WO2017074151A1 - Composition de pâte d'électrode pour cellule solaire et cellule solaire préparée au moyen de ladite composition - Google Patents

Composition de pâte d'électrode pour cellule solaire et cellule solaire préparée au moyen de ladite composition Download PDF

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Publication number
WO2017074151A1
WO2017074151A1 PCT/KR2016/012346 KR2016012346W WO2017074151A1 WO 2017074151 A1 WO2017074151 A1 WO 2017074151A1 KR 2016012346 W KR2016012346 W KR 2016012346W WO 2017074151 A1 WO2017074151 A1 WO 2017074151A1
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Prior art keywords
solar cell
electrode
paste composition
line width
firing
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PCT/KR2016/012346
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English (en)
Korean (ko)
Inventor
전태현
고민수
노화영
최영훈
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엘에스니꼬동제련 주식회사
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Publication of WO2017074151A1 publication Critical patent/WO2017074151A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • H01L31/0224—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
    • H01L31/04—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
    • 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 an electrode paste composition for 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.
  • the solar cell device is generally configured using a p-type silicon semiconductor substrate having a thickness of 180 to 250 ⁇ m.
  • an n-type impurity layer having a thickness of 0.3 to 0.6 ⁇ m, an antireflection film and a front electrode are formed thereon.
  • a back electrode is formed on the back side of the p-type silicon semiconductor substrate.
  • the front electrode is formed by screen printing or the like using a conductive paste containing conductive particles containing silver as a main component, glass frit, and an organic vehicle, and the back electrode is formed of aluminum powder, glass frit, and organic vehicle.
  • the aluminum paste composition made of (organic vehicle) is applied by screen printing or the like and dried, and then fired at a temperature of 660 ⁇ ⁇ (melting point of aluminum) or higher.
  • a temperature of 660 ⁇ ⁇ (melting point of aluminum) or higher a temperature of 660 ⁇ ⁇ (melting point of aluminum) or higher.
  • 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 a p + layer is formed as an impurity layer by diffusion of aluminum atoms. do.
  • 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.
  • BSF back surface field
  • the anti-reflection film is eroded by the redox reaction of the glass frit powder, and the conductive metal crystals are precipitated in the form of the conductive powder crystals in the glass frit powder at the substrate interface.
  • the conductive metal crystals are precipitated in the form of the conductive powder crystals in the glass frit powder at the substrate interface.
  • it is known to exhibit contact by tunneling effect or direct adhesion with the bulk electrode depending on the thickness of the glass frit powder.
  • the line width of the metal pattern at the front electrode of the solar cell should be reduced because the loss due to light absorption or reflection to the metal electrode should be minimized, and the height of the pattern should be increased for the electrode resistance.
  • the aspect ratio of the height / line width of the electrode has been increased by changing the printing method or the screen mesh design, and in the case of the paste composition, the method of increasing the viscosity by simply considering the rheological properties is applied. Attempts have been made to reduce the line width.
  • An object of the present invention is to provide a solar cell electrode paste composition and a high efficiency solar cell that can reduce the line width of the electrode even under the same printing conditions and heat treatment process, and can reduce the increase in the line width of the electrode after firing.
  • the present invention provides a solar cell electrode paste composition
  • a solar cell electrode paste composition comprising a conductive metal powder, a glass frit, and an organic vehicle, wherein the polyether-modified silicon-based additive is further provided.
  • polyether modified silicone-based additive provides a paste composition for a solar cell electrode, characterized in that represented by the following formula (1).
  • R 1 is independently selected from hydrogen and methyl group, hydrogen and methyl group may exist together in one molecule, m is an integer from 5 to 100, m is an integer from 1 to 10, x is from 1 to 300 Integer, y is an integer from 1 to 100)
  • Silver provides a paste composition for a solar cell electrode, characterized in that in the range of 6: 4 ⁇ 8: 2.
  • x: y provides a paste composition for a solar cell electrode, characterized in that in the range of 10: 1 to 100: 1.
  • the content of the polyether-modified silicone-based additive provides a paste composition for a solar cell electrode, characterized in that in the range of 0.01% to 0.3% by weight based on the total paste composition.
  • the paste composition for solar cell electrodes was applied to the solar cell silicon substrate through screen printing of mesh size opening of 50 ⁇ m or less, and heated to 500 to 900 ° C. using a belt type kiln to perform baking for 25 seconds, and then measured electrode line width.
  • a paste composition for a solar cell electrode wherein an increase in electrode bleeding line width after firing relative to the electrode line width before firing is within an average of 12 ⁇ m.
  • the front electrode is manufactured by applying the solar cell electrode paste composition and baking To provide.
  • the present invention having the above-described structural features can reduce the line width of the electrode by using a highly polarized modified silicone-based additive even under the same printing conditions and heat treatment processes, and can significantly reduce the increase in the line width of the electrode after firing.
  • FIG. 4 is a schematic cross-sectional view of a general solar cell device.
  • the present invention provides a solar cell electrode paste composition
  • a solar cell electrode paste composition comprising a conductive metal powder, a glass frit, and an organic vehicle, wherein the polyether-modified silicon-based additive is further provided.
  • a special additive may be added to reduce the increase in the line width of the electrode during firing. That is, a polyether modified silicone additive may be added, and preferably a polyether modified silicone additive may be added. Incorporation of such additives can significantly reduce the increase in line width during firing.
  • the content of the polyether-modified silicone-based additive may be in the range of 0.01 wt% to 0.3 wt% based on the total paste composition. Below the range, the line width reduction effect is insignificant, and when the range is exceeded, the electrical characteristics of the solar cell electrode may be disadvantageous or the adhesion between the electrode and the silicon substrate may be degraded, thereby preventing the contact.
  • polyether modified polydimethylsiloxane As an example of polyether modified polydimethylsiloxane, the polyether modified polydimethylsiloxane of following General formula (1) can be used.
  • R 1 is independently selected from hydrogen and methyl group, and hydrogen and methyl group may be present together in one molecule.
  • ethylene oxide (EO) group and propylene oxide (PO) group coexist, the molar ratio of ethylene oxide group and propylene oxide group is 2 : 8 to 8: 2.
  • Polyether denaturation is expected to have a high polarity property to lower the surface tension, thereby reducing the increase in line width during firing. Since the ethylene oxide group is more polar compared to the propene oxide group, the molar ratio of the ethylene oxide group and the propylene oxide group is preferably 6: 4 to 8: 2.
  • m is an integer from 5 to 100
  • m is an integer from 1 to 10
  • x is an integer from 1 to 300
  • y is an integer from 1 to 100
  • x: y is 10: 1 to 100: 1 This is preferable.
  • the conductive metal powder silver powder, copper powder, nickel powder, aluminum powder, or the like may be used.
  • silver powder is mainly used, and for the back electrode, aluminum powder is mainly used.
  • the conductive metal material will be described using silver powder as an example. The following description is equally applicable to other metal powders.
  • 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.
  • the average particle diameter of the silver powder may be 0.1 to 10 ⁇ m, and 0.5 to 5 ⁇ 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 content of the silver powder is preferably 60 to 98% by weight based on the total weight of the electrode paste composition in consideration of the electrode thickness formed during printing and the wire resistance of the electrode.
  • the organic vehicle is not limited but may include an organic binder and a solvent. Sometimes the solvent can be omitted.
  • the organic vehicle is not limited but is preferably 1 to 10% by weight based on the total weight of the electrode paste composition.
  • the organic vehicle is required to maintain a uniformly mixed state of metal powder and glass frit.
  • the conductive paste is applied to a substrate by screen printing, the conductive paste is made homogeneous and the printed pattern is blurred. And properties for suppressing flow and improving the dischargeability and plate separation property of the conductive paste from the screen plate.
  • the binder used in the electrode paste composition according to the embodiment of the present invention is not limited, examples of the cellulose ester-based compound include cellulose acetate and cellulose acetate butylate, and the cellulose ether compound includes ethyl cellulose, methyl cellulose, and hydride.
  • examples of the acryl-based compound include poly acrylamide, poly methacrylate, poly methyl methacrylate, and polyethyl meta An acrylate etc. can be mentioned, For example, polyvinyl butyral, polyvinyl acetate, a polyvinyl alcohol, etc. are mentioned as a vinyl type. At least one or more of the binders may be selected and used.
  • Solvents used for dilution of the composition include alpha-terpineol, texanol, dioctyl phthalate, dibutyl phthalate, cyclohexane, hexane, toluene, benzyl alcohol, dioxane, diethylene glycol, ethylene glycol mono butyl ether, ethylene At least one compound selected from the group consisting of glycol mono butyl ether acetate, diethylene glycol mono butyl ether, diethylene glycol mono butyl ether acetate and the like is preferably used.
  • the glass frit used is not limited. Lead-free glass frits can be used as well as leaded glass frits. There is no restriction
  • PbO is 10 to 29 mol%
  • TeO2 is 20 to 34 mol%
  • Bi2O3 is 3 to 20 mol%
  • SiO2 is 20 mol% or less
  • B2O3 is 10 mol% or less
  • Alkali metals (Li, Na, K, etc.) and alkaline earth metals (Ca, Mg, etc.) may contain 10 to 20 mol%.
  • PbO is preferably included within the above range in the glass frit.
  • PbO exceeds 30 mol% and the content of alkali metals and alkaline earth metals falls below the above range, the Al2O3 layer removal performance in the insulating layer is not preferable, which is not preferable.
  • the average particle diameter of the glass frit is not limited, but may have a particle diameter within the range of 0.5 ⁇ 5 ⁇ m, it may be used by mixing a multi-sheet particles having a different average particle diameter.
  • at least one glass frit has a mean particle size (D50) of 3 ⁇ m or more and 10 ⁇ m or less.
  • the glass transition temperature (Tg) of the glass frit whose average particle diameter is 3 micrometers or more and 10 micrometers or less is less than 300 degreeC. Since particles having a relatively large particle size are used, problems such as uneven melting during firing can be prevented by lowering the glass transition temperature.
  • the content of the glass frit is preferably 1 to 15% 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.
  • Glass transition temperature (Tg) of the glass frit is not limited, but may be 200 ⁇ 600 °C, preferably the glass transition temperature is in the range of 200 °C to less than 300 °C.
  • melt uniformity can be increased and cell uniformity can be improved.
  • the crystallization properties of the glass frit can be treated as an important factor.
  • the initial crystallization temperature is generally higher than 550 ° C. during DSC measurement.
  • the crystallization occurs more quickly when firing by allowing the initial crystallization peak in the DSC measurement data of the glass frit to be less than 400 ° C.
  • the electrical characteristics can be excellent by remarkably reducing the increase in the line width of the electrodes.
  • the crystallization peak first occurs below 400 ° C on the DSC data, and the secondary crystallization peak occurs preferably above 400 ° C and below 500 ° C. More preferably, all of the crystallization peaks occur below 400 ° C. on the DSC data.
  • the paste composition for electrodes according to the present invention may further include additives commonly known as necessary, for example, a dispersant, a plasticizer, a viscosity modifier, a surfactant, an oxidant, a metal oxide, a metal organic compound, and the like.
  • additives commonly known as necessary, for example, a dispersant, a plasticizer, a viscosity modifier, a surfactant, an oxidant, a metal oxide, a metal organic compound, and the like.
  • the present invention also provides a method for forming an electrode of a solar cell and a solar cell electrode manufactured by the method, characterized in that the paste for the solar cell electrode is applied on a substrate, dried and baked.
  • the substrate, printing, drying and firing is a general method that can be used for the manufacture of a solar cell, of course.
  • the substrate may be a silicon wafer
  • the electrode made of the paste of the present invention may be a finger electrode or a busbar electrode on the front surface
  • the printing may be screen printing or offset printing
  • the drying may be 90 to 250. It may be made at °C, the firing may be made at 600 to 950 °C.
  • the high temperature / high speed firing is performed at 800 to 950 ° C., more preferably at 850 to 900 ° C. for 5 seconds to 1 minute, and the printing is preferably performed at a thickness of 20 to 60 ⁇ m.
  • the structure of the solar cell described in Korean Unexamined-Japanese-Patent No. 10-2006-0108550, 10-2006-0127813, Unexamined-Japanese-Patent No. 2001-202822, and 2003-133567, and its manufacturing method are mentioned. have.
  • a binder, a dispersant, a leveling agent, a glass frit (average particle diameter 1 ⁇ m) and the like were dispersed in a composition as shown in Table 1 below, and dispersed using a three-bone mill, followed by mixing silver powder (spherical shape, average particle diameter of 1 ⁇ m). It was dispersed using three bone mill. After that, degassed under reduced pressure to prepare a conductive paste.
  • the paste composition prepared in Examples 1 to 2 and Comparative Example 1 was pattern-printed on the front surface of the wafer by a 50 ⁇ m mesh screen printing technique, and dried at 200 to 350 ° C. for 20 to 30 seconds using a belt dryer. I was. 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 calcined for 20 seconds to 30 seconds between 500 to 900 ° C. using a belt type kiln, and the cell thus manufactured was manufactured using a solar cell efficiency measuring device (Halm, cetisPV-Celltest 3). Isc, Voc, Rseries, Rshadow, observing the efficiency of the relative values based on the value of the comparative example 100 is shown in Table 2 below.
  • the line width before firing and the line width after firing of the front electrode were measured and shown in Table 2 and FIGS. 1 to 3.
  • the electrode bleeding line width is generated by a phenomenon in which a glass frit or the like is buried in the outermost part of the electrode as the electrode bleeds after firing, and is defined as the outermost reference line width of the electrode.
  • Example 2 Comparative Example 1 Line width before firing 50.152 49.540 50.152 Line width of bleeding after firing 61.161 56.268 66.665 Isc 100.21 100.43 100.0 Rseries 100.58 101.22 100.0 Rshadow 96.18 91.98 100.0 Voc 100.0 100.0 100.0 efficiency 100.23 100.49 100.0
  • the embodiments of the present invention can be seen that the increase in the bleeding line width of the electrode after firing within 12 ⁇ m compared to the comparative example, significantly reducing the increase in line width, Isc is improved, Series Compared with the increase of the resistance, the decrease in the shadow resistance decreases the overall resistance, which shows that the efficiency is improved.

Abstract

La présente invention concerne une composition de pâte, pour électrode de cellule solaire, qui comprend une poudre métallique conductrice, une fritte de verre et un véhicule organique. La composition de pâte comprend en outre un additif de silicone modifiée par polyéther, ce qui permet une réduction de la largeur de ligne d'une électrode dans les mêmes conditions d'impression et le même processus de traitement thermique, ainsi qu'une réduction de l'augmentation de la largeur de ligne de l'électrode après le frittage.
PCT/KR2016/012346 2015-10-31 2016-10-31 Composition de pâte d'électrode pour cellule solaire et cellule solaire préparée au moyen de ladite composition WO2017074151A1 (fr)

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KR1020150152780A KR101733161B1 (ko) 2015-10-31 2015-10-31 태양전지용 전극 페이스트 조성물 및 이를 사용하여 제조된 태양전지
KR10-2015-0152780 2015-10-31

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109809699A (zh) * 2019-01-21 2019-05-28 西北大学 一种掺磷玻璃粉及制备方法和利用其制备太阳能电池用正银浆料的方法
CN114551000A (zh) * 2022-01-28 2022-05-27 广州市儒兴科技股份有限公司 一种窄线宽双面perc铝浆及其制备方法

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KR20090067992A (ko) * 2007-12-21 2009-06-25 제일모직주식회사 실리콘계 계면활성제를 포함하는 전극 형성용 페이스트조성물
JP2010087251A (ja) * 2008-09-30 2010-04-15 Dic Corp 太陽電池用導電性ペースト
KR20120025972A (ko) * 2010-09-08 2012-03-16 주식회사 동진쎄미켐 ＺｎＯ계 글래스 프릿 조성물 및 이를 이용한 태양전지의 후면 전극용 알루미늄 페이스트 조성물
KR20120077439A (ko) * 2010-12-30 2012-07-10 주식회사 동진쎄미켐 태양전지의 전극 형성용 페이스트 조성물 및 이를 이용한 전극
KR20130049751A (ko) * 2011-11-04 2013-05-14 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 전도성 페이스트용 유기 비히클

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109809699A (zh) * 2019-01-21 2019-05-28 西北大学 一种掺磷玻璃粉及制备方法和利用其制备太阳能电池用正银浆料的方法
CN114551000A (zh) * 2022-01-28 2022-05-27 广州市儒兴科技股份有限公司 一种窄线宽双面perc铝浆及其制备方法
CN114551000B (zh) * 2022-01-28 2023-08-15 广州市儒兴科技股份有限公司 一种窄线宽双面perc铝浆及其制备方法

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