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WO2017135138A1 - Poudre de cuivre revêtue d'argent et son procédé de fabrication - Google Patents

Poudre de cuivre revêtue d'argent et son procédé de fabrication Download PDF

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Publication number
WO2017135138A1
WO2017135138A1 PCT/JP2017/002676 JP2017002676W WO2017135138A1 WO 2017135138 A1 WO2017135138 A1 WO 2017135138A1 JP 2017002676 W JP2017002676 W JP 2017002676W WO 2017135138 A1 WO2017135138 A1 WO 2017135138A1
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Prior art keywords
silver
copper powder
coated copper
coated
containing layer
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PCT/JP2017/002676
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English (en)
Japanese (ja)
Inventor
洋 神賀
徳昭 野上
愛子 平田
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Dowa Electronics Materials Co Ltd
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Dowa Electronics Materials Co Ltd
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Priority claimed from JP2016227021A external-priority patent/JP6811080B2/ja
Application filed by Dowa Electronics Materials Co Ltd filed Critical Dowa Electronics Materials Co Ltd
Priority to KR1020187020738A priority Critical patent/KR102446790B1/ko
Priority to CN201780008234.2A priority patent/CN108495728B/zh
Priority to US16/071,578 priority patent/US10580910B2/en
Publication of WO2017135138A1 publication Critical patent/WO2017135138A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • 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

Definitions

  • the present invention relates to a silver-coated copper powder and a method for producing the same, and more particularly to a silver-coated copper powder used for a conductive paste and the like and a method for producing the same.
  • conductive pastes prepared by blending a conductive metal powder such as silver powder or copper powder with a solvent, resin, dispersant, etc. have been used. .
  • silver powder has a very small volume resistivity and is a good conductive material, it is a noble metal powder, so that the cost is high.
  • copper powder has a low volume resistivity and is a good conductive material.
  • it since it is easily oxidized, it has poor storage stability (reliability) compared to silver powder.
  • JP 2010-174411 A (paragraph number 0003) JP 2010-077745 (paragraph number 0006)
  • the present invention improves the conversion efficiency of solar cells over conventional silver-coated copper powder when used as a conductive paste for forming bus bar electrodes of solar cells.
  • An object of the present invention is to provide a silver-coated copper powder and a method for producing the same, which can produce a solar cell having a high conversion efficiency equivalent to that when silver powder is used.
  • the inventors of the present invention added copper powder having a surface coated with a silver-containing layer to a cyanide solution, and added cyan to the copper powder coated with the silver-containing layer.
  • the conversion efficiency of solar cells is improved over conventional silver-coated copper powder, and conversion is as high as when silver powder is used.
  • the present inventors have found that silver-coated copper powder can be produced, which can produce a solar cell having efficiency, and the present invention has been completed.
  • the silver-containing layer is preferably a layer made of silver or a silver compound, more preferably the silver-containing layer is a layer made of silver, and in this case, the cyan content is It is preferably 3 to 10 ppm.
  • the quantity of the silver containing layer with respect to silver covering copper powder is 5 mass% or more, and it is preferable that the copper powder coat
  • the cyan compound solution is preferably composed of a cyan silver potassium solution, a cyan gold potassium solution, a potassium cyanide solution or a sodium cyanide solution.
  • cumulative 50% particle diameter measured by a laser diffraction type particle size distribution apparatus copper powder (D 50 diameter) is preferably from 0.1 ⁇ 15 [mu] m.
  • phytic acid or azoles may be attached as a surface treatment agent to the surface of the copper powder coated with the silver-containing layer.
  • the silver-coated copper powder according to the present invention is a silver-coated copper powder comprising a copper powder coated on the surface with a silver-containing layer, and the amount of cyan in the silver-coated copper powder is 3 to 3000 ppm.
  • the silver-containing layer is preferably a layer made of silver or a silver compound, and the silver-containing layer is more preferably a layer made of silver.
  • the cyan content is 3 to 10 ppm. Is preferred.
  • the quantity of the silver content layer with respect to silver covering copper powder is 5 mass% or more.
  • the 50% cumulative particle diameter measured by a laser diffraction type particle size distribution apparatus copper powder is preferably from 0.1 ⁇ 15 [mu] m. Furthermore, it is preferable that the carbon content and the nitrogen content in the silver-coated copper powder are each 0.04% by mass or more. Moreover, phytic acid or azoles may adhere to the surface of the copper powder coated with the silver-containing layer as a surface treatment agent.
  • the conductive paste according to the present invention is characterized by using the above silver-coated copper powder as a conductor.
  • the conductive paste according to the present invention includes a solvent and a resin, and includes the above silver-coated copper powder as a conductive powder.
  • the method for manufacturing an electrode for solar cell according to the present invention is characterized in that the electrode is formed on the surface of the substrate by applying the conductive paste to the substrate and then curing it.
  • the conversion efficiency of the solar cell is improved as compared with the case where silver powder is used compared with conventional silver-coated copper powder.
  • Silver-coated copper powder capable of producing a solar cell having conversion efficiency can be produced.
  • FIG. 6 is a graph showing the relationship between the number of times the solar cells fabricated in Examples 4 to 7 and Comparative Example 5 are irradiated with light and the power generation efficiency Eff.
  • copper powder whose surface is coated with a silver-containing layer is added to a cyanide solution, and the copper powder coated with the silver-containing layer is added to 3 to 3000 ppm ( Preferably 3 to 1000 ppm, more preferably 3 to 100 ppm, more preferably 3 to 10 ppm, and most preferably 4 to 9 ppm) cyan (CN).
  • 3 to 3000 ppm Preferably 3 to 1000 ppm, more preferably 3 to 100 ppm, more preferably 3 to 10 ppm, and most preferably 4 to 9 ppm
  • CN cyan
  • the silver-containing layer is preferably a layer made of silver or a silver compound, and more preferably a layer (silver layer) made of 90% by mass or more of silver.
  • the coating amount of the silver-containing layer with respect to the silver-coated copper powder is preferably 5% by mass or more, more preferably 7 to 50% by mass, further preferably 8 to 40% by mass, and 9 to 20%. Most preferred is mass%. If the coating amount of the silver-containing layer is less than 5% by mass, the conductivity of the silver-coated copper powder is adversely affected. On the other hand, if it exceeds 50 mass%, the cost increases due to an increase in the amount of silver used, which is not preferable.
  • the cyanide solution is a solution that can contain cyan (or adsorb cyan on the surface of the copper powder coated with the silver-containing layer) to the copper powder coated with the silver-containing layer and does not dissolve the silver-containing layer.
  • cyanide compound solution a cyanogen gold potassium solution, a cyanogen silver potassium solution, a potassium cyanide solution, a sodium cyanide solution, or the like can be used.
  • gold or silver can be supported on the exposed portion of the copper powder not covered with the silver-containing layer of the silver-coated copper powder.
  • a surface treatment agent to the surface of the silver-coated copper powder.
  • the surface treatment agent phytic acid and azoles such as benzotriazole are preferably used.
  • an aqueous solution or an alcohol solution of the surface treatment agent while stirring the silver-coated copper powder in a slurry state.
  • the adhesion amount of the surface treatment agent is preferably 0.01 to 1.5% by mass, and more preferably 0.05 to 1.0% by mass with respect to the silver-coated copper powder.
  • Particle size of the copper powder is a is preferably 50% cumulative particle diameter measured by (Heroes method by) a laser diffraction type particle size distribution apparatus (D 50 diameter) is 0.1 ⁇ 15 ⁇ m, 0.3 ⁇ 10 ⁇ m More preferably, the thickness is 1 to 5 ⁇ m.
  • D 50 diameter a cumulative 50% particle diameter of less than 0.1 ⁇ m is not preferable because it adversely affects the conductivity of the silver-coated copper powder. On the other hand, if it exceeds 15 ⁇ m, it is not preferable because formation of fine wiring becomes difficult.
  • Copper powder may be manufactured by wet reduction, electrolysis, vapor phase, etc., but rapidly solidifies by dissolving copper above the melting temperature and colliding with high-pressure gas or high-pressure water while dropping from the bottom of the tundish. It is preferable to produce by a so-called atomizing method (such as a gas atomizing method or a water atomizing method) to obtain a fine powder.
  • a so-called atomizing method such as a gas atomizing method or a water atomizing method
  • copper powder having a small particle diameter can be obtained. Therefore, when copper powder is used in a conductive paste, the conductivity is improved by increasing the contact points between the particles. Can be achieved.
  • a method of coating copper powder with a silver-containing layer use a method of depositing silver or a silver compound on the surface of copper powder by a reduction method using a substitution reaction of copper and silver or a reduction method using a reducing agent.
  • a method of precipitating silver or a silver compound on the surface of a copper powder while stirring a solution containing copper powder and silver or a silver compound in a solvent, or a solution containing a copper powder and an organic substance in a solvent and a solvent For example, a method of precipitating silver or a silver compound on the surface of the copper powder while mixing and stirring a solution containing silver or a silver compound and an organic substance can be used.
  • the silver-containing layer tends to be non-uniform, so use a solution containing cyan when coating copper powder with a silver-containing layer.
  • the silver-coated copper powder before silver is supported does not contain cyan.
  • water As this solvent, water, an organic solvent, or a mixture of these can be used.
  • a mixed solvent of water and organic solvent it is necessary to use an organic solvent that becomes liquid at room temperature (20 to 30 ° C.).
  • the mixing ratio of water and organic solvent depends on the organic solvent used. It can be adjusted appropriately.
  • water used as a solvent distilled water, ion-exchanged water, industrial water, or the like can be used as long as there is no fear that impurities are mixed therein.
  • silver nitrate Since silver ions need to be present in the solution as a raw material for the silver-containing layer, it is preferable to use silver nitrate having high solubility in water and many organic solvents.
  • silver nitrate is dissolved in a solvent (water, organic solvent or a mixture of these) instead of solid silver nitrate. It is preferred to use a solution.
  • the amount of silver nitrate solution used, the concentration of silver nitrate in the silver nitrate solution, and the amount of organic solvent can be determined according to the amount of the target silver-containing layer.
  • a chelating agent may be added to the solution.
  • the chelating agent it is preferable to use a chelating agent having a high complex stability constant with respect to copper ions or the like so that copper ions or the like by-produced by substitution reaction between silver ions and metallic copper do not reprecipitate.
  • the copper powder serving as the core of the silver-coated copper powder contains copper as a main component, it is preferable to select a chelating agent while paying attention to the complex stability constant with copper.
  • a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriamine, triethylenediamine, and salts thereof can be used as the chelating agent.
  • a pH buffer may be added to the solution.
  • this pH buffering agent ammonium carbonate, ammonium hydrogen carbonate, aqueous ammonia, sodium hydrogen carbonate, or the like can be used.
  • the reaction temperature during the silver coating reaction may be any temperature that does not cause the reaction solution to solidify or evaporate, but is preferably set in the range of 10 to 40 ° C, more preferably 15 to 35 ° C.
  • the reaction time varies depending on the coating amount of silver or silver compound and the reaction temperature, but can be set in the range of 1 minute to 5 hours.
  • the embodiment of the silver-coated copper powder according to the present invention is a silver-coated copper powder comprising a copper powder whose surface is coated with a silver-containing layer, and the amount of cyan in the silver-coated copper powder (according to JIS K0102).
  • the amount of cyan determined by performing pretreatment and analysis by pyridine-pyrazolone spectrophotometry is 3 to 3000 ppm (preferably 3 to 1000 ppm, more preferably 3 to 100 ppm, more preferably 3 to 10 ppm, most preferably 4-9 ppm).
  • the silver-containing layer is preferably a layer made of silver or a silver compound, more preferably a layer (silver layer) made of 90% by mass or more of silver.
  • the coating amount of the silver-containing layer with respect to the silver-coated copper powder is preferably 5% by mass or more, more preferably 7 to 50% by mass, further preferably 8 to 40% by mass, and 9 to 20%. Most preferred is mass%.
  • the 50% cumulative particle diameter measured by a laser diffraction type particle size distribution apparatus copper powder (D 50 diameter) is preferably from 0.1 ⁇ 15 [mu] m.
  • the carbon content and the nitrogen content in the silver-coated copper powder are each 0.04% by mass or more.
  • the carbon content and nitrogen content in the silver-coated copper powder are preferably 1% by mass or less, and more preferably 0.3% by mass.
  • the surface treating agent has adhered to the surface of the copper powder coat
  • the surface treatment agent phytic acid and azoles such as benzotriazole are preferably used.
  • the adhesion amount of the surface treatment agent is preferably 0.01 to 1.5% by mass, and more preferably 0.05 to 1.0% by mass with respect to the silver-coated copper powder.
  • the silver-coated copper powder of the embodiment described above can be produced by the method for producing the silver-coated copper powder of the embodiment described above.
  • the substantially spherical shape or flake shape may be sufficient as the shape of the copper powder (silver covering copper powder) coat
  • the embodiment of the conductive paste according to the present invention can be manufactured.
  • This conductive paste may contain a solvent and a resin. This solvent can be appropriately selected according to the purpose of use of the conductive paste.
  • butyl carbitol acetate BCA
  • butyl carbitol BC
  • ethyl carbitol acetate ECA
  • ethyl carbitol EC
  • toluene methyl ethyl ketone, methyl isobutyl ketone, tetradecane, tetralin, propyl alcohol, isopropyl alcohol
  • One or more solvents can be selected and used from dihydroterpineol, dihydroterpineol acetate, ethyl carbitol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (texanol), and the like.
  • the resin contained in the conductive paste can be appropriately selected according to the purpose of use of the conductive paste.
  • cellulose derivatives such as methyl cellulose and ethyl cellulose, acrylic resin, alkyd resin, polypropylene resin, polyurethane resin, rosin resin, terpene resin, phenol resin, aliphatic petroleum resin, acrylate resin, xylene resin, coumarone indene resin
  • styrene resin dicyclopentadiene resin, polybutene resin, polyether resin, urea resin, melamine resin, vinyl acetate resin, polyisobutyl resin, olefinic thermoplastic elastomer (TPO), epoxy resin, polyester resin, etc.
  • the resins can be selected and used. Of these resins, it is preferable to use a heat-resistant resin such as ethyl cellulose, a naphthalene type epoxy resin (such as a naphthalene skeleton type tetrafunctional epoxy resin), a polyamideimide resin, or a phenol novolac resin.
  • the conductive paste may contain other components such as a surfactant, a dispersant, a rheology modifier, a silane coupling agent, and an ion collector.
  • the bus bar electrode of the solar cell is formed using the conductive paste of the above-described embodiment, the power generation efficiency of the solar cell can be improved as compared with the case where the conventional silver-coated copper powder is used.
  • a surface treatment agent is attached to the surface of silver-coated copper powder containing cyan (copper powder whose surface is coated with a silver-containing layer), the change in oxidation resistance of the silver-coated copper powder is suppressed, and the solar cell When used for forming the bus bar electrode, it is possible to suppress an increase in resistance of the electrode and suppress a decrease in power generation efficiency.
  • Example 1 A commercially available copper powder manufactured by the atomizing method (Atomized copper powder SF-Cu 5 ⁇ m manufactured by Nippon Atomizing Co., Ltd.) was prepared, and the particle size distribution of this copper powder (before silver coating) was determined.
  • the cumulative 10% particle diameter (D 10 ) was 2.26 ⁇ m
  • the cumulative 50% particle diameter (D 50 ) was 5.20 ⁇ m
  • the cumulative 90% particle diameter (D 90 ) was 9.32 ⁇ m.
  • the particle size distribution of the copper powder was measured with a laser diffraction particle size distribution device (Microtrack particle size distribution measurement device MT-3300 manufactured by Nikkiso Co., Ltd.), and the accumulated particle size was 10% (D 10 ) and accumulated 50% particle.
  • the diameter (D 50 ) and the cumulative 90% particle diameter (D 90 ) were determined.
  • solution 1 in which 112.6 g of EDTA-4Na (43%) and 9.1 g of ammonium carbonate are dissolved in 1440 g of pure water, 735 g of EDTA-4Na (43%) and 175 g of ammonium carbonate are dissolved in 1134 g of pure water.
  • solution 2 obtained by adding 120.9 g of an aqueous silver nitrate solution containing 38.9 g of silver to the prepared solution was prepared.
  • the silver supporting liquid As the silver supporting liquid, 2.95 mL of silver supporting liquid separated from an aqueous solution containing 100 g / L potassium cyanogen silver, 80 g / L potassium pyrophosphate and 35 g / L boric acid was used. Further, the concentrations of Ag and Cu in the filtrate were measured by an ICP mass spectrometer (ICP-MS), and were 2 mg / L and 65 mg / L, respectively.
  • ICP-MS ICP mass spectrometer
  • the silver-coated copper powder thus obtained (with silver supported on the surface) was dissolved in aqua regia, silver was recovered as silver chloride by adding pure water and filtering, and thus When the content of Ag was determined from the recovered silver chloride by a weight method, the Ag content in the silver-coated copper powder was 10.77% by mass.
  • the content of Ag in the silver-coated copper powder of Comparative Example 1 described later (a silver-coated copper powder that is not added to the silver-carrying liquid and does not carry silver on the surface) is 10.14% by mass.
  • the carbon content, nitrogen content, oxygen content and cyan content in this silver-coated copper powder are determined, and the particle size distribution and BET specific surface area of the silver-coated copper powder are determined. It was.
  • the carbon content is measured with a carbon / sulfur analyzer (EMIA-810W manufactured by Horiba, Ltd.), and the nitrogen content and oxygen content are measured with an oxygen / nitrogen / hydrogen analyzer (manufactured by LECO Japan LLC). did.
  • EMIA-810W carbon / sulfur analyzer
  • oxygen / nitrogen / hydrogen analyzer manufactured by LECO Japan LLC
  • the amount of cyan (CN-) 1 g of silver-coated copper powder was weighed and placed in a distillation flask, and 250 mL of water was added and distilled, and pretreatment (all cyan) was performed in accordance with JIS K0102. It was determined by analyzing by pyridine-pyrazolone spectrophotometry. As a result, the amount of cyan in the silver-coated copper powder was 1400 ppm.
  • the particle size distribution was measured with a laser diffraction particle size distribution device (Microtrack particle size distribution measurement device MT-3300 manufactured by Nikkiso Co., Ltd.). As a result, the accumulated 10% particle diameter (D 10 ) of the silver-coated copper powder was 2.5 ⁇ m, the accumulated 50% particle diameter (D 50 ) was 5.0 ⁇ m, and the accumulated 90% particle diameter (D 90 ) was 10.0 ⁇ m. there were.
  • a laser diffraction particle size distribution device Microtrack particle size distribution measurement device MT-3300 manufactured by Nikkiso Co., Ltd.
  • the BET specific surface area was measured by a BET single point method using a BET specific surface area measuring device (4 Sorb US manufactured by Yuasa Ionics Co., Ltd.). As a result, the BET specific surface area of the silver-coated copper powder was 0.29 m 2 / g.
  • the silver powder was subjected to a surface smoothing treatment with a Henschel mixer (high-speed stirrer) and then classified to remove silver aggregates larger than 11 ⁇ m.
  • the water washing was performed until the solid content obtained by filtration was poured with pure water until the potential of the liquid after the water washing was 0.5 mS / m or less.
  • each conductive paste 1 (conductive paste 1 obtained from silver-coated copper powder) was applied to a surface of each silicon wafer by a screen printer (MT-320T manufactured by Microtech Co., Ltd.) with a width of 1.3 mm. After printing in the shape of the three bus bar electrodes, a solar cell was produced by drying and curing at 200 ° C. for 40 minutes with a hot air dryer.
  • a battery characteristic test was performed by irradiating the above-mentioned solar battery with pseudo-sunlight having a light irradiation energy of 100 mW / cm 2 using a xenon lamp of a solar simulator (manufactured by Wacom Denso Co., Ltd.).
  • the current (short-circuit current) Isc flowing between the two terminals when the output terminal of the solar cell is short-circuited is 8.651 A
  • the voltage (open-circuit voltage) Voc between the two terminals when the output terminal of the solar cell is opened is 8.651 A, and the voltage (open-circuit voltage) Voc between the two terminals when the output terminal of the solar cell is opened.
  • Example 2 1.4633 g of cyanogen potassium potassium (manufactured by Kojima Chemical Co., Ltd.), 0.8211 g of anhydrous citric acid (manufactured by Wako Pure Chemical Industries, Ltd.), 0.1708 g of L-aspartic acid (manufactured by Wako Pure Chemical Industries, Ltd.), Then, 0.9998 g of tripotassium citrate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 100 g of pure water and stirred at 30 ° C. for 11 minutes to prepare a gold plating solution.
  • the amount of the filtrate was 650 g, and the concentrations of Au, Ag, and Cu in the filtrate were measured by the same method as in Example 1. As a result, they were 2 mg / L, less than 1 mg / L, and 150 mg / L, respectively. It was.
  • the silver-coated copper powder (having gold supported on the surface) thus obtained is dissolved in aqua regia, silver is recovered as silver chloride by adding pure water and filtering the filtrate.
  • the content of Au was measured by an ICP mass spectrometer (ICP-MS) and the content of Ag was determined from the recovered silver chloride by a gravimetric method.
  • the content of Au in the silver-coated copper powder was 0.10 mass. %, And the Ag content was 10.04% by mass.
  • the carbon content, nitrogen content, oxygen content and cyan content in the silver-coated copper powder were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined.
  • the carbon content in the silver-coated copper powder was 0.04 mass%
  • the nitrogen content was 0.18 mass%
  • the oxygen content was 0.08 mass%
  • the amount of cyan in the silver-coated copper powder was 220 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.5 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 5.0 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 10.0 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.34 m 2 / g.
  • a solar cell was produced by the same method as in Example 1 except that the conductive paste 1 obtained from the obtained silver-coated copper powder (having gold supported on the surface) was used.
  • a test was conducted. As a result, the short circuit current Isc is 8.670 A, the open circuit voltage Voc is 0.629 V, the current density Jsc is 0.0363 A / cm 2 , the fill factor FF is 88.11, the power generation efficiency Eff is 20.12%, and the series resistance Rs was 0.0042 ⁇ / ⁇ .
  • Example 3 The silver-coated copper powder (before the silver was supported on the surface) obtained by the same method as in Example 1 (sodium-coated copper powder) was immersed in an aqueous NaCN solution containing 1000 ppm of cyan (CN) for 30 minutes. After that, it is filtered while applying extruded water, and the solid matter on the filter paper is washed with pure water (until the potential of the liquid after washing becomes 0.5 mS / m or less), and is then washed at 70 ° C. with a vacuum dryer. It was dried for 5 hours to obtain a silver-coated copper powder having CN adsorbed on its surface.
  • CN cyan
  • the silver-coated copper powder thus obtained (with CN adsorbed on the surface) was dissolved in aqua regia, silver was recovered as silver chloride by adding pure water and filtering, and thus When the content of Ag was determined from the recovered silver chloride by a weight method, the Ag content in the silver-coated copper powder was 10.14% by mass.
  • the carbon content, nitrogen content, oxygen content, and cyan content in this silver-coated copper powder were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined.
  • the carbon content in the silver-coated copper powder was 0.05% by mass
  • the nitrogen content was 0.06% by mass
  • the oxygen content was 0.12% by mass
  • the amount of cyan in the silver-coated copper powder was 620 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 3.0 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 6.2 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 10.3 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.32 m 2 / g.
  • a solar cell was produced in the same manner as in Example 1 except that the conductive paste 1 obtained from the obtained silver-coated copper powder (with CN adsorbed on the surface) was used, and its battery characteristics were obtained.
  • a test was conducted. As a result, the short-circuit current Isc is 8.885 A, the open circuit voltage Voc is 0.626 V, the current density Jsc is 0.0372 A / cm 2 , the fill factor FF is 87.02, the power generation efficiency Eff is 20.25%, and the series resistance Rs was 0.0042 ⁇ / ⁇ .
  • Example 1 The silver-coated copper powder (before the silver was supported on the surface) obtained by the same method as in Example 1 (copper powder coated with silver) was dissolved in aqua regia, and then purified water was added and filtered. Thus, silver was recovered as silver chloride, and the Ag content in the silver-coated copper powder was 10.14% by mass when the Ag content was determined from the silver chloride thus recovered by a weight method.
  • the carbon content, nitrogen content, oxygen content and cyan content in the silver-coated copper powder were determined, and the particle size distribution and BET specific surface area of the silver-coated copper powder were determined. It was. As a result, the carbon content in the silver-coated copper powder is 0.02% by mass, the nitrogen content is 0.007% by mass, the oxygen content is 0.08% by mass, and the amount of cyan in the silver-coated copper powder was 0 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.5 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 5.2 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 10.1 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.31 m 2 / g.
  • a solar cell was produced in the same manner as in Example 1 except that the conductive paste 1 obtained from the obtained (copper powder coated with silver) silver-coated copper powder was used.
  • a test was conducted. As a result, the short-circuit current Isc is 8.718 A, the open circuit voltage Voc is 0.627 V, the current density Jsc is 0.0365 A / cm 2 , the fill factor FF is 80.04, the power generation efficiency Eff is 18.34%, and the series resistance Rs. Was 0.0058 ⁇ / ⁇ .
  • Example 2 A commercially available silver powder (atomized silver powder HWQ 5 ⁇ m manufactured by Fukuda Metal Foil Powder Co., Ltd.) manufactured by the atomization method is prepared, and Ag content, carbon content, nitrogen in this silver powder are prepared in the same manner as in Example 1.
  • the content, oxygen content and cyan content were determined, and the particle size distribution of the silver powder was determined, the Ag content was 99.9% by mass or more, the carbon content was 0.006% by mass, and the nitrogen content was 0.00. It was less than 01% by mass, the oxygen content was 0.03% by mass, and the amount of cyan was 0 ppm.
  • the silver powder has a cumulative 10% particle size (D 10 ) of 2.9 ⁇ m, a cumulative 50% particle size (D 50 ) of 4.8 ⁇ m, a cumulative 90% particle size (D 90 ) of 8.0 ⁇ m,
  • the BET specific surface area of the copper powder was 0.16 m 2 / g.
  • the solar cell was produced by the method similar to Example 1 except having used the electrically conductive paste 1 obtained from this silver powder, and the battery characteristic test was done.
  • the short-circuit current Isc is 8.885 A
  • the open circuit voltage Voc is 0.626 V
  • the current density Jsc is 0.0372 A / cm 2
  • the fill factor FF is 86.60
  • the power generation efficiency Eff is 20.18%
  • the series resistance Rs was 0.0040 ⁇ / ⁇ .
  • Comparative Example 3 A silver powder similar to that in Comparative Example 2 was immersed in an aqueous solution of NaCN containing 1000 ppm of cyan (CN) for 30 minutes, filtered while applying extruded water, and pure water was applied to the solid matter on the filter paper (liquid after washing). And then dried at 70 ° C. for 5 hours with a vacuum drier to obtain silver powder having CN adsorbed on the surface, and then in the same manner as in Example 1. In addition to determining the Ag content, carbon content, nitrogen content, oxygen content and cyan content in the silver powder (with CN adsorbed on the surface), the particle size distribution of the silver powder was determined.
  • the cumulative 10% particle diameter (D 10 ) of the silver powder is 3.7 ⁇ m, the cumulative 50% particle diameter (D 50 ) is 8.4 ⁇ m, the cumulative 90% particle diameter (D 90 ) is 16.5 ⁇ m, The BET specific surface area was 0.18 m 2 / g.
  • the solar cell was produced by the method similar to Example 1 except having used the electrically conductive paste 1 obtained from this silver powder, and the battery characteristic test was done.
  • the short-circuit current Isc is 8.861 A
  • the open circuit voltage Voc is 0.627 V
  • the current density Jsc is 0.0371 A / cm 2
  • the fill factor FF is 84.03
  • the power generation efficiency Eff is 19.58%
  • the series resistance Rs. was 0.0044 ⁇ / ⁇ .
  • Example 4 100 g of the same copper powder as in Example 1 was added to 500 g of pure water and stirred at 500 rpm with a stirrer. In the liquid in which the copper powder was dispersed by this stirring, 100 g / L of cyan cyan potassium potassium and 80 g / L. After adding 239.28 g of a cyan silver plating solution consisting of 30 g of potassium pyrophosphate and 35 g / L boric acid over 30 minutes, stirring was continued for 30 minutes to obtain silver-plated copper powder.
  • the Ag content, carbon content, nitrogen content, oxygen content and cyan content in this silver-plated copper powder were determined, and the particle size distribution and BET of the silver-plated copper powder were determined.
  • the specific surface area was determined.
  • the Ag content in the silver-plated copper powder is 8.10% by mass
  • the carbon content is 1.36% by mass
  • the nitrogen content is 1.53% by mass
  • the oxygen content is 0.19% by mass.
  • the amount of cyan in the silver-plated copper powder was 7100 ppm.
  • the silver-plated copper powder has a cumulative 10% particle diameter (D 10 ) of 3.1 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 7.7 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 16.4 ⁇ m.
  • the BET specific surface area of the silver-plated copper powder was 0.53 m 2 / g.
  • the solar cell was produced by the method similar to Example 1 except having used the electrically conductive paste 1 obtained from the obtained silver plating copper powder, and the battery characteristic test was done.
  • the short circuit current Isc is 2.221 A
  • the open circuit voltage Voc is 0.626 V
  • the current density Jsc is 0.0093 A / cm 2
  • the fill factor FF is 73.49
  • the power generation efficiency Eff is 4.35%
  • the series resistance Rs. was 0.1077 ⁇ / ⁇ .
  • Example 4 instead of the copper powder of Example 1, a commercially available copper powder manufactured by the atomizing method (atomized copper powder AO-PCG-19 manufactured by DOWA Electronics Co., Ltd.) was used. A silver-coated copper powder (with silver supported on the surface) was obtained. Incidentally, in the same manner as in Example 1, was determined the particle size distribution of the copper powder used, the cumulative 10% particle size of the copper powder (D 10) is 2.0 .mu.m, 50% cumulative particle diameter (D 50) The particle diameter (D 90 ) of 4.9 ⁇ m and cumulative 90% was 9.5 ⁇ m.
  • the content of Ag in the silver-coated copper powder thus obtained was determined in the same manner as in Example 1, the Ag content in the silver-coated copper powder was 11 It was 89 mass%.
  • the content of Ag in the silver-coated copper powder of Comparative Example 5 described later is 10.93% by mass.
  • the carbon content, nitrogen content, oxygen content and cyan content in this silver-coated copper powder were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined.
  • the carbon content in the silver-coated copper powder is 0.16% by mass
  • the nitrogen content is 0.15% by mass
  • the oxygen content is 0.13% by mass
  • the amount of cyan in the silver-coated copper powder was 900 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.9 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 6.5 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 13.2 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.41 m 2 / g.
  • Example 2 A solar cell was produced in the same manner as in Example 1 except that a silicon wafer (E & M Co., Ltd., 100 ⁇ / ⁇ , 6-inch single crystal) was used.
  • the short circuit current Isc is 9.24 A
  • the open circuit voltage Voc is 0.636 V
  • the current density Jsc is 0.0380 A / cm 2
  • the fill factor FF is 85.58
  • the power generation efficiency Eff is 20.72%
  • the series resistance Rs Was 0.0041 ⁇ / ⁇ .
  • Example 5 A silver-coated copper powder (with silver supported on the surface) was obtained in the same manner as in Example 4 except that the amount of silver-supported liquid added was 0.056 mL.
  • the content of Ag in the silver-coated copper powder thus obtained was determined in the same manner as in Example 1, the Ag content in the silver-coated copper powder was 11 .26% by mass.
  • the content of Ag in the silver-coated copper powder of Comparative Example 5 described later is 10.93% by mass.
  • the carbon content, nitrogen content, oxygen content and cyan content in this silver-coated copper powder were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined.
  • the carbon content in the silver-coated copper powder is 0.01% by mass
  • the nitrogen content is less than 0.01% by mass
  • the oxygen content is 0.10% by mass.
  • the amount was 5 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.6 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 5.6 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 10.9 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.31 m 2 / g.
  • a solar cell was produced in the same manner as in Example 4 except that the conductive paste 1 obtained from the obtained silver-coated copper powder (with silver supported on the surface) was used, and its battery characteristics were obtained.
  • a test was conducted. As a result, the short-circuit current Isc is 9.33 A, the open circuit voltage Voc is 0.636 V, the current density Jsc is 0.0384 A / cm 2 , the fill factor FF is 90.35, the power generation efficiency Eff is 22.06%, and the series resistance Rs was 0.0039 ⁇ / ⁇ .
  • Example 6 After adding 0.2 g of phytic acid in a state where 20 g of the silver-coated copper powder (with silver supported thereon) obtained in Example 5 was added and dispersed in pure water, the Nutsche method was applied while applying extrusion water. The solid on the filter paper was dried with a vacuum dryer at 70 ° C. for 5 hours, and the surface of the silver-coated copper powder (with silver supported on the surface) was coated with phytic acid.
  • the carbon content, the nitrogen content, the oxygen content, and the cyan content in the silver-coated copper powder (the surface was treated with phytic acid after silver was supported on the surface) While calculating
  • the carbon content in the silver-coated copper powder is 0.02% by mass
  • the nitrogen content is less than 0.01% by mass
  • the oxygen content is 0.12% by mass.
  • the amount was 5.7 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.7 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 5.9 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 10.7 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.31 m 2 / g.
  • the conductive paste 1 obtained from the obtained silver-coated copper powder (the surface was coated with phytic acid after supporting silver on the surface) was used in the same manner as in Example 4, A solar cell was produced and its battery characteristics were tested.
  • the short-circuit current Isc is 9.33 A
  • the open circuit voltage Voc is 0.641 V
  • the current density Jsc is 0.0384 A / cm 2
  • the fill factor FF is 88.81
  • the power generation efficiency Eff is 21.88%
  • the series resistance Rs was 0.0035 ⁇ / ⁇ .
  • Example 7 After adding 0.1 g of benzotriazole in a state where 20 g of the silver-coated copper powder (with silver supported thereon) obtained in Example 5 was added and dispersed in pure water, the Nutsche method was applied while applying extrusion water. The solid on the filter paper was dried with a vacuum dryer at 70 ° C. for 5 hours, and the surface of the silver-coated copper powder (with silver supported on the surface) was treated with benzotriazole.
  • the carbon content, nitrogen content, oxygen content, and cyan content in this silver-coated copper powder (the surface was treated with benzotriazole after supporting silver on the surface) While calculating
  • the carbon content in the silver-coated copper powder was 0.05% by mass
  • the nitrogen content was 0.02% by mass
  • the oxygen content was 0.10% by mass
  • the amount of cyan in the silver-coated copper powder was 7 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.6 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 5.8 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 10.5 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.40 m 2 / g.
  • the carbon content, nitrogen content, oxygen content and cyan content in the silver-coated copper powder were determined, and the particle size distribution and BET specific surface area of the silver-coated copper powder were determined. It was. As a result, the carbon content in the silver-coated copper powder is 0.01% by mass, the nitrogen content is less than 0.01% by mass, and the oxygen content is 0.10% by mass. The amount was 0 ppm.
  • the silver-coated copper powder has a cumulative 10% particle diameter (D 10 ) of 2.5 ⁇ m, a cumulative 50% particle diameter (D 50 ) of 5.8 ⁇ m, and a cumulative 90% particle diameter (D 90 ) of 11.6 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was 0.35 m 2 / g.
  • a solar cell was produced in the same manner as in Example 1 except that the conductive paste 1 obtained from the obtained (copper powder coated with silver) silver-coated copper powder was used.
  • a test was conducted. As a result, the short-circuit current Isc is 9.21 A, the open circuit voltage Voc is 0.632 V, the current density Jsc is 0.0379 A / cm 2 , the fill factor FF is 82.73, the power generation efficiency Eff is 19.83%, and the series resistance Rs was 0.0055 ⁇ / ⁇ .
  • Comparative Example 1 Compared with the case of using silver-coated copper powder (not containing cyan) of 5 and 5 and the case of using silver-plated copper powder (containing a large amount of cyan) of Comparative Example 4, the conversion efficiency Eff of the solar cell ( It can be greatly improved (to the same extent as when the silver powder of Comparative Example 2 is used).
  • Example 3 and Comparative Example 3 silver-coated copper powder (copper powder coated with silver) and commercially available silver powder (before silver was supported on the surface) and a commercially available silver powder were immersed in an aqueous NaCN solution under the same conditions. Nevertheless, the amount of cyan in the silver powder of Comparative Example 3 is extremely small compared to the amount of cyan in the silver-coated copper powder of Example 3, and the conductivity obtained from the silver powder of Comparative Example 3 The power generation efficiency of the solar cell using the conductive paste is considerably lower than the power generation efficiency of the solar cell using the conductive paste obtained from the silver-coated copper powder of Example 3.
  • the silver-coated copper powder (copper powder coated with silver) used in Example 3 (before silver is supported on the surface) has a portion that is not coated with silver on the surface of the copper powder that is easily oxidized. Since it exists moderately, when it immerses in NaCN aqueous solution, it is thought that it is because it contains cyan
  • the solar cells produced in Examples 4 to 7 and Comparative Example 5 were continuously irradiated with pseudo-sunlight having a light irradiation energy of 100 mW / cm 2 for 5 seconds by a xenon lamp of a solar simulator (manufactured by Wacom Denso Co., Ltd.). Then, the power generation efficiency Eff for each irradiation was obtained and the change over time in the power generation efficiency Eff was examined. As shown in FIG. 1, the solar cell of Example 5 had the highest initial power generation efficiency Eff.
  • the power generation efficiency Eff was slightly reduced by irradiation of the solar cell of Example 6 and Example 7 using silver-coated copper powder surface-treated with phytic acid or benzotriazole, it was earlier than the solar cell of Example 5. Although the power generation efficiency Eff is slightly inferior, the power generation efficiency Eff is not lowered by repeated irradiation, and it is found that the solar cell is highly reliable. It was. In particular, in the solar cell of Example 6 using the silver-coated copper powder front-treated with phytic acid, the power generation efficiency Eff higher than the power generation efficiency Eff of the solar cell of Example 5 when the number of times of light irradiation exceeded 8 times. Obtained.
  • the silver-coated copper powder according to the present invention can be used for the production of a conductive paste for use in electronic components such as conductor patterns of circuit boards, electrodes of boards such as solar cells, and circuits.

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Abstract

L'invention concerne : une poudre de cuivre revêtue d'argent qui, lorsqu'elle est utilisée dans une pâte conductrice pour la formation d'une électrode de barre omnibus d'une photopile, permet la production d'une photopile dont le rendement de conversion est amélioré par comparaison avec celles utilisant des poudres de cuivre revêtues d'argent classiques de manière à atteindre un haut rendement de conversion équivalent à celui obtenu par l'utilisation de poudre d'argent ; et un procédé pour la production de la poudre de cuivre revêtue d'argent. Selon l'invention, une poudre de cuivre revêtue d'argent, obtenue par revêtement de la surface d'une poudre de cuivre, préparée par un procédé d'atomisation ou similaire, d'une couche contenant de l'argent et comprenant au moins 5 % en masse (par rapport à la poudre de cuivre revêtue d'argent) d'argent ou d'un composé de l'argent, est ajoutée à une solution de composé cyanogène, telle qu'une solution de cyanure d'argent et de potassium, une solution de cyanure d'or et de potassium, une solution de cyanure de potassium ou une solution de cyanure de sodium, de sorte que 3 à 3000 ppm de cyanure est inclus dans la poudre de cuivre revêtue de la couche contenant de l'argent.
PCT/JP2017/002676 2016-02-03 2017-01-26 Poudre de cuivre revêtue d'argent et son procédé de fabrication Ceased WO2017135138A1 (fr)

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CN201780008234.2A CN108495728B (zh) 2016-02-03 2017-01-26 涂银铜粉及其制造方法
US16/071,578 US10580910B2 (en) 2016-02-03 2017-01-26 Silver-coated copper powder and method for producing same

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JP2016130365A (ja) * 2015-01-13 2016-07-21 Ｄｏｗａエレクトロニクス株式会社 銀被覆銅粉およびその製造方法
WO2019116874A1 (fr) * 2017-12-14 2019-06-20 株式会社ノリタケカンパニーリミテド Composition photosensible et son utilisation
JP2020015950A (ja) * 2018-07-25 2020-01-30 日立化成株式会社 接合用金属ペースト、接合体及び接合体の製造方法

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JP2007073545A (ja) * 2005-09-02 2007-03-22 Tsukuba Semi Technology:Kk 半導体デバイスの結晶質改善方法
JP2016130365A (ja) * 2015-01-13 2016-07-21 Ｄｏｗａエレクトロニクス株式会社 銀被覆銅粉およびその製造方法

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JPH0762274A (ja) * 1993-08-25 1995-03-07 Tatsuta Electric Wire & Cable Co Ltd 金属酸化物成形体との密着性の良い導電塗料
JP2002157918A (ja) * 2000-11-17 2002-05-31 Jsr Corp 導電性複合粒子およびそれを用いた応用製品
JP2007073545A (ja) * 2005-09-02 2007-03-22 Tsukuba Semi Technology:Kk 半導体デバイスの結晶質改善方法
JP2016130365A (ja) * 2015-01-13 2016-07-21 Ｄｏｗａエレクトロニクス株式会社 銀被覆銅粉およびその製造方法

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Publication number Priority date Publication date Assignee Title
JP2016130365A (ja) * 2015-01-13 2016-07-21 Ｄｏｗａエレクトロニクス株式会社 銀被覆銅粉およびその製造方法
WO2019116874A1 (fr) * 2017-12-14 2019-06-20 株式会社ノリタケカンパニーリミテド Composition photosensible et son utilisation
JP2019105792A (ja) * 2017-12-14 2019-06-27 株式会社ノリタケカンパニーリミテド 感光性組成物とその利用
CN111465899A (zh) * 2017-12-14 2020-07-28 株式会社则武 感光性组合物和其利用
KR20200097774A (ko) * 2017-12-14 2020-08-19 가부시키가이샤 노리타케 캄파니 리미티드 감광성 조성물과 그의 이용
CN111465899B (zh) * 2017-12-14 2023-05-16 株式会社则武 感光性组合物和其利用
KR102579847B1 (ko) 2017-12-14 2023-09-18 가부시키가이샤 노리타케 캄파니 리미티드 감광성 조성물과 그의 이용
JP2020015950A (ja) * 2018-07-25 2020-01-30 日立化成株式会社 接合用金属ペースト、接合体及び接合体の製造方法
JP7127407B2 (ja) 2018-07-25 2022-08-30 昭和電工マテリアルズ株式会社 接合用金属ペースト、接合体及び接合体の製造方法

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