KR101693841B1 - silver paste composition, a front electrode for solar cell formed using it, and a solar cell employing it - Google Patents
silver paste composition, a front electrode for solar cell formed using it, and a solar cell employing it Download PDFInfo
- Publication number
- KR101693841B1 KR101693841B1 KR1020150027786A KR20150027786A KR101693841B1 KR 101693841 B1 KR101693841 B1 KR 101693841B1 KR 1020150027786 A KR1020150027786 A KR 1020150027786A KR 20150027786 A KR20150027786 A KR 20150027786A KR 101693841 B1 KR101693841 B1 KR 101693841B1
- Authority
- KR
- South Korea
- Prior art keywords
- solar cell
- front electrode
- paste composition
- silver paste
- glass frit
- Prior art date
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 40
- 239000004332 silver Substances 0.000 title claims abstract description 40
- 239000011521 glass Substances 0.000 claims description 35
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 15
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- -1 Trimethyl Pentanyl Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- 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 3
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- RHFOYRRUVLOOJP-UHFFFAOYSA-N ethoxyethane;propanoic acid Chemical compound CCOCC.CCC(O)=O RHFOYRRUVLOOJP-UHFFFAOYSA-N 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000012461 cellulose resin Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 239000000843 powder Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000003667 anti-reflective effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- 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
-
- 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
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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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
- H01L31/04—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
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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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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
Abstract
본 발명은 태양전지 전면전극용 은 페이스트 조성물, 이를 이용하여 형성되는 태양전지 전면전극 및 이를 채용한 태양전지에 관한 것으로, 본 발명의 은 페이스트 조성물은 기판과의 접착력이 우수할 뿐만 아니라 반사방지막과의 접촉저항이 낮아 높은 효율의 태양전지를 제조할 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver paste composition for a solar cell front electrode, a solar cell front electrode formed using the same, and a solar cell employing the paste composition. The silver paste composition of the present invention is excellent in adhesion to a substrate, The contact resistance of the solar cell is low, so that a solar cell with high efficiency can be manufactured.
Description
본 발명은 은 페이스트 조성물, 이를 이용하여 형성된 태양전지용 전면전극 및 이를 채용한 태양전지에 관한 것이다.The present invention relates to a silver paste composition, a front electrode for a solar cell formed using the same, and a solar cell employing the same.
태양 전지는 태양 에너지로부터 전기 에너지를 생성하는 전지로서, 친환경적이고 에너지원인 태양 에너지가 무한할 뿐만 아니라 수명이 긴 장점을 가지고 있어 최근 석유나 석탄과 같은 기존 에너지 자원의 고갈이 예측되면서 이들을 대체할 대체 에너지로 가장 큰 관심을 받고 있다.Solar cells generate electricity from solar energy. They are environmentally friendly, have a long life span as well as an infinite number of solar energy sources. As the depletion of existing energy resources such as oil and coal is predicted, they can be replaced Energy is receiving the greatest attention.
태양전지는 원료 물질에 따라 크게 실리콘 태양전지 (silicon solar cell), 화합물 반도체 태양전지 (compound semiconductor solar cell) 및 적층형 태양전지 (tandem solar cell)로 구분되며, 이 중 주류는 실리콘 태양전지이다.Solar cells are divided into silicon solar cell, compound semiconductor solar cell and tandem solar cell according to the raw material, and the main one is silicon solar cell.
실리콘 태양전지는 빛 반사를 감소시키면서 빛 흡수가 잘 이루어지도록 하는 반사방지막(anti reflection coating, ARC)과 p/n접합, 에미터 및 베이스로 구성된 실리콘 웨이퍼, 빛에 의해 생성된 전기를 외부 회로로 유도하는 전면전극 및 후면전극으로 이루어져 있다. 양단 전극은 버스 바(bus bar), 후면 알루미늄, 전면 은(Ag) 페이스트의 순서로 인쇄와 건조를 번갈아 시행한 후, 600 ~ 950℃의 온도 범위에서 동시소성(co-firing) 과정을 거치면서 형성된다.Silicon solar cells are composed of an anti reflection coating (ARC) and p / n junction, a silicon wafer composed of an emitter and a base, which allows light to be absorbed while reducing light reflection, And a front electrode and a rear electrode. Both electrodes were printed and dried alternately in the order of bus bar, back aluminum, and silver (Ag) paste, followed by co-firing in the temperature range of 600 to 950 ° C .
실리콘 태양전지의 전면전극은 전면전극 형성용 금속 페이스트와 반사방지막과의 계면 반응을 통해서 형성되며, 이 때 상기 금속 페이스트에 포함된 은이 고온에서 액상이 되었다가 다시 고상으로 재결정되면서, 글래스 프릿 분말(glass frit)을 매개로 하여 반사방지막을 관통하는 펀치 스루(punch through) 현상을 통해 에미터층과 접촉하게 된다.The front electrode of the silicon solar cell is formed through an interfacial reaction between the metal paste for forming the front electrode and the antireflection film. The silver contained in the metal paste becomes a liquid at a high temperature and is then recrystallized into a solid phase to form a glass frit powder glass frit through the punch-through phenomenon through the anti-reflection film.
글래스 프릿 분말은 반사방지막과 계면 반응을 일으켜 반사방지막을 에칭하게 되는데, 이는 산화-환원 반응으로서 일부 원소가 환원되어 부산물로 생성된다. 종래의 글래스 프릿 분말은 산화납(PbO)을 주성분으로 하기 때문에, 계면 반응 후 납이 환원되어 환경적으로 문제점이 있었다.The glass frit powder causes an interfacial reaction with the antireflective film to etch the antireflective film, which is an oxidation-reduction reaction in which some elements are reduced to form byproducts. Since the conventional glass frit powder contains lead oxide (PbO) as a main component, lead is reduced after the interface reaction, which is environmentally problematic.
이러한 문제점을 해결하기 위해, 산화납 대신에 산화비스무트(Bi2O3)를 사용한 납 프리 글래스 프릿 분말이 소개되었다. 하지만, 산화비스무트계 글래스 프릿 분말은 종래의 산화납을 포함하는 글래스 프릿 분말보다 전극과 기판 사이의 접촉저항이 낮은 문제점이 있다.In order to solve this problem, a lead-free glass frit powder using bismuth oxide (Bi 2 O 3 ) instead of lead oxide has been introduced. However, the bismuth oxide-based glass frit powder has a lower contact resistance between the electrode and the substrate than the conventional glass frit powder containing lead oxide.
따라서, 친환경적이면서도 종래보다 우수한 성능을 갖는 태양전지를 제조할 수 있는 유리 프릿 분말의 개발이 시급하다.Therefore, it is urgent to develop a glass frit powder which can produce a solar cell that is eco-friendly and has better performance than the prior art.
본 발명은 태양전지의 전면전극을 형성할 수 있는 태양전지 전면전극용 은 페이스트 조성물을 제공한다.The present invention provides a silver paste composition for a solar cell front electrode capable of forming a front electrode of a solar cell.
또한 본 발명은 본 발명의 태양전지 전면전극용 은 페이스트 조성물을 이용하여 형성된 태양전지 전면전극을 제공한다.The present invention also provides a solar cell front electrode formed using the silver paste composition for a solar cell front electrode of the present invention.
또한 본 발명은 본 발명의 태양전지 전면전극을 채용한 태양전지를 제공한다.The present invention also provides a solar cell employing the solar cell front electrode of the present invention.
본 발명은 에칭능력이 우수하여 넓은 범위에서 에칭이 일어나 전면전극의 영역이 넓어지고 접촉저항도 낮아 변환효율이 높은 태양전지 전면전극용 은 페이스트 조성물을 제공하는 것으로, 본 발명의 태양전지 전면전극용 은 페이스트 조성물은 The present invention provides a silver paste composition for a front electrode of a solar cell having a high etching efficiency and a high conversion efficiency due to etching in a wide range to widen the area of the front electrode and low contact resistance, The silver paste composition
(a) 은 분말(a) is powder
(b) Bi2O3, TeO2 및 V2O5를 포함하는 무연 글래스 프릿 및 (b) a lead-free glass frit comprising Bi 2 O 3 , TeO 2 and V 2 O 5 and
(c)유기 비히클;을 포함하되 상기 글래스 프릿은 납(Pb), 특히 PbO를 함유하지 않는 것을 특징으로 한다.(c) an organic vehicle, wherein the glass frit is free of lead (Pb), especially PbO.
본 발명의 일 실시예에 따른 상기 글래스 프릿은 SiO2, ZnO, Li2O, B2O3, Al2O3, CuO, Na2O, ZrO2, MgO, P2O5, CaO, BaO, SnO, SrO, K2O, TiO2, 및 MnO2로 이루어진 군으로부터 선택되는 1종 이상을 더 포함할 수 있다.The glass frit according to an exemplary embodiment of the present invention may include at least one selected from the group consisting of SiO 2 , ZnO, Li 2 O, B 2 O 3 , Al 2 O 3 , CuO, Na 2 O, ZrO 2 , MgO, P 2 O 5 , , SnO 2 , SrO, K 2 O, TiO 2 , and MnO 2 .
본 발명의 일 실시예에 따른 글래스 프릿은 Bi2O3 40 내지 80wt%, TeO2 1 내지 30wt%, V2O5 1 내지 30wt%로 포함될 수 있다.The glass frit according to an embodiment of the present invention may include 40 to 80 wt% of Bi 2 O 3 , 1 to 30 wt% of TeO 2, and 1 to 30 wt% of V 2 O 5 .
바람직하게는 본 발명의 일 실시예에 따른 글래스 프릿은 Bi2O3 40 내지 80wt%, TeO2 1 내지 30wt%, V2O5 1 내지 30wt%, ZnO 0.1 내지 10wt%, SiO2 0.1 내지 15wt%, Li2O 0.1 내지 10wt%, B2O3 0.1 내지 10wt%로 포함될 수 있다.Preferably, the glass frit according to an embodiment of the present invention comprises 40 to 80 wt% of Bi 2 O 3 , 1 to 30 wt% of TeO 2, 1 to 30 wt% of V 2 O 5 , 0.1 to 10 wt% of ZnO, 0.1 to 15 wt% of SiO 2 %, Li 2 O 0.1 to 10 wt%, and B 2 O 3 0.1 to 10 wt%.
본 발명의 일 실시예에 따른 글래스 프릿은 은 페이스트 조성물에 대하여 0.1 내지 15wt%로 포함될 수 있다.The glass frit according to an embodiment of the present invention may be contained in an amount of 0.1 to 15 wt% based on the silver paste composition.
본 발명의 일 실시예에 따른 은 분말은 유리 전이온도가 420℃ 이하이고, 녹는점이 550℃이하일 수 있다.The silver powder according to an embodiment of the present invention may have a glass transition temperature of 420 ° C or less and a melting point of 550 ° C or less.
본 발명의 일 실시예에 따른 유기 비히클은 TXIB(Trimethyl Pentanyl Diisobutylate), 디베이직 에스테르(Dibasic ester), BC(BUTYL CARBITOL), 디메틸 글루타레이트, 부틸카비톨아세테이트, 부틸카비톨, 부틸셀루솔브, 부틸셀루솔브아세테이트, 프로필렌 글리콜 모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르프로피오네이트, 에틸에테르프로피오네이트, 테르피네올(terpineol), 프로필렌글리콜모노메틸에테르아세테이트, 디메틸아미노포름알데히드, 메틸에틸케톤, 감마 부티로락톤, 에틸락테이트 및 텍사놀(Texanol) 중에서 선택된 하나 이상의 용매 중에 셀룰로스계 수지, 아크릴계 수지 및 폴리비닐계 수지 중에서 선택된 하나 이상의 수지를 첨가한 것일 수 있다.The organic vehicle according to an embodiment of the present invention may be selected from the group consisting of TXIB (Trimethyl Pentanyl Diisobutylate), Dibasic ester, BC (BUTYL CARBITOL), dimethylglutarate, butyl carbitol acetate, butyl carbitol, butyl cellosolve, Butyl cellosolve acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, ethyl ether propionate, terpineol, propylene glycol monomethyl ether acetate, dimethylaminoform Acrylic resin and polyvinyl resin may be added to at least one solvent selected from the group consisting of aldehyde, methyl ethyl ketone, gamma butyrolactone, ethyl lactate and Texanol.
또한 본 발명은 본 발명의 태양전지 전면전극용 은 페이스트 조성물을 이용하여 형성된 태양전지 전면전극을 제공한다.The present invention also provides a solar cell front electrode formed using the silver paste composition for a solar cell front electrode of the present invention.
또한 본 발명은 본 발명의 태양전지 전면전극을 채용한 태양전지를 제공한다.The present invention also provides a solar cell employing the solar cell front electrode of the present invention.
본 발명에서 제공하는 은 페이스트 조성물은 우수한 에칭능력을 가지는 동시에 반사방지막과의 접촉저항도 낮아 이로 형성된 태양전지용 전면전극을 채용한 태양전지는 높은 효율을 가진다.The silver paste composition of the present invention has excellent etching ability and low contact resistance with the antireflection film, and thus the solar cell employing the front electrode for the solar cell has high efficiency.
즉, 본 발명의 은 페이스트 조성물은 기판과 전면전극 사이의 부착력을 향상시키고, 우수한 에칭능력으로 에칭이 넓은 범위에서 일어나 은의 재결정으로 형성되는 전면전극 영역도 넓어지며 반사방지막과의 접촉저항이 낮고 개방전압이 높아 태양전지의 효율을 향상시킨다.That is, the silver paste composition of the present invention improves the adhesion between the substrate and the front electrode, the etching is performed in a wide range due to the excellent etching ability, the front electrode region formed by recrystallization of silver is widened and the contact resistance with the anti- The voltage is high, thereby improving the efficiency of the solar cell.
본 발명은 태양전지 전면전극용 은 페이스트 조성물을 제공하는 것으로, 본 발명의 은 페이스트 조성물은 The present invention provides a silver paste composition for a solar cell front electrode, wherein the silver paste composition of the present invention comprises
(a) 은 분말(a) is powder
(b) Bi2O3, TeO2 및 V2O5를 포함하는 무연 글래스 프릿 및(b) a lead-free glass frit comprising Bi 2 O 3 , TeO 2 and V 2 O 5 and
(c)유기 비히클;을 포함한다.(c) an organic vehicle.
본 발명의 은 페이스트 조성물은 납, 특히 PbO를 함유하지 않은 대신 Bi2O3를 포함하여 PbO없이도 에칭능력이 우수하며, 친환경적이다.The paste composition of the present invention comprises instead of Bi 2 O 3 which does not contain lead, in particular PbO It has excellent etching ability and is environment-friendly without PbO.
나아가 본 발명의 은 페이스트 조성물은 Bi2O3 뿐만아니라 TeO2 및 V2O5를 함유함으로써 기판과 전면전극사이의 접착력을 높이는 동시에 에칭능력을 더욱 향상시키고 반사방지막과의 접촉저항을 낮추어 개방전압을 높인다.Further, since the silver paste composition of the present invention contains not only Bi 2 O 3 but also TeO 2 and V 2 O 5 , the adhesion between the substrate and the front electrode is increased, the etching ability is further improved, the contact resistance with the antireflection film is lowered, .
본 발명의 일 실시예에 따른 글래스 프릿은 Bi2O3 40 내지 80wt%, TeO2 1 내지 30wt%, V2O5 1 내지 30wt%로 포함될 수 있다.The glass frit according to an embodiment of the present invention may include 40 to 80 wt% of Bi 2 O 3 , 1 to 30 wt% of TeO 2, and 1 to 30 wt% of V 2 O 5 .
본 발명의 일 실시예에 따른 상기 글래스 프릿은 보다 높은 에칭능력을 가지면서도 반사방지막과의 접촉저항을 낮추기위한 측면에서 바람직하게 SiO2, ZnO, Li2O, B2O3, Al2O3, CuO, Na2O, ZrO2, MgO, P2O5, CaO, BaO, SnO, SrO, K2O, TiO2, 및 MnO2로 이루어진 군으로부터 선택되는 1종 이상을 더 포함할 수 있으며, 보다 바람직하게는 ZnO, SiO2, Li2O, B2O3를 더 포함할 수 있으며, Bi2O3 40 내지 80wt%, TeO2 1 내지 30wt%, V2O5 1 내지 30wt%, ZnO 1 내지 10wt%, SiO2 0.1 내지 10wt%, Li2O 0.1 내지 10wt%, B2O3 0.1 내지 10wt%로 포함될 수 있다.The glass frit according to an embodiment of the present invention preferably has SiO 2 , ZnO, Li 2 O, B 2 O 3 , Al 2 O 3 , or the like, in view of lowering the contact resistance with the anti- , CuO, Na 2 O, ZrO 2, MgO, P 2 O 5, CaO, can further include BaO, SnO, SrO, K 2 O, TiO 2, and at least one selected from the group consisting of MnO 2, and , and more preferably may further include ZnO, SiO 2, Li 2 O , B 2 O 3, Bi 2 O 3 40 to 80wt%, TeO 2 1 to 30wt%, V 2 O 5 1 to 30wt%, 1 to 10 wt% of ZnO, 0.1 to 10 wt% of SiO 2, 0.1 to 10 wt% of Li 2 O, and 0.1 to 10 wt% of B 2 O 3 .
본 발명의 일 실시예에 따른 글래스 프릿은 변환효율을 높이기위한 측면에서 보다 좋게는 Bi2O3, TeO2, V2O5, ZnO, SiO2, Li2O 및 B2O3로 이루어질 수 있으며, 보다 구체적으로 Bi2O3 40 내지 70wt%, TeO2 5 내지 20wt%, V2O5 1 내지 20wt%, ZnO 1 내지 10wt%, SiO2 3 내지 10wt%, Li2O 0.5 내지 5wt%, B2O3 1 내지 8wt%로 포함될 수 있다.The glass frit according to an embodiment of the present invention may be made of Bi 2 O 3 , TeO 2 , V 2 O 5 , ZnO, SiO 2 , Li 2 O, and B 2 O 3 , and, more specifically, Bi 2 O 3 40 to 70wt%, TeO 2 5 to 20wt%, V 2 O 5 1 to 20wt%, ZnO 1 to 10wt%, SiO 2 3 to 10wt%, Li 2 O 0.5 to 5wt% , And B 2 O 3 1 to 8 wt%.
본 발명의 일 실시예에 따른 은(Ag)분말은 태양전지 전면전극을 형성하기 위한 은 페이스트 조성물에 전기적 특성을 부여하는 도전성 금속으로, 순수한 은 분말 외에도 산화 은, 은 합금, 은 화합물 및 기타 소성에 의해 은 분말의 석출이 가능한 물질도 포함되며, 상기 물질을 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The silver (Ag) powder according to an embodiment of the present invention is a conductive metal that imparts electrical characteristics to a silver paste composition for forming a front electrode of a solar cell. In addition to pure silver powder, silver oxide, silver alloy, silver compound, A material capable of precipitating a silver powder by the above-mentioned method, and the above materials may be used singly or in a mixture of two or more.
은 분말의 형상은 본 발명의 기술 분야에 알려진 형상이라면 특별히 제한되지 않고 적용될 수 있다. 예를 들면 구형, 플레이크(flake)형, 또는 이들의 조합을 사용할 수 있으나, 이에 한정되는 것은 아니다. 은 분말의 입경은 원하는 소결 속도와 전극을 형성하는 공정에 있어서의 영향 등을 고려하여 적절한 범위로 조절할 수 있다. 본 발명의 일 실시예를 따른 상기 은 분말의 평균입경(d50)은 약 0.5 내지 4μm의 크기를 가질 수 있으나 이에 한정되는 것은 아니다.The shape of the silver powder is not particularly limited as long as the shape is known in the technical field of the present invention. For example, a spherical shape, a flake shape, or a combination thereof may be used, but the present invention is not limited thereto. The particle diameter of the silver powder can be adjusted to an appropriate range in consideration of the desired sintering speed and the influence in the process of forming the electrode. The average particle size (d50) of the silver powder according to an exemplary embodiment of the present invention may have a size of about 0.5 to 4 mu m, but is not limited thereto.
은 분말의 순도는 80% 이상, 바람직하게는 95% 이상인 은 분말을 사용할 수 있으나, 전극으로서 통상 요구되는 조건을 만족시키기 위한 순도라면 특별히 한정되는 것은 아니다.Silver powder having a purity of 80% or more, preferably 95% or more can be used, but is not particularly limited as long as it is a purity for satisfying the conditions generally required for the electrode.
은 분말은 은 페이스트 조성물 전체 100wt%에 대하여, 약 60 내지 95wt%, 페이스트의 점도가 낮아지거나 상분리가 되어 인쇄성에 문제가 되지 않으면서도 경제적인 측면에서 바람직하게는 약 70 내지 약 85wt%로 함유될 수 있다. Silver powder is contained in an amount of about 60 to 95 wt% based on 100 wt% of the silver paste composition as a whole, and is preferably contained in an amount of about 70 to about 85 wt% on the economic point of view, .
은 분말은 상기 은 페이스트 조성물 중에서 유기 용매를 제외한 고형분 중에서는, 고형분 전체 100wt%에 대하여 약 80 내지 99wt%로 포함될 수 있다.The silver powder may be contained in the silver paste composition in an amount of about 80 to 99% by weight based on 100% by weight of the total solid content in the solid content excluding the organic solvent.
본 발명의 일 실시예에 따른 글래스 프릿은 은 페이스트 조성물에 대하여 0.1 내지 15wt%로 포함될 수 있다.The glass frit according to an embodiment of the present invention may be contained in an amount of 0.1 to 15 wt% based on the silver paste composition.
본 발명의 일 실시예에 따른 글래스 분말은 바람직하게 유리 전이온도가 420℃ 이하이고, 녹는점이 550℃이하일 수 있다.The glass powder according to an embodiment of the present invention preferably has a glass transition temperature of 420 ° C or less and a melting point of 550 ° C or less.
즉 본 발명의 일 실시예에 따른 은 페이스트 조성물은 은 페이스트 조성물 전체에 대하여 은 분말 60 내지 95wt%, 글래스 프릿 0.1 내지 15wt% 잔량의 유기 비히클을 포함한다.That is, the silver paste composition according to one embodiment of the present invention includes 60 to 95 wt% silver powder and 0.1 to 15 wt% balance of glass frit organic vehicle over the silver paste composition as a whole.
본 발명의 일 실시예에 따른 상기 유기 비히클은 통상적으로 태양전지 전극 페이스트에 사용되는 유기 비히클이 사용될 수 있으며, 일예로 고분자와 용매의 혼합물일 수 있다. 바람직하게는, 유기 비히클은 TXIB(Trimethyl Pentanyl Diisobutylate), 디베이직 에스테르(Dibasic ester), BC(BUTYL CARBITOL), 부틸카비톨아세테이트, 부틸카비톨, 부틸셀루솔브, 부틸셀루솔브아세테이트, 프로필렌글리콜 모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 디메틸 아디페이트, 디메틸 글루타레이트, 프로필렌글리콜모노메틸에테르프로피오네이트, 에틸에테르프로피오네이트, 테르피네올(terpineol), 프로필렌글리콜모노메틸에테르아세테이트, 디메틸아미노포름알데히드, 메틸에틸케톤, 감마 부티로락톤, 에틸락테이트 및 텍사놀(Texanol) 중에서 선택된 하나 이상의 용매 중에 에틸셀룰로스, 메틸셀룰로스, 니트로셀룰로스, 셀룰로오스 에스테르 등의 셀룰로스계 수지, 로진(rosin) 또는 알콜의 폴리메타크릴레이트, 아크릴산 에스테르 등의 아크릴계 수지 및 폴리비닐 알코올, 폴리비닐 부티랄 등의 폴리비닐계 수지 중에서 선택된 하나 이상의 수지를 첨가한 것이다.The organic vehicle according to an exemplary embodiment of the present invention may be an organic vehicle commonly used in a solar cell electrode paste. For example, the organic vehicle may be a mixture of a polymer and a solvent. Preferably, the organic vehicle is selected from the group consisting of TXIB (Trimethyl Pentanyl Diisobutylate), Dibasic ester, BC (BUTYL CARBITOL), butyl carbitol acetate, butyl carbitol, butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl But are not limited to, ether, dipropylene glycol monomethyl ether, dimethyl adipate, dimethyl glutarate, propylene glycol monomethyl ether propionate, ethyl ether propionate, terpineol, propylene glycol monomethyl ether acetate, Cellulose resins such as ethyl cellulose, methyl cellulose, nitrocellulose and cellulose ester, rosin or alcohols in at least one solvent selected from aldehyde, methyl ethyl ketone, gamma butyrolactone, ethyl lactate and Texanol. Acrylic resins such as polymethacrylate and acrylic acid esters, And polyvinyl resins such as polyvinyl alcohol, polyvinyl butyral, and the like.
은 분말을 용이하게 분산시키고 소성후 잔류 탄소에 의한 저항증가로 태양전지의 변환효율이 저하되는 문제점을 발생시키기 않도록 하기위해서 본 발명의 일 실시예에 따른 유기 비히클은 전체 조성물 대비 4 중량% 내지 35 중량% 범위 이내로 포함된 것이 바람직하다. The organic vehicle according to an embodiment of the present invention may be used in an amount of 4 wt% to 35 wt% relative to the total composition in order to easily disperse the silver powder and to avoid the problem that the conversion efficiency of the solar cell is lowered due to the increase of the resistance due to the residual carbon after firing. By weight or less.
본 발명의 은 페이스트 조성물은 유기 첨가제를 더 포함할 수 있으며, 유기 첨가제는 분산제, 증점제, 요변제, 레벨링제 등으로부터 선택될 수 있다. 상기 분산제로는 LUBRISOL사 SOLSPERSE, BYK사의 DISPERBYK-180, 110, 996, 및 997 등을 들 수 있으나 이에 한정되지는 않는다. 상기 증점제로는 BYK사의 BYK-410, 411, 420 등을 들 수 있으나 이에 한정되지는 않는다. 상기 요변제로는 ELEMENTIS사 THIXATROL MAX, BYK사의 ANTI-TERRA-203, 204, 205 등을 들 수 있으나 이에 한정되지는 않는다. 상기 레벨링제로는 BYK사의 BYK-3932 P, BYK-378, BYK-306, BYK-3440 등을 들 수 있으나 이에 한정되지는 않는다. 유기 첨가제는 은 페이스트 조성물 전체 100wt%에 대하여, 약 1 내지 20wt%로 함유될 수 있다.The silver paste composition of the present invention may further include an organic additive, and the organic additive may be selected from a dispersant, a thickener, a thixotropic agent, a leveling agent and the like. Examples of the dispersing agent include, but are not limited to, SOLSPERSE from LUBRISOL, DISPERBYK-180, 110, 996 and 997 from BYK. Examples of the thickener include but are not limited to BYK-410, 411, and 420 manufactured by BYK. Examples of the shrinkage agent include THIXATROL MAX manufactured by ELEMENTIS, ANTI-TERRA-203 manufactured by BYK, 204, 205, and the like. Examples of the leveling agent include but are not limited to BYK-3932 P, BYK-378, BYK-306 and BYK-3440 manufactured by BYK. The organic additive may be contained in an amount of about 1 to 20 wt% based on 100 wt% of the entire silver paste composition.
또한, 본 발명은 상기의 은 페이스트 조성물을 이용하여 형성된 태양전지 전면 전극을 제공한다.Further, the present invention provides a solar cell front electrode formed using the above silver paste composition.
전면 전극은 상기의 은 페이스트 조성물을 웨이퍼 기판 상에 인쇄하고 건조 및 소성하는 공정을 통하여 형성된다. 인쇄방법은 스크린 인쇄 등을 이용할 수 있으며, 특별히 한정되는 것은 아니다.The front electrode is formed through a process of printing, drying and firing the above silver paste composition on a wafer substrate. The printing method may be screen printing or the like, and is not particularly limited.
또한, 본 발명은 본 발명의 태양전지 전면전극을 포함하는 태양전지를 제공한다.The present invention also provides a solar cell comprising the solar cell front electrode of the present invention.
본 발명의 일 실시예에 따른 태양전지는 제 1 도전성 타입의 기판; 상기 기판상에 형성된 제 2 도전성 타입의 에미터층; 상기 에미터층 상에 형성된 반사방지막; 상기 반사방지막을 관통하여 상기 에미터층에 접속되며 상기의 은 페이스트 조성물을 이용하여 제조되는 전면 전극; 및 상기 기판의 배면에 형성된 후면 전극을 포함한다.A solar cell according to an embodiment of the present invention includes a substrate of a first conductivity type; An emitter layer of a second conductivity type formed on the substrate; An antireflection film formed on the emitter layer; A front electrode formed through the antireflection film and connected to the emitter layer using the silver paste composition; And a rear electrode formed on the back surface of the substrate.
제 1 도전성 타입의 기판은 P형 또는 N형에서 선택된다. 제 2 도전성 타입의 에미터층은 기판과 반대 도전형을 가지는 것으로 선택된다. P+층의 형성을 위해서는 3족 원소가 불순물로 도핑되고, N+층의 형성을 위해서는 5족 원소가 불순물로 도핑된다. 예를 들어, P+층 형성을 위해 B, Ga, In이 도핑되고, N+층 형성을 위해 P, As, Sb가 도핑될 수 있다. 상기 기판 및 에미터층 사이 계면에 P-N접합이 형성되고, 이는 태양광을 받아 광기전력효과에 의해 전류를 발생시키는 부분이다. 광기전력효과에 의해 발생된 전자와 정공은 각각 P층 및 N층으로 끌어 당겨져 각각 기판 하부 및 에미터층 상부와 접합된 전극으로 이동하며, 전극에 부하를 걸어 여기에서 발생한 전기를 이용할 수 있다.The substrate of the first conductivity type is selected from P-type or N-type. The emitter layer of the second conductivity type is selected to have the opposite conductivity type to the substrate. For the formation of the P + layer, a group III element is doped as an impurity and a group 5 element is doped as an impurity for the formation of an N + layer. For example, B, Ga, In may be doped to form a P + layer, and P, As, and Sb may be doped to form an N + layer. A P-N junction is formed at the interface between the substrate and the emitter layer, which is a portion that receives sunlight to generate a current by the photovoltaic effect. Electrons and holes generated by the photovoltaic effect are attracted to the P layer and the N layer, respectively, and are moved to the electrodes bonded to the lower part of the substrate and the upper part of the emitter layer, and electricity generated here can be used by applying a load to the electrodes.
반사방지막은 태양전지 전면으로 입사되는 태양광의 반사율을 감소시킨다. 태양광의 반사율이 감소되면 P-N접합까지 도달하는 광량이 증대되어 태양전지의 단락전류가 증가되고, 태양전지의 변환효율이 향상된다.The antireflection film reduces the reflectance of sunlight incident on the front surface of the solar cell. When the reflectance of solar light is reduced, the amount of light reaching the P-N junction is increased, short circuit current of the solar cell is increased, and conversion efficiency of the solar cell is improved.
반사방지막은 예를 들면 실리콘 질화막, 수소를 포함한 실리콘 질화막, 실리콘 산화막, 실리콘 산화질화막에서 선택된 어느 하나의 단일막 또는 2개 이상이 조합된 다중막 구조를 가질 수 있으나, 이에 한정되는 것은 아니다.The antireflection film may have any one single film selected from, for example, a silicon nitride film, a silicon nitride film including hydrogen, a silicon oxide film, and a silicon oxynitride film, or a multi-film structure formed by combining two or more films.
전면 전극과 후면 전극은 공지된 여러 가지 기술에 의해 제조 가능하지만, 바람직하게는 스크린 인쇄법에 의해 형성된다. 전면 전극은 본 발명의 은 페이스트 조성물을 이용하여 전면 전극 형성 지점에 스크린 인쇄한 후 열처리를 수행 하여 형성한다. 열처리가 수행되면 펀치 스루 현상에 의해 전면 전극이 반사방지막을 뚫고 에미터층과 접촉된다.The front electrode and the rear electrode can be manufactured by various known techniques, but are preferably formed by screen printing. The front electrode is formed by screen printing at the front electrode formation point using the silver paste composition of the present invention and then performing heat treatment. When the heat treatment is performed, the front electrode contacts the emitter layer through the anti-reflection film due to the punch through phenomenon.
후면 전극은 도전성 금속으로 알루미늄을 포함하는 페이스트 조성물을 기판 배면에 인쇄한 후 열처리를 수행하여 형성한다. 후면 전극 열처리시에는 알루미늄이 기판 배면을 통해 확산됨으로써 후면 전극과 기판 경계면에 후면 전계층이 형성될 수 있다. 후면 전계층이 형성되면 캐리어가 기판 배면으로 이동하여 재결합되는 것을 방지할 수 있어 태양전지의 변환효율이 향상된다.
The back electrode is formed by printing a paste composition containing aluminum as a conductive metal on the back surface of the substrate and then performing heat treatment. During the heat treatment of the rear electrode, aluminum may diffuse through the backside of the substrate to form a backside layer at the backside electrode and substrate interface. When the rear whole layer is formed, it is possible to prevent carriers from moving to the rear surface of the substrate and recombine, thereby improving the conversion efficiency of the solar cell.
이하, 본 발명을 구체적인 실시예에서 상세히 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail with reference to specific examples. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
[실시예 1 내지 11] 글래스 프릿의 제조[Examples 1 to 11] Preparation of glass frit
하기 표 1에 기재된 성분들을 표시된 비율(중량%)로 혼합한 다음, 1100℃에서 30분동안 용융시킨 후 순수(H2O)로 Quenching하여 급냉시켰다. 급냉된 유리 용융물은 Ball-mill 분쇄기로 분쇄하여, 1~3 ㎛의 평균입경을 갖는 글래스 프릿을 제조하였다. To a mixture in a ratio (% by weight) of the components shown in Table 1, and then, it was quenched by Quenching with pure water (H 2 O) was melted at 1100 ℃ for 30 minutes. The quenched glass melt was pulverized with a ball-mill grinder to prepare glass frit having an average particle size of 1 to 3 mu m.
하기 표 1에 각 실시예에 해당하는 글래스 프릿의 성분 및 함량을 나타내었다.Table 1 below shows the contents and contents of glass frit corresponding to each example.
[비교예 1 내지 2] 글래스 프릿의 제조[Comparative Examples 1 and 2] Preparation of glass frit
실시예 1 내지 11에서 하기 표 2에 기재된 성분과 함량을 사용한 것을 제외하고는 실시예 1 내지 11과 동일한 방법으로 실시하여 글래스 프릿을 제조하였다.Glass frit was prepared in the same manner as in Examples 1 to 11, except that the components and contents described in Table 2 were used in Examples 1 to 11.
[실시예 12 내지 22 및 비교예 3 내지 4] 은 페이스트 조성물의 제조[Examples 12 to 22 and Comparative Examples 3 to 4] Silver paste
상기에서 실시예 1 내지 11 및 비교예 1 내지 2에서 제조된 글래스 프릿을 사용하여 은 페이스트 조성물을 각각 제조하였다.Silver paste compositions prepared in Examples 1 to 11 and Comparative Examples 1 and 2 were used to prepare silver paste compositions, respectively.
은 분말은 평균입경 기준으로 3종이 선택되었으며, 0.3um 2wt%, 1.6um 43.5wt%, 2.2um 43.5wt% 조합으로 사용하였다. 글래스 프릿은 표1의 실시예 1 내지 11 및 비교예 1 내지 2의 조성을 각 2wt% 사용하였다. 유기 바인더로는 셀룰로오스 에스테르(EASTMAN사 CAB-382-20)와 에틸 셀룰로오스 수지(AQUALON사 ECN-50)를 각 1wt%로 사용하였으며, 유기 용제로는 TXIB(Trimethyl Pentanyl Diisobutylate) 2.0wt% 디베이직 에스테르(Dibasic ester, 제조사)3.0wt%(TCI사 Dimethyl adipate /dimethyl glutarate/ dimethyl succinate 혼합물) BC(BUTYL CARBITOL) 1.0wt%를 사용하였으며, 첨가제로는 요변성 조정제(ELEMENTIS사 THIXATROL MAX) 0.5wt%와 분산제(LUBRISOL사 SOLSPERSE) 0.5wt%를 첨가하여 은페이스트 조성물을 제조하였다.
Three kinds of silver powders were selected on the basis of the average particle size, and 0.3um 2wt%, 1.6um 43.5wt%, and 2.2um 43.5wt% were used in combination. Glass frit used the compositions of Examples 1 to 11 and Comparative Examples 1 and 2 in Table 1, each of 2 wt%. Cellulose ester (CAB-382-20) and ethyl cellulose resin (ECN-50, AQUALON) were used as the organic binder in an amount of 1 wt%, and as an organic solvent, TXIB (Trimethyl Pentanyl Diisobutylate) 2.0 wt% 1.0 wt% of BC (BUTYL CARBITOL), 3.0 wt% of a dibasic ester (manufacturer), 0.5 wt% of a thixotropic agent (ELEMENTIS Co., Ltd. THIXATROL MAX) And 0.5 wt% of a dispersant (SOLSPERSE, manufactured by LUBRISOL) was added to prepare a silver paste composition.
[실시예 23 내지 33 및 비교예 5 내지 6]태양전지의 제조[Examples 23 to 33 and Comparative Examples 5 to 6] Production of solar cell
태양전지의 제조는 156mm 단결정 실리콘 웨이퍼를 이용하여 관상로(tube furnace)에서 810℃로 POCl3을 사용하는 확산 공정을 통해 인(P)을 도핑하여 100Ω/sq 시트 저항을 가지는 에미터층을 형성하고, 상기 에미터층 상에 화학기상증착법(PECVD 방법)으로 전구체 SiH4와 NH3를 사용하여 실리콘 질화막을 증착하여 70nm두께로 형성하여 반사방지막을 형성하였다. The fabrication of the solar cell was performed using a 156 mm single crystal silicon wafer by doping phosphorous (P) through a diffusion process using POCl 3 at 810 ° C in a tube furnace to form an emitter layer having a sheet resistance of 100 Ω / sq , A silicon nitride film was deposited on the emitter layer by chemical vapor deposition (PECVD) using precursors SiH 4 and NH 3 to form a 70 nm thick anti-reflective film.
3um 크기의 알루미늄 분말과 및 무연 글래스를 유기바인더로는 에틸셀룰로오스(DOW사 STD-10)과 용제로는 테르리네올(TERPINEOL)을 사용하였다. 상기 알루미늄 분말(JINHAO사) 75wt%와 무연 글래스 분말로 2wt%를 유기바인더 23wt%에 혼합하여 2000rpm 의 교반속도에서 4시간 동안 분산시켜서 알루미늄 페이스트를 제조하였다. 알루미늄 페이스트를 이용하여 후면에 스크린 프린팅법으로 30um두께로 도포한 후 250℃의 건조로에서 60초간 건조하였다. 전면전극은 상기 본 발명의 실시예 12 내지 22 및 비교예 3 내지 4에서 제조된 은 페이스트 조성물을 이용하여 스크린 프린팅법으로 20um 두께로 도포하고 이후 200℃의 건조로에서 60초간 건조하였다. Alumina powder and lead-free glass having a size of 3 μm were used. Ethyl cellulose (DOW company STD-10) was used as an organic binder and TERPINEOL was used as a solvent. 75 wt% of aluminum powder (JINHAO) and 2 wt% of lead-free glass powder were mixed in 23 wt% of organic binder and dispersed at a stirring speed of 2000 rpm for 4 hours to prepare an aluminum paste. The aluminum paste was applied to the backside by screen printing method to a thickness of 30 μm and then dried in an oven at 250 ° C. for 60 seconds. The front electrode was applied by screen printing using a silver paste composition prepared in Examples 12 to 22 and Comparative Examples 3 to 4 to a thickness of 20 μm, and then dried in a drying furnace at 200 ° C. for 60 seconds.
인쇄가 완료된 태양전지는 820℃의 벨트 소성로에서 1분간 소성과정을 진행하여 태양전지를 제작하였다.The printed solar cell was fired in a belt firing furnace at 820 ° C for 1 minute to produce a solar cell.
<광변환 효율 측정>≪ Measurement of light conversion efficiency &
수득한 태양전지의 전기적 성능은 Oriel 사의 광원을 적용한 cell simulator를 이용하여 측정하였다. 태양전지의 성능은 1.0 태양 조건하에서 측정되었으며, 측정값을 하기 표 3의 광변환 효율(%)로 나타내었다.The electrical performance of the obtained solar cell was measured using a cell simulator using Oriel 's light source. The performance of the solar cell was measured under 1.0 solar conditions, and the measured values are shown in Table 3 in terms of the photo-conversion efficiency (%).
Claims (9)
(b) Bi2O3, TeO2, V2O5, ZnO, SiO2, Li2O 및 B2O3로 이루어지는 무연 글래스 프릿 및
(c) 유기 비히클을 포함하는 태양전지 전면전극용 은 페이스트 조성물.(a)
(b) lead-free glass frit consisting of Bi 2 O 3 , TeO 2 , V 2 O 5 , ZnO, SiO 2 , Li 2 O and B 2 O 3 and
(c) A silver paste composition for a solar cell front electrode comprising an organic vehicle.
상기 글래스 프릿은 Bi2O3 40 내지 80wt%, TeO2 1 내지 30wt%, V2O5 1 내지 30wt%, ZnO 0.1 내지 10wt%, SiO2 0.1 내지 15wt%, Li2O 0.1 내지 10wt%, B2O3 0.1 내지 10wt%로 포함되는 태양전지 전면전극용 은 페이스트 조성물.The method according to claim 1,
The glass frit is Bi 2 O 3 40 to 80wt%, TeO 2 1 to 30wt%, V 2 O 5 1 to 30wt%, ZnO 0.1 to 10wt%, SiO 2 0.1 to 15wt%, Li 2 O 0.1 to 10wt%, 0.1 to 10 wt% of B 2 O 3 .
상기 글래스 프릿은 유리 전이온도가 420℃ 이하이고, 녹는점이 550℃이하인 것을 특징으로 하는 태양전지 전면전극용 은 페이스트 조성물.The method according to claim 1,
Wherein the glass frit has a glass transition temperature of 420 DEG C or less and a melting point of 550 DEG C or less.
상기 글래스 프릿은 은 페이스트 조성물에 대하여 0.1 내지 15wt%로 포함되는 태양전지 전면전극용 은 페이스트 조성물.The method according to claim 1,
Wherein the glass frit is contained in an amount of 0.1 to 15 wt% based on the silver paste composition.
상기 유기 비히클은 TXIB(Trimethyl Pentanyl Diisobutylate), 디베이직 에스테르(Dibasic ester), BC(BUTYL CARBITOL), 부틸카비톨아세테이트, 부틸카비톨, 부틸셀루솔브, 부틸셀루솔브아세테이트, 프로필렌 글리콜 모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르프로피오네이트, 에틸에테르프로피오네이트, 테르피네올(terpineol), 프로필렌글리콜모노메틸에테르아세테이트, 디메틸아미노포름알데히드, 메틸에틸케톤, 감마 부티로락톤, 에틸락테이트 및 텍사놀(Texanol) 중에서 선택된 하나 이상의 용매 중에 셀룰로스계 수지, 아크릴계 수지 및 폴리비닐계 수지 중에서 선택된 하나 이상의 수지를 첨가한 것인 태양전지 전면전극용 은 페이스트 조성물.The method according to claim 1,
The organic vehicle may be selected from the group consisting of TXIB (Trimethyl Pentanyl Diisobutylate), Dibasic ester, BC (BUTYL CARBITOL), butyl carbitol acetate, butyl carbitol, butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether, Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, ethyl ether propionate, terpineol, propylene glycol monomethyl ether acetate, dimethylamino formaldehyde, methyl ethyl ketone, gamma butyrolactone, ethyl Wherein at least one resin selected from the group consisting of a cellulose resin, an acrylic resin and a polyvinyl resin is added to at least one solvent selected from lactate and Texanol.
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| CN201580076963.2A CN107258002B (en) | 2015-02-27 | 2015-06-11 | Silver paste composition, front electrode for solar cell formed using same, and solar cell using same |
| PCT/KR2015/005870 WO2016137059A1 (en) | 2015-02-27 | 2015-06-11 | Silver paste composition, front electrode for solar cell formed using it, and solar cell employing it |
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