KR20150057453A - Aluminium paste composition and solar cell device using the same - Google Patents
Aluminium paste composition and solar cell device using the same Download PDFInfo
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- KR20150057453A KR20150057453A KR1020130140842A KR20130140842A KR20150057453A KR 20150057453 A KR20150057453 A KR 20150057453A KR 1020130140842 A KR1020130140842 A KR 1020130140842A KR 20130140842 A KR20130140842 A KR 20130140842A KR 20150057453 A KR20150057453 A KR 20150057453A
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- South Korea
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- weight
- paste composition
- solar cell
- glass frit
- aluminum paste
- Prior art date
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 53
- 239000004411 aluminium Substances 0.000 title 1
- 239000011521 glass Substances 0.000 claims abstract description 46
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 11
- -1 polyethylene terephthalates Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000005033 polyvinylidene chloride Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 241000270666 Testudines Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 238000007650 screen-printing Methods 0.000 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 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 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
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 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
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- 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
-
- 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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
- H01B1/023—Alloys based on aluminium
-
- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- 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
- H01L31/0248—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
-
- 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
-
- 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
Description
본 발명은 알루미늄 페이스트 조성물 및 이를 이용한 태양전지 소자에 관한 것이다.
The present invention relates to an aluminum paste composition and a solar cell element using the same.
최근 들어 급속하게 보급되고 있는 태양전지는 차세대 에너지원으로서 클린 에너지인 태양 에너지를 직접 전기로 변환하는 전자 소자이다.Solar cells, which are rapidly spreading in recent years, are next-generation energy sources, and are electronic devices that convert solar energy, which is clean energy, directly to electricity.
태양전지 소자는, 도 1에 나타낸 바와 같이, 실리콘 웨이퍼 기판(10)의 수광면측에 N+층(20), 반사방지막(30)과 전면전극(40)이 형성되어 있고, 기판(10)의 반대면측에 P+층(50)과 후면전극(60)이 형성된 구조를 갖는다. 이러한 구조의 태양전지 소자에 태양광을 비추면 내부에서 전자(-)와 정공(+)이 발생하고, 발생된 전자(-)는 N+층(20)으로 정공(+)은 P+층(50)으로 각각 이동하게 된다. 이 현상에 의해 P+층(50)과 N+층(20) 사이에 전위차가 발생하며, 이때 부하를 연결하면 전류가 발생하게 되는 원리로 태양 에너지가 전기 에너지로 변환된다.1, an N +
이 중 후면전극(60)은 알루미늄 페이스트 조성물을 스크린 인쇄 등에 의해 도포하고 건조한 후 소성함으로써 형성되는데, 소성 시 알루미늄이 실리콘 웨이퍼 기판(10)의 내부로 확산됨으로써 후면전극(60)과 기판(10) 사이에 Al-Si 합금층이 형성됨과 동시에 알루미늄 원자의 확산에 의한 P+층(50)이 형성된다. 이러한 P+층(50)은 전자의 재결합을 방지하고 생성 캐리어의 수집 효율을 향상시키는 후면전계(back surface field, BSF)의 작용을 할 뿐만 아니라 태양광의 장파장광을 반사하는 반사판의 역할도 한다.The
이러한 후면전극(60)을 형성하기 위한 알루미늄 페이스트 조성물은 알루미늄 분말, 유리 프릿 및 유기 비히클(vehicle)을 포함하여 구성된다. 이 중 유리 프릿은 실리콘 웨이퍼 기판(10)과의 결합을 더욱 강화시키기 위한 성분으로서 통상 주성분으로 PbO-B2O3-SiO2계, PbO-B2O3-Al2O3계, PbO-B2O3-ZnO계 산화물을 포함하는 것이 주로 사용되었다.The aluminum paste composition for forming such a
최근에는 환경 문제로 인해 PbO 성분을 함유하지 않으면서도 상기 PbO계 산화물과 유사한 특성을 갖는 Bi2O3계 산화물, 예컨대 Bi2O3-B2O3-SiO2계, Bi2O3-B2O3-ZnO계 산화물을 포함하는 것이 제안되었다. 한국등록특허 제0890866호에는 SiO2 0.5-35중량%, Al2O3 0-5중량%, B2O3 1-15중량%, ZnO 0-15중량% 및 Bi2O3 55-90중량%를 포함하는 유리 프릿이 개시되어 있다. 그러나, Bi2O3 성분이 함유된 유리 프릿은 알루미늄층의 알루미늄 분말 표면의 산화막을 열에칭시켜 수분과 반응성을 증가시키며, 이로 인해 태양전지 소자 자체의 내구성이 저하되는 단점이 있다.
Recently, Bi 2 O 3 -based oxides such as Bi 2 O 3 -B 2 O 3 -SiO 2 -based, Bi 2 O 3 -B 2 O 3 -ZnO-based oxide. Korean Patent No. 0890866 discloses a method of manufacturing a honeycomb structure, which comprises 0.5-35 wt% of SiO 2 , 0-5 wt% of Al 2 O 3 , 1-15 wt% of B 2 O 3 , 0-15 wt% of ZnO and 55-90 wt% of Bi 2 O 3 % ≪ / RTI > However, the glass frit containing the Bi 2 O 3 component is disadvantageous in that the oxide film on the aluminum powder surface of the aluminum layer is thermally etched to increase moisture and reactivity, thereby deteriorating the durability of the solar cell element itself.
본 발명은 친환경적인 동시에 내수성을 개선한 알루미늄 페이스트 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide an aluminum paste composition which is environmentally friendly and improved in water resistance.
본 발명은 직렬 저항 상승을 억제할 수 있는 알루미늄 페이스트 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an aluminum paste composition capable of suppressing an increase in series resistance.
또한, 본 발명은 상기 알루미늄 페이스트 조성물로부터 형성된 전극을 제공하는 것을 다른 목적으로 한다.It is another object of the present invention to provide an electrode formed from the aluminum paste composition.
또한, 본 발명은 상기 전극이 구비된 태양전지 소자를 제공하는 것을 또 다른 목적으로 한다.
It is another object of the present invention to provide a solar cell element having the electrode.
1. ZnF2를 포함하는 무연계 유리 프릿; 알루미늄 분말; 및 유기 비히클을 포함하는 알루미늄 페이스트 조성물.1. Non-bonded glass frit containing ZnF 2 ; Aluminum powder; And an organic vehicle.
2. 위 1에 있어서, 상기 ZnF2는 무연계 유리 프릿 총 중량에 대하여 0.1 내지 10중량%로 포함되는 알루미늄 페이스트 조성물.2. The aluminum paste composition according to 1 above, wherein the ZnF 2 is contained in an amount of 0.1 to 10% by weight based on the total weight of the non-bonded glass frit.
3. 위 1에 있어서, 상기 무연계 유리 프릿은 Bi2O3-Al2O3-B2O3-SiO2-ZnF2계 유리 프릿인 알루미늄 페이스트 조성물.3. The aluminum paste composition of claim 1, wherein the non-bonded glass frit is a Bi 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 -ZnF 2 glass frit.
4. 위 3에 있어서, 상기 무연계 유리 프릿은 Bi2O3 20 내지 40중량%, Al2O3 5 내지 20중량%, B2O3 10 내지 35중량%, SiO2 10 내지 20중량% 및 ZnF2 0.1 내지 10중량%를 포함하는 알루미늄 페이스트 조성물.4. In the above 3, wherein the non-linked glass frit is Bi 2 O 3 20 to 40% by weight, Al 2 O 3 5 to 20 wt%, B 2 O 3 10 to 35% by weight,
5. 위 1에 있어서, 상기 무연계 유리 프릿은 조성물 총 중량에 대하여 0.01 내지 10중량%로 포함되는 알루미늄 페이스트 조성물.5. The aluminum paste composition according to item 1 above, wherein the non-bonded glass frit is contained in an amount of 0.01 to 10% by weight based on the total weight of the composition.
6. 위 1에 있어서, 상기 알루미늄 분말은 조성물 총 중량에 대하여 60 내지 78중량%로 포함되는 알루미늄 페이스트 조성물.6. The aluminum paste composition according to item 1 above, wherein the aluminum powder is contained in an amount of 60 to 78% by weight based on the total weight of the composition.
7. 위 1에 있어서, 상기 유기 비히클은 조성물 총 중량에 대하여 20 내지 35중량%로 포함되는 알루미늄 페이스트 조성물.7. The aluminum paste composition according to 1 above, wherein the organic vehicle is contained in an amount of 20 to 35% by weight based on the total weight of the composition.
8. 위 1에 있어서, 상기 유기 비히클은 고분자 수지 1 내지 25중량%와 유기 용매 75 내지 99중량%가 혼합된 것인 알루미늄 페이스트 조성물.8. The aluminum paste composition according to 1 above, wherein the organic vehicle is a mixture of 1 to 25% by weight of a polymer resin and 75 to 99% by weight of an organic solvent.
9. 위 1 내지 8 중 어느 한 항의 알루미늄 페이스트 조성물로 형성된 전극.9. An electrode formed from the aluminum paste composition of any one of claims 1 to 8.
10. 위 9의 전극이 구비된 태양전지 소자.
10. A solar cell device comprising the above electrode.
본 발명에 따른 알루미늄 페이스트 조성물은 친환경적이며, 내수성이 개선되어 태양전지 소자 자체의 내구성을 증진시킬 수 있다.The aluminum paste composition according to the present invention is eco-friendly, and water resistance is improved, so that the durability of the solar cell element itself can be improved.
또한, 본 발명의 알루미늄 페이스트 조성물은 직렬저항 상승을 억제한다.Further, the aluminum paste composition of the present invention suppresses an increase in series resistance.
또한, 본 발명의 알루미늄 페이스트 조성물은 실리콘 웨이퍼 기판의 휨 현상을 억제할 수 있으며, 태양전지 소자의 최대출력전류(Isc)를 높이고 효율도 향상시킬 수 있다.
In addition, the aluminum paste composition of the present invention can suppress the warpage of the silicon wafer substrate, increase the maximum output current Isc of the solar cell element, and improve the efficiency.
도 1은 태양전지 소자의 단면도를 개략적으로 나타낸 도면이다.
도 2는 본 발명에 따른 실시예 1의 무연계 유리 프릿으로 제조한 태양전지 후면 전극을 촬영한 사진이다.
도 3은 ZnF2를 포함하지 않는 비교예 1의 무연계 유리 프릿으로 제조한 태양전지 후면 전극을 촬영한 사진이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of a solar cell element. FIG.
2 is a photograph of a rear electrode of a solar cell manufactured from the non-bonded glass frit of Example 1 according to the present invention.
3 is a photograph of a back electrode of a solar cell manufactured from the non-bonded glass frit of Comparative Example 1 which does not contain ZnF 2 .
본 발명은 ZnF2를 포함하는 무연계 유리 프릿; 알루미늄 분말; 및 유기 비히클을 포함함으로써, 친환경적이며, 내수성이 개선되어 태양전지 소자 자체의 내구성이 증진되며, 직렬 저항 상승을 억제하고 또한 실리콘 웨이퍼 기판의 휨 현상을 억제할 수 있으며, 태양전지 소자의 최대출력전류(Isc)를 높이고 효율도 개선할 수 있는 알루미늄 페이스트 조성물 및 이를 이용한 태양전지 소자에 관한 것이다.
The present invention relates to a non-bonded glass frit comprising ZnF 2 ; Aluminum powder; And an organic vehicle, it is eco-friendly and has improved water resistance, thereby enhancing the durability of the solar cell element itself, suppressing the increase in series resistance and suppressing the warping of the silicon wafer substrate, (Isc) and improve the efficiency, and a solar cell device using the same.
이하, 본 발명을 보다 상세하게 설명하도록 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 알루미늄 페이스트 조성물은 ZnF2를 함유하는 무연계 유리 프릿; 알루미늄 분말; 및 유기 비히클을 포함한다.The aluminum paste composition of the present invention comprises a non-bonded glass frit containing ZnF 2 ; Aluminum powder; And organic vehicles.
종래에 사용된 PbO계(유연계) 유리 프릿은 융점 제어가 용이하고 열팽창계수가 낮은 장점이 있으나, 근래에는 환경 문제로 인해 사용이 제한되고 있다.Conventionally used PbO-based (glass-based) glass frit has advantages of easy control of melting point and low coefficient of thermal expansion, but its use has been limited in recent years due to environmental problems.
이에 대하여 대안으로 제시된 Bi2O3계 무연계 유리 프릿은 친환경적이며 PbO계 유리 프릿과 유사한 특성을 가지나, 알루미늄 산화막을 열에칭하는 반응성이 커서 알루미늄 전극의 내수성이 저하되어 태양전지 소자의 내구성이 떨어질 수 있고, 후면 전극에 소위 터틀 쉘(도 3 참조)이라는 계면이 발생하여 직렬저항(시리즈저항)이 증가하게 되는 문제가 있다.As an alternative, the Bi 2 O 3 -based glass frit, which is proposed as an alternative, is environmentally friendly and has characteristics similar to those of PbO-based glass frit. However, since the reactivity of the aluminum oxide film to heat is high, the water resistance of the aluminum electrode is deteriorated, And there is a problem that an interface called a turtle shell (refer to FIG. 3) is generated in the rear electrode and the series resistance (series resistance) is increased.
이러한 문제를 해결하기 위하여 ZnO계 무연 유기 프릿이 사용되어 왔으나, ZnO계 무연계 유리 프릿은 Bi2O3계나 PbO계에 비해 비중이 낮고, 열팽창 계수가 커서 태양전지 제조 후 웨이퍼가 휘어 불량이 발생하는 단점이 있으며, 저항 상승 문제도 여전히 존재했다.In order to solve this problem, ZnO-based lead-free organic frit has been used. However, ZnO-based leadless glass frit has a lower specific gravity than Bi 2 O 3 or PbO and has a large thermal expansion coefficient. And there was still a problem of resistance increase.
이에, 본 발명에서는 무연계 유리 프릿에 ZnF2를 첨가하여 내수성 및 웨이퍼 휨 현상을 동시에 개선하고 후면 전극의 터틀 쉘 발생을 방지하여 직렬저항 상승을 억제한다. 이러한 효과는 Bi2O3계 무연계 유리 프릿에 ZnF2를 첨가하는 경우 보다 바람직할 수 있다.Accordingly, in the present invention, ZnF 2 is added to the non-bonded glass frit to simultaneously improve the water resistance and the wafer warping phenomenon, and to prevent the turtle shell from occurring in the rear electrode, thereby suppressing an increase in series resistance. Such an effect may be preferable to the case where ZnF 2 is added to a Bi 2 O 3 -based glass-free glass frit.
본 발명의 무연계 유리 프릿에 포함되는 ZnF2는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으며, 예를 들면 무연계 유리 프릿 총 중량에 대하여 0.1 내지 10중량%로 포함될 수 있다. ZnF2의 함량이 상기 범위에 해당하는 경우 직렬저항 상승 억제, 내수성 개선 및 웨이퍼 기판 휨 현상 억제 효과를 극대화할 수 있다.The content of the ZnF 2 contained in the non-bonded glass frit of the present invention is not particularly limited within a range that can function, and may be, for example, 0.1 to 10% by weight based on the total weight of the non-bonded glass frit . When the content of ZnF 2 falls within the above range, it is possible to maximize the suppression of the series resistance increase, the water resistance improvement, and the effect of suppressing the wafer substrate warping phenomenon.
본 발명에 따른 무연계 유리 프릿은 Bi2O3-Al2O3-B2O3-SiO2-ZnF2계 산화물인 것이 바람직하고, 보다 바람직하게는 Bi2O3 20 내지 40중량%, Al2O3 5 내지 20중량%, B2O3 10 내지 35중량%, SiO2 10 내지 20중량% 및 ZnF2 0.1 내지 10중량%를 포함하는 것이 좋다. 무연계 유리 프릿의 조성이 상기 범위에 해당하는 경우 직렬저항 상승 억제, 내수성 개선 및 웨이퍼 기판 휨 현상 억제 효과를 극대화할 수 있다.The non-bonded glass frit according to the present invention is preferably Bi 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 -ZnF 2 oxide, more preferably 20 to 40 wt% of Bi 2 O 3 , 5 to 20% by weight of Al 2 O 3 , 10 to 35% by weight of B 2 O 3 , 10 to 20% by weight of SiO 2 and 0.1 to 10% by weight of ZnF 2 . When the composition of the non-bonded glass frit falls within the above range, it is possible to maximize the suppression of the series resistance increase, the water resistance improvement, and the wafer substrate warpage inhibiting effect.
선택적으로, 무연계 유리 프릿은 K2O, Na2O, Li2O 등의 알칼리금속 산화물 0 내지 15중량%; MgO, CaO, SrO, BaO 등의 알칼리토금속 산화물 0 내지 15중량%; ZnO 0 내지 15중량%; TiO2 0 내지 10중량%; CuO 0 내지 10중량%; NiO 0 내지 10중량%; V2O5 0 내지 10중량% 등을 더 포함할 수 있다.Optionally, the non-consolidated glass frit may comprise from 0 to 15% by weight of an alkali metal oxide such as K 2 O, Na 2 O, Li 2 O, or the like; 0 to 15% by weight of an alkaline earth metal oxide such as MgO, CaO, SrO, or BaO; 0 to 15% by weight of ZnO; TiO 2 0 to 10% by weight; From 0 to 10% by weight of CuO; 0 to 10% by weight NiO; V 2 O 5 0 to 10 wt%, and the like.
무연계 유리 프릿은 연화점이 300 내지 600℃인 것이 바람직하다. 600℃를 초과하는 경우에는 유리 프릿이 용융되어 은 배선 층과 실리콘 웨이퍼 층 사이에서 밀착성을 부여해야 되는데 소성과정에서 유리 프릿이 충분히 용융되지 않아 밀착성이 저하될 수 있다.The non-bonded glass frit preferably has a softening point of 300 to 600 ° C. If the temperature is higher than 600 ° C, the glass frit is melted to provide adhesion between the silver wiring layer and the silicon wafer layer. However, the glass frit may not sufficiently melt during the firing process, and the adhesion may be deteriorated.
무연계 유리 프릿은 알루미늄 페이스트 조성물 총 함량 100중량%에 대하여 0.01 내지 10중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 0.05 내지 7중량%, 가장 바람직하게는 0.1 내지 5중량%인 것이 좋다. 함량이 0.01중량% 미만인 경우 소성 후 알루미늄 후면전극과 실리콘 웨이퍼 기재의 밀착력이 떨어질 수 있으며, 10중량% 초과인 경우 저항이 높아져 태양전지 소자의 효율이 저하될 수 있다.The non-bonded glass frit is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and most preferably 0.1 to 5% by weight based on 100% by weight of the total amount of the aluminum paste composition. If the content is less than 0.01% by weight, the adhesion between the aluminum back electrode and the silicon wafer substrate may deteriorate after firing, and if the content exceeds 10% by weight, the resistance may increase and the efficiency of the solar cell device may deteriorate.
알루미늄 분말은 후면전극을 형성하기 위한 페이스트 조성물의 주성분인 전도성 금속이다.The aluminum powder is a conductive metal which is the main component of the paste composition for forming the back electrode.
알루미늄 분말은 평균 입자 크기가 특별히 한정되지 않으며, 예컨대 1 내지 10㎛인 것일 수 있다.The average particle size of the aluminum powder is not particularly limited, and may be, for example, 1 to 10 mu m.
알루미늄 분말은 알루미늄 페이스트 조성물 총 함량 100중량% 중에 60 내지 78중량%로 포함되는 것이 바람직하다. 함량이 60중량% 미만인 경우 소성 후 인쇄된 알루미늄 후면전극의 두께가 얇아져 후면전계(BSF)가 충분히 형성되지 않고 효율이 저하될 수 있으며, 78중량% 초과인 경우 인쇄 두께가 너무 두꺼워져 실리콘 웨이퍼 기판의 휨을 초래할 수 있다.The aluminum powder is preferably contained in an amount of 60 to 78% by weight in 100% by weight of the total content of the aluminum paste composition. When the content is less than 60 wt%, the thickness of the aluminum back electrode printed after firing becomes thin, the back electric field (BSF) is not sufficiently formed and the efficiency may be lowered. When the content is more than 78 wt%, the printing thickness becomes too thick, Which may result in warpage.
유기 비히클은 알루미늄 페이스트 조성물에 인쇄에 적합한 점조도 및 유변학적 특성을 부여하기 위한 성분으로서, 유기 용매에 고분자 수지와 필요에 따라 각종 첨가제를 용해시킨 용액일 수 있다.The organic vehicle may be a solution for imparting viscoelasticity and rheological properties suitable for printing on an aluminum paste composition, and may be a solution in which a polymer resin and various additives are dissolved in an organic solvent.
유기 비히클은 유기 용매 75 내지 99중량%와 고분자 수지 1 내지 25중량%가 혼합된 것일 수 있으며, 여기에 첨가제 1 내지 10중량%가 더 혼합된 것일 수도 있다.The organic vehicle may be a mixture of 75 to 99% by weight of an organic solvent and 1 to 25% by weight of a polymer resin, and 1 to 10% by weight of an additive may be further mixed therewith.
유기 용매로는 공지된 것을 사용할 수 있으며, 인쇄 공정 중 페이스트 조성물의 건조를 방지하고 유동성을 조절할 수 있도록 끓는점이 150 내지 300℃인 용매를 사용할 수 있다. 구체적으로, 트리프로필렌글리콜메틸에테르, 트리프로필렌글리콜n-부틸에테르, 디프로필렌글리콜n-프로필에테르, 디프로필렌글리콜n-부틸에테르, 프로필렌글리콜페닐에테르, 디에틸렌글리콜에틸에테르, 디에틸렌글리콜n-부틸에테르, 디에틸렌글리콜헥실에테르, 에틸렌글리콜헥실에테르, 트리에틸렌글리콜메틸에테르, 트리에틸렌글리콜에틸에테르, 트리에틸렌글리콜n-부틸에테르, 에틸렌글리콜페닐에테르, 에틸렌글리콜, 테르피네올, 부틸카비톨, 부틸카비톨아세테이트, 2,2,4-트리메틸-1,3-펜탄디올모노이소부티레이트(texanol) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As the organic solvent, a known solvent may be used, and a solvent having a boiling point of 150 to 300 DEG C may be used so as to prevent drying of the paste composition in the printing process and to control fluidity. Specific examples thereof include tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, propylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol n- But are not limited to, ether, diethylene glycol hexyl ether, ethylene glycol hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-butyl ether, ethylene glycol phenyl ether, ethylene glycol, terpineol, butyl carbitol, Carbitol acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (texanol), etc. These may be used alone or in admixture of two or more.
유기 용매는 유기 비히클 총 함량 100중량%에 대하여 75 내지 99중량%로 포함되는 것이 바람직하다. 이 함량 범위에서는 페이스트 조성물에 최적의 유동성을 부여할 수 있다.The organic solvent is preferably contained in an amount of 75 to 99% by weight based on 100% by weight of the total amount of the organic vehicle. In this content range, an optimum fluidity can be imparted to the paste composition.
고분자 수지로는 공지된 것을 사용할 수 있으며, 예컨대 에틸셀룰로오스, 니트로셀룰로오스, 페놀, 아크릴, 로진, 폴리비닐알코올, 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐부티랄, 우레아, 자일렌, 알키드, 불포화 폴리에스테르, 폴리이미드, 퓨란, 우레탄, 이소시아네이트, 시아네이트, 폴리에틸렌, 폴리프로필렌, 폴리스티렌, 아크릴로니트릴-부타디엔-스티렌(ABS), 폴리메틸메타크릴레이트, 폴리염화비닐, 폴리염화비닐리덴, 폴리비닐아세테에트, 폴리아세탈, 폴리카보네이트, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리페닐렌옥사이드, 폴리술폰, 폴리이미드, 폴리에테르술폰, 폴리아릴레이트, 폴리에테르에테르케톤, 실리콘 등의 수지를 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As the polymer resin, those known can be used, and examples thereof include ethylcellulose, nitrocellulose, phenol, acrylic, rosin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyvinylbutyral, urea, xylene, alkyd, unsaturated Butadiene-styrene (ABS), polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene chloride, polyvinylidene chloride, polyvinylidene chloride, polyvinylidene chloride, A resin such as acetates, polyacetals, polycarbonates, polyethylene terephthalates, polybutylene terephthalates, polyphenylene oxides, polysulfones, polyimides, polyether sulfone, polyarylates, polyether ether ketones, . These may be used alone or in combination of two or more.
고분자 수지는 유기 비히클 총 함량 100중량%에 대하여 1 내지 25중량%, 바람직하게 5 내지 25중량%로 포함되는 것이 좋다. 함량이 1중량% 미만인 경우 페이스트 조성물의 인쇄성과 분산 안정성이 저하될 수 있고, 25중량% 초과인 경우 페이스트 조성물이 인쇄되지 않을 수 있다.The polymer resin is preferably contained in an amount of 1 to 25% by weight, preferably 5 to 25% by weight, based on 100% by weight of the total amount of the organic vehicle. If the content is less than 1% by weight, the printing property and dispersion stability of the paste composition may be deteriorated, and if more than 25% by weight, the paste composition may not be printed.
유기 비히클은 상기 성분들과 함께 첨가제로 분산제를 더 포함할 수 있다.The organic vehicle may further comprise a dispersant as an additive with the above components.
분산제로는 공지된 계면활성제를 사용할 수 있으며, 예컨대 알킬기의 탄소수가 6 내지 30인 폴리옥시에틸렌알킬에테르, 알킬기의 탄소수가 6 내지 30인 폴리옥시에틸렌알킬아릴에테르, 알킬기의 탄소수가 6 내지 30인 폴리옥시에틸렌-폴리옥시프로필렌 알킬에테르 등의 에테르계; 글리세린에스테르 부가형 폴리옥시에틸렌에테르, 소르비탄에스테르 부가형 폴리옥시에틸렌에테르, 소르비톨에스테르 부가형 폴리옥시에틸렌에테르 등의 에스테르에테르계; 폴리에틸렌글리콜지방산에스테르, 글리세린에스테르, 소르비탄에스테르, 프로필렌글리콜에스테르, 슈가에스테르, 알킬폴리글루코시드 등의 에스테르계; 지방산알카놀아미드, 폴리옥시에틸렌지방산아미드, 알킬기의 탄소수가 6 내지 30인 폴리옥시에틸렌알킬아민, 아민옥사이드 등의 질소함유계; 폴리비닐알코올, 폴리비닐피롤리돈, 폴리아크릴산, 폴리아크릴산-말레인산 공중합체, 폴리12-히드록시스테아린산 등의 고분자계 화합물 등을 들 수 있다. 또한, 시판되고 있는 제품으로서 하이퍼머(hypermer) KD(Uniqema), AKM 0531(일본유지㈜), KP(신에쯔 가가꾸 고교㈜), 폴리플로우(POLYFLOW)(교에이샤 가가꾸㈜), 에프톱(EFTOP)(토켐 프로덕츠사), 아사히가드(Asahi guard)(아사히 유리㈜), 서플론(Surflon)(아사히 유리㈜), 솔스퍼스(SOLSPERSE)(제네까㈜), EFKA(EFKA 케미칼스사), PB 821(아지노모또㈜), BYK-184, BYK-185, BYK-2160, Anti-Terra U(BYK사 제조) 등을 사용할 수도 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As the dispersing agent, known surfactants can be used. Examples thereof include polyoxyethylene alkyl ethers having 6 to 30 carbon atoms in the alkyl group, polyoxyethylene alkyl aryl ethers having 6 to 30 carbon atoms in the alkyl group, alkyl groups having 6 to 30 carbon atoms in the alkyl group Ether type such as polyoxyethylene-polyoxypropylene alkyl ether; Ester ethers such as glycerin ester addition type polyoxyethylene ether, sorbitan ester addition type polyoxyethylene ether and sorbitol ester addition type polyoxyethylene ether; Esters such as polyethylene glycol fatty acid esters, glycerin esters, sorbitan esters, propylene glycol esters, sugar esters and alkylpolyglucosides; Nitrogen-containing systems such as fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine having 6 to 30 carbon atoms in the alkyl group, and amine oxide; And polymeric compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylic acid-maleic acid copolymer, and poly 12-hydroxystearic acid. Also, commercially available products such as hypermer KD (Uniqema), AKM 0531 (Nippon Kayaku Co., Ltd.), KP (Shinetsugaku Kagaku Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.) Asahi Glass, Inc., Surflon (Asahi Glass Co., Ltd.), SOLSPERSE (Geneka Co., Ltd.), EFKA (EFKA Chemical Co., Ltd.) ), PB 821 (Ajinomoto Co., Ltd.), BYK-184, BYK-185, BYK-2160 and Anti-Terra U (manufactured by BYK). These may be used alone or in combination of two or more.
분산제는 유기 비히클 총 함량 100중량%에 대하여 1 내지 10중량%, 바람직하게 1 내지 5중량%로 포함되는 것이 좋다.The dispersing agent is preferably contained in an amount of 1 to 10% by weight, preferably 1 to 5% by weight based on 100% by weight of the total amount of the organic vehicle.
유기 비히클은 분산제 이외에도 요변성제, 습윤제, 산화방지제, 부식억제제, 소포제, 증점제, 분산제, 점착부여제, 커플링제, 대전방지제, 중합금지제, 침강방지제 등의 첨가제를 더 포함할 수 있다.The organic vehicle may further contain additives such as a thixotropic agent, a wetting agent, an antioxidant, a corrosion inhibitor, a defoaming agent, a thickener, a dispersant, a tackifier, a coupling agent, an antistatic agent, a polymerization inhibitor and an anti-
유기 비히클은 알루미늄 페이스트 조성물 총 함량 100중량%에 대하여 20 내지 35중량%로 포함되는 것이 바람직하다. 함량이 20중량% 미만인 경우 알루미늄 페이스트 조성물의 점도가 너무 높아져 유동성이 저하되고 인쇄성이 떨어질 수 있으며, 35중량% 초과인 경우 알루미늄 분말의 함유량이 상대적으로 적어져 충분한 페이스트층의 두께를 확보하기 어렵다.The organic vehicle is preferably contained in an amount of 20 to 35% by weight based on 100% by weight of the total amount of the aluminum paste composition. When the content is less than 20% by weight, the viscosity of the aluminum paste composition becomes too high to lower the fluidity and printability. When the content exceeds 35% by weight, the content of the aluminum powder is relatively small and it is difficult to secure a sufficient thickness of the paste layer .
상기한 바와 같은 성분을 포함하는 본 발명의 알루미늄 페이스트 조성물은 친환경적이며, 내수성이 개선되어 태양전지 소자 자체의 내구성이 증진되며, 후면전극의 터틀 쉘 발생을 억제하여 직렬 저항 상승을 억제하고 또한 실리콘 웨이퍼 기판의 휨 현상을 억제할 수 있으며, 태양전지 소자의 최대출력전류(Isc)를 높이고 효율도 개선할 수 있다.
The aluminum paste composition of the present invention including the above-described components is environmentally friendly and has improved water resistance, thereby enhancing the durability of the solar cell element itself, suppressing the turtle shell of the rear electrode, suppressing the increase in series resistance, It is possible to suppress the warping of the substrate, increase the maximum output current Isc of the solar cell element, and improve the efficiency.
또한, 본 발명은 상기 알루미늄 페이스트 조성물로부터 형성된 전극을 제공한다.The present invention also provides an electrode formed from the aluminum paste composition.
전극은 알루미늄 페이스트 조성물을 기재, 예컨대 은(Ag) 전면전극이 형성된 실리콘 웨이퍼 기판 상에 인쇄하고 건조 및 소성하는 공정을 통하여 형성된다. 인쇄방법은 특별히 한정되지 않으며, 예컨대 스크린 인쇄, 그라비아 인쇄, 오프셋 인쇄 등의 방법을 이용할 수 있다. 건조는 60 내지 300℃에서 수초 내지 수분 동안 수행되며, 소성은 600 내지 950℃에서 수초 동안 수행될 수 있다.The electrode is formed through a process in which the aluminum paste composition is printed on a substrate, for example, a silicon wafer substrate having a silver (Ag) front electrode formed thereon, and dried and baked. The printing method is not particularly limited, and for example, screen printing, gravure printing, offset printing, and the like can be used. Drying is performed at 60 to 300 ° C for several seconds to several minutes, and firing can be performed at 600 to 950 ° C for several seconds.
이와 같이 형성된 전극은 본 발명의 또 다른 구현예인 태양전지 소자의 후면전극으로 적용되면, 태양전지 소자의 내구성을 향상시키고 태양전지 소자의 최대출력전류(Isc)를 높이고 효율을 증가시킬 수 있다.
When the electrode thus formed is applied to the rear electrode of the solar cell element, which is another embodiment of the present invention, the durability of the solar cell element can be improved and the maximum output current Isc of the solar cell element can be increased and the efficiency can be increased.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
제조예Manufacturing example 1-5 1-5
하기 표 1에 나타낸 바와 같은 성분 및 함량으로 유리 프릿을 제조하였다.Glass frit was prepared with the components and contents shown in Table 1 below.
(10-7/℃)Coefficient of thermal expansion
(10 < -7 > / DEG C)
실시예Example 1 One
평균 입자 크기가 4-6㎛인 알루미늄 분말 65중량% 및 평균 입자 크기가 2-4㎛인 알루미늄 분말 9중량%의 혼합 분말 74중량%, 제조예 1의 유리 프릿 1.5중량%, 트리프로필렌글리콜메틸에테르에 에틸셀룰로오스 수지가 용해된 유기 비히클 24.5중량%를 첨가한 후 자전 및 공전을 동시에 수행하는 믹서를 이용하여 1,000rpm으로 3분 동안 교반하여 알루미늄 페이스트 조성물을 제조하였다.
65 wt% of an aluminum powder having an average particle size of 4-6 탆 and 74 wt% of a mixed powder of 9 wt% of an aluminum powder having an average particle size of 2-4 탆, 1.5 wt% of a glass frit of Preparation Example 1, 24.5% by weight of an organic vehicle in which an ethylcellulose resin was dissolved in ether was added, and the mixture was stirred at 1,000 rpm for 3 minutes using a mixer which simultaneously performs rotation and revolution to prepare an aluminum paste composition.
실시예Example 2 2
제조예 2의 유리 프릿을 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 알루미늄 페이스트 조성물을 제조하였다.
An aluminum paste composition was prepared in the same manner as in Example 1, except that the glass frit of Production Example 2 was included.
실시예Example 3 3
제조예 3의 유리 프릿을 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 알루미늄 페이스트 조성물을 제조하였다.
An aluminum paste composition was prepared in the same manner as in Example 1, except that the glass frit of Preparation Example 3 was included.
실시예Example 4 4
제조예 4의 유리 프릿을 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 알루미늄 페이스트 조성물을 제조하였다.
An aluminum paste composition was prepared in the same manner as in Example 1, except that the glass frit of Production Example 4 was included.
비교예Comparative Example 1 One
제조예 5의 유리 프릿을 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 알루미늄 페이스트 조성물을 제조하였다.
An aluminum paste composition was prepared in the same manner as in Example 1, except that the glass frit of Preparation Example 5 was included.
비교예Comparative Example 2 2
제조예 6의 유리 프릿을 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 알루미늄 페이스트 조성물을 제조하였다.
An aluminum paste composition was prepared in the same manner as in Example 1, except that the glass frit of Preparation Example 6 was included.
시험예Test Example
상기 실시예 및 비교예에서 제조된 알루미늄 페이스트 조성물을 사용하여 하기와 같이 태양전지 소자를 제조하였고, 그 물성을 하기 방법으로 측정하여 그 결과를 하기 표 2에 나타내었다.Using the aluminum paste composition prepared in Examples and Comparative Examples, a solar cell device was prepared as described below, and physical properties thereof were measured by the following methods. The results are shown in Table 2 below.
크기가 156㎜×156㎜이고 두께가 200㎛이며 텍스쳐링 공정에 의해 높이가 약 4-6㎛인 피라미드 구조가 형성된 단결정 실리콘 웨이퍼 기판의 후면에 은 페이스트 조성물로 버스 바(bus bar)를 인쇄하고 건조시켰다. 그 후 제조된 알루미늄 페이스트 조성물을 250메쉬(mesh)의 스크린 인쇄판을 이용하여 도포하고 건조시켰다. 이때, 도포량은 건조 전 1.5±0.1g이 되도록 하였다. 그 후 전면 SiNx측 상에 은 페이스트를 이용하여 핑거 라인(finger line)을 인쇄하고 건조시켰다. 위 과정을 거친 기판을 온도가 720-900℃인 적외선 연속 소성로에서 약 10초 동안 소성하였다. 소성 공정은 실리콘 웨이퍼 기판을 약 600℃의 번-아웃(burn-out) 구간과 800-950℃의 소성(firing) 구간을 포함하는 벨트 로(belt furnace) 내로 통과시키면서 전후면 동시 소성으로 수행하여, 페이스트 내 유기물을 태워 없앤 후 알루미늄을 용융시켜 전극이 형성되도록 하여 태양전지 소자를 제조하였다.A bus bar was printed with a silver paste composition on the back side of a single crystal silicon wafer substrate having a size of 156 mm x 156 mm and a thickness of 200 μm and a pyramid structure having a height of about 4-6 μm formed by a texturing process . The aluminum paste composition thus prepared was applied using a screen printing plate of 250 mesh and dried. At this time, the coating amount was adjusted to 1.5 ± 0.1 g before drying. Then, a finger line was printed and dried on the front SiNx side using a silver paste. The substrate thus processed was fired in an infrared continuous firing furnace having a temperature of 720-900 ° C for about 10 seconds. The firing process is performed by front and back co-firing while passing the silicon wafer substrate through a belt furnace including a burn-out zone at about 600 ° C and a firing zone at 800-950 ° C , Organic materials in the paste were burned off, and aluminum was melted to form an electrode, thereby manufacturing a solar cell device.
(1)직렬저항(1) series resistance
제조된 태양전지 소자의 직렬저항을 평가장치(SCM-1000, FitTech)를 이용하여 측정하였다.The series resistance of the manufactured solar cell device was measured using an evaluation device (SCM-1000, FitTech).
(2) 내수성(2) Water resistance
제조된 태양전지 소자를 80℃의 증류수가 채워진 항온조에 넣고 10분 동안 방치하였다. 항온조 내에서 형성된 알루미늄 전극과 수분의 반응에 의한 수소 기체(기포)의 발생 여부를 육안으로 관찰한 후 하기 기준에 의거하여 평가하였다.The manufactured solar cell element was placed in a thermostatic chamber filled with distilled water at 80 캜 and left for 10 minutes. Whether or not the hydrogen gas (bubbles) generated by the reaction of moisture with the aluminum electrode formed in the thermostatic chamber was visually observed was evaluated based on the following criteria.
<평가기준><Evaluation Criteria>
○: 기포 발생 없음(양호).○: No bubbles were generated (good).
×: 기포 발생 있음(불량).×: bubble occurred (poor).
(3) 휨(㎜)(3) Bending (mm)
제조된 태양전지 소자를 평평한 바닥에 놓고 네 모서리가 바닥과 일치되도록 한 후 중앙부의 들뜸 정도를 측정하였다. 통상, 휨이 1.50㎜ 이하이면 양호한 수준으로 간주한다.The manufactured solar cell device was placed on a flat surface, and four corners were made to coincide with the bottom. Generally, when the warp is 1.50 mm or less, it is considered to be a good level.
(4) 효율(%)(4) Efficiency (%)
제조된 태양전지 소자의 효율을 평가장치(SCM-1000, FitTech)를 이용하여 평가하였다.The efficiency of the manufactured solar cell device was evaluated using an evaluation device (SCM-1000, FitTech).
상기 표 2를 참고하면, 본 발명에 따른 실시예 1 및 3의 알루미늄 페이스트 조성물을 이용한 태양전지 소자는 친환경적인 동시에 수분과의 반응이 방지되어 내수성이 우수하여 태양전지 소자의 내구성을 향상시킬 수 있고 웨이퍼 기판의 휨 현상을 억제할 수 있으며 효율도 높은 것을 확인할 수 있었다.With reference to Table 2, the solar cell device using the aluminum paste composition of Examples 1 and 3 according to the present invention is eco-friendly and at the same time prevents the reaction with moisture and is excellent in water resistance to improve the durability of the solar cell element The warpage of the wafer substrate can be suppressed and the efficiency is high.
다만, ZnF2를 11중량% 함유한 Bi2O3계 유리 프릿을 포함한 실시예 4의 경우, 내수성 측면에서는 우수하였으나, 직렬저항, 휨 현상 억제 성능 및 효율 이 다소 저하됨을 확인하였다.However, Example 4 including Bi 2 O 3 glass frit containing 11% by weight of ZnF 2 was superior in terms of water resistance, but it was confirmed that the series resistance, the bending phenomenon inhibiting performance and the efficiency were somewhat lowered.
ZnF2 대신에 V2O5를 함유한 Bi2O3계 유리 프릿을 포함한 비교예 1의 경우는 직렬저항이 높아 효율이 떨어지고, 기포가 발생하여 내수성도 떨어졌다.In the case of Comparative Example 1 including Bi 2 O 3 glass frit containing V 2 O 5 instead of ZnF 2 , the efficiency was low due to the high series resistance, and bubbles were generated and the water resistance was also lowered.
ZnO계 유리 프릿을 포함한 비교예 2의 경우는, 웨이퍼 기판이 크게 휘어 불량이 발생하고. 기포가 발생하여 내수성도 떨어졌다.In the case of Comparative Example 2 including the ZnO-based glass frit, the wafer substrate was greatly deflected to cause defects. Bubbles were generated and the water resistance dropped.
참고로, 도 2 및 도 3에는 각각 실시예 1(도 2) 및 비교예 1(도 3)의 후면전극 사진이 도시되어 있다. 도 2와 달리 도 3의 후면전극에는 터틀 쉘 현상이 발생한 것을 확인할 수 있다.
2 and 3 are rear electrode photographs of Example 1 (FIG. 2) and Comparative Example 1 (FIG. 3), respectively. Unlike FIG. 2, it can be seen that the turtle shell phenomenon occurs in the rear electrode of FIG.
10: 실리콘 웨이퍼 기판 20: N+층
30: 반사방지막 40: 전면전극
50: P+층 60: 후면전극10: silicon wafer substrate 20: N + layer
30: antireflection film 40: front electrode
50: P + layer 60: rear electrode
Claims (10)
알루미늄 분말; 및
유기 비히클을 포함하는 알루미늄 페이스트 조성물.
Free glass frit containing ZnF 2 ;
Aluminum powder; And
An aluminum paste composition comprising an organic vehicle.
The aluminum paste composition according to claim 1, wherein the ZnF 2 is contained in an amount of 0.1 to 10% by weight based on the total weight of the non-bonded glass frit.
The aluminum paste composition according to claim 1, wherein the non-bonded glass frit is a Bi 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 -ZnF 2 glass frit.
The method according to claim 3, wherein the non-linked glass frit is Bi 2 O 3 20 to 40% by weight, Al 2 O 3 5 to 20% by weight, B 2 O 3 10 to 35% by weight, SiO 2 10 to 20% by weight and ZnF 2 0.1 to 10% by weight.
The aluminum paste composition according to claim 1, wherein the non-bonded glass frit is contained in an amount of 0.01 to 10% by weight based on the total weight of the composition.
The aluminum paste composition according to claim 1, wherein the aluminum powder is contained in an amount of 60 to 78% by weight based on the total weight of the composition.
The aluminum paste composition according to claim 1, wherein the organic vehicle is contained in an amount of 20 to 35% by weight based on the total weight of the composition.
The aluminum paste composition according to claim 1, wherein the organic vehicle is a mixture of 1 to 25% by weight of a polymer resin and 75 to 99% by weight of an organic solvent.
An electrode formed from the aluminum paste composition of any one of claims 1 to 8.
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