WO2018155393A1 - Pâte électroconductrice - Google Patents

Pâte électroconductrice Download PDF

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WO2018155393A1
WO2018155393A1 PCT/JP2018/005829 JP2018005829W WO2018155393A1 WO 2018155393 A1 WO2018155393 A1 WO 2018155393A1 JP 2018005829 W JP2018005829 W JP 2018005829W WO 2018155393 A1 WO2018155393 A1 WO 2018155393A1
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silver
conductive paste
copper powder
solar cell
manufactured
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PCT/JP2018/005829
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English (en)
Japanese (ja)
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愛子 平田
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Ｄｏｗａエレクトロニクス株式会社
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Publication of WO2018155393A1 publication Critical patent/WO2018155393A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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

Definitions

  • the present invention relates to a conductive paste, and more particularly to a conductive paste using silver-coated copper powder as a conductive metal powder.
  • 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.
  • electrodes are formed by firing a baking type conductive paste using silver powder at a high temperature of about 800 ° C. in an air atmosphere.
  • conductive paste that uses copper
  • copper powder and silver-coated copper powder will oxidize when firing at such high temperatures in an air atmosphere, so special techniques such as firing in an inert atmosphere Is required and the cost is high.
  • electrodes are generally formed by heating a resin-curing conductive paste using silver powder to about 200 ° C. in an air atmosphere and curing it. Copper powder and silver-coated copper powder can withstand oxidation even when heated at such a low temperature in an air atmosphere, making it possible to use resin-cured conductive paste using silver-coated copper powder Become.
  • the soldering temperature (380 ° C.)
  • the resin of the conductive paste is decomposed at a degree), and the electrode and the tab wire are connected using a conductive adhesive that is more expensive than solder.
  • JP 2010-174411 A (paragraph number 0003) JP 2010-077745 (paragraph number 0006)
  • a HIT solar cell is manufactured by connecting a bus bar electrode formed of a resin-type conductive paste using silver-coated copper powder as a conductive filler and using a bisphenol A type epoxy resin as a resin to a tab wire with a conductive adhesive. As a result, it was found that the solar cell had a high conversion efficiency equivalent to that when silver powder was used.
  • the bus bar electrode formed by the resin-type conductive paste obtained by kneading the silver-coated copper powder and the bisphenol A type epoxy resin as described above is connected to the tab wire by soldering, the resistance of the bus bar electrode is reduced. It turned out that the conversion efficiency of a solar cell may fall and it may become high. In addition, such a problem does not occur when silver powder is used instead of the silver-coated copper powder of the resin-type conductive paste.
  • the present invention provides a solar cell bus bar electrode made of a resin-type conductive paste using silver-coated copper powder and connected to the tab wire by soldering. It aims at providing the electrically conductive paste which can prevent the fall of conversion efficiency.
  • a resin-type conductive paste comprising a silver-coated copper powder whose surface is coated with a silver layer and an epoxy resin having a naphthalene skeleton.
  • the conductive paste according to the present invention is characterized in that it contains silver-coated copper powder whose surface is coated with a silver layer and an epoxy resin having a naphthalene skeleton.
  • This conductive paste preferably contains a solvent.
  • this electrically conductive paste contains a hardening
  • the amount of silver is 5 mass% or more to silver-coated copper powder, 50% cumulative particle diameter on a volume basis as measured by a laser diffraction type particle size distribution apparatus copper powder (D 50 diameter) is 0.1 ⁇ 15 [mu] m Is preferred.
  • the amount of the silver-coated copper powder in the conductive paste is preferably 50 to 90% by mass.
  • the method for manufacturing an electrode for a 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.
  • a solar cell bus bar electrode made of a resin-type conductive paste using silver-coated copper powder is connected to a tab wire by soldering, a reduction in conversion efficiency of the solar cell can be prevented.
  • An electrically conductive paste can be provided.
  • FIG. 8 It is a figure which shows the scanning electron microscope (SEM) image of the cross section of the bus-bar electrode formed in the surface side (cover glass side) of the cell with an interconnector of the solar cell module produced in the comparative example 8.
  • FIG. It is a figure which shows the SEM image of the cross section of the bus-bar electrode formed in the surface side (cover glass side) of the cell with an interconnector of the solar cell module produced in Example 5.
  • FIG. It is a figure which shows Ag map image by the mapping analysis of the cross section of the bus-bar electrode formed in the surface side (cover glass side) of the cell with an interconnector of the solar cell module produced in Example 5.
  • FIG. It is a figure which shows Cu map image by the mapping analysis of the cross section of the bus-bar electrode formed in the surface side (cover glass side) of the cell with an interconnector of the solar cell module produced in Example 5.
  • the embodiment of the conductive paste according to the present invention includes silver-coated copper powder whose surface is coated with a silver layer and an epoxy resin having a naphthalene skeleton.
  • an epoxy resin having a naphthalene skeleton as shown in Chemical Formula 1 (for example, HP4710 manufactured by Dainippon Ink & Chemicals, Inc.) can be used.
  • the content of the epoxy resin having a naphthalene skeleton is preferably 1 to 20% by mass, more preferably 3 to 10% by mass with respect to the conductive paste. If the content of the epoxy resin having a naphthalene skeleton is too small, the function of protecting the surface of the silver-coated copper powder from oxidation due to heat becomes insufficient.
  • This conductive paste preferably contains a curing agent, and it is preferable to use at least one of imidazole and boron trifluoride amine curing agent as the curing agent.
  • the content of the curing agent is preferably 1 to 10% by mass, more preferably 2 to 6% by mass with respect to the epoxy resin.
  • This conductive paste preferably contains a solvent, and this solvent can be appropriately selected according to the purpose of use of the conductive paste.
  • a solvent can be appropriately selected according to the purpose of use of the conductive paste.
  • BCA butyl carbitol acetate
  • BC butyl carbitol
  • ECA ethyl carbitol acetate
  • EC ethyl carbitol
  • toluene methyl ethyl ketone
  • methyl isobutyl ketone tetradecane
  • tetralin propyl 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 content of the solvent is preferably 0 to 20% by mass, more preferably 0 to 10% by mass
  • the conductive paste may also contain other components such as a surfactant, a dispersant, a rheology modifier, a silane coupling agent, and an ion collector.
  • silver-coated copper powder whose surface is coated with a silver layer is used as a conductor.
  • the shape of the copper powder coated with the silver layer may be substantially spherical or flaky.
  • the silver layer is preferably a layer made of silver or a silver compound, and more preferably a layer made of 90% by mass or more of silver.
  • the amount of silver based on 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% by mass. Most preferably. If the amount of silver 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.
  • Particle size of the copper powder is preferably 50% cumulative particle diameter on a volume basis as measured by a laser diffraction type particle size distribution apparatus (D 50 diameter) is 0.1 ⁇ 15 [mu] m, and even a 0.3 ⁇ 10 [mu] m More preferably, the thickness is 1 to 5 ⁇ m.
  • D 50 diameter 50% cumulative particle diameter on a volume basis as measured by a laser diffraction type particle size distribution apparatus
  • the thickness is 1 to 5 ⁇ m.
  • a cumulative 50% particle diameter (D 50 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 depositing silver or a silver compound on the surface of copper powder by a substitution method using a substitution reaction of copper and silver or a reduction method using a reducing agent may be used.
  • a method of precipitating silver or a silver compound on the surface of copper powder while stirring a solution containing copper powder and silver or a silver compound in a solvent, or a solution containing copper powder and an organic substance in a solvent and a solvent A method of depositing silver or a silver compound on the surface of copper powder while mixing and stirring a solution containing silver or a silver compound and an organic substance can be used.
  • 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 having high solubility in water and many organic solvents.
  • the amount of silver nitrate solution to be 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 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 amount of silver or silver compound and the reaction temperature, but can be set in the range of 1 minute to 5 hours.
  • the said electrically conductive paste (The electroconductive paste containing the silver covering copper powder by which the surface of the copper powder was coat
  • An electrode is formed, an interconnector is soldered to this electrode, and a cover glass is attached to the surface side (side on which sunlight is incident) of the cell with the interconnector having the interconnector soldered to this electrode via a protective sheet.
  • a polyolefin-based film such as a cycloolefin copolymer (COC) film.
  • COC cycloolefin copolymer
  • 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 volume-based cumulative 10% particle size (D 10 ) was 2.26 ⁇ m
  • the cumulative 50% particle size (D 50 ) was 5.20 ⁇ m
  • the cumulative 90% particle size (D 90 ) was 9.32 ⁇ m.
  • the particle size distribution of the copper powder was measured by a laser diffraction particle size distribution device (Microtrack particle size distribution measurement device MT-3300 manufactured by Nikkiso Co., Ltd.), and the volume-based cumulative 10% particle diameter (D 10 ), cumulative The 50% particle diameter (D 50 ) and the cumulative 90% particle diameter (D 90 ) were determined.
  • a laser diffraction particle size distribution device Microtrack particle size distribution measurement device MT-3300 manufactured by Nikkiso Co., Ltd.
  • solution 2 a solution of 2.6 kg of ammonium carbonate dissolved in 450 kg of pure water (solution 1), 319 kg of EDTA-4Na (43%) and 76 kg of ammonium carbonate in a solution of 284 kg of pure water, silver nitrate containing 16.904 kg of silver A solution (solution 2) obtained by adding 92 kg of an aqueous solution was prepared.
  • the silver-coated copper powder (5.0 g) thus obtained was dissolved in 40 mL of nitric acid aqueous solution obtained by diluting a nitric acid aqueous solution having a specific gravity of 1.38 with a pure water so as to have a volume ratio of 1: 1, and boiled with a heater to obtain silver.
  • a hydrochloric acid aqueous solution having a specific gravity of 1.18 was added little by little to a hydrochloric acid aqueous solution diluted with pure water so as to have a volume ratio of 1: 1, thereby precipitating silver chloride.
  • the addition of an aqueous hydrochloric acid solution was continued until no precipitation occurred, and the content of Ag was determined from the obtained silver chloride by a gravimetric method.
  • the Ag content in the silver-coated copper powder was 10.14% by mass.
  • this silver-coated copper powder is added to 40 mL of isopropyl alcohol, and dispersed for 2 minutes by an ultrasonic homogenizer (tip tip diameter: 20 mm). Measurement was performed with a microtrack particle size distribution measuring apparatus MT-3300 manufactured by Nikkiso Co., Ltd. As a result, the volume-based cumulative 10% particle diameter (D 10 ) of the silver-coated copper powder is 2.5 ⁇ m, the cumulative 50% particle diameter (D 50 ) is 5.2 ⁇ m, and the cumulative 90% particle diameter (D 90 ) is 10. .1 ⁇ m.
  • the BET specific surface area of the silver-coated copper powder was measured by a BET one-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 0.31 m 2 / g.
  • F value (The ratio of the silver coating copper powder with respect to the total amount of the silver coating copper powder as a conductive filler, resin, and a hardening
  • the viscosity of the conductive paste 1 was measured at 1 rpm at 25 ° C. with a viscometer (DV-III Ultra manufactured by Brookfield, CP52 was used as a cone), and was 40 Pa ⁇ s.
  • 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.
  • the silver tellurium-coated glass powder was produced as follows. First, 3.47 g of a 32% by mass silver nitrate aqueous solution was mixed with 787 g of pure water stirred in a 1 L beaker, and 28% by mass ammonia water as a complexing agent was added to this silver nitrate aqueous solution containing 1.11 g of silver. 2.5 g was added to obtain an aqueous silver ammine complex salt solution.
  • this silver ammine complex salt solution is 30 ° C.
  • 10 g of tellurium glass powder (BLT-77 manufactured by Asahi Glass Co., Ltd.) is added, and immediately after that, 0.3 g of hydrazine as a reducing agent and silver colloid 10
  • a mixture of 3 g and 20 g of pure water was added and aged for 5 minutes.
  • tellurium-based glass powder was coated with a layer mainly composed of silver and tellurium
  • the slurry containing silver tellurium-coated glass powder was suction filtered.
  • the resulting cake was washed with pure water until the potential became 0.5 mS / m or less, and the resulting cake was dried with a vacuum dryer at 75 ° C. for 10 minutes to obtain silver tellurium-coated glass powder (silver and tellurium as main components).
  • 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 being printed in the shape of the three bus bar electrodes, it was heated at 150 ° C. for 10 minutes by a hot air drier, then heated at 200 ° C. for 30 minutes, dried and cured to form a bus bar electrode.
  • the resistance (initial resistance value) of the bus bar electrode thus formed was measured, it was 3.15 ⁇ .
  • a soldering iron at 380 ° C. is applied to the bus bar electrode so that the same level of heat as that applied during soldering is applied to the bus bar electrode of one silicon wafer.
  • the resistance of the bus bar electrode was measured, it was 3.42 ⁇ , and the rate of change in resistance with respect to the initial resistance value was 109%.
  • the bus bar electrode and the tab wire of the other silicon wafer were soldered at 380 ° C. with SnPb eutectic solder (melting point 183 ° C.) to produce a solar cell.
  • This solar cell was irradiated with pseudo-sunlight with a light irradiation energy of 100 mW / cm 2 by a xenon lamp of a solar simulator (manufactured by Wacom Electric Co., Ltd.), and a battery characteristic test was performed.
  • the current (short-circuit current) Isc flowing between the two terminals when the output terminal of the solar cell is short-circuited is 9.23 A
  • the voltage (open-circuit voltage) Voc between the two terminals when the output terminal of the solar cell is opened is 9.23 A
  • Example 2 In the same manner as in Example 1, except that imidazole (2PHZ-PW manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used instead of imidazole (2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) as the curing agent. Produced. In addition, when the viscosity of the conductive paste 1 obtained in this example was measured by the same method as in Example 1, it was within the range of 40 ⁇ 5 Pa ⁇ s.
  • the resistance value before soldering of the bus bar electrode was 7.56 ⁇
  • the resistance value after soldering. was 6.58 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 87%.
  • the short-circuit current Isc was 9.23 A
  • the open-circuit voltage Voc was 0.630 V
  • the current density Jsc was 0.038 A / cm 2
  • the factor FF was 72.98
  • the power generation efficiency Eff was 17.45%
  • the series resistance Rs was 0.0091 ⁇ / ⁇ .
  • Example 3 Instead of imidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as the curing agent in the conductive paste 1, a boron trifluoride amine-based curing agent (BF3NH2Et manufactured by Wako Pure Chemical Industries, Ltd.) is used, and silver-coated copper Example 1 except that the amounts of powder, epoxy resin having a naphthalene skeleton, solvent and curing agent were 85.52 parts by weight, 8.44 parts by weight, 5.62 parts by weight and 0.32 parts by weight, respectively.
  • a solar cell was produced by the method described above.
  • the F value of the conductive paste 1 obtained in this example was 90.7%.
  • the viscosity of the conductive paste 1 obtained in this example was measured by the same method as in Example 1, it was within the range of 40 ⁇ 5 Pa ⁇ s.
  • the resistance value before soldering of the bus bar electrode was 6.58 ⁇
  • the resistance value after soldering was 7.71 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 117%.
  • the short-circuit current Isc was 9.20 A
  • the open-circuit voltage Voc was 0.628 V
  • the current density Jsc was 0.038 A / cm 2
  • the factor FF was 71.63
  • the power generation efficiency Eff was 17.02%
  • the series resistance Rs was 0.0102 ⁇ / ⁇ .
  • Example 4 Instead of the epoxy resin having a naphthalene skeleton (HP 4710 made by Dainippon Ink & Chemicals, Inc.) in the conductive paste 1, the epoxy resin having a naphthalene skeleton shown in Chemical formula 1 (HP 9500 made by Dainippon Ink & Chemicals, Inc.) A solar cell was produced in the same manner as in Example 1 except that was used. The F value of the conductive paste 1 obtained in this example was 90.9%. When the viscosity of the conductive paste 1 obtained in this example was measured by the same method as in Example 1, it was within the range of 40 ⁇ 5 Pa ⁇ s.
  • the resistance value of the bus bar electrode before soldering was 3.56 ⁇
  • the resistance value after soldering was 5.83 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 164%.
  • the short-circuit current Isc was 8.85 A
  • the open-circuit voltage Voc was 0.627 V
  • the current density Jsc was 0.036 A / cm 2
  • the factor FF was 70.47
  • the power generation efficiency Eff was 16.10%
  • the series resistance Rs was 0.0114 ⁇ / ⁇ .
  • the resistance value before soldering of the bus bar electrode (initial resistance value) was 4.05 ⁇ , and the resistance value after soldering. was 18.70 ⁇ , and the resistance change rate with respect to the initial resistance value was 462%.
  • the short-circuit current Isc was 6.71 A
  • the open-circuit voltage Voc was 0.634 V
  • the current density Jsc was 0.028 A / cm 2
  • the factor FF was 49.96
  • the power generation efficiency Eff was 8.74%
  • the series resistance Rs was 0.0162 ⁇ / ⁇ .
  • the resistance value before soldering of the bus bar electrode was 2.37 ⁇
  • the resistance value after soldering. was 7.73 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 326%.
  • the short-circuit current Isc was 7.93 A
  • the open-circuit voltage Voc was 0.632 V
  • the current density Jsc was 0.033 A / cm 2
  • the factor FF was 45.47
  • the power generation efficiency Eff was 9.39%
  • the series resistance Rs was 0.0228 ⁇ / ⁇ .
  • the resistance value before soldering of the bus bar electrode was 5.95 ⁇
  • the resistance value after soldering was 12.63 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 212%.
  • the short-circuit current Isc was 8.65 A
  • the open-circuit voltage Voc was 0.630 V
  • the current density Jsc was 0.036 A / cm 2
  • the factor FF was 64.69
  • the power generation efficiency Eff was 14.51%
  • the series resistance Rs was 0.0165 ⁇ / ⁇ .
  • the resistance value before soldering of the bus bar electrode was 3.50 ⁇
  • the resistance value after soldering was 34.93 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 998%.
  • the short-circuit current Isc was 7.78 A
  • the open-circuit voltage Voc was 0.635 V
  • the current density Jsc was 0.032 A / cm 2
  • the factor FF was 54.49
  • the power generation efficiency Eff was 11.07%
  • the series resistance Rs was 0.0181 ⁇ / ⁇ .
  • the resistance of the bus bar electrode before and after soldering the bus bar electrode and the tab wire of this solar cell was measured.
  • the resistance value before soldering of the bus bar electrode was 6.08 ⁇
  • the resistance value after soldering. was 23.53 ⁇
  • the rate of change in resistance with respect to the initial resistance value was 387%.
  • the short-circuit current Isc was 5.67 A
  • the open-circuit voltage Voc was 0.635 V
  • the current density Jsc was 0.023 A / cm 2
  • the factor FF was 54.52
  • the power generation efficiency Eff was 8.07%
  • the series resistance Rs was 0.0127 ⁇ / ⁇ .
  • the resistance value before soldering of the bus bar electrode was 4.73 ⁇
  • the resistance value after soldering was 21.67 ⁇
  • the resistance change rate with respect to the initial resistance value was 458%.
  • the short-circuit current Isc was 4.66 A
  • the open-circuit voltage Voc was 0.632 V
  • the current density Jsc was 0.019 A / cm 2
  • the factor FF was 55.01
  • the power generation efficiency Eff was 6.67%
  • the series resistance Rs was 0.0182 ⁇ / ⁇ .
  • Tables 1 to 3 show the results of these examples and comparative examples.
  • Example 5 79.0 parts by weight of the silver-coated copper powder of Example 1, 8.8 parts by weight of silver powder having an average primary particle diameter of 1 ⁇ m (Ag-2-IC manufactured by DOWA Electronics Co., Ltd.), and the naphthalene skeleton shown in Chemical Formula 1 6.6 parts by weight of an epoxy resin (HP 4710 manufactured by Dainippon Ink & Chemicals, Inc.), 5.3 parts by weight of butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, and imidazole (Shikoku Chemicals) as a curing agent 2E4MZ manufactured by Kogyo Co., Ltd.
  • an epoxy resin HP 4710 manufactured by Dainippon Ink & Chemicals, Inc.
  • butyl carbitol acetate manufactured by Wako Pure Chemical Industries, Ltd.
  • imidazole Shikoku Chemicals
  • this electroconductive paste A contains 87.8 mass% of silver covering copper powder and silver powder in total as an electroconductive filler.
  • the conductive paper (as a paste for bus bar electrodes on the back surface of the silicon wafer described later) is obtained. To obtain the door B.
  • a silicon wafer (100 ⁇ / ⁇ , 6-inch single crystal manufactured by E & M Co., Ltd.) is prepared, and the above conductive paste is applied to the back surface of the silicon wafer by a screen printer (MT-320T manufactured by Microtech Co., Ltd.).
  • B was printed in the shape of three bus bar electrodes having a width of 1.3 mm, and dried by heating at 200 ° C. for 10 minutes with a hot air dryer.
  • aluminum paste Alsolar 14-7021 manufactured by Toyo Aluminum Co., Ltd.
  • Alsolar 14-7021 manufactured by Toyo Aluminum Co., Ltd.
  • the conductive paste C is printed on the shape of 100 finger electrodes with a width of 50 ⁇ m by a screen printing machine (MT-320T manufactured by Microtech Co., Ltd.) on the surface of the silicon wafer, and then 200 times by a hot air dryer. Heated at 10 ° C for 10 minutes and dried, fired at a peak temperature of 820 ° C for 21 seconds in-out of a fast firing IR furnace (fast firing test 4 chamber furnace manufactured by NGK Co., Ltd.), and a bus bar on the back side of the silicon wafer An electrode and a surface finger electrode were formed.
  • a screen printing machine MT-320T manufactured by Microtech Co., Ltd.
  • the conductive paste A is printed in the shape of three bus bar electrodes having a width of 1.3 mm on a surface of a silicon wafer with a screen printer (MT-320T manufactured by Microtech Co., Ltd.), and then a hot air dryer. After heating and drying at 150 ° C. for 10 minutes, the substrate was heated and cured at 200 ° C. for 40 minutes to form a bus bar electrode on the surface of the silicon wafer.
  • a screen printer MT-320T manufactured by Microtech Co., Ltd.
  • the solar cell was placed on a hot plate at 50 ° C., and a size of 0.2 mm ⁇ 1.5 mm ⁇ 176 mm was formed thereon.
  • the interconnector material (SSA-SPS manufactured by Hitachi Metals, Ltd.) and solder on both sides of the solar cell by tracing from above at a speed of about 10mm / s while pressing the soldering iron heated to 380 ° C. As a result, a cell with an interconnector was obtained.
  • EVA sheet (Ever film), cycloolefin copolymer (COC) film (Topas Advanced Polymers GmbH, TOPAS (registered trademark), thickness 75 ⁇ m)
  • EVA sheet and the back sheet were laminated in this order, and this laminate was pressed by a vacuum laminator to obtain a solar cell module.
  • this solar cell module was irradiated with pseudo-sunlight using a solar simulator and the maximum output Pmax, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF were determined, the maximum output Pmax was 4.7 W and the open circuit voltage Voc was 0.8. 6V, short circuit current Isc was 10.0 A, and fill factor FF was 71%.
  • the solar cell module is placed in a chamber having a temperature of 85 ° C. and a humidity of 85%, and a voltage of ⁇ 000 V is applied for 1000 hours. Then, an accelerated deterioration test was conducted. Thereafter, the solar cell module taken out from the PID test apparatus was irradiated with simulated sunlight by a solar simulator, and the maximum output Pmax, the open circuit voltage Voc, the short-circuit current Isc, and the fill factor FF were obtained. The maximum output Pmax was 4.7 W. The open circuit voltage Voc was 0.6 V, the short circuit current Isc was 10.0 A, the fill factor FF was 71%, and it was confirmed that the solar cell characteristics were not deteriorated at all compared to before the PID test.
  • a PID test apparatus manufactured by Espec Corp.
  • Example 6 Cover glass, EVA sheet, COC film (Topas Advanced Polymers GmbH, TOPAS (registered trademark), thickness 75 ⁇ m), EPDM rubber, interconnector cell, EPDM rubber (transparent, thickness 300 ⁇ m)
  • a solar cell module was obtained in the same manner as in Example 5 except that the back sheets were laminated in this order.
  • the maximum output Pmax was 4.7 W and the open circuit voltage Voc was 0.8. 6V
  • the short circuit current Isc was 11.0 A
  • the fill factor FF was 71%.
  • the solar cell module was irradiated with pseudo sunlight by a solar simulator, and the maximum output Pmax, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF
  • the maximum output Pmax is 4.9 W
  • the open-circuit voltage Voc is 0.6 V
  • the short-circuit current Isc is 10.0 A
  • the fill factor FF is 70%
  • the maximum output is increased, so the PID test It was confirmed that the solar cell characteristics were not deteriorated at all compared to before.
  • a solar cell module was obtained by the same method as in Example 5 except that the laminated body was laminated in the order of the cover glass, the EVA sheet, the cell with an interconnector, the EVA sheet, and the back sheet in this order.
  • this solar cell module was irradiated with pseudo-sunlight using a solar simulator and the maximum output Pmax, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF were determined, the maximum output Pmax was 4.7 W and the open circuit voltage Voc was 0.8. 6V, the short circuit current Isc was 11.0 A, and the fill factor FF was 71%.
  • a bus bar electrode (conductive paste containing silver-coated copper powder of Example 1 and an epoxy resin having a naphthalene skeleton) formed on the surface side (cover glass side) of the cell with an interconnector of the solar cell module after the PID test
  • FE-AES Auger electron spectroscopic analyzer
  • the diameter of the analysis area is set to 1 ⁇ m
  • the silver-coated copper powder When the qualitative analysis of the center part of the cross section of the copper particles was performed, oxygen was detected.
  • the solar cell module produced in Example 5 (the same solar as Comparative Example 8 except that the EVA sheet between the cover glass and the interconnector-attached cell was replaced with an EVA sheet, a cycloolefin copolymer (COC) film, and an EVA sheet).
  • the same qualitative analysis was performed on the battery module), and oxygen was not detected. From these results, it can be seen that the solar cell module produced in Example 5 does not detect oxygen even after the PID test, and has higher oxidation resistance by combining an epoxy resin having a naphthalene skeleton and a COC film.
  • the SEM images of the cross sections of the bus bar electrodes formed on the surface side (cover glass side) of the cell with the interconnector of the solar cell module produced in this comparative example and Example 5 are shown in FIGS. 1 and 2, respectively.
  • the cross section of the bus bar electrode formed on the surface side (cover glass side) of the cell with the interconnector of the solar cell module after the PID test is subjected to mapping analysis using the above-mentioned Auger Electron Spectrometer (FE-AES)
  • FE-AES Auger Electron Spectrometer
  • the solar cell module produced in Example 5 can maintain the state of the silver-coated copper powder even after the PID test by combining the epoxy resin having a naphthalene skeleton and the COC film.
  • the Ag map image and Cu map image by the mapping analysis of the cross section of the bus-bar electrode formed in the surface side (cover glass side) of the cell with an interconnector of the solar cell module produced in Example 5 are respectively FIG. 3 and FIG. Shown in
  • Example 7 89 parts by weight of silver powder having an average primary particle size of 0.8 ⁇ m (AG-2-1C manufactured by DOWA Electronics Co., Ltd.), 4 parts by weight of an epoxy resin, 0.2 parts by weight of a curing agent, 2 parts by weight of a urethane resin, As a solvent, 0.4 part by weight of butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.1 part by weight of oleic acid as a dispersing agent, a self-revolving vacuum stirring deaerator (manufactured by Shinky Corporation) After mixing (preliminary kneading) by Awatori Netaro, the conductive paste D was obtained by kneading with three rolls (EXAKT80S manufactured by Otto Herman).
  • a heterojunction type silicon wafer is prepared, and the conductive paste D is printed on the entire back surface of the silicon wafer by a screen printer (MT-320T manufactured by Microtech Co., Ltd.). Was heated at 150 ° C. for 10 minutes and dried, and then heated at 200 ° C. for 30 minutes to be cured. Thereafter, the conductive paste D is printed on the shape of 100 finger electrodes with a width of 50 ⁇ m by a screen printing machine (MT-320T manufactured by Microtech Co., Ltd.) on the surface of the silicon wafer, and then is heated by a hot air dryer. After drying by heating at 10 ° C. for 10 minutes, it was cured by heating at 200 ° C. for 30 minutes.
  • a screen printer MT-320T manufactured by Microtech Co., Ltd.
  • the conductive paste A similar to that of Example 5 was applied to the surface of the silicon wafer by a screen printer (MT-320T manufactured by Microtech Co., Ltd.) with three finger bars having a shape of 100 finger electrodes and a width of 1.3 mm. After printing in the shape which matched the electrode shape, it heated and dried at 150 degreeC with the hot air type dryer for 10 minutes, Then, it heated at 200 degreeC for 30 minutes, and was hardened.
  • a screen printer MT-320T manufactured by Microtech Co., Ltd.
  • a solar cell module was obtained by the same method as in Example 5.
  • this solar cell module was irradiated with pseudo sunlight by a solar simulator and the maximum output Pmax, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF were determined, the maximum output Pmax was 5.3 W and the open circuit voltage Voc was 0. 7V, the short circuit current Isc was 11.0 A, and the fill factor FF was 71%.
  • the solar cell module was irradiated with pseudo sunlight by a solar simulator, and the maximum output Pmax, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF
  • the maximum output Pmax is 4.7 W
  • the open circuit voltage Voc is 0.7 V
  • the short circuit current Isc is 10.0 A
  • the fill factor FF is 67%
  • the output deterioration rate is only 11%, and it is used for a long time. It was confirmed that it could withstand
  • the conductive paste according to the present invention can be used for the production of electronic components such as conductor patterns of circuit boards, electrodes of boards such as solar cells, and circuits.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Photovoltaic Devices (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne une pâte électroconductrice dans laquelle, même lorsqu'une électrode de barre-bus d'une cellule solaire produite en utilisant une pâte électroconductrice résineuse dans laquelle est utilisée une poudre de cuivre enrobée d'argent est connectée à une ligne de languette par brasage, il est possible d'empêcher une diminution de l'efficacité de conversion de la cellule solaire. La pâte électroconductrice selon l'invention comprend une résine et une poudre de cuivre enrobée d'argent dans laquelle la surface d'une poudre de cuivre ayant un diamètre de particules cumulé de 50 % (diamètre D50), sur la base d'un volume mesuré à l'aide d'un dispositif de distribution de taille de particules par diffraction laser de 0,1 à 15 µm, est enrobée d'une couche d'argent. Une résine époxy ayant une structure de naphtalène est utilisée en tant que résine, et de préférence au moins l'un parmi l'imidazole et un agent de durcissement à base d'amine de trifluorure de bore est ajouté en tant qu'agent de durcissement.
PCT/JP2018/005829 2017-02-24 2018-02-20 Pâte électroconductrice WO2018155393A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006129487A1 (fr) * 2005-05-30 2006-12-07 Sumitomo Electric Industries, Ltd. Pâte conductrice et carte de circuit imprimé multicouche l’utilisant
JP2007019006A (ja) * 2005-06-08 2007-01-25 Hitachi Chem Co Ltd 導電ペーストおよびそれを用いた電子部品搭載基板
JP2010083952A (ja) * 2008-09-30 2010-04-15 Mitsubishi Materials Corp 導電性インク組成物及び該組成物を用いて形成された太陽電池モジュール
JP2011086397A (ja) * 2009-10-13 2011-04-28 Asahi Kasei E-Materials Corp 導電性ペースト及び半導体装置
JP2012504179A (ja) * 2008-09-26 2012-02-16 フライズ・メタルズ・インコーポレイテッド 無鉛伝導性組成物およびそれを用いた方法
WO2014203897A1 (fr) * 2013-06-19 2014-12-24 横浜ゴム株式会社 Composition électroconductrice et cellule solaire
WO2016088540A1 (fr) * 2014-12-05 2016-06-09 三井金属鉱業株式会社 Composition conductrice, tableau de connexions et leur procédé de production

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006129487A1 (fr) * 2005-05-30 2006-12-07 Sumitomo Electric Industries, Ltd. Pâte conductrice et carte de circuit imprimé multicouche l’utilisant
JP2007019006A (ja) * 2005-06-08 2007-01-25 Hitachi Chem Co Ltd 導電ペーストおよびそれを用いた電子部品搭載基板
JP2012504179A (ja) * 2008-09-26 2012-02-16 フライズ・メタルズ・インコーポレイテッド 無鉛伝導性組成物およびそれを用いた方法
JP2010083952A (ja) * 2008-09-30 2010-04-15 Mitsubishi Materials Corp 導電性インク組成物及び該組成物を用いて形成された太陽電池モジュール
JP2011086397A (ja) * 2009-10-13 2011-04-28 Asahi Kasei E-Materials Corp 導電性ペースト及び半導体装置
WO2014203897A1 (fr) * 2013-06-19 2014-12-24 横浜ゴム株式会社 Composition électroconductrice et cellule solaire
WO2016088540A1 (fr) * 2014-12-05 2016-06-09 三井金属鉱業株式会社 Composition conductrice, tableau de connexions et leur procédé de production

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