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WO2011074888A2 - Composition de pâte d'électrode pour surface arrière de cellules photovoltaïques - Google Patents

Composition de pâte d'électrode pour surface arrière de cellules photovoltaïques Download PDF

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Publication number
WO2011074888A2
WO2011074888A2 PCT/KR2010/009013 KR2010009013W WO2011074888A2 WO 2011074888 A2 WO2011074888 A2 WO 2011074888A2 KR 2010009013 W KR2010009013 W KR 2010009013W WO 2011074888 A2 WO2011074888 A2 WO 2011074888A2
Authority
WO
WIPO (PCT)
Prior art keywords
solar cell
paste composition
weight
silver paste
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2010/009013
Other languages
English (en)
Korean (ko)
Other versions
WO2011074888A3 (fr
Inventor
이창모
최형섭
홍승권
임대성
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Original Assignee
Dongwoo Fine Chem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Priority to CN2010800533415A priority Critical patent/CN102652339A/zh
Priority claimed from KR1020100128828A external-priority patent/KR20110069724A/ko
Publication of WO2011074888A2 publication Critical patent/WO2011074888A2/fr
Publication of WO2011074888A3 publication Critical patent/WO2011074888A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • 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
    • 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 a silver paste composition for a solar cell back electrode.
  • the present invention relates to the Korean Patent Application No. 10-2009-0125885 filed with the Korean Patent Office on December 17, 2009 and the Korean Patent Application No. 10-2010-0128828 filed to the Korean Patent Office on December 16, 2010. Claiming benefit, the entire contents of which are incorporated herein by reference.
  • the manufacturing method of a silicon crystalline solar cell is as follows.
  • an n-type impurity layer such as phosphorus (P) is formed on one surface of the P-type silicon substrate.
  • the P-type silicon substrate is preferably 180 to 220 ⁇ m thickness.
  • the n-type impurity layer preferably has a thickness of 0.2 to 0.6 ⁇ m.
  • an antireflection film is formed on the n-type impurity layer to reduce reflection loss of sunlight.
  • SiNx layer may be used as the anti-reflection film.
  • a front electrode is formed on the antireflection film.
  • a back electrode is formed on the P-type silicon on which the n-type impurity layer is not formed.
  • the electrode may be formed by applying an electroconductive paste by screen printing or the like, and drying it, followed by a two-step firing process of low temperature (about 600 ° C.) and high temperature (800-950 ° C.).
  • the conductive paste diffuses into the P-type silicon substrate during the firing process, thereby forming the conductive metal particle-Si alloy layer.
  • a BSF B ack S urface F ield
  • Carrier collection efficiency of generated carriers
  • Republic of Korea Patent Publication No. 10-2006-0108550 relates to a thick film conductive composition
  • a thick film conductive composition comprising metal particles, glass particles, organic vehicle having a size of 3 to 15 ⁇ m. Since the registered patent has a large size of the metal particles, the voids between the metal particles increase after firing, thereby increasing the resistance of the solar cell, thereby reducing efficiency.
  • Korean Patent Laid-Open Publication No. 10-2006-0108552 relates to an electrically conductive thick film composition comprising an electrically conductive metal particle, a Pb-free glass frit, and an organic medium.
  • the registered patent has a problem in that thermal stability such as crystallization occurs in the glass frit in the thermal process, and solder properties are not excellent.
  • An object of the present invention is to provide a silver paste composition for a solar cell back electrode that can improve the efficiency of the solar cell by reducing the resistance of the back electrode.
  • the present invention is to provide a silver paste composition for a solar cell back electrode that can improve the soldering characteristics when manufacturing a solar cell module.
  • the present invention (a) spherical or plate-like conductive silver powder having an average particle diameter (D50) of 0.3 to 1.5 ⁇ m; (b) Bi 2 O 3 -SiO 2 -Al 2 O 3 -B 2 O 3 -SrO-based glass frit; And (c) provides a silver paste composition for a solar cell back electrode comprising an organic vehicle.
  • the silver paste composition for solar cell back electrode of the present invention lowers the resistance of the back electrode, minimizes the impurity content, improves soldering properties, and improves the efficiency of the solar cell and the module.
  • the silver paste composition for solar cell back electrode of this invention contains (a) electroconductive silver powder, (b) glass frit, and (c) organic vehicle.
  • the (a) electrically conductive silver powder has a spherical or plate-shaped having an average particle diameter (D 50) is 0.3 to 1.5 ⁇ m contained in the paste composition.
  • the (a) conductive silver powder preferably has a maximum particle size (D MAX ) of 4.5 ⁇ m and a minimum particle size (D MIN ) of 0.1 ⁇ m. If the average particle diameter (D 50 ) and the minimum particle size (D MIN ) are less than the above-mentioned ranges, the specific surface area of the silver powder is widened, so that the paste viscosity is high. Due to the increased viscosity, the printability is poor and limited to increasing the content of silver powder.
  • the (a) conductive silver powder is preferably included in 65 to 75% by weight based on the total weight of the composition.
  • the printed silver wiring layer becomes thinner after firing, so that the back wiring resistance increases, and the soldering characteristics may decrease. If the above range is exceeded, the printing thickness becomes too thick, which may result in warpage of the silicon wafer.
  • a glass frit is a type Bi 2 O 3 -SiO 2 -Al 2 O 3 -B 2 O 3 -SrO contained in the paste composition.
  • the glass frit (b) is melted to impart adhesion between the silver wiring layer and the silicon wafer layer.
  • SrO included in the glass frit serves to control the transition temperature of the glass frit to alkaline earth metal. At this time, since SrO has a large size of the ion radius, problems of lowering thermal stability such as crystallization are suppressed. And SrO improves a solder characteristic. As a side effect, the efficiency of the solar cell is increased.
  • the glass frit is preferably included in an amount of 0.01 to 10% by weight, more preferably 0.5 to 7% by weight, and even more preferably 1 to 5% by weight, based on the total weight of the composition. .
  • the adhesion force with the P-type silicon substrate which is a substrate of the solar cell after the firing process, may be degraded. If it is included beyond the above range, the resistance may be increased and the efficiency of the solar cell may be reduced.
  • the composition ratio of the glass frit (b) is not particularly limited, but 20 to 30 mol% of Bi 2 O 3 , 25 to 35 mol% of SiO 2 , 5 to 15 mol% of Al 2 O 3 , 20 to 40 mol% of B 2 O 3, and SrO It is preferred to have a composition of 1 to 10 mol%.
  • the physical properties of the glass depend on a suitable ratio of the Si, B component, which is a mesh forming agent, and the Bi, Al component, which is a network intermediate oxide, and the Sr component, which is an alkali metal component. Therefore, it is preferable to use a frit having a composition within the above numerical limits.
  • the softening point (Tg) of the glass frit used by this invention is 400-500 degreeC. If it is less than the above-described range, while the thermal expansion coefficient of the glass frit is relatively large, the phenomenon that the wafer is bent after the firing process during the solar cell manufacturing process may be increased. When it exceeds the above-mentioned range, the glass frit may not be sufficiently melted during the firing process, and thus adhesion may be degraded.
  • the organic vehicle included in the silver paste composition for solar cell back electrode of the present invention is preferably included in 20 to 34.9% by weight based on the total weight of the composition.
  • the viscosity may be too high and printability may be degraded.
  • powder content may fall and it may be difficult to ensure the thickness of a sufficient silver wiring layer.
  • the organic vehicle (c) is prepared by dissolving a polymer resin in an organic solvent, and may further include a thixotropic agent, a humectant, an additive, and the like, as necessary.
  • the polymer resin is preferably contained in an amount of 1 to 25% by weight, more preferably 5 to 25% by weight based on the total weight of the organic vehicle (c).
  • the printability and dispersion stability of the silver paste prepared with the composition of the present invention may be lowered. If the above range is exceeded, the paste may not be printed.
  • polymer resin examples include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethyl cellulose, rosin, phenol resin or acrylic resin.
  • the solvent is a solvent having a breaking point in the range of about 150 to 300 °C to prevent the drying of the paste during the printing process and to control the fluidity.
  • the solvent is preferably included in the remaining amount so that the total weight of the organic vehicle (c) is 100% by weight.
  • the glycol ether series is tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, diethylene glycol Ethyl ether, diethylene glycol n-butyl ether, diethylene glycol hexyl ether, ethylene glycol hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-butyl ether, ethylene glycol phenyl ether, terpinol, Texanol® (brand name) or ethylene glycol etc. are mentioned.
  • the thixotropic agent and the wetting agent are preferably included in an amount of 5 wt% or less based on the total weight of the organic vehicle (c).
  • the thixotropic agent and the wetting agent are not particularly limited as long as they are generally used in this field. However, as the thixotropic agent THIXATROL @ ST of Elementis, the wetting agent may be used Silwet L-77, Silwet L-7500, Silwet L-7280, etc. of Momentive.
  • the additive is preferably included in an amount of 1 to 10% by weight, and more preferably in an amount of 1 to 5% by weight based on the total weight of the (c) organic vehicle.
  • the additives include those generally used in this field such as dispersants. Commercially available surfactants can be used as the dispersant, and these can be used alone or in combination of two or more thereof.
  • the surfactant examples include an ether type such as alkyl polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyoxyethylene polyoxypropylene copolymer as nonionic surfactant; Ester ether types such as polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, and polyoxyethylene ether of sorbitol ester; Ester type such as polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester, propylene glycol ester, sugar ester, alkyl polyglucoside; Nitrogen-containing types such as fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, amine oxides; Examples of the polymeric surfactant include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylic acid-maleic acid copolymer, poly 12-hydroxystearic acid, and the like.
  • products commercially available as the surfactant include hypermer KD (manufactured by Uniqema), AKM 0531 (manufactured by Nippon Yuji Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and polyflow (POLYFLOW) Esha Chemical Co., Ltd., EFTOP (Tochem Products Co., Ltd.), Asahi guard, Suflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Geneneka Co., Ltd.) Manufacture), EFKA (made by EFKA Chemicals Co., Ltd.), PB 821 (made by Ajinomoto Co., Ltd.), BYK-184, BYK-185, BYK-2160, Anti-Terra U (made by BYK Corporation), etc. are mentioned.
  • hypermer KD manufactured by Uniqema
  • AKM 0531 manufactured by Nippon Yuji Co., Ltd.
  • the silver paste composition for a solar cell back electrode of the present invention lowers the resistance of the back electrode, minimizes the impurity content, and improves soldering properties to improve the efficiency of the solar cell and the module.
  • Tg transition point
  • Tdsp softening point
  • a surface texturing process was performed on a single crystal wafer having a size of 156 ⁇ 156 mm and a thickness of 200 ⁇ m to form a pyramid height of about 4 to 6 ⁇ m. Thereafter, SiN x was coated on the N-side of the wafer. Subsequently, a bus bar was printed and dried on the back surface of the wafer using the silver paste composition for solar cell back electrodes of Examples 1 to 3 and Comparative Examples 1 to 4. Thereafter, Dongwoo Fine Chem's aluminum electrode paste (trade name: AMP-BL122C) was applied and dried using a screen printing plate, and a finger line was printed and dried on the front SiNx side using silver paste. It was.
  • the silicon wafer passed through the above process was fired in an infrared continuous firing furnace so that the temperature of the firing region was 800 to 950 ° C. to manufacture a solar cell.
  • the firing process may be performed by simultaneous firing of the front and rear surfaces while passing the silicon wafer into the belt furnace.
  • the belt furnace includes a burn-out section at about 600 ° C. and a firing section at about 860 ° C., after burning off the organic material in the paste, the front and rear surfaces of silver or silver Melt aluminum to form an electrode.
  • the soldering characteristics of the solar cells were evaluated using ribbons of 96.5Sn / 3.5Ag coated copper and ribbons of 62Sn / 36Pb / 2Ag.
  • the soldering temperature for Pb-containing (62Sn / 36Pb / 2Ag) soldering was 230 ° C.
  • the soldering temperature for Pb-free (96.5Sn / 3.5Ag) soldering was 320 ° C.
  • the soldering time was 5-7 seconds.
  • the flux used was MF200.
  • Adhesive strength was obtained by pulling the ribbon at an angle of 90 ° to the surface of the cell. Adhesive strength of less than 200 g is low and values in the range of 200 g to 300 g are appropriate; A value of 300 to 400 g or more was evaluated as good as the adhesive strength, the results are shown in Table 3.
  • the manufacturing examples according to the present invention is 0.2 ⁇ 0.5% difference in efficiency than the comparative manufacturing example, it can be seen that the efficiency is excellent, the soldering characteristics are also excellent.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne une composition de pâte d'électrode pour les surfaces arrière de cellules photovoltaïques, ladite composition comprenant (a) une poudre conductrice de particules sphériques ou planes de granulométrie moyenne (D50) comprise entre 0,3 et 1,5 µm ; (b) un fritté de verre Bi2O3-SiO2-Al2O3-B2O3-Sr O ; et (c) un vecteur organique.
PCT/KR2010/009013 2009-12-17 2010-12-16 Composition de pâte d'électrode pour surface arrière de cellules photovoltaïques Ceased WO2011074888A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010800533415A CN102652339A (zh) 2009-12-17 2010-12-16 太阳能电池背面电极用银浆组成物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2009-0125885 2009-12-17
KR20090125885 2009-12-17
KR10-2010-0128828 2010-12-16
KR1020100128828A KR20110069724A (ko) 2009-12-17 2010-12-16 태양전지 후면 전극용 은 페이스트 조성물

Publications (2)

Publication Number Publication Date
WO2011074888A2 true WO2011074888A2 (fr) 2011-06-23
WO2011074888A3 WO2011074888A3 (fr) 2011-10-27

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Application Number Title Priority Date Filing Date
PCT/KR2010/009013 Ceased WO2011074888A2 (fr) 2009-12-17 2010-12-16 Composition de pâte d'électrode pour surface arrière de cellules photovoltaïques

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WO (1) WO2011074888A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2496166C1 (ru) * 2012-02-02 2013-10-20 Закрытое акционерное общество "Монокристалл" (ЗАО "Монокристалл") Токопроводящая серебряная паста для тыльного электрода солнечного элемента
CN104246908A (zh) * 2012-03-23 2014-12-24 株式会社昌星 太阳能电池用电极糊组合物
CN113990958A (zh) * 2021-10-21 2022-01-28 海宁正泰新能源科技有限公司 一种N型TopCon电池及其制备方法
CN119833201A (zh) * 2024-12-31 2025-04-15 乐凯胶片股份有限公司 导电银浆、制备太阳能电池背面电极的方法、太阳能电池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7435361B2 (en) * 2005-04-14 2008-10-14 E.I. Du Pont De Nemours And Company Conductive compositions and processes for use in the manufacture of semiconductor devices
US7718092B2 (en) * 2005-10-11 2010-05-18 E.I. Du Pont De Nemours And Company Aluminum thick film composition(s), electrode(s), semiconductor device(s) and methods of making thereof
KR101280489B1 (ko) * 2007-05-09 2013-07-01 주식회사 동진쎄미켐 태양전지 전극 형성용 페이스트

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2496166C1 (ru) * 2012-02-02 2013-10-20 Закрытое акционерное общество "Монокристалл" (ЗАО "Монокристалл") Токопроводящая серебряная паста для тыльного электрода солнечного элемента
CN104246908A (zh) * 2012-03-23 2014-12-24 株式会社昌星 太阳能电池用电极糊组合物
CN113990958A (zh) * 2021-10-21 2022-01-28 海宁正泰新能源科技有限公司 一种N型TopCon电池及其制备方法
CN119833201A (zh) * 2024-12-31 2025-04-15 乐凯胶片股份有限公司 导电银浆、制备太阳能电池背面电极的方法、太阳能电池
CN119833201B (zh) * 2024-12-31 2025-10-28 乐凯胶片股份有限公司 导电银浆、制备太阳能电池背面电极的方法、太阳能电池

Also Published As

Publication number Publication date
WO2011074888A3 (fr) 2011-10-27

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