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WO2015118760A1 - Composition électroconductrice, cellule solaire, et module de cellule solaire - Google Patents

Composition électroconductrice, cellule solaire, et module de cellule solaire Download PDF

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Publication number
WO2015118760A1
WO2015118760A1 PCT/JP2014/082130 JP2014082130W WO2015118760A1 WO 2015118760 A1 WO2015118760 A1 WO 2015118760A1 JP 2014082130 W JP2014082130 W JP 2014082130W WO 2015118760 A1 WO2015118760 A1 WO 2015118760A1
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Prior art keywords
oxide
metal
conductive composition
metal oxide
powder
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English (en)
Japanese (ja)
Inventor
奈央 佐藤
石川　和憲
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Priority to JP2015561168A priority Critical patent/JPWO2015118760A1/ja
Publication of WO2015118760A1 publication Critical patent/WO2015118760A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/164—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells
    • H10F10/165—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells
    • H10F10/166—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells the Group IV-IV heterojunctions being heterojunctions of crystalline and amorphous materials, e.g. silicon heterojunction [SHJ] photovoltaic cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic 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 conductive composition, a solar battery cell used for a collector electrode using the conductive composition, and a solar battery module using the solar battery cell.
  • conductive particles such as silver particles and binders made of thermoplastic resin (for example, acrylic resin, vinyl acetate resin, etc.) or thermosetting resin (for example, epoxy resin, silicone resin, unsaturated polyester resin, etc.), organic
  • thermoplastic resin for example, acrylic resin, vinyl acetate resin, etc.
  • thermosetting resin for example, epoxy resin, silicone resin, unsaturated polyester resin, etc.
  • organic A conductive paste obtained by adding and mixing a solvent, a curing agent, a catalyst, etc. is printed on a substrate (for example, a silicon substrate, an epoxy resin substrate, etc.) so as to have a predetermined pattern.
  • a substrate for example, a silicon substrate, an epoxy resin substrate, etc.
  • a method of manufacturing a solar battery cell or a printed wiring board by forming electrodes and wirings by heating is known.
  • a conductive paste used for an electrode of a transparent conductive film which includes a binder resin, a conductive fine powder, and a solvent as essential components
  • the conductive fine powder is composed of 0.2 to 20% by mass of tin oxide fine powder and 99.8 to 80% by mass of fine silver powder
  • the binder resin is a copolymer of polyester resin, acrylic resin, phenol resin, vinyl chloride vinyl acetate.
  • a conductive paste for an electrode characterized in that " 1).
  • the present invention provides a conductive composition capable of forming an electrode having a low contact resistance against a transparent conductive layer or the like while maintaining a low volume resistivity, and a solar using the conductive composition as a collecting electrode It is an object to provide a battery cell and a solar battery module using the solar battery cell.
  • a low volume resistance is obtained by blending a metal powder (for example, silver powder) and a metal oxide (for example, tin oxide) with a fatty acid metal salt. It was found that an electrode having a low contact resistance with respect to the transparent conductive layer or the like was formed while maintaining the rate, and the present invention was completed. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the metal oxide (C) is at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide and titanium oxide;
  • the content of the fatty acid metal salt (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the metal powder (A),
  • the solar battery cell according to [7] comprising a transparent conductive layer as a base layer of the current collecting electrode.
  • 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 the conductive composition are collected.
  • a solar battery cell used for the electric electrode and a solar battery module using the solar battery cell can be provided.
  • the conductive composition of the present invention when used, an electrode having a low contact resistance against a transparent conductive layer or the like while maintaining a low volume resistivity even at low temperature (450 ° C. or less (particularly 200 ° C. or less)) firing. And the like can be formed, and the solar cell (especially a second preferred embodiment described later) has an effect of reducing damage caused by heat, which is very 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.
  • 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.
  • the conductive composition of the present invention contains a metal powder (A), a fatty acid metal salt (B), and a metal oxide (C).
  • the metal oxide (C) is at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide and titanium oxide, and the content of the fatty acid metal salt (B) is the metal
  • the amount of the metal oxide (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the metal powder (A).
  • the electroconductive composition of this invention may contain curable resin (D), the hardening
  • the contact resistance to the transparent conductive layer or the like is maintained while maintaining a low volume resistivity. It becomes an electroconductive composition which can form a low electrode etc.
  • This is not clear in detail, but is estimated to be as follows. First, as shown in Comparative Example 3 described later, when only the metal oxide (C) is added to the metal powder (A) without adding the fatty acid metal salt (B), the contact resistance is increased. I understand. This is presumably because the dispersibility of the metal oxide (C) is poor.
  • finger electrodes in recent solar cells are required to be thinned (for example, about 50 ⁇ m) from the viewpoint of improving the fill factor and reducing the amount of metal (mainly silver) paste used.
  • the dispersion of the compounding agent is important. Therefore, the conductive composition of the present invention in which the dispersibility of the metal oxide (C) is improved by blending the fatty acid metal salt (B) can suppress clogging of the screen printing mesh, and also has the above-mentioned required characteristics. It can respond and is extremely useful.
  • the metal powder (A), the fatty acid metal salt (B), the metal oxide (C), and other components that 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.
  • a metal material having an electrical resistivity of 20 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less can be used.
  • Specific examples of 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. Of these, silver powder and copper powder are preferable, and silver powder is more preferable because an electrode having a lower volume resistivity can be formed.
  • the metal powder (A) is preferably a metal powder having an average particle size of 0.5 to 10 ⁇ m because printability (particularly screen printability) is good.
  • the metal powders it is more preferable to use spherical silver particles and / or copper particles for the reason that an electrode having a lower volume resistivity can be formed.
  • the average particle diameter of the metal powder (A) refers to the average value of the particle diameter of the metal powder, and refers to the 50% volume cumulative diameter (D50) measured using a laser diffraction particle size distribution measuring apparatus.
  • 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 spherical shape refers to the shape of particles having a major axis / minor axis ratio of 2 or less.
  • the average particle diameter of the metal powder (A) is preferably 0.7 to 5.0 ⁇ m because the printability is better, and the sintering speed is appropriate and workability is improved. From the reason that the thickness is excellent, the thickness is more preferably 1.0 to 3.0 ⁇ m.
  • a commercial item can be used as said metal powder (A).
  • Specific examples of commercially available silver particles 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 Powder Co., Ltd.), AgC-103 (average particle size: 1.5 ⁇ m, Fukuda) Metal foil powder industry), EHD (average particle size: 0.5 ⁇ m, Mitsui Metals), and the like.
  • the fatty acid metal salt (B) contained in the conductive composition of the present invention 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, silver, magnesium, nickel, copper, zinc, yttrium, zirconium, tin, and It is preferable to use a carboxylic acid metal salt of at least one metal selected from the group consisting of lead.
  • a silver carboxylic acid metal salt hereinafter, also referred to as “carboxylic acid silver salt (B1)”.
  • a carboxylic acid silver salt of a metal other than silver is also referred to as “carboxylic acid metal salt (B2)”.
  • the carboxylic acid silver salt (B1) is not particularly limited as long as it is a silver salt of an organic carboxylic acid (fatty acid).
  • fatty acid fatty acid
  • Fatty acid metal salts particularly tertiary fatty acid silver salts
  • fatty acid silver salts described in paragraph [0030] of Japanese Patent No.
  • the volume resistivity of the formed electrode or the like is lower, and the contact resistance to the transparent conductive layer or the like is lower, so that the carboxylic acid silver salt (B1-1), carboxy, A carboxylic acid silver salt (B1-2) having at least one silver base (—COOAg) and one hydroxyl group (—OH), and two carboxy silver bases (—COOAg) having no hydroxyl group (—OH) It is preferable to use at least one kind of silver carboxylate selected from the group consisting of polycarboxylic acid silver salts (B1-3).
  • Examples of the carboxylic acid silver salt (B1-2) include compounds represented by any of the following formulas (I) to (III).
  • n represents an integer of 0 to 2
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents an alkylene group having 1 to 6 carbon atoms.
  • the plurality of R 2 may be the same or different
  • the plurality of R 1 may be the same or different.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • a plurality of R 1 may be the same or different.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 represents an alkylene group having 1 to 6 carbon atoms.
  • the plurality of R 1 may be the same or different.
  • Examples of the polycarboxylic acid silver salt (B1-3) include compounds represented by the following formula (IV).
  • m represents an integer of 2 to 6
  • R 4 represents an m-valent saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms
  • an m-valent unsaturated fat having 2 to 12 carbon atoms.
  • carboxylic acid silver salt (B1-1) examples include 2-methylpropanoic acid silver salt (also known as silver isobutyrate) and 2-methylbutanoic acid silver salt.
  • carboxylic acid silver salt (B1-2) examples include 2-hydroxyisobutyric acid silver salt and 2,2-bis (hydroxymethyl) -n-butyric acid silver salt.
  • polycarboxylic acid silver salt (B1-3) specifically, 1,3,5-pentanetricarboxylic acid silver salt, 1,2,3,4-butanetetracarboxylic acid silver salt and the like are preferable. Is exemplified.
  • the carboxylic acid metal salt (B2) is at least one selected from the group consisting of magnesium, nickel, copper, zinc, yttrium, zirconium, tin and lead, for example, organic carboxylic acids (fatty acids) as described above.
  • the metal salt of the above metal is mentioned.
  • organic carboxylic acid that forms the carboxylic acid metal salt (B2) examples include 2-methylpropanoic acid, 2-ethylhexanoic acid, octylic acid, naphthenic acid, and stearic acid. , Lauric acid and the like, and these may be used alone or in combination of two or more.
  • carboxylic acid metal salt (B2) specifically, for example, 2-methylpropanoic acid zinc salt
  • the content of the fatty acid metal salt (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the metal powder (A), and the dispersibility of the metal oxide (C) to be described later 1 to 10 parts by mass is more preferable because the contact resistance with respect to the transparent conductive layer and the like is further improved.
  • the metal oxide (C) used in the conductive composition of the present invention is at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide and titanium oxide.
  • said metal oxide (C) it is preferable that it is a tin oxide from the reason for which contact resistance with respect to a transparent conductive layer etc. becomes lower. Also, among tin oxides, the volume resistivity of the formed electrode or the like is lower, and the contact resistance to the transparent conductive layer or the like is lower, so that it is doped with a dopant (for example, antimony, phosphorus, etc.). More preferred is tin oxide. In addition, the doping with a dopant is preferably performed by doping up to about 0.1 to 20 parts by mass with respect to 100 parts by mass of tin oxide.
  • a dopant for example, antimony, phosphorus, etc.
  • the metal oxide (C) is a particulate material having an average particle diameter of 10 to 100 nm because the effect of adding the fatty acid metal salt (B), that is, the dispersibility of the metal oxide is more manifested. Of these, particles of 10 to 50 nm are more preferable.
  • the average particle diameter of the metal oxide (C) refers to the average value of the particle diameter of the metal oxide, and the 50% volume cumulative diameter (D50) measured using a laser diffraction particle size distribution measuring device.
  • the particle diameter that is 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, That diameter.
  • the metal oxide (C) has a BET specific surface area of 10 to 100 m 2 / g because of the effect of adding the fatty acid metal salt (B), that is, the dispersibility of the metal oxide. It is preferably 30 to 100 m 2 / g.
  • the BET specific surface area means a measured value measured using a BET method by nitrogen adsorption according to a test method defined in JIS K1477: 2007.
  • the shape of the metal oxide (C) is not particularly limited, but is preferably a particulate material having the above-described average particle diameter.
  • the volume resistivity of the formed electrode or the like is lower, and transparent
  • a core-shell structure having a core material and a coating material is more preferable because the contact resistance to the conductive layer or the like is lower.
  • the core material is not particularly limited, and only the coating material may be composed of the metal oxide.
  • the content of the metal oxide (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the metal powder (A), and the volume resistivity of the formed electrode or the like is higher.
  • the amount is more preferably 1 to 10 parts by mass because the contact resistance to the transparent conductive layer or the like becomes lower.
  • the fatty acid metal salt (B), the metal oxide (C), and the addition effect of the fatty acid metal salt (B) described above, that is, the dispersibility of the metal oxide is more expressed.
  • the mass ratio (fatty acid metal salt (B) / metal oxide (C)) is preferably 0.05 to 5, and more preferably 0.1 to 5.
  • thermosetting resin examples include epoxy resins, organopolysiloxanes, unsaturated polyester resins, and the like. These may be used alone or in combination of two or more. Good. Among these, the adhesion to the transparent conductive layer and the like is good, it is possible to form an electrode or the like having a lower contact resistance, the coating film strength is increased, and the strength of the formed electrode and the like is improved. An epoxy resin and / or an organopolysiloxane described later are preferable.
  • Epoxy resin is not particularly limited as long as it is a resin composed of a compound having two or more oxirane rings (epoxy groups) in one molecule, and generally has an epoxy equivalent of 90 to 2000.
  • 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, 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
  • bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable from the viewpoints of curability, heat resistance, durability, and cost.
  • organopolysiloxane refers to a polymer composed of one or more repeating units selected from the group consisting of the following four units.
  • R each independently represents a substituted or unsubstituted monovalent hydrocarbon group.
  • R include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group.
  • the alkenyl group include a vinyl group, a butenyl group, a pentenyl group, and an allyl group.
  • at least one of R is a vinyl group because of its high activity and high reactivity.
  • the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like. Among them, for the reason that the adhesion to the transparent conductive layer is good due to the ⁇ - ⁇ interaction, It is preferred that at least one of R is a phenyl group.
  • the organopolysiloxane (B) is represented by at least the above formula (S-3) because it has good adhesion to the transparent conductive layer and can form an electrode having a lower contact resistance. It is preferably a silicone resin having a T unit or a Q unit represented by the above formula (S-4), that is, a crosslinked resin.
  • the content when the curable resin (D) is contained is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the metal powder (A), and preferably 2 to 15 parts by mass. More preferably, it is 2 to 10 parts by mass.
  • the conductive composition of the present invention contains an epoxy resin or an organopolysiloxane having an epoxy group as the curable resin (D), the conductive composition preferably contains those curing agents (E).
  • the curing agent (E) for example, it is preferable to use a complex of boron trifluoride and an amine compound described in detail below.
  • a complex of boron trifluoride and an amine compound a complex of boron trifluoride and an aliphatic amine (aliphatic primary amine, aliphatic secondary amine, aliphatic tertiary amine), trifluoride
  • examples thereof include a complex of boron and an alicyclic amine, a complex of boron trifluoride and an aromatic amine, a complex of boron trifluoride and a heterocyclic amine, and the like.
  • the heterocyclic amine may be an alicyclic heterocyclic amine (hereinafter also referred to as “alicyclic heterocyclic amine”) or an aromatic heterocyclic amine (hereinafter referred to as “aromatic heterocyclic amine”).
  • aliphatic primary amine examples include methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-hexylamine, n-octylamine, 2 -Ethylhexylamine, laurylamine and the like.
  • aliphatic secondary amine examples include dimethylamine, diethylamine, methylethylamine, methylpropylamine, di-iso-propylamine, di-n-propylamine, ethylpropylamine, di-n-butylamine, di- Examples include iso-butylamine, dipropenylamine, chlorobutylpropylamine, di (chlorobutyl) amine, di (bromoethyl) amine and the like.
  • Specific examples of the aliphatic tertiary amine include trimethylamine, triethylamine, tributylamine, triethanolamine and the like.
  • alicyclic amine examples include cyclohexylamine.
  • aromatic amines include benzylamine.
  • alicyclic heterocyclic amine examples include pyrrolidine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, piperazine, and homopiperazine.
  • aromatic heterocyclic amine examples include pyridine, pyrrole, imidazole, pyridazine, pyrimidine, quinoline, triazine, tetrazine, isoquinoline, quinazoline, naphthyridine, pteridine, acridine, phenazine and the like.
  • the curing agent (E) has a lower volume resistivity and can form an electrode having a lower contact resistance with respect to the transparent conductive layer, etc., so that boron trifluoride piperidine, boron trifluoride ethylamine and trifluoride are used.
  • a complex selected from the group consisting of borohydride triethanolamine is preferred.
  • the content of the curing agent (E) is lower than the volume resistivity and can form an electrode having a lower contact resistance with respect to the transparent conductive layer, etc., so that the amount of the metal powder (A) is 100 parts by mass.
  • the amount is preferably 0.1 to 1 part 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 manufacturing method of the electroconductive composition of this invention is not specifically limited,
  • curing agent (E), the said solvent (F), etc. with a roll, a kneader, an extruder, a universal stirrer etc. is mentioned.
  • 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 the coating film formed in the wiring forming step.
  • the heat treatment is not particularly limited as long as it is at a temperature of 450 ° C. or lower, but it is preferably a heat treatment (baking) at a temperature of 150 to 350 ° C. for several seconds to several tens of minutes.
  • a heat treatment at a temperature of 150 to 350 ° C. for several seconds to several tens of minutes.
  • an electrode can be easily formed even when an antireflection film is formed on a silicon substrate.
  • the electrically conductive composition of this invention is used, even if it is a comparatively low temperature of 450 degrees C or less, it is favorable heat processing (baking). 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 cell (for example, a heterojunction solar cell) 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. Below, the 2nd suitable aspect of the photovoltaic cell of this invention is demonstrated using FIG.
  • 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, and the like.
  • ITO indium tin oxide
  • 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.
  • volume resistivity, contact resistance, and fill factor (FF) of each prepared conductive composition were evaluated by the following methods.
  • ITO indium oxide doped with Sn
  • AZO Al-doped ZnO
  • TLM Transfer Length Method
  • Metal powder Silver powder (AG4-8F, average particle size: 2.2 ⁇ m, manufactured by DOWA Electronics)
  • Silver salt of 2-methylpropanoate First, 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) are put into a ball mill and are allowed to stand at room temperature for 24 hours. The reaction was allowed to stir. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white 2-methylpropanoic acid silver salt.
  • MEK methyl ethyl ketone
  • Neodecanoic acid silver salt First, 50 g of silver oxide (manufactured by Toyo Kagaku Co., Ltd.), 74.3 g of neodecanoic acid (manufactured by Toyo Gosei Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are put into a ball mill and stirred at room temperature for 24 hours. Reacted. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare a white silver neodecanoate.
  • MEK methyl ethyl ketone
  • Silver stearate First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 122.7 g of stearic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are put into a ball mill and stirred at room temperature for 24 hours. Was reacted. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to obtain white silver stearate.
  • MEK methyl ethyl ketone
  • Silver salt of 2-hydroxyisobutyrate First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 45 g of 2-hydroxyisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are put into a ball mill and are allowed to stand at room temperature for 24 hours. The reaction was allowed to stir. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white 2-hydroxyisobutyric acid silver salt.
  • MEK methyl ethyl ketone
  • -1,2,3,4-butanetetracarboxylic acid silver salt First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 1,2,3,4-butanetetracarboxylic acid (manufactured by Shin Nippon Rika Co., Ltd.) 29 g 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 white 1,2,3,4-butanetetracarboxylic acid silver salt.
  • MEK methyl ethyl ketone
  • -Silver maleate First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 25.05 g of maleic acid (manufactured by Kanto 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. Reacted. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare a white silver maleate.
  • MEK methyl ethyl ketone
  • Silver salt of glutarate First, 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 57 g of glutaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are charged into a ball mill and reacted by stirring at room temperature for 24 hours. I let you. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white silver glutarate.
  • MEK methyl ethyl ketone
  • Zinc 2-methylpropanoate First, 50 g of zinc oxide (manufactured by Kanto Chemical Co., Ltd.), 54.11 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 allowed to stand at room temperature for 24 hours. The reaction was allowed to stir. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white 2-methylpropanoic acid zinc salt.
  • MEK methyl ethyl ketone
  • 2-methylpropanoic acid 2-methylpropanoic acid (manufactured by Kanto Chemical Co., Inc.)
  • -Tin oxide 1-5 Commercial products listed in Table 1-Curing resin: Bisphenol A type epoxy resin (YD-019, epoxy equivalent: 2400-3300 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
  • Curing agent Boron trifluoride ethylamine (manufactured by Stella Chemifa)
  • Solvent ⁇ -terpineol (manufactured by Yasuhara Chemical)
  • Comparative Example 1 prepared without blending the fatty acid metal salt (B) and the metal oxide (C) had high volume resistivity and poor contact resistance.
  • Comparative Example 2 prepared without mix
  • blending a fatty-acid metal salt (B) is an example corresponded to the electrically conductive paste described in patent document 1 (patent 5169501), and has a high volume resistivity, contact. It turns out that resistance is inferior.
  • the contact resistance of Comparative Example 4 prepared by blending a fatty acid not corresponding to the fatty acid metal salt (B) was slightly improved as compared with Comparative Example 3, it was found that it was not sufficient.
  • the conductive compositions of Examples 1 to 12 prepared by blending a predetermined amount of the fatty acid metal salt (B) and the metal oxide (C) with the metal powder (A) all have a low volume. It has been found that the contact resistance is lowered while maintaining the resistivity.
  • the conductive compositions of Examples 9 to 12 prepared by blending tin oxides 3 to 5 in which the average particle diameter of the metal oxide (C) is in the range of 10 to 100 nm are more than the other examples. It has been found that the contact resistance is lower.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)

Abstract

　La présente invention concerne une composition électroconductrice permettant de former une électrode ou analogue ayant une faible résistance de contact contre une couche électroconductrice transparente ou analogue tout en maintenant une faible résistivité transversale, une cellule solaire dans laquelle la composition électroconductrice est utilisée dans une électrode collectrice, et un module de cellule solaire dans lequel la cellule solaire est utilisée. Cette composition électroconductrice contient une poudre métallique (A), un sel métallique d'acide gras (B), et un oxyde métallique (C). L'oxyde métallique (C) est au moins un composant choisi dans le groupe constitué d'oxyde d'étain, d'oxyde d'indium, d'oxyde de zinc, et d'oxyde de titane. La teneur en sel métallique d'acide gras (B) est de 0,1 à 20 parties en masse pour 100 parties en masse de la poudre métallique (A). La teneur en oxyde métallique (C) est de 0,1 à 20 parties en masse pour 100 parties en masse de la poudre métallique (A). La cuisson est effectuée à une température inférieure ou égale à 450 °C.
PCT/JP2014/082130 2014-02-06 2014-12-04 Composition électroconductrice, cellule solaire, et module de cellule solaire Ceased WO2015118760A1 (fr)

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WO2019192847A1 (fr) 2018-04-04 2019-10-10 Huntsman Advanced Materials Licensing (Switzerland) Gmbh Composition d'accélérateur pour le durcissement de résines époxy avec des amines aromatiques

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JP2012038846A (ja) * 2010-08-05 2012-02-23 Yokohama Rubber Co Ltd:The 太陽電池電極用ペーストおよび太陽電池セル
JP2012178456A (ja) * 2011-02-25 2012-09-13 Yokohama Rubber Co Ltd:The 太陽電池集電電極形成用導電性組成物および太陽電池セル
JP2012238827A (ja) * 2011-04-25 2012-12-06 Yokohama Rubber Co Ltd:The 太陽電池集電電極形成用導電性組成物および太陽電池セル
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WO2007125879A1 (fr) * 2006-04-25 2007-11-08 Sharp Corporation Pate electroconductrice pour electrode a batterie solaire
JP2012038846A (ja) * 2010-08-05 2012-02-23 Yokohama Rubber Co Ltd:The 太陽電池電極用ペーストおよび太陽電池セル
JP2012178456A (ja) * 2011-02-25 2012-09-13 Yokohama Rubber Co Ltd:The 太陽電池集電電極形成用導電性組成物および太陽電池セル
JP2012238827A (ja) * 2011-04-25 2012-12-06 Yokohama Rubber Co Ltd:The 太陽電池集電電極形成用導電性組成物および太陽電池セル
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Publication number Priority date Publication date Assignee Title
CN114946039A (zh) * 2020-02-14 2022-08-26 硕禾电子材料股份有限公司 用于异质结太阳能电池的导电糊膏、异质结太阳能电池与电极结构

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