WO2017135138A1

WO2017135138A1 - Silver-coated copper powder and method for producing same

Info

Publication number: WO2017135138A1
Application number: PCT/JP2017/002676
Authority: WO
Inventors: 洋神賀; 徳昭野上; 愛子平田
Original assignee: Ｄｏｗａエレクトロニクス株式会社
Priority date: 2016-02-03
Filing date: 2017-01-26
Publication date: 2017-08-10

Abstract

Provided are: a silver-coated copper powder which, when used in a conductive paste for forming a bus bar electrode of a solar cell, enables production of a solar cell that improves the conversion efficiency of the solar cell as compared to conventional silver-coated copper powders so as to achieve a high conversion efficiency equivalent to that achieved by the use of silver powder; and a method for producing the silver-coated copper powder. A silver-coated copper powder, obtained by coating the surface of a copper powder prepared by an atomization method or the like with a silver-containing layer comprising at least 5 mass% (with respect to the silver-coated copper powder) of silver or a silver compound, is added to a cyanogen compound solution, such as a potassium silver cyanide solution, a potassium gold cyanide solution, a potassium cyanide solution, or a sodium cyanide solution, so that 3-3000 ppm of cyanide is included in the copper powder coated with the silver-containing layer.

Description

Silver-coated copper powder and method for producing the same

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.

Conventionally, in order to form electrodes and wiring of electronic parts by printing methods, etc., 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. .

However, although 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. On the other hand, copper powder has a low volume resistivity and is a good conductive material. However, since it is easily oxidized, it has poor storage stability (reliability) compared to silver powder.

In order to solve these problems, silver-coated copper powder in which the surface of the copper powder is coated with silver has been proposed as a metal powder used in the conductive paste (see, for example, Patent Documents 1 and 2).

JP 2010-174411 A (paragraph number 0003) JP 2010-077745 (paragraph number 0006)

In recent years, it has been attempted to use a conductive paste using silver-coated copper powder, which is cheaper than silver powder, instead of a conductive paste using silver powder as a conductive paste for forming bus bar electrodes for solar cells. .

However, when a conductive paste using a conventional silver-coated copper powder such as the silver-coated copper powder of

Patent Documents

1 and 2 is used as a conductive paste for forming a bus bar electrode of a solar cell, a conductive paste using silver powder is used. There is a problem that the conversion efficiency of the solar cell is reduced as compared with the case where the paste is used.

Therefore, in view of such conventional problems, 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.

As a result of diligent research to solve the above problems, 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. When used as a conductive paste for the formation of bus bar electrodes in solar cells, 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.

That is, in the method for producing a silver-coated copper powder according to the present invention, copper powder whose surface is coated with a silver-containing layer is added to a cyanide compound solution, and 3 to 3000 ppm of cyan is added to the copper powder coated with the silver-containing layer. It is characterized by containing. In this method for producing a silver-coated copper powder, 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. Moreover, it is preferable that 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 | covered with the silver containing layer before adding to a cyanide solution does not contain cyan. 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. Further, 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. Further, after cyan is contained in the copper powder coated with the silver-containing layer, 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.

Further, 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. Features. In this silver-coated copper powder, 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. In this case, the cyan content is 3 to 10 ppm. Is preferred. Moreover, it is preferable that 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 _{(D 50} diameter) 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. Alternatively, 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.

Furthermore, 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.

According to the present invention, when used in a conductive paste for forming a bus bar electrode of a solar cell, 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.

In the embodiment of the method for producing a silver-coated copper powder according to the present invention, 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).

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. Preferably there is. As such a 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. When a cyanogen gold potassium solution or a cyanogen silver potassium solution is used as the cyanide solution, 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.

After adding cyan to the copper powder (silver-coated copper powder) coated with the silver-containing layer, it is preferable to attach a surface treatment agent to the surface of the silver-coated copper powder. As the surface treatment agent, phytic acid and azoles such as benzotriazole are preferably used. In order to adhere the surface treatment agent to the surface of the silver-coated copper powder, it is preferable to add 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 ~ 15μm, 0.3 ~ 10μm More preferably, the thickness is 1 to 5 μm. A cumulative 50% particle diameter (D ₅₀ diameter) of less than 0.1 μm is not preferable because it adversely affects the conductivity of the silver-coated copper powder. On the other hand, if it exceeds 15 μm, 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. In particular, when manufactured by the so-called water atomization method in which high-pressure water is sprayed, 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.

As 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. For example, 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. If a solution containing cyan is used when coating copper powder with a silver-containing layer, the silver-containing layer tends to be non-uniform, so use a solution containing cyan when coating copper powder with a silver-containing layer. However, it is preferable that the silver-coated copper powder before silver is supported does not contain cyan.

As this solvent, water, an organic solvent, or a mixture of these can be used. When using 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. In addition, as 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.

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. In addition, in order to carry out the reaction of coating copper powder with a silver-containing layer (silver coating reaction) as uniformly as possible, 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.

In order to form a silver-containing layer more uniformly, a chelating agent may be added to the solution. As 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. . In particular, since 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. Specifically, 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.

In order to perform the silver coating reaction stably and safely, a pH buffer may be added to the solution. As this pH buffering agent, ammonium carbonate, ammonium hydrogen carbonate, aqueous ammonia, sodium hydrogen carbonate, or the like can be used.

During the silver coating reaction, stir copper powder in the solution before adding the silver salt, and add the solution containing the silver salt while the copper powder is sufficiently dispersed in the solution. Is preferred. 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).

In the silver-coated copper powder of this embodiment, 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. Moreover, 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. However, if the amount of carbon or nitrogen in the silver-coated copper powder is too large, the conductivity may deteriorate when used in the conductive paste, so the carbon content and nitrogen content in the silver-coated copper powder Each of them is preferably 1% by mass or less, and more preferably 0.3% by mass. Moreover, it is preferable that the surface treating agent has adhered to the surface of the copper powder coat | covered with the silver content layer. As 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. In addition, in the manufacturing method of the silver covering copper powder of embodiment mentioned above, the substantially spherical shape or flake shape may be sufficient as the shape of the copper powder (silver covering copper powder) coat | covered with the silver content layer.

Using the silver-coated copper powder of the above-described embodiment as a conductor, 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. For example, 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. Moreover, the resin contained in the conductive paste can be appropriately selected according to the purpose of use of the conductive paste. For example, 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 One or more of 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. These 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.

If 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. When 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.

Hereinafter, examples of the silver-coated copper powder and the production method thereof according to the present invention will be described in detail.

[Example 1]
A commercially available copper powder manufactured by the atomizing method (Atomized copper powder SF-Cu 5 μm 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 μm, the cumulative 50% particle diameter (D ₅₀ ) was 5.20 μm, and the cumulative 90% particle diameter (D ₉₀ ) was 9.32 μm. 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.

Further, a solution (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. A solution (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.

Next, 350 g of the above copper powder was added to Solution 1 in a nitrogen atmosphere, and the temperature was raised to 35 ° C. while stirring. The solution 2 was added to the solution in which the copper powder was dispersed and stirred for 30 minutes, followed by filtration, washing with water, and drying to obtain a copper powder coated with silver (silver-coated copper powder). 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.

Next, 35 g (25 ° C.) of pure water is added to 20 g of the obtained silver-coated copper powder, 2.95 mL of a silver-supported liquid is added, and the mixture is stirred for 60 minutes to react, and then extruded water is applied. , Filtered by Nutsche method, washed with pure water on the solid matter on the filter paper (until the potential of the liquid after washing becomes 0.5 mS / m or less), and dried at 70 ° C. for 5 hours with a vacuum dryer. Thus, a silver-coated copper powder having silver supported on the surface was obtained. 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.

After 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. In addition, since 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 amount of silver supported on the surface of the silver-coated copper powder of this example was 0.63% by mass (= 10.77% by mass to 10.14% by mass).

In addition, the carbon content, nitrogen content, oxygen content and cyan content in this silver-coated copper powder (with silver supported on the surface) 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. As a result, the carbon content in the silver-coated copper powder was 0.13% by mass, the nitrogen content was 0.112% by mass, and the oxygen content was 0.10% by mass.

As for 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 μm, the accumulated 50% particle diameter (D ₅₀ ) was 5.0 μm, and the accumulated 90% particle diameter (D ₉₀ ) was 10.0 μm. there were.

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.

Further, 87.0% by mass of the obtained silver-coated copper powder (supporting silver on the surface), 3.8% by mass of an epoxy resin (JER1256 manufactured by Mitsubishi Chemical Corporation), and butyl carbitol acetate ( 8.6% by mass, manufactured by Wako Pure Chemical Industries, Ltd., 0.5% by mass of a curing agent (M-24, manufactured by Ajinomoto Fine Techno Co., Ltd.), and oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant. 0.1% by mass is mixed (preliminary kneading) with a self-revolving vacuum stirring deaerator (Shinky Co., Ltd. Awatori Nertaro), and then kneaded with three rolls (EXAKT80S manufactured by Ottoman). As a result, conductive pastes 1 were obtained.

Further, 45 L of industrial ammonia water was added to 502.7 L of silver nitrate solution of 21.4 g / L as silver ions to produce a silver ammine complex solution. To the resulting silver ammine complex solution, 8.8 L of a sodium hydroxide solution having a concentration of 100 g / L was added to adjust pH, diluted by adding 462 L of water, and 48 L of industrial formalin was added as a reducing agent. Immediately thereafter, 121 g of a 16% by weight stearic acid emulsion was added as stearic acid. The silver slurry thus obtained was filtered, washed with water, and dried to obtain 21.6 kg of silver powder. 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 μm. 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.

85.4% by mass of the silver powder thus obtained, 1.2% by mass of ethyl cellulose resin (manufactured by Wako Pure Chemical Industries, Ltd.), solvent (Texanol manufactured by JMC Co., Ltd. and Wako Pure Chemical Industries, Ltd.) 7.9% by mass of a solvent in which butyl carbitol acetate is mixed 1: 1), 1.5% by mass of glass frit (ASF-1898B manufactured by Asahi Glass Co., Ltd.) and tellurium dioxide (Wako Pure Chemical Industries, Ltd.) as additives 3.2% by mass was mixed (preliminarily kneaded) with a self-revolving vacuum stirring and degassing apparatus (Shinky Co., Ltd. Awatori Nertaro), and then three rolls (EXAKT80S manufactured by Ottoman). The conductive paste 2 was obtained by kneading.

Next, two silicon wafers (E & M Co., Ltd., 80Ω / □, 6 inch single crystal) are prepared, and aluminum is applied to the back of each silicon wafer by a screen printer (MT-320T manufactured by Microtech Co., Ltd.). After the paste (Alsolar 14-7021 manufactured by Toyo Aluminum Co., Ltd.) was printed, it was dried with a hot air dryer at 200 ° C. for 10 minutes, and a screen printer (MT- 320T), the conductive paste 2 is printed in the shape of 100 finger electrodes having a width of 50 μm, and then dried at 200 ° C. for 10 minutes with a hot air dryer, and a high-speed firing IR furnace (manufactured by NGK Corporation) Baking test was performed at a peak temperature of 820 ° for 21 seconds in-out of a four-chamber furnace. Thereafter, 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.). As a result, 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, and the voltage (open-circuit voltage) Voc between the two terminals when the output terminal of the solar cell is opened. Is 0.623 V, current density Jsc (short-circuit current Isc per cm ² ) is 0.0362 A / cm ² , and maximum output Pmax (= Imax · Vmax) is divided by the product of open-circuit voltage Voc and current density Jsc (curve Factor) FF (= Pmax / Voc · Isc) is 88.35, and power generation efficiency Eff (value obtained by dividing the maximum output Pmax by the irradiation light quantity (W) (per 1 cm ² ) by 100) is 19.94. %, The series resistance Rs was 0.0043Ω / □.

[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.

Next, 100 g of silver-coated copper powder (copper powder coated with silver) obtained by the same method as in Example 1 (before supporting silver on the surface) was added to 150 g of pure water, and the above gold plating was performed. After adding 10.299 g of liquid and stirring at 30 ° C. for 30 minutes, the solution was filtered while applying extrusion water, and pure water was applied to the solid matter on the filter paper (the potential of the liquid after washing was 0.5 mS / m). It was washed and dried at 70 ° C. for 5 hours with a vacuum dryer to obtain a silver-coated copper powder having gold supported on the surface. 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.

After 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.

Further, in the same manner as in Example 1, the carbon content, nitrogen content, oxygen content and cyan content in the silver-coated copper powder (with gold supported on the surface) were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined. As a result, 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%, and 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 5.0 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 10.0 μm. The BET specific surface area of the silver-coated copper powder was 0.34 m ² / g.

Further, 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 0.0042Ω / □.

[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.

After 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.

Further, in the same manner as in Example 1, the carbon content, nitrogen content, oxygen content, and cyan content in this silver-coated copper powder (with CN adsorbed on the surface) were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined. As a result, 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, and 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 6.2 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 10.3 μm. The BET specific surface area of the silver-coated copper powder was 0.32 m ² / g.

Further, 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 0.0042Ω / □.

[Comparative 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.

Further, in the same manner as in Example 1, 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 5.2 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 10.1 μm. The BET specific surface area of the silver-coated copper powder was 0.31 m ² / g.

Further, 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 0.0058Ω / □.

[Comparative Example 2]
A commercially available silver powder (atomized silver powder HWQ 5 μm 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. When 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 μm, a cumulative 50% particle size (D ₅₀ ) of 4.8 μm, a cumulative 90% particle size (D ₉₀ ) of 8.0 μm, The BET specific surface area of the copper powder was 0.16 m ² / g.

Moreover, 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. 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 86.60, the power generation efficiency Eff is 20.18%, and the series resistance Rs Was 0.0040Ω / □.

[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. 99.9% by mass or more, carbon content was 0.005% by mass, nitrogen content was less than 0.01% by mass, oxygen content was 0.02% by mass, and the amount of cyan was 3 ppm. The cumulative 10% particle diameter (D ₁₀ ) of the silver powder is 3.7 μm, the cumulative 50% particle diameter (D ₅₀ ) is 8.4 μm, the cumulative 90% particle diameter (D ₉₀ ) is 16.5 μm, The BET specific surface area was 0.18 m ² / g.

Moreover, 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. As a result, 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%, and the series resistance Rs. Was 0.0044Ω / □.

[Comparative 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.

Further, by the same method as in Example 1, 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. As a result, 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, and 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 7.7 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 16.4 μm. The BET specific surface area of the silver-plated copper powder was 0.53 m ² / g.

Moreover, 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. As a result, 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%, and the series resistance Rs. Was 0.1077Ω / □.

[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 μm and cumulative 90% was 9.5 μm.

When the content of Ag in the silver-coated copper powder thus obtained (with silver supported thereon) 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%. In addition, since the content of Ag in the silver-coated copper powder of Comparative Example 5 described later (a silver-coated copper powder that is not added to the silver-supported liquid and does not support silver on the surface) is 10.93% by mass. The amount of silver supported on the surface of the silver-coated copper powder of this example was 0.96% by mass (= 11.89% by mass-10.93% by mass).

Further, by the same method as in Example 1, the carbon content, nitrogen content, oxygen content and cyan content in this silver-coated copper powder (with silver supported thereon) were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined. As a result, 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, and 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 6.5 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 13.2 μm. The BET specific surface area of the silver-coated copper powder was 0.41 m ² / g.

Moreover, it replaced with the silicon wafer (E & M Co., Ltd., 80 ohms / square, 6 inches single crystal) using the obtained conductive paste 1 obtained from the silver-coated copper powder (with silver supported on the surface). A solar cell was produced in the same manner as in Example 1 except that a silicon wafer (E & M Co., Ltd., 100Ω / □, 6-inch single crystal) was used. As a result, 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%, and the series resistance Rs Was 0.0041Ω / □.

[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.

When the content of Ag in the silver-coated copper powder thus obtained (with silver supported thereon) was determined in the same manner as in Example 1, the Ag content in the silver-coated copper powder was 11 .26% by mass. In addition, since the content of Ag in the silver-coated copper powder of Comparative Example 5 described later (a silver-coated copper powder that is not added to the silver-supported liquid and does not support silver on the surface) is 10.93% by mass. The amount of silver supported on the surface of the silver-coated copper powder of this example was 0.33% by mass (= 111.26% by mass-10.93% by mass).

Further, by the same method as in Example 1, the carbon content, nitrogen content, oxygen content and cyan content in this silver-coated copper powder (with silver supported thereon) were determined, and the silver-coated copper powder The particle size distribution and the BET specific surface area were determined. 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 5 ppm. The silver-coated copper powder has a cumulative 10% particle diameter (D ₁₀ ) of 2.6 μm, a cumulative 50% particle diameter (D ₅₀ ) of 5.6 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 10.9 μm. The BET specific surface area of the silver-coated copper powder was 0.31 m ² / g.

Further, 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 0.0039Ω / □.

[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.

When the content of Ag in the silver-coated copper powder thus obtained (the surface was treated with phytic acid after supporting silver on the surface) was determined in the same manner as in Example 1, The Ag content in the copper powder was 11.39% by mass.

Further, in the same manner as in Example 1, 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 | requiring the quantity, the particle size distribution and BET specific surface area of silver covering copper powder were calculated | required. As a result, the carbon content in the silver-coated copper powder is 0.02% by mass, the nitrogen content is less than 0.01% by mass, and 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 5.9 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 10.7 μm. The BET specific surface area of the silver-coated copper powder was 0.31 m ² / g.

Add about 5-10 mL of ion-exchanged water and 5 mL of nitric acid (reagent for precision analysis (UGR)) to 1 g of the obtained silver-coated copper powder (the surface was treated with phytic acid after supporting silver on the surface). The mixture is heated and allowed to cool, diluted to a constant volume of 100 mL, diluted, and phosphorus in silver-coated copper powder is measured using an inductively coupled plasma optical emission spectrometer (ICP-OES) (SPS-5100 manufactured by Hitachi High-Tech Science Co., Ltd.). It was 0.034 mass% when content was measured. Moreover, it was 0.12 mass% when the quantity (surface treatment agent adhesion amount) of the phytic acid adhering to the surface of silver covering copper powder was computed from this phosphorus content.

Further, except that 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. As a result, 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%, and the series resistance Rs Was 0.0035Ω / □.

[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.

When the content of Ag in the silver-coated copper powder thus obtained (the surface was treated with benzotriazole after supporting silver on the surface) was determined by the same method as in Example 1, the silver coating The Ag content in the copper powder was 11.50% by mass.

Further, in the same manner as in Example 1, 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 | requiring the quantity, the particle size distribution and BET specific surface area of silver covering copper powder were calculated | required. As a result, 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, and the amount of cyan in the silver-coated copper powder Was 7 ppm. Moreover, it was 0.06 mass% when the quantity (surface treatment agent adhesion amount) of the benzotriazole adhering to the surface of silver coating copper powder was computed from nitrogen content in silver coating copper powder. The silver-coated copper powder has a cumulative 10% particle diameter (D ₁₀ ) of 2.6 μm, a cumulative 50% particle diameter (D ₅₀ ) of 5.8 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 10.5 μm. The BET specific surface area of the silver-coated copper powder was 0.40 m ² / g.

Further, except that the conductive paste 1 obtained from the obtained silver-coated copper powder (the surface was treated with benzotriazole 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. As a result, the short-circuit current Isc is 9.30 A, the open circuit voltage Voc is 0.641 V, the current density Jsc is 0.0383 A / cm ² , the fill factor FF is 88.91, the power generation efficiency Eff is 21.81%, and the series resistance Rs Was 0.0044Ω / □.

[Comparative Example 5]
The silver-coated copper powder (before the silver was supported on the surface) obtained by the same method as in Example 4 (copper powder coated with silver) was dissolved in aqua regia and then filtered with pure water. Then, silver was recovered as silver chloride, and the Ag content in the silver-coated copper powder was 10.93 mass% when the Ag content was determined from the silver chloride thus recovered by a weight method.

Further, in the same manner as in Example 1, 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 μm, a cumulative 50% particle diameter (D ₅₀ ) of 5.8 μm, and a cumulative 90% particle diameter (D ₉₀ ) of 11.6 μm. The BET specific surface area of the silver-coated copper powder was 0.35 m ² / g.

Further, 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 0.0055Ω / □.

Tables 1 to 3 show the results of these examples and comparative examples.

As can be seen from Tables 1 to 3, when the conductive paste using the silver-coated copper powder (containing 3 to 3000 ppm of cyan) of Examples 1 to 7 was used for forming bus bar electrodes of solar cells, 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).

In 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. This is because 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 | cyanogen moderately by a copper ion and cyanide reacting.

Further, 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. Although 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.

Claims

Production of silver-coated copper powder, characterized in that copper powder coated on the surface with a silver-containing layer is added to a cyanide solution so that the copper powder coated with the silver-containing layer contains 3 to 3000 ppm of cyanide. Method.
The method for producing a silver-coated copper powder according to claim 1, wherein the silver-containing layer is a layer made of silver or a silver compound.
The method for producing a silver-coated copper powder according to claim 1, wherein the silver-containing layer is a layer made of silver.
The method for producing a silver-coated copper powder according to claim 3, wherein the cyan content is 3 to 10 ppm.
The method for producing a silver-coated copper powder according to claim 1, wherein the amount of the silver-containing layer with respect to the silver-coated copper powder is 5% by mass or more.
The method for producing a silver-coated copper powder according to claim 1, wherein the copper powder coated with the silver-containing layer before being added to the cyanide solution does not contain cyan.
2. The method for producing a silver-coated copper powder according to claim 1, wherein the cyanide compound solution comprises a cyanogen silver potassium solution, a cyanogen gold potassium solution, a potassium cyanide solution, or a sodium cyanide solution.
Wherein the cumulative 50% particle diameter measured by a laser diffraction type particle size distribution apparatus of the copper powder (D 50 diameter) is 0.1 ~ 15 [mu] m, the manufacturing method of the silver-coated copper powder according to claim 1 .
The silver according to claim 1, wherein a surface treatment agent is adhered to the surface of the copper powder coated with the silver-containing layer after cyan is contained in the copper powder coated with the silver-containing layer. A method for producing coated copper powder.
The method for producing a silver-coated copper powder according to claim 9, wherein the surface treatment agent is phytic acid or azoles.
A silver-coated copper powder comprising a silver-coated copper powder having a surface coated with a silver-containing layer, wherein the amount of cyan in the silver-coated copper powder is 3 to 3000 ppm.
The silver-coated copper powder according to claim 11, wherein the silver-containing layer is a layer made of silver or a silver compound.
The silver-coated copper powder according to claim 11, wherein the silver-containing layer is a layer made of silver.
The silver-coated copper powder according to claim 13, wherein the cyan content is 3 to 10 ppm.
The amount of the said silver containing layer with respect to the said silver covering copper powder is 5 mass% or more, The silver covering copper powder of Claim 11 characterized by the above-mentioned.
Wherein the cumulative 50% particle diameter measured by a laser diffraction type particle size distribution apparatus of the copper powder (D 50 diameter) is 0.1 ~ 15 [mu] m, silver-coated copper powder of claim 11.
The silver-coated copper powder according to claim 11, wherein a carbon content and a nitrogen content in the silver-coated copper powder are each 0.04% by mass or more.
The silver-coated copper powder according to claim 11, wherein a surface treatment agent is attached to a surface of the copper powder coated with the silver-containing layer.
The silver-coated copper powder according to claim 18, wherein the surface treatment agent is phytic acid or azoles.
A conductive paste using the silver-coated copper powder according to any one of claims 11 to 19 as a conductor.
A conductive paste comprising a solvent and a resin, and containing the silver-coated copper powder according to claim 11 as a conductive powder.
A method for producing an electrode for a solar cell, comprising forming an electrode on a surface of a substrate by applying the conductive paste of claim 20 to the substrate and then curing the paste.