WO2012096128A1 - Pâte conductrice et cellule de batterie solaire utilisant ladite pâte conductrice - Google Patents

Pâte conductrice et cellule de batterie solaire utilisant ladite pâte conductrice Download PDF

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Publication number
WO2012096128A1
WO2012096128A1 PCT/JP2011/080156 JP2011080156W WO2012096128A1 WO 2012096128 A1 WO2012096128 A1 WO 2012096128A1 JP 2011080156 W JP2011080156 W JP 2011080156W WO 2012096128 A1 WO2012096128 A1 WO 2012096128A1
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WO
WIPO (PCT)
Prior art keywords
conductive paste
glass
semiconductor silicon
solar cell
layer
Prior art date
Application number
PCT/JP2011/080156
Other languages
English (en)
Japanese (ja)
Inventor
耕治 富永
潤 濱田
Original Assignee
セントラル硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 JP2012552658A priority Critical patent/JP5910509B2/ja
Priority to CN201180064818.4A priority patent/CN103298759B/zh
Priority to KR1020137018765A priority patent/KR101474677B1/ko
Publication of WO2012096128A1 publication Critical patent/WO2012096128A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • 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
    • 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
    • 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.
  • 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 5 to 5% of SiO 2 by mass%. 15, B 2 O 3 20-40, Al 2 O 3 0-10, ZnO 30-45, RO (total of at least one selected from the group consisting of MgO, CaO, SrO and BaO) 5
  • a conductive paste comprising 0.1 to 6, R 2 O (total of at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O) .
  • 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 coefficient of thermal expansion at 30 ° C. to 300 ° C. is (55 to 85) ⁇ 10 ⁇ 7 / ° C. and the softening point is 550 ° C. or higher and 650 ° C. or lower.
  • the above thermal expansion coefficient means a linear expansion coefficient.
  • SiO 2 is a glass-forming component.
  • B 2 O 3 which is another glass-forming component, a stable glass can be formed, and 5 to 15% ( (The same applies to the mass% below). If it exceeds 15%, the softening point of the glass will rise, making it difficult to use as a conductive paste. More preferably, it is in the range of 7 to 13%.
  • 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 20 to 40% in the glass. If it is less than 20%, the sinterability is impaired due to insufficient fluidity of the glass, while if it exceeds 40%, the stability of the glass is lowered. More preferably, it is in the range of 25 to 35%.
  • ZnO is a component that lowers the softening point of glass and is contained in the glass at 30 to 45%. If it is less than 30%, the above effect cannot be exhibited, and if it exceeds 45%, the glass becomes unstable and crystals are likely to be formed. Further, it is preferably in the range of 35 to 42%.
  • CuO, TiO 2 , In 2 O 3 , Bi 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 (55 to 80) ⁇ 10 ⁇ 7 / ° C. and a softening point of 550 ° C. to 650 ° C. at 30 ° C. to 300 ° C. .
  • the coefficient of thermal expansion is outside (55 to 85) ⁇ 10 ⁇ 7 / ° C., problems such as peeling and substrate warpage occur during electrode formation.
  • it is in the range of (60 to 75) ⁇ 10 ⁇ 7 / ° C.
  • the softening point exceeds 650 ° 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 580 ° C. or higher and 630 ° 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.
  • 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. Glass was obtained. A part of the glass was poured into a mold, made into a block shape, and used for measurement of thermal properties (thermal expansion coefficient, softening point). The remaining glass was formed into flakes with a rapid cooling twin roll molding machine and sized with a pulverizer into a powder having an average particle size of 1 to 4 ⁇ m and a maximum particle size of less than 10 ⁇ m.
  • said softening point was measured using thermal analyzer TG-DTA (made 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.
  • paste oil composed of ⁇ -terpineol and butyl carbitol acetate is mixed with ethyl cellulose as binder and the above glass powder, and aluminum powder as conductive powder at a predetermined ratio to prepare a conductive paste having a viscosity of about 500 ⁇ 50 poise. did.
  • 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 550 ° C. to 650 ° C., and a suitable thermal expansion coefficient (55 to 85) ⁇ 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 4 in Table 2 out of 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 glass after melting. Since it exhibits deliquescence, it cannot be applied as a conductive paste for semiconductor silicon solar cells.

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

Abstract

[Problème] L'objectif de l'invention est d'obtenir une pâte conductrice ne contenant pas de plomb qui peut être utilisée en tant qu'électrode formée dans une cellule solaire à silicium à semi-conducteur. [Solution] La présente invention concerne une pâte conductrice pour une cellule solaire qui utilise un substrat en silicium à semi-conducteur, la pâte conductrice étant caractérisée en ce que la composition de la fritte de verre contenue dans la pâte conductrice ne contient sensiblement pas de composant de plomb, et comprend en % en masse, de 5 à 15 de SiO2, de 20 à 40 de B2O3, de 0 à 10 de Al2O3, de 30 à 45 de ZnO, de 5 à 30 de RO (total d'au moins un type choisi dans le groupe constitué de MgO, CaO, SrO et BaO), et de 0,1 à 6 de R2O (total d'au moins un type choisi dans le groupe constitué de Li2O, Na2O et K2O).
PCT/JP2011/080156 2011-01-13 2011-12-27 Pâte conductrice et cellule de batterie solaire utilisant ladite pâte conductrice WO2012096128A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2012552658A JP5910509B2 (ja) 2011-01-13 2011-12-27 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
CN201180064818.4A CN103298759B (zh) 2011-01-13 2011-12-27 导电性糊剂及使用该导电性糊剂的太阳能电池元件
KR1020137018765A KR101474677B1 (ko) 2011-01-13 2011-12-27 도전성 페이스트 및 그 도전성 페이스트를 사용한 태양전지 소자

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-004738 2011-01-13
JP2011004738 2011-01-13

Publications (1)

Publication Number Publication Date
WO2012096128A1 true WO2012096128A1 (fr) 2012-07-19

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PCT/JP2011/080156 WO2012096128A1 (fr) 2011-01-13 2011-12-27 Pâte conductrice et cellule de batterie solaire utilisant ladite pâte conductrice

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JP (1) JP5910509B2 (fr)
KR (1) KR101474677B1 (fr)
CN (1) CN103298759B (fr)
TW (1) TWI422547B (fr)
WO (1) WO2012096128A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018154532A (ja) * 2017-03-17 2018-10-04 東洋アルミニウム株式会社 太陽電池用ペースト組成物
CN110550864A (zh) * 2019-09-29 2019-12-10 长沙新材料产业研究院有限公司 一种低膨胀系数绝缘介质浆料及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107673601B (zh) * 2017-08-28 2019-10-18 广州市儒兴科技开发有限公司 一种perc铝浆用玻璃粉及其制备方法
CN115895332B (zh) * 2022-12-29 2024-02-02 湖南松井新材料股份有限公司 一种爽滑性低黑度玻璃高温油墨及其制备方法和应用

Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2001163635A (ja) * 1999-12-06 2001-06-19 Asahi Glass Co Ltd 隔壁形成用無鉛低融点ガラスおよびガラスセラミックス組成物
JP2002326839A (ja) * 2001-02-28 2002-11-12 Nippon Electric Glass Co Ltd プラズマディスプレイパネル用隔壁形成材料及びガラス組成物
JP2007070196A (ja) * 2005-09-09 2007-03-22 Central Glass Co Ltd 無鉛低融点ガラス
JP2009120472A (ja) * 2007-10-24 2009-06-04 Nippon Electric Glass Co Ltd プラズマディスプレイパネル用誘電体材料
JP2010184852A (ja) * 2009-01-16 2010-08-26 Hitachi Powdered Metals Co Ltd 低融点ガラス組成物、それを用いた低温封着材料及び電子部品

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DE60318517T2 (de) * 2002-04-24 2009-07-23 Central Glass Co., Ltd., Ube Bleifreies niedrigschmelzendes Glas
CN100524834C (zh) * 2005-06-07 2009-08-05 E.I.内穆尔杜邦公司 铝厚膜组合物、电极、半导体器件及其制造方法
CN101395723A (zh) * 2006-03-07 2009-03-25 株式会社村田制作所 导电性糊及太阳电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001163635A (ja) * 1999-12-06 2001-06-19 Asahi Glass Co Ltd 隔壁形成用無鉛低融点ガラスおよびガラスセラミックス組成物
JP2002326839A (ja) * 2001-02-28 2002-11-12 Nippon Electric Glass Co Ltd プラズマディスプレイパネル用隔壁形成材料及びガラス組成物
JP2007070196A (ja) * 2005-09-09 2007-03-22 Central Glass Co Ltd 無鉛低融点ガラス
JP2009120472A (ja) * 2007-10-24 2009-06-04 Nippon Electric Glass Co Ltd プラズマディスプレイパネル用誘電体材料
JP2010184852A (ja) * 2009-01-16 2010-08-26 Hitachi Powdered Metals Co Ltd 低融点ガラス組成物、それを用いた低温封着材料及び電子部品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018154532A (ja) * 2017-03-17 2018-10-04 東洋アルミニウム株式会社 太陽電池用ペースト組成物
CN110550864A (zh) * 2019-09-29 2019-12-10 长沙新材料产业研究院有限公司 一种低膨胀系数绝缘介质浆料及其制备方法
CN110550864B (zh) * 2019-09-29 2022-09-02 长沙新材料产业研究院有限公司 一种低膨胀系数绝缘介质浆料及其制备方法

Also Published As

Publication number Publication date
JP5910509B2 (ja) 2016-04-27
TW201231430A (en) 2012-08-01
KR101474677B1 (ko) 2014-12-18
TWI422547B (zh) 2014-01-11
CN103298759B (zh) 2016-05-11
CN103298759A (zh) 2013-09-11
JPWO2012096128A1 (ja) 2014-06-09
KR20130100369A (ko) 2013-09-10

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