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WO2011090214A1 - Composition en pâte pour électrodes, et batterie solaire - Google Patents

Composition en pâte pour électrodes, et batterie solaire Download PDF

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Publication number
WO2011090214A1
WO2011090214A1 PCT/JP2011/051364 JP2011051364W WO2011090214A1 WO 2011090214 A1 WO2011090214 A1 WO 2011090214A1 JP 2011051364 W JP2011051364 W JP 2011051364W WO 2011090214 A1 WO2011090214 A1 WO 2011090214A1
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Prior art keywords
particles
electrode
copper
paste composition
mass
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PCT/JP2011/051364
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English (en)
Japanese (ja)
Inventor
野尻　剛
吉田　誠人
岩室　光則
修一郎 足立
木沢　桂子
拓也 青柳
山本　浩貴
内藤　孝
隆彦 加藤
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Resonac Corp
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Hitachi Chemical Co Ltd
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Publication of WO2011090214A1 publication Critical patent/WO2011090214A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H10F77/219—Arrangements for electrodes of back-contact photovoltaic cells
    • H10F77/223—Arrangements for electrodes of back-contact photovoltaic cells for metallisation wrap-through [MWT] photovoltaic cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an electrode paste composition and a solar cell.
  • a solar cell is provided with a surface electrode, and the wiring resistance and contact resistance of this surface electrode are related to voltage loss related to conversion efficiency, and the wiring width and shape affect the amount of incident sunlight (See, for example, Yasuhiro Sasakawa, “Solar Power Generation: Latest Technologies and Systems”, CMC Publishing Company, 2001, p. 26-27).
  • the surface electrode of a solar cell is usually formed as follows. That is, a conductive composition is applied by screen printing or the like on an n-type semiconductor layer formed by thermally diffusing phosphorus or the like at a high temperature on the light-receiving surface side of a p-type silicon substrate, and this is applied to 800 to 900 A surface electrode is formed by baking at ° C.
  • the conductive composition forming the surface electrode includes conductive metal powder, glass particles, various additives, and the like.
  • the conductive metal powder As the conductive metal powder, silver powder is generally used. However, use of metal powders other than silver powder has been studied for various reasons. For example, a conductive composition capable of forming a solar cell electrode containing silver and aluminum is disclosed (see, for example, JP-A-2006-313744). An electrode-forming composition containing metal nanoparticles containing silver and metal particles other than silver such as copper has been disclosed (see, for example, JP-A-2008-226816).
  • silver used for electrode formation is a noble metal, and due to the problem of resources, and the metal itself is expensive, a proposal of a paste material to replace the silver-containing conductive composition (silver-containing paste) is desired.
  • a promising material that can replace silver is copper that is applied to semiconductor wiring materials. Copper is abundant in terms of resources, and the cost of bullion is as low as about 1/100 of silver. However, copper is a material that is easily oxidized at a high temperature of 200 ° C. or higher.
  • an atmosphere such as nitrogen is used in order to form an electrode by firing the composition. A special process of firing was necessary.
  • the present invention suppresses the formation of a copper oxide film during firing, and can form an electrode paste composition having a low resistivity, and a solar electrode having an electrode formed using the electrode paste composition It is an object to provide a battery.
  • the first aspect of the present invention is an electrode paste composition containing metal particles mainly composed of copper, a flux, glass particles, a solvent, and a resin.
  • the electrode paste composition preferably further contains silver particles.
  • the copper-based metal particles include phosphorus-containing copper alloy particles, silver-coated copper particles, and triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, And at least one selected from copper particles surface-treated with at least one selected from the group consisting of metal alkoxides.
  • the flux is preferably at least one selected from fatty acids, boric acid compounds, fluorinated compounds, and borofluorinated compounds.
  • the glass particles preferably contain an oxide containing phosphorus.
  • a second aspect of the present invention is a solar cell having an electrode formed by firing the electrode paste composition applied on a silicon substrate.
  • the addition of a flux suppresses the formation of a copper oxide film even during firing, and an electrode paste composition capable of forming an electrode having a low resistivity and the electrode paste composition are used.
  • a solar cell having the formed electrode can be provided.
  • the electrode paste composition of the present invention comprises at least one metal particle mainly composed of copper, at least one flux, at least one glass particle, at least one solvent, and at least one resin. Seeds. With such a configuration, generation of a copper oxide film is suppressed even during firing, and an electrode with low resistivity can be formed.
  • the metal particles containing copper as a main component in the present invention mean metal particles in which the content of the copper component in one metal particle is 50% by mass or more.
  • the copper constituting the copper particles may be pure copper or metal particles that may contain other atoms within a range that does not impair the effects of the present invention.
  • the metal particle containing the component to provide may be sufficient.
  • Examples of other atoms in the metal particles substantially composed of copper include, for example, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
  • Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
  • grain can be 3 mass% or less in the said copper containing particle
  • the metal particles containing copper and a component imparting oxidation resistance to copper preferably have a peak temperature of an exothermic peak exhibiting a maximum area in differential thermal-thermal mass measurement (TG-DTA) of 280 ° C. or higher.
  • the temperature is more preferably 280 to 800 ° C, and further preferably 350 to 750 ° C.
  • the copper-containing particles having a peak temperature of 280 ° C. or more at the exothermic peak showing the maximum area in the differential thermal-thermal mass simultaneous measurement include, for example, phosphorus-containing copper alloy particles, silver-coated copper There may be mentioned particles and surface-treated copper particles.
  • the copper-containing particles may be used alone or in combination of two or more.
  • the particle diameter of the copper-containing particles is not particularly limited, but the particle diameter when the integrated mass is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to 10 ⁇ m. Is preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the copper containing particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
  • the particle size of the copper-containing particles is measured with a microtrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300 type).
  • the shape of the copper-containing particles is not particularly limited and may be spherical, flat, block-like, plate-like, scale-like, etc., but from the viewpoint of oxidation resistance and low resistivity, spherical, It is preferably a flat shape or a plate shape.
  • the content of the copper-containing particles contained in the electrode paste composition of the present invention, and the total content of the copper-containing particles and the silver particles in the case of containing silver particles described later are, for example, 70 to 94% by mass. In view of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, more preferably 74 to 88% by mass.
  • phosphorus copper brazing As a phosphorus-containing copper alloy, a brazing material called phosphorus copper brazing (phosphorus concentration: about 7 mass%) is known. Phosphorus copper brazing is also used as a bonding agent between copper and copper, but by using phosphorous-containing copper alloy particles as copper-containing particles contained in the electrode paste composition of the present invention, oxidation resistance is improved. An electrode having excellent and low resistivity can be formed. Further, the electrode can be fired at a low temperature, and the effect that the process cost can be reduced can be obtained.
  • the phosphorus content contained in the phosphorus-containing copper alloy in the present invention is preferably such that the peak temperature of the exothermic peak showing the maximum area is 280 ° C. or more in simultaneous differential heat-thermal mass measurement.
  • the phosphorus content contained in the phosphorus-containing copper alloy is preferably 0.01 to 8% by mass, and preferably 0.5 to 7.8% by mass in the total mass of the phosphorus-containing copper alloy. More preferably, the content is 1 to 7.5% by mass.
  • the phosphorus content contained in the phosphorus-containing copper alloy is 8% by mass or less, a lower resistivity can be achieved, and the productivity of the phosphorus-containing copper alloy is excellent.
  • the more outstanding acid resistance can be achieved because it is 0.01 mass% or more.
  • the phosphorus-containing copper alloy particles are an alloy containing copper and phosphorus, but may further contain other atoms.
  • other atoms include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
  • Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
  • the content rate of the other atom contained in the said phosphorus containing copper alloy particle can be 3 mass% or less in the said phosphorus containing copper alloy particle, for example, from a viewpoint of oxidation resistance and a low resistivity, it is 1 It is preferable that it is below mass%.
  • the particle diameter of the phosphorus-containing copper alloy particles is not particularly limited, but the particle diameter when the accumulated mass is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to 10 ⁇ m. It is preferably 1 ⁇ m to 5 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the phosphorus containing copper alloy particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
  • the shape of the phosphorus-containing copper alloy particles is not particularly limited, and may be any of spherical, flat, block, plate, scale, etc., from the viewpoint of oxidation resistance and low resistivity. A spherical shape, a flat shape, or a plate shape is preferable.
  • the phosphorus-containing copper alloy can be produced by a commonly used method.
  • the phosphorus-containing copper alloy particles can be prepared using a normal method of preparing metal powder using a phosphorus-containing copper alloy prepared so as to have a desired phosphorus content, for example, a water atomization method Can be produced by a conventional method.
  • the water atomization method is described in Metal Handbook (Maruzen Publishing Division). Specifically, for example, after phosphorus-containing copper alloy is dissolved and powdered by nozzle spray, the obtained powder is dried and classified, whereby desired phosphorus-containing copper alloy particles can be produced.
  • grains which have a desired particle diameter can be manufactured by selecting classification conditions suitably.
  • the content of the phosphorus-containing copper alloy particles contained in the electrode paste composition of the present invention, and the total content of the phosphorus-containing copper alloy particles and silver particles in the case of containing silver particles described later are, for example, 70 to 94 From the viewpoint of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, and more preferably 74 to 88% by mass.
  • the phosphorus-containing copper alloy particles may be used singly or in combination of two or more. Moreover, you may use in combination with copper containing particles other than a phosphorus copper alloy particle.
  • phosphorus-containing copper alloy particles having a phosphorus content of 0.01 to 8% by mass are contained in the electrode paste composition in an amount of 70 to 94% by mass.
  • the phosphorus-containing copper alloy particles having a phosphorus content of 1 to 7.5% by mass are preferably included in the electrode paste composition in an amount of 74 to 88% by mass.
  • the silver-coated copper particles in the present invention it is sufficient that at least a part of the surface of the copper particles is coated with silver.
  • silver-coated copper particles as the copper-containing particles contained in the electrode paste composition of the present invention, an electrode having excellent oxidation resistance and low resistivity can be formed.
  • the copper particle is coat
  • water is mixed in the electrode paste composition the use of silver-coated copper particles can suppress the oxidation of copper at room temperature and can improve the pot life.
  • the coating amount (silver content) in the silver-coated copper particles such that the peak temperature of the exothermic peak showing the maximum area in the differential thermal-thermogravimetric simultaneous measurement is 280 ° C. or more. It is preferable that Specifically, it is preferably 1% by mass or more based on the total mass of the silver-coated copper particles, and 1 to 88% by mass based on the total mass of the silver-coated copper particles from the viewpoint of oxidation resistance and low resistivity of the electrode. Preferably, it is 3 to 80% by mass, more preferably 5 to 75% by mass.
  • the particle diameter of the silver-coated copper particles is not particularly limited, but the particle diameter when the accumulated mass is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to 10 ⁇ m. It is preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the silver covering copper particle in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively. Further, the shape of the silver-coated copper particles is not particularly limited, and may be any of spherical, flat, block, plate, scale-like, etc., but from the viewpoint of oxidation resistance and low resistivity, it is spherical. It is preferably flat, plate-like.
  • the copper constituting the silver-coated copper particles may contain other atoms as long as the effects of the present invention are not impaired.
  • other atoms include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
  • Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
  • the content rate of the other atom contained in the said silver covering copper particle can be 3 mass% or less in the said silver covering copper particle, for example, and 1 mass% from a viewpoint of oxidation resistance and a low resistivity. The following is preferable.
  • the silver-coated copper particles are those in which the above-described phosphorus-containing copper alloy is silver-coated.
  • the oxidation resistance is further improved, and the resistivity of the formed electrode is further reduced.
  • the phosphorus containing copper alloy in a silver covering copper particle it is synonymous with the above-mentioned phosphorus containing copper alloy, and its preferable aspect is also the same.
  • the method for preparing the silver-coated copper particles is not particularly limited as long as at least a part of the surface of the copper particles (preferably phosphorus-containing copper alloy particles) can be coated with silver.
  • it can be prepared as follows. That is, copper powder (or phosphorus-containing copper alloy powder) is dispersed in an acidic solution such as sulfuric acid, hydrochloric acid, and phosphoric acid, and a chelating agent is added to the copper powder dispersion to prepare a copper powder slurry.
  • an acidic solution such as sulfuric acid, hydrochloric acid, and phosphoric acid
  • a chelating agent is added to the copper powder dispersion to prepare a copper powder slurry.
  • a silver ion solution to the obtained copper powder slurry, a silver layer can be formed on the surface of the copper powder by a substitution reaction.
  • ethylenediaminetetraacetic acid salt triethylenediamine, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc.
  • ethylenediaminetetraacetic acid salt triethylenediamine, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc.
  • silver ion solution a silver nitrate solution etc. can be used, for example.
  • the content of the silver-coated copper particles contained in the paste composition for an electrode of the present invention, and the total content of silver-coated copper particles and silver particles in the case of containing silver particles described later are, for example, 70 to 94% by mass. In view of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, more preferably 74 to 88% by mass.
  • the silver-coated copper particles may be used singly or in combination of two or more. Moreover, you may use in combination with copper containing particles other than a silver covering copper particle.
  • silver-coated copper particles having a silver content of 1% by mass to 88% by mass in the total mass of the silver-coated copper particles are used as an electrode paste composition.
  • the silver-coated copper preferably contains 70 to 94% by mass (total content of silver-coated copper particles and silver particles when silver particles described later are included), and the silver content is 5 to 75% by mass. More preferably, the particles are contained in the electrode paste composition in an amount of 74 to 88% by mass (the total content of silver-coated copper particles and silver particles when silver particles described later are included).
  • silver-coated phosphorus-containing copper alloy particles having a silver content of 1 to 88% by mass and a phosphorus content of 0.01 to 8% by mass in the electrode paste composition.
  • Total content of silver-coated phosphorus-containing copper alloy particles and silver particles when silver particles described later are included is preferably included, the silver content is 5% to 75% by mass, and the phosphorus content is 1 to
  • the silver-coated phosphorus-containing copper alloy particles of 7.5% by mass are contained in the electrode paste composition in an amount of 74 to 88% by mass (the total content of silver-coated phosphorus-containing copper alloy particles and silver particles in the case of containing silver particles described later More preferably).
  • the copper-containing particles in the present invention are a group consisting of a triazole compound, a saturated fatty acid, an unsaturated fatty acid, an inorganic metal compound salt, an organic metal compound salt, a polyaniline resin, and a metal alkoxide (hereinafter sometimes referred to as “surface treatment agent”). It is also preferable that the copper particles are surface-treated with at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, and inorganic metal compound salts. More preferably, it is a copper particle.
  • Forming an electrode with excellent oxidation resistance and low resistivity by using copper particles surface-treated with at least one surface treatment agent as the copper-containing particles contained in the electrode paste composition of the present invention Can do. Further, when moisture is mixed in the electrode paste composition, the use of the surface-treated copper particles can suppress the oxidation of copper at room temperature and can improve the pot life.
  • the surface treatment agents may be used singly or in combination of two or more.
  • the surface-treated copper particles are at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides. Although it has been treated, other surface treatment agents may be used in combination as required.
  • Examples of the triazole compound in the surface treatment agent include benzotriazole and triazole.
  • Examples of the saturated fatty acid in the surface treatment agent include enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, stearic acid, nonadecanoic acid, arachic acid, Examples include behenic acid.
  • Examples of the unsaturated fatty acid in the surface treatment agent include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetreic acid, brassic acid, erucic acid, sorbic acid, and linoleic acid. Linolenic acid, arachidonic acid and the like.
  • Examples of the inorganic metal compound salt in the surface treatment agent include sodium silicate, sodium stannate, tin sulfate, zinc sulfate, sodium zincate, zirconium nitrate, sodium zirconate, zirconium chloride, titanium sulfate, and titanium chloride. And potassium oxalate titanate.
  • organometallic compound salt in the surface treatment agent examples include lead stearate, lead acetate, p-cumylphenyl derivative of tetraalkoxyzirconium, and p-cumylphenyl derivative of tetraalkoxytitanium.
  • metal alkoxide in the surface treatment agent examples include titanium alkoxide, zirconium alkoxide, lead alkoxide, silicon alkoxide, tin alkoxide, and indium alkoxide.
  • the surface treatment agent examples include dodecylbenzene sulfonic acid.
  • stearic acid or lead stearate is used as the surface treatment agent, the oxidation resistance is further improved and the resistivity is improved by using at least one of stearic acid and lead stearate and lead acetate as the surface treatment agent.
  • Lower electrodes can be formed.
  • the surface-treated copper particles in the present invention it is sufficient that at least a part of the surface of the copper particles is coated with at least one of the surface treatment agents.
  • the content of the surface treatment agent contained in the surface-treated copper particles is preferably such that the peak temperature of the exothermic peak showing the maximum area in the differential thermal-thermal mass simultaneous measurement is 280 ° C. or higher. .
  • the content is preferably 0.01% by mass or more in the mass of the surface-treated copper particles, and 0% in the mass of the surface-treated copper particles from the viewpoint of oxidation resistance and low resistivity of the electrode.
  • the content is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass in the mass of the surface-treated copper particles.
  • the copper constituting the surface-treated copper particles may contain other atoms as long as the effects of the present invention are not impaired.
  • other atoms include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
  • Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
  • the content rate of the other atom contained in the said surface-treated copper particle can be 3 mass% or less in the said surface-treated copper particle, for example from a viewpoint of oxidation resistance and a low resistivity. It is preferable that it is 1 mass% or less.
  • the surface-treated copper particles are also preferably those obtained by surface-treating the above-described phosphorus-containing copper alloy. As a result, the oxidation resistance is further improved, and the resistivity of the formed electrode is further reduced.
  • the phosphorus containing alloy in the surface-treated copper particle it is synonymous with the above-mentioned phosphorus containing alloy, and a preferable aspect is also the same.
  • the particle diameter of the surface-treated copper particles is not particularly limited, but the particle diameter when the accumulated mass is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to
  • the thickness is preferably 10 ⁇ m, more preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the said surface-treated copper particle in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
  • the shape of the surface-treated copper particles is not particularly limited and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, etc., but has an oxidation resistance and a low resistivity. From the viewpoint, it is preferably substantially spherical, flat, or plate-shaped.
  • the surface treatment method for copper particles using a surface treatment agent can be appropriately selected according to the surface treatment agent to be used. For example, by preparing a surface treatment solution in which the surface treatment agent is dissolved in a solvent capable of dissolving the surface treatment agent, and immersing and drying the copper particles in this, at least a part of the surface of the copper particles is coated with the surface treatment agent. Can be coated.
  • the solvent capable of dissolving the surface treatment agent can be appropriately selected according to the surface treatment agent.
  • water alcohol solvents such as methanol, ethanol, isopropanol, glycol solvents such as ethylene glycol monoethyl ether, carbitol solvents such as diethylene glycol monobutyl ether, carbitol acetate solvents such as diethylene glycol monoethyl ether acetate, etc.
  • a surface treatment solution can be prepared using an alcohol solvent to treat the copper particles.
  • stearic acid or lead stearate is used as the surface treatment agent
  • a surface treatment solution can be prepared using an alcohol solvent.
  • the concentration of the surface treatment agent in the surface treatment solution can be appropriately selected according to the type of surface treatment agent to be used and the desired surface treatment amount. For example, it can be 1 to 90% by mass, and preferably 2 to 85% by mass.
  • the content of the surface-treated copper particles contained in the electrode paste composition of the present invention, and the total content of the surface-treated copper particles and silver particles in the case of containing silver particles described later are, for example, 70 From the viewpoint of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, and more preferably 74 to 88% by mass.
  • the surface-treated copper particles may be used singly or in combination of two or more. Moreover, you may use in combination with copper containing particles other than the surface-treated copper particle.
  • the electrode from the viewpoint of oxidation resistance and low resistivity of the electrode, it is selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides.
  • the copper particles surface-treated so that at least one kind contained in an amount of 0.01 to 10% by mass was contained in the electrode paste composition in an amount of 70 to 94% by mass (in the case where silver particles described later were included, the surface treatment was performed).
  • Total content of copper particles and silver particles is preferably included, and 0.05 to 8% by mass of at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, and inorganic metal compound salts is included.
  • the surface-treated copper particles are contained in an electrode paste composition in an amount of 74 to 88% by mass (the total content of the surface-treated copper particles and silver particles in the case of containing silver particles described later). Rate) more preferably contains. Further, the surface contains 0.01 to 10% by mass of at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides.
  • the surface-treated phosphorus-containing copper alloy particles having been treated and having a phosphorus content of 8% by mass or less were 70 to 94% by mass in the electrode paste composition (when silver particles described later were included, the surface treatment was performed).
  • Total content of phosphorus-containing copper alloy particles and silver particles preferably 0.05 to 8% by mass of at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids and inorganic metal compound salts
  • the electrode paste composition of the present invention contains at least one kind of glass particles.
  • the silicon nitride film which is an antireflection film, is removed by so-called fire-through at the electrode formation temperature, and an ohmic contact between the electrode and the silicon substrate is formed.
  • the glass particles are usually used in the technical field as long as they can soften and melt at the electrode formation temperature, oxidize the contacted silicon nitride film, and take the oxidized silicon dioxide to remove the antireflection film.
  • the glass particles used can be used without particular limitation.
  • glass particles containing glass having a glass softening point of 600 ° C. or lower and a crystallization start temperature exceeding 600 ° C. are preferable.
  • the glass softening point is measured by a usual method using a thermomechanical analyzer (TMA), and the crystallization start temperature is measured using a differential thermal-thermogravimetric analyzer (TG / DTA). Measured by method.
  • the glass particles contained in the electrode paste composition may be composed of a glass containing lead because silicon dioxide can be taken in efficiently.
  • lead-containing glass examples include those described in Japanese Patent No. 03050064, and these can also be suitably used in the present invention.
  • lead-free glass it is preferable to use lead-free glass that does not substantially contain lead in consideration of the influence on the environment. Examples of the lead-free glass include lead-free glass described in paragraphs 0024 to 0025 of JP-A-2006-313744 and lead-free glass described in JP-A-2009-188281. It is also preferable that the lead-free glass is appropriately selected and applied to the present invention.
  • the glass particles are preferably made of glass containing an oxide containing phosphorus so as to efficiently incorporate silicon dioxide, and made of glass containing phosphorous pentoxide (phosphate glass, P 2 O 5 glass). It is more preferable. Further, it is preferably made of glass (P 2 O 5 —V 2 O 5 based glass) further containing divanadium pentoxide in addition to diphosphorus pentoxide. By further containing divanadium pentoxide, the oxidation resistance is further improved, and the resistivity of the electrode is further reduced. This can be attributed to, for example, that the softening point of the glass is lowered by further containing divanadium pentoxide.
  • the content of divanadium pentoxide is 1 in the total mass of the glass.
  • the content is preferably at least mass%, more preferably 1 to 70 mass%.
  • the diphosphorus pentoxide-divanadium pentoxide glass may further contain other components as required.
  • silicon dioxide derived from silicon nitride can be incorporated more efficiently. Further, the softening / dissolution temperature can be further reduced. Furthermore, reaction with copper containing particle
  • the content of the glass particles is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total mass of the electrode paste composition, and 1 to 7% by mass. % Is more preferable.
  • the glass particles preferably contain 0.1% by mass to 10% by mass of glass particles made of P 2 O 5 —V 2 O 5 based glass, and the content of V 2 O 5 is 1% by mass. More preferably, it contains 0.1 to 10% by mass of glass particles made of the above P 2 O 5 —V 2 O 5 glass.
  • the electrode paste composition of the present invention contains at least one solvent and at least one resin.
  • the liquid physical property for example, a viscosity, surface tension, etc.
  • the paste composition for electrodes of this invention can be adjusted to the required liquid physical property according to the provision method at the time of providing to a silicon substrate.
  • the solvent is not particularly limited.
  • hydrocarbon solvents such as hexane, cyclohexane and toluene
  • chlorinated hydrocarbon solvents such as dichloroethylene, dichloroethane and dichlorobenzene
  • cyclics such as tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane and trioxane Ether solvents
  • amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide
  • sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone
  • ethanol Alcohol compounds such as 2-propanol, 1-butanol and diacetone alcohol; 2,2,4-trimethyl-1,3-pentane
  • a polyhydric alcohol ester solvent from the viewpoints of coatability and printability when the electrode paste composition is formed on a silicon substrate, a polyhydric alcohol ester solvent, a terpene solvent, a polyhydric alcohol ether solvent. It is preferably at least one selected, and more preferably at least one selected from an ester solvent of a polyhydric alcohol and a terpene solvent.
  • the said solvent may be used individually by 1 type or in combination of 2 or more types.
  • any resin that is usually used in the technical field can be used as long as it can be thermally decomposed by firing.
  • cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and nitrocellulose
  • polyvinyl alcohols such as polyvinyl alcohols
  • polyvinyl pyrrolidones acrylic resins
  • vinyl acetate-acrylic acid ester copolymers such as polyvinyl butyral
  • phenol examples thereof include alkyd resins such as modified alkyd resins and castor oil fatty acid modified alkyd resins; epoxy resins; phenol resins; rosin ester resins.
  • the resin in the present invention is preferably at least one selected from a cellulose resin and an acrylic resin, and more preferably at least one selected from a cellulose resin, from the viewpoint of disappearance during firing.
  • the said resin may be used individually by 1 type or in combination of 2 or more types.
  • the content of the solvent and the resin can be appropriately selected according to the desired liquid properties and the type of solvent and resin used.
  • the resin content is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and more preferably 0.1 to 5% by mass with respect to the total mass of the electrode paste composition.
  • the content is more preferably 3% by mass, and further preferably 0.15 to 2.5% by mass.
  • the total content of the solvent and the resin is preferably 3 to 29.8% by mass, more preferably 5 to 25% by mass, and more preferably 7 to 20% by mass based on the total mass of the electrode paste composition. % Is more preferable.
  • the electrode paste composition contains at least one flux. By containing the flux, the oxidation resistance is further improved, and the resistivity of the formed electrode is further reduced. Furthermore, the effect that the adhesiveness of an electrode material and a silicon substrate improves is also acquired.
  • the flux in the present invention is not particularly limited as long as it can suppress the formation of an oxide film on the surface of the copper-containing particles.
  • fatty acids, boric acid compounds, fluorinated compounds, borofluorinated compounds and the like can be mentioned as preferred fluxes.
  • potassium borate and potassium borofluoride are particularly preferable fluxes from the viewpoints of heat resistance at the time of firing the electrode material (characteristic that the flux does not volatilize at a low temperature during firing) and supplementing the oxidation resistance of the copper-containing particles.
  • each of these fluxes may be used alone or in combination of two or more.
  • the total amount of the electrode paste composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and 0.5 to 3.5% by mass. More preferably, it is particularly preferably 0.7 to 3% by mass.
  • the electrode paste composition of the present invention preferably further contains at least one silver particle.
  • the oxidation resistance is further improved, and the resistivity as an electrode is further reduced.
  • the effect that the solder connection property at the time of setting it as a solar cell module improves is also acquired. This can be considered as follows, for example.
  • a small amount of silver is dissolved in copper and a small amount of copper is dissolved in silver, and copper is formed at the interface between copper and silver.
  • -A silver solid solution layer (solid solution region) is formed.
  • Such a copper-silver solid solution layer can be considered to contribute to the oxidation resistance of the copper-containing particles at the electrode formation temperature.
  • the copper-silver solid solution layer starts to be formed at a temperature of 300 ° C. to 500 ° C. or higher. Accordingly, by using silver particles together with copper-containing particles having a peak temperature of an exothermic peak showing a maximum area in differential heat-thermal mass measurement of 280 ° C. or more, the oxidation resistance of the copper-containing particles can be more effectively improved. It can be considered that the resistivity of the formed electrode is further reduced.
  • the silver constituting the silver particles may contain other atoms inevitably mixed.
  • other atoms inevitably mixed for example, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W , Mo, Ti, Co, Ni, Au and the like.
  • the particle size of the silver particles in the present invention is not particularly limited, but when the integrated mass is 50%, the particle size (D50%) is preferably 0.4 to 10 ⁇ m, and preferably 1 to 7 ⁇ m. It is more preferable. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of metal particles, such as a silver particle and copper containing particle
  • the relationship between the particle diameter of the copper-containing particles (D50%) and the particle diameter of the silver particles (D50%) is not particularly limited, but either one of the particle diameters (D50 %) Is smaller than the other particle size (D50%), and the ratio of the other particle size to any one particle size is more preferably 1 to 10.
  • the resistivity of an electrode falls more effectively. This can be attributed to, for example, an increase in contact area between metal particles such as copper-containing particles and silver particles in the electrode.
  • the silver particle content in the electrode paste composition of the present invention is 8.4 to 85.5% by mass in the electrode paste composition from the viewpoint of oxidation resistance and low electrode resistivity. It is preferably 8.9 to 80.1% by mass.
  • the content of the copper-containing particles is 9 to 88% by mass when the total amount of the copper-containing particles and the silver particles is 100% by mass. Preferably, it is more preferably 17 to 77% by mass.
  • the content of the copper-containing particles with respect to the silver particles is 9% by mass or more, for example, when the glass particles contain divanadium pentoxide, the reaction between silver and vanadium is suppressed, and the volume resistance of the electrode is reduced. It will be lower.
  • the electrode material is resistant to hydrofluoric acid (the property that the electrode material does not peel off from the silicon substrate by the hydrofluoric acid aqueous solution). Will improve. Moreover, it is suppressed that the content rate of the said copper containing particle
  • the total content of the copper-containing particles and the silver particles is 70 to 94% by mass from the viewpoints of oxidation resistance, low resistivity of the electrode, and coatability to a silicon substrate. It is preferably 72 to 92% by mass, more preferably 74 to 88% by mass.
  • the total content of the copper-containing particles and the silver particles is 70% by mass or more, a suitable viscosity can be easily achieved when the electrode paste composition is applied.
  • production of the blurring at the time of providing the paste composition for electrodes can be suppressed more effectively because the total content of the said copper containing particle
  • the total content of the copper-containing particles and the silver particles is 70 to 94% by mass, and the glass particles
  • the total content of the solvent and the resin is 3 to 29.8% by mass, and the content of the flux is 0.1 to 5% by mass.
  • the total content of the copper-containing particles and the silver particles is 74 to 88% by mass
  • the content of the glass particles is 1 to 7% by mass
  • the total amount of the solvent and the resin More preferably, the content is 7 to 20% by mass, and the content of the flux is 0.7 to 3% by mass.
  • the electrode paste composition preferably further includes at least one phosphorus-containing compound.
  • oxidation resistance improves more effectively and the resistivity of an electrode falls more.
  • the element in the phosphorus-containing compound diffuses as an n-type dopant, and an effect that power generation efficiency is improved when a solar cell is obtained.
  • the phosphorus-containing compound is a compound having a large phosphorus atom content in the molecule from the viewpoint of oxidation resistance and low resistivity of the electrode, and does not cause evaporation or decomposition under a temperature condition of about 200 ° C. Preferably there is.
  • the phosphorus-containing compound include phosphorous inorganic acids such as phosphoric acid, phosphates such as ammonium phosphate, phosphoric acid esters such as alkyl phosphates and aryl aryl esters, and cyclic phosphazenes such as hexaphenoxyphosphazene.
  • the phosphorus-containing compound in the present invention is preferably at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene, from the viewpoint of oxidation resistance and low electrode resistivity. More preferably, it is at least one selected from the group consisting of phosphate esters and cyclic phosphazenes.
  • the content of the phosphorus-containing compound in the present invention is preferably 0.5 to 10% by mass in the total mass of the electrode paste composition from the viewpoints of oxidation resistance and low electrode resistivity. More preferably, it is ⁇ 7% by mass. Furthermore, in the present invention, at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene is used as the phosphorus-containing compound in an amount of 0.5 to 10 in the total mass of the electrode paste composition. It is preferable to include 1% by mass, and more preferably 1-7% by mass of at least one selected from the group consisting of phosphate esters and cyclic phosphazenes in the total mass of the electrode paste composition.
  • the electrode paste composition of the present invention contains a phosphorus-containing compound
  • the total content of the copper-containing particles and the silver particles is 70 to 94% by mass from the viewpoint of oxidation resistance and low resistivity of the electrode.
  • the glass particle content is 0.1 to 10% by mass
  • the total content of the solvent, the resin and the phosphorus-containing compound is 5 to 20% by mass
  • the flux content is 0.00.
  • the content is preferably 1 to 5% by mass.
  • the total content of the copper-containing particles and the silver particles is 74 to 88% by mass
  • the content of the glass particles is 1 to 7% by mass
  • the solvent, the resin and the phosphorus-containing compound The total content is preferably 1 to 7% by mass
  • the flux content is preferably 0.7 to 3% by mass.
  • the electrode paste composition of the present invention can further contain other components usually used in the technical field, if necessary, in addition to the components described above.
  • other components include a plasticizer, a dispersant, a surfactant, an inorganic binder, a metal oxide, a ceramic, and an organometallic compound.
  • the copper-containing particles, glass particles, solvent, resin, and silver particles contained as necessary can be produced by dispersing and mixing them using a commonly used dispersion and mixing method.
  • the electrode paste composition is applied to a region where an electrode is to be formed, and after drying, the electrode is formed in a desired region by firing. be able to.
  • the paste composition for an electrode an electrode having a low resistivity can be formed even when a baking treatment is performed in the presence of oxygen (for example, in the air).
  • the electrode paste composition is applied on a silicon substrate so as to have a desired shape, and dried and fired. Thereby, a solar cell electrode with low resistivity can be formed in a desired shape.
  • an electrode having a low resistivity can be formed even when a baking treatment is performed in the presence of oxygen (for example, in the air).
  • Examples of the method for applying the electrode paste composition onto the silicon substrate include screen printing, an ink jet method, a dispenser method, and the like. From the viewpoint of productivity, application by screen printing is preferable.
  • the electrode paste composition of the present invention When the electrode paste composition of the present invention is applied by screen printing, it preferably has a viscosity in the range of 80 to 1000 Pa ⁇ s.
  • the viscosity of the electrode paste composition is measured at 25 ° C. using a Brookfield HBT viscometer.
  • the application amount of the electrode paste composition can be appropriately selected according to the size of the electrode to be formed.
  • the applied amount of the electrode paste composition can be 2 to 10 g / m 2, and preferably 4 to 8 g / m 2 .
  • heat treatment conditions when forming an electrode using the electrode paste composition of the present invention, heat treatment conditions usually used in the technical field can be applied.
  • the heat treatment temperature (firing temperature) is 800 to 900 ° C.
  • heat treatment conditions at a lower temperature can be applied, for example, 600 to 850.
  • An electrode having good characteristics can be formed at a heat treatment temperature of ° C.
  • the heat treatment time can be appropriately selected according to the heat treatment temperature and the like, and can be, for example, 1 second to 20 seconds.
  • the solar cell of this invention has the electrode formed by baking the said paste composition for electrodes provided on the silicon substrate in presence of oxygen. Thereby, the solar cell which has a favorable characteristic is obtained, and it is excellent in the productivity of this solar cell.
  • single crystal or polycrystalline Si is used for the semiconductor substrate 130 of the solar cell element.
  • the semiconductor substrate 130 contains boron or the like and constitutes a p-type semiconductor.
  • irregularities are formed by etching in order to suppress reflection of sunlight.
  • an n-type semiconductor diffusion layer 131 is provided with a thickness of submicron order, and a pn junction is formed at the boundary with the p-type bulk portion.
  • an antireflection layer 132 such as silicon nitride is provided on the diffusion layer 131 with a film thickness of about 100 nm by vapor deposition or the like.
  • the light receiving surface electrode 133 provided on the light receiving surface side, and the current collecting electrode 134 and the output extraction electrode 135 formed on the back surface will be described.
  • the light-receiving surface electrode 133 and the output extraction electrode 135 are formed from the electrode paste composition.
  • the collecting electrode 134 is formed from an aluminum electrode paste composition containing glass powder. These electrodes are formed by applying the paste composition to a desired pattern by screen printing or the like, and then baking the paste composition at about 600 to 850 ° C. in the atmosphere.
  • the glass particles contained in the electrode paste composition forming the light-receiving surface electrode 133 react with the antireflection layer 132 (fire-through), and the light-receiving surface electrode 133 and the diffusion layer are reacted. 131 is electrically connected (ohmic contact).
  • the light-receiving surface electrode 133 is formed using the electrode paste composition, so that copper is suppressed as a conductive metal, and the oxidation of copper is suppressed. Formed with excellent productivity.
  • aluminum in the aluminum electrode paste composition that forms the collecting electrode 134 during firing diffuses to the back surface of the semiconductor substrate 130 to form the electrode component diffusion layer 136, thereby forming the semiconductor substrate 130.
  • Ohmic contact can be obtained between the current collector electrode 134 and the output extraction electrode 135.
  • FIG. 4 shows a perspective view (a) of a light receiving surface and an AA cross-sectional structure of an example of a solar cell element which is another embodiment of the present invention, and a plan view (b) of a back surface side electrode structure.
  • the cell wafer 1 made of a p-type semiconductor silicon substrate
  • through holes penetrating both the light receiving surface side and the back surface side are formed by laser drilling or etching.
  • a texture (not shown) for improving the light incident efficiency is formed on the light receiving surface side.
  • an n-type semiconductor layer 3 by n-type diffusion treatment and an antireflection film are formed on the n-type semiconductor layer 3. These are manufactured by the same process as a conventional crystalline Si type solar battery cell.
  • the electrode paste composition of the present invention is filled into the previously formed through-holes by a printing method or an ink jet method, and the electrode paste composition of the present invention is also formed in a grid on the light receiving surface side.
  • the composition layer which is printed and forms the through-hole electrode 4 and the current collecting grid electrode 2 is formed.
  • a heavily doped layer 5 for preventing carrier recombination is formed on the opposite side (back side) of the light receiving surface.
  • boron (B) or aluminum (Al) is used as an impurity element for forming the high-concentration doped layer 5, and a p + layer is formed.
  • the high-concentration doped layer 5 may be formed by performing a thermal diffusion process using, for example, B as a diffusion source in a cell manufacturing process before forming the antireflection film, or when using Al. May be formed by printing an Al paste on the opposite surface side in the printing step.
  • the electrode paste composition fired at 650 to 850 ° C., filled in and printed on the antireflection film formed inside the through hole and on the light receiving surface side, and the lower n-type layer by the fire through effect. Ohmic contact is achieved.
  • the electrode paste composition according to the present invention is printed and fired in stripes on the n side and the p side, respectively. 7 is formed.
  • the through-hole electrode 4, the current collecting grid electrode 2, the back electrode 6 and the back electrode 7 are formed by using the electrode paste composition, so as to contain copper as a conductive metal, Copper oxidation is suppressed, and the low resistivity through-hole electrode 4, current collecting grid electrode 2, back electrode 6 and back electrode 7 are formed with excellent productivity.
  • the solar cell electrode paste composition of the present invention is not limited to the use of solar cell electrodes as described above. For example, electrode wiring and shield wiring of plasma displays, ceramic capacitors, antenna circuits, and various sensors. It can also be suitably used for applications such as heat dissipation materials for circuits and semiconductor devices.
  • Example 1A Preparation of electrode paste composition A phosphorus-containing copper alloy containing 1% by mass of phosphorus was prepared, dissolved and powdered by the water atomization method, and then dried and classified. The classified powders were blended and subjected to deoxygenation / dehydration treatment to produce phosphorus-containing copper alloy particles containing 1% by mass of phosphorus. The particle diameter (D50%) of the phosphorus-containing copper alloy particles was 1.5 ⁇ m.
  • V 2 O 5 vanadium oxide
  • P 2 O 5 barium oxide
  • WO 3 tungsten oxide
  • 1 part of sodium oxide (Na 2 O) oxidation A glass (hereinafter sometimes abbreviated as “G19”) composed of 3 parts of potassium (K 2 O), 10 parts of zinc oxide (ZnO) and 8 parts of manganese oxide (ZnO) was prepared.
  • the obtained glass G19 had a softening point of 447 ° C. and a crystallization temperature of 600 ° C. or higher.
  • glass particles having a particle diameter (D50%) of 1.7 ⁇ m were obtained.
  • an aluminum electrode paste was similarly printed on the back surface by screen printing.
  • the printing conditions were appropriately adjusted so that the film thickness after firing was 40 ⁇ m. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation. Subsequently, heat treatment (baking) was performed at 850 ° C. for 2 seconds in an infrared rapid heating furnace in an air atmosphere to produce a solar battery cell 1A on which a desired electrode was formed.
  • Example 2A a solar cell on which a desired electrode was formed in the same manner as in Example 1A, except that the temperature of the heat treatment (firing) at the time of electrode formation was changed to 750 ° C. for 10 seconds instead of 850 ° C. Cell 2A was produced.
  • Example 3A> In Example 1A, 1 part of phosphoric acid was further added, and the solar cell 3A on which a desired electrode was formed was obtained in the same manner as in Example 1A, except that the particle diameter (D50%) of the silver particles was changed to 1 ⁇ m. Produced.
  • Example 4A> In Example 1A, the addition amount of potassium borofluoride as Lux was changed from 1 part to 2 parts, and the addition amount of butyl carbitol acetate (BCA) solution containing 4% ethylcellulose (EC) was changed to 10.2 parts. Except having changed, it carried out similarly to Example 1A, and produced the photovoltaic cell 4A in which the desired electrode was formed.
  • BCA butyl carbitol acetate
  • EC 4% ethylcellulose
  • Example 6A> a solar cell 6A on which a desired electrode was formed was produced in the same manner as in Example 5A, except that instead of glass particles (G19), the following prepared glass particles (AY1) were used.
  • Glass particles (AY1) are 45 parts vanadium oxide (V 2 O 5 ), 24.2 parts phosphorus oxide (P 2 O 5 ), 20.8 parts barium oxide (BaO), and antimony oxide (Sb 2 O 3 ) 5.
  • the glass had a softening point of 492 ° C. and a crystallization temperature of 600 ° C. or higher.
  • Example 1A A comparative solar cell 1A in which a desired electrode was formed was produced in the same manner as in Example 1A, except that no flux was added in the preparation of the electrode paste composition in Example 1A.
  • Example 1B silver prepared by silver-coated copper particles (manufactured by our company, silver coating amount 20 mass%, particle diameter 5.8 ⁇ m) prepared by the method described in JP-A-14-100191 instead of phosphorus-containing copper alloy Except having used the coated copper particle, it carried out similarly to Example 1A, and produced the photovoltaic cell 1B in which the desired electrode was formed.
  • Example 2B a solar cell on which a desired electrode was formed in the same manner as Example 1B, except that the temperature of the heat treatment (firing) at the time of electrode formation was changed to 750 ° C. for 10 seconds instead of 850 ° C. Cell 2B was produced.
  • Example 3B In Example 1B, 1 part of phosphoric acid was further added, and the solar cell 3B on which a desired electrode was formed was obtained in the same manner as in Example 1B, except that the particle diameter (D50%) of the silver particles was changed to 1 ⁇ m. Produced.
  • Example 4B In Example 1B, the addition amount of potassium borofluoride as Lux was changed from 1 part to 2 parts, and the addition amount of butyl carbitol acetate (BCA) solution containing 4% ethylcellulose (EC) was changed to 10.2 parts. Except having changed, it carried out similarly to Example 1B, and produced the photovoltaic cell 4B in which the desired electrode was formed.
  • BCA butyl carbitol acetate
  • EC 4% ethylcellulose
  • Examples 5B and 7B> Except having replaced with the flux shown in Table 3 in Example 1B, it carried out similarly to Example 1B, and produced the photovoltaic cell 5B, 7B in which the desired electrode was formed.
  • Example 6B a solar cell 6B on which a desired electrode was formed was produced in the same manner as in Example 5B, except that the glass particle (AY1) was used instead of the glass particle (G19).
  • Example 1B A comparative solar cell 1B on which a desired electrode was formed was produced in the same manner as in Example 1B, except that no flux was used in the preparation of the electrode paste composition in Example 1B.
  • Example 1C a solar cell 1C on which a desired electrode was formed was produced in the same manner as in Example 1A, except that instead of the phosphorus-containing copper alloy, surface-treated copper particles prepared as described below were used. did.
  • benzotriazole BTA
  • Copper powder Frukuda Metal Foil Powder Co., Ltd., purity 99.9%, particle diameter 5 ⁇ m
  • the content of the surface treatment agent in the surface-treated copper particles was 1% in the total mass of the surface-treated copper particles.
  • the particle diameter (D50%) was 5 ⁇ m.
  • Example 2C A solar cell on which a desired electrode was formed in the same manner as in Example 1C, except that the temperature of the heat treatment (firing) at the time of electrode formation in Example 1C was changed to 750 ° C. for 10 seconds instead of 850 ° C. Cell 2C was produced.
  • Example 3C In Example 1C, 1 part of phosphoric acid was further added, and the solar cell 3C on which a desired electrode was formed was obtained in the same manner as in Example 1C, except that the particle diameter (D50%) of the silver particles was changed to 1 ⁇ m. Produced.
  • Example 4C ⁇ Example 4C>
  • the addition amount of potassium borofluoride as Lux was changed from 1 part to 2 parts, and the addition amount of butyl carbitol acetate (BCA) solution containing 4% ethylcellulose (EC) was changed to 10.2 parts. Except having changed, it carried out similarly to Example 1C, and produced the photovoltaic cell 4C in which the desired electrode was formed.
  • BCA butyl carbitol acetate
  • EC 4% ethylcellulose
  • Examples 5C and 7C> Except having replaced with the flux shown in Table 5 in Example 1C, it carried out similarly to Example 1C, and produced the photovoltaic cell 5C, 7C in which the desired electrode was formed.
  • Example 6C a solar cell 6C on which a desired electrode was formed was produced in the same manner as in Example 5C, except that the glass particle (AY1) was used instead of the glass particle (G19).
  • Example 1C A comparative solar cell 1C in which a desired electrode was formed was produced in the same manner as in Example 1C, except that no flux was used in the preparation of the electrode paste composition in Example 1C.
  • Eff conversion efficiency
  • FF fill factor
  • Voc open circuit voltage
  • Jsc short circuit current

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Abstract

L'invention concerne une composition en pâte pour électrodes dans laquelle la formation d'un film d'oxyde de cuivre au cours de la cuisson est supprimée, et qui peut être utilisée pour former des électrodes faiblement résistantes. L'invention concerne en outre une élément de batterie solaire dont les électrodes sont formées au moyen de ladite composition en pâte. La composition en pâte pour électrodes contient des particules métalliques dont le cuivre est le constituant principal, un flux, des particules de verre, un solvant et une résine. Les électrodes de l'élément de batterie solaire sont formées au moyen de ladite composition en pâte.
PCT/JP2011/051364 2010-01-25 2011-01-25 Composition en pâte pour électrodes, et batterie solaire Ceased WO2011090214A1 (fr)

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JP2010222205A JP5633286B2 (ja) 2010-01-25 2010-09-30 電極用ペースト組成物および太陽電池

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WO2013012071A1 (fr) * 2011-07-21 2013-01-24 日立化成工業株式会社 Matériau électroconducteur
WO2013015172A1 (fr) * 2011-07-25 2013-01-31 日立化成工業株式会社 Élément et cellule solaire
WO2013015285A1 (fr) * 2011-07-25 2013-01-31 日立化成工業株式会社 Élément et photopile
EP2586752A1 (fr) * 2011-10-25 2013-05-01 Heraeus Precious Metals North America Conshohocken LLC Composition de pâte électroconductrice contenant des nanoparticules métalliques
WO2013073478A1 (fr) * 2011-11-14 2013-05-23 日立化成株式会社 Composition de pâte pour électrode, élément de cellule solaire, cellule solaire
WO2015115565A1 (fr) * 2014-01-31 2015-08-06 日立化成株式会社 Composition de formation d'électrode, électrode, élément de cellule solaire, leur procédé de fabrication, et cellule solaire
CN113889293A (zh) * 2021-09-24 2022-01-04 暄泰电子(苏州)有限公司 一种用于电子元件的导电膏

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US20130248777A1 (en) * 2012-03-26 2013-09-26 Heraeus Precious Metals North America Conshohocken Llc Low silver content paste composition and method of making a conductive film therefrom
JP5598739B2 (ja) 2012-05-18 2014-10-01 株式会社マテリアル・コンセプト 導電性ペースト
JP2013243045A (ja) * 2012-05-21 2013-12-05 Kanto Gakuin 導電性積層体、導電性積層体の製造方法
US10593439B2 (en) * 2016-10-21 2020-03-17 Dupont Electronics, Inc. Conductive paste composition and semiconductor devices made therewith

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