KR20120025950A - Zno-based glass frit composition and aluminium paste composition for rear contacts of solar cell using the same - Google Patents
Zno-based glass frit composition and aluminium paste composition for rear contacts of solar cell using the same Download PDFInfo
- Publication number
- KR20120025950A KR20120025950A KR1020100131354A KR20100131354A KR20120025950A KR 20120025950 A KR20120025950 A KR 20120025950A KR 1020100131354 A KR1020100131354 A KR 1020100131354A KR 20100131354 A KR20100131354 A KR 20100131354A KR 20120025950 A KR20120025950 A KR 20120025950A
- Authority
- KR
- South Korea
- Prior art keywords
- zno
- glass frit
- bao
- composition
- sio
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 239000011521 glass Substances 0.000 title claims abstract description 94
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 42
- 239000004411 aluminium Substances 0.000 title abstract 2
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- -1 Polypropylene Polymers 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical group CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims 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 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical group CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- RHFOYRRUVLOOJP-UHFFFAOYSA-N ethoxyethane;propanoic acid Chemical compound CCOCC.CCC(O)=O RHFOYRRUVLOOJP-UHFFFAOYSA-N 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 229940079938 nitrocellulose Drugs 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 claims 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229940116411 terpineol Drugs 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 33
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005452 bending Methods 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910011255 B2O3 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 238000010304 firing Methods 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 9
- 229910052797 bismuth Inorganic materials 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000012461 cellulose resin Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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Abstract
Description
본 발명은 태양전지의 후면 전극의 제조과정에서, 소성후 기판의 휨 현상이 최소화되고 알루미늄 소성막의 수분안정성을 가지며, 개방전압 및 광변환 효율을 향상시킬 수 있는 ZnO계 글래스 프릿 조성물과 이를 이용한 태양전지의 후면 전극용 알루미늄 페이스트 조성물에 관한 것이다.The present invention provides a ZnO-based glass frit composition which minimizes warpage of a substrate after firing, has moisture stability of an aluminum fired film, and improves open voltage and light conversion efficiency in the manufacturing process of a back electrode of a solar cell. The present invention relates to an aluminum paste composition for a back electrode of a solar cell.
태양전지는 에너지 자원이 풍부하고 환경오염에 대한 문제점이 없어 최근 주목받고 있다. 태양전지는 p형 반도체와 n형 반도체의 접합 구조를 가진다. 태양전지에 빛이 입사되면, 빛과 태양전지의 반도체를 구성하는 물질과의 상호작용에 의해, (-) 전하를 띤 전자와 전자가 빠져나가 (+) 전하를 띤 정공이 발생하여, 이들이 이동하면서 전류가 흐르게 된다. 즉, 전자는 n형 반도체 쪽으로 끌어당겨지며, 정공은 p형 반도체 쪽으로 끌어당겨져서, 각각 n형 반도체 및 p형 반도체와 접합된 n형 전극 및 p형 전극으로 이동하게 된다. 상기의 전극들을 전선으로 연결하면 전기가 흘러 전력을 얻게 된다.Solar cells are attracting attention recently because they are rich in energy resources and have no problems with environmental pollution. The solar cell has a junction structure of a p-type semiconductor and an n-type semiconductor. When light is incident on a solar cell, the interaction between the light and the material constituting the semiconductor of the solar cell causes electrons with negative charges to escape and electrons with positive charges, which cause them to move. Current flows. That is, electrons are attracted to the n-type semiconductor, and holes are attracted to the p-type semiconductor, thereby moving to the n-type electrode and the p-type electrode bonded to the n-type semiconductor and the p-type semiconductor, respectively. When the electrodes are connected by wires, electricity flows to obtain power.
또한 태양전지는 소재와 제조 기술에 따라 실리콘 태양전지와 화합물 반도체 태양전지로 구분될 수 있으며, 소재의 형태에 따라 기판형과 박막형으로 나뉜다.In addition, solar cells may be classified into silicon solar cells and compound semiconductor solar cells according to materials and manufacturing techniques, and are divided into a substrate type and a thin film type according to the material type.
한편, 상기 태양전지에서 실리콘 태양전지는 도전성 금속을 포함하는 페이스트를 이용하여 실리콘 기판 위에 인쇄하고 건조 및 소성하여 형성하고 있으며, 후면전극을 형성하기 위해 일반적으로 알루미늄 분말이 주로 사용되고 있다.Meanwhile, in the solar cell, the silicon solar cell is formed by printing, drying, and baking the silicon substrate using a paste containing a conductive metal, and aluminum powder is generally used to form a back electrode.
이러한 알루미늄 분말을 포함하는 알루미늄 페이스트는 변환효율이 높은 태양전지를 제작하는데 사용될 수 있다. 또한 상기 알루미늄 페이스트는 납을 포함하는 유연계와 납을 미포함하는 무연계로 구분한다. 상기 유연계 알루미늄 페이스트는 유연계 글래스 프릿을 포함하는 것으로서, 높은 변환효율 구현이 가능하다. 하지만, 상기 유연계 글래스 프릿은 환경적인 문제 이슈로 인해, 최근에는 알루미늄 페이스트에 무연계 글래스 프릿을 이용하는 방법으로 전향하는 추세이다.An aluminum paste containing such aluminum powder may be used to fabricate a solar cell having high conversion efficiency. In addition, the aluminum paste is classified into a lead-based containing lead and a lead-free containing no lead. The flexible aluminum paste includes a flexible glass frit, and high conversion efficiency can be realized. However, due to environmental issues, the flexible glass frit has recently been shifted to a method of using lead-free glass frit in aluminum paste.
상기 무연계 유리조성은 보통 비스무스계(Bi2O3) 글래스를 사용하게 되는데, 기본적인 성분은 Bi2O3이며, Al2O3, B2O3, SiO2가 글래스 주조성 중에 포함된다. 또한 부수적인 성분으로 Fe2O3, P2O5, MgO, Ga2O3, Li2O, Na2O, ZrO2, AgO, Sc2O5, SrO, BaO, CaO, Pd, Pt 및 Rh로부터 선택된 1종 혹은 모두 선택되어 조성에 적용된다.The lead-free glass composition is usually used bismuth (Bi 2 O 3 ) glass, the basic component is Bi 2 O 3 , Al 2 O 3 , B 2 O 3 , SiO 2 is included in the glass castability. In addition, as an additional component, Fe 2 O 3 , P 2 O 5 , MgO, Ga 2 O 3 , Li 2 O, Na 2 O, ZrO 2 , AgO, Sc 2 O 5 , SrO, BaO, CaO, Pd, Pt and One or all selected from Rh are selected and applied to the composition.
하지만, 상기 비스무스계 글래스 조성은 고가의 Bi2O3를 사용해야 하며, 높은 열팽창계수로 인해 소성후 기판의 휨 현상이 발생하여 웨이퍼의 파손률을 증가시키며, 수분 안정성이 저하되거나 상대적으로 낮은 전지의 효율을 나타낼 가능성이 있다.
However, the bismuth-based glass composition has to use expensive Bi 2 O 3 , and due to the high coefficient of thermal expansion, warpage of the substrate occurs after firing, thereby increasing the breakage rate of the wafer, deteriorating moisture stability or relatively low battery There is a possibility of showing efficiency.
본 발명의 목적은 태양전지의 후면 전극의 제조과정에서, 알루미늄 페이스트 조성물에 무기바인더로 사용되어 기판 소성후, 냉각시 수축률 차이에 의한 기판의 휨을 최소화하여 기판의 파손을 방지하며, 기판의 수분안정성을 나타내어 수분에 의한 알루미늄 소성막의 부식을 방지하고 전지의 개방전압 증가와 광변환 효율도 증진시킬 수 있는 ZnO계 글래스 프릿 조성물을 제공하는 것이다.An object of the present invention is to use as an inorganic binder in the aluminum paste composition in the manufacturing process of the back electrode of the solar cell, to minimize the warpage of the substrate due to the shrinkage difference during cooling after the substrate firing to prevent breakage of the substrate, moisture stability of the substrate It is to provide a ZnO-based glass frit composition which can prevent corrosion of the aluminum fired film by moisture, and also increase the open voltage of the battery and improve the light conversion efficiency.
본 발명의 다른 목적은 상기 글래스 프릿 조성물을 무기 바인더로 이용하는 태양전지의 후면 전극 형성용 무연계 알루미늄 페이스트 조성물을 제공하고자 한다.
Another object of the present invention is to provide a lead-free aluminum paste composition for forming a back electrode of a solar cell using the glass frit composition as an inorganic binder.
본 발명은 (a) ZnO 40 내지 60 중량%,The present invention (a) 40 to 60% by weight of ZnO,
(b) SiO2, B2O3 및 Al2O3 로 이루어진 군에서 선택된 1종 이상의 금속산화물 5 내지 40 중량%,(b) 5 to 40% by weight of at least one metal oxide selected from the group consisting of SiO 2 , B 2 O 3 and Al 2 O 3 ,
(c) CeO, MnO2, CoO 및 CuO 로 이루어진 군에서 선택된 1종 이상의 전이금속 산화물 0.1 내지 30 중량%,(c) 0.1 to 30% by weight of at least one transition metal oxide selected from the group consisting of CeO, MnO 2 , CoO and CuO,
(d) P2O5 0.1 내지 10 중량%, 및(d) 0.1 to 10 weight percent of P 2 O 5 , and
(e) BaO 0.1 내지 10 중량%(e) 0.1 to 10% by weight of BaO
를 포함하는 글래스 프릿 조성물을 제공한다. It provides a glass frit composition comprising a.
상기 글래스 프릿 조성물은 0.5 내지 20 ㎛의 평균 입도 및 5% 이하의 수분 함량을 가지며, 열팽창계수가 50×10-7/℃ 내지 150×10-7/℃인 것이 바람직하다.The glass frit composition has an average particle size of 0.5 to 20 μm and a water content of 5% or less, and a thermal expansion coefficient of 50 × 10 −7 / ° C. to 150 × 10 −7 / ° C. is preferable.
또한 본 발명은 알루미늄 분말, 무기 바인더 및 유기 비히클을 포함하는 알루미늄 페이스트 조성물로서,In addition, the present invention is an aluminum paste composition comprising an aluminum powder, an inorganic binder and an organic vehicle,
상기 ZnO계 글래스 프릿 조성물을 무기바인더로 포함하는 태양전지의 후면 전극 형성용 무연계 알루미늄 페이스트 조성물을 제공한다.
It provides a lead-free aluminum paste composition for forming a back electrode of a solar cell comprising the ZnO-based glass frit composition as an inorganic binder.
이하에서 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 태양전지의 후면 전극 형성용 조성물에서 무기 바인더로 사용할 수 있는 ZnO계 글래스 프릿 조성물에 관한 것이다. 또한 본 발명은 상기 글래스 프릿 조성물을 이용하여 태양전지의 후면 전극 형성용으로 사용하기 적합한 무연계 알루미늄 페이스트 조성물을 제공한다.The present invention relates to a ZnO-based glass frit composition that can be used as an inorganic binder in a composition for forming a back electrode of a solar cell. The present invention also provides a lead-free aluminum paste composition suitable for use for forming the back electrode of a solar cell using the glass frit composition.
본원 발명의 경우 주성분이 PbO이거나 비스무스인 기존의 글래스 프릿 조성과 달리, 비스무스를 포함하지 않는 무연계 글래스 프릿 조성물을 제공한다.The present invention provides a lead-free glass frit composition that does not contain bismuth, unlike conventional glass frit compositions whose main component is PbO or bismuth.
따라서, 본 발명의 글래스 프릿 조성물은 ZnO를 주조성으로 하며, 글래스 생성을 위해 B2O3, Al2O3, SiO2가 포함되며, 기판의 전기적 특성(변환 효율) 및 수분반응성을 제어하기 위해 전이금속 원소인Ce, Mn, Co, Cu과 함께 P2O5, BaO성분이 포함되는 것이 바람직하다.Accordingly, the glass frit composition of the present invention is castable ZnO, and includes B 2 O 3 , Al 2 O 3 , SiO 2 for glass generation, to control the electrical properties (conversion efficiency) and moisture reactivity of the substrate It is preferable to include P 2 O 5 and BaO components together with the transition metal elements Ce, Mn, Co, and Cu.
이러한 본 발명의 방법은 상기 특정 조성의 글래스 프릿 조성물을 사용하여, 기존 비스무스계 조성보다 낮은 열팽창계수를 갖는 조성 설계를 통해 기판 소성 및 냉각시 수축률 차이에 의한 기판의 휨(Bow) 및 파손의 영향을 크게 감소시킬 수 있다. 더욱이 본 발명은 납 성분을 포함하지 않아 환경친화적이면서, 동시에 고가의 비스무스 화합물을 사용하지 않고 구입이 용이한 금속 산화물을 이용한 ZnO계 글래스 프릿을 이용하므로 비용을 크게 절감할 수 있어서 경제적인 효과가 있다. 또한 본 발명은 상기 Ce, Mn, Co 및 Cu로 이루어진 군에서 선택된 1종 이상의 전이금속 산화물을 포함시킴으로써 p형 기판에서 후면 P++층 형성에 효과를 부여하여 개방전압을 증가시킬 수 있다. 이러한 현상은 기판의 상하 양단간의 전압(Voc) 증가와 연계하여 변환 효율을 증가시키는 역할을 한다.This method of the present invention, using the glass frit composition of the specific composition, through the composition design having a coefficient of thermal expansion lower than the existing bismuth-based composition through the effect of the bow (Bow) and failure of the substrate due to the shrinkage difference during substrate firing and cooling Can be greatly reduced. Furthermore, the present invention is economical because it does not include lead, and thus it is environmentally friendly and uses a ZnO-based glass frit using metal oxide, which is easy to purchase without using expensive bismuth compounds. . In addition, the present invention may include at least one transition metal oxide selected from the group consisting of Ce, Mn, Co, and Cu to increase the open voltage by providing an effect on the backside P ++ layer formed on the p-type substrate. This phenomenon increases the conversion efficiency in connection with the increase in the voltage (Voc) between the upper and lower ends of the substrate.
상기 특성을 가지는 본 발명의 바람직한 구현예에 따르면, (a) ZnO 40 내지 60 중량%, (b) SiO2, B2O3 및 Al2O3 로 이루어진 군에서 선택된 1종 이상의 금속산화물 5 내지 40 중량%, (c) CeO, MnO2, CoO 및 CuO 로 이루어진 군에서 선택된 1종 이상의 전이금속 산화물 0.1 내지 30 중량%, (d) P2O5 0.1 내지 10 중량%, 및 (e) BaO 0.1 내지 10 중량%를 포함하는 글래스 프릿 조성물이 제공된다.According to a preferred embodiment of the present invention having the above characteristics, (a) 40 to 60% by weight of ZnO, (b) at least one metal oxide 5 to 5 selected from the group consisting of SiO 2 , B 2 O 3 and Al 2 O 3 40% by weight, (c) 0.1-30% by weight of one or more transition metal oxides selected from the group consisting of CeO, MnO 2 , CoO and CuO, (d) 0.1-10% by weight of P 2 O 5 , and (e) BaO There is provided a glass frit composition comprising 0.1 to 10% by weight.
본 발명의 글래스 프릿 조성물에서 (a) ZnO는 주성분으로 사용되어 다른 구성 성분과의 골격 구조를 이루며 안정성을 증대시켜 열적 안정성 및 내수성, 내습성을 높이는 역할을 한다. ZnO 함량은 전체 글래스 프릿 조성물을 기준으로 40 내지 60 중량% 범위로 사용하는 것이 바람직하다. 상기 ZnO의 함량이 40중량% 미만이면 다른 성분의 상대 비율이 높아져 글래스의 유동에 필요한 점도를 얻을 수 없으며, 60 중량%를 초과하면 유리 형성 자체가 어렵거나 구조가 지나치게 경화되어 유리 전이 온도를 상승시키는 문제가 있다. 따라서, 상기 ZnO는 글래스 프릿 조성물 중에 상기 함량으로 사용해야 물성 향상에 기여할 수 있다.In the glass frit composition of the present invention (a) ZnO is used as a main component to form a skeletal structure with other constituents, thereby increasing stability and increasing thermal stability, water resistance, and moisture resistance. The ZnO content is preferably used in the range of 40 to 60% by weight based on the total glass frit composition. If the content of ZnO is less than 40% by weight, the relative proportion of other components is increased to obtain the viscosity required for the flow of glass, and if it exceeds 60% by weight, glass formation itself is difficult or the structure is excessively hardened to increase the glass transition temperature. There is a problem. Therefore, ZnO should be used in the content of the glass frit composition to contribute to the improvement of physical properties.
또한 본 발명의 글래스 프릿 조성물에서, 상기 (b)성분은 글래스 프릿을 안정하게 형성하는데 기본적인 역할을 한다. 또한 상기 SiO2, B2O3 및 Al2O3로 이루어진 군에서 선택된 1종 이상의 금속산화물은 서로 혼합 사용하는 것이 바람직하며, 예를 들면 SiO2, B2O3 및 Al2O3의 혼합물을 포함할 수 있다. 이때, 상기 SiO2는 열팽창계수 및 글래스의 겔화 빈도를 낮춰 주는 역할을 하며, 상기 Al2O3는 유리의 결정화도를 감소시키고 열팽창계수를 낮추며 유리의 화학적 내구성을 높여주는 역할을 위해 사용할 수 있다. 상기 B2O3는 열팽창계수를 낮추며 글래스의 안정성을 높이기 위해 사용할 수 있다. 상기 (b)의 금속산화물의 함량은 전체 글래스 프릿 조성물을 기준으로 5 내지 40 중량% 범위로 사용하는 것이 바람직하다. 상기 (b)의 금속산화물의 함량이 5 중량% 미만이면 유리 형성이 되지 않는 문제가 있으며, 40 중량%를 초과하면 전이 온도가 과도하게 상승되고 화학적 내구성이 저하되는 문제가 있다.In addition, in the glass frit composition of the present invention, the (b) component plays a basic role in stably forming the glass frit. In addition, at least one metal oxide selected from the group consisting of SiO 2 , B 2 O 3 and Al 2 O 3 is preferably mixed with each other, for example, a mixture of SiO 2 , B 2 O 3 and Al 2 O 3 . It may include. At this time, the SiO 2 serves to lower the thermal expansion coefficient and the gelation frequency of the glass, the Al 2 O 3 can be used for reducing the crystallinity of the glass, lowering the coefficient of thermal expansion and increasing the chemical durability of the glass. The B 2 O 3 can be used to lower the coefficient of thermal expansion and increase the stability of the glass. The content of the metal oxide of (b) is preferably used in the range of 5 to 40% by weight based on the total glass frit composition. If the content of the metal oxide of (b) is less than 5% by weight, there is a problem in that glass is not formed. If the content of the metal oxide is more than 40% by weight, the transition temperature is excessively increased and chemical durability is lowered.
또한, 본 발명의 글래스 프릿 조성물에서, (c) 성분은 상술한 바와 같이, p형 기판에서 후면 전극의 p++층 형성에 효과적이어서 태양전지의 광전환 효율과 개방전압을 향상시킬 수 있다. 또한, 상기 CeO, MnO2, CoO 및 CuO 로 이루어진 군에서 선택된 1종 이상의 전이금속 산화물은 MnO2 ; MnO2 및 CuO의 조성; MnO2, CeO 및 CuO의 조성; CeO 및 CoO의 조성; MnO2, CeO, CoO 및 CuO의 조성을 사용할 수 있다. 상기 (c)성분의 함량은 전체 글래스 프릿 조성물에 대하여 0.1 내지 30 중량%로 사용한다. 상기 (c)의 전이금속 금속산화물의 함량이 0.1 중량% 미만이면 p++층 형성을 위한 기능이 저하되는 문제가 있으며, 30 중량%를 초과하면 상대적으로 다른 성분의 함량이 저하됨에 따라 글래스 형성이 곤란해질 수 있다.In addition, in the glass frit composition of the present invention, the (c) component is effective in forming a p ++ layer of the rear electrode on the p-type substrate, as described above, so that the light conversion efficiency and the open voltage of the solar cell can be improved. In addition, the at least one transition metal oxide selected from the group consisting of CeO, MnO 2 , CoO and CuO MnO 2 ; Composition of MnO 2 and CuO; Composition of MnO 2 , CeO and CuO; Composition of CeO and CoO; Compositions of MnO 2 , CeO, CoO and CuO can be used. The content of the component (c) is used in an amount of 0.1 to 30 wt% based on the total glass frit composition. If the content of the transition metal metal oxide of (c) is less than 0.1% by weight, there is a problem in that the function for forming the p ++ layer is lowered. If the content of the other components exceeds 30% by weight, glass formation is difficult as the content of other components decreases. Can be done.
또한 본 발명의 글래스 프릿 조성물은 글래스의 안정적 구조를 위해, 그리고 과잉으로 인한 수분반응성을 방지하고 전기적 특성을 개선하기 위해 전체 글래스 프릿 조성물에 대하여 P2O5 및 BaO를 필수로 포함한다. 즉, 본 발명의 경우 상기 P2O5 및 BaO의 사용에 따라 알루미늄 소성막의 수분 안정성을 증가시켜 부식을 방지함으로써 기판과 소성막 간의 뜯김을 방지할 수 있다. 여기서 상기 두 성분 중에서 어느 한 성분이라도 포함되지 않으면, 전기적 특성이 우수하며 수분과의 반응성이 제어되는 물성을 갖는 글래스를 얻을 수 없다.In addition, the glass frit composition of the present invention includes P 2 O 5 and BaO as essential for the whole glass frit composition for the stable structure of the glass and to prevent water reactivity due to excess and to improve the electrical properties. That is, in the case of the present invention it is possible to prevent the tearing between the substrate and the fired film by increasing the water stability of the aluminum fired film in accordance with the use of the P 2 O 5 and BaO to prevent corrosion. Here, if any one of the two components is not included, it is not possible to obtain a glass having excellent physical properties and physical properties of controlled reactivity with moisture.
바람직하게, 글래스 프릿 조성물에서 (d) P2O5는 전체 글래스 프릿 조성물에 대하여 0.1 내지 10 중량%로, 바람직하게는 0.1 내지 5 중량%로 포함한다.Preferably, (d) P 2 O 5 in the glass frit composition comprises 0.1 to 10% by weight, preferably 0.1 to 5% by weight relative to the total glass frit composition.
또한, 글래스 프릿 조성물에서 (e) BaO는 전체 글래스 프릿 조성물에 대하여 0.1내지 10 중량%로, 바람직하게는 0.1 내지 5 중량%로 포함한다.In addition, in the glass frit composition, (e) BaO is included in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight based on the total glass frit composition.
이때, P2O5 및 BaO 첨가시 태양전지의 전기적 특성이 증가되지만 그 함량이 각각 10중량%를 초과하는 범위에서는 태양전지의 전기적 특성을 저하시키며, 페이스트 소성시 알루미늄 파우더 입자 피막 성분과 글래스와의 반응에 의한 소성막 자체의 수분 반응성을 증가시켜 안정성을 저하시키는 문제가 발생한다. 또한, 그 함량이 각각 0.1 중량% 미만으로 너무 적게 사용하면 전기적 특성 개선에 큰 효과를 볼 수 없고, 알루미늄 소성막과의 반응성이 커져 수분에 의한 부식성이 증가하는 문제가 있다.At this time, the electrical properties of the solar cell is increased when P 2 O 5 and BaO is added, but the electrical properties of the solar cell are deteriorated when the content exceeds 10 wt%, respectively. Increasing the water reactivity of the fired film itself by the reaction of the problem occurs to reduce the stability. In addition, if the content is less than 0.1% by weight, respectively, the amount is less than 0.1, it is not a great effect on the improvement of the electrical characteristics, there is a problem that the reactivity with the aluminum calcined film is increased to increase the corrosiveness by moisture.
이러한 글래스 프릿 조성물은 0.5 내지 20 ㎛의 평균 입도 및 5% 이하의 수분 함량을 가지며, 열팽창계수가 50×10-7/℃ 내지 150 ×10-7/℃ 일 수 있다. 소성후 기판의 휨(Bowing) 현상을 제어하기 위해 글래스 프릿의 평균 입경은 0.5~10um 로 하는 것이 더 좋다.The glass frit composition has an average particle size of 0.5 to 20 μm and a water content of 5% or less, and the thermal expansion coefficient may be 50 × 10 −7 / ° C. to 150 × 10 −7 / ° C. In order to control the bending of the substrate after firing, the average particle diameter of the glass frit is preferably set to 0.5 to 10 μm.
또한 글래스 프릿 조성물의 연화점(Ts)은 400 내지 600℃이고 유리전이온도 (Tg)가 350 내지 550 ℃인 것이 바람직하다In addition, the softening point (Ts) of the glass frit composition is preferably 400 to 600 ℃ and glass transition temperature (Tg) is 350 to 550 ℃.
바람직하기로는, 상기 글래스 프릿 조성물은 ZnO-SiO2-B2O3-Al2O3-BaO-P2O5-CeO-CoO, ZnO-SiO2-B2O3-BaO-P2O5-MnO2-CoO-CeO-CuO, ZnO-SiO2-B2O3 Al2O3-BaO-P2O5-MnO2-CoO-CeO, ZnO-SiO2-B2O3-BaO-P2O5-MnO2-CuO, ZnO-SiO2-B2O3-BaO-P2O5-MnO2, ZnO-SiO2-B2O3-Al2O3-BaO-P2O5-Na2O-CeO, ZnO-SiO2-B2O3-BaO-P2O5-Na2O-CoO 및 ZnO-SiO2-Al2O3-BaO-P2O5-MnO2-CuO로 이루어진 군에서 선택된 어느 하나를 사용할 수 있다. 바람직하게는 ZnO-SiO2-B2O3-Al2O3-BaO-P2O5-MnO2-CoO-CeO 를 사용하는 것이 기판의 휨을 크게 감소시키고, 파손 방지에 효과적이다.Preferably, the glass frit composition is ZnO-SiO 2 -B 2 O 3 -Al 2 O 3 -BaO-P 2 O 5 -CeO-CoO, ZnO-SiO 2 -B 2 O 3 -BaO-P 2 O 5 -MnO 2 -CoO-CeO-CuO, ZnO-SiO 2 -B 2 O 3 Al 2 O 3 -BaO-P 2 O 5 -MnO 2 -CoO-CeO, ZnO-SiO 2 -B 2 O 3 -BaO -P 2 O 5 -MnO 2 -CuO, ZnO-SiO 2 -B 2 O 3 -BaO-P 2 O 5 -MnO 2 , ZnO-SiO 2 -B 2 O 3 -Al 2 O 3 -BaO-P 2 O 5 -Na 2 O-CeO, ZnO-SiO 2 -B 2 O 3 -BaO-P 2 O 5 -Na 2 O-CoO and ZnO-SiO 2 -Al 2 O 3 -BaO-P 2 O 5 -MnO Any one selected from the group consisting of 2 -CuO can be used. Preferably, the use of ZnO-SiO 2 -B 2 O 3 -Al 2 O 3 -BaO-P 2 O 5 -MnO 2 -CoO-CeO greatly reduces the warpage of the substrate and is effective in preventing breakage.
또한 본 발명의 글래스 프릿 조성물의 제조방법은 특별히 한정되지 않으며 통상의 방법으로 제조될 수 있다.In addition, the method for producing the glass frit composition of the present invention is not particularly limited and may be prepared by conventional methods.
예를 들면, 상기 글래스 프릿 조성물은 상기의 각 성분을 완전히 혼합되도록 2시간 정도 충분한 시간을 두고 혼합하는 혼합단계, 용융단계, 퀀칭(quenching) 및 분쇄단계를 거쳐 유리분말을 제조할 수 있다.For example, the glass frit composition may be prepared through a mixing step, a melting step, a quenching and a pulverizing step of mixing the above components at a sufficient time for about 2 hours to completely mix the above components.
상기 용융단계는 용융온도가 1,000 내지 1,500℃인 것이 바람직하며, 1,300 내지 1,450℃인 것이 더욱 바람직하다. 또한 용융시간은 10분 내지 60분을 유지하여 유리 조성물이 용융상태에서 고르게 혼합될 수 있도록 한다. 용융온도가 1,000℃ 미만인 경우에는 용융점도가 높아 각 성분이 고르게 혼합되지 못하는 경우가 발생하여 좋지 못하므로 적절한 범위로 조절하는 것이 좋다.The melting step is preferably a melting temperature of 1,000 to 1,500 ℃, more preferably 1,300 to 1,450 ℃. In addition, the melting time is maintained for 10 to 60 minutes to allow the glass composition to be evenly mixed in the molten state. If the melting temperature is less than 1,000 ℃ because the melt viscosity is not high because each component is not evenly mixed it is good to adjust to the appropriate range.
상기 퀀칭 단계는 용융 단계에서 용융된 유리 조성물에 대한 급냉단계이다. 이 단계에서는 유리 조성물에 대하여 건식과 습식을 모두 수행하거나 둘 중에 한가지 공정만 수행할 수 있다.The quenching step is a quenching step for the molten glass composition in the melting step. In this step, both dry and wet or only one of the two processes may be performed on the glass composition.
상기 분쇄단계는 급냉된 유리 용융물을 볼밀 등의 통상의 분쇄장치를 통해 이용하여 1차 조분쇄하고, 2차로 원하는 크기의 미세 입자로 재분쇄하여 유리 분말을 제조하는 단계일 수 있다.The pulverizing step may be a step of preparing a glass powder by pulverizing the first quenched glass melt through a conventional pulverization apparatus such as a ball mill, and re-pulverizing into fine particles of a desired size in a second manner.
한편, 본 발명은 상기 ZnO계 글래스 프릿 조성물을 이용한 태양전지의 후면 전극 형성용 알루미늄 페이스트 조성물을 제공한다.On the other hand, the present invention provides an aluminum paste composition for forming a back electrode of a solar cell using the ZnO-based glass frit composition.
이러한 알루미늄 페이스트 조성물은 알루미늄 분말, 무기 바인더 및 유기 비히클을 포함하는 무연계 조성물이며, 상술한 ZnO계 글래스 프릿 조성물을 무기바인더로 포함하는 특징이 있다.The aluminum paste composition is a lead-free composition including an aluminum powder, an inorganic binder, and an organic vehicle, and has a feature of including the ZnO-based glass frit composition as an inorganic binder.
상기 알루미늄 페이스트 조성물은 알루미늄 분말 40 내지 90 중량%, 무기바인더 0.1 내지 10 중량% 및 유기 비히클 1 내지 50 중량%를 포함할 수 있다. 이때, 상기 유기 비히클은 유기바인더 1 내지 50 중량, 유기용제 45 내지 95 중량% 및 첨가제 0.1 내지 10 중량%가 포함된 혼합물을 사용하는 것이 바람직하다.The aluminum paste composition may include 40 to 90% by weight of aluminum powder, 0.1 to 10% by weight of an inorganic binder, and 1 to 50% by weight of an organic vehicle. In this case, the organic vehicle is preferably used a mixture containing 1 to 50% by weight of the organic binder, 45 to 95% by weight of the organic solvent and 0.1 to 10% by weight of the additive.
여기서, 상기 알루미늄 분말의 함량이 40 중량% 미만이면 치밀도가 떨어져 전기적 특성이 저하하는 문제가 있고, 90 중량%를 초과하면 점도 제어가 어려우며 페이스트 제조가 곤란한 문제가 있다. 특히, 상기 알루미늄 페이스트 조성물에서 무기 바인더의 함량이 0.1 중량% 미만이면 소성막과 웨이퍼와의 부착력이 저하되며, 10 중량%를 초과하면 소성시 글래스의 알루미늄과 웨이퍼간의 반응을 저해하여 전기적 특성을 저하시키는 문제가 있다. 또한 상기 유기 비히클의 함량이 1 중량% 미만이면 알루미늄 분말이 90 중량% 초과시와 마찬가지로 페이스트의 레올로지 특성 구현이 곤란한 문제가 있고, 50 중량%를 초과하면 소성시 공극의 증가로 전기적 특성이 저하되는 문제가 있다.Here, if the content of the aluminum powder is less than 40% by weight, there is a problem that the density is lowered, the electrical properties are lowered. If the content of the aluminum powder is more than 90% by weight, viscosity control is difficult and paste manufacturing is difficult. In particular, when the content of the inorganic binder in the aluminum paste composition is less than 0.1% by weight, the adhesion between the fired film and the wafer is lowered. When the amount of the inorganic binder exceeds 10% by weight, the electrical properties are inhibited by inhibiting the reaction between the aluminum and the wafer during firing. There is a problem. In addition, when the content of the organic vehicle is less than 1% by weight, it is difficult to implement the rheological properties of the paste as in the case of when the aluminum powder is more than 90% by weight, and when it exceeds 50% by weight, the electrical properties are deteriorated due to the increase of voids during firing. there is a problem.
이와 같이, 본 발명의 알루미늄 페이스트 조성물에서 무기 바인더인 글래스 프릿은 본 발명의 ZnO계 글래스프릿이 단독으로 사용되고, 그 함량은 10 중량% 이하일 때 휨특성을 더욱 개선시키는 효과를 가져올 수 있다. 또한 본 발명은 필요에 따라 무기바인더로서 Bi2O3계 글래스 프릿과 ZnO계 글래스 프릿을 혼용하여 사용할 수 있다.As such, the glass frit as the inorganic binder in the aluminum paste composition of the present invention may have the effect of further improving the bending property when the ZnO-based glass frit of the present invention is used alone, and its content is 10% by weight or less. In addition, according to the present invention, Bi 2 O 3 -based glass frit and ZnO-based glass frit may be used as an inorganic binder.
또한 본 발명에 있어서, 알루미늄 페이스트 조성물에 사용하는 각 성분은 ZnO계 글래스 프릿을 제외하고는 이 분야의 통상의 기술을 가진자에게 자명한 물질을 사용할 수 있고, 그 종류가 특별히 한정되지 않는다.In addition, in this invention, each component used for an aluminum paste composition can use the substance known to the person skilled in the art except ZnO type glass frit, The kind is not specifically limited.
예를 들면, 알루미늄 분말은 구형, 비구형 혹은 플레이크 형상으로 순도가 80% 이상이며, 평균입도가 1 내지 30 미크론, 바람직하게 1 내지 20 미크론인 것을 사용할 수 있다. 알루미늄 분말내에는 B, Ga, In, Tl 및 Si에 해당하는 성분 중 선택된 1종 이상이 포함될 수 있다.For example, aluminum powder may have a spherical, non-spherical or flake shape with a purity of 80% or more, and an average particle size of 1 to 30 microns, preferably 1 to 20 microns. The aluminum powder may include one or more selected from components corresponding to B, Ga, In, Tl, and Si.
상기 유기 바인더는 메틸 셀룰로오스, 에틸 셀룰로오스, 니트로 셀룰로오스 또는 하이드록시 셀룰로오스인 셀룰로오스 유도체; 아크릴수지; 알키드 수지; 폴리프로필렌계 수지; 폴리염화비닐계 수지; 폴리우레탄계 수지; 에폭시계 수지; 실리콘계 수지; 로진계 수지; 테르펜계 수지; 페놀계 수지; 지방족계 석유 수지; 아크릴산 에스테르계 수지; 크실렌계 수지; 쿠마론인덴(Coumarone-Indene)계 수지; 스틸렌계 수지; 디시클로펜타디엔계 수지; 폴리부텐계 수지; 폴리에테르계 수지; 요소계 수지; 멜라민계 수지; 초산비닐계 수지; 및 폴리이소부틸계 수지로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.The organic binder is a cellulose derivative which is methyl cellulose, ethyl cellulose, nitro cellulose or hydroxy cellulose; Acrylic resins; Alkyd resins; Polypropylene resin; Polyvinyl chloride resins; Polyurethane-based resins; Epoxy resins; Silicone resin; Rosin-based resins; Terpene-based resins; Phenolic resins; Aliphatic petroleum resins; Acrylic ester resins; Xylene-based resins; Coumarone-indene resins; Styrene resin; Dicyclopentadiene-based resins; Polybutene resin; Polyether resins; Urea resins; Melamine-based resins; Vinyl acetate type resin; And it may be used one or more selected from the group consisting of polyisobutyl resin.
또한 유기 용제는 부틸카비톨아세테이트, 부틸카비톨, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르프로피오네이트, 에틸에테르프로피오네이트, 프로필렌글리콜모노메틸에테르아세테이트, 터피네올, 텍사놀, 디메틸아미노 포름알데히드, 메틸에틸케톤, 감마부티로락톤 및 에틸락테이트로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.Organic solvents include butyl carbitol acetate, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, ethyl ether propionate, propylene glycol monomethyl ether acetate, terpine One or more selected from the group consisting of ol, texanol, dimethylamino formaldehyde, methyl ethyl ketone, gamma butyrolactone and ethyl lactate can be used.
상기 첨가제는 젖음성 및 유동성을 향상시키기 위한 지방산 계열의 올레인산, 말레인산, 팔미트산, 미리스틴산, 라우린산, 스테아린산 및 기포를 줄여주는 소포제, 분산성을 개선시켜주는 분산제, 유기바인더의 용해도를 조절하는 가소제 등에서 역할에 맞게 선택된 1종 이상을 사용할 수 있다.The additive is an antifoaming agent for reducing fatty acid-based oleic acid, maleic acid, palmitic acid, myristic acid, lauric acid, stearic acid and air bubbles to improve the wettability and fluidity, dispersant to improve dispersibility, organic binder solubility At least one selected according to the role of the plasticizer to be adjusted, etc. may be used.
한편, 본 발명은 상기 무연계 알루미늄 페이스트 조성물을 이용하여 제조된 태양전지용 후면 전극을 제공한다. 상기 태양전지는 실리콘 태양전지일 수 있다.On the other hand, the present invention provides a solar cell back electrode manufactured using the lead-free aluminum paste composition. The solar cell may be a silicon solar cell.
또한 상기 태양전지용 후면 전극의 제조방법 또한 이 분야의 당업자들에게 자명한 것이므로, 구체적인 기재는 생략하기로 한다.In addition, the manufacturing method of the back electrode for a solar cell is also apparent to those skilled in the art, so a detailed description thereof will be omitted.
예를 들면, 본 발명은 상기 알루미늄 페이스트 조성물을 스크린 인쇄, 닥터블레이드, 잉크젯 인쇄, 그라비아 인쇄와 같은 통상의 방법으로 기재 위에 인쇄하고 건조 및 소성하여 후면전극을 형성할 수 있다. 상기 기재는 실리콘 태양전지에 포함되는 전면전극에 사용되는 실리콘 기판일 수 있으며, 그 종류가 특별히 한정되지 않는다. 또한, 건조는 150 내지 350 ℃의 온도에서 1 내지 30분 동안 진행할 수 있고, 소성은 최고온도가 750 내지 950 ℃의 온도조건에서 수초 내지 5분 동안 진행할 수 있다.For example, the present invention can print the aluminum paste composition on the substrate by a conventional method such as screen printing, doctor blade, inkjet printing, gravure printing, drying and baking to form a back electrode. The substrate may be a silicon substrate used for a front electrode included in a silicon solar cell, and the type thereof is not particularly limited. In addition, the drying may proceed for 1 to 30 minutes at a temperature of 150 to 350 ℃, firing may be carried out for several seconds to 5 minutes at the maximum temperature of 750 to 950 ℃.
이러한 방법으로 본 발명은 두께 20 내지 40um의 후면전극을 갖는 태양전지를 제조할 수 있으며, 이렇게 형성된 후면 전극은 기판과의 밀착성도 좋고 기계적 강도도 기존과 비교하여 동등 이상이며, 특히 낮은 열팽창계수를 갖는 ZnO계 글래스 프릿 조성물을 사용하여 기판 소성후 냉각시 수축률 차이에 의한 기판의 휨 및 파손의 영향을 최소화할 수 있다.In this way, the present invention can manufacture a solar cell having a back electrode having a thickness of 20 to 40um, the back electrode formed in this way has good adhesion to the substrate and the mechanical strength is equal to or higher than conventional, especially low coefficient of thermal expansion By using the ZnO-based glass frit composition having, it is possible to minimize the influence of the warpage and breakage of the substrate due to the shrinkage rate difference during cooling after substrate firing.
따라서 본 발명은 상기 후면전극을 이용하여, 전면전극, 에미터층, 반사방지막 등을 구비하여 성능이 우수한 실리콘 태양전지를 제조할 수 있다.
Therefore, the present invention can be used to manufacture a silicon solar cell having excellent performance by providing a front electrode, an emitter layer, an antireflection film, and the like.
본 발명에 따르면, 열팽창계수가 낮은 특정 조성의 ZnO계 글래스 프릿 조성물을 사용하여 태양전지의 후면 전극을 형성함으로써, 태양전지의 기판 상하 양단간의 전압 증가에 의해 개방 전압 (Open circuit voltage)을 향상시킬 수 있고, 이에 따라 광 변환 효율이 증진되며, 특히 기판의 휨 현상을 크게 감소시킬 수 있다. 또한, 본 발명의 ZnO계 글래스 프릿 조성물은 열팽창계수가 높고 고가의 비스무스계를 전혀 사용하지 않아 효율 증진과 함께 비용 절감에도 기여할 수 있다. 더욱이, 본 발명의 경우 기판의 수분반응성에 대한 안정성을 향상시켜 기판에서의 알루미늄 소성막의 뜯김을 방지할 수 있다.
According to the present invention, by forming a rear electrode of a solar cell using a ZnO-based glass frit composition of a specific composition having a low coefficient of thermal expansion, the open circuit voltage can be improved by increasing the voltage between the upper and lower ends of the substrate of the solar cell. In this way, the light conversion efficiency is enhanced, and in particular, the warpage phenomenon of the substrate can be greatly reduced. In addition, the ZnO-based glass frit composition of the present invention has a high thermal expansion coefficient and does not use an expensive bismuth system at all, thereby contributing to efficiency and cost reduction. Furthermore, in the case of the present invention, it is possible to improve the stability of the water reactivity of the substrate to prevent tearing of the aluminum fired film on the substrate.
이하 본 발명을 하기 실시예 및 비교예를 참조로 하여 설명한다. 그러나, 이들 예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이에 제한되는 것은 아니다.
Hereinafter, the present invention will be described with reference to the following Examples and Comparative Examples. However, these examples are only for illustrating the present invention, but the present invention is not limited thereto.
비교예Comparative example 1 내지 8 및 1 to 8 and 실시예Example 1 내지 8 1 to 8
하기 표 1의 조성을 갖도록 각 금속 산화물을 다음의 방법으로 혼합하여 글래스 프릿 조성물을 제조하였다 (단위: 중량%).Each metal oxide was mixed by the following method to have a composition shown in Table 1 to prepare a glass frit composition (unit: wt%).
즉, 하기 표 1의 조성에 해당하는 각 원료를 무중력혼합기(송영테크 DC200W (실험용 혼합기))를 이용하여 완전히 혼합되도록 2hr 동안 충분한 시간을 두고 혼합하였다. 이후, 상기 혼합물에 대하여 1500℃에서 30분간 용융하였다. That is, each raw material corresponding to the composition of Table 1 was mixed with a sufficient time for 2hr to be completely mixed using a gravity-free mixer (Songyoung Tech DC200W (experimental mixer)). Thereafter, the mixture was melted at 1500 ° C. for 30 minutes.
이어서, 상기 용융된 유리 조성물을 건식 퀀칭시켜 급냉시켰다. 이를 위해, 용융로로부터 이송 밸트를 통해, 상기 유리 조성물을 이동시켜 10초 이내에 상온인 용융로 밖으로 빼내 급냉시키고 30분간 유지하여 안정화시켰다. 급냉된 유리 용융물은 볼밀을 통해 1차 조분쇄 과정을 거치고 2차로 원하는 크기의 미세 입자로 재 분쇄하여 유리 분말을 제조하였다.The molten glass composition was then quenched by dry quenching. To this end, through the transfer belt from the melting furnace, the glass composition was moved and pulled out of the melting furnace at room temperature within 10 seconds, quenched and held for 30 minutes to stabilize. The quenched glass melt was subjected to a first coarse grinding process through a ball mill and secondly to regrind into fine particles of a desired size to prepare a glass powder.
유리 분말을 제조한 후, 통상적인 방법으로 각 조성물에 대하여 Tg, Ts, 및 CTE(열팽창계수) 값을 측정하였고, 그 결과를 표 2에 나타내었다.After the glass powder was prepared, Tg, Ts, and CTE (thermal expansion coefficient) values were measured for each composition by a conventional method, and the results are shown in Table 2.
표 2의 결과를 통해, 본 발명의 실시예 1 내지 8은 비교예 1 내지 8에 비해 열팽창계수가 낮아 소성후 기판의 휨 현상을 방지할 수 있음을 확인하였다.
Through the results in Table 2, Examples 1 to 8 of the present invention was confirmed that the thermal expansion coefficient is lower than the comparative examples 1 to 8 can prevent the warpage of the substrate after firing.
비교예Comparative example 9 내지 16 및 9 to 16 and 실시예Example 9 내지 16 9 to 16
하기 표 3의 조성과 함량으로, 글래스 프릿과 알루미늄 분말, 유기 비히클을 이용하여 각각 비교예 및 실시예의 알루미늄 페이스트를 제조하였다 (단위: 중량%). 이때 알루미늄 분말은 평균입경이 3 미크론인 것을 사용하고, 유기 비히클에서 유기 바인더는 에틸셀룰로오스를 사용하고, 유기 용제는 부틸카비톨아세테이트를 사용하고, 첨가제는 올레인산 및 분산제 (disperbyk-183 1.5%)를 사용하였다. 이후, 수분안정성 및 통상적인 방법으로 광전환 특성을 측정하였다.To the composition and content of Table 3 below, using the glass frit, aluminum powder, and the organic vehicle, aluminum pastes of Comparative Examples and Examples were prepared (unit: wt%), respectively. In this case, the aluminum powder has an average particle diameter of 3 microns, the organic binder is an organic binder using ethyl cellulose, the organic solvent is butyl carbitol acetate, and the additive is oleic acid and a dispersant (disperbyk-183 1.5%). Used. Then, light conversion properties were measured by moisture stability and conventional methods.
상기 수분반응성에 대한 안정성 평가 방법은 다음과 같다.The stability evaluation method for the water reactivity is as follows.
비이커에 탈이온수(DI water)를 채우고 오븐 또는 핫플레이트에서 70℃가 유지되도록 하였다. 온도가 유지되는 비이커 내에 소성된 웨이퍼를 10분 동안 함침시켜 기포 발생 유무를 확인하고, 꺼내진 웨이퍼는 완벽하게 건조후 테이핑 테스트(Taping test)를 통해 막 부착력을 확인하였다(수분 반응 안정성이 낮은 경우 막의 뜯김이 발생). 이때 평가 기준은 다음과 같다.The beaker was filled with DI water and maintained at 70 ° C. in an oven or hotplate. The baked wafer was immersed for 10 minutes in the beaker maintaining the temperature to check for bubble generation, and the wafer was completely dried and checked for film adhesion through a taping test (when the moisture reaction stability was low). Tearing of the membrane). The evaluation criteria are as follows.
○: 기포발생이 없고 소성막 뜯김이 없는 경우○: no foaming and no tearing of the fired film
△: 기포발생하거나 소성막 뜯김이 있는 경우(Triangle | delta): When a bubble generate | occur | produces or there is tearing of a fired film
×: 기포발생이 심하고 소성막 뜯김이 있는 경우X: When foaming is severe and there is a burnt film tearing
9Comparative example
9
10Comparative example
10
1Comparative example
One
12Comparative example
12
13Comparative example
13
14Comparative example
14
15Comparative example
15
16Comparative example
16
분말aluminum
powder
(Bowing)Flexural characteristics
(Bowing)
안정성Water reaction
stability
9Example
9
10Example
10
11Example
11
12Example
12
13Example
13
14Example
14
15Example
15
16Example
16
분말aluminum
powder
(Bowing)Flexural characteristics
(Bowing)
안정성Water reaction
stability
상기 표 3 및 표 4에서 보면, 본 발명의 실시예 9 내지 16은 특정 조성의 글래스 프릿을 사용하여, 기존 비스무스계 글래스 프릿(비교예 1 내지 8)을 사용한 비교예 9 내지 16 대비 개방전압이 증가하고 광전환 효율이 더 우수하였다.In Tables 3 and 4, Examples 9 to 16 of the present invention, using a glass frit of a specific composition, the open voltage compared to Comparative Examples 9 to 16 using the conventional bismuth-based glass frit (Comparative Examples 1 to 8) Increased and the light conversion efficiency was better.
또한, 본 발명의 실시예 9 내지 16은 기판의 휨 특성이 작아 파손을 최소화하였으며, 소성막의 수분반응성에 대한 안정성도 우수하였다.In addition, Examples 9 to 16 of the present invention had a small bending property of the substrate to minimize breakage, and also excellent stability to moisture reactivity of the fired film.
반면, 비교예 9의 경우 수분 반응성이 안정하더라도 비스무스계를 사용해야 하고 휨특성이 높아 기판 파손 가능성이 있다. 또한, 비교예 10 내지 16의 경우 휨정도가 높고 수분안정성이 불량하여 기판 소성막의 뜯김이 발생하였다.
On the other hand, in the case of Comparative Example 9, even if the moisture reactivity is stable, bismuth-based should be used and the bending property is high, there is a possibility of damage to the substrate. In addition, in Comparative Examples 10 to 16, the degree of warpage was high and the moisture stability was poor, resulting in tearing of the substrate fired film.
실시예Example 17 내지 22 17 to 22
최적 글래스 조성에 대한 추가 웨이퍼 평가를 실시하기 위하여, 휨 특성이 가장 우수한 실시예 3에서 사용된 글래스 프릿을 사용하여 다음 표 5의 조성과 함량으로 알루미늄 페이스트를 제조하였다 (단위: 중량%). 또한 알루미늄 분말, 유기바인더, 유기용제 및 첨가제는 상기 실시예 9 내지 16과 동일한 것을 사용하였다.In order to perform further wafer evaluation for the optimum glass composition, aluminum paste was prepared in the composition and content of the following Table 5 using the glass frit used in Example 3 having the best warping properties (unit: wt%). In addition, the aluminum powder, the organic binder, the organic solvent and the additives used were the same as in Examples 9 to 16 above.
상기 표 5의 결과를 보면, 본 발명의 실시예 3의 글래스 프릿을 사용한 실시예 17 내지 22의 경우, 휨특성이 우수할 뿐 아니라, 수분 안정성도 매우 우수하였다. In the results of Table 5, in Examples 17 to 22 using the glass frit of Example 3 of the present invention, not only the bending property was excellent, but also the moisture stability was very excellent.
Claims (13)
(b) SiO2, B2O3 및 Al2O3 로 이루어진 군에서 선택된 1종 이상의 금속산화물 5 내지 40 중량%,
(c) CeO, MnO2, CoO 및 CuO 로 이루어진 군에서 선택된 1종 이상의 전이금속 산화물 0.1 내지 30 중량%,
(d) P2O5 0.1 내지 10 중량%, 및
(e) BaO 0.1 내지 10 중량%
를 포함하는 글래스 프릿 조성물.(a) 40 to 60 weight percent of ZnO,
(b) 5 to 40% by weight of at least one metal oxide selected from the group consisting of SiO 2 , B 2 O 3 and Al 2 O 3 ,
(c) 0.1 to 30% by weight of at least one transition metal oxide selected from the group consisting of CeO, MnO 2 , CoO and CuO,
(d) 0.1 to 10 weight percent of P 2 O 5 , and
(e) 0.1 to 10% by weight of BaO
Glass frit composition comprising a.
제1항 내지 제 4항 중 어느 한 항에 따른 ZnO계 글래스 프릿 조성물을 무기바인더로 포함하는 태양전지의 후면 전극 형성용 무연계 알루미늄 페이스트 조성물.An aluminum paste composition comprising an aluminum powder, an inorganic binder and an organic vehicle,
A lead-free aluminum paste composition for forming a back electrode of a solar cell comprising the ZnO-based glass frit composition according to any one of claims 1 to 4 as an inorganic binder.
알루미늄 분말 40 내지 90 중량%, 무기바인더 0.1 내지 10 중량% 및 유기 비히클 1 내지 50 중량%를 포함하는 태양전지의 후면 전극 형성용 무연계 알루미늄 페이스트 조성물.The method of claim 5, wherein the aluminum paste composition
A lead-free aluminum paste composition for forming a back electrode of a solar cell comprising 40 to 90% by weight of aluminum powder, 0.1 to 10% by weight of an inorganic binder and 1 to 50% by weight of an organic vehicle.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020110066024A KR20120025965A (en) | 2010-09-08 | 2011-07-04 | Zno-based glass frit composition and aluminium paste composition for rear contacts of solar cell using the same |
| KR1020110080698A KR101159787B1 (en) | 2010-09-08 | 2011-08-12 | ZnO-based glass frit composition and aluminium paste composition for rear contacts of solar cell using the same |
| CN201180043055.5A CN103097318B (en) | 2010-09-08 | 2011-08-31 | Zinc oxide-based glass frit composition and aluminum paste composition for back contact of solar cell using the same |
| PCT/KR2011/006469 WO2012033303A2 (en) | 2010-09-08 | 2011-08-31 | Zno-based glass frit composition and aluminum paste composition for back contacts of solar cell using the same |
| TW100132128A TWI537226B (en) | 2010-09-08 | 2011-09-06 | Zno-based glass frit composition and aluminum paste composition for back contacts of solar cell using the same |
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| KR1020110066024A KR20120025965A (en) | 2010-09-08 | 2011-07-04 | Zno-based glass frit composition and aluminium paste composition for rear contacts of solar cell using the same |
| KR1020110080698A KR101159787B1 (en) | 2010-09-08 | 2011-08-12 | ZnO-based glass frit composition and aluminium paste composition for rear contacts of solar cell using the same |
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| KR102098589B1 (en) | 2013-07-04 | 2020-04-09 | 삼성전자주식회사 | Wavelength-converted element, manufacturing method of the same and semiconductor light emitting apparatus having the same |
| CN103387340B (en) * | 2013-07-24 | 2016-02-10 | 宁波广博纳米新材料股份有限公司 | For the lead-free glass powder and preparation method thereof of solar cell aluminium paste |
| CN103531719B (en) * | 2013-10-25 | 2016-04-13 | 上海大学 | OLED encapsulating structure |
| CN104751939B (en) * | 2013-12-31 | 2017-05-31 | 比亚迪股份有限公司 | A kind of crystal silicon solar energy battery aluminum conductive electric slurry |
| TWI547958B (en) * | 2014-10-27 | 2016-09-01 | High efficiency solar cells with conductive aluminum and the application of the conductive aluminum plastic solar cells | |
| KR101683538B1 (en) * | 2015-04-29 | 2016-12-08 | 주식회사 베이스 | Glass frit having low melting point for sealing organic light emitting diode panel and glass paste including the same |
| KR101733161B1 (en) * | 2015-10-31 | 2017-05-08 | 엘에스니꼬동제련 주식회사 | Electrode Paste Composition For Solar Cell's Electrode And Solar Cell |
| KR101736773B1 (en) * | 2016-04-06 | 2017-05-29 | 대주전자재료 주식회사 | Rear electrode paste for solar cell |
| KR101930285B1 (en) * | 2016-10-31 | 2018-12-19 | 엘에스니꼬동제련 주식회사 | Electrode Paste For Solar Cell's Electrode And Solar Cell using the same |
| JP6885188B2 (en) * | 2017-04-28 | 2021-06-09 | 住友金属鉱山株式会社 | Method for manufacturing conductive composition and terminal electrode |
| CN109119181B (en) * | 2018-07-13 | 2020-07-24 | 苏州博望新能源科技有限公司 | Front silver paste for crystalline silicon solar cell and preparation method and application thereof |
| CN111592228B (en) * | 2020-06-01 | 2021-09-14 | 常州聚和新材料股份有限公司 | Gallium-containing high-lead glass material, silver-aluminum slurry, preparation method and application thereof |
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| US6664567B2 (en) * | 2001-06-28 | 2003-12-16 | Kyocera Corporation | Photoelectric conversion device, glass composition for coating silicon, and insulating coating in contact with silicon |
| KR20060000515A (en) * | 2004-06-29 | 2006-01-06 | 대주전자재료 주식회사 | Pb-free glass composition for barrier ribs of plasma display panel |
| JP2006342018A (en) | 2005-06-09 | 2006-12-21 | Nihon Yamamura Glass Co Ltd | Zinc phosphate-based lead-free glass composition |
| US8575474B2 (en) * | 2006-03-20 | 2013-11-05 | Heracus Precious Metals North America Conshohocken LLC | Solar cell contacts containing aluminum and at least one of boron, titanium, nickel, tin, silver, gallium, zinc, indium and copper |
| JP5219355B2 (en) * | 2006-10-27 | 2013-06-26 | 京セラ株式会社 | Method for manufacturing solar cell element |
| JP5683778B2 (en) | 2008-09-29 | 2015-03-11 | 日本山村硝子株式会社 | Lead free bismuth glass composition |
| KR20110051451A (en) * | 2009-11-10 | 2011-05-18 | 동우 화인켐 주식회사 | New glass composition, the glass frit manufactured with the same and aluminium paste for a back electrode of solar cell comprising the glass frit |
| CN101728439B (en) * | 2009-12-01 | 2011-07-20 | 洛阳神佳电子陶瓷有限公司 | Aluminum pulp composition of crystal silicon solar cell and preparation method thereof |
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| KR20120025972A (en) | 2012-03-16 |
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| TWI537226B (en) | 2016-06-11 |
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