WO2012108290A1 - Pâte électroconductrice et élément de cellule solaire obtenu en utilisant la pâte électroconductrice - Google Patents

Pâte électroconductrice et élément de cellule solaire obtenu en utilisant la pâte électroconductrice Download PDF

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Publication number
WO2012108290A1
WO2012108290A1 PCT/JP2012/052055 JP2012052055W WO2012108290A1 WO 2012108290 A1 WO2012108290 A1 WO 2012108290A1 JP 2012052055 W JP2012052055 W JP 2012052055W WO 2012108290 A1 WO2012108290 A1 WO 2012108290A1
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WIPO (PCT)
Prior art keywords
conductive paste
glass
glass frit
solar cell
semiconductor silicon
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PCT/JP2012/052055
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English (en)
Japanese (ja)
Inventor
耕治 富永
潤 濱田
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セントラル硝子株式会社
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Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Priority to KR1020137020740A priority Critical patent/KR101455019B1/ko
Priority to CN201280005074.3A priority patent/CN103314414B/zh
Publication of WO2012108290A1 publication Critical patent/WO2012108290A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells

Definitions

  • the present invention relates to a lead-free conductive paste that can be used as an electrode formed in a semiconductor silicon solar cell.
  • the solar cell element As an electronic component using a semiconductor silicon substrate, a solar cell element as shown in FIG. 1 is known. As shown in FIG. 1, the solar cell element is formed by forming an n-type semiconductor silicon layer 2 on the light-receiving surface side of a p-type semiconductor silicon substrate 1 having a thickness of about 200 ⁇ m, and nitriding to increase the light-receiving efficiency on the light-receiving surface side surface.
  • An antireflection film 3 such as a silicon film, and a surface electrode 4 connected to the semiconductor are formed on the antireflection film 3.
  • an aluminum electrode layer 5 is uniformly formed on the back side of the p-type semiconductor silicon substrate 1.
  • the aluminum electrode layer 5 is generally formed by applying an aluminum paste material composed of an aluminum powder, glass frit, an organic vehicle containing a binder such as ethyl cellulose or acrylic resin by screen printing or the like, and having a temperature of about 600 to 900 ° C. It is formed by baking for a short time.
  • the glass frit containing the lead component described above can be used for a conductive paste such as an aluminum paste material to obtain a high BSF effect, and is an important component for lowering the melting point of the conductive paste. However, it has a great negative effect on the human body and the environment.
  • Patent Document 1 and Patent Document 2 described above have a problem that the conductive paste contains a lead component.
  • an object of the present invention is to obtain a lead-free conductive paste that can be used as an electrode formed in a semiconductor silicon solar cell.
  • the present invention relates to a conductive paste for a solar cell using a semiconductor silicon substrate, and the composition of the glass frit contained in the conductive paste is substantially free of a lead component and contains 1 to 2 SiO 2 by mass%. 20, 5 to 30 for B 2 O 3 , 0 to 10 for Al 2 O 3 , 5 to 35 for ZnO, 5 for RO (total of at least one selected from the group consisting of MgO, CaO, SrO, and BaO) 30 to 30, R 2 O (total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O) 0.1 to 6 and Bi 2 O 3 to 10 to 60
  • the conductive paste is characterized.
  • the surface resistance of the p + layer is about 20 to 30 ⁇ / ⁇ , so that the p + layer when the conductive paste of the present invention is used.
  • the surface resistance is preferably 30 ⁇ / ⁇ or less. When the surface resistance is lower, conversion efficiency is improved when used as a solar cell element.
  • the glass frit of the present invention is characterized in that the thermal expansion coefficient at 30 ° C. to 300 ° C. is (70 to 110) ⁇ 10 ⁇ 7 / ° C. and the softening point is 450 ° C. or higher and 600 ° C. or lower.
  • the above thermal expansion coefficient means a linear expansion coefficient.
  • the conductive paste of the present invention is an aluminum paste material having aluminum powder.
  • the conductive paste of the present invention is characterized in that the composition of the glass frit contains at least K 2 O as R 2 O.
  • the conductive paste of the present invention is characterized in that the composition of the glass frit contains at least BaO as RO.
  • the present invention it is possible to obtain a conductive paste containing glass frit that does not contain lead.
  • the conductive paste of the present invention as a solar cell element, a high BSF effect can be obtained. Also, good adhesion to the semiconductor silicon substrate can be obtained. Furthermore, since it does not substantially contain a lead component, there is no harmful effect on the human body and the environment.
  • the conductive paste of the present invention contains glass frit (1 to 5% by mass) in addition to an organic vehicle containing aluminum powder and a binder such as ethyl cellulose or acrylic resin, and the glass frit is substantially free of a lead component.
  • a binder such as ethyl cellulose or acrylic resin
  • R 2 O total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O
  • Bi 2 O 3 is an electrically conductive paste characterized by containing 10-60.
  • SiO 2 is a glass forming component.
  • B 2 O 3 which is another glass forming component, a stable glass can be formed, and 1 to 20% ( (The same applies to the mass% below). If it exceeds 20%, the softening point of the glass will rise, making it difficult to use as a conductive paste. More preferably, it is 5 to 17%, and further preferably 8 to 15%.
  • B 2 O 3 is a glass-forming component, facilitates glass melting, suppresses an excessive increase in the thermal expansion coefficient of glass, imparts fluidity to glass during firing, and lowers the dielectric constant of glass. And 5 to 30% in the glass. If it is less than 5, the fluidity of the glass becomes insufficient and the sinterability is impaired. On the other hand, if it exceeds 30%, the stability of the glass decreases. Further, it is more preferably in the range of 10 to 25%, still more preferably 15 to 25%.
  • Al 2 O 3 is an optional component that suppresses crystallization of glass. If it exceeds 10%, the softening point of the glass rises, making it difficult to use as a conductive paste. More preferably, it may be 0 to 5%.
  • ZnO is a component that lowers the softening point of glass and is contained in the glass in an amount of 5 to 35%. If it is less than 5%, the above-mentioned action cannot be exhibited. If it exceeds 35%, the glass becomes unstable and crystals are likely to be formed. Further, it is more preferably in the range of 8-30%, still more preferably 10-20%.
  • RO total of at least one selected from the group consisting of MgO, CaO, SrO and BaO
  • RO lowers the softening point of the glass and is contained in the glass in an amount of 5 to 30%. If it is less than 5%, the softening point of the glass is not sufficiently lowered and the sinterability is impaired. On the other hand, if it exceeds 30%, the thermal expansion coefficient of the glass may become too high.
  • the range is preferably 10 to 30%, more preferably 10 to 20%.
  • RO may be a single component or a mixture of a plurality of components, but more preferably contains BaO.
  • R 2 O (total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O) lowers the softening point of the glass and adjusts the thermal expansion coefficient to an appropriate range. It is contained in the range of 1 to 6%. If it is less than 0.1%, the softening point of the glass is not sufficiently lowered and the sinterability is impaired. On the other hand, if it exceeds 6%, the thermal expansion coefficient may be excessively increased. More preferably, it is in the range of 1 to 6%, more preferably 1 to 3%.
  • the surface resistance of the p + layer can be made lower than 30 ⁇ / ⁇ , but the R 2 O exceeds 6% by mass. If containing Te, the order by R 2 O alkali component increases sometimes exhibit deliquescence, in the present invention to 6% by mass or less the R 2 O.
  • R 2 O may be a single component or a mixture of a plurality of components.
  • the “main component” mentioned above may be such that the mass of K 2 O with respect to the total mass of R 2 O components is 50% by mass or more, and preferably 70% by mass or more.
  • Bi 2 O 3 lowers the softening point of the glass and adjusts the thermal expansion coefficient, and is contained in the range of 10 to 60%. If it is less than 10%, the softening point of the glass is not sufficiently lowered, and the sinterability is impaired. On the other hand, if it exceeds 60%, the thermal expansion coefficient is excessively increased. More preferably, it is in the range of 15 to 55%.
  • CuO, TiO 2 , In 2 O 3 , SnO 2 , TeO 2 or the like represented by a general oxide may be added.
  • substantially not containing lead hereinafter sometimes referred to as PbO
  • substantially free of PbO means an amount of PbO mixed as an impurity in the glass raw material. For example, if it is in the range of 0.3% or less in the low-melting glass, there is almost no influence on the adverse effects described above, that is, the influence on the human body and the environment, the insulation characteristics, etc., and it is not substantially affected by PbO. Become.
  • the glass frit By using the glass frit, it is possible to obtain a conductive paste having a thermal expansion coefficient of (70 to 110) ⁇ 10 ⁇ 7 / ° C. and a softening point of 450 to 600 ° C. at 30 to 300 ° C. .
  • the coefficient of thermal expansion is outside (70 to 110) ⁇ 10 ⁇ 7 / ° C., problems such as peeling and substrate warpage occur during electrode formation.
  • it is in the range of (75-100) ⁇ 10 ⁇ 7 / ° C.
  • the softening point exceeds 600 ° C., it does not flow sufficiently at the time of firing, so that problems such as poor adhesion to the semiconductor silicon substrate occur.
  • the softening point is preferably 480 ° C or higher and 580 ° C or lower.
  • the conductive paste of the present invention can be used for solar cell elements as described above. Furthermore, since the conductive paste can be baked at a low temperature, it can be used as a substrate for electronic materials such as a wiring pattern forming material using silver or aluminum or various electrodes.
  • One of the preferred embodiments of the conductive paste of the present invention is a conductive paste containing glass frit, aluminum powder, and an organic vehicle, and the viscosity of the conductive paste is preferably 200 Pa ⁇ s or less.
  • the conductive paste is applied and fired on a semiconductor silicon substrate to form an aluminum electrode layer. If the viscosity is out of the above range, the moldability and workability may be deteriorated.
  • the particle size of the glass frit contained in the conductor paste is preferably 1 to 10 ⁇ m in average particle size and 30 ⁇ m or less in maximum particle size.
  • the particle size of the glass frit was measured using a laser diffraction / scattering soot particle size / particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.). If the average particle diameter of the glass frit exceeds 10 ⁇ m and the maximum particle diameter exceeds 30 ⁇ m, the adhesion between the semiconductor silicon substrate and the aluminum electrode layer may be reduced when the aluminum electrode layer is formed on the semiconductor silicon substrate. .
  • the aluminum powder has conductivity, and in order to exhibit conductivity usable as an aluminum electrode layer, it is preferable to have 50 to 80% by mass with respect to the conductive paste.
  • the organic vehicle is composed of an organic solvent and a binder, and volatilizes when fired to form an aluminum electrode layer.
  • the viscosity of the organic solvent and the binder may be adjusted as appropriate so that the viscosity is in the above-described range and volatilizes during the baking process. %, And the binder may be contained in an amount of 1 to 10% by mass.
  • Organic solvents include, for example, N, N′-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl Ether, diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO) N- methyl-2-pyrrolidone and the like can be used.
  • DMSO dimethyl sulfoxide
  • DMSO dimethyl
  • acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like
  • acrylic acid ester, nitrocellulose, and ethylcellulose are preferable because of their good thermal decomposability.
  • the glass powder was prepared by weighing and mixing various inorganic raw materials so as to have the predetermined composition described in the examples.
  • This raw material batch was put into a platinum crucible and heated and melted in an electric heating furnace at 1000 to 1300 ° C. for 1 to 2 hours to have the compositions shown in Examples 1 to 6 in Table 1 and Comparative Examples 1 to 5 in Table 2.
  • Glass was obtained.
  • a part of the glass was poured into a mold and made into a block shape for use in measuring the thermal expansion coefficient.
  • the remaining glass was flaked with a rapid cooling twin roll molding machine and sized with a pulverizer into a powder having an average particle size of 1 to 10 ⁇ m and a maximum particle size of less than 30 ⁇ m.
  • the softening point was measured using a thermal analyzer TG-DTA (manufactured by Rigaku Corporation).
  • the thermal expansion coefficient was determined from the amount of elongation at 30 to 300 ° C. when the temperature was raised at 5 ° C./min using a thermal dilatometer.
  • a p-type semiconductor silicon substrate 1 was prepared, and the conductive paste prepared above was screen-printed thereon. These test pieces were dried in an oven at 140 ° C. for 10 minutes and then baked in an electric furnace at 800 ° C. for 1 minute to form an aluminum electrode layer 5 and a BSF layer 6 on the p-type semiconductor silicon substrate 1. A structure was obtained.
  • a p-type semiconductor silicon substrate 1 formed with the aluminum electrode layer 5 was immersed in an aqueous solution of sodium hydroxide, the p + layer 7 by an aluminum electrode layer 5 and the BSF layer 6 is etched to expose the surface, p +
  • the surface resistance of the layer 7 was measured with a four-probe type surface resistance measuring instrument.
  • the softening point is 450 ° C. to 600 ° C., and a suitable thermal expansion coefficient (70 to 110) ⁇ 10 ⁇ 7 / ° C. And had good adhesion to the p-type semiconductor silicon substrate 1.
  • the resistance value of the p + layer 7 related to the conversion efficiency of the solar cell element is also 26 ⁇ / ⁇ or less, and can be used as a conductive paste for semiconductor silicon solar cells.
  • Comparative Examples 1 to 5 in Table 2 outside the composition range of the present invention do not provide good adhesion to the p-type semiconductor silicon substrate 1, have a high resistance value of the p + layer 7, or have a glass after melting. Since it exhibits deliquescence, it cannot be applied as a conductive paste for semiconductor silicon solar cells.

Abstract

[Problème] L'invention a pour objet d'obtenir une pâte électroconductrice qui ne contient pas de plomb et qui peut être utilisée comme une électrode à former dans une cellule solaire au silicium semiconducteur. [Solution] L'invention concerne une pâte électroconductrice pour cellules solaires dans laquelle est utilisé un substrat au silicium semiconducteur et caractérisée en ce qu'elle contient un verre fritté qui présente une composition ne contenant pour l'essentiel aucun composant à base de plomb et qui comprend, en % massiques, 1-20 % de SiO2, 5-30 % de B2O3, 0-10 % d'Al2O3, 5-35 % de ZnO, 5-30 % de RO (somme d'un ou plusieurs composés choisis dans le groupe constitué du MgO, du CaO, du SrO et du BaO), 0,1-6 % de R2O (somme d'un ou plusieurs composés choisis dans le groupe constitué du Li2O, du Na2O et du K2O) et 10-60 % de Bi2O3.
PCT/JP2012/052055 2011-02-10 2012-01-31 Pâte électroconductrice et élément de cellule solaire obtenu en utilisant la pâte électroconductrice WO2012108290A1 (fr)

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KR1020137020740A KR101455019B1 (ko) 2011-02-10 2012-01-31 도전성 페이스트 및 그 도전성 페이스트를 사용한 태양전지 소자
CN201280005074.3A CN103314414B (zh) 2011-02-10 2012-01-31 导电性糊剂及使用了该导电性糊剂的太阳能电池元件

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JP2011026781 2011-02-10
JP2011-026781 2011-02-10
JP2011270958A JP5888493B2 (ja) 2011-02-10 2011-12-12 導電性ペースト及び該導電性ペーストを用いた太陽電池素子
JP2011-270958 2011-12-12

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WO (1) WO2012108290A1 (fr)

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CN106396417A (zh) * 2016-08-31 2017-02-15 安徽斯迈尔电子科技有限公司 一种大功率电阻中玻璃相的制备方法

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CN109994247A (zh) * 2017-12-29 2019-07-09 白金光学科技（苏州）有限公司 一种导电浆料
JP7088811B2 (ja) * 2018-11-09 2022-06-21 Ａｇｃ株式会社 ガラス、ガラス粉末、導電ペーストおよび太陽電池
JP7444552B2 (ja) * 2019-06-04 2024-03-06 Ａｇｃ株式会社 ガラス組成物、ガラス組成物の製造方法、導電ペースト、及び太陽電池

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CN103440899A (zh) * 2013-08-15 2013-12-11 广东风华高新科技股份有限公司 银电极浆料
CN103440900A (zh) * 2013-09-10 2013-12-11 乐凯胶片股份有限公司 一种晶体硅太阳能电池用无铅正银浆料
CN106396417A (zh) * 2016-08-31 2017-02-15 安徽斯迈尔电子科技有限公司 一种大功率电阻中玻璃相的制备方法

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