WO2011090213A1 - Composition de pâte pour électrode et cellule solaire - Google Patents

Composition de pâte pour électrode et cellule solaire Download PDF

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Publication number
WO2011090213A1
WO2011090213A1 PCT/JP2011/051363 JP2011051363W WO2011090213A1 WO 2011090213 A1 WO2011090213 A1 WO 2011090213A1 JP 2011051363 W JP2011051363 W JP 2011051363W WO 2011090213 A1 WO2011090213 A1 WO 2011090213A1
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Prior art keywords
electrode
particles
silver
paste composition
mass
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PCT/JP2011/051363
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English (en)
Japanese (ja)
Inventor
修一郎 足立
吉田　誠人
野尻　剛
岩室　光則
木沢　桂子
拓也 青柳
山本　浩貴
内藤　孝
隆彦 加藤
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日立化成工業株式会社
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Publication of WO2011090213A1 publication Critical patent/WO2011090213A1/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
    • 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
    • H01L31/06—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 characterised by potential barriers
    • H01L31/068—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 characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0682—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 characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction 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
    • Y02E10/547—Monocrystalline silicon PV cells

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. (See, for example, Yasuhiro Sasakawa, “Solar Power Generation, Latest Technologies and Systems,” CMC Publishing Company, 2001, p26-27).
  • 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.
  • 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). Also disclosed is an electrode-forming composition containing metal nanoparticles containing silver and metal particles other than silver (see, for example, JP-A-2008-226816).
  • the first problem of the present invention is to form an electrode paste composition capable of forming an electrode in which the amount of silver used is reduced and the increase in resistivity is suppressed, and the electrode paste composition. It is to provide a solar cell having a formed electrode.
  • the lead-free glass is preferably made of glass containing phosphorous pentoxide (phosphate glass, P 2 O 5 glass) from the viewpoint of low contact resistivity.
  • diphosphorus pentoxide divanadium pentoxide. More preferably, it is made of a glass further containing (P 2 O 5 —V 2 O 5 glass).
  • a second problem of the present invention is that an electrode paste composition capable of forming an electrode having a low resistivity even when lead-free glass is used, and a sun having an electrode formed using the electrode paste composition It is to provide a battery.
  • the first aspect of the present invention is an electrode paste composition containing silver alloy particles, glass particles, a resin, and a solvent.
  • the electrode paste composition preferably further contains silver particles.
  • the glass particles are preferably glass containing P 2 O 5 and V 2 O 5 .
  • the electrode paste composition has a total content of the silver alloy particles and the silver particles of 70% by mass to 94% by mass, and a content of the glass particles of 0.1% by mass to 10% by mass. It is preferable that the total content of the solvent and the resin is 3% by mass or more and 29.9% by mass or less.
  • the second aspect of the present invention includes copper particles, silver or silver alloy particles, glass particles containing P 2 O 5 and V 2 O 5 , a resin, and a solvent, and the inclusion of copper particles with respect to the silver or silver alloy particles
  • the electrode paste composition has a rate of 9% by mass to 88% by mass.
  • the third aspect of the present invention is a solar cell having an electrode formed by applying the electrode paste composition to a silicon substrate and then firing.
  • the electrode paste composition which can form the electrode which reduced the usage-amount of silver, and the raise of the resistivity was suppressed, and the electrode formed using this paste composition for electrodes A solar cell can be provided. Further, according to the present invention, there is provided an electrode paste composition capable of forming an electrode having low resistivity even using lead-free glass, and a solar cell having an electrode formed using the electrode paste composition. Can be provided.
  • the electrode paste composition according to the first aspect of the present invention includes silver alloy particles, glass particles, a resin, and a solvent. By using silver alloy particles, it is possible to form an electrode that can reduce the amount of silver used and suppress an increase in resistivity. Below, each component which comprises the paste composition for electrodes of a 1st aspect is demonstrated in detail.
  • the silver alloy particles according to the present invention are alloys containing at least silver, and as constituent elements other than silver, Cu, P, Zn, Mn, Mg, V, Sn, Zr, W, Mo, Ti, Co, Sb And Ni may be used, each of which may be used alone or in combination of two or more.
  • silver may further 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.
  • Suitable silver alloy compositions are Ag—Cu, Ag—Cu—P, Ag—Cu—Mn, Ag—Cu—Zn, Ag—Cu—Mg, Ag—Cu—V, Ag—Cu—Sn, Ag— Cu-Ti, Ag-Cu-Co, Ag-Cu-Sb, Ag-Cu-P-Mn, Ag-Cu-P-Zn, Ag-Cu-P-Mg, Ag-Cu-P-V, Ag- Cu—P—Sn, Ag—Cu—P—Ti, Ag—Cu—P—Co, Ag—Cu—P—Sb, and the like.
  • the Ag content is preferably 12 to 91% by mass, the Cu content is preferably 9 to 88% by mass, and the Ag content is 23 to 83% by mass. More preferably, the Cu content is 17 to 77 mass%.
  • the Ag content is 12 to 91 mass%, the Cu content is 1 to 87.99 mass%, and the P content is 0.01 to 8 mass%.
  • the Ag content is 23 to 83% by mass, the Cu content is 9.5 to 76% by mass, and the P content is 1 to 7.5% by mass.
  • the silver content in the silver alloy particles in the present invention is preferably 12 to 91% by mass, more preferably 23 to 83% by mass, based on the total mass of the silver alloy particles. Within the above range, there is an effect of reducing the amount of silver used, and an increase in the low efficiency of the electrode can be suppressed.
  • Silver alloys may be used singly or in combination of two or more.
  • the particle diameter of the silver 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. 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 alloy particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
  • the shape of the silver 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, from the viewpoint of oxidation resistance and low resistivity. It is preferably substantially spherical, flat, or plate-shaped.
  • the silver alloy can be produced by a commonly used method. Further, the silver alloy particles can be prepared using a usual method of preparing a metal powder using a silver alloy prepared so as to have a desired silver content, for example, a standard method using a water atomizing method. Can be manufactured. The water atomization method is described in Metal Handbook (Maruzen Publishing Division). Specifically, for example, a desired phosphorus-containing copper alloy particle can be produced by dissolving a silver alloy, pulverizing this by nozzle spraying, and drying and classifying the obtained powder. Moreover, the silver alloy particle which has a desired particle diameter can be manufactured by selecting classification conditions suitably.
  • the content of the silver alloy particles contained in the paste composition for an electrode of the present invention, and the total content of silver alloy particles and silver particles when 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 total content of the silver alloy 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 glaze at the time of providing the paste composition for electrodes can be suppressed more effectively because the total content of the said silver alloy particle and the said silver particle is 94 mass% or less.
  • the content of silver alloy particles having a silver content of 12 to 91% by mass, or 12 to 91 when silver particles described later are included.
  • Silver alloy particles having a silver content of mass% and a total content of silver particles are preferably 70 to 94 mass% in the electrode paste composition, and a silver alloy having a silver content of 23 to 83 mass%
  • the silver alloy particles having a silver content of 23 to 83% by mass and the total content of silver particles are more preferably 74 to 88% by mass in the electrode paste composition.
  • conductive particles other than the silver alloy particles may be used in combination. Examples of such conductive particles include silver particles described later.
  • the paste composition for an electrode according to the first aspect of the present invention contains at least one kind of glass particles.
  • the electrode paste composition contains glass particles, the silicon nitride film as the 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 from the viewpoint of oxidation resistance and low resistivity of the electrode.
  • the glass softening point is more preferably 450 ° C. or less from the viewpoint of the 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 composed of glass containing lead because silicon dioxide can be taken up 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 diphosphorus pentoxide (phosphate glass, P 2 O 5 glass) from the viewpoint of low contact resistivity.
  • diphosphorus pentoxide phosphate glass, P 2 O 5 glass
  • divanadium pentoxide More preferably, it is made of a glass further containing (P 2 O 5 —V 2 O 5 glass).
  • 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 reaction between silver and vanadium proceeds.
  • the reaction is suppressed and the volume resistance of the electrode is further reduced.
  • 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.
  • 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 of the first aspect. More preferably, it is 1 to 7% by mass.
  • glass particles made of P 2 O 5 —V 2 O 5 glass are contained as glass particles in an amount of 0.1 to 10% by mass in the total mass of the electrode paste composition of the first aspect. It is more preferable to include 1 to 7% by mass of glass particles made of P 2 O 5 —V 2 O 5 based glass having a V 2 O 5 content of 0.1% by mass or more.
  • the electrode paste composition according to the first aspect of the present invention includes at least one solvent and at least one resin.
  • the liquid physical property (for example, a viscosity, surface tension, etc.) of 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, 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.
  • 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, 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 contents 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 to 29.9% by mass, more preferably 5 to 25% by mass, based on the total mass of the electrode paste composition of the first aspect. 7 to 20% by mass is more preferable.
  • the application suitability when applying the electrode paste composition to the silicon substrate is improved, and an electrode having a desired width and height is more easily formed. can do.
  • the electrode paste composition according to the first aspect 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. Furthermore, the effect that the solder connection property at the time of setting it as a solar cell module improves is also acquired.
  • 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 accumulated weight is 50%, the particle size (D50%) is preferably 0.4 ⁇ m to 10 ⁇ m, which promotes sintering. From the viewpoint, it is preferably 0.4 ⁇ m to 2.0 ⁇ m.
  • the particle diameter of the silver particles 0.4 ⁇ m or more the oxidation resistance is more effectively improved.
  • grains in an electrode becomes large because it is 10 micrometers or less, and resistivity falls more effectively.
  • the relationship between the particle diameter of the silver alloy 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 the contact area between metal particles such as silver alloy particles and silver particles in the electrode.
  • the silver particle content in the electrode paste composition according to the first aspect of the present invention is 8.4 to 85.5 in the electrode paste composition from the viewpoint of oxidation resistance and low electrode resistivity.
  • the content is preferably mass%, more preferably 8.9 to 80.1 mass%.
  • the content of the silver alloy particles is 9 to 88% by mass when the total amount of the silver alloy particles and the silver particles is 100% by mass. Preferably, it is 17 to 77% by mass.
  • the content rate of the silver alloy 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 further reduced.
  • the electrode material is resistant to hydrofluoric acid (the property that the electrode material does not separate from the silicon substrate by the hydrofluoric acid aqueous solution). Will improve. Moreover, the contact resistance of an electrode falls more because the content rate of the said silver alloy particle
  • the total content of the silver alloy 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 preferably 0.1 to 10% by mass, and the total content of the solvent and the resin is preferably 3 to 29.9% by mass.
  • the silver alloy particles and the silver The total content of the particles is 74 to 88% by mass, the content of the glass particles is 1 to 7% by mass, and the total content of the solvent and the resin is 7 to 20% by mass. More preferred.
  • the electrode paste composition according to the first aspect of the present invention may further contain other components that are 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.
  • Method for producing electrode paste composition There is no restriction
  • the silver 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, 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 first aspect of the present invention When the electrode paste composition of the first aspect 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 the electrode using the electrode paste composition of the first aspect 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.
  • 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 electrode paste composition of the second aspect of the present invention comprises copper particles, silver or silver alloy particles, glass particles containing P 2 O 5 and V 2 O 5 , a resin, and a solvent, and the silver or silver alloy
  • the content of the copper particles with respect to the particles is 9% by mass to 88% by mass.
  • V 2 O 5 diadium pentoxide contained therein is electrically conductive. Since it reacts with the silver contained as the metal powder to produce silver vanadate, the resistivity of the formed electrode increases. Then, when metal other than silver was examined as conductive metal powder, it was effective for formation of the electrode which suppressed the rise in resistivity that copper (Cu) and silver (Ag) were used together in a specific ratio. Became clear.
  • the electrode paste composition has a copper particle content of 9% by mass to 88% by mass with respect to silver or silver alloy particles, an increase in electrode resistivity can be suppressed.
  • the content of the copper particles relative to the silver or silver alloy particles is less than 9% by mass, the high resistivity of the silver vanadate produced by the reaction of V 2 O 5 (divanadium pentoxide) and Ag (silver)
  • the content exceeds 88% by mass, the electrode has a high resistivity due to the copper oxide generated by the oxidation of copper.
  • 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. Therefore, by using silver particles together with copper-containing particles having a peak temperature of an exothermic peak showing a maximum area in simultaneous differential heat-thermogravimetric 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 copper particles in the present invention impart oxidation resistance to copper and copper, even if they are metal particles that may contain other atoms in addition to pure copper as long as the effects of the present invention are not impaired.
  • the metal particle containing a component 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 particle diameter of the copper 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 copper particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
  • the particle diameter of the copper particles is measured by a microtrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300 type).
  • the shape of the 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, 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 total content of copper particles, silver particles, and silver alloy particles (silver-containing particles) contained in the electrode paste composition of the second aspect of the present invention can be, for example, 70 to 94% by mass, From the viewpoint of oxidation resistance and low resistivity, the content is preferably 72 to 90% by mass, and more preferably 74 to 88% by mass.
  • the total content of the copper particles and the silver-containing particles is 70% by mass or more, 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 suppressed more effectively because the total content of the said copper particle and the said silver containing particle
  • conductive particles other than copper particles, silver particles and silver alloy particles may be used in combination.
  • the electrode paste composition of the present invention further includes at least one kind of silver particles or silver alloy particles (hereinafter sometimes referred to as “silver-containing particles”).
  • the silver particles and the silver alloy particles may be pure silver, metal particles containing only other atoms which are inevitably mixed, or silver alloy particles.
  • Examples of other atoms inevitably mixed in the metal particles consisting essentially of silver include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, and Tl. V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, and the like.
  • the silver alloy particles As the silver alloy particles, the silver alloy particles described in the electrode paste composition of the first aspect can be applied, and the preferred range is also the same.
  • the particle diameter (D50%) when the integrated mass is 50% is preferably 0.4 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 5 ⁇ m.
  • the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved.
  • it is 10 ⁇ m or less, the contact area between metal particles such as silver-containing particles and copper particles in the electrode is increased, and the resistivity is more effectively reduced.
  • the content of copper particles with respect to silver or silver alloy particles is 9 to 88% by mass, and preferably 17 to 77% by mass.
  • the electrode paste composition according to the second aspect of the present invention is a glass particle containing P 2 O 5 and V 2 O 5 (“P 2 O 5 —V 2 O 5 glass particle” in consideration of the influence on the environment. At least one of them may be used.
  • the electrode paste composition contains 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 metal and the silicon substrate is formed.
  • the glass particles according to the present invention contain diphosphorus pentoxide, a low contact resistivity can be achieved. Further, since divanadium pentoxide is contained in addition to diphosphorus pentoxide, the softening point of the glass is lowered, the oxidation resistance is further improved, and the resistivity of the electrode is further lowered.
  • the increase in resistivity due to the silver vanadate produced by the reaction between V 2 O 5 (divanadium pentoxide) and Ag (silver) is suppressed by the addition of copper particles, so P 2 O
  • the content of divanadium pentoxide in the 5- V 2 O 5 glass particles is not particularly limited.
  • the content of divanadium pentoxide in the P 2 O 5 —V 2 O 5 glass particles is 1 to 70% by mass.
  • the P 2 O 5 —V 2 O 5 glass particles may further contain other components as necessary.
  • other components include barium oxide, manganese dioxide, sodium oxide, potassium oxide, zinc oxide, zirconium dioxide, tungsten trioxide, tellurium oxide, antimony oxide, and iron oxide.
  • silicon dioxide derived from silicon nitride can be incorporated more efficiently. Further, the softening / dissolution temperature can be further reduced. Furthermore, reaction with copper particles, silver particles, or silver alloy particles can be suppressed.
  • the content of the P 2 O 5 —V 2 O 5 glass particles is preferably 0.1 to 10% by mass in the total mass of the electrode paste composition of the second aspect, More preferably, it is ⁇ 8% by mass, and further preferably 1 ⁇ 7% by mass.
  • glass particles with a content in such a range By including glass particles with a content in such a range, oxidation resistance, low resistivity of the electrode, and low contact resistance can be achieved more effectively.
  • the electrode paste composition according to the second aspect of the present invention includes at least one solvent and at least one resin.
  • the liquid physical property (for example, a viscosity, surface tension, etc.) of 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.
  • Solvents and resins applicable to the electrode paste composition of the second embodiment are the same as the solvents and resins described in the electrode paste composition of the first embodiment, and the same applies to the preferred range and content. Therefore, the description is omitted.
  • the total content of the copper particles and the silver-containing particles is 70 to 94% by mass, and the silver-containing particles
  • the content of copper particles is 9% by mass to 88% by mass and the content of the P 2 O 5 —V 2 O 5 glass particles is 0.1% to 10% by mass
  • the solvent and The total content of the resin is preferably 3 to 29.9% by mass
  • the total content of the copper particles and the silver-containing particles is 74 to 88% by mass
  • the content of the P 2 O 5 —V 2 O 5 glass particles is 1 to 7% by mass
  • the total content of the solvent and the resin is 17% by mass to 77% by mass. It is more preferably 7 to 20% by mass.
  • the electrode paste composition of the second aspect of the present invention can further contain other components that are 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.
  • Method for producing electrode paste composition There is no restriction
  • the electrode paste composition is applied to a region where the electrode is formed, dried and then baked to form an electrode in a desired region. Can be formed.
  • 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).
  • the electrode paste composition of the second aspect of the present invention When the electrode paste composition of the second aspect 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 for forming an electrode using the electrode paste composition of the second aspect of the present invention
  • heat treatment conditions that are usually used in the technical field
  • the heat treatment 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.
  • unevenness is formed by etching in order to suppress reflection of sunlight.
  • the light receiving surface is doped with phosphorus or the like, an n-type semiconductor diffusion layer 131 is provided with a thickness of the order of submicrons, 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.
  • 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 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 silver alloy particles A silver alloy containing 63% Ag, 35% Cu, and 2% P was prepared, dissolved and powdered by a water atomization method, and then dried and classified. The classified powder was blended and subjected to deoxygenation / dehydration treatment to produce silver alloy particles. The particle diameter (D50%) of the silver alloy particles was 1.5 ⁇ m.
  • Glass 1 composition (P19) is composed of 32 parts by weight of vanadium oxide (V 2 O 5 ), 26 parts by weight of phosphorus oxide (P 2 O 5 ), 10 parts by weight of barium oxide (BaO), and manganese oxide (MnO 2 ). 8 parts by weight, sodium oxide (Na 2 O) 1 part by weight, potassium oxide (K 2 O) 3 parts by weight, zinc oxide (ZnO) 10 parts by weight, tungsten oxide (WO 3 ) 10 parts by weight there were.
  • the glass had a softening point of 447 ° C. and a crystallization temperature of 600 ° C. or higher.
  • Glass 2 composition (AY1) is 45 parts of vanadium oxide (V 2 O 5 ), 24.2 parts of phosphorus oxide (P 2 O 5 ), 20.8 parts of barium oxide (BaO), 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.
  • BCA containing 4% of EC was prepared using diethylene glycol monobutyl ether acetate (hereinafter referred to as BCA) as the solvent and ethyl cellulose (hereinafter referred to as EC) as the resin, and the viscosity of the paste was 80 so as to be suitable for screen printing.
  • the amount of solvent was adjusted so as to be ⁇ 200 Pa ⁇ s.
  • a p-type semiconductor substrate having a film thickness of 190 ⁇ m having an n-type semiconductor layer, a texture and an antireflection film (silicon nitride film) formed on the light receiving surface is prepared and cut into a size of 125 mm ⁇ 125 mm It was.
  • the electrode paste composition 1 obtained above was printed so as to have an electrode pattern as shown in FIG.
  • the electrode pattern was composed of a finger line with a width of 150 ⁇ m and a bus bar with a width of 1.1 mm, and the printing conditions (screen plate mesh, printing speed, printing pressure) were appropriately adjusted so that the film thickness after firing was 20 ⁇ m. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation.
  • 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 1 on which a desired electrode was formed.
  • Example 1 except that the blending ratio of silver alloy particles and silver particles, the particle diameter (D50%) of silver particles, the type and content of glass particles in Example 1 were changed as shown in Table 1.
  • Solar cells 2 to 13 were produced in the same manner as described above.
  • Example 1 A comparative solar cell 1 was produced in the same manner as in Example 1 except that the electrode paste composition was prepared without containing silver alloy particles.
  • Evaluation of the produced solar cell element is as follows: WXS-155S-10 manufactured by Wacom Denso Co., Ltd. as pseudo-sunlight, and IV CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT) as a current-voltage (IV) evaluation measuring instrument. The measurement apparatus was combined. Table 1 shows the results of power generation performance as solar cells of the pastes produced in Examples and Comparative Examples. Table 1 shows each measured value of the power generation performance as a solar cell as a relative value with the measured value of Comparative Example 1 as 100.0.
  • Eff conversion efficiency
  • FF fill factor
  • Voc open circuit voltage
  • Jsc short circuit current
  • the total content of the silver alloy particles and the silver particles is 70% by mass to 94% by mass, and the content of the glass particles is 0.1% by mass to 10% by mass. %, And the total content of the solvent and the resin was 3% by mass or more and 29.9% by mass or less, and good electrical characteristics were obtained.
  • the FF value since the FF value is increased, it is considered that the contact resistance between the electrode and the substrate is decreased. This is because the reaction between V 2 O 5 and Ag is suppressed by the presence of silver alloy particles, and as a result, the contact resistance may be reduced.
  • the electrode paste compositions of Examples 1 to 13 of the present invention are suitable for forming solar cell electrodes. Further, since the amount of expensive silver used can be reduced, it can also contribute to cost reduction. Furthermore, since the glass particles used in the electrode paste compositions of Examples 1 to 13 do not contain a lead component, it is possible to reduce the influence on the environment.
  • Example 14 Using the electrode paste composition 9 obtained above, a solar battery cell 14 having a structure as shown in FIG. 4 was produced. The heat treatment was performed at 750 ° 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.

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Abstract

L'invention concerne une composition de pâte pour électrode qui peut être utilisée afin de former des électrodes, qui réduit la quantité d'argent utilisée, et qui minimise les augmentations de résistivité. L'invention concerne également une cellule solaire comprenant des électrodes formées à partir de cette composition de pâte pour électrode. La composition de pâte pour électrode comprend des particules d'alliage d'argent, des particules de verre, une résine et un solvant.
PCT/JP2011/051363 2010-01-25 2011-01-25 Composition de pâte pour électrode et cellule solaire WO2011090213A1 (fr)

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EP2750142A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant un système de réaction inorganique avec une température de transition vitreuse élevée dans la préparation d'électrodes pour cellules solaires MWT
EP2750141A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant des particules d'oxyde inorganiques grossières dans la préparation d'électrodes pour cellules solaires MWT
EP2750140A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant un vanadium contenant un composé et un phosphore contenant le matériau dans la préparation d'électrodes pour cellules solaires MWT
EP2750139A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant un vanadium contenant un composé dans la préparation d'électrodes pour cellules solaires MWT

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CN102368391B (zh) * 2011-10-26 2013-05-22 南昌大学 一种用于晶体硅太阳电池的高电导率无铅银浆及制备方法
WO2013069727A1 (fr) * 2011-11-10 2013-05-16 株式会社村田製作所 Pâte conductrice et procédé de production d'électrode traversante
CN102568649B (zh) * 2011-12-29 2013-11-06 彩虹集团公司 一种埋栅型晶体硅太阳能电池用电极浆料的制备方法
FR2992466A1 (fr) 2012-06-22 2013-12-27 Soitec Silicon On Insulator Procede de realisation de contact pour led et structure resultante
JP6371099B2 (ja) * 2014-04-18 2018-08-08 ナミックス株式会社 導電性ペースト及び結晶系シリコン太陽電池
CN106229026B (zh) * 2016-07-12 2018-08-28 常州聚和新材料股份有限公司 合金银粉及其制备方法及由其制备的太阳能导电浆料
JP7190989B2 (ja) * 2019-09-17 2022-12-16 富士フイルム株式会社 導電膜、フィルムセンサー、タッチパネル、液晶表示装置、導電膜の製造方法、及び組成物

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EP2750142A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant un système de réaction inorganique avec une température de transition vitreuse élevée dans la préparation d'électrodes pour cellules solaires MWT
EP2750141A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant des particules d'oxyde inorganiques grossières dans la préparation d'électrodes pour cellules solaires MWT
EP2750140A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant un vanadium contenant un composé et un phosphore contenant le matériau dans la préparation d'électrodes pour cellules solaires MWT
EP2750139A1 (fr) * 2012-12-28 2014-07-02 Heraeus Precious Metals GmbH & Co. KG Pâte électroconductrice comprenant un vanadium contenant un composé dans la préparation d'électrodes pour cellules solaires MWT
WO2014101999A1 (fr) * 2012-12-28 2014-07-03 Heraeus Precious Metals Gmbh & Co. Kg Pâte électroconductrice contenant des particules d'oxyde inorganique grossières, utilisée dans la préparation d'électrodes pour cellules solaires mwt
WO2014102004A1 (fr) * 2012-12-28 2014-07-03 Heraeus Precious Metals Gmbh & Co. Kg Pâte électroconductrice comprenant un composé contenant du vanadium et un matériau contenant du phosphore utilisée dans la fabrication d'électrodes pour cellules solaires mwt
WO2014102002A1 (fr) * 2012-12-28 2014-07-03 Heraeus Precious Metals Gmbh & Co. Kg Pâte conductrice électrique comprenant un composé contenant du vanadium pour la préparation d'électrodes dans des cellules solaires mwt
WO2014102000A1 (fr) * 2012-12-28 2014-07-03 Heraeus Precious Metals Gmbh & Co. Kg Pâte électro-conductrice comprenant un système de réaction inorganique à température de transition vitreuse élevée utilisée dans la préparation d'électrodes dans des cellules photovoltaïques mwt
CN105144304A (zh) * 2012-12-28 2015-12-09 赫劳斯德国有限两和公司 制备mwt太阳能电池电极中的包含含钒化合物的导电浆料
CN105164761A (zh) * 2012-12-28 2015-12-16 赫劳斯德国有限两和公司 制备mwt太阳能电池电极中的包含具有高玻璃化转变温度的无机反应体系的导电浆料
US10002977B2 (en) 2012-12-28 2018-06-19 Heraeus Deutschland GmbH & Co. KG Electro-conductive paste comprising coarse inorganic oxide particles in the preparation of electrodes in MWT solar cells

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