WO2013058417A1 - Composition de pâte d'argent (1) pour l'électrode arrière d'une photopile - Google Patents

Composition de pâte d'argent (1) pour l'électrode arrière d'une photopile Download PDF

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Publication number
WO2013058417A1
WO2013058417A1 PCT/KR2011/007730 KR2011007730W WO2013058417A1 WO 2013058417 A1 WO2013058417 A1 WO 2013058417A1 KR 2011007730 W KR2011007730 W KR 2011007730W WO 2013058417 A1 WO2013058417 A1 WO 2013058417A1
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WO
WIPO (PCT)
Prior art keywords
group
silver paste
paste composition
solar cell
silver
Prior art date
Application number
PCT/KR2011/007730
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English (en)
Korean (ko)
Inventor
이창준
임대성
이창모
최형섭
홍승권
Original Assignee
동우 화인켐 주식회사
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 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to PCT/KR2011/007730 priority Critical patent/WO2013058417A1/fr
Publication of WO2013058417A1 publication Critical patent/WO2013058417A1/fr

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022408Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Definitions

  • the present invention relates to a silver paste composition for a solar cell back electrode.
  • a PN junction is formed by diffusing phosphorus (P) on the surface of a P-type silicon wafer, and an antireflection film is coated to reduce reflection loss of sunlight incident on the P-type silicon wafer.
  • the Ag electrode is formed, and Ag and Al electrodes are formed on the back side P layer.
  • the silver paste used as the front electrode is connected to the N-side of silicon to form an electrode, and the aluminum paste is connected to the backside of silicon, that is, the P layer, to form an electrode.
  • Silicon crystalline solar cells generally use P-type silicon substrates with a thickness of 180-220 ⁇ m.
  • Phosphorus diffusion source in the front of the substrate typically phosphorus oxychloride (POCl) 3
  • POCl phosphorus oxychloride
  • N-type emitter layer with a thickness of 0.2-0.6 ⁇ m, and on top of it, a SiNx layer for antireflection is formed through plasma chemical vapor deposition (CVD).
  • CVD plasma chemical vapor deposition
  • the front silver paste is applied by screen printing and dried, and then the front electrode is formed by firing several seconds or several minutes at a temperature of 800-950 ° C. in an infrared belt furnace. .
  • An aluminum electrode is formed on the rear side.
  • the aluminum electrode is formed by applying an aluminum paste by screen printing or the like through drying and baking.
  • the silver or silver / aluminum paste printed on the back side is also fired at the same time to form the silver or silver / aluminum back electrode.
  • aluminum is diffused into the P-type silicon wafer to form an Al—Si alloy layer.
  • the diffusion layer (P + layer) forms a back surface field (BSF) that prevents recombination of electrons generated in the solar cell and improves the collection efficiency of the generated carriers.
  • BSF back surface field
  • Korean Patent No. 10-0798255 includes silver particles, glass particles, and an organic vehicle, and a conductive thick film used as an electrode for connecting with a rear terminal on a silicon substrate of a solar cell.
  • An electroconductive paste is disclosed which has an average particle diameter of the composition, in particular of the silver particles, between 3.0 and 15.0 ⁇ m.
  • the back electrode paste including the silver particles having a large size as described above has a disadvantage in that the internal porosity between the particles is high, so that voids remain in the electrode after the firing process, thereby increasing the resistance of the wiring. .
  • Korean Patent No. 10-0890866 discloses an electrode paste including silver and aluminum, including aluminum particles, to improve thermal expansion characteristics with a rear aluminum electrode.
  • an electrode paste has the disadvantage that the resistance of the wiring is increased by adding aluminum particles having relatively low conductivity to the silver paste, and the soldering property with the ribbon is degraded in the module manufacturing process of the solar cell.
  • the present invention which is to solve the above problems of the prior art, improves the efficiency of the solar cell by reducing the wiring resistance of the rear electrode and improve the adhesion to the silicon substrate, and also the soldering characteristics during solar cell module manufacturing greatly
  • An object of the present invention is to provide a silver paste for solar cell rear electrodes that can be improved.
  • a silver paste composition for solar cell back electrode comprising 0.1 to 5% by weight of a group 3 element or a compound containing a group 3 element, or a salt thereof or a hydrate thereof.
  • the present invention also provides a solar cell comprising a back electrode formed of the silver paste composition for the solar cell back electrode.
  • the silver paste composition of the present invention uses silver particles having an average particle diameter of D 50 of 0.3 ⁇ m to 1.5 ⁇ m to minimize internal voids of the rear electrode and to improve adhesion to the silicon substrate.
  • the resistance of the electrode wiring is reduced to improve the efficiency of the solar cell.
  • the silver paste composition of the present invention does not include aluminum, soldering properties are greatly improved during manufacturing of the solar cell module.
  • FIG. 1 shows a solar cell with a back field (BSF) layer.
  • BSF back field
  • FIG. 2 shows a solar cell having a P or P + type diffusion layer and a backside electric field (BSF) layer.
  • BSF backside electric field
  • the present invention relates to a silver paste composition for solar cell rear electrodes comprising 0.1 to 5% by weight of a group 3 element or a compound containing a group 3 element, or a salt thereof or a hydrate thereof.
  • the silver paste composition of the present invention uses silver powder having a specific average particle size as described above, and includes a group 3 element or a compound containing a group 3 element, or a salt thereof or a hydrate thereof, thereby providing resistance to electrode wiring. It has the characteristic to minimize.
  • the silver paste composition of the present invention may include some aluminum powder within the composition ratio range of the silver powder, but more preferably does not include aluminum powder in order to improve soldering characteristics in manufacturing a solar cell module.
  • the powder contained in the paste composition of the present invention has preferably a mean particle diameter (D 50) of particles is 0.3 ⁇ m ⁇ 1.5 ⁇ m.
  • D 50 of the silver particles is less than 0.3 ⁇ m, the specific surface area of the particles is widened, so that the viscosity of the paste composition is high and printability is reduced. In addition, this limits the content of silver particles.
  • the D 50 of the silver particles exceeds 1.5 ⁇ m, the density of the silver particles in the paste decreases, and a large amount of voids are generated in the wiring after the firing process, thereby increasing the resistance of the wiring.
  • the silver powder is preferably contained in 65 to 75% by weight relative to the total weight of the composition, when included in less than 65% by weight, the printed silver wiring layer is thinned after firing to increase the rear wiring resistance, soldering characteristics This will be lowered, and if it exceeds 75% by weight, the printing thickness will be too thick, which may result in warping of the silicon wafer.
  • the maximum particle diameter (Dmax) of the silver particles is preferably 4.5 ⁇ m or less, and the silver particles may be spherical or plate-shaped.
  • the glass frit included in the silver paste composition of the present invention is contained in an amount of 0.01 to 10% by weight, preferably 0.5 to 7% by weight, and more preferably 1 to 5% by weight, based on the total weight of the composition. If the glysprit is contained in less than 0.01% by weight, the problem that the adhesion force to the wafer of the silver wiring is reduced after the firing process, and when contained in excess of 10% by weight, the problem is that the resistance is high to decrease the efficiency of the solar cell .
  • the glass frit examples include a Bi 2 O 3 -Al 2 O 3 -SiO 2 -SrO-B 2 O 3 system.
  • the composition ratio of the glass frit is not particularly limited, 20-30 mol% of Bi 2 O 3, 5-15 mol% of Al 2 O 3, 25-35 mol% of SiO 2, 1-10 mol% of SrO, and 20-40 mol% of B 2 O 3 It is preferable to have a composition containing.
  • the softening point of the glass frit used by this invention is 400-500 degreeC. If the softening point of the glass frit is less than 400 ° C, the thermal expansion coefficient of the glass frit becomes relatively large, causing a problem of increasing the warpage of the wafer after the firing step during the solar cell manufacturing process.
  • the glass frit may be melted to provide adhesion between the silver wiring layer and the silicon wafer layer, but the glass frit may not be sufficiently melted, thereby causing a problem in that the adhesion is reduced.
  • the organic vehicle solution included in the silver paste composition of the present invention is preferably included in 20 to 34.8% by weight based on the total weight of the composition. If the organic vehicle solution is contained in less than 20% by weight, the viscosity is too high, the printability is lowered, and when contained in excess of 34.8% by weight, the silver powder content is low, it is difficult to secure a sufficient thickness of the silver wiring layer.
  • the organic vehicle solution 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 organic vehicle solution used in the present invention may be composed of 75% by weight or more of solvent and 1 to 25% by weight of the polymer resin, and, if necessary, about 5% by weight or less of a wetting agent and thixotropic agent, And 1 to 10% by weight may further include an additive.
  • a solvent having a breaking point in the range of about 150-300 ° C. is suitable to prevent drying of the paste during the printing process and to control fluidity.
  • Widely used solvents include glycol ether-based 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 (Texanol ), Ethylene glycol, and the like.
  • polymer resin examples include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethyl cellulose, rosin, phenol resin, acrylic resin and the like.
  • the content of the polymer resin is 1 to 25% by weight, preferably 5 to 25% by weight based on the total weight of the organic vehicle solution. If the amount of the polymer resin is less than 1% by weight, the printability and dispersion stability of the paste may be lowered. If the amount of the polymer resin exceeds 25% by weight, the paste may not be printed.
  • any one generally used in the art may be used without limitation.
  • 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 may be, for example, an ether type such as alkyl polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyoxyethylene polyoxypropylene copolymer as a 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; Polymeric surfactants include poly
  • Hypermer KD manufactured by Uniqema
  • AKM 0531 manufactured by Nippon Yuji Co., Ltd.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • POLYFLOW polyflow
  • EFTOP manufactured by Tochem Products
  • Asahi guard above, manufactured by Asahi Glass
  • SOLSPERSE manufactured by Geneva
  • EFKA EFKA Chemicals, Inc.
  • PB 821 manufactured by Ajinomoto Co., Ltd.
  • BYK-111, BYK-184, BYK-185, BYK-2160, Anti-Terra U manufactured by BYK
  • the dispersant is preferably included in 1 to 10% by weight based on the total weight of the organic vehicle solution, more preferably 1 to 5% by weight.
  • the Group 3 element or the compound containing a Group 3 element, or a salt thereof or a hydrate thereof contained in the silver paste composition of the present invention is preferably included in 0.1 to 5% by weight based on the total weight of the composition.
  • Compounds containing the Group 3 elements or Group 3 elements, or salts or hydrates thereof are doped on the back of the base layer (P-type) on the back of the solar cell to form a P + layer. This allows holes to be effectively transferred from the electron hole pair generated by sunlight to the back electrode, thereby reducing energy loss and lowering series resistance. This improves the fill factor (FF) and ultimately increases the solar cell efficiency.
  • P-type base layer
  • FF fill factor
  • Group 3 element or the compound containing a Group 3 element, or salts thereof or hydrates thereof include metal powders of B, Ga, In, or Tl, metal alloys containing Group 3 elements, and Group 3 elements. Containing organic compounds, inorganic compounds containing group III elements, oxides containing group III elements, acids containing group III elements, alkoxide salts containing group III elements, acetate salts containing group III elements And glass containing a Group 3 element, and more specific examples thereof include boron oxide, triethyl borate, and the like. In addition, these may be used alone or in combination of two or more.
  • a silver paste composition was prepared in the same manner as in Example 1, except that 0.5 wt% of triethyl borate was used instead of boron oxide as a group 3 element compound.
  • a silver paste was prepared in the same manner as in Example 1 except that the Group 3 element compound was not contained.
  • a silver paste was prepared in the same manner as in Example 1, except that boron oxide was 7% by weight.
  • Silver paste was prepared in the same manner as in Example 1 except that silver powder having a D 50 of 4.5 ⁇ m was used.
  • a surface texturing process was performed on a 156 ⁇ 156 mm, 200 ⁇ m thick single crystal wafer to form a pyramid height of about 4-6 ⁇ m, followed by coating SiNx on the N-side of the wafer. Subsequently, after printing and drying the respective Bus Bars using the paste compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2 on the back of the wafer, Dongwoo Fine Chem Co., Ltd. aluminum electrode paste (trade name: AMP- BL125) was applied using a screen printing plate and dried. The Finger Line was then printed and dried using silver paste on the front SiNx side.
  • the silicon wafer passed through the above process was fired in an infrared continuous firing furnace such that the temperature of the firing region was 720 to 900 ° 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 a belt furnace.
  • the belt furnace includes a burn-out section at about 600 ° C. and a firing section at about 800 ° C. to 950 ° C., after burning off the organic material in the paste composition, the front and rear surfaces are melted with aluminum to form an electrode. To be.
  • soldering characteristics were evaluated by using a ribbon of 96.5Sn / 3.5Ag coated copper and a ribbon of 62Sn / 36Pb / 2Ag coated.
  • 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
  • the ribbon was pulled at an angle of 90 ° to the surface of the battery to measure the adhesive strength.
  • the silver paste composition of Example 1 of the present invention exhibited superior properties to the paste compositions of Comparative Examples 1 to 3 in all the investigation items of the wiring resistance, the efficiency of the solar cell, the bending, and the soldering characteristics. .
  • the paste composition of Comparative Example 3 exhibited excellent characteristics in warpage and soldering properties, but the wiring resistance and the efficiency of the solar cell were not good due to the use of silver particles having a large average particle diameter.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Sustainable Development (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention concerne une composition de pâte d'argent pour l'électrode arrière d'une photopile. La composition de pâte d'argent comprend a) 65 % en masse à 75 % en masse de poudre d'argent présentant un diamètre de particule moyen (D50) de 0,3 μm à 1,5 μm, b) 0,01 % en masse à 10 % en masse de fritte de verre, c) 20 % en masse à 34,8 % en masse de solution de véhicule organique et d) un élément du groupe III ou un composé comprenant l'élément du groupe III ou un sel de celui-ci, ou 0,1 % en masse à 5 % en masse d'un composé liquide de celui-ci par rapport au poids brut de la composition.
PCT/KR2011/007730 2011-10-18 2011-10-18 Composition de pâte d'argent (1) pour l'électrode arrière d'une photopile WO2013058417A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2011/007730 WO2013058417A1 (fr) 2011-10-18 2011-10-18 Composition de pâte d'argent (1) pour l'électrode arrière d'une photopile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2011/007730 WO2013058417A1 (fr) 2011-10-18 2011-10-18 Composition de pâte d'argent (1) pour l'électrode arrière d'une photopile

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WO2013058417A1 true WO2013058417A1 (fr) 2013-04-25

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006093433A (ja) * 2004-09-24 2006-04-06 Sharp Corp 太陽電池の製造方法
KR100837994B1 (ko) * 2005-04-14 2008-06-13 이 아이 듀폰 디 네모아 앤드 캄파니 전도성 조성물 및 반도체 소자의 제조에 사용하는 방법
KR20080099406A (ko) * 2007-05-09 2008-11-13 주식회사 동진쎄미켐 태양전지 전극 형성용 페이스트
US20110000531A1 (en) * 2009-07-06 2011-01-06 Lg Electronics Inc. Electrode paste for solar cell, solar cell using the paste, and fabrication method of the solar cell
KR20110069724A (ko) * 2009-12-17 2011-06-23 동우 화인켐 주식회사 태양전지 후면 전극용 은 페이스트 조성물
KR20110121427A (ko) * 2010-04-30 2011-11-07 동우 화인켐 주식회사 태양전지 후면 전극용 은 페이스트 조성물

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006093433A (ja) * 2004-09-24 2006-04-06 Sharp Corp 太陽電池の製造方法
KR100837994B1 (ko) * 2005-04-14 2008-06-13 이 아이 듀폰 디 네모아 앤드 캄파니 전도성 조성물 및 반도체 소자의 제조에 사용하는 방법
KR20080099406A (ko) * 2007-05-09 2008-11-13 주식회사 동진쎄미켐 태양전지 전극 형성용 페이스트
US20110000531A1 (en) * 2009-07-06 2011-01-06 Lg Electronics Inc. Electrode paste for solar cell, solar cell using the paste, and fabrication method of the solar cell
KR20110069724A (ko) * 2009-12-17 2011-06-23 동우 화인켐 주식회사 태양전지 후면 전극용 은 페이스트 조성물
KR20110121427A (ko) * 2010-04-30 2011-11-07 동우 화인켐 주식회사 태양전지 후면 전극용 은 페이스트 조성물

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