WO2016017618A1 - 導電性組成物、太陽電池セルおよび太陽電池モジュール - Google Patents

導電性組成物、太陽電池セルおよび太陽電池モジュール Download PDF

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WO2016017618A1
WO2016017618A1 PCT/JP2015/071328 JP2015071328W WO2016017618A1 WO 2016017618 A1 WO2016017618 A1 WO 2016017618A1 JP 2015071328 W JP2015071328 W JP 2015071328W WO 2016017618 A1 WO2016017618 A1 WO 2016017618A1
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epoxy resin
type
conductive composition
mass
electrode
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PCT/JP2015/071328
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English (en)
French (fr)
Japanese (ja)
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奈央 佐藤
石川　和憲
亜星・ウイリアム 川口
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横浜ゴム株式会社
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Priority to JP2016538355A priority Critical patent/JP6579108B2/ja
Publication of WO2016017618A1 publication Critical patent/WO2016017618A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • 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
    • 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
    • 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 conductive composition, a solar battery cell, and a solar battery module.
  • Solar cells that convert light energy such as sunlight into electrical energy have been actively developed in various structures and configurations as interest in global environmental issues increases.
  • solar cells using a semiconductor substrate such as silicon are most commonly used due to advantages such as conversion efficiency and manufacturing cost.
  • Patent Document 1 discloses “conductivity containing silver powder (A), fatty acid silver salt (B), epoxy resin (C), core-shell type particles (D) and / or phenoxy resin (E).
  • the composition is disclosed ([Claim 1])
  • Examples 2 and 3 disclose a conductive composition containing an epoxy resin and a phenoxy resin ([0121]).
  • the present inventors examined the conductive composition described in Patent Document 1, the volume resistivity of the formed electrodes and wirings (hereinafter also referred to as “electrodes”) is sufficiently low. It has been clarified that the contact resistance increases when an electrode or the like is formed on a transparent conductive layer (for example, a transparent conductive oxide layer (TCO)).
  • a transparent conductive layer for example, a transparent conductive oxide layer (TCO)
  • the present invention provides a conductive composition capable of forming an electrode having a low contact resistance with respect to a transparent conductive layer or the like while maintaining a low volume resistivity, and a solar cell having a current collecting electrode formed using the same It is an object to provide a cell and a solar battery module.
  • the present inventors As a result of intensive studies to solve the above problems, the present inventors, as an epoxy resin to be added together with the metal powder, by blending a specific amount of urethane-modified epoxy resin and phenoxy resin, while maintaining a low volume resistivity, The inventors have found that an electrode having a low contact resistance with respect to a transparent conductive layer or the like is formed, and completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the epoxy resin (B) contains 5 to 50% by mass of the urethane-modified epoxy resin (B1) with respect to the total mass of the epoxy resin (B),
  • D a fatty acid metal salt
  • a solar battery cell having a collecting electrode formed using the conductive composition according to any one of [1] to [3].
  • a conductive composition capable of forming an electrode having a low contact resistance with respect to a transparent conductive layer or the like while maintaining a low volume resistivity, and a collector formed using the same.
  • a solar battery cell and a solar battery module having electric electrodes can be provided.
  • the conductive composition of the present invention when used, a low volume resistivity is maintained even in heat treatment (drying or firing) at a low temperature to a medium temperature (less than 450 ° C.), particularly at a low temperature (about 150 to 350 ° C.).
  • a medium temperature less than 450 ° C.
  • the solar cell since an electrode or the like having a low contact resistance with respect to the transparent conductive layer or the like can be formed, the solar cell (especially a second preferred embodiment described later) has an effect of reducing damage caused by heat. Useful.
  • an electronic circuit, an antenna, etc. not only on a material having high heat resistance such as indium tin oxide (ITO) or silicon but also on a material having low heat resistance such as PET film. This circuit is very useful because it can be manufactured easily and in a short time.
  • ITO indium tin oxide
  • PET film a material having low heat resistance
  • FIG. 1 is a cross-sectional view showing a first preferred embodiment of a solar battery cell.
  • FIG. 2 is a cross-sectional view showing a second preferred embodiment of the solar battery cell.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the conductive composition of the present invention contains a metal powder (A), an epoxy resin (B), and a phenoxy resin (C), and the epoxy resin (B) is a urethane-modified epoxy resin (B1). 5 to 50% by mass based on the total mass of the epoxy resin (B), and the content of the phenoxy resin (C) is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin (B). It is a conductive composition.
  • the electroconductive composition of this invention may contain the fatty-acid metal salt (D), the cationic hardening
  • a specific amount of the urethane-modified epoxy resin (B1) is blended as the epoxy resin (B), and a specific amount of the phenoxy resin (C) is blended with respect to the epoxy resin (B).
  • an electrically conductive composition capable of forming an electrode or the like having a low contact resistance with respect to the transparent conductive layer or the like while maintaining a low volume resistivity is obtained.
  • a texture (unevenness) structure is generally provided on the surface of a silicon substrate (silicon wafer) generally used for a solar cell substrate from the viewpoint of reducing the reflectance.
  • the metal powder (A), the epoxy resin (B) and the phenoxy resin (C) contained in the conductive composition of the present invention, and other components which may be optionally contained, will be described in detail.
  • the metal powder (A) contained in the conductive composition of the present invention is not particularly limited, and for example, a metal material having an electric resistivity of 20 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less can be used.
  • the metal material include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and the like.
  • One species may be used alone, or two or more species may be used in combination.
  • silver is coated on at least a part of the surface of silver powder or metal powder other than silver (for example, nickel powder, copper powder, etc.) because a collector electrode with low contact resistance can be formed.
  • the coated silver coated metal powder is not particularly limited, and for example, a metal material having an electric resistivity of 20 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less.
  • the metal material include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and the like.
  • One species may be used alone, or two or
  • the metal powder (A) is preferably a spherical metal powder (A1) because of good printability (particularly screen printability), together with the spherical metal powder (A1). It is more preferable to use the flake (scale) -like metal powder (A2) in combination, and the mass ratio (A1: A2) of the spherical metal powder (A1) to the flake-like metal powder (A2) is 70:30 to 30. : It is more preferable to use together in the ratio used as 70.
  • the spherical shape refers to the shape of a particle having a major axis / minor axis ratio of 2 or less
  • the flake shape refers to a shape having a major axis / minor axis ratio of more than 2.
  • the average particle size of the spherical metal powder (A1) as the metal powder (A) is preferably from 0.5 to 10 ⁇ m, and more preferably from 0.5 to 5.0 ⁇ m, because the printability is better. Is more preferable.
  • the average particle diameter of the spherical metal powder (A1) refers to the average value of the particle diameter of the spherical metal powder, and the 50% volume cumulative diameter (D50) measured using a laser diffraction particle size distribution analyzer.
  • the particle diameter used as the basis for calculating the average value is an average value obtained by dividing the total value of the major axis and the minor axis by 2, and in the case of a perfect circle, Refers to the diameter.
  • the average thickness of the flaky metal powder (A2) as the metal powder (A) is preferably 0.05 to 2.0 ⁇ m because the printing property is better and it is easy to form a paste. More preferably, the thickness is from 05 to 1.0 ⁇ m.
  • a commercially available product can be used as the metal powder (A).
  • Specific examples of commercially available spherical silver powder include AG2-1C (average particle size: 1.0 ⁇ m, manufactured by DOWA Electronics), AG4-8F (average particle size: 2.2 ⁇ m, manufactured by DOWA Electronics), AG3 -11F (average particle size: 1.4 ⁇ m, manufactured by DOWA Electronics), AgC-102 (average particle size: 1.5 ⁇ m, manufactured by Fukuda Metal Foil Co., Ltd.), AgC-103 (average particle size: 1.5 ⁇ m, Fukuda Metal Foil Powder Industry Co., Ltd.), EHD (average particle size: 0.5 ⁇ m, Mitsui Metals Co., Ltd.) and the like.
  • specific examples of commercially available flaky silver powder include Ag-XF301K (average thickness: 0.1 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.).
  • the epoxy resin (B) contained in the conductive composition of the present invention contains 5 to 50% by mass of the urethane-modified epoxy resin (B1).
  • the “urethane-modified epoxy resin” is obtained by introducing a urethane bond into an epoxy resin, and is not particularly limited as long as it has a urethane bond and two or more epoxy groups in the molecule.
  • the epoxy equivalent of the epoxy resin (B) is preferably 50 to 10,000 g / eq, more preferably 90 to 5000 g / eq.
  • Examples of the urethane-modified epoxy resin (B1) include a urethane bond-containing compound (b1) having an isocyanate group obtained by reacting a polyhydroxy compound and a polyisocyanate compound, and a hydroxy group-containing epoxy compound (b2). A resin obtained by reaction is preferred.
  • examples of the polyhydroxy compound include polyether polyol, polyester polyol, adduct of hydroxycarboxylic acid and alkylene oxide, polybutadiene polyol, polyolefin polyol, and the like.
  • the polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples thereof include aliphatic polymer isocyanates, aromatic polyisocyanates, and polyisocyanates having aromatic hydrocarbon groups. Can be mentioned. Of these, aromatic polyisocyanates are preferred. Examples of the aromatic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate.
  • urethane prepolymer containing a free isocyanate group at the terminal is obtained.
  • an epoxy resin having at least one hydroxyl group in one molecule for example, diglycidyl ether of bisphenol A type epoxy resin, diglycidyl ether of bisphenol F type epoxy resin, aliphatic polyvalent
  • the urethane-modified epoxy resin (B1) is obtained by reacting with alcohol diglycidyl ether and glycidol.
  • the urethane-modified epoxy resin (B1) preferably has an epoxy equivalent of 100 to 400 g / eq, and more preferably 200 to 350 g / eq. Further, the urethane-modified epoxy resin (B1) may be used alone or in combination of two or more.
  • the epoxy resin (B) containing 5 to 50% by mass of the urethane-modified epoxy resin (B1) is blended to maintain a low volume resistivity while maintaining a low volume resistivity. It becomes an electroconductive composition which can form an electrode etc. with low contact resistance. And, from the reason that an electrode having a lower contact resistance can be formed, the content of the urethane-modified epoxy resin (B1) contained in the epoxy resin (B) is preferably 5 to 45% by mass.
  • an epoxy resin other than the urethane-modified epoxy resin (B1) contained in the epoxy resin (B)
  • two or more oxirane rings are contained in one molecule.
  • the resin is not particularly limited as long as it is made of a compound having a group), and generally has an epoxy equivalent of 50 to 10,000 g / eq, preferably 90 to 5000 g / eq.
  • Conventionally known epoxy resins can be used as such other epoxy resins.
  • epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, and polyalkylene Bifunctional glycidyl ether type epoxy resins such as glycol type, alkylene glycol type epoxy compounds, epoxy compounds having a naphthalene ring, and epoxy compounds having a fluorene group; Polyfunctional glycidyl ether type epoxy resins such as phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type; Glycidyl ester epoxy resins of synthetic fatty acids such as dimer acid; N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyldiaminodiphenylsulfone (TGDDM), te
  • epoxy resins may be used alone or in combination of two or more.
  • bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable from the viewpoints of curability, heat resistance, durability, and cost.
  • an epoxy resin with less curing shrinkage is preferable to use as the other epoxy resin. Since a silicon wafer as a substrate is easily damaged, using an epoxy resin having a large curing shrinkage causes cracking or chipping of the wafer. In recent years, silicon wafers have been made thinner for cost reduction, and an epoxy resin with little curing shrinkage also has an effect of suppressing warpage of the wafer. Epoxy resin to which ethylene oxide and / or propylene oxide has been added for the reason that curing shrinkage is reduced, the contact resistance of the current collecting electrode to be formed is lower, and the adhesion to the transparent conductive layer is also better. Is preferred.
  • the epoxy resin to which ethylene oxide and / or propylene oxide has been added is prepared by adding ethylene and / or propylene when preparing an epoxy resin by reacting bisphenol A, bisphenol F or the like with epichlorohydrin, for example. And then added (modified).
  • Commercially available products can be used as the epoxy resin to which ethylene oxide and / or propylene oxide are added. Specific examples thereof include ethylene oxide-added bisphenol A type epoxy resin (BEO-60E, manufactured by Shin Nippon Rika Co., Ltd.), propylene oxide addition.
  • Bisphenol A type epoxy resin (BPO-20E, manufactured by Shin Nippon Chemical Co., Ltd.), Propylene oxide added bisphenol A type epoxy resin (EP-4010S, manufactured by ADEKA), Propylene oxide added bisphenol A type epoxy resin (EP-4000S, ADEKA) Manufactured) and the like.
  • the urethane-modified epoxy resin (B1) is used because the curing shrinkage is reduced, the contact resistance of the current collecting electrode to be formed is lower, and the adhesion to the transparent conductive layer is better.
  • bisphenol A type epoxy resin (B2) having an epoxy equivalent of 1500 to 4000 g / eq
  • a polyhydric alcohol-based glycidyl type epoxy resin (B3) having an epoxy equivalent of 1000 g / eq or less, or a dilution type of 1000 g / eq or less
  • the total content of the bisphenol A type epoxy resin (B2), the polyhydric alcohol glycidyl type epoxy resin (B3), and the bisphenol A type epoxy resin (B4) is 55 to 95% by mass is preferable, and 60 to 95% by mass is more preferable.
  • the bisphenol A type epoxy resin (B2) is a bisphenol A type epoxy resin having an epoxy equivalent of 1500 to 4000 g / eq. Since the epoxy equivalent of the bisphenol A type epoxy resin (B2) is within the above range, when the bisphenol A type epoxy resin (B2) is used in combination as described above, the curing shrinkage of the conductive composition of the present invention is suppressed, and the substrate In addition, adhesion to the transparent conductive layer is also improved. Since the volume resistivity becomes lower, the epoxy equivalent is preferably 2000 to 4000 g / eq, more preferably 2000 to 3500 g / eq.
  • the polyhydric alcohol glycidyl type epoxy resin (B3) is a polyhydric alcohol glycidyl type epoxy resin having an epoxy equivalent of 1000 g / eq or less. Since the polyhydric alcohol glycidyl type epoxy resin (B3) has an epoxy equivalent in the above range, when the polyhydric alcohol glycidyl type epoxy resin (B3) is used in combination as described above, the viscosity of the conductive composition of the present invention. Becomes good and printability becomes good.
  • the epoxy equivalent of the polyhydric alcohol glycidyl type epoxy resin (B3) is preferably 100 to 400 g / eq, and preferably 100 to 300 g / eq, because the viscosity at the time of screen printing becomes appropriate. More preferably.
  • the dilution type bisphenol A type epoxy resin (B4) is a bisphenol A type epoxy resin having an epoxy equivalent of 1000 g / eq or less. The viscosity is lowered by using a reactive diluent without impairing the properties of the epoxy resin. Since the epoxy equivalent of the bisphenol A type epoxy resin (B4) is in the above range, when the bisphenol A type epoxy resin (B4) is used in combination as described above, the viscosity of the conductive composition of the present invention is improved and the printability is increased. Becomes better.
  • the epoxy equivalent of the bisphenol A type epoxy resin (B4) is preferably 100 to 400 g / eq, and preferably 100 to 300 g / eq, because the viscosity at the time of screen printing becomes appropriate. More preferred.
  • the urethane-modified epoxy resin (B1) is used because the curing shrinkage is reduced, the contact resistance of the current collecting electrode to be formed is lower, and the adhesion to the transparent conductive layer is better.
  • trifunctional epoxy resin (B5) and / or bisphenol E type epoxy resin (B6) having the structural formula represented by the following formula (1).
  • the content of the trifunctional epoxy resin (B5) and the bisphenol E-type epoxy resin (B6) (the content of either one when only one of them is used in combination) Is preferably 20 to 80% by mass.
  • the content of the epoxy resin (B) is such that the contact resistance of the current collecting electrode to be formed becomes lower, and the adhesion to the transparent conductive layer becomes better, so that the metal powder (A)
  • the amount is preferably 2 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 2 to 10 parts by mass with respect to 100 parts by mass.
  • the phenoxy resin (C) contained in the conductive composition of the present invention is not particularly limited, and a conventionally known phenoxy resin can be used.
  • the phenoxy resin is a polyhydroxy polyether (thermoplastic resin) synthesized from bisphenols and epichlorohydrin. Since it is a thermoplastic resin, it is generally free of epoxy groups and has a certain molecular weight (weight average molecular weight (Mw) of tens of thousands or more).
  • the weight average molecular weight of the phenoxy resin (C) is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, and preferably 120,000 or less, more preferably 100. , 000 or less, more preferably 90,000 or less.
  • Specific examples of the phenoxy resin (C) include a bisphenol A type phenoxy resin and a bisphenol F type phenoxy because they are compatible with the above-described epoxy resin (B) to obtain a stable paste state. Resins are preferred.
  • phenoxy resin (C) commercially available products can be used as the phenoxy resin (C).
  • Specific examples thereof include bisphenol A type phenoxy resin (1256, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol A type phenoxy resin (YP-50).
  • YP-70 a copolymer type of bisphenol A type and bisphenol F type
  • the content of the phenoxy resin (C) is 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin (B).
  • the content of the phenoxy resin (C) is such that the contact resistance of the current collecting electrode to be formed is lower and the adhesiveness with the transparent conductive layer is better, so that the metal powder (A) 100
  • the amount is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to parts by mass.
  • the conductive composition of the present invention preferably contains a fatty acid metal salt (D) for the reason that the contact resistance of the formed electrode or the like becomes lower.
  • the fatty acid metal salt (D) is not particularly limited as long as it is a metal salt of an organic carboxylic acid.
  • a metal salt of an organic carboxylic acid For example, at least selected from the group consisting of silver, magnesium, nickel, copper, zinc, yttrium, zirconium, tin and lead It is preferred to use one or more metal carboxylic acid metal salts. Among these, it is preferable to use a silver carboxylic acid metal salt (hereinafter also referred to as “a carboxylic acid silver salt”).
  • the carboxylic acid silver salt is not particularly limited as long as it is a silver salt of an organic carboxylic acid (fatty acid).
  • fatty acid described in paragraphs [0063] to [0068] of JP-A-2008-198595 Metal salts (particularly tertiary fatty acid silver salts), fatty acid silver salts described in paragraph [0030] of Japanese Patent No.
  • the content in the case of containing the fatty acid metal salt (D) is 0 with respect to 100 parts by mass of the metal powder (A) because the contact resistance of the current collecting electrode to be formed is further reduced.
  • the amount is preferably from 1 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight.
  • the conductive composition of the present invention preferably contains a cationic curing agent (E) as a curing agent for the epoxy resin (B).
  • the cationic curing agent (E) is not particularly limited, and amine-based, sulfonium-based, ammonium-based, and phosphonium-based curing agents are preferable.
  • cationic curing agent (E) examples include boron trifluoride ethylamine, boron trifluoride piperidine, boron trifluoride phenol, p-methoxybenzenediazonium hexafluorophosphate, diphenyliodonium hexa Fluorophosphate, tetraphenylsulfonium, tetra-n-butylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, sulfonium salts represented by the following formula (I), and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a sulfonium salt represented by the following formula (I) because the curing time is shortened.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom
  • R 2 is substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents an alkyl group having 1 to 4 carbon atoms
  • Q is represented by any of the following formulas (a) to (c):
  • X represents SbF 6 , PF 6 , CF 3 SO 3 , (CF 3 SO 2 ) 2 N, BF 4 , B (C 6 F 5 ) 4 or Al (CF 3 SO 3 ) 4 .
  • R represents a hydrogen atom, an acetyl group, a methoxycarbonyl group or a benzyloxycarbonyl group.
  • X in the above formula (I) is a sulfonium salt represented by SbF 6 because an electrode having good solderability can be formed.
  • SbF 6 a sulfonium salt represented by SbF 6 because an electrode having good solderability can be formed.
  • the content of the epoxy resin (B) can be sufficiently activated by heat to allow the ring-opening reaction of the epoxy group to proceed sufficiently.
  • It is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass.
  • the conductive composition of the present invention preferably contains a solvent (F) from the viewpoint of workability such as printability.
  • the solvent (F) is not particularly limited as long as the conductive composition of the present invention can be applied onto a substrate. Specific examples thereof include butyl carbitol, methyl ethyl ketone, isophorone, ⁇ -terpineol, and the like. These may be used alone or in combination of two or more.
  • the electrically conductive composition of this invention may contain additives, such as a reducing agent, as needed.
  • a reducing agent include ethylene glycols.
  • the conductive composition of the present invention is not particularly necessary for a glass frit generally used as a high-temperature (700 to 800 ° C.) firing type conductive paste, and is based on 100 parts by mass of the metal powder (A). The amount is preferably less than 0.1 parts by mass, and is preferably substantially not contained.
  • the method for producing the conductive composition of the present invention is not particularly limited, and examples thereof include a method of mixing the above-described components using a roll, a kneader, an extruder, a universal agitator, or the like.
  • the solar battery cell of the present invention is a solar battery cell using the above-described conductive composition of the present invention as a collecting electrode.
  • a 1st suitable aspect of the photovoltaic cell of this invention comprises the surface electrode by the side of a light-receiving surface, a semiconductor substrate, and a back electrode,
  • the said surface electrode and / or the said back electrode are the electroconductivity of this invention mentioned above.
  • a solar battery cell formed using the composition can be mentioned.
  • the 1st suitable aspect of the photovoltaic cell of this invention is demonstrated using FIG.
  • the solar cell 1 includes a surface electrode 4 on the light receiving surface side, a pn junction silicon substrate 7 in which a p layer 5 and an n layer 2 are joined, and a back electrode 6.
  • the solar battery cell 1 is preferably provided with an antireflection film 3, for example, by etching the wafer surface to form a pyramidal texture in order to reduce reflectivity.
  • an antireflection film 3 for example, by etching the wafer surface to form a pyramidal texture in order to reduce reflectivity.
  • the arrangement (pitch), shape, height, width and the like of the electrode are not particularly limited.
  • the height of the electrode is usually designed to be several to several tens of ⁇ m, but the ratio of the height and width of the cross section of the electrode formed using the conductive composition of the present invention (height / width) (below) , “Aspect ratio”) can be adjusted to a large value (for example, about 0.4 or more).
  • the front surface electrode and the back surface electrode usually have a plurality, but, for example, only a part of the plurality of surface electrodes is formed of the conductive composition of the present invention.
  • part of the plurality of front surface electrodes and part of the plurality of back surface electrodes may be formed of the conductive composition of the present invention.
  • the antireflection film is a film (film thickness: about 0.05 to 0.1 ⁇ m) formed on a portion of the light receiving surface where the surface electrode is not formed.
  • a silicon oxide film, a silicon nitride film, a titanium oxide It is comprised from a film
  • the silicon substrate has a pn junction, which means that a second conductivity type light-receiving surface impurity diffusion region is formed on the surface side of the first conductivity type semiconductor substrate.
  • the second conductivity type is p-type.
  • the impurity imparting p-type include boron and aluminum
  • examples of the impurity imparting n-type include phosphorus and arsenic.
  • the silicon substrate is not particularly limited, and a known silicon substrate (plate thickness: about 80 to 450 ⁇ m) for forming a solar cell can be used, and either a monocrystalline or polycrystalline silicon substrate can be used. Good.
  • the solar battery cell has a large electrode aspect ratio because the surface electrode and / or the back electrode is formed using the conductive composition of the present invention.
  • the electromotive force generated by light reception can be efficiently taken out as a current.
  • the conductive composition of the present invention described above can also be applied to the formation of the back electrode of an all-back electrode type (so-called back contact type) solar cell, it can also be applied to an all-back electrode type solar cell. Can do.
  • the manufacturing method of a photovoltaic cell (1st suitable aspect) is not specifically limited,
  • the antireflection film can be formed by a known method such as a plasma CVD method.
  • the wiring formation step is a step of forming a wiring by applying the conductive composition of the present invention on a silicon substrate.
  • specific examples of the coating method include inkjet, screen printing, gravure printing, offset printing, letterpress printing, and the like.
  • the heat treatment step is a step of forming a conductive wiring (electrode) by heat-treating (drying or baking) the coating film formed in the wiring forming step.
  • the heat treatment is not particularly limited, but is preferably a treatment in which heating (firing) is performed at a relatively low temperature of 150 to 350 ° C. for several seconds to several tens of minutes. When the temperature and time are within this range, an electrode can be easily formed even when an antireflection film is formed on a silicon substrate. Further, in the first preferred embodiment of the solar battery cell of the present invention, since the conductive composition of the present invention is used, good heat treatment (firing) can be achieved even at a relatively low temperature of 150 to 350 ° C. ) Can be applied.
  • the heat treatment step may be performed by irradiation with ultraviolet rays or infrared rays.
  • an amorphous silicon layer and a transparent conductive layer are provided above and below an n-type single crystal silicon substrate, and the transparent conductive layer is disposed below.
  • the base layer include a solar battery (for example, a heterojunction solar battery) cell in which a collecting electrode is formed on the transparent conductive layer using the conductive composition of the present invention described above.
  • the solar battery cell (second preferred embodiment) is a solar battery cell in which single crystal silicon and amorphous silicon are hybridized and exhibits high conversion efficiency.
  • the solar battery cell 100 has an n-type single crystal silicon substrate 11 as a center, i-type amorphous silicon layers 12 a and 12 b, and p-type amorphous silicon layers 13 a and n-type amorphous silicon layers above and below it. 13b, transparent conductive layers 14a and 14b, and current collecting electrodes 15a and 15b formed using the above-described conductive composition of the present invention.
  • the n-type single crystal silicon substrate is a single crystal silicon layer doped with an n-type impurity. Impurities that give n-type are as described above.
  • the i-type amorphous silicon layer is an undoped amorphous silicon layer.
  • the p-type amorphous silicon is an amorphous silicon layer doped with an impurity imparting p-type. Impurities that give p-type are as described above.
  • the n-type amorphous silicon is an amorphous silicon layer doped with an n-type impurity. Impurities that give n-type are as described above.
  • the said collector electrode is a collector electrode formed using the electrically conductive composition of this invention mentioned above. A specific aspect of the current collecting electrode is the same as that of the front surface electrode or the back surface electrode described above.
  • Transparent conductive layer Specific examples of the material for the transparent conductive layer include single metal oxides such as zinc oxide, tin oxide, indium oxide, and titanium oxide, indium tin oxide (ITO), indium zinc oxide, indium titanium oxide, tin cadmium oxide, Various metal oxides such as gallium-doped zinc oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, titanium-doped zinc oxide, titanium-doped indium oxide, zirconium-doped indium oxide, and fluorine-doped tin oxide. Can be mentioned.
  • ITO indium tin oxide
  • ITO indium zinc oxide
  • titanium oxide titanium oxide
  • tin cadmium oxide Various metal oxides such as gallium-doped zinc oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, titanium-doped zinc oxide, titanium-doped indium oxide, zirconium-doped indium oxide, and fluorine-doped
  • the method for producing the solar battery cell is not particularly limited, and can be produced by, for example, the method described in JP 2010-34162 A.
  • the i-type amorphous silicon layer 12a is formed on one main surface of the n-type single crystal silicon substrate 11 by a PECVD (plasma enhanced chemical vapor deposition) method or the like.
  • a p-type amorphous silicon layer 13a is formed on the formed i-type amorphous silicon layer 12a by PECVD or the like.
  • an i-type amorphous silicon layer 12b is formed on the other main surface of the n-type single crystal silicon substrate 11 by PECVD or the like. Further, an n-type amorphous silicon layer 13b is formed on the formed i-type amorphous silicon layer 12b by PECVD or the like.
  • transparent conductive layers 14a and 14b such as ITO are formed on the p-type amorphous silicon layer 13a and the n-type amorphous silicon layer 13b by sputtering or the like.
  • the conductive composition of the present invention is applied on the formed transparent conductive layers 14a and 14b to form wirings, and the formed wirings are heat-treated to form current collecting electrodes 15a and 15b.
  • the method for forming the wiring is the same as the method described in the wiring formation step of the above-described solar battery cell (first preferred embodiment).
  • the method of heat-treating the wiring is the same as the method described in the heat treatment step of the above-described solar battery cell (first preferred embodiment), but the heat treatment temperature (firing temperature) is preferably 150 to 200 ° C.
  • Examples 1 to 5 Comparative Examples 1 to 3
  • a metal powder or the like shown in Table 1 below was added so as to have a composition ratio (mass ratio) shown in Table 1 below, and these were mixed to prepare a conductive composition.
  • ITO indium oxide doped with Sn
  • each of the prepared conductive compositions was applied on the transparent conductive layer by screen printing to form six thin line-shaped test patterns having a width of 0.08 mm and a length of 15 mm arranged at intervals of 1.8 mm.
  • the sample was dried in an oven at 200 ° C. for 30 minutes to form a thin wire-shaped conductive film (thin wire electrode), and a solar cell sample was produced.
  • Spherical metal powder A1-1 AgC-103 (shape: spherical, average particle diameter: 1.5 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.)
  • Flake metal powder A2-1 AgC-224 (shape: flake, average thickness: 0.7 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
  • Urethane-modified epoxy resin B1-1 EPU-1395 (epoxy equivalent: 215 g / eq, manufactured by ADEKA)
  • Urethane-modified epoxy resin B1-2 EPU-11F (epoxy equivalent: 320 g / eq, manufactured by ADEKA)
  • Urethane-modified epoxy resin B1-3 EPU-78-11 (epoxy equivalent: 230 g / eq, manufactured by ADEKA)
  • Bisphenol A type epoxy resin B4-1 EP-4100E (epoxy equivalent: 190 g / eq, manufactured by ADEKA)
  • Bisphenol A type epoxy resin B2-1: YD-019 (epoxy equivalent: 2400-3300 g / eq, manufactured by Nippon Steel & Sumikin Co., Ltd.)
  • Polyhydric alcohol glycidyl type epoxy resin B3-1 EX-850 (epoxy equivalent: 122 g / eq, manufactured by Nagase ChemteX
  • Bisphenol A type phenoxy resin C-1 YP-50 (weight average molecular weight: 70,000, manufactured by Tohto Kasei Co., Ltd.) Copolymerized phenoxy resin C-2: ZX-1356-2 (weight average molecular weight: 70,000, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
  • Bisphenol F-type phenoxy resin C-3 FX-316 (weight average molecular weight: 50,000, manufactured by Tohto Kasei Co., Ltd.)
  • Bisphenol A type phenoxy resin C-4 PKHB (weight average molecular weight: 37,000, manufactured by InChem)
  • Bisphenol A type phenoxy resin C-5 PKHJ (weight average molecular weight: 57,000, manufactured by InChem)
  • Silver salt of 2-methylpropanoate 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 38 g of 2-methylpropanoic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-methylpropanoate.
  • MEK methyl ethyl ketone
  • 2-hydroxyisobutyric acid silver salt Silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.) 50 g, 2-hydroxyisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 45 g, and methyl ethyl ketone (MEK) 300 g were charged into a ball mill and reacted by stirring at room temperature for 24 hours. . Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-hydroxyisobutyrate.
  • MEK methyl ethyl ketone
  • 1,2,3,4-Butanetetracarboxylic acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 25.29 g of 1,2,3,4-butanetetracarboxylic acid (manufactured by Shin Nippon Chemical Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are placed in a ball mill and stirred at room temperature for 24 hours. It was made to react. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white 1,2,3,4-butanetetracarboxylic acid silver salt.
  • MEK methyl ethyl ketone
  • Cationic curing agent Boron trifluoride ethylamine (manufactured by Stella Chemifa) ⁇ Solvent: Terpinel: Terpineol (manufactured by Yasuhara Chemical)
  • the conductive composition prepared without blending either or both of the urethane-modified epoxy resin (B1) and the phenoxy resin (C) has high contact resistance ( Comparative Examples 1 to 3).
  • the conductive compositions of Examples 1 to 5 prepared by blending predetermined amounts of the urethane-modified epoxy resin (B1) and the phenoxy resin (C) all have a low volume resistivity and a transparent conductive layer. It has been found that the contact resistance to is also low.

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WO2018216739A1 (ja) * 2017-05-25 2018-11-29 横浜ゴム株式会社 導電性組成物
WO2023026764A1 (ja) * 2021-08-27 2023-03-02 日本ゼオン株式会社 太陽電池用導電性組成物、太陽電池用電極、太陽電池、及び太陽電池モジュール

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JP2011529121A (ja) * 2008-07-22 2011-12-01 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 薄膜太陽電池用ポリマー厚膜銀電極組成物
JP2010092684A (ja) * 2008-10-07 2010-04-22 Yokohama Rubber Co Ltd:The 導電性組成物、導電性被膜の形成方法および導電性被膜
JP2012023096A (ja) * 2010-07-12 2012-02-02 Yokohama Rubber Co Ltd:The 導電性組成物および太陽電池セル
JP2014503614A (ja) * 2010-11-17 2014-02-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 薄膜光電池およびその他の用途に使用するためのはんだ付け可能なポリマー厚膜銀電極組成物
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JP2018037526A (ja) * 2016-08-31 2018-03-08 横浜ゴム株式会社 接続部付太陽電池セル及び太陽電池モジュール
WO2018216739A1 (ja) * 2017-05-25 2018-11-29 横浜ゴム株式会社 導電性組成物
JPWO2018216739A1 (ja) * 2017-05-25 2020-04-02 横浜ゴム株式会社 導電性組成物
JP7231537B2 (ja) 2017-05-25 2023-03-01 東洋アルミニウム株式会社 導電性組成物
WO2023026764A1 (ja) * 2021-08-27 2023-03-02 日本ゼオン株式会社 太陽電池用導電性組成物、太陽電池用電極、太陽電池、及び太陽電池モジュール

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