TWI521548B - 一種含無鉛玻璃熔塊之導電漿（四） - Google Patents
一種含無鉛玻璃熔塊之導電漿（四） Download PDFInfo
- Publication number
- TWI521548B TWI521548B TW103142666A TW103142666A TWI521548B TW I521548 B TWI521548 B TW I521548B TW 103142666 A TW103142666 A TW 103142666A TW 103142666 A TW103142666 A TW 103142666A TW I521548 B TWI521548 B TW I521548B
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- TW
- Taiwan
- Prior art keywords
- oxide
- conductive paste
- lead
- weight
- glass frit
- Prior art date
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- 239000011521 glass Substances 0.000 title claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 25
- 239000006117 anti-reflective coating Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000013538 functional additive Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000013008 thixotropic agent Substances 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 2
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 claims description 2
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- 239000003906 humectant Substances 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 229910001923 silver oxide Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 238000001764 infiltration Methods 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000005355 lead glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 alcohol ethers Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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Description
本發明係關於一種包含導電金屬、一無鉛玻璃熔塊及一有機載體的導電漿，及一種應用該導電漿之製品。
習知之太陽能電池或光電池包含半導體基材、擴散層、抗反射塗層、背面電極及正面電極，其中，使用該抗反射塗層係為促進光的吸收，進而提高光電效率。該抗反射塗層通常包含矽(例如：一氮化矽或二氧化矽)。然而，抗反射塗層使得從半導體基材至正面電極間之電阻增加，產生減弱激發態電子流動的絕緣作用。
因此，在形成正面電極時，通常使用混合包含導電金屬或其衍生物(例如：銀粒子)、玻璃(例如：包含氧化鉛)、有機載體等而製成之導電漿，因為玻璃具有低熔點、低熔融黏度及防止非控制性失透的穩定性。藉由網版印刷、刻板印刷等方式，在半導體基材上將導電漿印刷為柵線或其他圖案，之後進行燒滲(fire-through)，該導電漿於燒結期間穿透該抗反射塗層，使該半導體基材與該柵線或其他圖案間，透過金屬觸點而電性接觸，進而形成正面電極。
為了達成合適之燒滲，較佳地使用對於抗反射塗層具有良好溶解度之玻璃，作為導電漿中之玻璃熔塊。習知用於形成正面電極之導電漿中，玻璃熔塊經常含有氧化鉛之玻璃，因為易於調整玻璃之軟化點，可提供良好之基材黏著性，可輕易地燒滲之可焊性及製備性能優異之太陽能電池等特性。
近年來大幅提升之環境意識，汽車、電子和太陽能電池等工業上，希望使用對環境友好之無鉛材料。但在燒結後，具備穿透該抗反射塗
層並與該半導體基材形成良好黏著之能力，以及具備優異的太陽能電池轉換效率，又取決於該導電漿之組成，以及經燒滲之該導電漿與該半導體基材間電性接觸之品質。
因此，提供一種可於低溫燒結的含無鉛玻璃熔塊之導電漿，其具備前述之習知含鉛材料的特性，實為業界所期盼。
本發明之主要目的係提供一可於低溫燒結的含無鉛玻璃熔塊之導電漿，以及一包含該導電漿之製品，其不含鉛，但能夠於燒滲後具備良好之基材黏著性及優異之轉換效率，以達成提供環保導電漿材料之目的。
為了達成上述目的，本發明一方面提供一種導電漿，包含：(a)一導電金屬或其衍生物，佔固體重量之約85至約99.5重量%；(b)一包含碲-鉍-鋰-氧化物之無鉛玻璃熔塊，佔固體重量之約0.5至約15重量%；以及(c)一有機載體；所述之固體重量係指(a)導電金屬及(b)無鉛玻璃熔塊之總重量。
在本發明之一較佳實施例中，該導電金屬或其衍生物包含銀粉。
在本發明之一較佳實施例為該無鉛玻璃熔塊中，氧化碲、氧化鉍及氧化鋰之比例分別為約60至約90重量%、約0.1至約20重量%及約0.1至約20重量%。
本發明之一較佳實施例為該有機載體係一包含聚合物與溶劑之溶液。
在本發明之進一步較佳實施例中，該無鉛玻璃熔塊包含一種或多種下列組成的群組之元素或其氧化物：磷(P)、鋇(Ba)、鈉(Na)、鎂(Mg)、鋅(Zn)、鈣(Ca)、鍶(Sr)、鎢(W)、鋁(Al)、鉀(K)、鋯(Zr)、釩(V)、硒(Se)、鐵(Fe)、銦(In)、錳(Mn)、錫(Sn)、鎳(Ni)、銻(Sb)、銀(Ag)、矽(Si)、鉺(Er)、鍺(Ge)、鈦(Ti)、鎵(Ga)、鈰(Ce)、鈮(Nb)、釤(Sm)及鑭(La)等，其比例為該無鉛玻璃熔塊之約0.1至約10重量%。本發明之另一進一步較佳實施例為該有機載體包含一種或多種功能性添加劑，例如：黏度調整劑、分散劑、觸變劑、濕潤劑等添加劑。
本發明另一方面提供一種製品，包含一半導體基材，以及設置在該半導體基材上如上述之導電漿。在本發明之一較佳實施例中，該製品為一半導體裝置。在本發明之另一較佳實施例中，該半導體裝置為一太陽能電池。
上述內容已廣泛地概述本發明之技術特徵及其技術效果。本發明所屬領域技術中具有通常知識者應暸解，所公開的具體實施方式可輕易地被組合、修飾、置換及/或轉用於本發明之技術思想範圍內之其他物品、方法或用途，此均等範圍並不違反後附申請專利範圍中所請求發明的保護範圍。
為了充分瞭解本發明，於下文對本發明之例示性實施方式為詳細說明，其並非用以限定本發明。本發明亦可為其他形式的實施方式進行實施。
本發明的含無鉛玻璃塊之導電漿可應用於各種產業，較佳可應用於半導體製造業，更佳可應用於太陽能電池製造業。所述導電漿包含：(a)一導電金屬或其衍生物，(b)一包含碲-鉍-鋰-氧化物之無鉛玻璃熔塊，以及(c)一有機載體。其中，(a)導電金屬及(b)無鉛玻璃熔塊等無機成分係均勻分散在(c)有機載體中。
於本發明中，有機載體不屬於固體成分的一部分，因此，固體重量係指(a)導電金屬及(b)無鉛玻璃熔塊等固體成分的總重量。
本發明之導電金屬並未特別地限制，只要對本發明之技術效果沒有負面影響即可。該導電金屬可為單一元素，選自於銀、鋁及銅；亦可為合金或混合之金屬，例如：金、鉑、鈀及鎳等。然而由導電度之觀點，使用純銀為較佳者。
當該導電金屬為銀時，可為銀金屬、銀衍生物及/或其混合物之形式。例示性之銀衍生物包含氧化銀(Ag2O)、銀鹽(例如：氯化銀(AgCl)、硝酸銀(AgNO3)、醋酸銀(AgOOCCH3)、三氟醋酸銀(AgOOCF3)或磷酸銀(Ag3PO4))、表面上塗佈銀層之塗銀複合物或以銀為主成分之銀合金等。
該導電金屬可為粉末形式(例如：球形、片形、不定形及/或其混合)或膠態懸浮液形式等習知者。該導電金屬之平均粒度並未特別地
限制，較佳為0.1至10微米，亦可使用平均粒度、粒度分布或形狀等不同之導電金屬混合物。
在本發明之一較佳實施例中，該導電金屬或其衍生物佔該導電漿之固體成分的約85至約99.5重量%。
本發明之無鉛玻璃熔塊係完全不含鉛之成分，具體而言，不含任何鉛及其衍生物(例如：一氧化鉛(PbO)、二氧化鉛(PbO2)或四氧化三鉛(Pb3O4)等鉛氧化物)。在本發明之一具體實施例中，該無鉛玻璃熔塊係以氧化碲、氧化鉍及氧化鋰為主要成分。在本發明之一較佳實施例中，氧化碲、氧化鉍及氧化鋰之比例分別為約60至約90重量%、約0.1至約20重量%及約0.1至約20重量%，此係以三者的總重量為基礎。
在本發明之進一步較佳實施例中，氧化碲、氧化鉍及氧化鋰之混合物包含一種或多種金屬氧化物，例如：氧化鋯(ZrO2)、五氧化二釩(V2O5)、氧化銀(Ag2O)、三氧化二鉺(Er2O3)、氧化錫(SnO)、氧化鎂(MgO)、三氧化二銣(Nd2O3)、三氧化二鋁(Al2O3)、二氧化硒(SeO2)、二氧化鈦(TiO2)、氧化鈉(Na2O)、氧化鉀(K2O)、五氧化二磷(P2O5)、二氧化鉬(MoO2)、二氧化錳(MnO2)、氧化鎳(NiO)、三氧化鎢(WO3)、三氧化二釤(Sm2O3)、二氧化鍺(GeO2)、二氧化鋅(ZnO)、三氧化二銦(In2O3)、三氧化二鎵(Ga2O3)、二氧化矽(SiO2)及三氧化二鐵(Fe2O3)等。因此，本發明所述「碲-鉍-鋰-氧化物」亦可包含有一種或多種金屬元素或其氧化物，例如：磷(P)、鋇(Ba)、鈉(Na)、鎂(Mg)、鋅(Zn)、鈣(Ca)、鍶(Sr)、鎢(W)、鋁(Al)、鉀(K)、鋯(Zr)、釩(V)、硒(Se)、鐵(Fe)、銦(In)、錳(Mn)、錫(Sn)、鎳(Ni)、銻(Sb)、銀(Ag)、矽(Si)、鉺(Er)、鍺(Ge)、鈦(Ti)、鎵(Ga)、鈰(Ce)、鈮(Nb)、釤(Sm)及鑭(La)等，其比例為該無鉛玻璃熔塊之約0.1至約10重量%。
本發明之(a)導電金屬及(b)無鉛玻璃熔塊等固體之無機成分與(c)液體之有機載體混合而形成一導電漿。適合的有機載體，可使該等無機成分均勻分散於其中，並具有適當之黏度而使該等無機成分可藉由網版印刷、刻板印刷等方式傳遞至抗反射塗層的表面上。該導電漿且須具有良好之乾燥速率及優異之燒滲性質。
網版印刷、刻板印刷等方式傳遞至抗反射塗層的表面上。該導電漿且須具有良好之乾燥速率及優異之燒滲性質。
該有機載體係一溶劑，其並未特別地限制，可適當地選擇自習知用於導電漿之溶劑。例示性的溶劑包含醇類(例如：異丙醇)、醇酯(例如：丙酸酯、鄰苯二甲酸二丁酯)及醇醚(例如：二乙二醇丁醚)等或其混合物；較佳地，該溶劑係一沸點約120℃至約300℃的醇醚；最佳地，該溶劑係二乙二醇丁醚(butyl carbitol)。該有機載體可進一步包含揮發性液體，以促進導電漿施用到半導體基材上之後的快速硬化。
在本發明之一較佳實施例中，該有機載體係一包含聚合物與溶劑之溶液。因為由溶劑和溶解的聚合物組成的有機載體分散導電金屬及無鉛玻璃熔塊等無機成分，容易製備具有適當黏度的導電漿；於印刷至抗反射塗層之表面並經乾燥後，聚合物也提高了導電漿的黏著度及原始強度。
例示性之聚合物包含纖維素(例如：乙基纖維素(ethyl cellulose)、硝化纖維素、乙基羥乙基纖維素、羧甲基纖維素、羥丙基纖維素或其他纖維素衍生物)、低級醇之聚(甲基)丙烯酸樹脂、酚樹脂(例如：苯酚樹脂)、醇酸樹脂(例如：乙二醇單乙酸酯)等或其混合物；較佳地，該聚合物係一纖維素；最佳地，該聚合物係一乙基纖維素。
在本發明之一較佳實施例中，有機載體包含溶於二乙二醇丁醚的乙基纖維素。
在本發明之另一進一步較佳實施例中，該有機載體包含一種或多種功能性添加劑。例示性之功能性添加劑包含黏度調整劑、分散劑、觸變劑、濕潤劑及/或視需要之其他添加劑(例如：著色劑、防腐劑或氧化劑)等習知者，只要對本發明之技術效果沒有負面影響即可。
在本發明之導電漿中，(a)導電金屬及(b)無鉛玻璃熔塊等無機成分與(c)有機載體的比值，係由印刷該導電漿至抗反射塗層的需求而決定該導電漿所需的黏度。通常該導電漿包含約70至約95重量%的無機成分及約5至約30重量%的有機載體。
本發明之導電漿先進行一印刷步驟(例如：網版印刷、刻板印刷等習知方式)，在抗反射塗層上將該導電漿印刷為柵線或其他圖案。
之後於一含氧氣的環境(例如：空氣)中進行一燒滲步驟(加熱至約850至約950℃的溫度，加熱時間約0.05至約5分鐘)，以去除有機載體並燒結導電金屬，使得該導電漿沒有任何有機物質，並使得該導電漿於燒結期間穿透該抗反射塗層，接觸到下方之半導體基材及一個或多個抗反射塗層。此燒滲步驟使得該半導體基材與該柵線或其他圖案間，透過金屬觸點而電性接觸，進而形成正面電極。
本發明另一方面涉及一製品，較佳地，可用於製備一半導體裝置，更佳地，可用於製備太陽能電池。在本發明之一實施例中，係提供一半導體基材(該半導體基材包含半導體晶片、玻璃基材或適合形成太陽能電池的其他基材)，於該半導體基材上設置本發明的含無鉛玻璃熔塊之導電漿及一個或多個抗反射塗層(該抗反射塗層可由習知方法塗佈於該半導體基材上，例如化學氣相沉積、電漿增強氣相沉積等)，並經包含上述燒滲步驟的習知半導體製程，即可製得該製品。
在本發明之一較佳實施例中，該半導體基材包含不定形的、多晶的或單晶的矽。在本發明之另一較佳實施例中，該抗反射塗層包含二氧化矽、二氧化鈦、氮化矽或其他習知的塗層。
以下透過實施例對本發明進行更詳細地說明，並無任何限制本發明的目的。
導電漿之有機載體製備係先將5至25克重之乙基纖維素溶解於5至75克重的二乙二醇丁醚中，並添加少量黏度調整劑、分散劑、觸變劑、濕潤劑而得。再將80至99.5克重的工業級銀粉原料、0.1至10克重的無鉛玻璃熔塊(表1，實施例G1至G15)及10至30克重的有機載體，於三輥研磨機(three-roll mill)混合分散均勻，以製得一糊狀或膏狀的導電漿。
另以相同方式製備含鉛玻璃熔塊(表2，比較例PG1至PG5)。
使用網版印刷將含無鉛玻璃之導電漿(實施例G1至G15)塗佈於太陽能電池基材的正面，該太陽能電池基材的表面已預先經抗反射塗層(一氮化矽)處理，而該太陽能電池基材的背面電極已預先經鋁膠(GSMC公司，型號A136)處理。網版印刷後的乾燥溫度為約100至約250℃、乾燥時間為約5至約30分鐘(視有機載體之種類及印刷重量之不同而有差異)，網版印刷步驟即完成。
使用紅外線傳送帶式燒結爐對乾燥後的含無鉛玻璃導電漿進行燒滲步驟，燒結溫度為約850至約950℃，燒滲後的太陽能電池基材
之正面及背面皆具備固態電極。
另以相同方式製備含鉛玻璃熔塊(比較例PG1至PG5)為正面電極的太陽能電池。
將已製得太陽能電池置於一太陽能測試機台(Berger公司，Pulsed Solar Load PSL-SCD)，於AM1.5G的太陽狀態下測量該太陽能電池的開路電壓(Uoc，單位V)、短路電流(Isc，單位A)、串聯電阻(Rs，單位Ω)、填充因子(FF，單位%)及轉換效率(Ncell，單位%)等電氣特性，詳見於表3及表4。
由表3及表4之性能測試可知，本發明之包含碲-鉍-鋰-氧化物的無鉛玻璃熔塊之導電漿(實施例G1至G15)皆具備與含鉛玻璃熔塊之導電漿(比較例PG1至PG5)相近的轉換效率。
因此，本發明已提供一對環境友好、可於低溫燒結、卻仍具備習知含鉛玻璃熔塊特性等優異功效之無鉛導電漿。
上述較佳實施例僅舉例說明本發明之技術特徵及其技術效果，該實施例之技術仍可適當地進行各種實質等效組合、修飾、置換及/或轉用方式予以實施。因此，本發明之權利範圍須以後附申請專利範圍中所界定之發明範圍為準。
Claims (11)
- 一種導電漿，包含：(a)一導電金屬或其衍生物，佔固體重量之約85至約99.5重量%；(b)一包含碲-鉍-鋰-氧化物之無鉛玻璃熔塊，佔固體重量之約0.5至約15重量%；以及(c)一有機載體；所述固體重量係指(a)導電金屬及(b)無鉛玻璃熔塊之總重量；其中該無鉛玻璃熔塊中氧化碲及氧化鉍之比例分別為約60至約90重量%及約0.1至約20重量%。
- 如請求項1所述之導電漿，其中該導電金屬或其衍生物包含銀粉。
- 如請求項1所述之導電漿，其中該無鉛玻璃熔塊中氧化鋰之比例為約0.1至約20重量%。
- 如請求項1所述之導電漿，進一步包含一或多種選自下列組成的群組之金屬氧化物：氧化鋯(ZrO2)、五氧化二釩(V2O5)、氧化銀(Ag2O)、三氧化二鉺(Er2O3)、氧化錫(SnO)、氧化鎂(MgO)、三氧化二銣(Nd2O3)、三氧化二鋁(Al2O3)、二氧化硒(SeO2)、二氧化鈦(TiO2)、氧化鈉(Na2O)、氧化鉀(K2O)、五氧化二磷(P2O5)、二氧化鉬(MoO2)、二氧化錳(MnO2)、氧化鎳(NiO)、三氧化鎢(WO3)、三氧化二釤(Sm2O3)、二氧化鍺(GeO2)、氧化鋅(ZnO)、三氧化二銦(In2O3)、三氧化二鎵(Ga2O3)、二氧化矽(SiO2)及三氧化二鐵(Fe2O3)。
- 如請求項1所述之導電漿，其中該無鉛玻璃熔塊進一步包含一或多種選自下列組成的群組之金屬元素或其氧化物：磷(P)、鋇(Ba)、鈉(Na)、鎂(Mg)、鋅(Zn)、鈣(Ca)、鍶(Sr)、鎢(W)、鋁(Al)、鉀(K)、鋯(Zr)、釩(V)、硒(Se)、鐵(Fe)、銦(In)、錳(Mn)、錫(Sn)、鎳(Ni)、銻(Sb)、銀(Ag)、矽(Si)、鉺(Er)、鍺(Ge)、鈦(Ti)、鎵(Ga)、鈰(Ce)、鈮(Nb)、釤(Sm)及鑭(La)，其比例為該無鉛玻璃熔塊之約0.1至約10重量%。
- 如請求項1所述之導電漿，其中該有機載體係一包含聚合物與溶劑之溶液。
- 如請求項1所述之導電漿，其中該有機載體進一步包含一或多種選自黏度調整劑、分散劑、觸變劑及濕潤劑組成的群組之功能性添加劑。
- 一種製品，包含一半導體基材，以及設置在該半導體基材上如請求項1至7中任一項的導電漿。
- 如請求項8所述之製品，進一步包含一個或多個設置於該半導體基材上的抗反射塗層，且該導電漿與該抗反射塗層接觸並與該半導體基材電性接觸。
- 如請求項9所述之製品，其中該製品為一半導體裝置。
- 如請求項10所述之製品，其中該半導體裝置為一太陽能電池。
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| JP2015083286A JP6039731B2 (ja) | 2014-12-08 | 2015-04-15 | 鉛フリーのガラスフリットを含む導電ペースト |
| US14/920,140 US20160163893A1 (en) | 2014-12-08 | 2015-10-22 | Conductive paste containing lead-free glass frit |
| TR2019/01630T TR201901630T4 (tr) | 2014-12-08 | 2015-10-29 | Kurşunsuz cam firit içeren iletken bir macun. |
| EP15192068.3A EP3032546B1 (en) | 2014-12-08 | 2015-10-29 | A conductive paste containing lead-free glass frit |
| CN201510831104.1A CN105679403B (zh) | 2014-12-08 | 2015-11-25 | 含无铅玻璃料的导电浆及其制品 |
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| US20190322572A1 (en) | 2016-11-18 | 2019-10-24 | Samtec Inc. | Filling materials and methods of filling through holes of a substrate |
| WO2018221578A1 (ja) * | 2017-05-31 | 2018-12-06 | 東洋アルミニウム株式会社 | 太陽電池用ペースト組成物 |
| CN107746184B (zh) * | 2017-10-20 | 2020-11-24 | 苏州晶银新材料股份有限公司 | 一种玻璃粉组合物及含有其的导电银浆和制备方法 |
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