O 5 —SiO 2 glass (P 2 O 5 : 25%, SiO 2 : 65%, CaO: 5%, Al 2) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. Except that O 3 : 5%), an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder was 930 ° C.
  • the crystallization temperature exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 83 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition including the back surface was not applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 14 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 50 ⁇ / ⁇ , and an n-type diffusion layer was also formed on the back surface.
  • a solution was prepared by mixing 1 g of ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) powder, 7 g of pure water, 0.7 g of polyvinyl alcohol, and 1.5 g of isopropyl alcohol.
  • the prepared solution was applied to the surface of the p-type silicon substrate by a spin coater (2000 rpm, 30 sec) and dried on a hot plate at 150 ° C. for 5 minutes.
  • 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 dried.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 10 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 100 ⁇ / ⁇ , and an n-type diffusion layer was also formed on the back surface.
  • the glass powder was P 2 O 5 —SiO 2 glass (P 2 O 5 : 10%, SiO 2 : 20%, NaO: 70%) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. Except for the above, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition. The softening temperature of the glass powder was 230 ° C. The sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 61 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer. However, the sheet resistance of the part where the n-type diffusion layer forming composition including the back surface is not applied is 65 ⁇ / ⁇ , and the n-type diffusion layer is formed even in an unnecessary part, An n-type diffusion layer could not be formed.
  • the glass powder was P 2 O 5 —SiO 2 glass (P 2 O 5 : 5%, SiO 2 : 93%, NaO: 2%) having a substantially spherical particle shape and an average particle diameter of 3.2 ⁇ m. Except for the above, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
  • the softening temperature of the glass powder exceeded the measurement range of the thermal analyzer and was 1100 ° C. or higher.
  • the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was too large to be measured, and it was determined that the n-type diffusion layer was not substantially formed.
  • the n-type diffusion layer forming composition of the present invention can be uniformly formed only at a specific site.

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Abstract

L'invention concerne une composition formant une couche de diffusion de type N, caractérisée en ce qu'elle contient une poudre de verre contenant un élément donneur et présentant une température de ramollissement de 300 à 950°C, ainsi qu'un milieu de dispersion. En appliquant un revêtement de ladite composition formant une couche de diffusion de type N et en effectuant un traitement de diffusion thermique, une couche de diffusion de type N et un élément de cellule solaire comprenant la couche de diffusion de type N sont produits.
PCT/JP2011/059973 2010-04-23 2011-04-22 COMPOSITION FORMANT UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION D'UN ÉLÉMENT DE CELLULE SOLAIRE Ceased WO2011132781A1 (fr)

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JP2012511723A JP5541358B2 (ja) 2010-04-23 2011-04-22 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
CN201180018428.3A CN102834898B (zh) 2010-04-23 2011-04-22 n型扩散层形成组成物、n型扩散层的制造方法及太阳能电池元件的制造方法
KR1020127030146A KR20130066613A (ko) 2010-04-23 2011-04-22 ｎ 형 확산층 형성 조성물, ｎ 형 확산층의 제조 방법, 및 태양 전지 소자의 제조 방법

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WO2013005738A1 (fr) * 2011-07-05 2013-01-10 日立化成工業株式会社 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
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
US9722102B2 (en) 2014-02-26 2017-08-01 Heraeus Precious Metals North America Conshohocken Llc Glass comprising molybdenum and lead in a solar cell paste

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