TW201835144A - Electrically conductive paste - Google Patents
Electrically conductive paste Download PDFInfo
- Publication number
- TW201835144A TW201835144A TW107106177A TW107106177A TW201835144A TW 201835144 A TW201835144 A TW 201835144A TW 107106177 A TW107106177 A TW 107106177A TW 107106177 A TW107106177 A TW 107106177A TW 201835144 A TW201835144 A TW 201835144A
- Authority
- TW
- Taiwan
- Prior art keywords
- silver
- conductive paste
- copper powder
- solar cell
- manufactured
- Prior art date
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 115
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052709 silver Inorganic materials 0.000 claims abstract description 101
- 239000004332 silver Substances 0.000 claims abstract description 101
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000001186 cumulative effect Effects 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 239000006059 cover glass Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 9
- 239000004848 polyfunctional curative Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 5
- -1 boron trifluoride amine Chemical class 0.000 claims description 4
- 229910000679 solder Inorganic materials 0.000 claims description 4
- 238000005476 soldering Methods 0.000 abstract description 37
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000000126 substance Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 235000012431 wafers Nutrition 0.000 description 18
- 239000010949 copper Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 229910001961 silver nitrate Inorganic materials 0.000 description 11
- 238000010248 power generation Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 229940100890 silver compound Drugs 0.000 description 7
- 150000003379 silver compounds Chemical class 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 4
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- 244000205754 Colocasia esculenta Species 0.000 description 2
- 235000006481 Colocasia esculenta Nutrition 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- XGNPDAJLBIWMNQ-UHFFFAOYSA-N C(C(C)C)(=O)O.CC(CC(CC)O)O Chemical compound C(C(C)C)(=O)O.CC(CC(CC)O)O XGNPDAJLBIWMNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910007116 SnPb Inorganic materials 0.000 description 1
- LVMBEXJKZGJYRH-UHFFFAOYSA-N [Ag].[Ce] Chemical compound [Ag].[Ce] LVMBEXJKZGJYRH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- VGVYRHYDNGFIGF-UHFFFAOYSA-N fumarin Chemical compound OC=1OC2=CC=CC=C2C(=O)C=1C(CC(=O)C)C1=CC=CO1 VGVYRHYDNGFIGF-UHFFFAOYSA-N 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GPTFURBXHJWNHR-UHFFFAOYSA-N protopine acetate Natural products C1=C2C(=O)CC3=CC=C4OCOC4=C3CN(C)CCC2=CC2=C1OCO2 GPTFURBXHJWNHR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
-
- 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
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Abstract
Description
本發明關於一種導電性糊，尤其關於一種導電性的金屬粉末使用了銀被覆銅粉之導電性糊。The present invention relates to a conductive paste, and more particularly to a conductive metal powder using a conductive paste of silver-coated copper powder.
以往，為了藉由印刷法等形成電子零件的電極或配線，一直是使用在銀粉或銅粉等的導電性的金屬粉末中摻合溶劑、樹脂、分散劑等所製作出的導電糊。Conventionally, in order to form an electrode or a wiring of an electronic component by a printing method or the like, a conductive paste prepared by blending a solvent, a resin, a dispersant or the like with a conductive metal powder such as silver powder or copper powder has been used.
但是，銀粉雖然體積電阻率極小，而為良好的導電性物質，然而是貴金屬的粉末，因此成本會變高。另一方面，銅粉雖然體積電阻率低，為良好的導電性物質，然而容易氧化，因此與銀粉相比，保存安定性(信賴性)較差。However, although the silver powder has a very small volume resistivity and is a good conductive material, it is a powder of a precious metal, so the cost becomes high. On the other hand, although the copper powder has a low volume resistivity and is a good conductive material, it is easily oxidized, so that the storage stability (reliability) is inferior to that of the silver powder.
為了解決這些問題，作為使用於導電糊的金屬粉末，有文獻提出一種將銅粉表面以銀被覆的銀被覆銅粉(參考例如專利文獻1～2)。In order to solve these problems, as a metal powder used for a conductive paste, there has been proposed a silver-coated copper powder in which a copper powder surface is coated with silver (see, for example, Patent Documents 1 and 2).
近年來，正在嘗試以使用比銀粉還廉價的銀被覆銅粉的導電性糊代替使用銀粉的導電性糊，作為太陽能電池的母線電極形成用的導電性糊。In recent years, a conductive paste using a silver-coated copper powder which is cheaper than silver powder has been used as a conductive paste for forming a bus bar electrode of a solar cell, instead of using a conductive paste using silver powder.
一般的結晶矽型太陽能電池，是藉由將使用銀粉的燒成型導電性糊在大氣環境下以800℃左右的高溫燒成而形成電極，然而若使用銅粉或使用了銀被覆銅粉的導電性糊，則在大氣環境下以這樣的高溫燒成時，銅粉或銀被覆銅粉氧化，因此須要在惰性氣體環境下燒成等的特殊技術，成本會變高。In a general crystalline germanium solar cell, an electrode is formed by firing a fire-molded conductive paste using silver powder at a high temperature of about 800 ° C in an atmospheric environment. However, if copper powder or silver-coated copper powder is used, When the conductive paste is fired at such a high temperature in an atmospheric environment, copper powder or silver-coated copper powder is oxidized, so that a special technique such as firing in an inert gas atmosphere is required, and the cost is increased.
另一方面，HIT(單結晶系混合型)太陽能電池等，一般是藉由將使用了銀粉的樹脂硬化型導電性糊在大氣環境下加熱至200℃左右，使其硬化而形成電極，由於在大氣環境下以這樣的低溫度下加熱，銅粉或銀被覆銅粉仍可承受氧化，因此能夠使用已採用銀被覆銅粉之樹脂硬化型導電性糊。On the other hand, an HIT (single crystal type hybrid type) solar cell or the like is generally formed by heating a resin-curable conductive paste using silver powder to about 200 ° C in an atmosphere to form an electrode. When the copper powder or the silver-coated copper powder is subjected to oxidation at such a low temperature in an atmospheric environment, it is possible to use a resin-curable conductive paste which has been coated with copper powder.
另外，在將藉由以往的樹脂硬化型導電性糊形成的電極連接至極耳線，製作出HIT太陽能電池時，若將電極與極耳線焊接而連接，則在焊接的溫度(380℃左右)下，導電性糊的樹脂會分解，因此使用了比焊料還高價的導電性接著劑來連接電極與極耳線。 [先前技術文獻] [專利文獻]In addition, when an electrode formed of a conventional resin-curable conductive paste is connected to a tab wire to produce an HIT solar cell, when the electrode is connected to the tab wire and connected, the temperature at the soldering (about 380 ° C) Since the resin of the conductive paste is decomposed, a conductive adhesive which is expensive than solder is used to connect the electrode and the tab wire. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本特開2010-174311號公報(段落編號0003) [專利文獻2]日本特開2010-077495號公報(段落編號0006)[Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-174311 (paragraph No. 0003) [Patent Document 2] Japanese Laid-Open Patent Publication No. 2010-077495 (paragraph No. 0006)
[發明所欲解決的課題][Problems to be solved by the invention]
已知藉由已使用銀被覆銅粉作為導電性填料並使用雙酚A型環氧樹脂作為樹脂而得的樹脂型導電性糊來形成母線電極，並藉由導電性接著劑將該母線電極連接至極耳線，製作出HIT太陽能電池時，太陽能電池是具有與使用銀粉的情況同等的高轉換效率的太陽能電池。It is known that a bus bar electrode is formed by using a resin-based conductive paste obtained by using silver-coated copper powder as a conductive filler and using a bisphenol A-type epoxy resin as a resin, and the bus bar electrode is connected by a conductive adhesive. In the case of the HIT solar cell, the solar cell is a solar cell having a high conversion efficiency equivalent to the case of using silver powder.
但是，已知若將如上述之由銀被覆銅粉與雙酚A型環氧樹脂等混練而得的樹脂型導電性糊所形成的母線電極藉由焊接來與極耳線連接，則會有母線電極的電阻變高，太陽能電池的轉換效率降低的情形。此外，在使用銀粉來代替上述樹脂型導電性糊的銀被覆銅粉的情況下，則不會發生這種問題。However, it is known that the bus bar electrode formed of the resin-type conductive paste obtained by kneading the silver-coated copper powder and the bisphenol A-type epoxy resin as described above is joined to the tab wire by soldering. The resistance of the bus bar electrode becomes high, and the conversion efficiency of the solar cell is lowered. Further, in the case where silver powder is used in place of the silver-coated copper powder of the above-mentioned resin-type conductive paste, such a problem does not occur.
所以，本發明鑑於這樣的問題點，目的為提供一種導電性糊，即使藉由使用了銀被覆銅粉之樹脂型導電性糊來製作太陽能電池母線電極且將該母線電極藉由焊接與極耳線連接，也能夠防止太陽能電池的轉換效率降低。 [用於解決課題的手段]Therefore, the present invention has been made in view of such a problem, and an object thereof is to provide a conductive paste in which a solar cell bus electrode is fabricated by using a resin-type conductive paste of a silver-coated copper powder, and the bus bar electrode is welded and tabbed. The wire connection also prevents the conversion efficiency of the solar cell from being lowered. [Means for solving problems]
本發明人等為了解決上述課題而全心鑽研，結果發現，只要藉由包含銅粉表面經銀層被覆之銀被覆銅粉與具萘骨架之環氧樹脂的樹脂型導電性糊來製作太陽能電池的母線電極，則即使藉由焊接將母線電極與極耳線連接，也能夠防止太陽能電池的轉換效率降低，而完成了本發明。In order to solve the above-mentioned problems, the inventors of the present invention have found that a solar cell can be produced by a resin-based conductive paste containing a silver-coated copper powder coated with a silver layer on a surface of a copper powder and an epoxy resin having a naphthalene skeleton. The bus bar electrode can prevent the conversion efficiency of the solar cell from being lowered even if the bus bar electrode is connected to the tab wire by soldering, and the present invention has been completed.
亦即，依據本發明所得到的導電性糊，其特徵為包含：銅粉表面經銀層被覆之銀被覆銅粉與具萘骨架之環氧樹脂。此導電性糊係以含有溶劑為佳。另外，此導電性糊係以含有硬化劑為佳，此硬化劑係以咪唑及三氟化硼胺系硬化劑的至少一者為佳。銀相對於銀被覆銅粉的量係以5質量%以上為佳，銅粉藉由雷射繞射式粒度分布裝置所測得的體積基準累積50%粒徑(D50 徑)係以0.1～15μm為佳。導電性糊中之銀被覆銅粉的量係以50～90質量%為佳。That is, the conductive paste obtained according to the present invention is characterized by comprising a silver-coated copper powder coated with a silver layer on the surface of the copper powder and an epoxy resin having a naphthalene skeleton. The conductive paste is preferably a solvent. Further, it is preferable that the conductive paste contains a curing agent, and at least one of the curing agent is preferably an imidazole or a boron trifluoride-based curing agent. The amount of silver relative to the silver-coated copper powder is preferably 5% by mass or more, and the volume fraction of the copper powder measured by the laser diffraction type particle size distribution device is 50% of the particle diameter (D 50 diameter) is 0.1 to 0.1. 15 μm is preferred. The amount of the silver-coated copper powder in the conductive paste is preferably 50 to 90% by mass.
另外，依據本發明所得到的太陽能電池用電極之製造方法，其特徵為：藉由將上述導電性糊塗佈於基板之後使其硬化，而在基板的表面形成電極。 [發明效果]Further, according to the method for producing an electrode for a solar cell obtained by the present invention, the conductive paste is applied to a substrate and then cured to form an electrode on the surface of the substrate. [Effect of the invention]
依據本發明，可提供一種導電性糊，即使藉由使用了銀被覆銅粉之樹脂型導電性糊來製作太陽能電池的母線電極且將該母線電極藉由焊接與極耳線連接，也能夠防止太陽能電池的轉換效率降低。According to the present invention, it is possible to provide a conductive paste which can be prevented by forming a bus bar electrode of a solar cell by using a resin-type conductive paste of silver-coated copper powder and bonding the bus bar electrode to the tab wire by soldering. The conversion efficiency of solar cells is reduced.
依據本發明所得到的導電性糊的實施形態，包含銅粉表面經銀層被覆之銀被覆銅粉、及具萘骨架之環氧樹脂。According to an embodiment of the conductive paste obtained by the present invention, a silver-coated copper powder coated with a silver layer on a surface of a copper powder and an epoxy resin having a naphthalene skeleton are included.
此導電性糊中所包含的具萘骨架之樹脂，可使用如化1所示之具萘骨架之環氧樹脂(例如大日本Ink化學工業股份有限公司製的HP4710)。此具萘骨架之環氧樹脂的含量，相對於導電性糊，係以1～20質量%為佳，3～10質量%為更佳。若此具萘骨架之環氧樹脂的含量過少，則保護銀被覆銅粉表面不因熱而氧化的效果不足。另一方面，若過多，則藉由導電性糊印刷成太陽能電池的母線電極形狀時的印刷性、或將母線電極焊接至極耳線時焊料的接著強度會惡化，同時藉由導電性糊製作出的太陽能電池的母線電極的電阻上升。此外，是否為具萘骨架之環氧樹脂，可藉由氣相層析質量分析計(GC-MS)或C13-NMR來鑑定。As the resin having a naphthalene skeleton contained in the conductive paste, an epoxy resin having a naphthalene skeleton (for example, HP4710 manufactured by Dainippon Ink Chemical Co., Ltd.) can be used. The content of the epoxy resin having a naphthalene skeleton is preferably from 1 to 20% by mass, more preferably from 3 to 10% by mass, based on the conductive paste. If the content of the epoxy resin having a naphthalene skeleton is too small, the effect of protecting the surface of the silver-coated copper powder from oxidation by heat is insufficient. On the other hand, if it is too large, the printability when printing a bus bar electrode shape of a solar cell by a conductive paste, or the soldering strength of the solder when soldering a bus bar electrode to a tab wire may be deteriorated, and it is produced by a conductive paste. The resistance of the bus electrode of the solar cell rises. Further, whether or not the epoxy resin having a naphthalene skeleton can be identified by a gas chromatography mass spectrometer (GC-MS) or C13-NMR.
[化1] [Chemical 1]
此導電性糊係以含有硬化劑為佳，此硬化劑以使用咪唑及三氟化硼胺系硬化劑的至少一者為佳。此硬化劑的含量，相對於環氧樹脂，以1～10質量%為佳，2～6質量%為更佳。It is preferable that the conductive paste contains a curing agent, and at least one of an imidazole and a boron trifluoride amine-based curing agent is preferably used. The content of the curing agent is preferably from 1 to 10% by mass, more preferably from 2 to 6% by mass, based on the epoxy resin.
此導電性糊係以含有溶劑為佳，此溶劑可因應導電性糊的使用目的適當地選擇。例如可由丁基卡必醇醋酸酯(BCA)、丁基卡必醇(BC)、乙基卡必醇醋酸酯(ECA)、乙基卡必醇(EC)、甲苯、甲基乙基酮、甲基異丁基酮、十四烷、四氫萘、丙基醇、異丙醇、二氫萜品醇、二氫萜品醇醋酸酯、乙基卡必醇、2,2,4-三甲基-1,3-戊二醇單異丁酸酯(TEXANOL)等選擇1種以上的溶劑來使用。此溶劑的含量，相對於導電性糊，係以0～20質量%為佳，0～10質量%為更佳。The conductive paste is preferably a solvent, and the solvent can be appropriately selected depending on the purpose of use of the conductive paste. For example, butyl carbitol acetate (BCA), butyl carbitol (BC), ethyl carbitol acetate (ECA), ethyl carbitol (EC), toluene, methyl ethyl ketone, Methyl isobutyl ketone, tetradecane, tetrahydronaphthalene, propyl alcohol, isopropanol, dihydroterpineol, dihydroterpineol acetate, ethyl carbitol, 2,2,4-three One or more solvents selected from methyl-1,3-pentanediol monoisobutyrate (TEXANOL) or the like are used. The content of the solvent is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the conductive paste.
另外，導電性糊亦可含有界面活性劑、分散劑、流變調整劑、矽烷偶合劑、離子捕集材料等的其他成分。Further, the conductive paste may contain other components such as a surfactant, a dispersant, a rheology modifier, a decane coupling agent, and an ion trap.
在導電性糊中，使用了銅粉表面經銀層被覆之銀被覆銅粉作為導體。經銀層被覆之銅粉(銀被覆銅粉)的形狀可為略球狀或碎片狀。In the conductive paste, a silver-coated copper powder coated with a silver layer on the surface of the copper powder was used as a conductor. The shape of the copper powder (silver-coated copper powder) coated with the silver layer may be slightly spherical or fragmented.
銀層係以由銀或銀化合物所構成之層為佳，由90質量%以上的銀所構成之層為更佳。銀相對於銀被覆銅粉的量，係以5質量%以上為佳，7～50質量%為較佳，8～40質量%為更佳，9～20質量%為最佳。在銀的量少於5質量%的情況，會對銀被覆銅粉的導電性造成不良影響，故為不佳。另一方面，若超過50質量%，則因為銀的使用量增加，成本變高，故為不佳。The silver layer is preferably a layer composed of silver or a silver compound, and a layer composed of 90% by mass or more of silver is more preferable. The amount of silver relative to the silver-coated copper powder is preferably 5% by mass or more, preferably 7 to 50% by mass, more preferably 8 to 40% by mass, and most preferably 9 to 20% by mass. When the amount of silver is less than 5% by mass, the conductivity of the silver-coated copper powder is adversely affected, which is not preferable. On the other hand, when it exceeds 50% by mass, the amount of silver used increases, and the cost becomes high, which is not preferable.
銅粉的粒徑，係以藉由雷射繞射式粒度分布裝置所測得的體積基準累積50%粒徑(D50 徑)為0.1～15μm為佳，0.3～10μm為更佳，1～5μm為最佳。若累積50%粒徑(D50 徑)小於0.1μm，會對銀被覆銅粉的導電性造成不良影響，故為不佳。另一方面，若超過15μm，則難以形成微細的配線故為不佳。The particle size of the copper powder is preferably 50% by particle diameter (D 50 diameter) of 0.1 to 15 μm, more preferably 0.3 to 10 μm, more preferably 0.3 to 10 μm, as measured by a laser diffraction type particle size distribution device. 5 μm is the best. When the cumulative 50% particle diameter (D 50 diameter) is less than 0.1 μm, the conductivity of the silver-coated copper powder is adversely affected, which is not preferable. On the other hand, when it exceeds 15 μm, it is difficult to form fine wiring, which is not preferable.
銅粉可藉由濕式還原法、電解法、氣相法等來製造，而以藉由使銅在熔解溫度以上熔解，使其由餵槽下部落下並同時衝撞高壓氣體或高壓水，使其急冷凝固而製成微粉末的(氣體霧化法、水霧化法等)所謂霧化法來製造為佳。尤其，若藉由吹送高壓水，所謂的水霧化法來製造，則可得到粒徑小的銅粉，因此將銅粉使用於導電糊時，可謀求利用粒子間的接觸點增加來提升導電性。The copper powder can be produced by a wet reduction method, an electrolysis method, a gas phase method, or the like, and is melted by melting the copper at a temperature higher than the melting temperature to cause the high-pressure gas or the high-pressure water to collide with the high-pressure gas or the high-pressure water. It is preferably produced by a so-called atomization method which is rapidly cooled and solidified to form a fine powder (gas atomization method, water atomization method, etc.). In particular, when high-pressure water is blown and produced by the so-called water atomization method, copper powder having a small particle diameter can be obtained. Therefore, when copper powder is used for the conductive paste, it is possible to increase the conductivity by increasing the contact point between the particles. Sex.
將銅粉以銀層被覆的方法，可使用藉由利用銅與銀的取代反應的取代法、或使用還原劑的還原法使銀或銀化合物在銅粉表面析出的方法，例如可使用將溶劑中含有銅粉與銀或銀化合物的溶液在攪拌下使銀或銀化合物在銅粉表面析出的方法、或將溶劑中含有銅粉及有機物的溶液與溶劑中含有銀或銀化合物及有機物的溶液混合，在攪拌下使銀或銀化合物在銅粉表面析出的方法等。The method of coating the copper powder with a silver layer may be a method of depositing silver or a silver compound on the surface of the copper powder by a substitution method using a substitution reaction of copper and silver or a reduction method using a reducing agent, for example, a solvent may be used. a method comprising a solution of a copper powder and a silver or a silver compound for precipitating silver or a silver compound on a surface of a copper powder, or a solution containing a copper powder and an organic substance in a solvent, and a solution containing silver or a silver compound and an organic substance in a solvent. A method of mixing silver or a silver compound on the surface of copper powder under stirring, or the like.
此溶劑可使用水、有機溶劑或該等混合成的溶劑。在使用水與有機溶劑混合成的溶劑的情況，必須使用在室溫(20～30℃)下為液體的有機溶劑，水與有機溶劑的混合比率，可藉由所使用的有機溶劑適當地調整。另外，作為溶劑使用的水，只要沒有雜質混入的顧慮，則可使用蒸餾水、離子交換水、工業用水等。As the solvent, water, an organic solvent or a solvent obtained by mixing them may be used. In the case of using a solvent in which water and an organic solvent are mixed, it is necessary to use an organic solvent which is liquid at room temperature (20 to 30 ° C), and a mixing ratio of water and an organic solvent can be appropriately adjusted by the organic solvent to be used. . Further, as the water used as the solvent, distilled water, ion-exchanged water, industrial water or the like can be used as long as there is no fear of impurities being mixed.
作為銀層的原料，必須使銀離子存在於溶液中，因此以使用對於水或大多數有機溶劑具有高溶解度的硝酸銀為佳。另外，為了使以銀層被覆銅粉的反應(銀被覆反應)儘量均勻地進行，以使用將硝酸銀溶解於溶劑(水、有機溶劑或將該等混合成的溶劑)的硝酸銀溶液為佳，而非固體的硝酸銀。此外，所使用的硝酸銀溶液的量、硝酸銀溶液中的硝酸銀的濃度及有機溶劑的量，可因應目標的銀層量來決定。As a raw material of the silver layer, silver ions must be present in the solution, so it is preferred to use silver nitrate having high solubility for water or most organic solvents. In addition, in order to carry out the reaction (silver coating reaction) in which the copper layer is coated with the silver layer as much as possible, it is preferable to use a silver nitrate solution in which silver nitrate is dissolved in a solvent (water, an organic solvent or a solvent in which these are mixed). Non-solid silver nitrate. Further, the amount of the silver nitrate solution to be used, the concentration of the silver nitrate in the silver nitrate solution, and the amount of the organic solvent can be determined in accordance with the target silver layer amount.
為了更均勻地形成銀層，亦可在溶液中添加螯合劑。螯合劑係以使用對於銅離子等而言錯合穩定度常數高的螯合劑，以使藉由銀離子與金屬銅的取代反應而副生成的銅離子等不會再析出為佳。尤其，成為銀被覆銅粉核心的銅粉，其主構成要素含有銅，因此宜留意與銅的錯合穩定度常數來選擇螯合劑。具體而言，螯合劑可使用選自乙二胺四醋酸(EDTA)、亞胺基二醋酸、二乙三胺、三乙二胺及該等的鹽所構成的群組之螯合劑。In order to form the silver layer more uniformly, a chelating agent may also be added to the solution. The chelating agent is preferably a chelating agent having a high stability-stability constant for copper ions or the like, so that copper ions or the like which are produced by substitution reaction of silver ions and metallic copper are not precipitated. In particular, since the copper powder which is the core of the silver-coated copper powder contains copper as its main constituent element, it is preferable to select a chelating agent by paying attention to the stability constant of copper. Specifically, as the chelating agent, a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriamine, triethylenediamine, and the like can be used.
為了安定且安全地進行銀被覆反應，亦可在溶液中添加pH緩衝劑。此pH緩衝劑可使用碳酸銨、碳酸氫銨、氨水、碳酸氫鈉等。In order to carry out the silver coating reaction in a stable and safe manner, a pH buffer may also be added to the solution. As the pH buffering agent, ammonium carbonate, ammonium hydrogencarbonate, ammonia water, sodium hydrogencarbonate or the like can be used.
銀被覆反應時，在添加銀鹽之前，在溶液中加入銅粉，並且攪拌，在銅粉充分分散於溶液中的狀態下添加含有銀鹽的溶液為佳。此銀被覆反應時的反應溫度，只要不是反應液凝固或蒸發的溫度即可，宜設定在10～40℃，更佳為15～35℃的範圍。另外，反應時間會依照銀或銀化合物的量或反應溫度而有所不同，可設定在1分鐘～5小時的範圍。In the silver coating reaction, copper powder is added to the solution before the addition of the silver salt, and the mixture is stirred, and a solution containing a silver salt is preferably added in a state where the copper powder is sufficiently dispersed in the solution. The reaction temperature at the time of the silver coating reaction is not particularly limited to a temperature at which the reaction solution is solidified or evaporated, and is preferably in the range of 10 to 40 ° C, more preferably 15 to 35 ° C. Further, the reaction time varies depending on the amount of silver or silver compound or the reaction temperature, and can be set in the range of 1 minute to 5 hours.
另外，可藉由將上述導電性糊(包含銅粉表面經銀層被覆之銀被覆銅粉與具萘骨架之環氧樹脂的導電性糊)塗佈於基板後，使其硬化，而在基板表面形成電極，將內部連接材(interconnector)焊接至該電極，在具有該已焊接於電極之內部連接材的附內部連接材單元的表面側(太陽光入射側)透過保護片層合蓋玻璃，而製作出太陽能電池模組。保護片宜使用環烯烴共聚物(COC)薄膜等的聚烯烴系薄膜。已知聚烯烴系薄膜會透氧，而使用由上述導電性糊(包含銅粉表面經銀層被覆之銀被覆銅粉與具萘骨架之環氧樹脂的導電性糊)所形成之電極的太陽能電池模組中，若使用聚烯烴系薄膜作為保護片，則電極的氧化會受到抑制，可維持作為太陽能電池的性能。 [實施例]In addition, the conductive paste (a conductive paste containing a silver-coated copper powder coated with a silver layer on a surface of a copper powder and an epoxy resin having a naphthalene skeleton) may be applied to a substrate and then cured to be on the substrate. Forming an electrode on the surface, soldering an internal connecting member to the electrode, and laminating the cover glass through the protective sheet on the surface side (sunlight incident side) of the internal connecting material unit having the internal connecting material welded to the electrode. And made a solar cell module. As the protective sheet, a polyolefin-based film such as a cycloolefin copolymer (COC) film is preferably used. It is known that a polyolefin-based film is permeable to oxygen, and solar energy using an electrode formed of the above-mentioned conductive paste (a conductive paste containing a silver-coated copper powder coated with a silver layer and an epoxy resin having a naphthalene skeleton) is used. In the battery module, when a polyolefin-based film is used as the protective sheet, oxidation of the electrode is suppressed, and the performance as a solar cell can be maintained. [Examples]
以下針對依據本發明所得到的導電性糊的實施例詳細說明。Hereinafter, an embodiment of the conductive paste obtained according to the present invention will be described in detail.
[實施例1] 準備藉由霧化法製造的市售銅粉(日本ATOMIZE加工股份有限公司製的霧化銅粉SF-Cu 5μm)，求得其(銀被覆前的)銅粉的粒度分布，結果，銅粉的體積基準累積10%粒徑(D10 )為2.26μm、累積50%粒徑(D50 )為5.20μm、累積90%粒徑(D90 )為9.32μm。此外，銅粉的粒度分布是藉由雷射繞射式粒度分布裝置(日機裝股份有限公司製的Microtrac粒度分布測定裝置MT-3300)作測定，求得體積基準的累積10%粒徑(D10 )、累積50%粒徑(D50 )、累積90%粒徑(D90 )。[Example 1] A commercially available copper powder (atomized copper powder SF-Cu 5 μm manufactured by ATOMIZE Co., Ltd., Japan) manufactured by an atomization method was prepared, and the particle size distribution of the copper powder (before silver coating) was determined. As a result, the volume-based cumulative 10% particle diameter (D 10 ) of the copper powder was 2.26 μm, the cumulative 50% particle diameter (D 50 ) was 5.20 μm, and the cumulative 90% particle diameter (D 90 ) was 9.32 μm. Further, the particle size distribution of the copper powder was measured by a laser diffraction type particle size distribution apparatus (Microtrac particle size distribution measuring apparatus MT-3300 manufactured by Nikkiso Co., Ltd.) to obtain a cumulative 10% particle diameter on a volume basis ( D 10 ), cumulative 50% particle size (D 50 ), cumulative 90% particle size (D 90 ).
另外，準備已將碳酸銨2.6kg溶解至純水450kg的溶液(溶液1)、及在已將EDTA-4Na(43%)319kg與碳酸銨76kg溶解至純水284kg之溶液中加入含銀16.904kg之硝酸銀水溶液92kg而得的溶液(溶液2)。In addition, a solution in which 2.6 kg of ammonium carbonate was dissolved in 450 kg of pure water (solution 1), and 16.904 kg of silver containing EDTA-4Na (43%) 319 kg and 76 kg of ammonium carbonate dissolved in pure water of 284 kg were prepared. A solution of 92 kg of a silver nitrate aqueous solution (solution 2).
接下來，在氮氣環境下，將上述銅粉100kg添加至溶液1，在攪拌下升溫至35℃。在該分散有銅粉的溶液中添加溶液2，攪拌30分鐘之後，過濾、水洗、乾燥，而得到被銀被覆之銅粉(銀被覆銅粉)。此外，水洗是對藉由過濾所得到的固體成分添加純水來進行，至水洗後的液體的電位成為0.5mS/m以下為止。Next, 100 kg of the above copper powder was added to the solution 1 under a nitrogen atmosphere, and the temperature was raised to 35 ° C with stirring. The solution 2 was added to the solution in which the copper powder was dispersed, and after stirring for 30 minutes, it was filtered, washed with water, and dried to obtain a silver-coated copper powder (silver-coated copper powder). Further, the water washing is performed by adding pure water to the solid component obtained by the filtration, and the potential of the liquid after washing with water is 0.5 mS/m or less.
使以這種方式所得到的銀被覆銅粉5.0g溶於已將比重1.38之硝酸水溶液利用純水以體積比1：1進行稀釋而成之硝酸水溶液40mL，以加熱器煮沸，使銀被覆銅粉完全溶解之後，在此水溶液中，逐次以少量添加已將比重1.18之鹽酸水溶液利用純水以體積比1：1進行稀釋而成之鹽酸水溶液，使氯化銀析出，繼續添加鹽酸水溶液至沒有沉澱產生為止，藉由重量法自所得到的氯化銀求Ag含量，銀被覆銅粉中的Ag含量為10.14質量%。5.0 g of the silver-coated copper powder obtained in this manner was dissolved in 40 mL of an aqueous nitric acid solution obtained by diluting a nitric acid aqueous solution having a specific gravity of 1.38 with pure water at a volume ratio of 1:1, and boiling it with a heater to form a silver-coated copper After the powder is completely dissolved, a hydrochloric acid aqueous solution obtained by diluting a hydrochloric acid aqueous solution having a specific gravity of 1.18 with a volume ratio of 1:1 by a volume ratio of 1:1 is added to the aqueous solution to precipitate a silver chloride, and the aqueous hydrochloric acid solution is continuously added thereto. Before the precipitation occurred, the Ag content was determined from the obtained silver chloride by a gravimetric method, and the Ag content in the silver-coated copper powder was 10.14% by mass.
另外，將此銀被覆銅粉0.1g添加至異丙醇40mL，藉由超音波均質機(均質棒尖端直徑20mm)使其分散2分鐘之後，藉由雷射繞射式粒度分布裝置(日機裝股份有限公司製的Microtrac粒度分布測定裝置MT-3300)測定銀被覆銅粉的粒度分布。其結果，銀被覆銅粉的體積基準累積10%粒徑(D10 )為2.5μm、累積50%粒徑(D50 )為5.2μm、累積90%粒徑(D90 )為10.1μm。Further, 0.1 g of this silver-coated copper powder was added to 40 mL of isopropyl alcohol, and dispersed by an ultrasonic homogenizer (homogeneous rod tip diameter of 20 mm) for 2 minutes, followed by a laser diffraction type particle size distribution device (Japanese machine) The Microtrac particle size distribution measuring apparatus MT-3300 manufactured by Seiko Co., Ltd. was used to measure the particle size distribution of the silver-coated copper powder. As a result, the volume-based cumulative 10% particle diameter (D 10 ) of the silver-coated copper powder was 2.5 μm, the cumulative 50% particle diameter (D 50 ) was 5.2 μm, and the cumulative 90% particle diameter (D 90 ) was 10.1 μm.
另外，使用BET比表面積測定器(Yuasa Ionics股份有限公司製的4Sorb US)，藉由BET單點法，測定此銀被覆銅粉的BET比表面積。其結果，銀被覆銅粉的BET比表面積為0.31m2 /g。Further, the BET specific surface area of the silver-coated copper powder was measured by a BET single-point method using a BET specific surface area measuring instrument (4Sorb US manufactured by Yuasa Ionics Co., Ltd.). As a result, the silver-coated copper powder had a BET specific surface area of 0.31 m 2 /g.
另外，將所得到的銀被覆銅粉87.64重量份、化1所示之具萘骨架之環氧樹脂(大日本Ink化學工業股份有限公司製的HP4710)6.49重量份、作為溶劑的丁基卡必醇醋酸酯(和光純藥工業股份有限公司製)5.52重量份、作為硬化劑的咪唑(四國化成工業股份有限公司製的2E4MZ)0.25重量份、及作為分散劑的油酸(和光純藥工業股份有限公司製)0.10重量份，藉由自公轉式真空攪拌脫泡裝置(Thinky股份有限公司製的除泡練太郎)混合(預備混練)之後，藉由三輥機(Otto Herrmann公司製的EXAKT80S)混練，分別得到導電性糊1(作為母線電極用糊)。此外，此導電性糊1的F值(銀被覆銅粉相對於作為導電填料的銀被覆銅粉、樹脂、及硬化劑的總量的比例)為92.9%。藉由黏度計(BROOKFIELD公司製的DV-III Ultra、錐體使用CP52)，在25℃下以1rpm測定此導電性糊1的黏度，結果為40Pa･s。In addition, 87.64 parts by weight of the obtained silver-coated copper powder and 6.47 parts by weight of an epoxy resin having a naphthalene skeleton (HP4710 manufactured by Dainippon Ink Chemical Co., Ltd.) and a butyl group as a solvent were used. 5.52 parts by weight of an alcohol acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.25 parts by weight of imidazole (2E4MZ manufactured by Shikoku Chemicals Co., Ltd.) as a curing agent, and oleic acid as a dispersing agent (Wako Pure Chemical Industries, Ltd.) 0.10 parts by weight of the Co., Ltd. product, which was mixed by a revolving vacuum agitation degassing apparatus (defoaming Taro) made by Thinky Co., Ltd. (premixed), and then passed by a three-roller (EXAKT80S manufactured by Otto Herrmann). In the kneading, the conductive paste 1 (as a paste for the bus bar electrode) was obtained. Further, the F value of the conductive paste 1 (the ratio of the silver-coated copper powder to the total amount of the silver-coated copper powder, the resin, and the curing agent as the conductive filler) was 92.9%. The viscosity of the conductive paste 1 was measured at 25 ° C for 1 rpm by a viscometer (DV-III Ultra manufactured by BROOKFIELD Co., Ltd., CP52 using a cone), and it was 40 Pa·s.
另外，在銀離子21.4g/L的硝酸銀溶液502.7L中，加入工業用的氨水45L，產生銀氨錯合物溶液。在所產生的銀氨錯合物溶液中加入濃度100g/L的氫氧化鈉溶液8.8L，調整pH，加入水462L進行稀釋，並加入作為還原劑的工業用福馬林48L。在這之後，加入作為硬脂酸的16質量%的硬脂酸乳膠121g。將以這種方式所得之銀泥漿過濾，水洗之後，使其乾燥，而得到銀粉21.6kg。將此銀粉以亨舍爾混合機(高速攪拌機)表面平滑化處理之後，進行分級，將大於11μm的銀凝集體除去。此外，水洗是對藉由過濾所得到的固體成分添加純水來進行，至水洗後的液的電位成為0.5mS/m以下為止。Further, 45 L of industrial ammonia water was added to 502.7 L of a silver nitrate solution having a silver ion of 21.4 g/L to produce a silver ammonia complex solution. To the resulting silver ammonia complex solution, 8.8 L of a sodium hydroxide solution having a concentration of 100 g/L was added, the pH was adjusted, and 462 L of water was added for dilution, and 48 L of industrial fumarin as a reducing agent was added. After that, 121 g of a 16% by mass stearic acid latex as stearic acid was added. The silver slurry obtained in this manner was filtered, washed with water, and dried to obtain 21.6 kg of silver powder. This silver powder was subjected to smoothing treatment on a Henschel mixer (high speed mixer), and then classified, and silver aggregates larger than 11 μm were removed. In addition, water washing is performed by adding pure water to the solid component obtained by filtration, and the potential of the liquid after washing is 0.5 mS/m or less.
將以這種方式所得到的銀粉88重量份、銦粉末0.2重量份、銀碲被覆玻璃粉1.5重量份、作為黏結劑樹脂的乙基纖維素(和光純藥工業股份有限公司製)0.12重量份及丙烯酸樹脂(日本Carbide工業股份有限公司製的NISSETSU EU-5638)1.1重量份、作為添加劑的油酸(和光純藥工業股份有限公司製)0.5重量份、作為搖變劑的硬脂酸鎂(和光純藥工業股份有限公司製)0.3重量份、作為溶劑的甲基異丁醚(MIBE)(JNC股份有限公司製)3.4重量份、及丁基卡必醇醋酸酯(和光純藥工業股份有限公司製)3.4重量份，藉由自公轉式真空攪拌脫泡裝置(Thinky股份有限公司製的除泡練太郎)混合(預備混練)之後，藉由三輥機(Otto Herrmann公司製的EXAKT80S)混練，得到導電性糊2(作為燒成型Ag糊)。88 parts by weight of the silver powder obtained in this manner, 0.2 parts by weight of the indium powder, 1.5 parts by weight of the silver-coated glass powder, and 0.12 parts by weight of ethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd.) as a binder resin. And 0.1 parts by weight of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as an additive, and 0.5 parts by weight of oleic acid (manufactured by Nippon Carbide Co., Ltd., NISSETSU EU-5638), magnesium stearate as a shaker 0.3 parts by weight of methyl isobutyl ether (MIBE) (manufactured by JNC Co., Ltd.) as a solvent, and butyl carbitol acetate (manufactured by Wako Pure Chemical Industries Co., Ltd.) 3.4 parts by weight of the company, which was mixed by a revolving vacuum agitation degassing apparatus (defoaming Taro) made by Thinky Co., Ltd. (premixed), and then kneaded by a three-roller (EXAKT80S manufactured by Otto Herrmann Co., Ltd.). The conductive paste 2 (as a paste-forming Ag paste) was obtained.
此外，銀碲被覆玻璃粉是如以下所述方式來製作。首先，在1L燒杯中，將32質量%的硝酸銀水溶液3.47g混合至攪拌狀態的純水787g，在此含有銀1.11g的硝酸銀水溶液中添加作為錯化劑的28質量%的氨水2.5g，得到銀氨錯鹽水溶液。使此銀氨錯鹽水溶液的液溫到達30℃之後，添加碲系玻璃粉(旭硝子股份有限公司製的BLT-77)10g，在這之後，添加作為還原劑的聯胺0.3g、銀膠體10.3g與純水20g的混合液，使其熟成5分鐘，藉由以銀與碲為主成分的層被覆碲系玻璃粉之後，將此含有銀碲被覆玻璃粉的泥漿抽氣過濾，以純水洗淨至電位成為0.5mS/m以下，以75℃的真空乾燥機使所得到的濾餅乾燥10分鐘，得到銀碲被覆玻璃粉(被以銀與碲為主成分的層被覆的玻璃粉)。Further, the silver enamel coated glass powder was produced as described below. First, 3.47 g of a 32% by mass aqueous silver nitrate solution was mixed with 787 g of pure water in a stirred state in a 1 L beaker, and 2.5 g of 28% by mass aqueous ammonia as a distorting agent was added to the silver nitrate aqueous solution containing 1.11 g of silver. Silver ammonia wrong salt aqueous solution. After the liquid temperature of the aqueous solution of the silver ammonia salt solution reached 30° C., 10 g of bismuth-based glass frit (BLT-77, manufactured by Asahi Glass Co., Ltd.) was added, and thereafter, 0.3 g of hydrazine as a reducing agent and silver colloid 10.3 were added. a mixture of g and 20 g of pure water was allowed to mature for 5 minutes, and the ceramsite-like glass powder was coated with a layer mainly composed of silver and cerium, and then the slurry containing the silver cerium-coated glass powder was suction-filtered to obtain pure water. After washing to a potential of 0.5 mS/m or less, the obtained cake was dried in a vacuum dryer at 75 ° C for 10 minutes to obtain a silver-coated glass frit (a glass powder coated with a layer mainly composed of silver and rhodium). .
接下來，準備兩枚矽晶圓(E＆M股份有限公司製，100Ω/□、6英吋單結晶)，在各矽晶圓背面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)印刷鋁糊(東洋Aluminium股份有限公司製的Al solar 14-7021)之後，藉由熱風式乾燥機在200℃下乾燥10分鐘，同時在矽晶圓表面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)印刷上述導電性糊2成寬40μm的100根指狀電極形狀之後，藉由熱風式乾燥機，在200℃下乾燥10分鐘，並將高速燒成IR爐(日本碍子股份有限公司製的高速燒成測試4室爐)的IN-OUT定為21秒，以峰溫度820℃燒成，而形成指狀電極。然後，各在矽晶圓表面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)，將各導電性糊1(由銀被覆銅粉所得到的導電性糊1)印刷成寬1.3mm的3根母線電極形狀之後，藉由熱風式乾燥機，在150℃下加熱10分鐘之後，在200℃下加熱30分鐘使其乾燥，同時使其硬化，而形成母線電極。測定以這種方式形成的母線電極的電阻(初始電阻值)，結果為3.15Ω。另外，以對另一矽晶圓的母線電極上施加與焊接時之熱相同程度的熱的方式，將380℃的烙鐵抵住母線電極，使其以10mm/秒的速度移動，測定此加熱後的母線電極的電阻，結果為3.42Ω，相對於初始電阻值的電阻變化率為109%。Next, two wafers (100 Ω/□, 6-inch single crystal, manufactured by E&M Co., Ltd.) were prepared, and a screen printer (MT-320T manufactured by Microtek Co., Ltd.) was used on the back of each wafer. After printing aluminum paste (Al solar 14-7021, manufactured by Toyo Aluminium Co., Ltd.), it was dried at 200 ° C for 10 minutes by a hot air dryer while using a screen printing machine on the surface of the tantalum wafer (Microtek Co., Ltd. After the above-mentioned conductive paste 2 was printed into a shape of 100 finger electrodes having a width of 40 μm, it was dried at 200 ° C for 10 minutes by a hot air dryer, and fired at a high speed IR furnace (Japan Insulators Co., Ltd.) The IN-OUT of the high-speed firing test 4-bed furnace manufactured by the company was set at 21 seconds, and was fired at a peak temperature of 820 ° C to form a finger electrode. Then, each conductive paste 1 (conductive paste 1 obtained from silver-coated copper powder) was printed to a width of 1.3 by a screen printer (MT-320T manufactured by Microtek Co., Ltd.) on the surface of the wafer. After the shape of the three busbar electrodes of mm, the film was heated at 150 ° C for 10 minutes by a hot air dryer, and then dried at 200 ° C for 30 minutes to be dried, and hardened to form a bus bar electrode. The electric resistance (initial resistance value) of the bus bar electrode formed in this manner was measured, and as a result, it was 3.15 Ω. Further, a soldering iron of 380 ° C was applied to the bus bar electrode at a speed of 10 mm/sec by applying heat of the same degree as the heat of the bonding to the bus bar electrode of the other silicon wafer, and the heating was measured. The resistance of the bus bar electrode was 3.42 Ω, and the rate of change in resistance with respect to the initial resistance value was 109%.
接下來，藉由SnPb共晶焊料(熔點183℃)在380℃下將另一矽晶圓的母線電極與極耳線焊接，製作出太陽能電池。藉由陽光模擬器(WACOM電創股份有限公司製)的氙燈，對此太陽能電池照射照光能量100mW/cm2 的模擬太陽光，進行電池特性測試。其結果，使太陽能電池的輸出端子短路時，流過兩端子間的電流(短路電流)Isc為9.23A，將太陽能電池的輸出端子開放時，兩端子間的電壓(開放電壓)Voc為0.631V，電流密度Jsc(每1cm2 的短路電流Isc)為0.038A/cm2 ，最大輸出Pmax(＝Imax･Vmax)除以開放電壓Voc與電流密度Jsc之積之值(曲線因子)FF(＝Pmax/Voc･Isc)為73.64，發電效率Eff(最大輸出Pmax除以(每1cm2 的)照射光量(W)之值乘以100之值)為17.65%、串聯電阻Rs為0.0089Ω/□。Next, a bus electrode of another tantalum wafer was soldered to the tab wire at 380 ° C by SnPb eutectic solder (melting point 183 ° C) to fabricate a solar cell. The solar cell was irradiated with simulated sunlight having an illumination energy of 100 mW/cm 2 by a xenon lamp of a sunlight simulator (manufactured by WACOM Electric Co., Ltd.), and battery characteristics were tested. As a result, when the output terminal of the solar cell is short-circuited, the current (short-circuit current) Isc flowing between the terminals is 9.23 A, and when the output terminal of the solar cell is opened, the voltage (open voltage) Voc between the terminals is 0.631 V. The current density Jsc (short circuit Isc per 1 cm 2 ) is 0.038 A/cm 2 , and the maximum output Pmax (=Imax·Vmax) divided by the product of the open voltage Voc and the current density Jsc (curve factor) FF (= Pmax /Voc·Isc) is 73.64, and the power generation efficiency Eff (the maximum output Pmax divided by the value of the amount of irradiation light (W per 1 cm 2 ) multiplied by 100) is 17.65%, and the series resistance Rs is 0.0089 Ω/□.
[實施例2] 使用咪唑(四國化成工業股份有限公司製的2PHZ-PW)來代替咪唑(四國化成工業股份有限公司製的2E4MZ)作為硬化劑，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。此外，藉由與實施例1同樣的方法測定此實施例所得到的導電性糊1的黏度，結果，在40±5Pa･s的範圍內。[Example 2] Imidazole (2PHZ-PW manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used as a hardener instead of imidazole (2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the examples were 1 The same method was used to make a solar cell. Further, the viscosity of the conductive paste 1 obtained in this example was measured in the same manner as in Example 1, and as a result, it was in the range of 40 ± 5 Pa·s.
測定此太陽能電池之母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為7.56Ω、焊接後的電阻值為6.58Ω，相對於初始電阻值的電阻變化率為87%。The resistance of the bus bar electrode before and after the bonding of the bus bar electrode of the solar cell to the tab wire was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 7.56 Ω, and the resistance value after soldering was 6.58 Ω, which was relative to the initial. The resistance change rate of the resistance value was 87%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為9.23A、開放電壓Voc為0.630V、電流密度Jsc為0.038A/cm2 、曲線因子FF為72.98、發電效率Eff為17.45%、串聯電阻Rs為0.0091Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 9.23 A, the open voltage Voc was 0.630 V, the current density Jsc was 0.038 A/cm 2 , and the curve factor FF was 72.98. The power generation efficiency Eff is 17.45%, and the series resistance Rs is 0.0091 Ω/□.
[實施例3] 使用三氟化硼胺系硬化劑(和光純藥工業股份有限公司製的BF3NH2Et)來代替咪唑(四國化成工業股份有限公司製的2E4MZ)作為導電性糊1中的硬化劑，將銀被覆銅粉、具萘骨架之環氧樹脂、溶劑及硬化劑的量分別定為85.52重量份、8.44重量份、5.62重量份及0.32重量份，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。此外，此實施例所得到的導電性糊1的F值為90.7%。藉由與實施例1同樣的方法測定此實施例所得到的導電性糊1的黏度，結果在40±5Pa･s的範圍內。[Example 3] A boron trifluoride-based hardener (BF3NH2Et manufactured by Wako Pure Chemical Industries, Ltd.) was used as a hardener in the conductive paste 1 instead of imidazole (2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.). The amount of the silver-coated copper powder, the epoxy resin having a naphthalene skeleton, the solvent, and the hardener is 85.52 parts by weight, 8.44 parts by weight, 5.62 parts by weight, and 0.32 parts by weight, respectively, by the same examples. 1 The same method was used to make a solar cell. Further, the F value of the conductive paste 1 obtained in this example was 90.7%. The viscosity of the conductive paste 1 obtained in this example was measured in the same manner as in Example 1. As a result, it was in the range of 40 ± 5 Pa·s.
測定此太陽能電池之母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為6.58Ω、焊接後的電阻值為7.71Ω，相對於初始電阻值的電阻變化率為117%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 6.58 Ω, and the resistance value after soldering was 7.71 Ω, which was relative to the initial. The resistance change rate of the resistance value was 117%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為9.20A、開放電壓Voc為0.628V、電流密度Jsc為0.038A/cm2 、曲線因子FF為71.63、發電效率Eff為17.02%、串聯電阻Rs為0.0102Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 9.20 A, the open voltage Voc was 0.628 V, the current density Jsc was 0.038 A/cm 2 , and the curve factor FF was 71.63. The power generation efficiency Eff is 17.02%, and the series resistance Rs is 0.0102 Ω/□.
[實施例4] 使用化1所示之具萘骨架之環氧樹脂(大日本Ink化學工業股份有限公司製的HP9500)來代替導電性糊1中的具萘骨架之環氧樹脂(大日本Ink化學工業股份有限公司製的HP4710)，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。此外，此實施例所得到的導電性糊1的F值為90.9%。藉由與實施例1同樣的方法測定此實施例所得到的導電性糊1的黏度，結果在40±5Pa･s的範圍內。[Example 4] An epoxy resin having a naphthalene skeleton (HP9500 manufactured by Dainippon Ink Chemical Co., Ltd.) was used in place of the epoxy resin having a naphthalene skeleton in the conductive paste 1 (Greater Japan Ink) A solar cell was produced in the same manner as in Example 1 except that HP4710) manufactured by Chemical Industry Co., Ltd. was used. Further, the F value of the conductive paste 1 obtained in this example was 90.9%. The viscosity of the conductive paste 1 obtained in this example was measured in the same manner as in Example 1. As a result, it was in the range of 40 ± 5 Pa·s.
測定此太陽能電池的母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極的焊接前的電阻值(初始電阻值)為3.56Ω、焊接後的電阻值為5.83Ω，相對於初始電阻值的電阻變化率為164%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 3.56 Ω, and the resistance value after soldering was 5.83 Ω, which was relative to the initial. The resistance change rate of the resistance value was 164%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為8.85A、開放電壓Voc為0.627V、電流密度Jsc為0.036A/cm2 、曲線因子FF為70.47、發電效率Eff為16.10%、串聯電阻Rs為0.0114Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 8.85 A, the open voltage Voc was 0.627 V, the current density Jsc was 0.036 A/cm 2 , and the curve factor FF was 70.47. The power generation efficiency Eff is 16.10%, and the series resistance Rs is 0.0114 Ω/□.
[比較例1] 使用化2所示之雙酚F型環氧樹脂(ADEKA股份有限公司製的EP4901E)來代替導電性糊1中的具萘骨架之環氧樹脂，使用咪唑(四國化成工業股份有限公司製的2E4MZ)作為硬化劑，將溶劑的量定為1.94重量份以使導電性糊1的黏度在40±5Pa･s的範圍內，除此之外，藉由與實施例3同樣的方法製作出太陽能電池。此外，此導電性糊1的F值為90.7%。[Comparative Example 1] The bisphenol F-type epoxy resin (EP4901E, manufactured by ADEKA Co., Ltd.) shown in Chemical Formula 2 was used instead of the epoxy resin having a naphthalene skeleton in the conductive paste 1, and imidazole was used. In the same manner as in the third embodiment, the amount of the solvent is set to 1.94 parts by weight so that the viscosity of the conductive paste 1 is in the range of 40 ± 5 Pa·s. The method of making a solar cell. Further, the F value of this conductive paste 1 was 90.7%.
[化2] [Chemical 2]
測定此太陽能電池之母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為4.05Ω、焊接後的電阻值為18.70Ω，相對於初始電阻值的電阻變化率為462%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 4.05 Ω, and the resistance value after soldering was 18.70 Ω, which was relative to the initial. The resistance change rate of the resistance value was 462%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為6.71A、開放電壓Voc為0.634V、電流密度Jsc為0.028A/cm2 、曲線因子FF為49.96、發電效率Eff為8.74%、串聯電阻Rs為0.0162Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 6.71 A, the open voltage Voc was 0.634 V, the current density Jsc was 0.028 A/cm 2 , and the curve factor FF was 49.96. The power generation efficiency Eff is 8.74%, and the series resistance Rs is 0.0162 Ω/□.
[比較例2] 使用化2所示之雙酚F型環氧樹脂(ADEKA股份有限公司製的EP4901E)來代替具萘骨架之環氧樹脂，將溶劑的量定為1.99重量份以使導電性糊1的黏度在40±5Pa･s的範圍內，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。[Comparative Example 2] A bisphenol F-type epoxy resin (EP4901E, manufactured by ADEKA Co., Ltd.) shown in Chemical Formula 2 was used instead of the epoxy resin having a naphthalene skeleton, and the amount of the solvent was 1.99 parts by weight to make conductivity. A solar cell was produced in the same manner as in Example 1 except that the viscosity of the paste 1 was in the range of 40 ± 5 Pa·s.
測定此太陽能電池的母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為2.37Ω、焊接後的電阻值為7.73Ω，相對於初始電阻值的電阻變化率為326%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 2.37 Ω, and the resistance value after soldering was 7.73 Ω, which was relative to the initial. The resistance change rate of the resistance value was 326%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為7.93A、開放電壓Voc為0.632V、電流密度Jsc為0.033A/cm2 、曲線因子FF為45.47、發電效率Eff為9.39%、串聯電阻Rs為0.0228Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 7.93 A, the open voltage Voc was 0.632 V, the current density Jsc was 0.033 A/cm 2 , and the curve factor FF was 45.47. The power generation efficiency Eff is 9.39%, and the series resistance Rs is 0.0228 Ω/□.
[比較例3] 使用化2所示之雙酚F型環氧樹脂(ADEKA股份有限公司製的EP4901E)來代替具萘骨架之環氧樹脂，將溶劑的量定為1.94重量份以使導電性糊1的黏度在40±5Pa･s的範圍內，除此之外，藉由與實施例3同樣的方法製作出太陽能電池。[Comparative Example 3] A bisphenol F-type epoxy resin (EP4901E, manufactured by ADEKA CORPORATION) was used instead of the epoxy resin having a naphthalene skeleton, and the amount of the solvent was 1.94 parts by weight to make conductivity. A solar cell was produced in the same manner as in Example 3 except that the viscosity of the paste 1 was in the range of 40 ± 5 Pa·s.
測定此太陽能電池的母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為5.95Ω、焊接後的電阻值為12.63Ω，相對於初始電阻值的電阻變化率為212%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 5.95 Ω, and the resistance value after soldering was 12.63 Ω, which was relative to the initial. The resistance change rate of the resistance value was 212%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為8.65A、開放電壓Voc為0.630V、電流密度Jsc為0.036A/cm2 、曲線因子FF為64.69、發電效率Eff為14.51%、串聯電阻Rs為0.0165Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 8.65 A, the open voltage Voc was 0.630 V, the current density Jsc was 0.036 A/cm 2 , and the curve factor FF was 64.69. The power generation efficiency Eff is 14.51%, and the series resistance Rs is 0.0165 Ω/□.
[比較例4] 使用化3所示之雙酚A型環氧樹脂(三菱化學股份有限公司製的JER828)來代替具萘骨架之環氧樹脂，將溶劑的量定為1.99重量份以使導電性糊1的黏度在40±5Pa･s的範圍內，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。[Comparative Example 4] A bisphenol A type epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation) was used instead of the epoxy resin having a naphthalene skeleton, and the amount of the solvent was set to 1.99 parts by weight to make electricity. A solar cell was produced in the same manner as in Example 1 except that the viscosity of the paste 1 was in the range of 40 ± 5 Pa·s.
[化3] [Chemical 3]
測定此太陽能電池的母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為3.50Ω、焊接後的電阻值為34.93Ω，相對於初始電阻值的電阻變化率為998%。 另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為7.78A、開放電壓Voc為0.635V、電流密度Jsc為0.032A/cm2 、曲線因子FF為54.49、發電效率Eff為11.07%、串聯電阻Rs為0.0181Ω/□。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 3.50 Ω, and the resistance value after soldering was 34.93 Ω, which was relative to the initial. The resistance change rate of the resistance value was 998%. Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 7.78 A, the open voltage Voc was 0.635 V, the current density Jsc was 0.032 A/cm 2 , and the curve factor FF was 54.49. The power generation efficiency Eff is 11.07%, and the series resistance Rs is 0.0181 Ω/□.
[比較例5] 使用化4所示之聯苯骨架的環氧樹脂(日本化藥股份有限公司製的NC-3000-H)來代替具萘骨架之環氧樹脂，將溶劑的量定為5.32重量份以使導電性糊1的黏度在40±5Pa･s的範圍內，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。[Comparative Example 5] An epoxy resin having a biphenyl skeleton (Nippon Chemical Co., Ltd., NC-3000-H) was used instead of the epoxy resin having a naphthalene skeleton, and the amount of the solvent was 5.32. A solar cell was produced in the same manner as in Example 1 except that the viscosity of the conductive paste 1 was in the range of 40 ± 5 Pa·s.
[化4] [Chemical 4]
測定此太陽能電池的母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為6.08Ω、焊接後的電阻值為23.53Ω，相對於初始電阻值的電阻變化率為387%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 6.08 Ω, and the resistance value after soldering was 23.53 Ω, which was relative to the initial. The resistance change rate of the resistance value was 387%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為5.67A、開放電壓Voc為0.635V、電流密度Jsc為0.023A/cm2 、曲線因子FF為54.52、發電效率Eff為8.07%、串聯電阻Rs為0.0127Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 5.67 A, the open voltage Voc was 0.635 V, the current density Jsc was 0.023 A/cm 2 , and the curve factor FF was 54.52. The power generation efficiency Eff is 8.07%, and the series resistance Rs is 0.0127 Ω/□.
[比較例6] 使用化5所示之環戊二烯骨架的環氧樹脂(日本化藥股份有限公司製的XD-1000)來代替具萘骨架之環氧樹脂，將溶劑的量定為5.32重量份以使導電性糊1的黏度在40±5Pa･s的範圍內，除此之外，藉由與實施例1同樣的方法製作出太陽能電池。[Comparative Example 6] An epoxy resin having a cyclopentadiene skeleton (XD-1000 manufactured by Nippon Kayaku Co., Ltd.) was used instead of the epoxy resin having a naphthalene skeleton, and the amount of the solvent was 5.32. A solar cell was produced in the same manner as in Example 1 except that the viscosity of the conductive paste 1 was in the range of 40 ± 5 Pa·s.
[化5] [Chemical 5]
測定此太陽能電池之母線電極與極耳線焊接前後的母線電極的電阻，結果，母線電極在焊接前的電阻值(初始電阻值)為4.73Ω、焊接後的電阻值為21.67Ω，相對於初始電阻值的電阻變化率為458%。The resistance of the bus bar electrode before and after the soldering of the bus bar electrode of the solar cell was measured. As a result, the resistance value (initial resistance value) of the bus bar electrode before soldering was 4.73 Ω, and the resistance value after soldering was 21.67 Ω, which was relative to the initial. The resistance change rate of the resistance value was 458%.
另外，藉由與實施例1同樣的方法進行太陽能電池的電池特性測試，結果，短路電流Isc為4.66A、開放電壓Voc為0.632V、電流密度Jsc為0.019A/cm2 、曲線因子FF為55.01、發電效率Eff為6.67%、串聯電阻Rs為0.0182Ω/□。Further, the battery characteristics test of the solar cell was carried out in the same manner as in Example 1. As a result, the short-circuit current Isc was 4.66 A, the open voltage Voc was 0.632 V, the current density Jsc was 0.019 A/cm 2 , and the curve factor FF was 55.01. The power generation efficiency Eff is 6.67%, and the series resistance Rs is 0.0182 Ω/□.
將這些實施例及比較例的結果揭示於表1～表3。The results of these examples and comparative examples are disclosed in Tables 1 to 3.
[表1]
[表2]
[表3]
由表1～表3可知，若將實施例1～3的導電性糊使用於太陽能電池的母線電極的形成，則與使用比較例1～6的導電性糊的情況相比，即使藉由焊接將母線電極與極耳線連接，也能夠防止母線電極的電阻變高，可防止太陽能電池的轉換效率的降低。As can be seen from Tables 1 to 3, when the conductive pastes of Examples 1 to 3 were used for the formation of the bus bar electrodes of the solar cells, even when the conductive pastes of Comparative Examples 1 to 6 were used, even by soldering. By connecting the bus bar electrode to the tab wire, the resistance of the bus bar electrode can be prevented from becoming high, and the conversion efficiency of the solar cell can be prevented from being lowered.
[實施例5] 將實施例1的銀被覆銅粉79.0重量份、平均一次粒徑1μm的銀粉(DOWA ELECTRONICS股份有限公司製的Ag-2-IC)8.8重量份、化1所示之具萘骨架之環氧樹脂(大日本Ink化學工業股份有限公司製的HP4710)6.6重量份、作為溶劑的丁基卡必醇醋酸酯(和光純藥工業股份有限公司製)5.3重量份、作為硬化劑的咪唑(四國化成工業股份有限公司製的2E4MZ)0.3重量份、及作為分散劑的油酸(和光純藥工業股份有限公司製)0.1重量份，藉由自公轉式真空攪拌脫泡裝置(Thinky股份有限公司製的除泡練太郎)混合(預備混練)之後，藉由三輥機(Otto Herrmann公司製的EXAKT80S)混練，得到導電性糊A(作為後述矽晶圓表面的母線電極用糊)。此外，此導電性糊A含有作為導電填料的銀被覆銅粉與銀粉合計87.8質量%。[Example 5] 79.0 parts by weight of silver-coated copper powder of Example 1, 8.8 parts by weight of silver powder (Ag-2-IC manufactured by DOWA ELECTRONICS Co., Ltd.) having an average primary particle diameter of 1 μm, and naphthalene represented by Chemical Formula 1 6.6 parts by weight of 8.5 parts by weight of epoxy resin (HP4710 manufactured by Dainippon Ink Chemical Co., Ltd.) and butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, as a hardener 0.3 parts by weight of imidazole (2E4MZ manufactured by Shikoku Chemicals Co., Ltd.) and 0.1 parts by weight of oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersing agent, by a self-rotating vacuum stirring defoaming device (Thinky After mixing (preparation and kneading) of the company, the company was kneaded by a three-roller (EXAKT80S, manufactured by Otto Herrmann Co., Ltd.) to obtain a conductive paste A (a paste for a bus bar electrode on the surface of a tantalum wafer to be described later). . Further, the conductive paste A contained 81.8% by mass in total of the silver-coated copper powder and the silver powder as the conductive filler.
另外，將平均一次粒徑1.9μm的銀粉(DOWA ELECTRONICS股份有限公司製的AG-4-8F)88重量份、乙基纖維素樹脂(和光純藥工業股份有限公司製)2.4重量份、TEXANOL(JMC股份有限公司製)與丁基卡必醇醋酸酯(和光純藥工業股份有限公司製)以1：1混合的溶劑9.5重量份、玻璃料(日本電氣硝子股份有限公司製的GA-12)1重量份、及作為分散劑的油酸(和光純藥工業股份有限公司製)0.5重量份，藉由自公轉式真空攪拌脫泡裝置(Thinky股份有限公司製的除泡練太郎)混合(預混練)之後，藉由三輥機(Otto Herrmann公司製的EXAKT80S)混練，得到導電性糊B(作為後述矽晶圓背面的母線電極用糊)。In addition, 88 parts by weight of a silver powder having an average primary particle diameter of 1.9 μm (AG-4-8F manufactured by DOWA ELECTRONICS CO., LTD.), and 2.4 parts by weight of ethyl cellulose resin (manufactured by Wako Pure Chemical Industries, Ltd.), TEXANOL ( JMC Co., Ltd.) 9.5 parts by weight of a solvent mixed with butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and a glass frit (GA-12 manufactured by Nippon Electric Glass Co., Ltd.) 1 part by weight, and 0.5 parts by weight of oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersing agent, mixed by a revolving vacuum agitating defoaming device (Dinking Co., Ltd., manufactured by Thinky Co., Ltd.) After the kneading, a conductive paste B (a paste for a bus bar electrode on the back surface of a tantalum wafer to be described later) was obtained by kneading by a three-roller (EXAKT 80S manufactured by Otto Herrmann Co., Ltd.).
此外，將平均一次粒徑1.3μm的銀粉(DOWA ELECTRONICS股份有限公司製的AG-2.5-8F)87.9重量份、乙基纖維素樹脂(和光純藥工業股份有限公司製)0.1重量份、丙烯酸樹脂(日本Carbide工業股份有限公司製的EU-5638)1.1重量份、甲基異丁醚(MIBE)(JNC股份有限公司製)與丁基卡必醇醋酸酯(和光純藥工業股份有限公司製)以1：1混合的溶劑6.1重量份、玻璃料(Te-Bi-Li系)1.5重量份、硬脂酸鎂0.3重量份、及作為分散劑的油酸(和光純藥股份有限公司製)0.5重量份，藉由自公轉式真空攪拌脫泡裝置(Thinky股份有限公司製的除泡練太郎)混合(預備混練)之後，藉由三輥機(Otto Herrmann公司製的EXAKT80S)混練，得到導電性糊C(作為指狀電極用糊)。In addition, 87.9 parts by weight of a silver powder having an average primary particle diameter of 1.3 μm (AG-2.5-8F manufactured by DOWA ELECTRONICS CO., LTD.) and an ethyl cellulose resin (manufactured by Wako Pure Chemical Industries, Ltd.) of 0.1 part by weight, an acrylic resin (Euro-5638, manufactured by Carbide Industrial Co., Ltd.) 1.1 parts by weight, methyl isobutyl ether (MIBE) (manufactured by JNC Co., Ltd.) and butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 6.1 parts by weight of a 1:1 mixed solvent, 1.5 parts by weight of a glass frit (Te-Bi-Li system), 0.3 parts by weight of magnesium stearate, and oleic acid (manufactured by Wako Pure Chemical Co., Ltd.) as a dispersing agent After the mixture was mixed (prepared and kneaded) by a revolving vacuum agitation degassing apparatus (manufactured by Thinky Co., Ltd.), the mixture was kneaded by a three-roller (EXAKT80S manufactured by Otto Herrmann Co., Ltd.) to obtain conductivity. Paste C (as a paste for finger electrodes).
接下來，準備矽晶圓(E＆M股份有限公司製，100Ω/□、6英吋單結晶)，在此矽晶圓背面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)將上述導電性糊B印刷成寬1.3mm的3根母線電極形狀之後，藉由熱風式乾燥機，在200℃下加熱10分鐘，使其乾燥。然後，在矽晶圓背面印刷導電性糊B的部分以外的部分印刷鋁糊(東洋Aluminium股份有限公司製的Al solar 14-7021)之後，藉由熱風式乾燥機，在200℃下加熱10分鐘，使其乾燥。然後，在矽晶圓表面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)，將上述導電性糊C印刷成寬50μm的100根指狀電極形狀之後，藉由熱風式乾燥機，在200℃下加熱10分鐘，使其乾燥，並將高速燒成IR爐(日本碍子股份有限公司製的高速燒成測試4室爐)的IN-OUT定為21秒，以峰溫度820℃燒成，而形成矽晶圓背面的母線電極與表面的指狀電極。然後，在矽晶圓表面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)，將上述導電性糊A印刷成寬1.3mm的3根母線電極形狀之後，藉由熱風式乾燥機，在150℃下加熱10分鐘，使其乾燥之後，在200℃下加熱40分鐘，使其硬化，而形成矽晶圓表面的母線電極。Next, a silicon wafer (100 Ω/□, 6-inch single crystal, manufactured by E&M Co., Ltd.) was prepared, and the above-mentioned wafer back surface was formed by a screen printer (MT-320T manufactured by Microtek Co., Ltd.). The conductive paste B was printed in the shape of three bus bar electrodes having a width of 1.3 mm, and then dried by heating at 200 ° C for 10 minutes in a hot air dryer. Then, an aluminum paste (Al solar 14-7021, manufactured by Toyo Aluminium Co., Ltd.) was printed on a portion other than the portion where the conductive paste B was printed on the back surface of the wafer, and then heated at 200 ° C for 10 minutes by a hot air dryer. Let it dry. Then, the conductive paste C was printed on a surface of a crucible wafer by a screen printer (MT-320T manufactured by Microtek Co., Ltd.) into a shape of 100 finger electrodes having a width of 50 μm, and then passed through a hot air dryer. After heating at 200 ° C for 10 minutes, it was dried, and the IN-OUT of the high-speed firing IR furnace (high-speed firing test 4-chamber furnace manufactured by Nippon Insulator Co., Ltd.) was set to 21 seconds at a peak temperature of 820 ° C. The firing is performed to form the bus electrodes on the back surface of the wafer and the finger electrodes on the surface. Then, the conductive paste A was printed on the surface of the crucible wafer by a screen printer (MT-320T manufactured by Microtek Co., Ltd.) into three bus bar electrodes having a width of 1.3 mm, and then passed through a hot air dryer. After heating at 150 ° C for 10 minutes, it was dried, and then heated at 200 ° C for 40 minutes to be hardened to form a bus bar electrode on the surface of the tantalum wafer.
在以這種方式製作出的太陽能電池表背面的母線電極塗佈助焊劑(flux)之後，將此太陽能電池配置於50℃的熱板上，於其上放置0.2mm×1.5mm×176mm的大小的內部連接材(日立金屬股份有限公司製的SSA-SPS)，以加熱至380℃的烙鐵按壓住，同時以約10mm/s的速度由上方劃過，對太陽能電池表背兩面進行焊接，而得到附內部連接材單元。然後，由表面側開始依序層合蓋玻璃、EVA薄片(EVA膜)、環烯烴共聚物(COC)薄膜(Topas Advanced Polymers GmbH製的TOPAS(註冊商標)、厚度75μm)、EVA薄片、上述附內部連接材單元、EVA薄片、背板，藉由真空層壓機對此層合體壓延加工，而得到太陽能電池模組。藉由陽光模擬器對此太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為4.7W、開放電壓Voc為0.6V、短路電流Isc為10.0A、曲線因子FF為71%。After the bus electrode on the back surface of the solar cell watch fabricated in this manner was coated with a flux, the solar cell was placed on a hot plate at 50 ° C, and a size of 0.2 mm × 1.5 mm × 176 mm was placed thereon. The internal connecting material (SSA-SPS manufactured by Hitachi Metals Co., Ltd.) is pressed by a soldering iron heated to 380 ° C, and is passed over at a speed of about 10 mm / s to weld the back sides of the solar cell. The internal connecting material unit is obtained. Then, a cover glass, an EVA sheet (EVA film), a cycloolefin copolymer (COC) film (TOPAS (registered trademark) manufactured by Topas Advanced Polymers GmbH, a thickness of 75 μm), an EVA sheet, and the like are laminated in this order from the surface side. The inner connecting material unit, the EVA sheet, and the back sheet are calendered by a vacuum laminator to obtain a solar cell module. The solar cell module is irradiated with simulated sunlight by a solar simulator, and the maximum output Pmax, the open voltage Voc, the short-circuit current Isc, and the curve factor FF are obtained. As a result, the maximum output Pmax is 4.7 W, and the open voltage Voc is 0.6 V. The short-circuit current Isc was 10.0 A, and the curve factor FF was 71%.
另外，此太陽能電池模組的PID測試，是使用PID測試裝置(Espec股份有限公司製)，將太陽能電池模組裝入溫度85℃、濕度85%的腔體內，施加-000V的電壓1000小時，進行加速劣化測試。然後，藉由陽光模擬器對由PID測試裝置取出的太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為4.7W、開放電壓Voc為0.6V、短路電流Isc為10.0A、曲線因子FF為71%，確認了與PID測試前相比，太陽能電池特性完全沒有劣化。In addition, the PID test of the solar cell module was carried out by using a PID tester (manufactured by Espec Co., Ltd.), and the solar cell module was placed in a cavity having a temperature of 85 ° C and a humidity of 85%, and a voltage of -000 V was applied for 1000 hours. Perform an accelerated degradation test. Then, the solar cell module taken out by the PID test device is irradiated with simulated sunlight by a sunlight simulator, and the maximum output Pmax, the open voltage Voc, the short-circuit current Isc, and the curve factor FF are obtained, and as a result, the maximum output Pmax is 4.7 W, The open voltage Voc was 0.6 V, the short-circuit current Isc was 10.0 A, and the curve factor FF was 71%, and it was confirmed that the solar cell characteristics were not deteriorated at all compared with before the PID test.
[比較例7] 使用化2所示之雙酚F型環氧樹脂(ADEKA股份有限公司製的EP4901E)來代替具萘骨架之環氧樹脂，除此之外，藉由與實施例5同樣的方法，得到導電性糊A(作為母線電極用糊)。使用此導電性糊A，除此之外，藉由與實施例5同樣的方法，嘗試製作出太陽能力電池模組，然而內部連接材與母線並未接著，無法製作出太陽能電池模組。[Comparative Example 7] The same procedure as in Example 5 was carried out except that the bisphenol F-type epoxy resin (EP4901E manufactured by ADEKA Co., Ltd.) shown in Chemical Formula 2 was used instead of the epoxy resin having a naphthalene skeleton. In the method, a conductive paste A (as a paste for a bus bar electrode) was obtained. A solar cell module was attempted in the same manner as in Example 5 except that the conductive paste A was used. However, the internal connecting material and the bus bar were not followed, and the solar cell module could not be produced.
[實施例6] 在製作層合體時，依序層合蓋玻璃、EVA薄片、COC薄膜(Topas Advanced Polymers GmbH製的TOPAS(註冊商標)、厚度75μm)、EPDM橡膠、附內部連接材單元、EPDM橡膠(透明、厚度300μm)、背板，除此之外，藉由與實施例5同樣的方法，得到太陽能電池模組。藉由陽光模擬器對此太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為4.7W、開放電壓Voc為0.6V、短路電流Isc為11.0A、曲線因子FF為71%。另外，對此太陽能電池模組進行與實施例5同樣的PID測試之後，藉由陽光模擬器對太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為4.9W、開放電壓Voc為0.6V、短路電流Isc為10.0A、曲線因子FF為70%，最大輸出上升，因此確認了與PID測試前相比，太陽能電池特性完全沒有劣化。[Example 6] In the production of a laminate, a cover glass, an EVA sheet, a COC film (TOPAS (registered trademark) manufactured by Topas Advanced Polymers GmbH, thickness: 75 μm), EPDM rubber, internal connecting material unit, EPDM were laminated in this order. A solar cell module was obtained in the same manner as in Example 5 except that rubber (transparent, thickness: 300 μm) and a backing plate were used. The solar cell module is irradiated with simulated sunlight by a solar simulator, and the maximum output Pmax, the open voltage Voc, the short-circuit current Isc, and the curve factor FF are obtained. As a result, the maximum output Pmax is 4.7 W, and the open voltage Voc is 0.6 V. The short-circuit current Isc was 11.0 A, and the curve factor FF was 71%. In addition, after the solar cell module was subjected to the same PID test as in the fifth embodiment, the solar cell module was irradiated with simulated sunlight by a solar simulator to obtain a maximum output Pmax, an open voltage Voc, a short-circuit current Isc, and a curve factor. FF, as a result, the maximum output Pmax is 4.9 W, the open voltage Voc is 0.6 V, the short-circuit current Isc is 10.0 A, the curve factor FF is 70%, and the maximum output rises, thus confirming that the solar cell characteristics are completely compared with those before the PID test. No deterioration.
[比較例8] 在製作層合體時，由表面側開始依序層合蓋玻璃、EVA薄片、附內部連接材單元、EVA薄片、背板，除此之外，以與實施例5同樣的方法得到太陽能電池模組。藉由陽光模擬器對此太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為4.7W、開放電壓Voc為0.6V、短路電流Isc為11.0A、曲線因子FF為71%。另外，對此太陽能電池模組進行與實施例5同樣的PID測試，結果，經過265小時後，在附內部連接材單元與EVA薄片之間發生層間剝離(delamination)，無法測定1000小時後的最大輸出等。若比較此比較例與實施例5及6，可知使用含有實施例1的銀被覆銅粉與具萘骨架之環氧樹脂的導電性糊製作出太陽能電池模組時，蓋玻璃側的EVA薄片與附內部連接材單元之間層合COC薄膜者為佳。[Comparative Example 8] The same method as in Example 5 was carried out, except that the cover glass, the EVA sheet, the internal connecting material unit, the EVA sheet, and the back sheet were laminated in this order from the surface side. Get a solar cell module. The solar cell module is irradiated with simulated sunlight by a solar simulator, and the maximum output Pmax, the open voltage Voc, the short-circuit current Isc, and the curve factor FF are obtained. As a result, the maximum output Pmax is 4.7 W, and the open voltage Voc is 0.6 V. The short-circuit current Isc was 11.0 A, and the curve factor FF was 71%. Further, the solar cell module was subjected to the same PID test as in Example 5, and as a result, delamination occurred between the internal connecting member unit and the EVA sheet after 265 hours, and the maximum after 1000 hours could not be measured. Output, etc. Comparing this comparative example with Examples 5 and 6, it is understood that when a solar cell module is produced using a conductive paste containing the silver-coated copper powder of Example 1 and an epoxy resin having a naphthalene skeleton, the EVA sheet on the cover glass side is It is preferred to laminate the COC film between the internal connecting material units.
另外，對於PID測試後的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)的母線電極(藉由含有實施例1的銀被覆銅粉與具萘骨架之環氧樹脂的導電性糊A所形成的母線電極)的剖面，使用歐傑電子分光分析裝置(FE-AES)(日本電子股份有限公司製的JAMP-9500F)，將分析區的直徑定為1μm，進行銀被覆銅粉的銅粒子的剖面中央部的定性分析，結果偵測到氧。另外，將實施例5所製作出的太陽能電池模組(蓋玻璃與附內部連接材單元之間的EVA薄片改成EVA薄片與環烯烴共聚物(COC)薄膜與EVA薄片，除此之外與比較例8同樣的太陽能電池模組)也進行同樣的定性分析，結果並未偵測到氧。由這些結果可知，實施例5所製作出的太陽能電池模組，在PID測試後也並未偵測到氧，藉由組合具萘骨架之環氧樹脂與COC薄膜，耐氧化性提高。將本比較例與實施例5所製作出的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)的母線電極的剖面的SEM影像分別表示於圖1及圖2。Further, in the solar cell module after the PID test, the bus bar electrode (on the surface side (cover glass side) to which the internal connecting material unit is attached (by the silver-coated copper powder of Example 1 and the epoxy having a naphthalene skeleton) The profile of the bus bar electrode formed by the conductive paste A of the resin was set to 1 μm by using the Eugene Electron Spectroscopic Analyzer (FE-AES) (JAMP-9500F manufactured by JEOL Ltd.). Qualitative analysis of the central portion of the cross section of the copper-coated copper powder, and oxygen was detected. Further, the solar cell module produced in Example 5 (the EVA sheet between the cover glass and the internal connecting member unit was changed to an EVA sheet and a cyclic olefin copolymer (COC) film and an EVA sheet, in addition to The same qualitative analysis was also carried out for the same solar cell module of Comparative Example 8, and no oxygen was detected as a result. From these results, it was found that the solar cell module produced in Example 5 did not detect oxygen after the PID test, and the oxidation resistance was improved by combining the epoxy resin having a naphthalene skeleton and the COC film. In the solar cell module produced in the comparative example and the fifth embodiment, the SEM images of the cross section of the bus bar electrode formed on the surface side (the cover glass side) of the internal connecting material unit are shown in FIGS. 1 and 2, respectively.
另外，對於PID測試後的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)的母線電極的剖面，使用上述歐傑電子分光分析裝置(FE-AES)，進行映射分析，結果在銅粒子大略全體觀察到氧，幾乎無法確認被覆銅之銀的存在。另外，對於實施例5所製作出的太陽能電池模組也進行同樣的映射分析，結果，在銅粒子的表面偵測到銀，確認了即使在PID測試後，仍然以銀被覆銅粉的狀態存在。由這些結果可知，實施例5所製作出的太陽能電池模組，藉由組合具萘骨架之環氧樹脂與COC薄膜，即使在PID測試後，也能夠維持銀被覆銅粉的狀態。此外，將實施例5所製作出的太陽能電池模組的形成於附內部連接材單元的表面側(蓋玻璃側)的母線電極剖面的映射分析所得到的Ag映射影像與Cu映射影像分別表示於圖3及圖4。In addition, in the solar cell module after the PID test, the cross section of the bus bar electrode formed on the surface side (the cover glass side) of the internal connecting material unit is mapped using the above-mentioned Auger electronic spectroscopic analyzer (FE-AES). As a result, oxygen was observed in almost all of the copper particles, and the presence of silver of the coated copper was hardly confirmed. Further, the same mapping analysis was performed on the solar cell module produced in Example 5, and as a result, silver was detected on the surface of the copper particles, and it was confirmed that even after the PID test, the copper-coated copper powder was present. . From these results, it was found that the solar cell module produced in Example 5 was able to maintain the state of the silver-coated copper powder even after the PID test by combining the epoxy resin having a naphthalene skeleton and the COC film. In addition, the Ag map image and the Cu map image obtained by the map analysis of the bus bar electrode cross section formed on the surface side (cover glass side) of the internal connecting material unit of the solar cell module produced in the fifth embodiment are respectively shown in Figure 3 and Figure 4.
[實施例7] 將平均一次粒徑0.8μm的銀粉(DOWA ELECTRONICS股份有限公司製的AG-2.1C)89重量份、環氧樹脂4重量份、硬化劑0.2重量份、胺甲酸乙酯樹脂2重量份、作為溶劑的丁基卡必醇醋酸酯(和光純藥工業股份有限公司製)0.4重量份、及作為分散劑的油酸0.1重量份，藉由自公轉式真空攪拌脫泡裝置(Thinky股份有限公司製的除泡練太郎)混合(預備混練)之後，藉由三輥機(Otto Herrmann公司製的EXAKT80S)混練，而得到導電性糊D。[Example 7] 89 parts by weight of silver powder having an average primary particle diameter of 0.8 μm (AG-2.1C manufactured by DOWA ELECTRONICS Co., Ltd.), 4 parts by weight of an epoxy resin, 0.2 parts by weight of a curing agent, and urethane resin 2 0.4 parts by weight of butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, and 0.1 parts by weight of oleic acid as a dispersing agent, by means of a self-rotating vacuum stirring defoaming device (Thinky) After mixing (prepared and kneaded) by the company, the company was kneaded by a three-roller (EXAKT80S manufactured by Otto Herrmann Co., Ltd.) to obtain a conductive paste D.
接下來，準備異質接面型矽晶圓，在此矽晶圓背面的全面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)印刷上述導電性糊D之後，藉由熱風式乾燥機，在150℃下加熱10分鐘，使其乾燥之後，在200℃下加熱30分鐘，使其硬化。然後，在矽晶圓表面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)將上述導電性糊D印刷成寬50μm的100根指狀電極形狀之後，藉由熱風式乾燥機，在150℃下加熱10分鐘，使其乾燥之後，在200℃下加熱30分鐘，使其硬化。然後，在矽晶圓表面藉由絲網印刷機(Microtek股份有限公司製的MT-320T)將與實施例5同樣的導電性糊A印刷成將100根指狀電極形狀與寬1.3mm的3根母線電極形狀合併成的形狀之後，藉由熱風式乾燥機，在150℃下加熱10分鐘使其乾燥，然後在200℃下加熱30分鐘使其硬化。Next, a heterojunction type germanium wafer was prepared, and the conductive paste D was printed on the back surface of the wafer by a screen printer (MT-320T manufactured by Microtek Co., Ltd.), and then dried by hot air drying. The machine was heated at 150 ° C for 10 minutes, dried, and then heated at 200 ° C for 30 minutes to harden it. Then, the conductive paste D was printed on a surface of a tantalum wafer by a screen printer (MT-320T manufactured by Microtek Co., Ltd.) into a shape of 100 finger electrodes having a width of 50 μm, and then dried by a hot air dryer. After heating at 150 ° C for 10 minutes, it was dried, and then heated at 200 ° C for 30 minutes to be hardened. Then, the same conductive paste A as in Example 5 was printed on the surface of the crucible wafer by a screen printer (MT-320T manufactured by Microtek Co., Ltd.) to have 100 finger electrode shapes and a width of 1.3 mm. After the shape of the root bus bar electrode was combined, it was dried by heating at 150 ° C for 10 minutes in a hot air dryer, and then hardened by heating at 200 ° C for 30 minutes.
使用以這種方式製作出的太陽能電池，以與實施例5同樣的方法得到太陽能電池模組。藉由陽光模擬器對此太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為5.3W、開放電壓Voc為0.7V、短路電流Isc為11.0A、曲線因子FF為71%。另外，對此太陽能電池模組進行與實施例5同樣的PID測試之後，藉由陽光模擬器對太陽能電池模組照射模擬太陽光，求得最大輸出Pmax、開放電壓Voc、短路電流Isc、曲線因子FF，結果，最大輸出Pmax為4.7W、開放電壓Voc為0.7V、短路電流Isc為10.0A、曲線因子FF為67%，輸出劣化率不過11%，確認了可充分承受長期使用。 [產業上的可利用性]A solar cell module was obtained in the same manner as in Example 5 using the solar cell fabricated in this manner. The solar cell module is irradiated with simulated sunlight by a solar simulator, and the maximum output Pmax, the open voltage Voc, the short-circuit current Isc, and the curve factor FF are obtained. As a result, the maximum output Pmax is 5.3 W, and the open voltage Voc is 0.7 V. The short-circuit current Isc was 11.0 A, and the curve factor FF was 71%. In addition, after the solar cell module was subjected to the same PID test as in the fifth embodiment, the solar cell module was irradiated with simulated sunlight by a solar simulator to obtain a maximum output Pmax, an open voltage Voc, a short-circuit current Isc, and a curve factor. FF, as a result, the maximum output Pmax was 4.7 W, the open voltage Voc was 0.7 V, the short-circuit current Isc was 10.0 A, the curve factor FF was 67%, and the output deterioration rate was only 11%, and it was confirmed that it can withstand long-term use. [Industrial availability]
依據本發明所得到的導電性糊，可利用於電路基板的導體圖型、太陽能電池等的基板的電極或電路等的電子零件的製作。The conductive paste obtained by the present invention can be used for the production of electronic components such as a conductor pattern of a circuit board, an electrode of a substrate such as a solar cell, or a circuit.
圖1為表示比較例8所製作出的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)之母線電極的剖面的掃描式電子顯微鏡(SEM)像之圖。 圖2為表示實施例5所製作出的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)之母線電極的剖面的SEM影像之圖。 圖3為表示實施例5所製作出的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)之母線電極的剖面的映射分析所得到的Ag映射影像之圖。 圖4為表示實施例5所製作出的太陽能電池模組中，形成於附內部連接材單元的表面側(蓋玻璃側)之母線電極的剖面的映射分析所得到的Cu映射影像之圖。1 is a scanning electron microscope (SEM) image showing a cross section of a bus bar electrode formed on a surface side (cover glass side) of an internal connecting material unit in a solar battery module produced in Comparative Example 8. 2 is a view showing an SEM image of a cross section of a bus bar electrode formed on the surface side (cover glass side) of the internal connecting material unit in the solar battery module produced in the fifth embodiment. 3 is a view showing an Ag map image obtained by a map analysis of a cross section of a bus bar electrode formed on the surface side (cover glass side) of the internal connecting material unit in the solar cell module produced in the fifth embodiment. 4 is a view showing a Cu map image obtained by a map analysis of a cross section of a bus bar electrode formed on the surface side (cover glass side) of the internal connecting material unit in the solar battery module produced in the fifth embodiment.
Claims (10)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-033123 | 2017-02-24 | ||
| JP2017033123 | 2017-02-24 | ||
| JP2017224502 | 2017-11-22 | ||
| JP2017-224502 | 2017-11-22 | ||
| JP2018025982A JP6357599B1 (en) | 2017-02-24 | 2018-02-16 | Conductive paste |
| JP2018-025982 | 2018-02-16 |
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| Publication Number | Publication Date |
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| TW201835144A true TW201835144A (en) | 2018-10-01 |
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| TW107106177A TW201835144A (en) | 2017-02-24 | 2018-02-23 | Electrically conductive paste |
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| JP (1) | JP6357599B1 (en) |
| TW (1) | TW201835144A (en) |
| WO (1) | WO2018155393A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006129487A1 (en) * | 2005-05-30 | 2006-12-07 | Sumitomo Electric Industries, Ltd. | Conductive paste and multilayer printed wiring board using same |
| JP4893104B2 (en) * | 2005-06-08 | 2012-03-07 | 日立化成工業株式会社 | Conductive paste and electronic component mounting board using the same |
| JP2012504179A (en) * | 2008-09-26 | 2012-02-16 | フライズ・メタルズ・インコーポレイテッド | Lead-free conductive composition and method using the same |
| JP5353163B2 (en) * | 2008-09-30 | 2013-11-27 | 三菱マテリアル株式会社 | Conductive ink composition and solar cell in which collector electrode is formed using the composition |
| JP2011086397A (en) * | 2009-10-13 | 2011-04-28 | Asahi Kasei E-Materials Corp | Conductive paste and semiconductor device |
| KR20160021178A (en) * | 2013-06-19 | 2016-02-24 | 요코하마 고무 가부시키가이샤 | Electrically conductive composition and solar cell |
| WO2016088540A1 (en) * | 2014-12-05 | 2016-06-09 | 三井金属鉱業株式会社 | Conductive composition, wiring board and method for producing same |
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- 2018-02-16 JP JP2018025982A patent/JP6357599B1/en not_active Expired - Fee Related
- 2018-02-20 WO PCT/JP2018/005829 patent/WO2018155393A1/en active Application Filing
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| Publication number | Publication date |
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| WO2018155393A1 (en) | 2018-08-30 |
| JP6357599B1 (en) | 2018-07-11 |
| JP2019083182A (en) | 2019-05-30 |
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