WO2018084464A1 - Pâte conductrice pour électrode de cellule solaire, et cellule solaire fabriquée à l'aide de cette dernière - Google Patents

Pâte conductrice pour électrode de cellule solaire, et cellule solaire fabriquée à l'aide de cette dernière Download PDF

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WO2018084464A1
WO2018084464A1 PCT/KR2017/011513 KR2017011513W WO2018084464A1 WO 2018084464 A1 WO2018084464 A1 WO 2018084464A1 KR 2017011513 W KR2017011513 W KR 2017011513W WO 2018084464 A1 WO2018084464 A1 WO 2018084464A1
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solvent
solar cell
conductive paste
electrode
powder
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PCT/KR2017/011513
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English (en)
Korean (ko)
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장문석
전태현
노화영
김충호
김인철
고민수
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엘에스니꼬동제련 주식회사
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Priority to CN201780077375.XA priority Critical patent/CN110337727A/zh
Publication of WO2018084464A1 publication Critical patent/WO2018084464A1/fr

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    • 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
    • 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
    • H01L31/0216—Coatings
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for 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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a conductive paste used for forming an electrode of a solar cell and a solar cell manufactured using the same.
  • a solar cell is a semiconductor device that converts solar energy into electrical energy and generally has a p-n junction.
  • the basic structure is the same as that of a diode.
  • 1 is a structure of a general solar cell device, and the solar cell device is generally configured using a p-type silicon semiconductor substrate 10 having a thickness of 180 to 250 ⁇ m.
  • an n-type impurity layer 20 having a thickness of 0.3 to 0.6 ⁇ m, an antireflection film 30 and a front electrode 100 are formed thereon.
  • the back electrode 50 is formed on the back side of the p-type silicon semiconductor substrate.
  • the front electrode 100 is formed by applying a conductive paste mixed with silver powder, glass frit, organic vehicle solvent, and additives containing silver as a main component on the anti-reflection film 30. After baking, the electrode is formed, and the back electrode 50 is coated with an aluminum paste composition composed of aluminum powder, glass frit, organic vehicle, and additives by screen printing and dried, and then dried at 660 ° C. (melting point of aluminum). It is formed by baking at the temperature above. During the firing, aluminum diffuses into the p-type silicon semiconductor substrate, whereby an Al-Si alloy layer is formed between the back electrode and the p-type silicon semiconductor substrate, and the p + layer 40 is formed as an impurity layer by diffusion of aluminum atoms. ) Is formed. The presence of such a p + layer results in a back surface field (BSF) effect that prevents electron recombination and improves the collection efficiency of product carriers.
  • the rear silver electrode 60 may be further positioned below the rear aluminum electrode 50.
  • the front and rear electrode paste compositions are also manufactured in consideration of the printability of the screen printing process.
  • a high boiling point solvent suitable for screen printing is used or
  • a polar solvent is used, but in particular, the front electrode is difficult to realize a good resolution by reproducing a desired line width.
  • the conventional method uses a silver conductive paste composition for the front electrode, and even if the line width of the screen printing mask for the front electrode is 80 ⁇ m, the line width of the front electrode is 10 to 20 ⁇ m wider after actual printing. many. As a result, the light receiving surface of the cell is reduced, and as a result, a problem of deterioration of battery characteristics occurs.
  • Korean Patent Publication No. 2013-0139022 (December 20, 2013) uses a hydrophobic binder and a hydrophobic solvent when the hydrophilic conductive metal is included in the conductive paste composition, and a hydrophobic binder and a hydrophobic solvent when the hydrophobic conductive metal is included.
  • a hydrophobic binder and a hydrophobic solvent when the hydrophilic conductive metal is included in the conductive paste composition.
  • a hydrophobic binder and a hydrophobic solvent when the hydrophobic conductive metal is included.
  • the solvent is used by controlling the properties (hydrophilicity and hydrophobicity) of the solvent according to the properties of the conductive metal used as described above, the selection of the binder or powder is restricted, and particularly when the hydrophilic solvent is used This weakness has a problem of poor storage stability.
  • An object of the present invention is to improve the efficiency of a solar cell including an electrode formed using the prepared conductive paste by adjusting the composition of the solvent in the composition of the conductive paste for solar cell electrodes.
  • the present invention comprises a metal powder, a glass frit, an organic binder and a solvent, wherein the solvent is characterized by controlling the surface tension and boiling point by using a mixture of at least two or more solvents including a first solvent and a second solvent. It provides a conductive paste for a solar cell electrode.
  • the solvent is ethyl acetate, butyl carbitol acetate, ethyl carbitol acetate, ethyl carbitol acetate, texanol, diethylene glycol monobutyl ether, It is characterized in that it comprises a first solvent and a second solvent selected from the group consisting of propylene glycol monophenyl ether (Propylene glycol butyl ether) and diethylene glycol monophenyl Ether (Diethylene Glycol Monophenyl Ether).
  • propylene glycol monophenyl ether Propylene glycol butyl ether
  • diethylene glycol monophenyl Ether Diethylene Glycol Monophenyl Ether
  • the solvent is a solvent having a surface tension of 20 to 60mN / m by mixing at least two or more solvents comprising a first solvent 20 to 30m / Nm and a second solvent having a surface tension of 40 to 50m / Nm It features.
  • the solvent is a solvent having a boiling point of 150 to 300 °C by mixing at least two or more solvents including a first solvent having a boiling point of 150 to 220 °C and a second solvent having a boiling point of 190 to 300 °C.
  • the mixing ratio of the first solvent and the second solvent is characterized in that 8: 2 to 5: 5 by weight.
  • the conductive paste for the solar cell electrode further comprises a dispersant
  • the dispersant is characterized in that it comprises any one or more of vegetable oil and animal oil.
  • a solar cell including a front electrode on an upper substrate and a back electrode on a lower substrate, wherein the front electrode is manufactured by coating and firing the conductive paste for the solar cell electrode.
  • a battery Provide a battery.
  • the present invention can improve the conductivity by controlling the surface tension of the solvent used in the conductive paste for solar cell electrodes, thereby improving the aspect ratio, that is, the line width and line height of the electrode formed using the prepared conductive paste. As the line width of the electrode decreases, the light receiving surface increases, thereby providing a solar cell having high power generation efficiency.
  • a solvent having different boiling points is mixed with a conductive paste for solar cell electrodes, and pin-holes, cracks, etc. of electrodes formed by gradually evaporating the solvent during electrode formation using the prepared conductive paste.
  • the solvent composition according to the present invention does not depend on the kind or characteristics of other components (conductive metal powder and binder) used in the conductive paste, it is limited to the kind or characteristics of the conductive metal powder and binder when manufacturing the conductive paste for solar cell electrodes. It doesn't work.
  • FIG. 1 is a schematic cross-sectional view of a general solar cell device.
  • the paste according to an embodiment of the present invention is a paste suitable for use in forming a solar cell electrode, and provides a conductive paste for a solar cell electrode including two or more solvents in order to control surface tension and boiling point. More specifically, the conductive paste according to the present invention comprises a metal powder, a glass frit, a binder, a solvent and other additives.
  • the metal powder silver (Ag) powder, gold (Au) powder, platinum (Pt) powder, nickel (Ni) powder, copper (Cu) powder, or the like may be used. It may be used as, the alloy of the above-described metal may be used, or at least two of the above-described powder may be used as a mixed powder.
  • the surface of the metal powder can be used as a surface-treated metal powder such as hydrophilic treatment can be used regardless of the surface properties such as hydrophobicity, hydrophilicity of the metal powder.
  • silver (Ag) powder which has excellent electrical conductivity and is mainly used for front electrodes.
  • the silver powder is preferably a pure silver powder.
  • a silver-coated composite powder having at least a surface of a silver layer, an alloy containing silver as a main component, and the like can be used.
  • other metal powders may be mixed and used. For example, aluminum, gold, palladium, copper, nickel, etc. are mentioned.
  • the content of the metal powder is preferably 40 to 95% by weight based on the total weight of the conductive paste composition in consideration of the electrode thickness formed during printing and the wire resistance of the electrode. If less than 40% by weight may be a high specific resistance of the electrode formed, when more than 95% by weight there is a problem that the metal powder is not uniformly dispersed due to insufficient content of other components. More preferably included in 70 to 90% by weight.
  • the average particle diameter of the silver powder may be 0.1 to 10 ⁇ m, and 0.1 to 3 ⁇ m is preferable in consideration of the ease of pasting and the density at the time of baking, and the shape may be at least one of spherical, needle, plate and amorphous. have.
  • Silver powder may mix and use 2 or more types of powder from which an average particle diameter, particle size distribution, shape, etc. differ.
  • the glass frit component may include at least one selected from the group consisting of Bi 2 O 3 , Si-B-Pb, Si-Bi-Zn and Si-Pb-Al-Zn.
  • the average particle diameter of the glass frit is not limited, but may have a particle diameter within the range of 0.1 to 10 ⁇ m, and may be used by mixing multi-sheet particles having different average particle diameters.
  • at least 1 type of glass frit uses that whose average particle diameter (D50) is 0.1 micrometer or more and 5 micrometers or less.
  • the content of the glass frit is preferably 1 to 10% by weight based on the total weight of the conductive paste composition. If the content is less than 1% by weight, incomplete firing may occur to increase the electrical resistivity. There are too many components, and there exists a possibility that an electrical resistivity may also become high.
  • the organic vehicle including the organic binder and the solvent is required to maintain a uniformly mixed state of the metal powder and the glass frit.
  • the conductive paste is used. It is required to have a property of making it homogeneous, suppressing the blurring and flow of the printing pattern, and improving the dischargeability and plate separation property of the conductive paste from the screen plate.
  • the organic binder may be a cellulose compound, an acrylic compound, an epoxy compound, a polyester compound, a polyvinyl compound, or the like.
  • the cellulose compounds include cellulose acetate, cellulose acetate butylate, ethyl cellulose, methyl cellulose, hydroxy flophyll cellulose, hydroxy ethyl cellulose, hydroxy propyl methyl cellulose, hydroxy ethyl methyl cellulose, and the like.
  • examples thereof include poly acrylamide, poly methacrylate, poly methyl methacrylate, polyethyl methacrylate, and the like
  • epoxy compounds include bisphenol-A type, bisphenol-F type, bromine type, and novolac.
  • Type, alcohol type, and the like, and examples of the polyvinyl compound include polyvinyl butyral, polyvinyl acetate, and polyvinyl alcohol. At least one organic binder may be selected and used.
  • the organic binder is not limited but is preferably 1 to 15% by weight based on the total weight of the conductive paste composition.
  • the content of the organic binder is less than 1% by weight, the viscosity of the composition and the adhesion of the formed electrode pattern may be lowered.
  • the content of the organic binder exceeds 15% by weight, the amount of the metal powder, the solvent, and the dispersant may not be sufficient.
  • the solvent may control the surface tension and the boiling point by using a mixture of at least two or more solvents including a first solvent and a second solvent.
  • the solvent included in the conductive paste according to the present invention is ethyl acetate, butyl carbitol acetate, ethyl carbitol acetate, texanol, texanol, diethylene glycol
  • a solvent having a surface tension of 20 to 60 mN / m is used by mixing the first and second solvents selected from the above solvents.
  • a solvent in which a first solvent having a surface tension of 20 to 30 m / Nm and a second solvent having a surface tension of 40 to 50 m / Nm is used.
  • a butyl carbitol acetate, texanol, and the like may be used as the first solvent
  • diethylene glycol monobutyl ether, propylene glycol monophenyl, and the like may be used as the second solvent.
  • the mixing ratio of the first solvent and the second solvent is preferably 8: 2 to 5: 5.
  • the conductivity can be improved by improving the aspect ratio, that is, the line width and line height, of the electrode formed using the prepared conductive paste, and the light receiving surface increases as the line width of the electrode decreases. It is possible to provide a solar cell having a high power generation efficiency.
  • a solvent having a boiling point of 150 to 300 ° C. is used by mixing the first and second solvents selected from the above solvents.
  • the solvent which mixed the 1st solvent whose boiling point is 150-220 degreeC, and the 2nd solvent whose boiling point is 190-300 degreeC is used.
  • ethyl carbitol acetate, propylene glycol monobutyl ether, and the like may be used as the first solvent
  • butyl carbitol acetate, and tex may be used as the second solvent.
  • the mixing ratio of the first solvent and the second solvent is preferably 8: 2 to 5: 5.
  • butyl carbitol acetate and diethylene glycol monophenyl ether are mixed at a 7: 3 (weight) ratio to use a solvent having a surface tension of 35 mN / m and a boiling point of 250 ° C.
  • the content of the solvent is preferably 5 to 15% by weight based on the total weight of the conductive paste composition. If the content is less than 5% by weight, the electrode may break due to rapid drying during printing. If the content exceeds 15% by weight, the solvent may not be suitable for printing. There is a problem that is formed.
  • the solvent composition according to the present invention does not depend on the kind or properties of other components (conductive metal powder and binder) used in the conductive paste, the solvent composition is not limited to the kind or properties of the conductive metal powder and the binder when manufacturing the conductive paste for solar cell electrodes. Do not.
  • the conductive paste composition according to the present invention may further include additives commonly known as necessary, for example, a dispersant, a leveling agent, a plasticizer, a viscosity modifier, a surfactant, an oxidizing agent, a metal oxide, a metal organic compound, and the like.
  • additives commonly known as necessary, for example, a dispersant, a leveling agent, a plasticizer, a viscosity modifier, a surfactant, an oxidizing agent, a metal oxide, a metal organic compound, and the like.
  • the dispersant may be a vegetable oil, an animal oil, or the like.
  • the dispersant may be included in an amount of 0.1 to 5 wt% based on the total weight of the conductive paste composition. When included in less than 0.1% by weight, there is a problem that the dispersibility is lowered due to insufficient dispersion effect, when included in excess of 5% by weight, the viscosity is lowered due to overdispersion, and stability problems due to paste phase separation during long-term storage Can cause. More preferably included in 0.1 to 3% by weight.
  • the above-mentioned conductive paste composition for a solar cell electrode may be prepared by mixing and dispersing a metal powder, a glass frit, an organic binder, a solvent and an additive, and then filtering and defoaming.
  • the present invention also provides a method for forming an electrode of a solar cell and a solar cell electrode produced by the method, wherein the conductive paste is coated on a substrate, dried and baked. Except for using the conductive paste containing the silver powder of the above characteristics in the method of forming a solar cell electrode of the present invention, the substrate, printing, drying and firing can be used as the method commonly used in the manufacture of solar cells as well to be.
  • the substrate may be a silicon wafer.
  • Metal powder, glass frit, organic binder, solvent and dispersant were added in a composition as shown in Table 1 below, and dispersed using a three-bone mill, followed by mixing silver powder (spherical, average particle diameter of 1 ⁇ m) and further using a three-bone mill. And dispersed. After that, degassed under reduced pressure to prepare a conductive paste.
  • the composition of the solvent is shown separately in Table 2 below.
  • the line width of the electrode formed of the conductive paste according to the embodiment of the present invention is narrow, the line height is high, and the aspect ratio is high, and thus the electrical conductivity of the solar cell manufactured is excellent. Can be.
  • the obtained conductive paste was pattern printed on the front surface of the wafer by a 40 ⁇ m mesh screen printing technique, and dried at 200 to 350 ° C. for 40 to 50 seconds using a belt type drying furnace. After printing the Al paste on the back of the wafer and dried in the same way.
  • the cell formed by the above process was fired for 60 seconds to 80 seconds between 500 to 900 ° C. using a belt type kiln to manufacture solar cells.
  • the manufactured cell is analyzed by the conversion efficiency (Eff), short circuit current (Isc), open circuit voltage (Voc), curve factor (FF) using a solar cell efficiency measurement equipment (Halm, cetisPV-Celltest 3) It is shown in Table 4, it was shown in Table 4 to measure the line resistance of the electrode pattern.
  • Example 1 9.491 0.6386 19.746 77.74 0.00168
  • Example 2 9.4918 0.6393 19.767 77.749 0.00177
  • Comparative Example 1 9.472 0.6384 19.651 77.7 0.00198
  • Comparative Example 2 9.477 0.6371 19.619 77.05 0.00211
  • Comparative Example 3 9.459 0.6378 19.589 77.75 0.00173
  • Comparative Example 4 9.4266 0.6379 19.524 78.21 0.00156
  • Example 5 9.4116 0.6393 19.518 76.957 0.00207
  • a solar cell divides efficiency into 0.2% units, and considering that the 0.2% efficiency increase is a value having a very large meaning, an electrode made of a conductive paste containing a solvent according to the present invention as shown in Table 3 above is shown.
  • Table 3 an electrode made of a conductive paste containing a solvent according to the present invention as shown in Table 3 above is shown.
  • the power generation efficiency of the solar cell is improved.

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Abstract

La présente invention concerne une pâte conductrice pour une électrode de cellule solaire comprenant une poudre métallique, une fritte de verre, un liant organique et un solvant. Par un mélange d'au moins deux types de solvants, ou plus, comprenant un premier solvant et un second solvant en tant que solvant servant à ajuster une tension de surface et un point d'ébullition du solvant, il est possible d'améliorer la conductivité par une amélioration d'un facteur de forme, c'est-à-dire une largeur de ligne et un pas de lignes, d'une électrode qui est formée à l'aide de la pâte conductrice selon la présente invention. De plus, à mesure que la largeur de ligne de l'électrode diminue, une surface de réception de lumière augmente, ce qui fournit une cellule solaire ayant un haut rendement de génération.
PCT/KR2017/011513 2016-11-01 2017-10-18 Pâte conductrice pour électrode de cellule solaire, et cellule solaire fabriquée à l'aide de cette dernière WO2018084464A1 (fr)

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CN117079860A (zh) * 2023-10-12 2023-11-17 上海银浆科技有限公司 一种低耗银异质结太阳能电池低温银浆及其制备方法和应用

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KR20120048436A (ko) * 2010-11-05 2012-05-15 현대자동차주식회사 잉크젯 인쇄용 반도체 산화물 잉크 조성물과 이의 제조방법 및 이를 이용한 광전변환 소자의 제조방법
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WO2016076213A1 (fr) * 2014-11-13 2016-05-19 住友化学株式会社 Composition d'encre et élément de conversion photoélectrique produit à l'aide de celle-ci

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