WO2011090215A1 - 電極用ペースト組成物及び太陽電池 - Google Patents
電極用ペースト組成物及び太陽電池 Download PDFInfo
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- WO2011090215A1 WO2011090215A1 PCT/JP2011/051366 JP2011051366W WO2011090215A1 WO 2011090215 A1 WO2011090215 A1 WO 2011090215A1 JP 2011051366 W JP2011051366 W JP 2011051366W WO 2011090215 A1 WO2011090215 A1 WO 2011090215A1
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- copper
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- 239000000203 mixture Substances 0.000 title claims abstract description 170
- 239000002245 particle Substances 0.000 claims abstract description 372
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 197
- 239000010949 copper Substances 0.000 claims abstract description 196
- 229910052802 copper Inorganic materials 0.000 claims abstract description 191
- 239000011521 glass Substances 0.000 claims abstract description 100
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- 238000010304 firing Methods 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 145
- 229910052709 silver Inorganic materials 0.000 claims description 144
- 239000004332 silver Substances 0.000 claims description 144
- 239000002003 electrode paste Substances 0.000 claims description 134
- 229910052698 phosphorus Inorganic materials 0.000 claims description 103
- 239000011574 phosphorus Substances 0.000 claims description 102
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 100
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 59
- -1 triazole compounds Chemical class 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 26
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000005259 measurement Methods 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 13
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 13
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 150000004703 alkoxides Chemical class 0.000 claims description 11
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 229920000767 polyaniline Polymers 0.000 claims description 9
- 239000004254 Ammonium phosphate Substances 0.000 claims description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 8
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 8
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 abstract description 66
- 238000007254 oxidation reaction Methods 0.000 abstract description 66
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000004455 differential thermal analysis Methods 0.000 abstract 1
- 238000002411 thermogravimetry Methods 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000004065 semiconductor Substances 0.000 description 20
- 238000007639 printing Methods 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 13
- 239000001856 Ethyl cellulose Substances 0.000 description 13
- 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 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
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- 235000019325 ethyl cellulose Nutrition 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 238000007650 screen-printing Methods 0.000 description 11
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- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000004907 flux Effects 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- 229910052716 thallium Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 238000005219 brazing Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000700 radioactive tracer Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000009692 water atomization Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 229910018068 Li 2 O Inorganic materials 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910052796 boron Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
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- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 239000003759 ester based solvent Substances 0.000 description 2
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- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
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- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
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- 229940046892 lead acetate Drugs 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
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- 235000003270 potassium fluoride Nutrition 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 239000005365 phosphate glass Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
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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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- 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
- H01L31/02—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
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
- H01L31/02245—Electrode arrangements specially adapted for back-contact solar cells for metallisation wrap-through [MWT] type solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—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
- H01L31/042—PV modules or arrays of single PV cells
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K99/00—Subject matter not provided for in other groups of this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to an electrode paste composition and a solar cell.
- a crystalline silicon solar cell is provided with a surface electrode.
- the wiring resistance and contact resistance of the surface electrode are related to voltage loss related to conversion efficiency, and the wiring width and shape affect the amount of incident sunlight. (See, for example, Yasuhiro Sasakawa, “Solar Power Generation, Latest Technologies and Systems,” CMC Publishing Company, 2001, p26-27).
- the surface electrode of a solar cell is usually formed as follows. That is, a conductive composition is applied by screen printing or the like on an n-type semiconductor layer formed by thermally diffusing phosphorus or the like at a high temperature on the light-receiving surface side of a p-type silicon substrate, and this is applied to 800 to 900 A surface electrode is formed by baking at ° C.
- the conductive composition forming the surface electrode includes conductive metal powder, glass particles, various additives, and the like.
- conductive metal powder As the conductive metal powder, silver powder is generally used. However, use of metal powders other than silver powder has been studied for various reasons. For example, a conductive composition capable of forming a solar cell electrode containing silver and aluminum is disclosed (see, for example, JP-A-2006-313744). Also disclosed is an electrode-forming composition containing metal nanoparticles containing silver and metal particles other than silver (see, for example, JP-A-2008-226816).
- silver used for electrode formation is a noble metal, and due to the problem of resources, and the metal itself is expensive, a proposal of a paste material to replace the silver-containing conductive composition (silver-containing paste) is desired.
- a promising material that can replace silver is copper that is applied to semiconductor wiring materials. Copper is abundant in terms of resources, and the cost of bullion is as low as about 1/100 of silver. However, copper is a material that is easily oxidized at a high temperature of 200 ° C. or higher.
- the electrode forming composition described in Japanese Patent Application Laid-Open No. 2008-226816 when copper is contained as a conductive metal, this is fired. In order to form an electrode, a special process of firing in an atmosphere of nitrogen or the like was necessary.
- the present invention provides a paste composition for an electrode capable of forming an electrode having a low resistivity while suppressing copper oxidation during firing, and a solar cell having an electrode formed using the paste composition for an electrode The task is to do.
- a copper-containing particle having a peak temperature of an exothermic peak showing a maximum area of 280 ° C. or higher in differential thermal-thermogravimetric simultaneous measurement (TG-DTA), glass particles, a solvent, and a resin And an electrode paste composition.
- TG-DTA differential thermal-thermogravimetric simultaneous measurement
- the copper-containing particles include phosphorus-containing copper alloy particles, silver-coated copper particles, and triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides. It is preferably at least one selected from copper particles that have been surface-treated with at least one selected from the group.
- the glass particles preferably have a glass softening point of 600 ° C. or less and a crystallization start temperature exceeding 600 ° C., and are based on diphosphorus pentoxide-divanadium pentoxide (P 2 O 5 —V 2 O 5 ) system. More preferably, glass is included.
- the electrode paste composition preferably further includes silver particles, and the content of the copper-containing particles is 9% by mass to 88% by mass when the total amount of the copper-containing particles and the silver particles is 100% by mass.
- the following is more preferable.
- the total content of the copper-containing particles and the silver particles is 70% by mass or more and 94% by mass or less, and the content of the glass particles is 0.1% by mass or more and 10% by mass or less, and the solvent and The total content of the resin is more preferably 3% by mass or more and 29.9% by mass or less.
- the electrode paste composition preferably further includes a phosphorus-containing compound, and the phosphorus-containing compound is at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene. Is more preferable.
- the second aspect of the present invention is an electrode paste composition containing phosphorus-containing copper alloy particles, glass particles, a solvent, and a resin.
- the glass particles preferably have a glass softening point of 600 ° C. or less and a crystallization start temperature exceeding 600 ° C., and are based on diphosphorus pentoxide-divanadium pentoxide (P 2 O 5 —V 2 O 5 ) system. More preferably, glass is included.
- the electrode paste composition preferably further includes silver particles, and the content of the copper-containing particles is 9% by mass to 88% by mass when the total amount of the copper-containing particles and the silver particles is 100% by mass.
- the following is more preferable.
- the total content of the copper-containing particles and the silver particles is 70% by mass or more and 94% by mass or less, and the content of the glass particles is 0.1% by mass or more and 10% by mass or less, and the solvent and The total content of the resin is more preferably 3% by mass or more and 29.9% by mass or less.
- the electrode paste composition preferably further includes a phosphorus-containing compound, and the phosphorus-containing compound is at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene. Is more preferable.
- a third aspect of the present invention is an electrode paste composition containing silver-coated copper particles, glass particles, a solvent, and a resin.
- the glass particles preferably have a glass softening point of 600 ° C. or lower and a crystallization start temperature of 600 ° C. or higher, and more preferably contain diphosphorus pentoxide-bivanadium pentoxide glass.
- the electrode paste composition preferably further includes silver particles, and the content of the copper-containing particles is 9% by mass to 88% by mass when the total amount of the copper-containing particles and the silver particles is 100% by mass.
- the following is more preferable.
- the total content of the copper-containing particles and the silver particles is 70% by mass or more and 94% by mass or less, and the content of the glass particles is 0.1% by mass or more and 10% by mass or less, and the solvent and The total content of the resin is more preferably 3% by mass or more and 29.9% by mass or less.
- the electrode paste composition preferably further includes a phosphorus-containing compound, and the phosphorus-containing compound is at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene. Is more preferable.
- the surface treatment was performed with at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides.
- An electrode paste composition comprising copper particles, glass particles, a solvent, and a resin.
- the glass particles preferably have a glass softening point of 600 ° C. or lower and a crystallization start temperature of 600 ° C. or higher, and more preferably contain diphosphorus pentoxide-bivanadium pentoxide glass.
- the electrode paste composition preferably further includes silver particles, and the content of the copper-containing particles is 9% by mass to 88% by mass when the total amount of the copper-containing particles and the silver particles is 100% by mass.
- the following is more preferable.
- the total content of the copper-containing particles and the silver particles is 70% by mass or more and 94% by mass or less, and the content of the glass particles is 0.1% by mass or more and 10% by mass or less, and the solvent and The total content of the resin is more preferably 3% by mass or more and 29.9% by mass or less.
- the electrode paste composition preferably further includes a phosphorus-containing compound, and the phosphorus-containing compound is at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene. Is more preferable.
- a fifth aspect of the present invention is a solar cell having an electrode formed by firing the electrode paste composition applied on a silicon substrate.
- the oxidation of copper at the time of baking is suppressed, the paste composition for electrodes which can form an electrode with low resistivity, and the solar cell which has an electrode formed using this paste composition for electrodes Can be provided.
- the electrode paste composition of the present invention comprises at least one copper-containing particle having a peak temperature of an exothermic peak showing a maximum area of 280 ° C. or more in simultaneous differential thermal-thermogravimetric measurement, at least one glass particle, It contains at least one solvent and at least one resin. With such a configuration, oxidation of copper during firing is suppressed, and an electrode with low resistivity can be formed.
- the peak temperature of the exothermic peak showing the maximum area in differential thermal-thermogravimetric simultaneous measurement is 280 ° C. or higher.
- the differential thermal-thermogravimetric simultaneous measurement is performed in a normal atmosphere using a measuring device: differential thermal-thermogravimetric analyzer (TG / DTA-6200, manufactured by SII NanoTechnology Co., Ltd.). Range: room temperature to 1000 ° C., heating rate: 40 ° C./min, air flow rate: 200 ml / min.
- the peak temperature at the exothermic peak showing the maximum area is around 200 ° C., but the peak temperature is 280 for the copper-containing particles used in the present invention. It is above °C.
- the peak temperature is preferably 280 to 800 ° C., more preferably 290 to 750 ° C., and further preferably 350 to 750 ° C. preferable.
- Copper-containing particles having a peak temperature of 280 ° C. or higher at the exothermic peak showing the maximum area can be constituted by imparting oxidation resistance to the copper particles.
- the copper particle surface-treated by at least 1 sort (s) chosen from a group can be mentioned, It is preferable to use at least 1 sort (s) chosen from these.
- the copper-containing particles may be used alone or in combination of two or more.
- the particle diameter of the copper-containing particles is not particularly limited, but the particle diameter when the accumulated weight is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to 10 ⁇ m. Is preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the copper containing particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
- the particle diameter of the copper-containing particles is measured by a microtrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300 type).
- the shape of the copper-containing particles is preferably substantially spherical, flat, or plate-like from the viewpoint of oxidation resistance and low resistivity.
- the content of the copper-containing particles contained in the electrode paste composition of the present invention, and the total content of the copper-containing particles and the silver particles in the case of containing silver particles described later are, for example, 70 to 94% by mass. In view of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, more preferably 74 to 88% by mass. In the present invention, conductive particles other than the copper-containing particles may be used in combination.
- phosphorus copper brazing As a phosphorus-containing copper alloy, a brazing material called phosphorus copper brazing (phosphorus concentration: about 7% by mass or less) is known. Phosphorus copper brazing is also used as a bonding agent between copper and copper, but by using phosphorous-containing copper alloy particles as copper-containing particles contained in the electrode paste composition of the present invention, oxidation resistance is improved. An electrode having excellent and low resistivity can be formed. Further, the electrode can be fired at a low temperature, and the effect that the process cost can be reduced can be obtained.
- the phosphorus content contained in the phosphorus-containing copper alloy in the present invention is not limited as long as the content is such that the peak temperature of the exothermic peak showing the maximum area in the differential thermal-thermogravimetric simultaneous measurement is 280 ° C. or higher. Specifically, it can be 0.01% by mass or more in the total mass of the phosphorus-containing copper alloy particles.
- the phosphorus content is preferably 0.01% by mass or more and 8% by mass or less, and 0.5% by mass or more and 7.8% by mass or less. More preferably, the content is 1% by mass or more and 7.5% by mass or less.
- the phosphorus content contained in the phosphorus-containing copper alloy is 8% by mass or less, a lower resistivity can be achieved, and the productivity of the phosphorus-containing copper alloy is excellent. Moreover, the more outstanding oxidation resistance can be achieved because it is 0.01 mass% or more.
- the phosphorus-containing copper alloy particles are an alloy containing copper and phosphorus, but may further contain other atoms.
- other atoms include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
- Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
- the content rate of the other atom contained in the said phosphorus containing copper alloy particle can be 3 mass% or less in the said phosphorus containing copper alloy particle, for example, from a viewpoint of oxidation resistance and a low resistivity, it is 1 It is preferable that it is below mass%.
- the particle diameter of the phosphorus-containing copper alloy particles is not particularly limited, but the particle diameter when the accumulated weight is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to 10 ⁇ m. It is preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the phosphorus containing copper alloy particles in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively. Moreover, there is no restriction
- the shape of the phosphorus-containing copper alloy particles is preferably substantially spherical, flat, or plate-like from the viewpoint of oxidation resistance and low resistivity.
- the phosphorous copper alloy can be produced by a commonly used method.
- the phosphorus-containing copper alloy particles can be prepared using a normal method of preparing metal powder using a phosphorus-containing copper alloy prepared so as to have a desired phosphorus content, for example, a water atomization method Can be produced by a conventional method. Details of the water atomization method are described in Metal Handbook (Maruzen Co., Ltd. Publishing Division). Specifically, for example, after phosphorus-containing copper alloy is dissolved and powdered by nozzle spray, the obtained powder is dried and classified, whereby desired phosphorus-containing copper alloy particles can be produced. Moreover, the phosphorus containing copper alloy particle
- the content of the phosphorus-containing copper alloy particles contained in the electrode paste composition of the present invention, and the total content of the phosphorus-containing copper alloy particles and silver particles in the case of containing silver particles described later are, for example, 70 to 94 From the viewpoint of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, and more preferably 74 to 88% by mass.
- the phosphorus-containing copper alloy particles may be used singly or in combination of two or more. Furthermore, it may be used in combination with copper-containing particles other than phosphor copper alloy particles, the peak temperature of the exothermic peak showing the maximum area being 280 ° C. or higher.
- phosphorus-containing copper alloy particles having a phosphorus content of 0.01% by mass or more and 8% by mass or less are contained in the electrode paste composition. It is preferable to contain ⁇ 94% by mass, and it is more preferable that phosphorus-containing copper alloy particles having a phosphorus content of 1 to 7.5% by mass are contained in the electrode paste composition in an amount of 74 to 88% by mass.
- conductive particles other than the phosphorus-containing copper alloy particles may be used in combination.
- the silver-coated copper particles in the present invention it is sufficient that at least a part of the surface of the copper particles is coated with silver.
- silver-coated copper particles as the copper-containing particles contained in the electrode paste composition of the present invention, an electrode having excellent oxidation resistance and low resistivity can be formed.
- the copper particles are coated with silver, the interface resistance between the silver-coated copper particles and the silver particles is reduced, and an electrode with a lower resistivity can be formed.
- water is mixed in the electrode paste composition, the use of silver-coated copper particles can suppress the oxidation of copper at room temperature and can improve the pot life.
- the coating amount (silver content) in the silver-coated copper particles the coating amount (silver content) such that the peak temperature of the exothermic peak showing the maximum area in the differential thermal-thermogravimetric simultaneous measurement is 280 ° C. or more. It is preferable that Specifically, it can be 1% by mass or more in the total mass of the silver-coated copper particles.
- the coating amount of silver is preferably 1 to 88% by mass and more preferably 3 to 80% by mass in the total mass of the silver-coated copper particles from the viewpoint of oxidation resistance and low resistivity of the electrode. Preferably, it is 5 to 75% by mass.
- the particle diameter of the silver-coated copper particles is not particularly limited, but the particle diameter when the accumulated weight is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to 10 ⁇ m. It is preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the silver covering copper particle in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively. Moreover, there is no restriction
- the shape of the silver-coated copper particles is preferably substantially spherical, flat or plate-like from the viewpoint of oxidation resistance and low resistivity.
- the copper constituting the silver-coated copper particles may contain other atoms.
- other atoms include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
- Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
- the content rate of the other atom contained in the said silver covering copper particle can be 3 mass% or less in the said silver covering copper particle, for example, and 1 mass% from a viewpoint of oxidation resistance and a low resistivity. The following is preferable.
- the silver-coated copper particles are those in which the above-described phosphorus-containing copper alloy is silver-coated.
- the oxidation resistance is further improved, and the resistivity of the formed electrode is further reduced.
- the phosphorus containing copper alloy in a silver covering copper particle it is synonymous with the above-mentioned phosphorus containing copper alloy, and its preferable aspect is also the same.
- the method for preparing the silver-coated copper particles is not particularly limited as long as at least a part of the surface of the copper particles (preferably phosphorus-containing copper alloy particles) can be coated with silver.
- it can be prepared as follows. That is, copper powder (or phosphorus-containing copper alloy powder) is dispersed in an acidic solution such as sulfuric acid, hydrochloric acid, and phosphoric acid, and a chelating agent is added to the copper powder dispersion to prepare a copper powder slurry.
- an acidic solution such as sulfuric acid, hydrochloric acid, and phosphoric acid
- a chelating agent is added to the copper powder dispersion to prepare a copper powder slurry.
- a silver ion solution to the obtained copper powder slurry, a silver layer can be formed on the surface of the copper powder by a substitution reaction to prepare silver-coated copper particles.
- ethylenediaminetetraacetic acid salt triethylenediamine, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc.
- ethylenediaminetetraacetic acid salt triethylenediamine, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc.
- silver ion solution a silver nitrate solution etc. can be used, for example.
- the content of the silver-coated copper particles contained in the paste composition for an electrode of the present invention, and the total content of silver-coated copper particles and silver particles in the case of containing silver particles described later are, for example, 70 to 94% by mass. In view of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, more preferably 74 to 88% by mass.
- the silver-coated copper particles may be used singly or in combination of two or more. Moreover, you may use in combination with the copper containing particle
- the silver-coated copper particles having a silver content of 1 to 88% by mass in the total mass of the silver-coated copper particles are contained in the electrode paste composition. 70 to 94% by mass (the total content of silver-coated copper particles and silver particles when silver particles described later are included) is preferable, and the silver-coated copper particles having a silver content of 5 to 75% by mass Is more preferably contained in the electrode paste composition in an amount of 74 to 88% by mass (the total content of silver-coated copper particles and silver particles when silver particles described later are included).
- silver-coated phosphorus-containing copper alloy particles having a silver content of 1 to 88% by mass and a phosphorus content of 0.01 to 8% by mass in the electrode paste composition (described later).
- the silver particles to be included it is preferable to include silver-coated phosphorus-containing copper alloy particles and silver particles), the silver content is 5 to 75% by mass, and the phosphorus content is 1 to 7.5.
- 74 to 88% by mass of silver-coated phosphorus-containing copper alloy particles in an electrode paste composition (the total content of silver-coated phosphorus-containing copper alloy particles and silver particles when silver particles described later are included). ) Is more preferable.
- conductive particles other than the silver-coated copper particles may be used in combination.
- the copper-containing particles in the present invention are a group consisting of a triazole compound, a saturated fatty acid, an unsaturated fatty acid, an inorganic metal compound salt, an organic metal compound salt, a polyaniline resin, and a metal alkoxide (hereinafter sometimes referred to as “surface treatment agent”). It is also preferable that the copper particles have been surface treated with at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, and inorganic metal compound salts. More preferably, it is a copper particle.
- Forming an electrode with excellent oxidation resistance and low resistivity by using copper particles surface-treated with at least one surface treatment agent as the copper-containing particles contained in the electrode paste composition of the present invention Can do. Further, when moisture is mixed in the electrode paste composition, the use of the surface-treated copper particles can suppress the oxidation of copper at room temperature and can improve the pot life.
- the surface treatment agents may be used singly or in combination of two or more.
- the surface-treated copper particles are at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides. Although it has been treated, other surface treatment agents may be used in combination as required.
- Examples of the triazole compound in the surface treatment agent include benzotriazole and triazole.
- Examples of the saturated fatty acid in the surface treatment agent include enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, stearic acid, nonadecanoic acid, arachic acid, Examples include behenic acid.
- Examples of the unsaturated fatty acid in the surface treatment agent include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetreic acid, brassic acid, erucic acid, sorbic acid, and linoleic acid. Linolenic acid, arachidonic acid and the like.
- Examples of the inorganic metal compound salt in the surface treatment agent include sodium silicate, sodium stannate, tin sulfate, zinc sulfate, sodium zincate, zirconium nitrate, sodium zirconate, zirconium chloride, titanium sulfate, and titanium chloride. And potassium oxalate titanate.
- organometallic compound salt in the surface treatment agent examples include lead stearate, lead acetate, p-cumylphenyl derivative of tetraalkoxyzirconium, p-cumylphenyl derivative of tetraalkoxytitanium, and the like.
- metal alkoxide in the surface treatment agent examples include titanium alkoxide, zirconium alkoxide, lead alkoxide, silicon alkoxide, tin alkoxide, and indium alkoxide.
- Examples of other surface treatment agents include dodecylbenzene sulfonic acid.
- stearic acid or lead stearate is used as the surface treatment agent, the oxidation resistance is further improved and the resistivity is improved by using at least one of stearic acid and lead stearate and lead acetate as the surface treatment agent.
- Lower electrodes can be formed.
- the surface-treated copper particles in the present invention it is sufficient that at least a part of the surface of the copper particles is coated with at least one of the surface treatment agents.
- the content of the surface treating agent contained in the surface-treated copper particles is preferably such that the peak temperature of the exothermic peak showing the maximum area in the differential thermal-thermogravimetric simultaneous measurement is 280 ° C. or higher. . Specifically, it can be 0.01% by mass or more based on the total mass of the surface-treated copper particles.
- the content of the surface treatment agent is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass in the total mass of the copper particles from the viewpoint of oxidation resistance and low resistivity of the electrode. More preferably.
- Copper constituting the surface-treated copper particles may contain other atoms.
- other atoms include Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W, Mo, Ti, Co, Ni, Au, etc. can be mentioned.
- Al is preferably contained from the viewpoint of adjusting characteristics such as oxidation resistance and melting point.
- the content rate of the other atom contained in the said surface-treated copper particle can be 3 mass% or less in the said surface-treated copper particle, for example from a viewpoint of oxidation resistance and a low resistivity. It is preferable that it is 1 mass% or less.
- the surface-treated copper particles are also preferably those obtained by surface-treating the above-described phosphorus-containing copper alloy. As a result, the oxidation resistance is further improved, and the resistivity of the formed electrode is further reduced.
- the phosphorus containing copper alloy in the surface-treated copper particle it is synonymous with the above-mentioned phosphorus containing copper alloy, and a preferable aspect is also the same.
- the particle diameter of the surface-treated copper particles is not particularly limited, but the particle diameter when the accumulated weight is 50% (hereinafter sometimes abbreviated as “D50%”) is 0.4 ⁇ m to
- the thickness is preferably 10 ⁇ m, more preferably 1 ⁇ m to 7 ⁇ m. When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of the said surface-treated copper particle in an electrode becomes large because it is 10 micrometers or less, and a resistivity falls more effectively.
- limiting in particular as a shape of the said surface-treated copper particle Any of substantially spherical shape, flat shape, block shape, plate shape, scale shape, etc. may be sufficient.
- the surface-treated copper particles preferably have a substantially spherical shape, a flat shape, or a plate shape from the viewpoint of oxidation resistance and low resistivity.
- the surface treatment method for copper particles using a surface treatment agent can be appropriately selected according to the surface treatment agent to be used. For example, by preparing a surface treatment solution in which the surface treatment agent is dissolved in a solvent capable of dissolving the surface treatment agent, and immersing and drying the copper particles in this, at least a part of the surface of the copper particles is coated with the surface treatment agent. Can be coated.
- the solvent capable of dissolving the surface treatment agent can be appropriately selected according to the surface treatment agent.
- water alcohol solvents such as methanol, ethanol, isopropanol, glycol solvents such as ethylene glycol monoethyl ether, carbitol solvents such as diethylene glycol monobutyl ether, carbitol acetate solvents such as diethylene glycol monoethyl ether acetate, etc.
- a surface treatment solution can be prepared using an alcohol solvent to treat the copper particles.
- stearic acid or lead stearate is used as the surface treatment agent
- a surface treatment solution can be prepared using an alcohol solvent.
- the concentration of the surface treatment agent in the surface treatment solution can be appropriately selected according to the type of surface treatment agent to be used and the desired surface treatment amount. For example, it can be 1 to 90% by mass, and preferably 2 to 85% by mass.
- the content of the surface-treated copper particles contained in the electrode paste composition of the present invention, and the total content of the surface-treated copper particles and silver particles in the case of containing silver particles described later are, for example, 70 From the viewpoint of oxidation resistance and low resistivity, it is preferably 72 to 90% by mass, and more preferably 74 to 88% by mass.
- the surface-treated copper particles may be used singly or in combination of two or more.
- the peak temperature in the exothermic peak which shows the maximum area is 280 degreeC or more.
- the electrode from the viewpoint of oxidation resistance and low resistivity of the electrode, it is selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides.
- the copper particles surface-treated so that at least one kind contained in an amount of 0.01 to 10% by mass was contained in the electrode paste composition in an amount of 70 to 94% by mass (in the case where silver particles described later were included, the surface treatment was performed).
- Total content of copper particles and silver particles is preferably included, and 0.05 to 8% by mass of at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, and inorganic metal compound salts is included. 74 to 88% by mass of the surface-treated copper particles in the electrode paste composition (in the case of containing silver particles described later, the total content of the surface-treated copper particles and silver particles) ) It is more preferable to include. Further, the surface contains 0.01 to 10% by mass of at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyaniline resins, and metal alkoxides.
- the surface-treated phosphorus-containing copper alloy particles having been treated and having a phosphorus content of 8% by mass or less were 70 to 94% by mass in the electrode paste composition (when silver particles described later were included, the surface treatment was performed).
- Total content of phosphorus-containing copper alloy particles and silver particles preferably 0.05 to 8% by mass of at least one selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids and inorganic metal compound salts
- conductive particles other than the surface-treated copper particles may be used in combination.
- the electrode paste composition of the present invention contains at least one kind of glass particles.
- the silicon nitride film as the antireflection film is removed by so-called fire-through at the electrode formation temperature, and an ohmic contact between the electrode and the silicon substrate is formed.
- the glass particles are usually used in the technical field as long as they can soften and melt at the electrode formation temperature, oxidize the contacted silicon nitride film, and take the oxidized silicon dioxide to remove the antireflection film.
- the glass particles used can be used without particular limitation.
- glass particles containing glass having a glass softening point of 600 ° C. or lower and a crystallization start temperature exceeding 600 ° C. are preferable from the viewpoint of oxidation resistance and low resistivity of the electrode.
- the glass softening point is measured by a usual method using a thermomechanical analyzer (TMA), and the crystallization start temperature is measured using a differential heat-thermogravimetric analyzer (TG-DTA). Measured by method.
- TMA thermomechanical analyzer
- TG-DTA differential heat-thermogravimetric analyzer
- the glass particles contained in the electrode paste composition are composed of glass containing lead because silicon dioxide can be taken up efficiently.
- lead-containing glass examples include those described in Japanese Patent No. 03050064, and these can also be suitably used in the present invention.
- lead-free glass it is preferable to use lead-free glass that does not substantially contain lead in consideration of the influence on the environment.
- Examples of the lead-free glass include lead-free glass described in paragraphs 0024 to 0025 of JP-A-2006-313744 and lead-free glass described in JP-A-2009-188281. It is also preferable that the lead-free glass is appropriately selected and applied to the present invention.
- the glass particles are preferably made of glass containing diphosphorus pentoxide (phosphate glass, P 2 O 5 glass) from the viewpoint of low contact resistivity.
- diphosphorus pentoxide phosphate glass, P 2 O 5 glass
- divanadium pentoxide More preferably, it is made of a glass further containing (P 2 O 5 —V 2 O 5 glass).
- the oxidation resistance is further improved, and the resistivity of the electrode is further reduced. This can be attributed to, for example, that the softening point of the glass is lowered by further containing divanadium pentoxide.
- the content of divanadium pentoxide is 1 in the total mass of the glass.
- the content is preferably at least mass%, more preferably 1 to 70 mass%.
- the diphosphorus pentoxide-divanadium pentoxide glass may further contain other components as required.
- silicon dioxide derived from silicon nitride can be incorporated more efficiently. Further, the softening / dissolution temperature can be further reduced. Furthermore, reaction with copper containing particle
- the glass particles are glass particles not containing divanadium pentoxide.
- divanadium pentoxide By not containing divanadium pentoxide, rapid softening of the glass particles when the electrode paste composition is heated can be suppressed, and a more homogeneous electrode can be formed.
- the glass component material constituting the glass particles not containing divanadium pentoxide include silicon dioxide (SiO 2 ), phosphorus oxide (P 2 O 5 ), aluminum oxide (Al 2 O 3 ), and boron oxide (B 2 O 3).
- the content of the glass particles is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total mass of the electrode paste composition, and 1 to 7% by mass. % Is more preferable.
- the glass particles preferably contain 0.1 to 10% by mass of glass particles made of P 2 O 5 —V 2 O 5 based glass, and the content of V 2 O 5 is 1% by mass or more. more preferably include some P 2 O 5 -V 2 O 5 based 0.5-8 wt% glass particles consisting of glass, P 2 O 5 -V content of V 2 O 5 is at least 1 mass% More preferably, it contains 1 to 7% by mass of glass particles made of 2 O 5 glass.
- glass particles SiO 2, Al 2 O 3 , B 2 O 3, K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 It is also preferable to contain 0.1 to 10% by mass of glass particles composed of at least one selected from WO 3 and MoO 3, from SiO 2 , Al 2 O 3 , B 2 O 3 , ZnO, and PbO. More preferably, it contains 1 to 7% by mass of at least one selected glass particle.
- the electrode paste composition of the present invention contains at least one solvent and at least one resin.
- the liquid physical property for example, a viscosity, surface tension, etc.
- the paste composition for electrodes of this invention can be adjusted to the required liquid physical property according to the provision method at the time of providing to a silicon substrate.
- the solvent is not particularly limited.
- hydrocarbon solvents such as hexane, cyclohexane and toluene
- chlorinated hydrocarbon solvents such as dichloroethylene, dichloroethane and dichlorobenzene
- cyclics such as tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane and trioxane Ether solvents
- amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide
- sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide
- ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone
- ethanol Alcohol compounds such as 2-propanol, 1-butanol and diacetone alcohol; 2,2,4-trimethyl-1,3-pentane
- a polyhydric alcohol ester solvent, a terpene solvent, and a polyhydric alcohol ether solvent from the viewpoints of coatability and printability when the electrode paste composition is formed on a silicon substrate.
- the said solvent may be used individually by 1 type or in combination of 2 or more types.
- any resin that is usually used in the technical field can be used as long as it can be thermally decomposed by firing.
- cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and nitrocellulose
- polyvinyl alcohols such as polyvinyl alcohols
- polyvinyl pyrrolidones acrylic resins
- vinyl acetate-acrylic acid ester copolymers such as polyvinyl butyral
- phenol examples thereof include alkyd resins such as modified alkyd resins and castor oil fatty acid modified alkyd resins; epoxy resins; phenol resins; rosin ester resins.
- the resin in the present invention is preferably at least one selected from cellulosic resins and acrylic resins, and more preferably at least one selected from cellulosic resins, from the viewpoint of disappearance during firing. preferable.
- the said resin may be used individually by 1 type or in combination of 2 or more types.
- the content of the solvent and the resin can be appropriately selected according to the desired liquid properties and the type of solvent and resin used.
- the total content of the solvent and the resin is preferably 3% by mass or more and 29.9% by mass or less, and more preferably 5% by mass or more and 25% by mass or less based on the total mass of the electrode paste composition. Preferably, it is 7 mass% or more and 20 mass% or less.
- the electrode paste composition of the present invention preferably further contains at least one silver particle.
- the oxidation resistance is further improved, and the resistivity as an electrode is further reduced.
- the effect that the solder connection property at the time of setting it as a solar cell module improves is also acquired. This can be considered as follows, for example.
- a small amount of solid solution of silver in copper and a small amount of solid solution of copper in silver occur.
- -A silver solid solution layer (solid solution region) is formed.
- a mixture of copper-containing particles and silver particles is heated to a high temperature and then slowly cooled to room temperature, it is considered that a solid solution region does not occur, but at the time of electrode formation, it is cooled from the high temperature region to room temperature in a few seconds.
- the solid solution layer covers the surface of silver particles and copper-containing particles as a non-equilibrium solid solution phase or a eutectic structure of copper and silver.
- Such a copper-silver solid solution layer can be considered to contribute to the oxidation resistance of the copper-containing particles at the electrode formation temperature.
- the copper-silver solid solution layer starts to be formed at a temperature of 300 ° C. to 500 ° C. or higher. Therefore, by using silver particles together with copper-containing particles having a peak temperature of an exothermic peak showing a maximum area in simultaneous differential heat-thermogravimetric measurement of 280 ° C. or more, the oxidation resistance of the copper-containing particles can be more effectively improved. It can be considered that the resistivity of the formed electrode is further reduced.
- the silver constituting the silver particles may contain other atoms inevitably mixed.
- other atoms inevitably mixed for example, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, Zr, W , Mo, Ti, Co, Ni, Au, and the like.
- the particle diameter of the silver particles in the present invention is not particularly limited, but the particle diameter (D50%) when the accumulated weight is 50% is preferably 0.4 ⁇ m or more and 10 ⁇ m or less, and 1 ⁇ m or more and 7 ⁇ m or less. It is more preferable that When the thickness is 0.4 ⁇ m or more, the oxidation resistance is more effectively improved. Moreover, the contact area of metal particles, such as a silver particle and copper containing particle
- the relationship between the particle diameter of the copper-containing particles (D50%) and the particle diameter of the silver particles (D50%) is not particularly limited, but either one of the particle diameters (D50 %) Is smaller than the other particle size (D50%), and the ratio of the other particle size to any one particle size is more preferably 1 to 10.
- the resistivity of an electrode falls more effectively. This can be attributed to, for example, an increase in the contact area between metal particles such as copper-containing particles and silver particles in the electrode.
- the silver particle content in the electrode paste composition of the present invention is 8.4 to 85.5% by mass in the electrode paste composition from the viewpoint of oxidation resistance and low electrode resistivity. It is preferably 8.9 to 80.1% by mass. Furthermore, in the present invention, from the viewpoint of oxidation resistance and low resistivity of the electrode, the content of the copper-containing particles is 9 to 88% by mass when the total amount of the copper-containing particles and the silver particles is 100% by mass. Preferably, it is 17 to 77% by mass. When the content of the copper-containing particles is 9% by mass or more, for example, when the glass particles contain divanadium pentoxide, the reaction between silver and vanadium is suppressed, and the volume resistance of the electrode is further reduced.
- the electrode material is resistant to hydrofluoric acid (the property that the electrode material does not separate from the silicon substrate by the hydrofluoric acid aqueous solution). Will improve. Moreover, it becomes more suppressed that the content rate of the said copper containing particle
- the total content of the copper-containing particles and the silver particles is 70% by mass or more and 94 from the viewpoint of oxidation resistance, low resistivity of the electrode, and applicability to a silicon substrate. It is preferable that it is mass% or less, and it is more preferable that it is 74 mass% or more and 88 mass% or less.
- a suitable viscosity can be easily achieved when the electrode paste composition is applied.
- production of the glaze at the time of providing the paste composition for electrodes can be suppressed more effectively because the total content of the said copper containing particle
- the total content of the copper-containing particles and the silver particles is 70% by mass or more and 94% by mass or less, Preferably, the glass particle content is 0.1% by mass or more and 10% by mass or less, and the total content of the solvent and the resin is 3% by mass or more and 29.9% by mass or less.
- the total content of the particles and the silver particles is 74 mass% or more and 88 mass% or less, the content of the glass particles is 0.5 mass% or more and 8 mass% or less, and the total content of the solvent and the resin
- the content is more preferably 7% by mass or more and 20% by mass or less, and the total content of the copper-containing particles and the silver particles is 74% by mass or more and 88% by mass or less, and the content of the glass particles is 1% to 7% by mass It is more preferable that the total content of the solvent and the resin is 20 mass% or less 7 mass% or more.
- the electrode paste composition preferably further includes at least one phosphorus-containing compound.
- oxidation resistance improves more effectively and the resistivity of an electrode falls more.
- the element in the phosphorus-containing compound diffuses as an n-type dopant, and the effect that the power generation efficiency is further improved when a solar cell is obtained.
- the phosphorus-containing compound is a compound having a large phosphorus atom content in the molecule from the viewpoint of oxidation resistance and low resistivity of the electrode, and does not cause evaporation or decomposition under a temperature condition of about 200 ° C. Preferably there is.
- the phosphorus-containing compound include phosphorus-based inorganic acids such as phosphoric acid, phosphates such as ammonium phosphate, phosphate esters such as phosphate alkyl esters and aryl phosphate esters, and cyclic phosphazenes such as hexaphenoxyphosphazene. As well as their derivatives.
- the phosphorus-containing compound in the present invention is preferably at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene, from the viewpoint of oxidation resistance and low electrode resistivity. More preferably, it is at least one selected from the group consisting of phosphate esters and cyclic phosphazenes.
- the content of the phosphorus-containing compound in the present invention is preferably 0.5 to 10% by mass in the total mass of the electrode paste composition from the viewpoints of oxidation resistance and low electrode resistivity. More preferably, it is ⁇ 7% by mass. Furthermore, in the present invention, at least one selected from the group consisting of phosphoric acid, ammonium phosphate, phosphate ester, and cyclic phosphazene is used as the phosphorus-containing compound in an amount of 0.5 to 10 in the total mass of the electrode paste composition. It is preferable to include at least 1 mass%, and more preferably at least one selected from the group consisting of phosphate esters and cyclic phosphazenes is included in the total mass of the electrode paste composition.
- the total content of the copper-containing particles and the silver particles is from 70% by mass to 94% by mass from the viewpoint of oxidation resistance and low resistivity of the electrode. It is below, Comprising: The content rate of the said glass particle is 0.1 mass% or more and 10 mass% or less, Comprising: The total content rate of the said solvent, the said resin, and the said phosphorus containing compound is 3 mass% or more and 29.9 mass%.
- the total content of the copper-containing particles and the silver particles is preferably 74% by mass or more and 88% by mass or less, and the content of the glass particles is 0.5% by mass or more and 8% by mass or less.
- the total content of the solvent, the resin and the phosphorus-containing compound is more preferably 7% by mass or more and 20% by mass or less, and the total content of the copper-containing particles and the silver particles is 74% by mass or more. 88% by mass or less
- the content of the glass particles is not more than 7 mass% to 1 mass%, the solvent, it is more preferable that the total content of the resin and the phosphorus-containing compound is 20 mass% or less 7 mass% or more.
- the electrode paste composition may further include at least one flux.
- the oxidation resistance is further improved, and the resistivity of the formed electrode is further reduced. Furthermore, the effect that the adhesiveness of an electrode material and a silicon substrate improves is also acquired.
- the flux in the present invention is not particularly limited as long as the oxide film formed on the surface of the copper-containing particles can be removed.
- fatty acids, boric acid compounds, fluorinated compounds, borofluorinated compounds and the like can be mentioned as preferred fluxes.
- examples include lithium, acidic potassium fluoride, acidic sodium fluoride, acidic lithium fluoride, potassium fluoride, sodium fluoride, and lithium fluoride.
- potassium borate and potassium borofluoride are particularly preferable fluxes from the viewpoints of heat resistance at the time of firing the electrode material (characteristic that the flux does not volatilize at low temperatures during firing) and supplementing the oxidation resistance of the copper-containing particles.
- each of these fluxes may be used alone or in combination of two or more.
- the total amount of the electrode paste composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and 0.5 to 3.5% by mass. More preferably, it is 0.7 to 3% by mass, particularly preferably 1 to 2.5% by mass.
- the electrode paste composition of the present invention can further contain other components usually used in the technical field, if necessary, in addition to the components described above.
- other components include a plasticizer, a dispersant, a surfactant, an inorganic binder, a metal oxide, a ceramic, and an organometallic compound.
- the copper-containing particles, glass particles, solvent, resin, and silver particles contained as necessary can be produced by dispersing and mixing them using a commonly used dispersion and mixing method.
- the electrode paste composition is applied to a region where an electrode is to be formed, and after drying, the electrode is formed in a desired region by firing. be able to.
- an electrode having a low resistivity can be formed even when a baking treatment is performed in the presence of oxygen (for example, in the air).
- the electrode paste composition is applied on a silicon substrate so as to have a desired shape, and dried and fired. Thereby, a solar cell electrode with low resistivity can be formed in a desired shape.
- an electrode having a low resistivity can be formed even when a baking treatment is performed in the presence of oxygen (for example, in the air).
- Examples of the method for applying the electrode paste composition onto the silicon substrate include screen printing, an ink jet method, a dispenser method, and the like. From the viewpoint of productivity, application by screen printing is preferable.
- the electrode paste composition of the present invention When the electrode paste composition of the present invention is applied by screen printing, it preferably has a viscosity in the range of 80 to 1000 Pa ⁇ s.
- the viscosity of the electrode paste composition is measured at 25 ° C. using a Brookfield HBT viscometer.
- the application amount of the electrode paste composition can be appropriately selected according to the size of the electrode to be formed.
- the applied amount of the electrode paste composition can be 2 to 10 g / m 2, and preferably 4 to 8 g / m 2 .
- heat treatment conditions when forming an electrode using the electrode paste composition of the present invention, heat treatment conditions usually used in the technical field can be applied.
- the heat treatment temperature (firing temperature) is 800 to 900 ° C.
- heat treatment conditions at a lower temperature can be applied, for example, 600 to 850.
- An electrode having good characteristics can be formed at a heat treatment temperature of ° C.
- the heat treatment time can be appropriately selected according to the heat treatment temperature and the like, and can be, for example, 1 second to 20 seconds.
- the solar cell of this invention has the electrode formed by baking the said paste composition for electrodes provided on the silicon substrate. Thereby, the solar cell which has a favorable characteristic is obtained, and it is excellent in the productivity of this solar cell.
- single crystal or polycrystalline Si is used for the semiconductor substrate 130 of the solar cell element.
- the semiconductor substrate 130 contains boron or the like and constitutes a p-type semiconductor.
- irregularities are formed by etching in order to suppress reflection of sunlight.
- an n-type semiconductor diffusion layer 131 is provided with a thickness of submicron order, and a pn junction is formed at the boundary with the p-type bulk portion.
- an antireflection layer 132 such as silicon nitride is provided on the diffusion layer 131 with a film thickness of about 100 nm by vapor deposition or the like.
- the light receiving surface electrode 133 provided on the light receiving surface side, and the current collecting electrode 134 and the output extraction electrode 135 formed on the back surface will be described.
- the light-receiving surface electrode 133 and the output extraction electrode 135 are formed from the electrode paste composition.
- the collecting electrode 134 is formed from an aluminum electrode paste composition containing glass powder. These electrodes are formed by applying the paste composition to a desired pattern by screen printing or the like, and then baking the paste composition at about 600 to 850 ° C. in the atmosphere. In the present invention, by using the electrode paste composition, an electrode having excellent resistivity and contact resistivity can be formed even when fired at a relatively low temperature.
- the glass particles contained in the electrode paste composition forming the light receiving surface electrode 133 react with the antireflection layer 132 (fire-through), and the light receiving surface electrode 133 and the diffusion layer are reacted. 131 is electrically connected (ohmic contact).
- the light-receiving surface electrode 133 is formed using the electrode paste composition, so that copper is suppressed as a conductive metal, and the oxidation of copper is suppressed. , Formed with good productivity.
- aluminum in the aluminum electrode paste composition that forms the collecting electrode 134 during firing diffuses to the back surface of the semiconductor substrate 130 to form the electrode component diffusion layer 136, thereby forming the semiconductor substrate 130.
- Ohmic contact can be obtained between the current collector electrode 134 and the output extraction electrode 135.
- FIG. 4 shows a perspective view (a) of a light receiving surface and an AA cross-sectional structure as an example of a solar cell element according to another aspect of the present invention, and a plan view (b) of a back surface side electrode structure.
- the cell wafer 1 made of a p-type semiconductor silicon substrate is formed with through holes penetrating both the light receiving surface side and the back surface side by laser drilling or etching. .
- a texture (not shown) for improving the light incident efficiency is formed on the light receiving surface side.
- an n-type semiconductor layer 3 by n-type diffusion treatment and an antireflection film are formed on the n-type semiconductor layer 3. These are manufactured by the same process as a conventional crystalline Si type solar battery cell.
- the electrode paste composition of the present invention is filled into the previously formed through-holes by a printing method or an ink jet method, and the electrode paste composition of the present invention is also formed in a grid on the light receiving surface side.
- the composition layer which is printed and forms the through-hole electrode 4 and the current collecting grid electrode 2 is formed.
- a heavily doped layer 5 for preventing carrier recombination is formed on the opposite side (back side) of the light receiving surface.
- boron (B) or aluminum (Al) is used as an impurity element for forming the heavily doped layer 5, and a p + layer is formed.
- the high-concentration doped layer 5 may be formed by performing a thermal diffusion process using, for example, B as a diffusion source in a cell manufacturing process before forming the antireflection film, or when using Al. May be formed by printing an Al paste on the opposite surface side in the printing step.
- the electrode paste composition fired at 650 to 850 ° C., filled in and printed on the antireflection film formed in the through hole and on the light receiving surface side, has a lower n-type layer due to the fire through effect. Ohmic contact is achieved.
- the electrode paste composition according to the present invention is printed and fired in stripes on the n side and the p side, respectively. 7 is formed.
- the through-hole electrode 4, the current collecting grid electrode 2, the back electrode 6 and the back electrode 7 are formed using the electrode paste composition, so that copper is contained as a conductive metal, Copper oxidation is suppressed, and the low resistivity through-hole electrode 4, current collecting grid electrode 2, back electrode 6 and back electrode 7 are formed with excellent productivity.
- the electrode paste composition of the present invention is not limited to the use of the solar cell electrode as described above.
- Example 1 Preparation of electrode paste composition A phosphorus-containing copper alloy containing 1% by mass of phosphorus was prepared, dissolved and powdered by the water atomization method, and then dried and classified. The classified powders were blended and subjected to deoxygenation / dehydration treatment to produce phosphorus-containing copper alloy particles containing 1% by mass of phosphorus. The particle diameter (D50%) of the phosphorus-containing copper alloy particles was 1.5 ⁇ m. Also, simultaneous differential thermal-thermogravimetric measurement (TG-DTA) is performed in a normal atmosphere using a measuring device: differential thermal-thermogravimetric analyzer (TG / DTA-6200, manufactured by SII Nanotechnology).
- TG-DTA simultaneous differential thermal-thermogravimetric measurement
- Measurement temperature range room temperature to 1000 ° C., heating rate: 40 ° C./min, atmospheric flow rate: 200 ml / min.
- V 2 O 5 vanadium oxide
- P 2 O 5 barium oxide
- WO 3 tungsten oxide
- Na 2 O sodium oxide
- G19 oxidation A glass (hereinafter sometimes abbreviated as “G19”) composed of 3 parts of potassium (K 2 O), 10 parts of zinc oxide (ZnO), and 8 parts of manganese oxide (MnO) was prepared.
- the obtained glass G19 had a softening point of 447 ° C. and a crystallization temperature of over 600 ° C.
- glass particles having a particle diameter (D50%) of 1.7 ⁇ m were obtained.
- an aluminum electrode paste was similarly printed on the back surface by screen printing.
- the printing conditions were appropriately adjusted so that the film thickness after firing was 40 ⁇ m. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation. Subsequently, heat treatment (baking) was performed at 850 ° C. for 2 seconds in an infrared rapid heating furnace in an air atmosphere to produce a solar battery cell 1 on which a desired electrode was formed.
- Example 2 the solar cell 2 on which the desired electrode was formed was obtained in the same manner as in Example 1 except that the temperature of the heat treatment (firing) at the time of electrode formation was changed to 750 ° C. instead of 850 ° C. Produced.
- Example 3 phosphorus content of phosphorus-containing copper alloy particles, particle diameter (D50%) and content, silver particle diameter (D50%) and content, glass particle type and content, 4% ethylcellulose Except that the content of butyl carbitol acetate (BCA) solution containing (EC) and the type and content of phosphorus-containing compounds contained as necessary were changed as shown in Table 1.
- electrode paste compositions 3 to 15 and electrode paste compositions 43 to 46 were prepared.
- the glass particles (AY1) are composed of 45 parts of vanadium oxide (V 2 O 5 ), 24.2 parts of phosphorus oxide (P 2 O 5 ), 20.8 parts of barium oxide (BaO), and antimony oxide (Sb 2 O 3). ) 5 parts and 5 parts of tungsten oxide (WO 3 ), and the particle diameter (D50%) was 1.7 ⁇ m.
- the glass had a softening point of 492 ° C. and a crystallization temperature of over 600 ° C.
- Glass particles (D10) are composed of 64 parts of lead oxide (PbO), 11 parts of boron oxide (B 2 O 3 ), 5 parts of aluminum oxide (Al 2 O 3 ), 10 parts of silicon dioxide (SiO 2 ), zinc oxide ( It consisted of 10 parts of ZnO) and the particle diameter (D50%) was 2.3 ⁇ m.
- the glass had a softening point of 440 ° C. and a crystallization temperature of over 600 ° C. Furthermore, triphenyl phosphate was used as the phosphate ester, and hexaphenoxyphosphazene was used as the cyclic phosphazene.
- Examples were used except that the obtained electrode paste compositions 3 to 15 and electrode paste compositions 43 to 46 were used, respectively, and the heat treatment temperature and treatment time were changed as shown in Table 1.
- solar cells 3 to 15 and solar cells 43 to 46 on which desired electrodes were formed were produced.
- Example 1 For electrode preparation in the same manner as in Example 1, except that the phosphorus-containing copper alloy particles were not used in the preparation of the electrode paste composition in Example 1 and each component was changed to the composition shown in Table 1.
- Paste composition C1 was prepared.
- a solar cell C1 was produced in the same manner as in Example 1 except that the electrode paste composition C1 containing no phosphorus-containing copper alloy particles was used.
- Comparative Example 2 a solar cell C2 was produced in the same manner as in Comparative Example 1, except that the temperature of the heat treatment (firing) at the time of electrode formation was changed to 750 ° C. instead of 850 ° C.
- Example 3 An electrode paste composition C3 was prepared in the same manner as in Example 1 except that in Example 1, pure copper not containing phosphorus (phosphorus content was 0%) was changed. A solar cell C3 was produced in the same manner as in Example 1 except that the electrode paste composition C3 was used.
- the performance of the solar cells produced in Examples 1 to 15 and Examples 43 to 46 was almost the same as the measured value of Comparative Example 1.
- the solar cells 44 to 46 formed electrodes without using silver particles, but exhibited high power generation performance.
- the diffraction angles (2 ⁇ , CuK ⁇ rays) were at least 43.4 °, 50.6 °, 74.2 ° and copper
- the characteristic diffraction peak was shown.
- the following principle can be cited as the reason why copper is detected from the light receiving surface electrode.
- the phosphorus-containing copper alloy particles in the electrode paste compositions 44 to 46 have a phosphorus content of 7% by mass.
- This composition consists of a Cu phase and a Cu 3 P phase from a Cu—P phase diagram.
- the Cu phase is oxidized and changed to CuO. It is considered that this CuO and Cu 3 P react to form a Cu phase.
- a phosphorus-containing copper particle having a phosphorus content of 7% by mass and a particle diameter (D50%) of 5.0 ⁇ m is subjected to a differential thermal-thermogravimetric analyzer in a normal atmosphere.
- TG / DTA-6200 manufactured by SII Nanotechnology Inc.
- TG-DTA differential heat -Simultaneous thermogravimetric measurement
- Example 16> Using the electrode paste composition 1 obtained above, a solar cell 16 having a structure as shown in FIG. 4 was produced. The heat treatment was performed at 750 ° C. for 10 seconds. When the obtained solar battery cell was evaluated in the same manner as described above, it was found that the same characteristics as described above were exhibited.
- Example 17 (A) Preparation of electrode paste composition
- Silver-coated copper particles prepared by the method described in JP-A-14-100191 (manufactured by Hitachi Chemical Co., Ltd., silver coating amount 20 mass%, particle diameter 5.8 ⁇ m) 85.1 parts, 1.7 parts of glass particles, and 13.2 parts of a butyl carbitol acetate (BCA) solution containing 4% ethyl cellulose (EC) are mixed together and stirred for 20 minutes in an agate mortar.
- An electrode paste composition 17 was prepared.
- an aluminum electrode paste was similarly printed on the back surface by screen printing.
- the printing conditions were appropriately adjusted so that the film thickness after firing was 40 ⁇ m. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation. Subsequently, heat treatment (baking) was performed at 850 ° C. for 2 seconds in an infrared rapid heating furnace in an air atmosphere to produce a solar battery cell 17 on which a desired electrode was formed.
- Example 17 the silver coating amount and content of the silver-coated copper particles, the particle diameter (D50%) of the silver particles used as necessary, and the content, the type and content of the glass particles, and 4% Electrode paste compositions 18 to 25 were prepared in the same manner as in Example 17 except that the content of the butyl carbitol acetate (BCA) solution containing ethyl cellulose (EC) was changed as shown in Table 3.
- BCA butyl carbitol acetate
- EC ethyl cellulose
- a desired electrode was formed in the same manner as in Example 17 except that the obtained electrode paste compositions 18 to 25 were used, respectively, and the heat treatment temperature and treatment time were changed as shown in Table 3.
- the solar cells 18 to 25 thus prepared were respectively produced.
- Example 4 The electrode paste was prepared in the same manner as in Example 17 except that the silver-coated copper particles were not used in the preparation of the electrode paste composition in Example 17 and each component was changed to the composition shown in Table 3. Composition C4 was prepared. A solar cell C4 was produced in the same manner as in Example 17 except that the electrode paste composition C4 containing no silver-coated copper particles was used.
- Comparative Example 5 a solar cell C5 was produced in the same manner as in Comparative Example 4 except that the temperature of the heat treatment (firing) at the time of electrode formation was changed to 750 ° C. instead of 850 ° C.
- Example 6 The electrode paste was prepared in the same manner as in Example 17 except that the silver-coated copper particles were not used in the preparation of the electrode paste composition in Example 17 and each component was changed to the composition shown in Table 3. Composition C6 was prepared. A solar cell C6 was produced in the same manner as in Example 17 except that the electrode paste composition C6 was used.
- Example 26 Using the electrode paste composition 19 obtained above, a solar battery cell 26 having a structure as shown in FIG. 4 was produced. The heat treatment was performed at 750 ° C. for 10 seconds. When the obtained solar battery cell was evaluated in the same manner as described above, it was found that the same characteristics as described above were exhibited.
- Example 27 (A) Preparation of electrode paste composition Benzotriazole (BTA) as a surface treatment agent was dissolved in a solvent ethanol to prepare a 50% surface treatment solution. Copper powder (Fukuda Metal Foil Powder Co., Ltd., purity 99.9%, particle diameter 5 ⁇ m) was immersed in this for 50 minutes, and then dried to prepare surface-treated copper particles. The content of the surface treatment agent in the surface-treated copper particles was 1% in the total mass of the surface-treated copper particles. The particle diameter (D50%) was 5 ⁇ m.
- BTA Benzotriazole
- an aluminum electrode paste was similarly printed on the back surface by screen printing.
- the printing conditions were adjusted as appropriate so that the film thickness after firing was 40 ⁇ m. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation. Subsequently, heat treatment (baking) was performed at 850 ° C. for 2 seconds in an infrared rapid heating furnace in an air atmosphere to produce a solar battery cell 27 on which a desired electrode was formed.
- Example 27 the type and content of the surface treatment agent for the surface-treated copper particles, the content of silver particles, the type and content of glass particles, butyl carbitol acetate (BCA) containing 4% ethyl cellulose (EC) ) Electrode paste composition 28 in the same manner as in Example 27, except that the content of the solution and the type and content of the phosphorus-containing compound contained as necessary were changed as shown in Table 5. ⁇ 41 were prepared.
- a desired electrode was formed in the same manner as in Example 27, except that the obtained electrode paste compositions 28 to 41 were used, respectively, and the heat treatment temperature and treatment time were changed as shown in Table 5. Thus produced solar cells 28 to 41 were produced.
- Example 7 The electrode was prepared in the same manner as in Example 27 except that each component was changed to the composition shown in Table 5 without using the surface-treated copper particles in the preparation of the electrode paste composition in Example 27.
- Paste composition C7 was prepared.
- a solar cell C7 was produced in the same manner as in Example 27 except that the electrode paste composition C7 containing no surface-treated copper particles was used.
- Comparative Example 8 a solar cell C8 was produced in the same manner as in Comparative Example 7, except that the temperature of the heat treatment (firing) at the time of electrode formation was changed to 750 ° C. instead of 850 ° C.
- Example 9 ⁇ Comparative Example 9>
- the surface treatment amount of the surface-treated copper particles was changed to 0.0001% where the peak temperature of the exothermic peak showing the maximum area in the differential thermal-thermogravimetric simultaneous measurement was 230 ° C.
- an electrode paste composition C9 was prepared.
- a solar cell C9 was produced in the same manner as in Example 27 except that the electrode paste composition C9 was used.
- Example 42 Using the electrode paste composition 27 obtained above, a solar battery cell 42 having a structure as shown in FIG. 4 was produced. The heat treatment was performed at 750 ° C. for 10 seconds. When the obtained solar battery cell was evaluated in the same manner as described above, it was found that the same characteristics as described above were exhibited.
- the electrode paste composition of the present invention even if copper is used as the conductive metal of the electrode, an electrode with low resistivity can be formed, and a solar cell exhibiting excellent characteristics can be configured. I understand that. Moreover, it turns out that the performance equivalent to or more than the conventional electrode paste composition using silver was shown also in the processing temperature (baking temperature) of 750 degreeC and 850 degreeC.
Abstract
Description
本発明の電極用ペースト組成物は、示差熱-熱重量同時測定において最大面積を示す発熱ピークのピーク温度が280℃以上である銅含有粒子の少なくとも1種と、ガラス粒子の少なくとも1種と、溶剤の少なくとも1種と、樹脂の少なくとも1種と、を含む。
かかる構成であることにより、焼成時における銅の酸化が抑制され、抵抗率の低い電極が形成可能である。
本発明における銅含有粒子は、示差熱-熱重量同時測定(TG-DTA)において最大面積を示す発熱ピークのピーク温度が280℃以上である。かかる耐酸化性が付与された銅含有粒子を用いることで焼成時における金属銅の酸化が抑制され、低抵抗率の電極を形成することができる。なお、示差熱-熱重量同時測定は通常の大気中で、測定装置:示差熱-熱重量分析装置(エスアイアイ・ナノテクノロジー社製、TG/DTA-6200型)を用いて、例えば、測定温度範囲:室温~1000℃、昇温速度:40℃/分、大気流量:200ml/分の条件で行われる。
一般に純銅(金属銅)について示差熱-熱重量同時測定を行うと、最大面積を示す発熱ピークにおけるピーク温度は200℃付近となるが、本発明に用いられる銅含有粒子においては該ピーク温度が280℃以上である。さらに本発明においては、電極としての低抵抗率の観点から、該ピーク温度が280~800℃であることが好ましく、290~750℃であることがより好ましく、350~750℃であることがさらに好ましい。
具体的には例えば、リン含有銅合金粒子、銀被覆された銅粒子、並びに、トリアゾール化合物、飽和脂肪酸、不飽和脂肪酸、無機金属化合物塩、有機金属化合物塩、ポリアニリン系樹脂、及び金属アルコキシドからなる群から選ばれる少なくとも1種で表面処理された銅粒子を挙げることができ、これらから選ばれる少なくとも1種を用いることが好ましい。また前記銅含有粒子は1種単独でも、2種以上を組み合わせて用いてもよい。
また前記銅含有粒子の形状としては特に制限はなく、略球状、扁平状、ブロック状、板状、及び鱗片状等のいずれであってもよい。前記銅含有粒子の形状は、耐酸化性と低抵抗率の観点から、略球状、扁平状、または板状であることが好ましい。
また本発明においては、前記銅含有粒子以外の導電性の粒子を組み合わせて用いても良い。
リン含有銅合金としては、リン銅ろう(リン濃度:7質量%程度以下)と呼ばれるろう付け材料が知られている。リン銅ろうは、銅と銅との接合剤としても用いられるものであるが、本発明の電極用ペースト組成物に含まれる銅含有粒子としてリン含有銅合金粒子を用いることで、耐酸化性に優れ、抵抗率の低い電極を形成することができる。さらに電極の低温焼成が可能となり、プロセスコストを削減できるという効果を得ることができる。
リン含有銅合金に含まれるリン含有率が8質量%以下であることで、より低い抵抗率を達成可能であり、また、リン含有銅合金の生産性に優れる。また0.01質量%以上であることで、より優れた耐酸化性を達成できる。
また前記リン含有銅合金粒子に含まれる他の原子の含有率は、例えば、前記リン含有銅合金粒子中に3質量%以下とすることができ、耐酸化性と低抵抗率の観点から、1質量%以下であることが好ましい。
また前記リン含有銅合金粒子の形状としては特に制限はなく、略球状、扁平状、ブロック状、板状、及び鱗片状等のいずれであってもよい。前記リン含有銅合金粒子の形状は、耐酸化性と低抵抗率の観点から、略球状、扁平状、または板状であることが好ましい。
具体的には例えば、リン含有銅合金を溶解し、これをノズル噴霧によって粉末化した後、得られた粉末を乾燥、分級することで、所望のリン含有銅合金粒子を製造することができる。また、分級条件を適宜選択することで所望の粒子径を有するリン含有銅合金粒子を製造することができる。
また本発明において前記リン含有銅合金粒子は1種単独でも、2種以上を組み合わせて用いてもよい。さらにリン銅合金粒子以外であって、最大面積を示す発熱ピークにおけるピーク温度が280℃以上である銅含有粒子と組み合わせて用いてもよい。
また本発明においては、前記リン含有銅合金粒子以外の導電性の粒子を組み合わせて用いてもよい。
本発明における銀被覆銅粒子としては、銅粒子の表面の少なくとも一部が銀で被覆されているものであればよい。本発明の電極用ペースト組成物に含まれる銅含有粒子として、銀被覆銅粒子を用いることで、耐酸化性に優れ、抵抗率の低い電極を形成することができる。さらに銅粒子が銀で被覆されていることで、銀被覆銅粒子と銀粒子との界面抵抗が低下し、抵抗率がより低下した電極を形成することができる。またさらに、電極用ペースト組成物に水分が混入した場合に、銀被覆銅粒子を用いることで、室温における銅の酸化を抑制でき、ポットライフを向上できるという効果を得ることができる。
また前記銀被覆銅粒子の形状としては特に制限はなく、略球状、扁平状、ブロック状、板状、及び鱗片状等のいずれであってもよい。前記銀被覆銅粒子の形状は、耐酸化性と低抵抗率の観点から、略球状、扁平状、または板状であることが好ましい。
また前記銀被覆銅粒子に含まれる他の原子の含有率は、例えば、前記銀被覆銅粒子中に3質量%以下とすることができ、耐酸化性と低抵抗率の観点から、1質量%以下であることが好ましい。
銀被覆銅粒子におけるリン含有銅合金の詳細については、既述のリン含有銅合金と同義であり、好ましい態様も同様である。
前記キレート化剤としては特に制限はないが、例えば、エチレンジアミン四酢酸塩、トリエチレンジアミン、ジエチレントリアミン五酢酸、イミノ二酢酸等を用いることができる。また銀イオン溶液としては、例えば、硝酸銀溶液等を用いることができる。
また本発明において前記銀被覆銅粒子は1種単独でも、2種以上を組み合わせて用いてもよい。また、銀被覆銅粒子以外であって、最大面積を示す発熱ピークにおけるピーク温度が280℃以上である銅含有粒子と組み合わせて用いてもよい。
さらに銀含有率が1~88質量%であって、リン含有率が0.01~8質量%である銀被覆リン含有銅合金粒子を、電極用ペースト組成物中に70~94質量%(後述する銀粒子を含む場合は、銀被覆リン含有銅合金粒子と銀粒子の総含有率)含むことが好ましく、銀含有率が5~75質量%であって、リン含有率が1~7.5質量%以下である銀被覆リン含有銅合金粒子を、電極用ペースト組成物中に74~88質量%(後述する銀粒子を含む場合は、銀被覆リン含有銅合金粒子と銀粒子の総含有率)含むことがより好ましい。
また本発明においては、前記銀被覆銅粒子以外の導電性の粒子を組み合わせて用いてもよい。
本発明における銅含有粒子は、トリアゾール化合物、飽和脂肪酸、不飽和脂肪酸、無機金属化合物塩、有機金属化合物塩、ポリアニリン系樹脂、及び金属アルコキシドからなる群(以下、「表面処理剤」ということがある)から選ばれる少なくとも1種で表面処理された銅粒子であることもまた好ましく、トリアゾール化合物、飽和脂肪酸、不飽和脂肪酸、及び無機金属化合物塩からなる群から選ばれる少なくとも1種で表面処理された銅粒子であることがより好ましい。
本発明の電極用ペースト組成物に含まれる銅含有粒子として、表面処理剤の少なくとも1種で表面処理された銅粒子を用いることで、耐酸化性に優れ、抵抗率の低い電極を形成することができる。さらに電極用ペースト組成物に水分が混入した場合に、表面処理された銅粒子を用いることで、室温における銅の酸化を抑制でき、ポットライフを向上できるという効果を得ることができる。
また本発明において前記表面処理剤は1種単独でも、2種以上を組み合わせて用いてもよい。
また、前記表面処理剤における無機金属化合物塩としては、例えば、ケイ酸ナトリウム、スズ酸ナトリウム、硫酸スズ、硫酸亜鉛、亜鉛酸ナトリウム、硝酸ジルコニウム、ジルコニウム酸ナトリウム、塩化酸化ジルコニウム、硫酸チタン、塩化チタン、シュウ酸チタン酸カリウム等が挙げられる。また、前記表面処理剤における有機金属化合物塩としては、例えば、ステアリン酸鉛、酢酸鉛、テトラアルコキシジルコニウムのp-クミルフェニル誘導体、テトラアルコキシチタニウムのp-クミルフェニル誘導体等が挙げられる。また、前記表面処理剤における金属アルコキシドとしては、例えば、チタニウムアルコキシド、ジルコニウムアルコキシド、鉛アルコキシド、シリコンアルコキシド、スズアルコキシド、インジウムアルコキシド等が挙げられる。
また、表面処理剤としてステアリン酸またはステアリン酸鉛を用いる場合、表面処理剤としてステアリン酸及びステアリン酸鉛の少なくとも1種と酢酸鉛とを併用することで、耐酸化性がより向上し、抵抗率のより低い電極を形成することができる。
また前記表面処理された銅粒子に含まれる他の原子の含有率は、例えば、前記表面処理された銅粒子中に3質量%以下とすることができ、耐酸化性と低抵抗率の観点から、1質量%以下であることが好ましい。
表面処理された銅粒子におけるリン含有銅合金の詳細については、既述のリン含有銅合金と同義であり、好ましい態様も同様である。
また前記表面処理された銅粒子の形状としては特に制限はなく、略球状、扁平状、ブロック状、板状、及び鱗片状等のいずれであってもよい。前記表面処理された銅粒子の形状は、耐酸化性と低抵抗率の観点から、略球状、扁平状、または板状であることが好ましい。
具体的には、例えば、表面処理剤としてベンゾトリアゾール、トリアゾール、ドデシルベンゼンスルホン酸を用いる場合、アルコール系溶剤を用いて表面処理溶液を調製し、銅粒子を表面処理することができる。
また表面処理剤としてステアリン酸またはステアリン酸鉛を用いる場合、アルコール系溶剤を用いて表面処理溶液を調製することができる。
また本発明において前記表面処理された銅粒子は1種単独でも、2種以上を組み合わせて用いてもよい。また、表面処理された銅粒子以外であって、最大面積を示す発熱ピークにおけるピーク温度が280℃以上である銅含有粒子と組み合わせて用いてもよい。
さらにトリアゾール化合物、飽和脂肪酸、不飽和脂肪酸、無機金属化合物塩、有機金属化合物塩、ポリアニリン系樹脂、及び金属アルコキシドからなる群から選ばれる少なくとも1種が0.01~10質量%含まれるように表面処理され、リン含有率が8質量%以下である表面処理されたリン含有銅合金粒子を、電極用ペースト組成物中に70~94質量%(後述する銀粒子を含む場合は、表面処理されたリン含有銅合金粒子と銀粒子の総含有率)含むことが好ましく、トリアゾール化合物、飽和脂肪酸、不飽和脂肪酸及び無機金属化合物塩からなる群から選ばれる少なくとも1種が0.05~8質量%含まれるように表面処理され、リン含有率が1~7.5質量%以下である表面処理されたリン含有銅合金粒子を、電極用ペースト組成物中に74~88質量%(後述する銀粒子を含む場合は、表面処理されたリン含有銅合金粒子と銀粒子の総含有率)含むことがより好ましい。
また、本発明において前記表面処理された銅粒子以外の導電性の粒子を組み合わせて用いてもよい。
本発明の電極用ペースト組成物は、ガラス粒子の少なくとも1種を含む。電極用ペースト組成物がガラス粒子を含むことにより、電極形成温度において、いわゆるファイアースルーによって反射防止膜である窒化ケイ素膜が取り除かれ、電極とシリコン基板とのオーミックコンタクトが形成される。
本発明においては、耐酸化性と電極の低抵抗率の観点から、ガラス軟化点が600℃以下であって、結晶化開始温度が600℃を超えるガラスを含むガラス粒子であることが好ましい。尚、前記ガラス軟化点は、熱機械分析装置(TMA)を用いて通常の方法によって測定され、また前記結晶化開始温度は、示差熱-熱重量分析装置(TG-DTA)を用いて通常の方法によって測定される。
また本発明においては、環境に対する影響を考慮すると、鉛を実質的に含まない鉛フリーガラスを用いることが好ましい。鉛フリーガラスとしては、例えば、特開2006-313744号公報の段落番号0024~0025に記載の鉛フリーガラスや、特開2009-188281号公報等に記載の鉛フリーガラスを挙げることができ、これらの鉛フリーガラスから適宜選択して本発明に適用することもまた好ましい。
五酸化二バナジウムを含まないガラス粒子を構成するガラス成分物質としては、二酸化ケイ素(SiO2)、酸化リン(P2O5)、酸化アルミニウム(Al2O3)、酸化ホウ素(B2O3)、酸化カリウム(K2O)、酸化ナトリウム(Na2O)、酸化リチウム(Li2O)、酸化バリウム(BaO)、酸化ストロンチウム(SrO)、酸化カルシウム(CaO)、酸化マグネシウム(MgO)、酸化ベリリウム(BeO)、酸化亜鉛(ZnO)、酸化鉛(PbO)、酸化カドミウム(CdO)、酸化スズ(SnO)、酸化ジルコニウム(ZrO2)、酸化タングステン(WO3)、酸化モリブデン(MoO3)、酸化ランタン(La2O3)、酸化ニオブ(Nb2O5)、酸化タンタル(Ta2O5)、酸化イットリウム(Y2O3)、酸化チタン(TiO2)、酸化ゲルマニウム(GeO2)、酸化テルル(TeO2)及び酸化ルテチウム(Lu2O3)等が挙げられる。中でも、SiO2、P2O5、Al2O3、B2O3、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2、WO3、及びMoO3から選択される少なくとも1種を用いることが好ましく、SiO2、P2O5、Al2O3、B2O3、ZnO、及びPbOから選択される少なくとも1種を用いることがより好ましい。
またガラス粒子として、SiO2、Al2O3、B2O3、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2、WO3、及びMoO3から選択される少なくとも1種からなるガラス粒子を0.1~10質量%含むこともまた好ましく、SiO2、Al2O3、B2O3、ZnO、及びPbOから選択される少なくとも1種からなるガラス粒子を1~7質量%含むことがさらに好ましい。
本発明の電極用ペースト組成物は、溶剤の少なくとも1種と樹脂の少なくとも1種とを含む。これにより本発明の電極用ペースト組成物の液物性(例えば、粘度、表面張力等)を、シリコン基板に付与する際の付与方法に応じて必要とされる液物性に調整することができる。
本発明において前記溶剤は1種単独でも、2種以上を組み合わせて用いてもよい。
本発明において前記樹脂は1種単独でも、2種以上を組み合わせて用いてもよい。
溶剤と樹脂の総含有量が前記範囲内であることにより、電極用ペースト組成物をシリコン基板に付与する際の付与適性が良好になり、所望の幅及び高さを有する電極をより容易に形成することができる。
本発明の電極用ペースト組成物は、銀粒子の少なくとも1種を更に含むことが好ましい。銀粒子を含むことで耐酸化性がより向上し、電極としての抵抗率がより低下する。さらに太陽電池モジュールとした場合のはんだ接続性が向上するという効果も得られる。このことは例えば、以下のように考えることができる。
さらに本発明においては、耐酸化性と電極の低抵抗率の観点から、前記銅含有粒子と前記銀粒子の総量を100質量%としたときの銅含有粒子の含有率が9~88質量%となることが好ましく、17~77質量%となることがより好ましい。
前記銅含有粒子の含有率が9質量%以上となることで、例えば、前記ガラス粒子が五酸化二バナジウムを含む場合に銀とバナジウムとの反応が抑制され、電極の体積抵抗がより低下する。また、太陽電池としたときのエネルギー変換効率向上を目的とした電極形成シリコン基板のフッ酸水溶液処理において、電極材の耐フッ酸水溶液性(フッ酸水溶液によって電極材がシリコン基板から剥離しない性質)が向上する。
また前記銅含有粒子の含有率が88質量%以下となることで、銅含有粒子に含まれる銅がシリコン基板と接触することがより抑制され、電極の接触抵抗がより低下する。
前記電極用ペースト組成物は、リン含有化合物の少なくとも1種を更に含むことが好ましい。これにより、より効果的に耐酸化性が向上し、電極の抵抗率がより低下する。さらにシリコン基板において、リン含有化合物中の元素がn型ドーパントとして拡散し、太陽電池としたときに発電効率がさらに向上するという効果も得られる。
前記リン含有化合物としては、耐酸化性と電極の低抵抗率の観点から、分子内におけるリン原子の含有率が大きい化合物であって、200℃程度の温度条件で蒸発や分解を起こさない化合物であることが好ましい。
本発明におけるリン含有化合物は、耐酸化性と電極の低抵抗率の観点から、リン酸、リン酸アンモニウム、リン酸エステル、及び環状ホスファゼンからなる群から選ばれる少なくとも1種であることが好ましく、リン酸エステル、及び環状ホスファゼンからなる群から選ばれる少なくとも1種であることがより好ましい。
さらに本発明においては、リン含有化合物としてリン酸、リン酸アンモニウム、リン酸エステル、及び環状ホスファゼンからなる群から選ばれる少なくとも1種を、電極用ペースト組成物の全質量中に0.5~10質量%含むことが好ましく、リン酸エステル及び環状ホスファゼンからなる群から選ばれる少なくとも1種を、電極用ペースト組成物の全質量中に1~7質量%含むことがより好ましい。
電極用ペースト組成物は、フラックスの少なくとも1種をさらに含むことができる。フラックスを含むことで耐酸化性がより向上し、形成される電極の抵抗率がより低下する。さらに電極材とシリコン基板の密着性が向上するという効果も得られる。
中でも、電極材焼成時の耐熱性(フラックスが焼成の低温時に揮発しない特性)及び銅含有粒子の耐酸化性補完の観点から、ホウ酸カリウム及びホウフッ化カリウムが特に好ましいフラックスとして挙げられる。
本発明においてこれらのフラックスは、それぞれ1種単独で使用してもよく、2種類以上を組み合わせて使用することもできる。
さらに本発明の電極用ペースト組成物は、上述した成分に加え、必要に応じて、当該技術分野で通常用いられるその他の成分をさらに含むことができる。その他の成分としては、例えば、可塑剤、分散剤、界面活性剤、無機結合剤、金属酸化物、セラミック、有機金属化合物等を挙げることができる。
本発明の電極用ペースト組成物を用いて電極を製造する方法としては、前記電極用ペースト組成物を電極を形成する領域に付与し、乾燥後に、焼成することで所望の領域に電極を形成することができる。前記電極用ペースト組成物を用いることで、酸素の存在下(例えば、大気中)で焼成処理を行っても、抵抗率の低い電極を形成することができる。
具体的には例えば、前記電極用ペースト組成物を用いて太陽電池用電極を形成する場合、電極用ペースト組成物はシリコン基板上に所望の形状となるように付与され、乾燥後に、焼成されることで、抵抗率の低い太陽電池電極を所望の形状に形成することができる。また前記電極用ペースト組成物を用いることで、酸素の存在下(例えば、大気中)で焼成処理を行っても、抵抗率の低い電極を形成することができる。
電極用ペースト組成物をシリコン基板上に付与する方法としては、例えば、スクリーン印刷、インクジェット法、ディスペンサー法等を挙げることができるが、生産性の観点から、スクリーン印刷による塗布であることが好ましい。
一般に、熱処理温度(焼成温度)としては800~900℃であるが、本発明の電極用ペースト組成物を用いる場合には、より低温での熱処理条件を適用することができ、例えば、600~850℃の熱処理温度で良好な特性を有する電極を形成することができる。
また熱処理時間は、熱処理温度等に応じて適宜選択することができ、例えば、1秒~20秒とすることができる。
本発明の太陽電池は、シリコン基板上に付与された前記電極用ペースト組成物を、焼成して形成された電極を有する。これにより、良好な特性を有する太陽電池が得られ、該太陽電池の生産性に優れる。
代表的な太陽電池素子の一例を示す断面図、受光面及び裏面の概要を図1、図2及び図3に示す。
通常、太陽電池素子の半導体基板130には、単結晶または多結晶Siなどが使用される。この半導体基板130には、ホウ素などが含有され、p型半導体を構成している。受光面側は、太陽光の反射を抑制するために、エッチングにより凹凸(テクスチャー、図示せず)が形成されている。その受光面側にはリンなどがドーピングされ、n型半導体の拡散層131がサブミクロンオーダーの厚みで設けられているとともに、p型バルク部分との境界にpn接合部が形成されている。さらに受光面側には、拡散層131上に窒化シリコンなどの反射防止層132が蒸着法などによって膜厚100nm前後で設けられている。
本発明においては前記電極用ペースト組成物を用いることで、比較的低温で焼成しても、抵抗率及び接触抵抗率に優れる電極を形成することができる。
本発明においては、前記電極用ペースト組成物を用いて受光面電極133が形成されることで、導電性金属として銅を含みながら、銅の酸化が抑制され、低抵抗率の受光面電極133が、良好な生産性で形成される。
図4(a)の斜視図に示すようにp型半導体のシリコン基板からなるセルウェハ1には、レーザドリルまたはエッチング等によって、受光面側及び裏面側の両面を貫通したスルーホールが形成されている。また受光面側には光入射効率を向上させるテクスチャー(図示せず)が形成されている。さらに受光面側にはn型化拡散処理によるn型半導体層3と、n型半導体層3上に反射防止膜(図示せず)が形成されている。これらは従来の結晶Si型太陽電池セルと同一の工程により製造される。
ここで、充填用と印刷用に用いるペーストでは、粘度を始めとして、それぞれのプロセスに最適な組成のペーストを使用するのが望ましいが、同じ組成のペーストで充填、印刷を一括で行ってもよい。
なお、本発明の電極用ペースト組成物は、上記したような太陽電池電極の用途に限定されるものではなく、例えば、プラズマディスプレイの電極配線及びシールド配線、セラミックスコンデンサ、アンテナ回路、各種センサー回路、半導体デバイスの放熱材料等の用途にも好適に使用することができる。
(a)電極用ペースト組成物の調製
1質量%のリンを含むリン含有銅合金を調製し、これを溶解して水アトマイズ法により粉末化した後、乾燥、分級した。分級した粉末をブレンドして、脱酸素・脱水分処理し、1質量%のリンを含むリン含有銅合金粒子を作製した。尚、リン含有銅合金粒子の粒子径(D50%)は1.5μmであった。
また、示差熱-熱重量同時測定(TG-DTA)を通常の大気中で、測定装置:示差熱-熱重量分析装置(エスアイアイ・ナノテクノロジー社製、TG/DTA-6200型)を用いて、測定温度範囲:室温~1000℃、昇温速度:40℃/分、大気流量:200ml/分の条件で行ったところ、示差熱-熱重量同時測定(TG-DTA)において最大面積を示す発熱ピークのピーク温度は292℃であった。
得られたガラスG19を用いて、粒子径(D50%)が1.7μmであるガラス粒子を得た。
受光面にn型半導体層、テクスチャー及び反射防止膜(窒化珪素膜)が形成された膜厚190μmのp型半導体基板を用意し、125mm×125mmの大きさに切り出した。その受光面にスクリーン印刷法を用い、上記で得られた電極用ペースト組成物1を図2に示すような電極パターンとなるように印刷した。電極のパターンは150μm幅のフィンガーラインと1.1mm幅のバスバーで構成され、焼成後の膜厚が20μmとなるよう、印刷条件(スクリーン版のメッシュ、印刷速度、印圧)を適宜調整した。これを150℃に加熱したオーブンの中に15分間入れ、溶剤を蒸散により取り除いた。
続いて、赤外線急速加熱炉内で大気雰囲気下、850℃で2秒間の加熱処理(焼成)を行って、所望の電極が形成された太陽電池セル1を作製した。
実施例1において、電極形成時の加熱処理(焼成)の温度を850℃の代わりに750℃に変更したこと以外は実施例1と同様にして、所望の電極が形成された太陽電池セル2を作製した。
実施例1において、リン含有銅合金粒子のリン含有率、粒子径(D50%)及び含有量、銀粒子の粒子径(D50%)及び含有量、ガラス粒子の種類及び含有量、4%のエチルセルロース(EC)を含むブチルカルビトールアセテート(BCA)溶液の含有量、ならびに、必要に応じて含有されるリン含有化合物の種類及び含有量を表1に示したように変更したこと以外は、実施例1と同様にして電極用ペースト組成物3~15、及び電極用ペースト組成物43~46を調製した。
尚、ガラス粒子(AY1)は、酸化バナジウム(V2O5)45部、酸化リン(P2O5)24.2部、酸化バリウム(BaO)20.8部、酸化アンチモン(Sb2O3)5部、酸化タングステン(WO3)5部からなり、粒子径(D50%)が1.7μmであった。またこのガラスの軟化点は492℃、結晶化温度は600℃を超えていた。
またガラス粒子(D10)は、酸化鉛(PbO)64部、酸化硼素(B2O3)11部、酸化アルミニウム(Al2O3)5部、二酸化ケイ素(SiO2)10部、酸化亜鉛(ZnO)10部からなり、粒子径(D50%)が、2.3μmであった。またこのガラスの軟化点は440℃、結晶化温度は600℃を超えていた。
さらに、リン酸エステルとしてトリフェニルホスフェートを、環状ホスファゼンとしてヘキサフェノキシホスファゼンを用いた。
実施例1における電極用ペースト組成物の調製においてリン含有銅合金粒子を用いずに、表1に示した組成となるように各成分を変更したこと以外は、実施例1と同様にして電極用ペースト組成物C1を調製した。
リン含有銅合金粒子を含まない電極用ペースト組成物C1を用いたこと以外は、実施例1と同様にして太陽電池セルC1を作製した。
比較例1において、電極形成時の加熱処理(焼成)の温度を850℃の代わりに750℃に変更したこと以外は比較例1と同様にして、太陽電池セルC2を作製した。
実施例1において、リンを含有しない純銅(リン含有量が0%)に変更したこと以外は、実施例1と同様にして電極用ペースト組成物C3を調製した。
電極用ペースト組成物C3を用いたこと以外は、実施例1と同様にして太陽電池セルC3を作製した。
作製した太陽電池セルの評価は、擬似太陽光として(株)ワコム電創製WXS-155S-10、電流-電圧(I-V)評価測定器としてI-V CURVE TRACER MP-160(EKO INSTRUMENT社製)の測定装置を組み合わせて行った。太陽電池としての発電性能を示すEff(変換効率)、FF(フィルファクター)、Voc(開放電圧)及びJsc(短絡電流)は、それぞれJIS-C-8912、JIS-C-8913及びJIS-C-8914に準拠して測定を行なうことで得られたものである。得られた各測定値を、比較例1の測定値を100.0とした相対値に換算して表2に示した。
尚、比較例3においては、銅粒子の酸化によって電極の抵抗率が大きくなり、評価不能であった。
また受光面電極をCuKα線を用い、X線回折法で回折X線を測定した結果、回折角度(2θ、CuKα線)の少なくとも43.4°、50.6°、74.2°に、銅の特徴的な回折ピークを示した。このように受光面電極から銅が検出された理由として、以下の原理が挙げられる。まず、電極用ペースト組成物44~46中のリン含有銅合金粒子は、リン含有率が7質量%である。この組成はCu-P系状態図から、Cu相とCu3P相からなる。焼成初期段階では、Cu相が酸化され、CuOに変わる。このCuOとCu3Pが反応し、Cu相が生成すると考えられる。
図5からこのリン含有銅合金粒子において、最大面積を示す発熱ピークのピーク温度が420℃であることが分かる。
上記で得られた電極用ペースト組成物1を用いて、図4に示したような構造を有する太陽電池セル16を作製した。尚、加熱処理は750℃、10秒間で行った。
得られた太陽電池セルについて上記と同様にして評価したところ、上記と同様に良好な特性を示すことが分かった。
(a)電極用ペースト組成物の調製
特開平14-100191に記載された方法により調製した銀被覆銅粒子(日立化成工業(株)製、銀被覆量20質量%、粒子径5.8μm)を85.1部、ガラス粒子を1.7部、及び、4%のエチルセルロース(EC)を含むブチルカルビトールアセテート(BCA)溶液13.2部を混ぜ合わせ、メノウ製乳鉢の中で20分間かき混ぜ、電極用ペースト組成物17を調製した。
受光面にn型半導体層、テクスチャー及び反射防止膜(窒化珪素膜)が形成された膜厚190μmのp型半導体基板を用意し、125mm×125mmの大きさに切り出した。その受光面にスクリーン印刷法を用い、上記で得られた電極用ペースト組成物17を図2に示すような電極パターンとなるように印刷した。電極のパターンは150μm幅のフィンガーラインと1.1mm幅のバスバーで構成され、焼成後の膜厚が20μmとなるよう、印刷条件(スクリーン版のメッシュ、印刷速度、印圧)を適宜調整した。これを150℃に加熱したオーブンの中に15分間入れ、溶剤を蒸散により取り除いた。
続いて、赤外線急速加熱炉内で大気雰囲気下、850℃で2秒間の加熱処理(焼成)を行って、所望の電極が形成された太陽電池セル17を作製した。
実施例17において、銀被覆銅粒子の銀被覆量及び含有量、必要に応じて用いた銀粒子の粒子径(D50%)を及び含有量、ガラス粒子の種類及び含有量、ならびに、4%のエチルセルロース(EC)を含むブチルカルビトールアセテート(BCA)溶液の含有量を表3に示したように変更したこと以外は、実施例17と同様にして電極用ペースト組成物18~25を調製した。
尚、銀粒子としては粒子径(D50%)1μmまたは3μmであるアルドリッチ社製高純度化学品を用いた。
実施例17における電極用ペースト組成物の調製において銀被覆銅粒子を用いずに、表3に示した組成となるように各成分を変更したこと以外は、実施例17と同様にして電極用ペースト組成物C4を調製した。
銀被覆銅粒子を含まない電極用ペースト組成物C4を用いたこと以外は、実施例17と同様にして太陽電池セルC4を作製した。
比較例4において、電極形成時の加熱処理(焼成)の温度を850℃の代わりに750℃に変更したこと以外は比較例4と同様にして、太陽電池セルC5を作製した。
実施例17における電極用ペースト組成物の調製において銀被覆銅粒子を用いずに、表3に示した組成となるように各成分を変更したこと以外は、実施例17と同様にして電極用ペースト組成物C6を調製した。
電極用ペースト組成物C6を用いたこと以外は、実施例17と同様にして太陽電池セルC6を作製した。
作製した太陽電池セルの評価は、擬似太陽光として(株)ワコム電創製WXS-155S-10、電流-電圧(I-V)評価測定器としてI-V CURVE TRACER MP-160(EKO INSTRUMENT社製)の測定装置を組み合わせて行った。太陽電池としての発電性能を示すEff(変換効率)、FF(フィルファクター)、Voc(開放電圧)及びJsc(短絡電流)は、それぞれJIS-C-8912、JIS-C-8913及びJIS-C-8914に準拠して測定を行なうことで得られたものである。得られた各測定値を、比較例4の測定値を100.0とした相対値に換算して表4に示した。
尚、比較例6においては、銅粒子の酸化によって電極の抵抗率が大きくなり、評価不能であった。
上記で得られた電極用ペースト組成物19を用いて、図4に示したような構造を有する太陽電池セル26を作製した。尚、加熱処理は750℃、10秒間で行った。
得られた太陽電池セルについて上記と同様にして評価したところ、上記と同様に良好な特性を示すことが分かった。
(a)電極用ペースト組成物の調製
表面処理剤としてベンゾトリアゾール(BTA)を溶剤エタノールに溶解して50%の表面処理溶液を調製した。これに銅粉末(福田金属箔粉社製、純度99.9%、粒子径5μm)を、50分間浸漬した後、乾燥して表面処理された銅粒子を調製した。該表面処理された銅粒子における表面処理剤の含有量は、表面処理された銅粒子の全質量中に1%であった。また粒子径(D50%)は5μmであった。
受光面にn型半導体層、テクスチャー及び反射防止膜(窒化珪素膜)が形成された膜厚190μmのp型半導体基板を用意し、125mm×125mmの大きさに切り出した。その受光面にスクリーン印刷法を用い、上記で得られた電極用ペースト組成物27を図2に示すような電極パターンとなるように印刷した。電極のパターンは150μm幅のフィンガーラインと1.1mm幅のバスバーで構成され、焼成後の膜厚が20μmとなるよう、印刷条件(スクリーン版のメッシュ、印刷速度、印圧)を適宜調整した。これを150℃に加熱したオーブンの中に15分間入れ、溶剤を蒸散により取り除いた。
続いて、赤外線急速加熱炉内で大気雰囲気下、850℃で2秒間の加熱処理(焼成)を行って、所望の電極が形成された太陽電池セル27を作製した。
実施例27において、表面処理された銅粒子の表面処理剤の種類及び含有量、銀粒子の含有量、ガラス粒子の種類及び含有量、4%のエチルセルロース(EC)を含むブチルカルビトールアセテート(BCA)溶液の含有量、ならびに、必要に応じて含有されるリン含有化合物の種類及び含有量を表5に示したように変更したこと以外は、実施例27と同様にして電極用ペースト組成物28~41を調製した。
実施例27における電極用ペースト組成物の調製において表面処理された銅粒子を用いずに、表5に示した組成となるように各成分を変更したこと以外は、実施例27と同様にして電極用ペースト組成物C7を調製した。
表面処理された銅粒子を含まない電極用ペースト組成物C7を用いたこと以外は、実施例27と同様にして太陽電池セルC7を作製した。
比較例7において、電極形成時の加熱処理(焼成)の温度を850℃の代わりに750℃に変更したこと以外は比較例7と同様にして、太陽電池セルC8を作製した。
実施例27において、表面処理された銅粒子の表面処理量を、示差熱-熱重量同時測定において最大面積を示す発熱ピークのピーク温度が230℃となる0.0001%に変更したこと以外は、実施例27と同様にして電極用ペースト組成物C9を調製した。
電極用ペースト組成物C9を用いたこと以外は、実施例27と同様にして太陽電池セルC9を作製した。
作製した太陽電池セルの評価は、擬似太陽光として(株)ワコム電創製WXS-155S-10、電流-電圧(I-V)評価測定器としてI-V CURVE TRACER MP-160(EKO INSTRUMENT社製)の測定装置を組み合わせて行った。太陽電池としての発電性能を示すEff(変換効率)、FF(フィルファクター)、Voc(開放電圧)及びJsc(短絡電流)は、それぞれJIS-C-8912、JIS-C-8913及びJIS-C-8914に準拠して測定を行なうことで得られたものである。得られた各測定値を、比較例7の測定値を100.0とした相対値に換算して表6に示した。
尚、比較例9においては、銅含有粒子の酸化によって電極の抵抗率が大きくなり、評価不能であった。
上記で得られた電極用ペースト組成物27を用いて、図4に示したような構造を有する太陽電池セル42を作製した。尚、加熱処理は750℃、10秒間で行った。
得られた太陽電池セルについて上記と同様にして評価したところ、上記と同様に良好な特性を示すことが分かった。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
131 拡散層
132 反射防止層
133 受光面電極
134 集電電極
135 出力取出し電極
136 電極成分拡散層
1 p型シリコン基板からなるセルウェハ
2 集電用グリッド電極
3 n型半導体層
4 スルーホール電極
5 高濃度ドープ層
6 裏面電極
7 裏面電極
Claims (13)
- 示差熱-熱重量同時測定において最大面積を示す発熱ピークのピーク温度が280℃以上である銅含有粒子と、ガラス粒子と、溶剤と、樹脂と、を含む電極用ペースト組成物。
- 前記銅含有粒子は、リン含有銅合金粒子、銀被覆された銅粒子、ならびに、トリアゾール化合物、飽和脂肪酸、不飽和脂肪酸、無機金属化合物塩、有機金属化合物塩、ポリアニリン系樹脂、及び金属アルコキシドからなる群から選ばれる少なくとも1種で表面処理された銅粒子から選ばれる少なくとも1種である請求項1に記載の電極用ペースト組成物。
- 前記ガラス粒子は、ガラス軟化点が600℃以下であって、結晶化開始温度が600℃を超える請求項1または請求項2に記載の電極用ペースト組成物。
- 前記ガラス粒子は、五酸化二リン-五酸化二バナジウム系ガラスを含む請求項1~請求項3のいずれか1項に記載の電極用ペースト組成物。
- 銀粒子を更に含む請求項1~請求項4のいずれか1項に記載の電極用ペースト組成物。
- 前記銅含有粒子と前記銀粒子の総量を100質量%としたときの銅含有粒子の含有率が9質量%以上88質量%以下である請求項5に記載の電極用ペースト組成物。
- 前記銅含有粒子及び前記銀粒子の総含有率が70質量%以上94質量%以下であって、前記ガラス粒子の含有率が0.1質量%以上10質量%以下であって、前記溶剤及び前記樹脂の総含有率が3質量%以上29.9質量%以下である請求項5または請求項6に記載の電極用ペースト組成物。
- リン含有化合物を更に含む請求項1~請求項7のいずれか1項に記載の電極用ペースト組成物。
- 前記リン含有化合物は、リン酸、リン酸アンモニウム、リン酸エステル、及び環状ホスファゼンからなる群から選ばれる少なくとも1種である請求項8に記載の電極用ペースト組成物。
- リン含有銅合金粒子と、ガラス粒子と、溶剤と、樹脂と、を含む電極用ペースト組成物。
- 銀被覆された銅粒子と、ガラス粒子と、溶剤と、樹脂と、を含む電極用ペースト組成物。
- トリアゾール化合物、飽和脂肪酸、不飽和脂肪酸、無機金属化合物塩、有機金属化合物塩、ポリアニリン系樹脂、及び金属アルコキシドからなる群から選ばれる少なくとも1種で表面処理された銅粒子と、ガラス粒子と、溶剤と、樹脂と、を含む電極用ペースト組成物。
- シリコン基板上に付与された請求項1~請求項12のいずれか1項に記載の電極用ペースト組成物を焼成して形成された電極を有する太陽電池。
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WO2013015172A1 (ja) * | 2011-07-25 | 2013-01-31 | 日立化成工業株式会社 | 素子及び太陽電池 |
WO2013015285A1 (ja) * | 2011-07-25 | 2013-01-31 | 日立化成工業株式会社 | 素子および太陽電池 |
WO2013073478A1 (ja) * | 2011-11-14 | 2013-05-23 | 日立化成株式会社 | 電極用ペースト組成物、太陽電池素子及び太陽電池 |
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0350064B2 (ja) | 1986-11-04 | 1991-07-31 | Junichi Go | |
JPH06290635A (ja) * | 1993-04-01 | 1994-10-18 | Toray Ind Inc | 感光性導電ペースト |
JP2002100191A (ja) | 2000-09-22 | 2002-04-05 | Toshiba Corp | 半導体記憶装置 |
JP2005222737A (ja) * | 2004-02-03 | 2005-08-18 | Sumitomo Metal Mining Co Ltd | 外部電極用銅ペースト組成物 |
JP2006004905A (ja) * | 2004-03-10 | 2006-01-05 | Murata Mfg Co Ltd | 導電性ペーストおよびこれを用いたセラミック電子部品 |
JP2006313744A (ja) | 2005-04-14 | 2006-11-16 | E I Du Pont De Nemours & Co | 導電性厚膜組成物、電極、およびそれから形成される半導体デバイス |
WO2008078374A1 (ja) * | 2006-12-25 | 2008-07-03 | Namics Corporation | 太陽電池用導電性ペースト |
JP2008226816A (ja) | 2006-10-11 | 2008-09-25 | Mitsubishi Materials Corp | 電極形成用組成物及び該組成物を用いた電極の形成方法 |
JP2008251324A (ja) * | 2007-03-30 | 2008-10-16 | Hitachi Powdered Metals Co Ltd | 導電性ペースト |
JP2009188281A (ja) | 2008-02-08 | 2009-08-20 | Hitachi Ltd | Cu系配線用材料およびそれを用いた電子部品 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4354047B2 (ja) * | 1998-06-19 | 2009-10-28 | 京都エレックス株式会社 | ビア充填用導電ペースト組成物 |
US6228288B1 (en) * | 2000-04-27 | 2001-05-08 | Cts Corporation | Electrically conductive compositions and films for position sensors |
US7252883B2 (en) * | 2000-10-23 | 2007-08-07 | Sekisui Chemical Co., Ltd. | Coated particles |
US7176152B2 (en) * | 2004-06-09 | 2007-02-13 | Ferro Corporation | Lead-free and cadmium-free conductive copper thick film pastes |
WO2006038720A1 (ja) * | 2004-10-06 | 2006-04-13 | Showa Denko K.K. | ニオブ粉、ニオブ造粒物、ニオブ焼結体及びコンデンサ並びにそれらの製造方法 |
CN101107678B (zh) * | 2005-01-25 | 2012-03-07 | 藤仓化成株式会社 | 导电浆料 |
JP4796815B2 (ja) * | 2005-10-25 | 2011-10-19 | 釜屋電機株式会社 | 超小形チップ抵抗器及び超小形チップ抵抗器用抵抗体ペースト。 |
JP4894266B2 (ja) * | 2006-01-06 | 2012-03-14 | 住友金属鉱山株式会社 | 導電粉の表面処理方法と導電粉及び導電性ペースト |
JP5139659B2 (ja) * | 2006-09-27 | 2013-02-06 | Dowaエレクトロニクス株式会社 | 銀粒子複合粉末およびその製造法 |
CN101295739B (zh) * | 2007-04-26 | 2010-09-29 | 比亚迪股份有限公司 | 太阳能电池正面电极用导电浆料及其制备方法 |
-
2010
- 2010-09-30 JP JP2010222203A patent/JP5633285B2/ja active Active
-
2011
- 2011-01-25 WO PCT/JP2011/051366 patent/WO2011090215A1/ja active Application Filing
- 2011-01-25 CN CN2011800066840A patent/CN102870167A/zh active Pending
- 2011-01-25 CN CN201410659024.8A patent/CN104392771B/zh active Active
- 2011-01-25 TW TW100102721A patent/TWI515946B/zh not_active IP Right Cessation
- 2011-01-25 TW TW104121141A patent/TWI591881B/zh not_active IP Right Cessation
- 2011-01-25 KR KR1020127020756A patent/KR101859236B1/ko active IP Right Grant
- 2011-01-25 EP EP11734821.9A patent/EP2530683B1/en not_active Not-in-force
- 2011-01-25 CN CN201510323228.9A patent/CN105006269A/zh active Pending
-
2015
- 2015-05-21 HK HK15104863.9A patent/HK1204386A1/xx unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0350064B2 (ja) | 1986-11-04 | 1991-07-31 | Junichi Go | |
JPH06290635A (ja) * | 1993-04-01 | 1994-10-18 | Toray Ind Inc | 感光性導電ペースト |
JP2002100191A (ja) | 2000-09-22 | 2002-04-05 | Toshiba Corp | 半導体記憶装置 |
JP2005222737A (ja) * | 2004-02-03 | 2005-08-18 | Sumitomo Metal Mining Co Ltd | 外部電極用銅ペースト組成物 |
JP2006004905A (ja) * | 2004-03-10 | 2006-01-05 | Murata Mfg Co Ltd | 導電性ペーストおよびこれを用いたセラミック電子部品 |
JP2006313744A (ja) | 2005-04-14 | 2006-11-16 | E I Du Pont De Nemours & Co | 導電性厚膜組成物、電極、およびそれから形成される半導体デバイス |
JP2008226816A (ja) | 2006-10-11 | 2008-09-25 | Mitsubishi Materials Corp | 電極形成用組成物及び該組成物を用いた電極の形成方法 |
WO2008078374A1 (ja) * | 2006-12-25 | 2008-07-03 | Namics Corporation | 太陽電池用導電性ペースト |
JP2008251324A (ja) * | 2007-03-30 | 2008-10-16 | Hitachi Powdered Metals Co Ltd | 導電性ペースト |
JP2009188281A (ja) | 2008-02-08 | 2009-08-20 | Hitachi Ltd | Cu系配線用材料およびそれを用いた電子部品 |
Non-Patent Citations (3)
Title |
---|
"Handbook of Metal", MARUZEN CO., LTD. PUBLISHING DEPT. |
"Sunlight Power Generation, Newest Technology and Systems", 2001, CMC BOOKS, pages: 26 - 27 |
See also references of EP2530683A4 |
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Also Published As
Publication number | Publication date |
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CN105006269A (zh) | 2015-10-28 |
TWI591881B (zh) | 2017-07-11 |
CN104392771A (zh) | 2015-03-04 |
EP2530683A4 (en) | 2013-11-06 |
TWI515946B (zh) | 2016-01-01 |
TW201541692A (zh) | 2015-11-01 |
TW201140914A (en) | 2011-11-16 |
EP2530683B1 (en) | 2018-07-25 |
CN104392771B (zh) | 2020-01-07 |
CN102870167A (zh) | 2013-01-09 |
JP5633285B2 (ja) | 2014-12-03 |
JP2011171272A (ja) | 2011-09-01 |
KR101859236B1 (ko) | 2018-05-18 |
HK1204386A1 (en) | 2015-11-13 |
KR20120124439A (ko) | 2012-11-13 |
EP2530683A1 (en) | 2012-12-05 |
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