WO2012111575A1 - COMPOSITION POUR FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCESSUS DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCESSUS DE PRODUCTION D'UNE CELLULE SOLAIRE - Google Patents

COMPOSITION POUR FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCESSUS DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCESSUS DE PRODUCTION D'UNE CELLULE SOLAIRE Download PDF

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WO2012111575A1
WO2012111575A1 PCT/JP2012/053182 JP2012053182W WO2012111575A1 WO 2012111575 A1 WO2012111575 A1 WO 2012111575A1 JP 2012053182 W JP2012053182 W JP 2012053182W WO 2012111575 A1 WO2012111575 A1 WO 2012111575A1
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type diffusion
diffusion layer
forming composition
ether
glass
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PCT/JP2012/053182
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English (en)
Japanese (ja)
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洋一 町井
吉田　誠人
野尻　剛
香 岡庭
岩室　光則
修一郎 足立
鉄也 佐藤
木沢　桂子
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日立化成工業株式会社
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Priority to KR1020137020896A priority Critical patent/KR20140041423A/ko
Priority to CN2012800083179A priority patent/CN103348449A/zh
Priority to JP2012557935A priority patent/JP5673694B2/ja
Publication of WO2012111575A1 publication Critical patent/WO2012111575A1/fr

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    • 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
    • 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
    • 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 n-type diffusion layer forming composition, a method for producing an n-type diffusion layer, and a method for producing a solar battery cell. More specifically, the present invention relates to an n-type diffusion in a specific portion of a silicon substrate which is a semiconductor substrate. The present invention relates to a technique capable of forming a layer.
  • a p-type silicon substrate having a textured structure is prepared so as to promote the light confinement effect and increase the efficiency.
  • a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen is used at 800 ° C. to An n-type diffusion layer is uniformly formed by performing several tens of minutes at 900 ° C.
  • 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. Therefore, after applying an aluminum paste containing aluminum as a group 13 element on the n-type diffusion layer on the back surface, heat treatment is performed, and at the same time the n-type diffusion layer is converted to the p + -type diffusion layer by the diffusion of aluminum. , Got ohmic contact.
  • an n-type diffusion layer is formed by applying a solution containing a phosphate such as phosphorus pentoxide (P 2 O 5 ) or ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ).
  • a phosphate such as phosphorus pentoxide (P 2 O 5 ) or ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ).
  • P 2 O 5 phosphorus pentoxide
  • NH 4 H 2 PO 4 ammonium dihydrogen phosphate
  • 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 battery cell using a crystalline silicon substrate, an n-type diffusion is performed in a specific portion without forming an unnecessary n-type diffusion layer.
  • An object is to provide an n-type diffusion layer forming composition capable of forming a layer, a method for producing an n-type diffusion layer forming composition, a method for producing an n-type diffusion layer, and a method for producing a solar battery cell.
  • Means for solving the problems are as follows. ⁇ 1> containing a dispersion medium and glass powder containing at least one selected from ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, SrO, and BaO and P 2 O 5 ; n-type diffusion layer forming composition.
  • n-type diffusion layer forming composition according to ⁇ 1> wherein the glass powder contains 30% by mass to 90% by mass of P 2 O 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 ⁇ 3>, and a step of performing a thermal diffusion treatment.
  • ⁇ 5> A step of applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 3> on the semiconductor substrate and a thermal diffusion treatment to form an n-type diffusion layer
  • the manufacturing method of the photovoltaic cell which has a process to do.
  • an n-type diffusion layer capable of forming an n-type diffusion layer in a specific portion without forming an unnecessary n-type diffusion layer in a manufacturing process of a solar battery cell using a crystalline silicon substrate.
  • a 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.
  • FIG. 2A It is sectional drawing which shows notionally an example of the manufacturing process of the photovoltaic cell of this invention. It is the top view which looked at the photovoltaic cell 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 an n-type diffusion layer using the n-type diffusion layer forming composition and a method for producing a solar battery cell 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 by using “to” indicates a range including the numerical values described before and after that as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • the n-type diffusion layer forming composition of the present invention contains glass powder and a dispersion medium, and may further contain other additives as required in consideration of applicability and the like.
  • the glass powder includes P 2 O 5 which is a phosphorus component as a donor element-containing material, and is selected from ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, and BaO as a glass component material. Including at least one kind.
  • the n-type diffusion layer forming composition refers to a material that contains a donor element and can form an n-type diffusion layer by thermally diffusing the donor element after being applied to a silicon substrate.
  • P phosphorus
  • the n-type diffusion layer forming composition of the present invention an n-type diffusion layer is formed only 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 required, and the process is simplified. Further, the process of converting the n-type diffusion layer into the p + -type diffusion layer on the back surface 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 diffused layer formation composition of this invention fuse
  • 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 glass powder suppresses the volatilization of the donor element even during firing. Therefore, the generation of the volatilized gas containing the donor element causes the n-type diffusion layer not only to the front but also to the back and side surfaces. Is prevented from being formed. 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, and thus it is difficult to volatilize.
  • n-type diffusion layer forming composition of the present invention as described above, P 2 O 5 is used as the donor element-containing material, and ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, At least one selected from MgO, CaO, SrO, and BaO is used.
  • ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, At least one selected from MgO, CaO, SrO, and BaO is used.
  • phosphorus oxide has a high solubility in water, it is considered that when the glass powder contained in the n-type diffusion layer forming composition absorbs moisture, phosphorus oxide reacts with water to generate phosphoric acid.
  • the phosphoric acid is evaporated by heating, and the evaporated phosphoric acid is diffused into the n-type diffusion on the back surface of the substrate.
  • an unnecessary n-type diffusion layer may be formed by adhering to a portion where the layer forming composition is not applied.
  • the water resistance of the n-type diffusion layer forming composition is improved. Therefore, it is considered that formation of an unnecessary n-type diffusion layer due to moisture absorption of the glass powder is suppressed. That is, since the n-type diffusion layer forming composition of the present invention has the above-described configuration, for example, even if the n-type diffusion layer is formed after storage in a high-temperature and high-humidity environment, the water resistance is high. Thus, the n-type diffusion layer is selectively formed.
  • ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, SrO, and BaO may be collectively referred to as “water resistance improving glass component substance”.
  • the glass powder according to the present invention includes P 2 O 5 that is a phosphorus component as a donor element-containing material, and includes at least one of the above water resistance improving glass component materials as a glass component material.
  • P (phosphorus) contained in P 2 O 5 which is a donor element-containing substance is a kind of element (donor element) that can form an n-type diffusion layer by doping into a silicon substrate.
  • donor element element
  • it is a suitable element from the viewpoints of safety, easiness of vitrification and the like.
  • the glass component substance at least one of the above water resistance-enhancing glass component substances is used. You may use 2 or more types of water resistance improvement glass component substances.
  • a glass component substance other than the water resistance-enhancing glass component substance hereinafter sometimes referred to as “other glass component substance” may be used in combination. It is possible to control water resistance, melting temperature, softening point, glass transition point, chemical durability, and the like by using the water resistance improving glass component material in combination with other glass component materials.
  • glass component materials examples include SiO 2 , K 2 O, Na 2 O, Li 2 O, BeO, PbO, CdO, SnO, MoO 3 , La 2 O 3 , Nb 2 O 5 , Ta 2 O 5. , Y 2 O 3 , GeO 2 , TeO 2, and Lu 2 O 3 .
  • SiO 2 , Y 2 O 3 , Nb 2 O 5 , and La 2 O 3 are more preferable from the viewpoint of water resistance.
  • Na 2 O, K 2 O, and Li 2 O that may cause a decrease in water resistance are 5% by mass or less of the entire glass powder from the viewpoint of water resistance. It is preferable that it is present, and it is more preferable not to include it.
  • the content ratio of P 2 O 5 is preferably 30% by mass to 90% by mass, and more preferably 35% by mass to 85% by mass.
  • the glass powder include, for example, P 2 O 5 —ZrO 2 system, P 2 O 5 —Al 2 O 3 system, P 2 O 5 —TiO 2 system, P 2 O 5 —ZnO system, and P 2 O.
  • 5 -MgO-based, P 2 O 5 -CaO-based, P 2 O 5 -BaO include P 2 O 3 -SrO based glass.
  • P 2 O 5 —Al 2 O 3 —ZnO, P 2 O 5 —CaO—SiO 2 or the like may be used as required.
  • the content ratio of the glass component substance (that is, the water resistance improving glass component substance and other glass component substances) in the glass powder is appropriately determined in consideration of water resistance, melting temperature, softening point, glass transition point, and chemical durability. It is desirable to set, and generally it is preferably 0.1% by mass or more and 95% by mass or less, and more preferably 0.5% by mass or more and 90% by mass or less. Further, the content ratio of the water resistance improving glass component substance in the glass powder is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less from the viewpoint of water resistance, and 5% by mass or more. 30 mass or less is still more preferable. Furthermore, from the viewpoint of water resistance, the content of the water resistance-enhancing glass component substance is preferably 0.05 times or more and 2 times or less, more preferably 0.1 times or more and 1 time or less of the content of the donor element-containing material.
  • the content ratio of CaO is preferably 1% by mass to 50% by mass, and preferably 5% by mass to 30% by mass. 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 glass powder preferably has a volume average particle size of 100 ⁇ m or less.
  • the particle size of the glass powder is more desirably 50 ⁇ m or less. 10 ⁇ m or less is more preferable.
  • the lower limit of the volume average particle diameter of the glass powder is not particularly limited, but in view of the dispersibility of coating and the production cost of the glass powder, 0.01 ⁇ m or more is preferable, 0.1 ⁇ m or more is more preferable, and 0.5 ⁇ m The above is more preferable.
  • the frequency distribution of the glass powder is measured, for example, by using a particle size distribution measuring device (manufactured by Beckman Coulter, Inc., model number: LS13320) as a measuring device, and measuring a dispersion in which the glass powder is dispersed in a solvent (eg, water) Is obtained.
  • a particle size distribution measuring device manufactured by Beckman Coulter, Inc., model number: LS13320
  • Examples of the shape of the glass powder 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 glass powder is produced by the following procedure. First, 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 is heated at a temperature according to the glass composition in an electric furnace to obtain a melt. At this time, it is desirable to stir the melt uniformly. Subsequently, the melt that has become uniform 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 in the n-type diffusion layer forming composition is determined in consideration of coating properties, 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, More preferably, it is 5 mass% or more and 80 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 dimethylaminoethyl (meth) acrylate polymer, polyvinyl alcohol, polyacrylamides, polyvinylamides, polyvinylpyrrolidone, poly (meth) acrylic acids, polyethylene oxides, polysulfonic acid, acrylamide alkyl sulfonic acid, and cellulose ether.
  • Cellulose derivatives carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch and starch derivatives, sodium alginate, xanthan, gua and gua derivatives, scleroglucan and scleroglucan derivatives, tragacanth and tragacanth derivatives, dextrin and dextrin derivatives, Acrylic resin, acrylic ester resin, butadiene resin, styrene resin and their Coalescence, and can appropriately select such as silicon dioxide. 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,
  • Aprotic polar solvent methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methyl
  • the content ratio of the dispersion medium in the n-type diffusion layer forming composition is determined in consideration of applicability and donor concentration (P (phosphorus) concentration).
  • 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.
  • FIG. 1 is a schematic cross-sectional view conceptually showing an example of a manufacturing process of a solar battery cell according to the present invention.
  • common constituent elements are denoted by the same reference numerals.
  • an alkaline solution is applied to crystalline silicon as the p-type semiconductor substrate 10 to remove the damaged layer, and 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 (front 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, but can be, for example, 10 g / m 2 to 250 g / m 2, and preferably 20 g / m 2 to 150 g / m 2. .
  • 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 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 high-concentration electric field layer 14 can be formed by applying the composition 13 containing a Group 13 element such as B (boron).
  • 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 to 1200 ° C.
  • 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 to 60 minutes, and more preferably 2 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, an increase in power loss and cell damage can be suppressed.
  • 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.
  • 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 pressure in the reaction chamber is 0.1 to 2 Torr (13.3 to 266.6 Pa)
  • the temperature during film formation Is formed under the conditions of 300 to 550 ° C. and a frequency for plasma discharge of 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 cells in the module process.
  • the electrode is fired to complete the solar cell.
  • the antireflection film 16 that is an insulating film is melted by the glass particles contained in the electrode metal paste on the surface side, and the surface of the silicon 10 is also partially melted.
  • 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 in which the surface electrode 18 includes a bus bar electrode 30 and a finger electrode 32 intersecting 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.
  • the solar cell 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. If a layer forming composition is used, it is also possible to produce a back contact solar cell.
  • the back contact type solar battery cell has all electrodes provided on the back surface to increase the area of the light receiving surface. That is, in the back contact solar cell, 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 solar cell.
  • the n-type diffusion layer forming composition of the present invention can also be applied to a selective emitter that forms, for example, a high-concentration n-type diffusion layer (n ++ layer) only directly under an electrode.
  • Example 1 P 2 O 5 —CaO-based glass (P 2 O 5 : 80%, CaO: 20%) powder (volume average particle diameter 3 ⁇ m) is put in an opened container, and the environment is at a temperature of 50 ° C. and a humidity of 70%. , Left for 24 hours. Next, 10 g of this glass powder, 5 g of ethyl cellulose, and 85 g of 2- (2-butoxyethoxy) ethyl acetate were mixed into a paste to prepare an n-type diffusion layer forming composition.
  • the n-type diffusion layer forming composition was applied to the surface of the p-type silicon substrate by screen printing so that the application amount was 15 to 20 g / m 2 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 hydrofluoric acid for 5 minutes in order 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 15 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • the value of the sheet resistance on the surface is obtained by measuring 5 points ⁇ 5 points at equal intervals in a region of 156 cm ⁇ 156 cm, and showing the average (the same applies to the following examples and comparative examples).
  • Example 2 N-type in the same manner as in Example 1 except that P 2 O 5 —ZnO-based glass (P 2 O 5 : 70%, ZnO: 30%) powder (volume average particle size 3 ⁇ m) was used as the glass powder. Diffusion layer formation was performed. The sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 20 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer. The sheet resistance on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 3 Implementation was carried out except that P 2 O 5 —SiO 2 —CaO glass (P 2 O 5 : 50%, SiO 2 : 40%, CaO: 10%) powder (volume average particle diameter 1 ⁇ m) was used as the glass powder.
  • P 2 O 5 —SiO 2 —CaO glass P 2 O 5 : 50%, SiO 2 : 40%, CaO: 10%
  • an n-type diffusion layer was formed.
  • 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 4 As the glass powder, P 2 O 5 —Al 2 O 3 —ZnO-based glass (P 2 O 5 : 65%, Al 2 O 3 : 5%, ZnO: 30%) powder (volume average particle diameter 5 ⁇ m) was used. Except for the above, an n-type diffusion layer was formed in the same manner as in Example 1. 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 5 Implementation was carried out except that P 2 O 5 —ZnO—TiO 2 glass (P 2 O 5 : 60%, ZnO: 35%, TiO 2 : 5%) powder (volume average particle size 3 ⁇ m) was used as the glass powder.
  • P 2 O 5 —ZnO—TiO 2 glass P 2 O 5 : 60%, ZnO: 35%, TiO 2 : 5%
  • an n-type diffusion layer was formed.
  • 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 6 Implementation was carried out except that P 2 O 5 —ZnO—ZrO 2 glass (P 2 O 5 : 63%, ZnO: 35%, ZrO 2 : 2%) powder (volume average particle size 2 ⁇ m) was used as the glass powder.
  • P 2 O 5 —ZnO—ZrO 2 glass P 2 O 5 : 63%, ZnO: 35%, ZrO 2 : 2%) powder (volume average particle size 2 ⁇ m) was used as the glass powder.
  • an n-type diffusion layer was formed.
  • 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 7 Example 1 except that P 2 O 5 —ZnO—MgO glass (P 2 O 5 : 60%, ZnO: 30%, MgO: 10%) powder (volume average particle diameter 4 ⁇ m) was used as the glass powder.
  • P 2 O 5 —ZnO—MgO glass P 2 O 5 : 60%, ZnO: 30%, MgO: 10%
  • an n-type diffusion layer was formed.
  • 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 8 Example 1 except that P 2 O 5 —BaO—CaO-based glass (P 2 O 5 : 60%, BaO: 20%, CaO: 20%) powder (volume average particle size 3 ⁇ m) was used as the glass powder. In the same manner as described above, an n-type diffusion layer was formed. 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • Example 9 Implementation was carried out except that P 2 O 5 —SiO 2 —SrO glass (P 2 O 5 : 45%, SiO 2 : 35%, SrO: 20%) powder (volume average particle diameter 1 ⁇ m) was used as the glass powder.
  • P 2 O 5 —SiO 2 —SrO glass P 2 O 5 : 45%, SiO 2 : 35%, SrO: 20%
  • volume average particle diameter 1 ⁇ m was used as the glass powder.
  • an n-type diffusion layer was formed.
  • 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 on the back surface was not measurable above the upper limit of measurement (1000000 ⁇ / ⁇ ), and no n-type diffusion layer was formed.
  • n-type diffusion layer composition was prepared by mixing 20 g of ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) powder, 3 g of ethyl cellulose, and 7 g of 2- (2-butoxyethoxy) ethyl acetate to prepare a paste.
  • the prepared paste 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.
  • 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 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 to prepare an n-type diffusion layer composition.
  • 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.

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Abstract

L'invention concerne une composition destinée à former une couche de diffusion de type n, comportant : un milieu de dispersion; et une poudre de verre comprenant au moins un constituant choisi parmi ZrO2, Al2O3, TiO2, ZnO, MgO, CaO, SrO, BaO et P2O5.
PCT/JP2012/053182 2011-02-17 2012-02-10 COMPOSITION POUR FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCESSUS DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCESSUS DE PRODUCTION D'UNE CELLULE SOLAIRE WO2012111575A1 (fr)

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CN2012800083179A CN103348449A (zh) 2011-02-17 2012-02-10 n型扩散层形成用组合物、n型扩散层的制造方法和太阳能电池单元的制造方法
JP2012557935A JP5673694B2 (ja) 2011-02-17 2012-02-10 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

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