WO2016021535A1 - 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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WO2016021535A1
WO2016021535A1 PCT/JP2015/071925 JP2015071925W WO2016021535A1 WO 2016021535 A1 WO2016021535 A1 WO 2016021535A1 JP 2015071925 W JP2015071925 W JP 2015071925W WO 2016021535 A1 WO2016021535 A1 WO 2016021535A1
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conductive composition
type
metal powder
epoxy resin
polymerizable compound
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PCT/JP2015/071925
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English (en)
French (fr)
Japanese (ja)
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奈央 佐藤
石川　和憲
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横浜ゴム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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

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 that “a silver powder (A), an epoxy resin (B), and a curing agent (C) are contained, and the epoxy resin (B) has at least an epoxy equivalent of 1500 to 4000 g / eq.
  • Electrodes the printability when forming electrodes and wirings (hereinafter also referred to as “electrodes”) was good. Depending on the amount and type of the solvent used, it has been revealed that the adhesion may be inferior 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 good adhesion to a transparent conductive layer or the like while maintaining excellent printability, and a solar electrode having a collector electrode formed using the same It is an object to provide a battery cell and a solar battery module.
  • the present inventors have formulated a specific cationic polymerizable compound having a predetermined viscosity, thereby maintaining adhesion to a transparent conductive layer and the like while maintaining excellent printability.
  • the inventors have found that a good electrode can be 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 electroconductive composition whose viscosity in 25 degreeC of the said cation polymeric compound (D) is 150 mPa * s or less.
  • the metal powder (A) uses a spherical metal powder (A1) and a flaky metal powder (A2) in combination, and the mass ratio (A1: A2) is 70:30 to 30:70.
  • a solar battery cell having a collecting electrode formed using the conductive composition according to any one of [1] to [5].
  • the solar battery cell according to [6] including a transparent conductive layer as a base layer of the current collecting electrode.
  • an electroconductive composition capable of forming an electrode having good adhesion to a transparent conductive layer and the like while maintaining excellent printability, and formed using the same.
  • a solar battery cell and a solar battery module having current collecting electrodes can be provided.
  • the conductive composition of the present invention when used, excellent printability is maintained even during 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 having good adhesion to the transparent conductive layer or the like can be formed, the solar cell (especially the second preferred embodiment described later) has an effect of reducing damage due to heat, Useful for.
  • 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 comprises a cationically polymerizable compound (D) having a metal powder (A), an epoxy resin (B), a cationic curing agent (C), and a cationically polymerizable functional group other than a glycidyl group.
  • the viscosity of the cationically polymerizable compound (D) at 25 ° C. is 150 mPa ⁇ s or less.
  • the electroconductive composition of this invention may contain the phenoxy resin (E), the solvent (F), etc. as needed so that it may mention later.
  • the cationic polymerizable compound (D) by blending the cationic polymerizable compound (D), a conductive composition capable of forming an electrode having good adhesion to a transparent conductive layer and the like while maintaining excellent printability. It becomes a thing. This is not clear in detail, but is estimated to be as follows. That is, the cationically polymerizable compound (D) has a viscosity at 25 ° C. of 150 mPa ⁇ s or less, so that it can be used as a viscosity modifier before heat treatment (drying or firing), as with a general solvent.
  • the adhesion strength to the transparent conductive layer and the like is improved by having the cation polymerizable functional group and being incorporated into the epoxy resin curing system after the heat treatment.
  • the cationically polymerizable compound (D) acts as a reactive diluent. This can be inferred from the result that the adhesiveness is not improved even if the amount of the solvent is changed in the comparative example in which the cationic polymerizable compound (D) is not blended as shown in the comparative example described later. .
  • the metal powder (A), the epoxy resin (B), the cationic curing agent (C) and the cationic polymerizable compound (D) contained in the conductive composition of the present invention and other optionally contained may be contained.
  • the components 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 the printability (particularly screen printability) is better, and the spherical metal powder (A1).
  • 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.).
  • Epoxy resin (B) contained in the conductive composition of the present invention is particularly limited as long as it is a resin composed of a compound having two or more oxirane rings (epoxy groups) (preferably glycidyl groups) in one molecule.
  • the epoxy equivalent is 50 to 10,000 g / eq, preferably 90 to 5000 g / eq.
  • a conventionally well-known epoxy resin can be used as such an epoxy resin.
  • epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, bisphenol E type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, and biphenyl type
  • bifunctional glycidyl ether type epoxy resins such as polyalkylene 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), t
  • bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable from the viewpoints of curability, heat resistance, durability, and cost.
  • the epoxy resin (B) is preferably an epoxy resin with little curing shrinkage. 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 to which ethylene oxide and / or propylene oxide is added because the shrinkage of curing is reduced, the contact resistance of the current collecting electrode formed is low, and the adhesion to the transparent conductive layer is also improved. A resin 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 epoxy resin (B) reduces curing shrinkage, lowers the contact resistance of the current collecting electrode to be formed, and has better adhesion to the transparent conductive layer and the like. For this reason, bisphenol A type epoxy resin (B1) having an epoxy equivalent of 1500 to 4000 g / eq, polyhydric alcohol glycidyl type epoxy resin (B2) having an epoxy equivalent of 1000 g / eq or less, and 1000 g / eq or less It is preferable to use two or more types of epoxy resins selected from the group consisting of dilution type bisphenol A type epoxy resins (B3).
  • the bisphenol A type epoxy resin (B1) 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 (B1) is in the above range, when the bisphenol A type epoxy resin (B1) is used together 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 (B2) 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 (B2) has an epoxy equivalent in the above range, when the polyhydric alcohol glycidyl type epoxy resin (B2) 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-based glycidyl type epoxy resin (B2) 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 (B3) 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 (B3) is in the above range, when the bisphenol A type epoxy resin (B3) 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 (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 preferred.
  • 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 and the like becomes better.
  • the amount is preferably 2 to 20 parts by mass, more preferably 2 to 15 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the powder (A).
  • the cationic curing agent (C) contained in the conductive composition of the present invention is not particularly limited, and amine-based, sulfonium-based, ammonium-based, and phosphonium-based curing agents are preferable.
  • cationic curing agent (C) 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 cationic curing agent (C) is activated by heat to sufficiently advance the ring opening reaction of the epoxy group, so that 100 parts by mass of the epoxy resin (B).
  • the amount is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.
  • the cationically polymerizable compound (D) contained in the conductive composition of the present invention is a cationically polymerizable compound having a viscosity at 25 ° C. of 150 mPa ⁇ s or less and having a cationically polymerizable functional group other than a glycidyl group.
  • the “viscosity at 25 ° C.” is determined by using a rotary viscometer (for example, RS-600 (manufactured by HAAKE)), keeping the thermostat at 25 ° C. A value measured in (1 / s).
  • “having a cationically polymerizable functional group other than a glycidyl group” is a rule for distinguishing from the epoxy resin (B) described above.
  • a vinyl ether group and / or an oxetanyl group is preferable.
  • the “vinyl ether group” refers to a group consisting of an optionally substituted vinyl group and oxygen atom.
  • the “oxetanyl group” refers to a group having an oxetane (trimethylene oxide) ring.
  • a conductive composition capable of forming an electrode having good adhesion to a transparent conductive layer and the like while maintaining excellent printability by blending the cationic polymerizable compound (D). It becomes.
  • the viscosity at 25 ° C. of the cationic polymerizable compound (D) is preferably 1 to 140 mPa ⁇ s because an electrode having better adhesion to the transparent conductive layer and the like can be formed. It is more preferably 1 to 100 mPa ⁇ s.
  • the cationically polymerizable compound (D) is preferably a polyfunctional type having two or more cationically polymerizable functional groups.
  • examples of the cationic polymerizable compound having a vinyl ether group include compounds represented by the following formula (3).
  • the compound represented by following formula (4) is mentioned, for example.
  • R 4 represents an n-valent aliphatic hydrocarbon group or an n-valent aromatic hydrocarbon group
  • n represents an integer of 1 to 4.
  • R 5 represents a hydrogen atom, a fluorine atom or a monovalent hydrocarbon group
  • R 6 represents a hydrogen atom, an m-valent aliphatic hydrocarbon group or an m-valent aromatic hydrocarbon group.
  • M represents an integer of 1-6. However, m is 1 when R 6 is a hydrogen atom. when m is an integer of 2 or more, a plurality of oxygen atoms bonded to R 6 may be bonded to the same carbon atom of R 6 to each other may be bonded to different carbon atoms of R 6.
  • BDVE 1,4-butanediol divinyl ether
  • DEGDVE diethylene glycol divinyl ether
  • CHDVE cyclohexanedimethanol divinyl ether
  • TEGDVE triethylene glycol divinyl ether
  • DEGDVE ethyl oxetane methyl vinyl ether
  • EOXTVE triethylene glycol divinyl ether
  • TDVE triethylene glycol divinyl ether
  • Specific examples of the cationically polymerizable compound having an oxetanyl group represented by the above formula (4) include 1,4-di [(3-oxetanyl-n-butoxy) methyl] benzene, 4 , 4′-bis [(3-oxetanyl-n-butoxy) methyl] biphenyl, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane, 3-ethyl-3-hydroxymethyl
  • Examples thereof include oxetane, bis (1-ethyl (3-oxetanyl)) methyl ether, xylylene bisoxetane, 2-ethylhexyl oxetane, and dicyclopentadiene vinyl ether.
  • examples of the cationically polymerizable compound having a cationically polymerizable functional group other than the vinyl ether group and the oxetanyl group include cyclopentadiene, ⁇ -methylstyrene, p-methylstyrene, N-vinylpyrrolidone, tetrahydrofuran, and coumarone. .
  • the content of the cationically polymerizable compound (D) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the metal powder (A), and is 1 to 5 parts by mass. Is more preferable.
  • the content of the cationic polymerizable compound (D) is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin (B).
  • the conductive composition of the present invention preferably contains the phenoxy resin (E) because it is compatible with the above-described epoxy resin (B) and can obtain a stable paste state.
  • 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 (E) is preferably 10,000 or more, more preferably 20,000 or more, still more 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 (E) include bisphenol A type phenoxy resin and bisphenol F type phenoxy resin.
  • phenoxy resin (E) commercially available products can be used as the phenoxy resin (E).
  • phenoxy resin (E) specific examples thereof include bisphenol A type phenoxy resin (1256, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol A type phenoxy resin (YP-50).
  • the contact resistance of the current collecting electrode to be formed becomes low, and the adhesion to the transparent conductive layer and the like becomes better.
  • the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the metal powder (A).
  • the conductive composition of the present invention may contain a solvent (F) as necessary from the viewpoint of workability and the like.
  • 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) , Referred to as “aspect ratio”) can be adjusted to be large (for example, about 0.35 or more).
  • FIG. 1 the ratio of the height and width of the cross section of the electrode formed using the conductive composition of the present invention
  • 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 11, Comparative Examples 1 to 4 To the ball mill, 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.
  • the viscosity (mPa ⁇ s) described in the item of the cationically polymerizable compound is a rotary viscometer (RS-600, manufactured by HAAKE) as described above. It is a value measured at a shear rate of 400 (1 / s) after maintaining the temperature at C and controlling the temperature.
  • 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.)
  • Bisphenol A type epoxy resin B3-1 EP-4100E (epoxy equivalent: 190 g / eq, manufactured by ADEKA)
  • Bisphenol A type phenoxy resin E-1 Bisphenol A type phenoxy resin E-1
  • 1,4-butanediol divinyl ether BDVE (viscosity: 1.2 mPa ⁇ s, manufactured by Nippon Carbide)
  • Cationic curing agent Boron trifluoride ethylamine (manufactured by Stella Chemifa) ⁇ Solvent: Terpineol: Terpineol (manufactured by Yasuhara Chemical)

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PCT/JP2015/071925 2014-08-08 2015-08-03 導電性組成物、太陽電池セルおよび太陽電池モジュール WO2016021535A1 (ja)

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JP6705568B1 (ja) * 2019-02-13 2020-06-03 横浜ゴム株式会社 導電性組成物
WO2020166137A1 (ja) * 2019-02-13 2020-08-20 横浜ゴム株式会社 導電性組成物

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JPH01165654A (ja) * 1987-12-23 1989-06-29 Sumitomo Bakelite Co Ltd 導電性樹脂ペースト
JPH06157819A (ja) * 1992-11-26 1994-06-07 Nitto Denko Corp 光学材料用組成物
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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
JP6705568B1 (ja) * 2019-02-13 2020-06-03 横浜ゴム株式会社 導電性組成物
WO2020166137A1 (ja) * 2019-02-13 2020-08-20 横浜ゴム株式会社 導電性組成物

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