WO2012086972A2 - Composition pour pâte d'aluminium et élément photovoltaïque en faisant usage - Google Patents

Composition pour pâte d'aluminium et élément photovoltaïque en faisant usage Download PDF

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Publication number
WO2012086972A2
WO2012086972A2 PCT/KR2011/009761 KR2011009761W WO2012086972A2 WO 2012086972 A2 WO2012086972 A2 WO 2012086972A2 KR 2011009761 W KR2011009761 W KR 2011009761W WO 2012086972 A2 WO2012086972 A2 WO 2012086972A2
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WO
WIPO (PCT)
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mol
aluminum paste
paste composition
glass frit
aluminum
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PCT/KR2011/009761
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English (en)
Korean (ko)
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WO2012086972A3 (fr
Inventor
이창모
최형섭
이창준
홍승권
Original Assignee
동우화인켐 주식회사
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Publication of WO2012086972A2 publication Critical patent/WO2012086972A2/fr
Publication of WO2012086972A3 publication Critical patent/WO2012086972A3/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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an aluminum paste composition which does not contain PbO and Bi 2 O 3 components, which is environmentally friendly and can also improve durability, and a solar cell device using the same.
  • Solar cells which are rapidly spreading in recent years, are electronic devices that directly convert solar energy, which is clean energy, into electricity as a next generation energy source.
  • an N + layer 20, an antireflection film 30, and a front electrode 40 are formed on the light-receiving surface side of the silicon wafer substrate 10, and the substrate 10 is opposite to the substrate 10.
  • P + layer 50 and the back electrode 60 is formed on the surface side.
  • the back electrode 60 is formed by applying an aluminum paste composition by screen printing, drying, and then firing the aluminum paste composition.
  • aluminum is diffused into the silicon wafer substrate 10 so that the back electrode 60 and the substrate 10 are baked.
  • An Al—Si alloy layer is formed therebetween and a P + layer 50 is formed by diffusion of aluminum atoms.
  • the P + layer 50 acts as a back surface field (BSF) that prevents recombination of electrons and improves the collection efficiency of product carriers, and also serves as a reflector reflecting long wavelength light of sunlight.
  • BSF back surface field
  • the aluminum paste composition for forming the back electrode 60 includes aluminum powder, glass frit, and an organic vehicle.
  • glass frit is a component for further strengthening the bond with the silicon wafer substrate 10 and is usually composed of PbO-B 2 O 3 -SiO 2 based, PbO-B 2 O 3 -Al 2 O 3 based, and PbO- Those containing B 2 O 3 -ZnO-based oxides were mainly used.
  • Bi 2 O 3 -based oxides having similar properties to the PbO-based oxides without containing PbO components, such as Bi 2 O 3 -B 2 O 3 -SiO 2 , Bi 2 O 3 -B 2 O 3 has been proposed to include -ZnO-based oxide.
  • Korean Patent No. 0890866 discloses 0.5-35% by weight of SiO 2 , 0-5% by weight of Al 2 O 3 , 1-15% by weight of B 2 O 3 , 0-15% by weight of ZnO and 55-90 weight of Bi 2 O 3.
  • a glass frit comprising% is disclosed.
  • the glass frit containing the Bi 2 O 3 component heat-etches the oxide film on the surface of the aluminum powder of the aluminum layer to increase the moisture and reactivity, which has the disadvantage of lowering the durability of the solar cell device itself.
  • Another object of the present invention is to provide an electrode formed from the aluminum paste composition.
  • Another object of the present invention is to provide a solar cell device provided with the electrode.
  • the glass frit is an aluminum paste composition further comprises one or more selected from the group consisting of Al 2 O 3 , B 2 O 3 , P 2 O 5 , SiO 2 , alkali metal oxides and alkaline earth metal oxides .
  • Al 2 O 3 is 0.5-5 mol%
  • B 2 O 3 is 0.5-5 mol%
  • P 2 O 5 is 0-30 mol%
  • SiO with respect to 100 mol% of the glass frit composition 2 is 0-15 mol%
  • an alkali metal oxide is 1-10 mol%
  • an alkaline earth metal oxide is contained in 0-30 mol%.
  • the glass frit is V 2 O 5 50-70 mol%, ZnO 10-30 mol%, Al 2 O 3 0.5-5 mol%, B 2 O 3 0.5-5 mol% and alkali metal oxide Aluminum paste composition containing 1-10 mol%.
  • the alkali metal oxide is at least one aluminum paste composition selected from the group consisting of K 2 O, Na 2 O and Li 2 O.
  • the glass frit has a softening point of 300-600 °C aluminum paste composition.
  • the aluminum powder is an aluminum paste composition of 60-95% by weight of the powder having an average particle size of 4-6 ⁇ m and 5-40% by weight of the powder having an average particle size of 2-4 ⁇ m.
  • the aluminum paste composition according to the present invention is environmentally friendly because it does not contain PbO components that are restricted in use due to environmental problems, and at the same time does not contain Bi 2 O 3 components having strong thermal etching properties, thereby preventing reaction with moisture. Through this, it is possible to enhance the durability of the solar cell element itself.
  • the aluminum paste composition of the present invention can suppress the warpage phenomenon of the silicon wafer substrate even with a relatively high coefficient of thermal expansion, can increase the maximum output current (Isc) of the solar cell device and improve the efficiency.
  • FIG. 1 is a diagram schematically illustrating a cross-sectional view of a solar cell element.
  • the present invention relates to an aluminum paste composition containing no PbO and Bi 2 O 3 components and a solar cell device using the same.
  • the aluminum paste composition of the present invention is aluminum powder; Glass frit; And V 2 O 5 -ZnO-based oxides, including organic vehicles, but not containing both PbO and Bi 2 O 3 components at the same time as the glass frit.
  • the glass frit is characterized by containing 50-80 mol% V 2 O 5 and 20-50 mol% ZnO.
  • the aluminum powder is a conductive metal which is a main component of the paste composition for forming the back electrode, and it is preferable to use two kinds of mixed powders having different average particle sizes.
  • the silicon wafer substrate for forming the back electrode has a structure in which fine pyramids are formed on the surface by texturing both surfaces to increase the light receiving area of sunlight. Normally formed fine pyramids have a height of 2-15 ⁇ m and a width of 2-20 ⁇ m, and have an irregular maze shape.
  • the aluminum paste composition is printed by a method such as screen printing, gravure printing, or offset printing, dried, and then baked to form a back electrode.
  • the particle size of the aluminum powder is too large, the contact between the aluminum paste composition and the silicon wafer substrate is not made well, and voids are formed between them after printing and drying. These voids pass through the aluminum paste layer and eject the surface during the firing process, resulting in aluminum bumps and bubbles. Therefore, it is desirable to minimize the size of the pores by mixing two kinds of aluminum powders having different average particle sizes.
  • the aluminum powder is preferably a mixture of 60-95 wt% of the powder having an average particle size of 4-6 ⁇ m and 5-40 wt% of the powder having an average particle size of 2-4 ⁇ m.
  • the powder having an average particle size of 4-6 ⁇ m suppresses shrinkage of the silicon wafer substrate after firing to form a high density low shrink electrode, and the powder having an average particle size of 2-4 ⁇ m acts as a binder between the aluminum powders.
  • the paste penetrates deeply and evenly into the textured surface of the substrate. In this case, the porosity between the substrate and the paste is reduced, the back electric field (BSF) is uniformly formed, the resistance of the back electrode is lowered, and the bending of the substrate is also suppressed. Therefore, it is possible to increase the maximum output current Isc of the solar cell device and increase efficiency, and to prevent yellowing occurring at the rear electrode after the firing process.
  • BSF back electric field
  • the aluminum powder is preferably included at 65-75% by weight relative to 100% by weight of the total content of the aluminum paste composition. If the content is less than 65% by weight, the thickness of the printed aluminum rear electrode after firing becomes thin so that the back field (BSF) may not be sufficiently formed and the efficiency may be lowered. When the content is more than 75% by weight, the thickness of the silicon wafer substrate is too thick. May cause warpage.
  • the glass frit is characterized by using a V 2 O 5 -ZnO-based oxide which does not contain a PbO component and a Bi 2 O 3 component at the same time.
  • glass frit containing PbO component has advantages of easy melting point control and low coefficient of thermal expansion, but its use is limited due to environmental problems.
  • Glass frit containing Bi 2 O 3 component has similar characteristics to PbO glass frit.
  • the reactivity of thermal etching the aluminum oxide film is too large, the water resistance of the aluminum electrode is lowered, and as a result, the durability of the solar cell device is deteriorated.
  • the present invention is characterized by using a glass frit containing 50-80 mol% of V 2 O 5 and 20-50 mol% of ZnO.
  • the glass frit is Al 2 O 3 ; B 2 O 3 ; P 2 O 5 ; SiO 2 ; Alkali metal oxides such as K 2 O, Na 2 O, and Li 2 O; Alkaline earth metal oxides such as MgO, CaO, SrO, and BaO may be contained alone or in combination of two or more thereof.
  • Al 2 O 3 is 0.5-5 mol%
  • B 2 O 3 is 0.5-5 mol%
  • P 2 O 5 is 0-30 mol%
  • SiO 2 is 0-15 mol based on 100 mol% of the glass frit.
  • Alkali metal oxide may be contained in 1-10 mol% and alkaline earth metal oxide in 0-30 mol%.
  • the glass frit is 50-70 mol% V 2 O 5 , 10-30 mol% ZnO, 0.5-5 mol% Al 2 O 3, 0.5-5 mol% B 2 O 3 and alkali metal oxide 1-10 It is preferable to contain mol%.
  • a glass frit has a softening point of 300-600 degreeC. If the softening point is higher than 600 ° C., the glass frit must be melted to impart adhesion between the aluminum paste layer and the silicon wafer substrate, but the glass frit may not be sufficiently applied in the firing process, thereby decreasing the adhesion.
  • the glass frit is preferably included in an amount of 0.01-10% by weight, more preferably 0.05-7% by weight, and most preferably 0.1-5% by weight, based on 100% by weight of the total content of the aluminum paste composition. If the content is less than 0.01% by weight, the adhesion between the aluminum back electrode and the silicon wafer substrate may be lowered after firing. If the content is more than 10% by weight, the resistance may be increased, thereby reducing the efficiency of the solar cell device.
  • the glass frit containing such a component does not contain a PbO component, which is environmentally friendly and does not contain a Bi 2 O 3 component, thereby preventing a decrease in water resistance due to thermal etching.
  • glass frits that do not contain PbO components and Bi 2 O 3 components usually have a high melting point, so that a large amount of wood-based planting agent is used, which causes a relatively high coefficient of thermal expansion, which causes warpage of the silicon wafer substrate during solar cell device manufacturing. I could.
  • the glass frit configured as in the present invention can be made to be negligible even if the thermal expansion coefficient is relatively high because each component is contained in the optimum molar ratio.
  • the organic vehicle is a component for imparting consistency and rheological properties suitable for printing to the aluminum paste composition, and may be a solution in which a polymer resin and various additives are dissolved in an organic solvent as necessary.
  • the organic vehicle may be a mixture of 75-99% by weight of the organic solvent and 1-25% by weight of the polymer resin, and may be a mixture of 1-10% by weight of the additive.
  • the organic solvent a known one may be used, and a solvent having a boiling point of 150 to 300 ° C. may be used to prevent drying of the paste composition and to control fluidity during the printing process.
  • a solvent having a boiling point of 150 to 300 ° C. may be used to prevent drying of the paste composition and to control fluidity during the printing process.
  • the organic solvent is preferably included at 75-99% by weight based on 100% by weight of the total organic vehicle. In this content range, optimum fluidity can be imparted to the paste composition.
  • polymer resin known ones can be used, for example, ethyl cellulose, nitrocellulose, phenol, acryl, rosin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyvinyl butyral, urea, xylene, alkyd, unsaturated Polyester, polyimide, furan, urethane, isocyanate, cyanate, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene (ABS), polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl Resins such as acetate, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polysulfone, polyimide, polyether sulfone, polyarylate, polyether ether ketone and silicone Can be. These can be used individually or in mixture of 2 or more types
  • the polymer resin may be included in an amount of 1-25 wt%, preferably 5-25 wt%, based on 100 wt% of the total organic vehicle content.
  • the content is less than 1% by weight, the printability and dispersion stability of the paste composition may be lowered, and when the content is more than 25% by weight, the paste composition may not be printed.
  • the organic vehicle may further comprise a dispersant as an additive together with the above components.
  • a known surfactant can be used, for example, polyoxyethylene alkyl ether having 6 to 30 carbon atoms in the alkyl group, polyoxyethylene alkyl aryl ether having 6 to 30 carbon atoms in the alkyl group, and 6 to 30 carbon atoms in the alkyl group.
  • Ethers such as polyoxyethylene-polyoxypropylene alkyl ether; Ester ethers such as glycerin ester addition polyoxyethylene ether, sorbitan ester addition polyoxyethylene ether, and sorbitol ester addition polyoxyethylene ether; Esters such as polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester, propylene glycol ester, sugar ester and alkyl polyglucoside; Nitrogen-containing systems such as fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine having 6 to 30 carbon atoms of an alkyl group, and amine oxide; And high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylic acid-maleic acid copolymer, and poly12-hydroxystearic acid.
  • Hypermer KD Uniqema
  • AKM 0531 Japan Oil Holding Co., Ltd.
  • KP Shin-Etsu Chemical Co., Ltd.
  • POLYFLOW Kyoeisha Chemical Co., Ltd.
  • EFTOP Tochem Products
  • Asahi guard Asahi Glass, Inc.
  • Suflon Asahi Glass, Inc.
  • SOLSPERSE Genekka
  • EFKA EFKA Chemicals, Inc.
  • PB 821 Ajinomoto Co., Ltd.
  • BYK-184, BYK-185 BYK-2160
  • Anti-Terra U manufactured by BYK
  • the dispersant may be included in an amount of 1-10% by weight, preferably 1-5% by weight, based on 100% by weight of the total amount of the organic vehicle.
  • the organic vehicle may further include additives such as thixotropic agents, wetting agents, antioxidants, corrosion inhibitors, antifoaming agents, thickeners, dispersants, tackifiers, coupling agents, antistatic agents, polymerization inhibitors, and antisettling agents.
  • additives such as thixotropic agents, wetting agents, antioxidants, corrosion inhibitors, antifoaming agents, thickeners, dispersants, tackifiers, coupling agents, antistatic agents, polymerization inhibitors, and antisettling agents.
  • the organic vehicle is preferably included in 20-34.9% by weight relative to 100% by weight of the total content of the aluminum paste composition. If the content is less than 20% by weight, the viscosity of the aluminum paste composition may be too high, which may lower fluidity and reduce printability. If the content is more than 34.9% by weight, the aluminum powder content may be relatively small to ensure sufficient thickness of the paste layer. It is difficult.
  • the aluminum paste composition containing the above components does not contain PbO, which is restricted in use due to environmental problems, and is not only environmentally friendly but also does not contain Bi 2 O 3 , which is highly thermally etchable, thereby preventing deterioration in water resistance. Can be.
  • the present invention provides an electrode formed from the aluminum paste composition.
  • the electrode is formed through a process of printing, drying and firing an aluminum paste composition on a substrate, such as a silicon wafer substrate on which an Ag front electrode is formed.
  • the printing method is not particularly limited, and for example, screen printing, gravure printing, offset printing and the like can be used. Drying is carried out at 60-300 ° C. for several seconds-minutes, and firing can be carried out at 600-950 ° C. for several seconds.
  • the electrode formed as described above may be applied to the rear electrode of the solar cell device, thereby improving durability of the solar cell device, increasing the maximum output current Isc of the solar cell device, and increasing efficiency.
  • the present invention provides a solar cell device provided with an electrode formed from the aluminum paste composition.
  • 250 mesh screen of aluminum paste composition prepared on the back side of a single crystal silicon wafer substrate having a size of 156 mm ⁇ 156 mm, a thickness of 200 ⁇ m, and a pyramid structure having a height of about 4-6 ⁇ m by a texturing process. It was applied using a printing plate. At this time, the coating amount was set to 1.4 ⁇ 0.1g before drying.
  • the applied paste was dried at 200 ° C. and then fired for about 10 seconds in an infrared continuous kiln at a temperature of 720-900 ° C. The firing process is carried out by simultaneous firing front and back while passing the silicon wafer substrate into a belt furnace comprising a burn-out section of about 600 ° C. and a firing section of 800-950 ° C. After removing the organic material in the paste, the aluminum was melted to form an electrode, thereby manufacturing a solar cell device.
  • the prepared solar cell device was placed in a thermostatic chamber filled with distilled water at 80 ° C. and left for 10 minutes. After visual observation of the generation of hydrogen gas (bubble) due to the reaction of the aluminum electrode formed in the thermostat and the moisture was evaluated based on the following criteria.
  • the manufactured solar cell device was placed on a flat bottom and four corners were aligned with the bottom, and then the degree of lifting of the center part was measured.
  • the efficiency of the manufactured solar cell device was evaluated using an evaluation device (SCM-1000, FitTech).
  • the solar cell device using the aluminum paste composition of Examples 1 and 2 including a glass frit containing P 2 O 5 and ZnO as a main component without PbO and Bi 2 O 3 according to the present invention As it is environmentally friendly and prevents reaction with moisture, it has excellent water resistance, which can improve the durability of the solar cell device, and it can be confirmed that the curvature can be suppressed even with a relatively high coefficient of thermal expansion and high efficiency.
  • an aluminum paste composition containing Al 2 O 3 , B 2 O 3 and alkali metal oxides with V 2 O 5 and ZnO in an optimum content it was most effective in securing water resistance while minimizing the amount of warpage.

Abstract

L'invention concerne une composition pour pâte d'aluminium et un élément photovoltaïque en faisant usage pour pâte d'aluminium et un élément photovoltaïque en faisant usage, ladite composition comprenant de la fritte de verre contenant entre 50 et 80% en mole de V2O5 et entre 20 et 50% en mole de ZnO ainsi qu'un excipient organique, aux propriétés écophiles de par l'absence d'oxyde de plomb (II) dont l'utilisation est limitée en raison des problèmes environnementaux qu'il induit, ce qui permet également de prévenir toute réaction avec l'humidité en raison de l'absence de Bi2O3, les propriétés marquées de gravure à chaud permettant également d'augmenter la durabilité dudit élément photovoltaïque.
PCT/KR2011/009761 2010-12-20 2011-12-19 Composition pour pâte d'aluminium et élément photovoltaïque en faisant usage WO2012086972A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0130581 2010-12-20
KR1020100130581A KR20120069159A (ko) 2010-12-20 2010-12-20 알루미늄 페이스트 조성물 및 이를 이용한 태양전지 소자

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WO2012086972A2 true WO2012086972A2 (fr) 2012-06-28
WO2012086972A3 WO2012086972A3 (fr) 2012-09-07

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JP6954130B2 (ja) * 2018-01-11 2021-10-27 Ａｇｃ株式会社 ガラス、ガラス粉末、導電ペーストおよび太陽電池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006342044A (ja) * 2005-05-09 2006-12-21 Nippon Electric Glass Co Ltd バナジウムリン酸系ガラス
US20060289055A1 (en) * 2005-06-03 2006-12-28 Ferro Corporation Lead free solar cell contacts
KR20080104179A (ko) * 2006-03-20 2008-12-01 페로 코포레이션 알루미늄-보론 태양전지 컨택
KR20100031727A (ko) * 2007-07-09 2010-03-24 페로 코포레이션 알루미늄과 보론, 티타늄, 니켈, 주석, 은, 갈륨, 아연, 인듐 및 구리 중 적어도 하나를 함유하는 태양 전지 컨택

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006342044A (ja) * 2005-05-09 2006-12-21 Nippon Electric Glass Co Ltd バナジウムリン酸系ガラス
US20060289055A1 (en) * 2005-06-03 2006-12-28 Ferro Corporation Lead free solar cell contacts
KR20080104179A (ko) * 2006-03-20 2008-12-01 페로 코포레이션 알루미늄-보론 태양전지 컨택
KR20100031727A (ko) * 2007-07-09 2010-03-24 페로 코포레이션 알루미늄과 보론, 티타늄, 니켈, 주석, 은, 갈륨, 아연, 인듐 및 구리 중 적어도 하나를 함유하는 태양 전지 컨택

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WO2012086972A3 (fr) 2012-09-07
KR20120069159A (ko) 2012-06-28

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