KR20100042766A - Conductive paste composition, preparation of electrode using same and solar cell comprising same - Google Patents
Conductive paste composition, preparation of electrode using same and solar cell comprising same Download PDFInfo
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- KR20100042766A KR20100042766A KR1020080101907A KR20080101907A KR20100042766A KR 20100042766 A KR20100042766 A KR 20100042766A KR 1020080101907 A KR1020080101907 A KR 1020080101907A KR 20080101907 A KR20080101907 A KR 20080101907A KR 20100042766 A KR20100042766 A KR 20100042766A
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- paste composition
- electrode
- conductive paste
- metal powder
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000013008 thixotropic agent Substances 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Conductive Materials (AREA)
Abstract
Description
본 발명은 도전성 페이스트 조성물, 이를 이용한 전극의 제조방법 및 이를 포함하는 태양전지에 관한 것이다.The present invention relates to a conductive paste composition, a method for producing an electrode using the same, and a solar cell including the same.
태양전지(solar cell)는 태양에너지를 전기에너지로 변환시켜주는 반도체 소자로서, 이의 전극 재료는 도전성 페이스트 조성물을 일반적인 스크린 프린팅 방법 등에 의해 기판에 도포하여 특정 형상의 전극 회로를 형성하고, 건조 및 열처리함으로써 도전성이 부여된다.A solar cell is a semiconductor device that converts solar energy into electrical energy, and its electrode material is coated with a conductive paste composition on a substrate by a general screen printing method to form an electrode circuit having a specific shape, drying and heat treatment. Electroconductivity is provided by this.
상용화된 인쇄타입의 태양전지용 전극재료는 미시적인 관점에서 열처리 공정시 유기물의 제거(burn out)로 인해 전극 내부에 결함이 발생하거나, 짧은 시간의 열처리 공정으로 인해 소결 밀도가 낮아져서, 선저항이 증가하고 실리콘 기판과의 접촉저항(contact resistance)이 높아지는 문제가 있다. 일반적으로 전극 내부의 결함은 대기중의 산소 또는 황성분과 결합하여 은산화물 또는 은황화물을 형성하기 때문에 전도성이 낮아져 시간 경과에 따른 실리콘 기판 태양전지의 효율이 점진적으로 낮아지는 문제가 야기될 수 있다.The commercially available printed electrode materials for solar cells have a microscopic point of view that defects inside the electrode due to burnout of organic matter during the heat treatment process or low sintering density due to a short time heat treatment process, resulting in increased line resistance. There is a problem that the contact resistance (contact resistance) with the silicon substrate is increased. In general, since defects inside the electrode combine with oxygen or sulfur in the air to form silver oxide or silver sulfide, the conductivity may be low, which may cause a problem that the efficiency of the silicon substrate solar cell gradually decreases over time.
이를 해결하기 위한 방법으로, 예를 들어 대한민국 특허공개 제2006-0108545호에는 유리(glass) 또는 옥사이드(oxide) 형태의 첨가제를 혼합하여 사용함으로써 은 분말 사이의 결함을 메꾸어 주어 소결 밀도와 실리콘 기판과의 접착력을 증가시키는 방법을 개시한다. 그러나, 상기 방법은 유리와 옥사이드 첨가제를 과다 사용하는 경우, 도체와 실리콘 기판과의 접촉저항을 증가시킬 수 있고, 특히 유리는 실리콘 기판의 N 층에 도핑(dopping)되어 있는 도펀트의 전극재료로의 확산을 유발시켜 태양전지의 효율에 악영향을 미칠 수 있다.As a method to solve this problem, for example, Korean Patent Publication No. 2006-0108545 uses a mixture of glass or oxide additives to fill the defects between the silver powder to provide sintered density and silicon substrate. A method of increasing the adhesion of However, the method can increase the contact resistance between the conductor and the silicon substrate when the glass and oxide additives are used excessively, in particular, the glass is used as an electrode material of the dopant doped in the N layer of the silicon substrate. It can cause diffusion and adversely affect the efficiency of solar cells.
또한, 대한민국 특허공개 제2005-0087249 호에서는, 100nm 이하의 은 분말로 구성된 페이스트를 사용하여 유리 및 옥사이드 첨가제의 사용을 제한하였으나, 이는 전극의 소결수축으로 인해 선저항을 증가시킬 수 있으며, 소성 후에 크랙과 같은 물리적인 결함이 발생하여 소결 밀도가 낮아져 장기 신뢰성에 취약한 문제를 유발시킬 수 있다.In addition, in Korean Patent Laid-Open Publication No. 2005-0087249, the use of glass and oxide additives is limited by using a paste composed of silver powder of 100 nm or less, which may increase the line resistance due to sintering shrinkage of the electrode, and after firing Physical defects, such as cracks, can result in low sintered densities, which leads to problems that are vulnerable to long-term reliability.
따라서 본 발명의 목적은 전극 제조시 높은 소결 밀도와 소성 후 낮은 소결 수축율을 나타내어 전극의 낮은 선저항 및 접촉저항을 제공함으로써 태양전지의 효 율을 증대시킬 수 있는 도전성 페이스트 조성물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a conductive paste composition that can increase the efficiency of a solar cell by providing a high sintered density and low sintered shrinkage rate after firing to provide an electrode with low wire resistance and contact resistance.
본 발명의 또 다른 목적은, 본 발명에 따른 도전성 페이스트 조성물을 이용한 전극의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing an electrode using the conductive paste composition according to the present invention.
본 발명의 또 다른 목적은, 본 발명에 따른 전극 제조방법으로 제조된 전극을 포함하는 태양전지를 제공하는 것이다.Still another object of the present invention is to provide a solar cell including an electrode manufactured by the electrode manufacturing method according to the present invention.
상기 목적에 따라, 본 발명에서는 평균 입자 크기가 0.5㎛ 미만인 미세 도전성 금속 분말과 0.5 내지 10㎛인 도전성 금속 분말의 혼합분말, 무기바인더 수지 및 유기 비히클을 포함하는 도전성 페이스트 조성물을 제공한다. In accordance with the above object, the present invention provides a conductive paste composition comprising a mixed powder, an inorganic binder resin, and an organic vehicle of a fine conductive metal powder having an average particle size of less than 0.5 μm and a conductive metal powder of 0.5 to 10 μm.
본 발명에 따른 도전성 페이스트 조성물은 전극 제조시 높은 소결 밀도와 소성 후 낮은 소결 수축율을 나타내어 전극의 낮은 선저항 및 접촉저항을 제공함으로써 태양전지의 효율을 증대시킬 수 있다.The conductive paste composition according to the present invention exhibits high sintered density and low sintered shrinkage after sintering during electrode production, thereby providing low wire resistance and contact resistance of the electrode, thereby increasing efficiency of the solar cell.
이하에서는 본 발명을 보다 구체적으로 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명에 따른 도전성 페이스트 조성물은 도전성 분말로서 평균 입자 크기 가 0.5㎛ 미만인 미세 도전성 금속 분말과 0.5 내지 10㎛인 도전성 금속 분말의 혼합분말을 사용하는 것을 특징으로 한다. 본 발명의 바람직한 실시예에 의하면 본 발명에 따른 조성물은 조성물 전체 중량에 대해 55 내지 90 중량%의 도전성 금속 분말의 혼합분말, 0.5 내지 8 중량%의 무기바인더 수지 및 5 내지 40 중량%의 유기 비히클을 포함할 수 있다. The conductive paste composition according to the present invention is characterized by using a mixed powder of a fine conductive metal powder having an average particle size of less than 0.5 μm and a conductive metal powder of 0.5 to 10 μm as the conductive powder. According to a preferred embodiment of the present invention, the composition according to the present invention comprises 55 to 90% by weight of a mixed powder of conductive metal powder, 0.5 to 8% by weight of an inorganic binder resin and 5 to 40% by weight of an organic vehicle. It may include.
이하에서는 각 성분에 대하여 설명한다. Hereinafter, each component is demonstrated.
(1) 도전성 금속 분말의 혼합분말(1) Mixed powder of conductive metal powder
본 발명에 따른 도전성 페이스트 조성물에 사용되는 도전성 금속 분말의 혼합분말은 평균 입자 크기가 0.5㎛ 미만, 바람직하게는 0.01 내지 0.5㎛ 미만인 미세 도전성 금속 분말과 0.5 내지 10㎛, 바람직하게는 1㎛ 내지 5㎛인 도전성 금속 분말의 혼합분말을 사용한다. 상기 평균 입자 크기가 0.5㎛ 미만인 미세 도전성 금속 분말과 0.5 내지 10㎛인 도전성 금속 분말의 혼합비는 10 중량% 내지 70 중량%:90 중량% 내지 30 중량%, 바람직하게는 10 중량% 내지 50 중량%:90 중량% 내지 50 중량%의 범위이다. The mixed powder of the conductive metal powder used in the conductive paste composition according to the present invention has a fine conductive metal powder having an average particle size of less than 0.5 µm, preferably 0.01 to 0.5 µm, and 0.5 to 10 µm, preferably 1 µm to 5 A mixed powder of conductive metal powder, which is 탆, is used. The mixing ratio of the fine conductive metal powder having an average particle size of less than 0.5 μm and the conductive metal powder of 0.5 to 10 μm is 10 wt% to 70 wt%: 90 wt% to 30 wt%, preferably 10 wt% to 50 wt% : 90 wt% to 50 wt%.
본 발명에 따른 페이스트 조성물에 사용되는 도전성 금속 분말은 은(Ag), 금(Au), 백금(Pt), 로듐(Rh), 팔라듐(Pd), 니켈(Ni), 알루미늄(Al) 및 구리(Cu)로 이루어진 군에서 선택된 하나 이상의 금속 분말을 사용 할 수 있는데, 그 중에서 은 분말이 가장 바람직하다. 예를 들어 은 분말을 사용할 경우, 그 형상이 무정형, 구형, 각형 및 플레이크형 중 하나 또는 둘 이상의 형태로 혼합된 것을 사용할 수 있다.The conductive metal powder used in the paste composition according to the present invention is silver (Ag), gold (Au), platinum (Pt), rhodium (Rh), palladium (Pd), nickel (Ni), aluminum (Al) and copper ( One or more metal powders selected from the group consisting of Cu) may be used, among which silver powder is most preferred. For example, when silver powder is used, the shape may be mixed with one or two or more of amorphous, spherical, angular and flake types.
평균 입자 크기가 0.5㎛ 미만인 미세 도전성 금속 분말은 입자간의 결합제 역할을 하여 낮은 온도와 짧은 열처리 조건에서도 쉽게 메탈라이징(metalizing)을 가능하게 하고, 표면 에너지가 커서 페이스트의 칙소성(thixotrophic index)을 증가시킴으로써 인쇄 후 페이스트의 형상의 변형이 적으므로, 실리콘 기판에서 차지하는 전극재료의 도포면적 비율을 최소로 할 수 있어 태양전지의 효율을 증가시킬 수 있다. 또한, 평균 입자 크기가 0.5 내지 10㎛인 도전성 금속 분말은 소성 후 수축을 억제시킬 수 있어 고밀도의 저수축 전극을 형성 할 수 있게 해준다.Fine conductive metal powder with an average particle size of less than 0.5 μm acts as a binder between particles, making it easy to metallize even at low temperatures and short heat treatment conditions, and the surface energy is large to increase the thixotrophic index of the paste. In this way, since the shape of the paste after printing is small, the ratio of the application area of the electrode material to the silicon substrate can be minimized, and the efficiency of the solar cell can be increased. In addition, the conductive metal powder having an average particle size of 0.5 to 10 μm can suppress shrinkage after firing, thereby making it possible to form a high density low shrink electrode.
상기 도전성 금속 분말의 혼합분말의 함량은 조성물 전체 중량에 대해 55 내지 90 중량%를 사용할 수 있으며, 55 중량% 미만인 경우 적은 도전성분으로 전극의 두께가 얇아져 소결 수축율이 커져 선저항값이 높아질 수 있고, 인쇄성이 부족하여 저항값 편차의 문제가 발생할 수 있으며, 90 중량%를 초과하는 경우 페이스트화 하기에 어려움이 있다.The content of the mixed powder of the conductive metal powder may be used from 55 to 90% by weight based on the total weight of the composition, if less than 55% by weight of the electrode with a small conductive powder is thinner the thickness of the electrode can be increased sintering shrinkage can be increased to increase the wire resistance value There is a problem of resistance value variation due to lack of printability, and if it exceeds 90% by weight, it is difficult to paste.
(2) 무기바인더 수지(2) inorganic binder resin
본 발명에서 사용되는 무기바인더 수지는 통상적으로 사용되는 유리프릿을 사용할 수 있으며, 연화 온도가 300 내지 800도, 바람직하게는 400 내지 700도이고, 평균 입경이 0.5 내지 10㎛인 레드-보로-실리케이트계 유리분말 또는 비스무스-보로 실리케이트계 유리분말을 사용하는 것이 바람직하다. The inorganic binder resin used in the present invention may be a glass frit that is commonly used, and has a softening temperature of 300 to 800 degrees, preferably 400 to 700 degrees, and an average particle diameter of 0.5 to 10 μm. Preference is given to using glass powders or bismuth-borosilicate glass powders.
상기 무기바인더 수지의 함량은 조성물 전체 중량에 대해 0.5 내지 8 중량%를 사용할 수 있으며, 0.5 중량% 미만인 경우 실리콘 기판과의 접착력이 약한 문제 가 발생할 수 있으며, 8 중량%를 초과하는 경우 전극의 선저항 및 접촉저항이 높아질 수 있다.The content of the inorganic binder resin may be 0.5 to 8% by weight based on the total weight of the composition, when less than 0.5% by weight may cause a problem of weak adhesion to the silicon substrate, if the content of the inorganic binder exceeds 8% by weight Resistance and contact resistance can be high.
(3) 유기 비히클(3) organic vehicle
본 발명의 페이스트 조성물에 포함되는 유기 비히클은 특별히 한정되지 않지만, 테르피네올, 부틸카비톨, 부틸카비톨아세테이트, 텍사놀, 에틸렌글리콜, 아세톤, 파인오일, 이소프로필알콜 및 에탄올 중에서 선택된 하나 이상의 용매를 사용하거나, 상기 용매 중에 에틸셀룰로스, 메틸셀룰로스, 니트로셀룰로스 등의 셀룰로스계 수지, 아크릴산 에스테르 등의 아크릴계 수지 및 폴리비닐 알코올, 폴리비닐 부티랄 등의 폴리비닐계 수지 중에서 선택된 하나 이상의 수지를 첨가하여 사용할 수 있다. 유기 비히클의 함량은 조성물 전체 중량에 대해 5 내지 40 중량%의 양을 사용할 수 있으며, 40 중량%를 초과하는 경우, 페이스트의 점도가 증대될 뿐만 아니라, 과잉의 유기 비히클의 존재로 소성 중 유기물이 완전히 제거(burn out)되지 않고 잔탄이 전극에 남아 있는 문제가 발생할 수 있다. The organic vehicle included in the paste composition of the present invention is not particularly limited, but at least one solvent selected from terpineol, butyl carbitol, butyl carbitol acetate, texanol, ethylene glycol, acetone, pine oil, isopropyl alcohol, and ethanol Or at least one resin selected from cellulose resins such as ethyl cellulose, methyl cellulose and nitrocellulose, acrylic resins such as acrylic esters and polyvinyl resins such as polyvinyl alcohol and polyvinyl butyral; Can be used. The content of the organic vehicle may be used in an amount of 5 to 40% by weight based on the total weight of the composition. When the content of the organic vehicle exceeds 40% by weight, the viscosity of the paste is increased, as well as the presence of excess organic vehicle causes the Problems may arise where xanthan remains in the electrode without being burned out completely.
(5) 기타 첨가제(5) other additives
본 발명에 따른 조성물은 필요에 따라 통상적으로 알려져 있는 첨가제, 예를 들면, 칙소제, 탈포제, 레벨링제 및 요변제로 이루어진 군으로부터 선택된 하나 이상의 첨가제를 더 포함할 수 있다. 이 중, 칙소제는 미세 인쇄 패턴의 레졸루션을 향상시키고, 인쇄 후 페이스트의 형상 유지를 증대시킬 수 있다. 본 발명에서 사용되는 칙소제의 예로는 비표면적 1.5㎠/g 이상, 바람직하게는 1.5 내지 10㎠/g의 옥사이드계 칙소제 또는 왁스계 칙소제를 사용할 수 있으며, 그 구체적인 예로는 에어로실, 아마이드 왁스(amide wax)를 들 수 있다. The composition according to the invention may further comprise one or more additives selected from the group consisting of additives commonly known as necessary, for example, thixotropic agents, defoamers, leveling agents and thixotropic agents. Among these, the thixotropic agent can improve the resolution of a fine printing pattern, and can increase the shape retention of a paste after printing. As an example of the thixotropic agent used in the present invention, an oxide-based or wax-based thixotropic agent having a specific surface area of 1.5 cm 2 / g or more, preferably 1.5 to 10 cm 2 / g may be used, and specific examples thereof include aerosil and amide. Amide wax.
상기 첨가제의 함량은 도전성 금속 혼합분말의 함량과 종류에 따라 달라질 수 있어 특별히 제한되지 않지만, 3 중량% 이하로 사용하는 것이 바람직하다. The amount of the additive may vary depending on the content and type of the conductive metal mixed powder, but is not particularly limited, but is preferably used in an amount of 3 wt% or less.
본 발명에 따른 도전성 페이스트 조성물은 점도가 50,000 내지 500,000cps의 점도(브룩필드 DVII 점도계, 스핀들 #14)로서, 태양전지의 표면 전극을 제조하는데 이용될 수 있으며, 본 발명에 따른 도전성 페이스트 조성물을 사용하여 전극을 제조하는 방법은 페이스트 조성물을 기판상에 도포하는 단계, 도포된 페이스트를 건조시키는 단계, 및 건조된 페이스트를 소성시켜 전극을 형성하는 단계를 포함한다. The conductive paste composition according to the present invention has a viscosity of 50,000 to 500,000 cps (Brookfield DVII viscometer, spindle # 14), which can be used to prepare a surface electrode of a solar cell, using the conductive paste composition according to the present invention. The method of manufacturing an electrode includes applying a paste composition onto a substrate, drying the applied paste, and firing the dried paste to form an electrode.
본 발명에 따른 도전성 페이스트 조성물은 스크린 프린팅 또는 특정한 직경의 노즐, 예를 들면 직경 50 내지 500㎛의 노즐을 이용한 분출 방식 등 다양한 코팅법을 사용하여 기판 상에 5 내지 50㎛의 두께로 도포될 수 있다.The conductive paste composition according to the present invention may be applied to the substrate with a thickness of 5 to 50 µm using various coating methods such as screen printing or a spraying method using a nozzle having a specific diameter, for example, a nozzle having a diameter of 50 to 500 µm. have.
본 발명에 따른 도전성 페이스트 조성물로 도포된 전극 페이스트는 60 내지 300℃에서 수분간 건조되고, 600 내지 850℃의 온도에서 수초간 소성될 수 있다. 이러한 방법으로 제조된 전극은 페이스트의 건조두께 대비 소성두께를 나타내는 소결 수축율이 -6.5 내지 +2%이고, 소성 후 소결 밀도가 8g/cm3 이상이고, 면적저항이 알루미나 기판에서 7mΩ/sq. 미만인 것이 바람직하다. The electrode paste coated with the conductive paste composition according to the present invention may be dried at 60 to 300 ° C. for several minutes and calcined at a temperature of 600 to 850 ° C. for several seconds. The electrode manufactured by this method has a sintering shrinkage ratio of -6.5 to + 2%, which represents a plastic thickness to a dry thickness of the paste, a sintered density of 8 g / cm 3 or more after firing, and an area resistance of 7 mPa / sq. It is preferable that it is less than.
상기와 같이 본 발명에 따른 도전성 페이스트 조성물을 이용하여 제조된 전 극은 통상적인 방법으로 태양전지의 표면 전극으로 유용하게 이용할 수 있다.As described above, the electrode prepared by using the conductive paste composition according to the present invention may be usefully used as a surface electrode of a solar cell in a conventional manner.
실시예Example
이하, 하기 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.
<도전성 페이스트 조성물의 제조><Production of Conductive Paste Composition>
실시예 1Example 1
평균 입자 크기 0.05㎛인 구형의 은 분말 16 중량%, 평균 입자 크기 3.5㎛인 판형의 은 분말 65 중량%, 연화온도가 500℃이고, 평균 입자 크기 1.5㎛인 레드-보로-실리케이트계 유리프릿 4 중량%, 에틸셀룰로스 수지를 부틸카비톨아세테이트 용제에 용해하여 제조한 유기 비히클 14 중량%, 아마이드 왁스 칙소제 및 유기산 레벨링제 1 중량%를 혼합하여, 이를 3축롤로 분산 및 분쇄하여 점도 150,000 내지 250,000cps의 점도(브룩필드 DVII 점도계, 스핀들 #14)를 갖는 페이스트 조성물을 제조하였다.16% by weight spherical silver powder with an average particle size of 0.05 μm, 65% by weight plate silver with an average particle size of 3.5 μm, red-boro-silicate glass frit with a softening temperature of 500 ° C. and an average particle size of 1.5 μm 4 % By weight, 14% by weight of an organic vehicle prepared by dissolving an ethyl cellulose resin in a butylcarbitol acetate solvent, 1% by weight of an amide wax thixotropic agent and an organic acid leveling agent, and dispersed and triturated with a triaxial roll to obtain a viscosity of 150,000 to 250,000. A paste composition was prepared having a viscosity of cps (Brookfield DVII viscometer, spindle # 14).
실시예 2Example 2
평균 입자 크기 0.05㎛인 구형의 은 분말 20 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 61 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하 여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.The same procedure as in Example 1 was carried out except that 20 wt% of the spherical silver powder having an average particle size of 0.05 μm and 61 wt% of the plate shaped silver powder having an average particle size of 3.5 μm had a viscosity of 150,000 to 250,000 cps. A paste composition was prepared.
실시예 3Example 3
평균 입자 크기 0.05㎛인 구형의 은 분말 5 중량%, 평균 입자 크기 0.2㎛인 구형의 은 분말 20 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 56 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.Example 1 and 5 except that 5% by weight of the spherical silver powder having an average particle size of 0.05 μm, 20% by weight of the spherical silver powder having an average particle size of 0.2 μm and 56% by weight of the plate-shaped silver powder having an average particle size of 3.5 μm were used. In the same manner, a paste composition having a viscosity of 150,000 to 250,000 cps was prepared.
실시예 4Example 4
평균 입자 크기 0.05㎛인 구형의 은 분말 5 중량%, 평균 입자 크기 0.2㎛인 구형의 은 분말 30 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 46 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.Example 1 and 5 except that 5% by weight of the spherical silver powder having an average particle size of 0.05 μm, 30% by weight of the spherical silver powder having an average particle size of 0.2 μm and 46% by weight of the plated silver powder having an average particle size of 3.5 μm were used. In the same manner, a paste composition having a viscosity of 150,000 to 250,000 cps was prepared.
실시예 5Example 5
평균 입자 크기 0.05㎛인 구형의 은 분말 10 중량%, 평균 입자 크기 0.2㎛인 구형의 은 분말 20 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 51 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.Example 1 and 10 except that 10% by weight of the spherical silver powder having an average particle size of 0.05 μm, 20% by weight of the spherical silver powder having an average particle size of 0.2 μm and 51% by weight of the plated silver powder having an average particle size of 3.5 μm were used. In the same manner, a paste composition having a viscosity of 150,000 to 250,000 cps was prepared.
실시예 6Example 6
평균 입자 크기 0.2㎛인 구형의 은 분말 22 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 59 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste having a viscosity of 150,000 to 250,000 cps was carried out in the same manner as in Example 1 except that 22 wt% of spherical silver powder having an average particle size of 0.2 μm and 59 wt% of plate-shaped silver powder having an average particle size of 3.5 μm were used. The composition was prepared.
실시예 7Example 7
평균 입자 크기 0.2㎛인 구형의 은 분말 28 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 53 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste having a viscosity of 150,000 to 250,000 cps by the same procedure as in Example 1 except that 28 wt% of spherical silver powder having an average particle size of 0.2 μm and 53 wt% of plate silver powder having an average particle size of 3.5 μm were used. The composition was prepared.
실시예 8Example 8
평균 입자 크기 0.2㎛인 구형의 은 분말 34 중량% 및 평균 입자 크기 3.5㎛인 판형의 은 분말 47 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste having a viscosity of 150,000 to 250,000 cps was carried out in the same manner as in Example 1 except that 34 wt% of the spherical silver powder having an average particle size of 0.2 μm and 47 wt% of the plate-shaped silver powder having an average particle size of 3.5 μm were used. The composition was prepared.
실시예 9Example 9
평균 입자 크기 0.2㎛인 구형의 은 분말 13 중량%, 평균 입자 크기 0.8㎛인 구형의 은 분말 19 중량% 및 평균 입자 크기 1.5㎛인 구형의 은 분말 49 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.Examples 1 and 13 were used except that 13 wt% of the spherical silver powder having an average particle size of 0.2 μm, 19 wt% of the spherical silver powder having an average particle size of 0.8 μm, and 49 wt% of the spherical silver powder having an average particle size of 1.5 μm were used. In the same manner, a paste composition having a viscosity of 150,000 to 250,000 cps was prepared.
비교예 1Comparative Example 1
평균 입자 크기 0.05㎛인 구형의 은 분말 81 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste composition having a viscosity of 150,000 to 250,000 cps was prepared in the same manner as in Example 1 except that 81 wt% of a spherical silver powder having an average particle size of 0.05 μm was used.
비교예 2Comparative Example 2
평균 입자 크기 0.2㎛인 구형의 은 분말 81 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste composition having a viscosity of 150,000 to 250,000 cps was prepared in the same manner as in Example 1 except that 81 wt% of spherical silver powder having an average particle size of 0.2 μm was used.
비교예 3Comparative Example 3
평균 입자 크기 0.8㎛인 구형의 은 분말 81 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste composition having a viscosity of 150,000 to 250,000 cps was prepared in the same manner as in Example 1 except that 81 wt% of a spherical silver powder having an average particle size of 0.8 μm was used.
비교예 4Comparative Example 4
평균 입자 크기 1.5㎛인 구형의 은 분말 81 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste composition having a viscosity of 150,000 to 250,000 cps was prepared in the same manner as in Example 1 except that 81 wt% of spherical silver powder having an average particle size of 1.5 μm was used.
비교예 5Comparative Example 5
평균 입자 크기 3.5㎛인 판형의 은 분말 81 중량%를 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 점도 150,000 내지 250,000cps의 점도를 갖는 페이스트 조성물을 제조하였다.A paste composition having a viscosity of 150,000 to 250,000 cps was prepared in the same manner as in Example 1 except that 81 wt% of a plate-shaped silver powder having an average particle size of 3.5 μm was used.
비교예 6Comparative Example 6
페로사의 CN 33-462 페이스트 조성물을 구입하여 물성을 평가하였다. Ferro's CN 33-462 paste composition was purchased and evaluated for physical properties.
페이스트 물성의 절대값은 실리콘 기판의 상태, 인쇄조건, 건조조건, 소성조건에 따라 다를 수 있다.The absolute value of the paste properties may vary depending on the condition of the silicon substrate, printing conditions, drying conditions, and firing conditions.
물성 평가Property evaluation
실시예 1 내지 9 및 비교예 1 내지 6에서 얻은 페이스트 조성물을 아래와 같은 방법으로 수행하여 평가하였으며, 그 결과를 하기 표 1에 나타내었다: The paste compositions obtained in Examples 1-9 and Comparative Examples 1-6 were evaluated in the following manner, and the results are shown in Table 1 below:
1) 변환 효율1) Conversion efficiency
페이스트 조성물을 스크린 프린팅 방법으로 두께가 200㎛, 크기가 127mm × 127mm인 n형 실리콘 반도체 기판상에 325 메쉬의 스크린 인쇄판을 이용하여 소성두께가 10 내지 20㎛가 되도록 도포하고 건조시켰다. The paste composition was coated and dried on an n-type silicon semiconductor substrate having a thickness of 200 μm and a size of 127 mm × 127 mm by screen printing using a screen printing plate of 325 mesh so as to have a firing thickness of 10 to 20 μm.
상기 페이스트가 도포된 n형 실리콘 반도체 기판을 200 ℃에서 건조한 후 최 고온도 740 내지 790℃인 소성로에서 약 10초 동안 소성하여 전극을 형성시켜 태양전지 셀을 제작했다.The paste-coated n-type silicon semiconductor substrate was dried at 200 ° C., and then fired in a firing furnace having a maximum temperature of 740 to 790 ° C. for about 10 seconds to form an electrode, thereby manufacturing a solar cell.
제작된 태양전지 셀을 효율측정기(PASAN사)를 이용하여 변환효율을 측정하였다:The fabricated solar cell was measured for conversion efficiency using an efficiency meter (PASAN):
2) 소결 수축율은 건조두께 대비 소성두께의 증감비로 계산하였다.2) Sintering shrinkage was calculated as the increase and decrease ratio of the plastic thickness to the dry thickness.
3) 소결 밀도는 페이스트를 막으로 형성하여 상기 조건으로 건조 및 소결하여 페이스트 소결막을 형성한 후 아르키메데스법을 이용하여 부피와 질량을 측정하여 계산하였다. 3) The sintered density was calculated by forming a paste into a film, drying and sintering under the above conditions to form a paste sintered film, and then measuring the volume and mass using the Archimedes method .
4) 면적저항(Rs)은 폭/길이의 비가 1/500인 패턴으로 알루미나 기판에 325 메시 스크린 인쇄판으로 인쇄하고 상기 조건으로 건조 및 소성한 후 저항 측정기(키슬리 2470)로 선저항값을 측정하고 아래와 같은 공식으로 계산하였다.4) The area resistance (Rs) is printed with a 325 mesh screen printing plate on an alumina substrate in a pattern having a width / length ratio of 1/500, dried and fired under the above conditions, and then measured with a resistance measuring instrument (Kisley 2470). Calculated by the formula below.
상기 표 1의 결과에서 알 수 있는 바와 같이, 본 발명에 따른 실시예 1 내지 9에서 얻은 본 발명의 페이스트 조성물은 전극 제조시 소결 수축율이 +2 내지 -6%로서 비교예 1 내지 6에서 얻은 페이스트 조성물에 비해 상대적으로 낮고, 소결 밀도가 8g/cm3 이상이며, 면적저항이 낮아 태양전지 셀의 중요 특성인 변환효율이 우수하였다. As can be seen from the results of Table 1, the paste composition of the present invention obtained in Examples 1 to 9 according to the present invention is a paste obtained in Comparative Examples 1 to 6 with a sintering shrinkage of +2 to -6% during electrode production Compared with the composition, the sintered density was 8 g / cm 3 or more, and the area resistance was low.
Claims (18)
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