WO2012137688A1 - 電極用ペースト組成物及び太陽電池 - Google Patents
電極用ペースト組成物及び太陽電池 Download PDFInfo
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- WO2012137688A1 WO2012137688A1 PCT/JP2012/058680 JP2012058680W WO2012137688A1 WO 2012137688 A1 WO2012137688 A1 WO 2012137688A1 JP 2012058680 W JP2012058680 W JP 2012058680W WO 2012137688 A1 WO2012137688 A1 WO 2012137688A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 239000002245 particle Substances 0.000 claims abstract description 175
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- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 91
- 239000011574 phosphorus Substances 0.000 claims abstract description 91
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 2
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
- H01L31/02245—Electrode arrangements specially adapted for back-contact solar cells for metallisation wrap-through [MWT] type solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- 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 crystalline silicon solar cell is provided with a surface electrode.
- the wiring resistance and contact resistance of the surface electrode are related to voltage loss related to conversion efficiency, and the wiring width and shape affect the amount of incident sunlight. (For example, refer nonpatent literature 1).
- 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 (for example, see Patent Document 1). Moreover, the composition for electrode formation containing the metal nanoparticle containing silver and metal particles other than silver is disclosed (for example, refer patent document 2).
- 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.
- Patent Document 2 when copper is contained as a conductive metal, this is baked to form an electrode. Therefore, a special process of baking in an atmosphere of nitrogen or the like is necessary.
- the present invention provides a paste composition for an electrode capable of forming an electrode having a low resistivity while suppressing copper oxidation during firing, and a solar cell having an electrode formed using the paste composition for an electrode The task is to do.
- An aspect of the present invention is an electrode paste composition containing phosphorus-containing copper alloy particles having a phosphorus content of 6% by mass or more and 8% by mass or less, glass particles, a solvent, and a resin.
- the glass particles preferably have a glass softening point of 600 ° C. or lower and a crystallization start temperature exceeding 600 ° C.
- the particle diameter (D50) of the phosphorus-containing copper alloy particles is preferably 0.4 ⁇ m to 10 ⁇ m.
- the particle diameter (D50) of the glass particles is preferably 0.5 ⁇ m to 10 ⁇ m.
- the ratio of the particle diameter (D50) of the glass particles to the particle diameter (D50) of the phosphorus-containing copper alloy particles is preferably 0.05 to 100.
- the paste composition for an electrode further preferably contains silver particles, and the silver particle content when the total amount of the phosphorus-containing copper alloy particles and the silver particles is 100% by mass is 5% by mass or more and 65% by mass. The following is more preferable.
- the total content of the phosphorus-containing copper alloy particles and the silver particles is preferably 70% by mass or more and 94% by mass or less, and the content of the glass particles is 0.1% by mass or more and 10% by mass or less. More preferably, the total content of the solvent and the resin is 3% by mass or more and 29.9% by mass or less.
- a second aspect of the present invention is a solar cell having an electrode formed by firing the paste composition for an electrode applied on a silicon substrate.
- the oxidation of copper at the time of baking is suppressed, the paste composition for electrodes which can form an electrode with low resistivity, and the solar cell which has an electrode formed using this paste composition for electrodes Can be provided.
- the paste composition for an electrode according to the present invention comprises phosphorus-containing copper alloy particles having a phosphorus content of 6% by mass or more and 8% by mass or less, at least one glass particle, at least one solvent, and at least one resin. Seeds. With such a configuration, oxidation of copper during firing is suppressed, and an electrode with low resistivity can be formed.
- the electrode paste composition of the present invention includes phosphorus-containing copper alloy particles having a phosphorus content of 6% by mass or more and 8% by mass or less.
- the phosphorus content contained in the phosphorus-containing copper alloy in the present invention is 6 mass% or more and 8 mass% or less, and 6.3 mass% or more and 7.8 mass%. It is preferably at most mass%, more preferably at least 6.5 mass% and at most 7.5 mass%.
- the productivity of the phosphorus-containing copper alloy is excellent.
- the more outstanding acid resistance can be achieved because it is 6 mass% or more.
- phosphorus copper brazing As a phosphorus-containing copper alloy, a brazing material called phosphorus copper brazing (phosphorus concentration: usually about 7% by mass or less) is known. Phosphor copper brazing is also used as a bonding agent between copper and copper.
- phosphorus-containing copper alloy particles in the electrode paste composition of the present invention it is possible to form an electrode having excellent oxidation resistance and low resistivity by utilizing the reducibility of phosphorus to copper oxide. 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-containing copper alloy particles are an alloy containing copper and phosphorus, but may further contain other atoms.
- other atoms include Ag, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Examples include Mo, Ti, Co, Ni, and Au.
- 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 phosphorus-containing copper alloy particles may be used singly or in combination of two or more.
- the particle diameter of the phosphorus-containing copper alloy particles is not particularly limited, but the particle diameter when the accumulated weight 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 phosphorus containing copper alloy particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
- the particle size of the phosphorus-containing copper alloy particles is measured by a microtrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300 type).
- the shape of the phosphorus-containing copper alloy 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, and the like.
- the shape of the phosphorus-containing copper alloy particles is preferably substantially spherical, flat, or plate-like from the viewpoint of oxidation resistance and low resistivity.
- 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 phosphorous 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. Details of the water atomization method are described in Metal Handbook (Maruzen Co., Ltd. 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. Moreover, the phosphorus containing copper alloy particle
- the electrode paste composition of the present invention contains at least one kind of glass particles.
- the adhesion between the electrode portion and the substrate is improved during firing. Also.
- the silicon nitride film as the antireflection film is removed by so-called fire-through, 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 from the viewpoint of oxidation resistance and low resistivity of the electrode.
- 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 heat-thermogravimetric analyzer (TG-DTA). Measured by method.
- TMA thermomechanical analyzer
- TG-DTA differential heat-thermogravimetric analyzer
- the glass particles contained in the electrode paste composition are preferably composed of glass containing lead because silicon dioxide can be taken up efficiently.
- glass containing lead examples include those described in Japanese Patent No. 03050064, and these can also be suitably used in the present invention.
- 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 paragraph numbers 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.
- Glass components used in the electrode paste composition of the present invention include silicon dioxide (SiO 2 ), phosphorus oxide (P 2 O 5 ), aluminum oxide (Al 2 O 3 ), boron oxide (B 2 O 3 ), and oxidation. Vanadium (V 2 O 5 ), potassium oxide (K 2 O), bismuth oxide (Bi 2 O 3 ), sodium oxide (Na 2 O), lithium oxide (Li 2 O), barium oxide (BaO), strontium oxide ( SrO), calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), zinc oxide (ZnO), lead oxide (PbO), cadmium oxide (CdO), tin oxide (SnO), zirconium oxide (ZrO 2) ), tungsten oxide (WO 3), molybdenum oxide (MoO 3), lanthanum oxide (La 2 O 3), niobium oxide (Nb O 5), tantalum oxide (Ta 2 O 5), yttrium oxide (Y 2 O 3
- At least one selected from SiO 2 , P 2 O 5 , Al 2 O 3 , B 2 O 3 , V 2 O 5 , Bi 2 O 3 , ZnO, and PbO are preferable to use at least one selected from SiO 2 , P 2 O 5 , Al 2 O 3 , B 2 O 3 , V 2 O 5 , Bi 2 O 3 , ZnO, and PbO.
- a glass component include those containing SiO 2, PbO, B 2 O 3, Bi 2 O 3 and Al 2 O 3.
- the softening point is effectively lowered, and the wettability with phosphorus-containing copper alloy particles and silver particles added as necessary is improved. Sintering progresses, and an electrode with low resistivity can be formed.
- glass particles containing phosphorous pentoxide (phosphate glass, P 2 O 5 glass particles) are preferable.
- diphosphorus pentoxide divanadium pentoxide is used.
- glass particles P 2 O 5 —V 2 O 5 glass particles.
- diphosphorus pentoxide-bivanadium pentoxide glass particles P 2 O 5 —V 2 O 5 glass particles
- the content of divanadium pentoxide is 1% by mass or more based on the total mass of the glass. Preferably, it is 1 to 70% by mass.
- the particle diameter of the glass particles in the present invention is not particularly limited, but the particle diameter (D50%) when the integrated weight is 50% is preferably 0.5 ⁇ m or more and 10 ⁇ m or less, and 0.8 ⁇ m or more. More preferably, it is 8 ⁇ m or less.
- the thickness is 0.5 ⁇ m or more, workability at the time of preparing the electrode paste composition is improved.
- it is 10 ⁇ m or less, it can be uniformly dispersed in the electrode paste composition, fire-through can be efficiently generated in the firing step, and adhesion to the silicon substrate is also improved.
- the shape of the glass 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, and the like, from the viewpoint of oxidation resistance and low resistivity.
- a spherical shape, a flat shape, or a plate shape is preferable.
- the ratio of the particle size (D50%) of the glass particles to the particle size (D50%) of the phosphorus-containing copper particles is preferably 0.05 to 100, and preferably 0.1 to 20. It is more preferable. By including the glass particles in such a range, oxidation resistance, low electrode resistivity, and low contact resistance can be achieved more effectively.
- the content of the glass particles is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and more preferably 1 to 7% by mass, based on the total mass of the electrode paste composition. More preferably. By including glass particles in such a range of content, oxidation resistance, lower electrode resistivity, and lower contact resistance can be achieved more effectively.
- 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 agents 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-pentanediol monoa
- a polyhydric alcohol ester solvent, a terpene solvent, and a polyhydric alcohol ether solvent from the viewpoints of coatability and printability when the electrode paste composition is formed on a silicon substrate.
- 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 cellulosic resins and acrylic resins, and more preferably at least one selected from cellulosic resins, from the viewpoint of disappearance during firing. preferable.
- the said resin may be used individually by 1 type or in combination of 2 or more types.
- the weight average molecular weight of the resin in the present invention is preferably 5,000 or more and 500,000 or more.
- an increase in the viscosity of the electrode paste composition can be suppressed. This can be considered to be because, for example, a phenomenon in which the three-dimensional repulsive action when adsorbed on phosphorus-containing copper alloy particles is insufficient and the particles are aggregated is suppressed.
- the weight average molecular weight of the resin is 500,000 or less, the phenomenon that the resins are aggregated in the solvent and as a result, the viscosity of the electrode paste composition increases is suppressed.
- the weight average molecular weight of the resin is suppressed to an appropriate size, the resin combustion temperature is prevented from increasing, and the resin is not completely burned when the electrode paste composition is baked, and remains as a foreign substance. Thus, the resistance of the electrode can be reduced.
- 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 total content of the solvent and the resin is preferably 3% by mass or more and 29.9% by mass or less, and more preferably 5% by mass or more and 25% by mass or less, based on the total mass of the electrode paste composition. Preferably, it is 7 mass% or more and 20 mass% or less.
- the electrode paste composition of the present invention preferably further contains silver particles.
- silver particles By containing silver particles, the oxidation resistance is further improved, and the resistivity as an electrode is further reduced. Furthermore, 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 solid solution of silver in copper and a small amount of solid solution of copper in silver occur.
- -A silver solid solution layer (solid solution region) is formed.
- the solid solution layer at high temperature is considered to cover the surface of silver particles and phosphorus-containing copper alloy particles as a non-equilibrium solid solution phase or a eutectic structure of copper and silver.
- Such a copper-silver solid solution layer can be considered to contribute to further oxidation resistance of the phosphorus-containing copper alloy particles at the electrode formation temperature.
- 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 diameter of the silver particles in the present invention is not particularly limited, but the particle diameter (D50%) when the accumulated weight is 50% is preferably 0.4 ⁇ m or more and 10 ⁇ m or less, and 1 ⁇ m or more and 7 ⁇ m or less. It is more preferable that When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, when it is 10 ⁇ m or less, the contact area between metal particles such as silver particles and phosphorus-containing copper alloy particles in the electrode is increased, and the resistivity is more effectively reduced.
- the relationship between the particle size (D50%) of the phosphorus-containing copper alloy particles and the particle size (D50%) of the silver particles is not particularly limited. (D50%) is preferably smaller than the other particle diameter (D50%), and the ratio of the other particle diameter to any one particle diameter is more preferably 1 to 10. Thereby, the resistivity of an electrode falls more effectively. This can be attributed, for example, to an increase in the contact area between metal particles such as phosphorus-containing copper alloy 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 silver particles when the total amount of the copper-containing particles and the silver particles is 100% by mass is The amount is preferably 5 to 65% by mass, more preferably 7 to 60% by mass, and still more preferably 10 to 55% by mass.
- the total content of the phosphorus-containing copper alloy particles and the silver particles is 70% by mass from the viewpoints of oxidation resistance, low resistivity of the electrode, and applicability to a silicon substrate.
- the content is preferably 94% by mass or less and more preferably 74% by mass or more and 88% by mass or less.
- a suitable viscosity can be easily achieved when the electrode paste composition is applied.
- production of the glaze at the time of providing the paste composition for electrodes can be more effectively suppressed because the total content rate of the said phosphorus containing copper alloy particle and the said silver particle is 94 mass% or less.
- the total content of the phosphorus-containing copper alloy particles and the silver particles is 70% by mass or more and 94% by mass or less from the viewpoint of oxidation resistance and low resistivity of the electrode.
- the glass particle content is 0.1% by mass or more and 10% by mass or less, and the total content of the solvent and the resin is preferably 3% by mass or more and 29.9% by mass or less.
- the total content of the phosphorus-containing copper alloy particles and the silver particles is 74% by mass or more and 88% by mass or less, and the content of the glass particles is 0.5% by mass or more and 8% by mass or less, and the solvent and More preferably, the total content of the resin is 7% by mass or more and 20% by mass or less, and the total content of the phosphorus-containing copper alloy particles and the silver particles is 74% by mass or more and 88% by mass or less,
- the content of glass particles is 1 mass Or 7 or less by mass%, it is more preferable that the total content of the solvent and the resin is 20 mass% or less 7 mass% or more.
- the electrode paste composition may further include at least one 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 remove the oxide film formed on the surface of the phosphorus-containing copper alloy 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 during electrode material firing (a property that the flux does not volatilize at low temperatures during firing) and supplementing oxidation resistance of the phosphorus-containing copper alloy particles.
- each of these fluxes may be used alone or in combination of two or more.
- the content of the flux in the electrode paste composition of the present invention includes the viewpoint of effectively expressing the oxidation resistance of the phosphorus-containing copper alloy particles, and the reduction in the porosity of the portion where the flux is removed when the electrode material is completely fired.
- it is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and 0.5 to 3.5% by mass in the total mass of the electrode paste composition.
- 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 phosphorus-containing copper alloy 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, dried and then fired to form an electrode in a desired region. can do.
- 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.
- any apparatus that can be heated to the above temperature can be used as appropriate, and examples thereof include an infrared heating furnace and a tunnel furnace.
- An infrared heating furnace is highly efficient because electric energy is directly input to a heating material in the form of electromagnetic waves and is converted into heat energy, and rapid heating is possible in a short time. Further, since there is no product due to combustion and non-contact heating, it is possible to suppress contamination of the generated electrode.
- the tunnel furnace automatically and continuously conveys the sample from the entrance to the exit and fires it, it can be fired uniformly by dividing the furnace body and controlling the transport speed. From the viewpoint of the power generation performance of the solar battery cell, it is preferable to perform heat treatment with a tunnel furnace.
- the solar cell of this invention has the electrode formed by baking the said paste composition for electrodes provided on the silicon substrate. Thereby, the solar cell which has a favorable characteristic is obtained, and it is excellent in the productivity of this solar cell.
- FIGS. 1, 2 and 3 Cross-sectional views showing examples of typical solar cell elements, and outlines of the light receiving surface and the back surface are shown in FIGS. 1, 2 and 3, respectively.
- 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.
- unevenness is formed by etching in order to suppress reflection of sunlight.
- the light receiving surface side is doped with phosphorus or the like, 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. Further, on the light receiving surface side, 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. In the present invention, by using the electrode paste composition, an electrode having excellent resistivity and contact resistivity can be formed even when fired at a relatively low temperature.
- 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 good 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 as an example of a solar cell element according to another aspect 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 is formed with through holes penetrating both the light receiving surface side and the back surface side 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 in the through hole and on the light receiving surface side, has a lower n-type layer due to the fire through effect. Ohmic contact is achieved.
- the electrode paste composition according to the present invention is printed on the stripes on both the n side and the p side, respectively, and fired, whereby the back electrode 6, 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 using the electrode paste composition, so that copper is contained 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 electrode paste composition of the present invention is not limited to the use of the solar cell electrode as described above.
- Example 1> Preparation of electrode paste composition Phosphorus-containing copper alloy particles containing 7% by mass of phosphorus were 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 7% by mass of phosphorus. The particle diameter (D50%) of the phosphorus-containing copper alloy particles was 1.5 ⁇ m.
- a glass composed of 9 parts of zinc oxide (ZnO) (hereinafter sometimes abbreviated as “G1”) was prepared.
- the obtained glass G1 had a softening point of 420 ° C. and a crystallization temperature of over 600 ° C.
- 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, using a tunnel furnace (manufactured by Noritake Co., Ltd., single-row transport W / B tunnel furnace), heat treatment (firing) is performed at a firing maximum temperature of 850 ° C. for 10 seconds in an air atmosphere to form a desired electrode. A solar cell 1 was produced.
- a tunnel furnace manufactured by Noritake Co., Ltd., single-row transport W / B tunnel furnace
- Example 2 a solar battery cell 2 was produced in the same manner as in Example 1 except that the firing condition during electrode formation was changed from a maximum temperature of 850 ° C. for 10 seconds to a maximum temperature of 750 ° C. for 15 seconds.
- Example 3 In Example 1, the electrode paste composition 3 and the solar battery cell 3 were produced in the same manner as in Example 1 except that the particle size of the phosphorus-containing copper alloy particles was changed from 1.5 ⁇ m to 5.0 ⁇ m.
- Example 4 In Example 1, the paste composition 4 for electrodes and the photovoltaic cell 4 were produced similarly to Example 1 except having changed the phosphorus content rate of the phosphorus containing copper alloy particle from 7 mass% to 6 mass%. .
- Example 5 the paste composition 5 for an electrode and the photovoltaic cell 5 were produced like Example 1 except having changed the phosphorus content rate of the phosphorus containing copper alloy particle from 7 mass% to 8 mass%. .
- Example 6 In the same manner as in Example 3, except that silver particles (particle diameter (D50%) 3 ⁇ m, high-purity chemical product manufactured by Aldrich) were further added to prepare electrode paste composition 6 and solar cell 6. Specifically, phosphorus-containing copper alloy particles (phosphorus content 7% by mass, particle diameter (D50%) 5 ⁇ m) 75.0 parts, silver particles 10.1 parts, glass particles (G1) 1.7 parts, and 3 An electrode paste composition 6 containing 13.2 parts of a terpineol (isomer mixture) solution containing ethyl cellulose (EC) in mass% was prepared, and the same as in Example 3 except that this electrode paste composition 6 was used. Thus, a solar battery cell 6 was produced.
- silver particles particle diameter (D50%) 3 ⁇ m, high-purity chemical product manufactured by Aldrich
- Example 7 a terpineol solution containing phosphorus content, particle diameter (D50%) and content of silver-containing copper alloy particles, silver particle content, glass particle type and content, and 3% ethyl cellulose (EC) Electrode paste compositions 7 to 17 were prepared in the same manner as in Example 1 except that the content of was changed as shown in Table 1.
- the glass particles (G2) 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 ). It consisted of 5 parts and 5 parts of tungsten oxide (WO 3 ), and the particle diameter (D50%) was 1.7 ⁇ m.
- the glass had a softening point of 492 ° C. and a crystallization temperature of over 600 ° C.
- a desired electrode was formed in the same manner as in Example 1 except that the obtained electrode paste compositions 7 to 17 were used, respectively, and the heat treatment temperature and treatment time were changed as shown in Table 1.
- the solar cells 7 to 17 thus prepared were respectively produced.
- Example 1 For electrode preparation in the same manner as in Example 1, except that the phosphorus-containing copper alloy particles were not used in the preparation of the electrode paste composition in Example 1 and each component was changed to the composition shown in Table 1.
- Paste composition C1 was prepared.
- a solar cell C1 was produced in the same manner as in Example 1 except that the electrode paste composition C1 containing no phosphorus-containing copper alloy particles was used.
- Comparative Example 2 a solar cell C2 was produced in the same manner as in Comparative Example 1, except that the firing condition at the time of electrode formation was changed from 10 seconds at the maximum temperature of 850 ° C. to 15 seconds at the maximum temperature of 750 ° C.
- Example 3 electrode paste composition C3 was prepared in the same manner as Example 1 except that pure copper containing no phosphorus (phosphorus content was 0%) was changed. A solar cell C3 was produced in the same manner as in Example 1 except that the electrode paste composition C3 was used.
- Comparative example 4 In Comparative Example 3, a solar cell C4 was produced in the same manner as in Comparative Example 1, except that the firing conditions during electrode formation were changed from the maximum temperature of 850 ° C. for 10 seconds to the maximum temperature of 700 ° C. for 20 seconds.
- the performance of the solar cells produced in Examples 1 to 17 was almost equal to or higher than the measured value of Comparative Example 1.
- solar cells 1 to 5 and solar cell 16 formed electrodes without using silver particles, but exhibited high power generation performance.
- the diffraction X-rays were measured by the X-ray diffraction method using CuK ⁇ rays.
- the characteristic diffraction peaks of copper were shown at 50.6 ° and 74.2 °. The following principle can be cited as the reason why copper is detected from the light receiving surface electrode.
- the phosphorus-containing copper alloy particles in the electrode paste compositions 1 to 5 and 16 have a phosphorus content of 6% by mass or more and 8% by mass or less.
- the composition of this portion is composed of an ⁇ -Cu phase and a Cu 3 P phase from a Cu—P phase diagram.
- the ⁇ -Cu phase is oxidized and converted to Cu 2 O. It is considered that this Cu 2 O is reduced again to ⁇ -Cu.
- the Cu 3 P phase contained in the phosphorus-containing copper alloy particles or phosphorus derived from this oxide contributes to this reduction reaction.
- the maximum temperature holding time is 10 seconds to Even for 20 seconds, it is considered that the oxidation of copper during firing was suppressed and an electrode having a low resistivity was formed.
- the sintering of the phosphorus-containing copper alloy particles proceeds by extending the firing time, it is possible to form a denser and lower resistivity electrode, and more effectively perform fire-through. The effect that the ohmic contact property with the semiconductor substrate is improved can be obtained.
- Example 18 Using the electrode paste composition 1 obtained above, a solar battery cell 18 having a structure as shown in FIG. 4 was produced. The heat treatment was performed at 850 ° C. for 10 seconds. When the obtained solar battery cell was evaluated in the same manner as described above, it was found that the same characteristics as described above were exhibited.
- SYMBOLS 1 Cell wafer which consists of p-type silicon substrate 2 Current collecting grid electrode 3 N-type semiconductor layer 4 Through-hole electrode 5 High concentration doped layer 6 Back surface electrode 7 Back surface electrode 130 Semiconductor substrate 131 Diffusion layer 132 Antireflection layer 133 Light-receiving surface electrode 134 Electrode 135 Output extraction electrode 136 Electrode component diffusion layer
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Abstract
Description
本発明の電極用ペースト組成物は、リン含有率が6質量%以上8質量%以下であるリン含有銅合金粒子と、ガラス粒子の少なくとも1種と、溶剤の少なくとも1種と、樹脂の少なくとも1種と、を含む。かかる構成であることにより、焼成時における銅の酸化が抑制され、抵抗率の低い電極が形成可能である。
本発明の電極用ペースト組成物は、リン含有率が6質量%以上8質量%以下であるリン含有銅合金粒子を含む。
本発明におけるリン含有銅合金に含まれるリン含有率は、耐酸化性と低抵抗率の観点から、リン含有率が6質量%以上8質量%以下であり、6.3質量%以上7.8質量%以下であることが好ましく、6.5質量%以上7.5質量%以下であることがより好ましい。リン含有銅合金に含まれるリン含有率が8質量%以下であることで、より低い抵抗率を達成可能であり、また、リン含有銅合金の生産性に優れる。また6質量%以上であることで、より優れた耐酸性を達成できる。
また前記リン含有銅合金粒子に含まれる他の原子の含有率は、例えば、前記リン含有銅合金粒子中に3質量%以下とすることができ、耐酸化性と低抵抗率の観点から、1質量%以下であることが好ましい。
具体的には例えば、リン含有銅合金を溶解し、これをノズル噴霧によって粉末化した後、得られた粉末を乾燥、分級することで、所望のリン含有銅合金粒子を製造することができる。また、分級条件を適宜選択することで所望の粒子径を有するリン含有銅合金粒子を製造することができる。
本発明の電極用ペースト組成物は、ガラス粒子の少なくとも1種を含む。電極用ペースト組成物がガラス粒子を含むことにより、焼成時に電極部と基板との密着性が向上する。また。電極形成温度において、いわゆるファイアースルーによって反射防止膜である窒化ケイ素膜が取り除かれ、電極とシリコン基板とのオーミックコンタクトが形成される。
本発明においては、耐酸化性と電極の低抵抗率の観点から、ガラス軟化点が600℃以下であって、結晶化開始温度が600℃を超えるガラスを含むガラス粒子であることが好ましい。尚、前記ガラス軟化点は、熱機械分析装置(TMA)を用いて通常の方法によって測定され、また前記結晶化開始温度は、示差熱-熱重量分析装置(TG-DTA)を用いて通常の方法によって測定される。
また本発明においては、環境に対する影響を考慮すると、鉛を実質的に含まない鉛フリーガラスを用いることが好ましい。鉛フリーガラスとしては、例えば、特開2006-313744号公報の段落番号0024~0025に記載の鉛フリーガラスや、特開2009-188281号公報等に記載の鉛フリーガラスを挙げることができ、これらの鉛フリーガラスから適宜選択して本発明に適用することもまた好ましい。
また前記ガラス粒子の形状としては特に制限はなく、略球状、扁平状、ブロック状、板状、及び鱗片状等のいずれであってもよいが、耐酸化性と低抵抗率の観点から、略球状、扁平状、または板状であることが好ましい。
本発明の電極用ペースト組成物は、溶剤の少なくとも1種と樹脂の少なくとも1種とを含む。これにより本発明の電極用ペースト組成物の液物性(例えば、粘度、表面張力等)を、シリコン基板に付与する際の付与方法に応じて必要とされる液物性に調整することができる。
本発明において前記溶剤は1種単独でも、2種以上を組み合わせて用いてもよい。
本発明において前記樹脂は1種単独でも、2種以上を組み合わせて用いてもよい。
溶剤と樹脂の総含有率が前記範囲内であることにより、電極用ペースト組成物をシリコン基板に付与する際の付与適性が良好になり、所望の幅及び高さを有する電極をより容易に形成することができる。
本発明の電極用ペースト組成物は、銀粒子を更に含むことが好ましい。銀粒子を含むことで耐酸化性がより向上し、電極としての抵抗率がより低下する。さらに太陽電池モジュールとした場合のはんだ接続性が向上するという効果も得られる。このことは例えば、以下のように考えることができる。
電極用ペースト組成物は、フラックスの少なくとも1種をさらに含むことができる。フラックスを含むことで耐酸化性がより向上し、形成される電極の抵抗率がより低下する。さらに電極材とシリコン基板の密着性が向上するという効果も得られる。
中でも、電極材焼成時の耐熱性(フラックスが焼成の低温時に揮発しない特性)及びリン含有銅合金粒子の耐酸化性補完の観点から、ホウ酸カリウム及びホウフッ化カリウムが特に好ましいフラックスとして挙げられる。
本発明においてこれらのフラックスは、それぞれ1種単独で使用してもよく、2種類以上を組み合わせて使用することもできる。
さらに本発明の電極用ペースト組成物は、上述した成分に加え、必要に応じて、当該技術分野で通常用いられるその他の成分をさらに含むことができる。その他の成分としては、例えば、可塑剤、分散剤、界面活性剤、無機結合剤、金属酸化物、セラミック、有機金属化合物等を挙げることができる。
本発明の電極用ペースト組成物を用いて電極を製造する方法としては、前記電極用ペースト組成物を、電極を形成する領域に付与し、乾燥後に、焼成することで所望の領域に電極を形成することができる。前記電極用ペースト組成物を用いることで、酸素の存在下(例えば、大気中)で焼成処理を行っても、抵抗率の低い電極を形成することができる。
具体的には例えば、前記電極用ペースト組成物を用いて太陽電池用電極を形成する場合、電極用ペースト組成物はシリコン基板上に所望の形状となるように付与され、乾燥後に、焼成されることで、抵抗率の低い太陽電池電極を所望の形状に形成することができる。また前記電極用ペースト組成物を用いることで、酸素の存在下(例えば、大気中)で焼成処理を行っても、抵抗率の低い電極を形成することができる。
一般に、熱処理温度(焼成温度)としては800~900℃であるが、本発明の電極用ペースト組成物を用いる場合には、より低温での熱処理条件を適用することができ、例えば、600~850℃の熱処理温度で良好な特性を有する電極を形成することができる。
また熱処理時間は、熱処理温度等に応じて適宜選択することができ、例えば、1秒~20秒とすることができる。
本発明の太陽電池は、シリコン基板上に付与された前記電極用ペースト組成物を、焼成して形成された電極を有する。これにより、良好な特性を有する太陽電池が得られ、該太陽電池の生産性に優れる。
代表的な太陽電池素子の一例を示す断面図、受光面及び裏面の概要を、それぞれ図1、図2及び図3に示す。
通常、太陽電池素子の半導体基板130には、単結晶または多結晶Siなどが使用される。この半導体基板130には、ホウ素などが含有され、p型半導体を構成している。受光面側は、太陽光の反射を抑制するために、エッチングにより凹凸(テクスチャー、図示せず)が形成されている。その受光面側にはリンなどがドーピングされ、n型半導体の拡散層131がサブミクロンオーダーの厚みで設けられているとともに、p型バルク部分との境界にpn接合部が形成されている。さらに受光面側には、拡散層131上に窒化シリコンなどの反射防止層132が蒸着法などによって膜厚100nm前後で設けられている。
本発明においては前記電極用ペースト組成物を用いることで、比較的低温で焼成しても、抵抗率及び接触抵抗率に優れる電極を形成することができる。
本発明においては、前記電極用ペースト組成物を用いて受光面電極133が形成されることで、導電性金属として銅を含みながら、銅の酸化が抑制され、低抵抗率の受光面電極133が、良好な生産性で形成される。
図4(a)の斜視図に示すようにp型半導体のシリコン基板からなるセルウェハ1には、レーザドリルまたはエッチング等によって、受光面側及び裏面側の両面を貫通したスルーホールが形成されている。また受光面側には光入射効率を向上させるテクスチャー(図示せず)が形成されている。さらに受光面側にはn型化拡散処理によるn型半導体層3と、n型半導体層3上に反射防止膜(図示せず)が形成されている。これらは従来の結晶Si型太陽電池セルと同一の工程により製造される。
ここで、充填用と印刷用に用いるペーストでは、粘度を始めとして、それぞれのプロセスに最適な組成のペーストを使用するのが望ましいが、同じ組成のペーストで充填、印刷を一括で行ってもよい。
なお、本発明の電極用ペースト組成物は、上記したような太陽電池電極の用途に限定されるものではなく、例えば、プラズマディスプレイの電極配線及びシールド配線、セラミックスコンデンサ、アンテナ回路、各種センサー回路、半導体デバイスの放熱材料等の用途にも好適に使用することができる。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
(a)電極用ペースト組成物の調製
7質量%のリンを含むリン含有銅合金粒子を調製し、これを溶解して水アトマイズ法により粉末化した後、乾燥、分級した。分級した粉末をブレンドして、脱酸素・脱水分処理し、7質量%のリンを含むリン含有銅合金粒子を作製した。尚、リン含有銅合金粒子の粒子径(D50%)は1.5μmであった。
得られたガラスG1を用いて、粒子径(D50%)が1.7μmであるガラス粒子を得た。
受光面にn型半導体層、テクスチャー及び反射防止膜(窒化珪素膜)が形成された膜厚190μmのp型半導体基板を用意し、125mm×125mmの大きさに切り出した。その受光面にスクリーン印刷法を用い、上記で得られた電極用ペースト組成物1を図2に示すような電極パターンとなるように印刷した。電極のパターンは150μm幅のフィンガーラインと1.1mm幅のバスバーで構成され、焼成後の膜厚が20μmとなるよう、印刷条件(スクリーン版のメッシュ、印刷速度、印圧)を適宜調整した。これを150℃に加熱したオーブンの中に15分間入れ、溶剤を蒸散により取り除いた。
続いてトンネル炉(ノリタケ社製、1列搬送W/Bトンネル炉)を用いて大気雰囲気下、焼成最高温度850℃で保持時間10秒間の加熱処理(焼成)を行って、所望の電極が形成された太陽電池セル1を作製した。
実施例1において、電極形成時の焼成条件を最高温度850℃で10秒間から、最高温度750℃15秒間に変更したこと以外は、実施例1と同様に太陽電池セル2を作製した。
実施例1において、リン含有銅合金粒子の粒子径を1.5μmから5.0μmに変更したこと以外は、実施例1と同様に電極用ペースト組成物3及び太陽電池セル3を作製した。
実施例1において、リン含有銅合金粒子のリン含有率を7質量%から6質量%に変更したこと以外は、実施例1と同様にして電極用ペースト組成物4及び太陽電池セル4を作製した。
実施例1において、リン含有銅合金粒子のリン含有率を7質量%から8質量%に変更したこと以外は、実施例1と同様にして電極用ペースト組成物5及び太陽電池セル5を作製した。
実施例3と同様にして、但し、更に銀粒子(粒子径(D50%)3μm、アルドリッチ社製高純度化学品)を添加して、電極用ペースト組成物6及び太陽電池セル6を作製した。
具体的には、リン含有銅合金粒子(リン含有率7質量%、粒子径(D50%)5μm)75.0部、銀粒子10.1部、ガラス粒子(G1)1.7部、及び3質量%のエチルセルロース(EC)を含むテルピネオール(異性混合体)溶液13.2部を含有する電極用ペースト組成物6を調製し、この電極用ペースト組成物6を用いた以外は実施例3と同様にして、太陽電池セル6を作製した。
実施例1において、リン含有銅合金粒子のリン含有率、粒子径(D50%)及び含有量、銀粒子の含有量、ガラス粒子の種類及び含有量、3%のエチルセルロース(EC)を含むテルピネオール溶液の含有量を表1に示したように変更したこと以外は、実施例1と同様にして電極用ペースト組成物7~17を調製した。
尚、ガラス粒子(G2)は酸化バナジウム(V2O5)45部、酸化リン(P2O5)24.2部、酸化バリウム(BaO)20.8部、酸化アンチモン(Sb2O3)5部、酸化タングステン(WO3)5部からなり、粒子径(D50%)が1.7μmであった。またこのガラスの軟化点は492℃、結晶化温度は600℃を超えていた。
実施例1における電極用ペースト組成物の調製においてリン含有銅合金粒子を用いずに、表1に示した組成となるように各成分を変更したこと以外は、実施例1と同様にして電極用ペースト組成物C1を調製した。
リン含有銅合金粒子を含まない電極用ペースト組成物C1を用いたこと以外は、実施例1と同様にして太陽電池セルC1を作製した。
比較例1において、電極形成時の焼成条件を最高温度850℃で10秒間から、最高温度750℃で15秒間に変更したこと以外は、比較例1と同様に太陽電池セルC2を作製した。
実施例1において、リンを含有しない純銅(リン含有率が0%)に変更したこと以外は、実施例1と同様にして電極用ペースト組成物C3を調製した。
電極用ペースト組成物C3を用いたこと以外は、実施例1と同様にして太陽電池セルC3を作製した。
比較例3において、電極形成時の焼成条件を最高温度850℃で10秒間から、最高温度700℃20秒間に変更したこと以外は、比較例1と同様に太陽電池セルC4を作製した。
作製した太陽電池セルの評価は、擬似太陽光として(株)ワコム電創製WXS-155S-10、電流-電圧(I-V)評価測定器としてI-V CURVE TRACER MP-160(EKO INSTRUMENT社製)の測定装置を組み合わせて行った。太陽電池としての発電性能を示すEff(変換効率)、FF(フィルファクター)、Voc(開放電圧)及びJsc(短絡電流)は、それぞれJIS-C-8912、JIS-C-8913及びJIS-C-8914に準拠して測定を行なうことで得られたものである。得られた各測定値を、比較例1の測定値を100.0とした相対値に換算して表2に示した。
尚、比較例3及び比較例4においては、銅粒子の酸化によって電極の抵抗率が大きくなり、評価不能であった。
上記で得られた電極用ペースト組成物1を用いて、図4に示したような構造を有する太陽電池セル18を作製した。尚、加熱処理は850℃、10秒間で行った。
得られた太陽電池セルについて上記と同様にして評価したところ、上記と同様に良好な特性を示すことが分かった。
2 集電用グリッド電極
3 n型半導体層
4 スルーホール電極
5 高濃度ドープ層
6 裏面電極
7 裏面電極
130 半導体基板
131 拡散層
132 反射防止層
133 受光面電極
134 集電電極
135 出力取出し電極
136 電極成分拡散層
Claims (9)
- リン含有率が6質量%以上8質量%以下であるリン含有銅合金粒子と、ガラス粒子と、溶剤と、樹脂と、を含む電極用ペースト組成物。
- 前記ガラス粒子は、ガラス軟化点が600℃以下であり、結晶化開始温度が600℃を超える請求項1に記載の電極用ペースト組成物。
- 前記リン含有銅合金粒子の粒子径(D50)が0.4μm~10μmである請求項1又は請求項2に記載の電極用ペースト組成物。
- 前記ガラス粒子の粒子径(D50)が0.5μm~10μmである請求項1~請求項3のいずれか1項に記載の電極用ペースト組成物。
- 前記リン含有銅合金粒子の粒子径(D50)に対する前記ガラス粒子の粒子径(D50)の比が0.05~100である請求項1~請求項4のいずれか1項に記載の電極用ペースト組成物。
- 銀粒子を更に含む請求項1~請求項5のいずれか1項に記載の電極用ペースト組成物。
- 前記リン含有銅合金粒子と前記銀粒子の総量を100質量%としたときの銀粒子の含有率が5質量%以上65質量%以下である請求項6に記載の電極用ペースト組成物。
- 前記リン含有銅合金粒子及び前記銀粒子の総含有率が70質量%以上94質量%以下であり、前記ガラス粒子の含有率が0.1質量%以上10質量%以下であり、前記溶剤及び前記樹脂の総含有率が3質量%以上29.9質量%以下である請求項6又は請求項7に記載の電極用ペースト組成物。
- シリコン基板上に付与された請求項1~請求項8のいずれか1項に記載の電極用ペースト組成物を焼成して形成された電極を有する太陽電池。
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CN103367546A (zh) * | 2013-07-12 | 2013-10-23 | 余小翠 | 一种光伏电池正面电极的制备工艺 |
US9793025B2 (en) * | 2013-12-03 | 2017-10-17 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
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Also Published As
Publication number | Publication date |
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CN104694778A (zh) | 2015-06-10 |
TW201251066A (en) | 2012-12-16 |
KR101350098B1 (ko) | 2014-01-10 |
CN102934174A (zh) | 2013-02-13 |
EP2696353A1 (en) | 2014-02-12 |
KR20130014599A (ko) | 2013-02-07 |
CN102934174B (zh) | 2015-04-29 |
TWI570748B (zh) | 2017-02-11 |
EP2696353A4 (en) | 2015-01-14 |
CN104694778B (zh) | 2017-05-03 |
TW201443923A (zh) | 2014-11-16 |
JP2012221703A (ja) | 2012-11-12 |
EP2696353B1 (en) | 2018-06-27 |
TWI450405B (zh) | 2014-08-21 |
JP5120477B2 (ja) | 2013-01-16 |
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