CN112441738A - Glass composition, glass powder and conductive paste - Google Patents
Glass composition, glass powder and conductive paste Download PDFInfo
- Publication number
- CN112441738A CN112441738A CN202010866654.8A CN202010866654A CN112441738A CN 112441738 A CN112441738 A CN 112441738A CN 202010866654 A CN202010866654 A CN 202010866654A CN 112441738 A CN112441738 A CN 112441738A
- Authority
- CN
- China
- Prior art keywords
- glass composition
- glass
- conductive paste
- percent
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 203
- 239000000203 mixture Substances 0.000 title claims abstract description 144
- 239000000843 powder Substances 0.000 title claims abstract description 75
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 230000001186 cumulative effect Effects 0.000 claims description 7
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 description 58
- 239000004065 semiconductor Substances 0.000 description 39
- 239000010410 layer Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 21
- 229910052581 Si3N4 Inorganic materials 0.000 description 17
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000004455 differential thermal analysis Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 238000001238 wet grinding Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012461 cellulose resin Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 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
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass 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
- 238000000227 grinding Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
- C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to a glass composition, a glass powder and a conductive paste. The invention aims to provide a glass composition, and the glass compositionThe conductive paste having high burnthrough property can be obtained by mixing the conductive metal powder and the organic vehicle and slurrying the mixture. The glass composition contains 0.1 to 30% of SiO in terms of mol% of oxide20.1 to 30 percent of B2O345 to 70 percent of PbO and 0.1 to 10 percent of Al2O30.1% -8% of V2O50.1 to 8 percent of Nb2O5And 0 to 5% of Y2O3。
Description
Technical Field
The present invention relates to a glass composition, a glass powder and a conductive paste, and particularly to a glass composition and a glass powder suitable for use in forming an electrode of a solar cell, and a conductive paste using the glass composition and the glass powder.
Background
Conventionally, electronic devices in which a conductive layer serving as an electrode is formed on a semiconductor substrate such as silicon (Si) have been used for various applications. The conductive layer to be an electrode is generally formed as follows: a conductive paste obtained by dispersing conductive metal powder such as silver (Ag), aluminum (a1), copper (Cu), or the like and glass powder in an organic vehicle is applied to a semiconductor substrate, and baked at 600 to 950 ℃ for a short time.
When forming an electrode on a semiconductor substrate, an insulating film may be formed on the semiconductor substrate, and a patterned electrode may be formed so as to partially penetrate the insulating film and be in contact with the semiconductor substrate. For example, in a solar cell, an antireflection film (insulating film) is provided on a light receiving surface of a semiconductor substrate, and a pattern-like electrode is provided thereon. The antireflection film is a film that reduces the surface reflectance while maintaining sufficient visible light transmittance to improve light reception efficiency, and is generally made of an insulating material such as silicon nitride, titanium oxide, silicon oxide, or aluminum oxide. In a double-sided light-receiving solar cell that can receive light on the back surface side, a passivation film made of the same insulating material as the antireflection film is provided on the back surface, and an electrode is formed on the passivation film so as to be in contact with the semiconductor substrate.
The electrodes need to be formed in contact with the semiconductor substrate. Therefore, when forming the electrode, the insulating film is removed according to the pattern of the electrode to be formed, and the electrode is formed in the portion where the insulating film is removed.
As a method for removing the insulating layer, a method of physically removing the insulating layer by laser or the like is cited, but this method involves an increase in the number of manufacturing steps and an increase in the cost of introducing the apparatus. Therefore, in recent years, a fire-through (fire-through) method has been adopted in which a conductive paste containing conductive metal powder and glass powder, that is, a paste-like electrode material, is applied to an insulating film and heat-treated to penetrate the insulating film.
As a glass composition contained in the conductive paste for burn-through, various glass compositions have been developed. For example, patent document 1 discloses a glass composition containing 60 to 95% by mass of PbO and 0 to 10% by mass of B as a specific glass composition of a glass used in a conductive paste for forming an electrode by penetrating an antireflection film on a light-receiving surface of a solar cell2O31 to 30 percent of SiO2+Al2O3The composition of (1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2013/103087
Disclosure of Invention
Problems to be solved by the invention
The conventional insulating film is generally formed of a single layer of silicon nitride, but in recent years, a two-layer structure including silicon nitride and silicon oxide or silicon nitride and aluminum oxide has become the mainstream for achieving high efficiency.
However, the glass composition described in patent document 1 is not sufficiently reactive with an insulating film having a two-layer structure, particularly on a semiconductor substrate such as silicon, when forming an electrode, and is desired to be improved.
In view of the above circumstances, an object of the present invention is to provide a glass composition capable of obtaining a conductive paste having high fire-through properties by being mixed with a conductive metal powder and an organic vehicle to form a paste, and a glass powder containing the glass composition.
Another object of the present invention is to provide a conductive paste having high burnthrough properties.
Means for solving the problems
The invention provides a glass composition, a glass powder, a conductive paste and a solar cell.
[1]A glass composition, wherein the glass composition comprises, in mol% on an oxide basis: 0.1 to 30 percent of SiO20.1 to 30 percent of B2O345 to 70 percent of PbO and 0.1 to 10 percent of Al2O30.1% -8% of V2O50.1 to 8 percent of Nb2O5And 0 to 5% of Y2O3。
[2]As described above [1]The glass composition, wherein V is represented by mol% in terms of oxide2O5And Nb2O5Total content (V) of2O5+Nb2O5) 0.2 to 10 percent.
[3]As described above [2]The glass composition, wherein V is represented by mol% in terms of oxide2O5And Nb2O5Total content (V) of2O5+Nb2O5) 0.5 to 8 percent.
[4]As described above [1]～[3]The glass composition according to any of the preceding claims, wherein Nb is contained in a molar percentage of oxide2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) 0.1 to 0.8.
[5]As described above [1]～[4]The glass composition according to any of the preceding claims, wherein Nb is contained in a molar percentage of oxide2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) ) is 0.2 to 0.7.
[6]As described above [1]～[5]The glass composition according to any one of the preceding claims, wherein the glass composition further comprises 0.1 to 10% of WO in mol% calculated as oxide3。
[7] The glass composition according to any one of the above [1] to [6], wherein a temperature difference (Ts-Tg) between a glass softening temperature (Ts) and a glass transition temperature (Tg) of the glass composition is 45 ℃ or more and less than 78 ℃.
[8]A glass powder comprising the above [1]]～[7]The glass powder of the glass composition according to any of the above claims, wherein a volume-based 50% particle diameter in a cumulative particle size distribution of the glass powder is defined as D50D of the glass powder500.3 to 3.0 μm.
[9] An electroconductive paste comprising the glass powder according to [8] above, an electroconductive metal powder and an organic vehicle.
[10] A solar cell having an electrode formed using the electroconductive paste according to [9 ].
[11]A conductive paste comprising a metal, a glass powder comprising a glass composition, and an organic vehicle, wherein the conductive paste comprises 63.0 to 97.9 mass% of the metal with respect to the total mass of the conductive paste, and the metal comprises at least one selected from the group consisting of a1, Ag, Cu, Au, Pd, and Pt, the conductive paste comprises 0.1 to 9.8 parts by mass of the glass composition with respect to 100 parts by mass of the metal, and the glass composition comprises, in terms of mole% converted to oxides: 0.1 to 30 percent of SiO20.1 to 30 percent of B2O345 to 70 percent of PbO and 0.1 to 10 percent of Al2O30.1% -8% of V2O50.1 to 8 percent of Nb2O5And 0 to 5% of Y2O3And the conductive paste includes the organic vehicle in an amount of 2 to 30 mass% with respect to the total mass of the conductive paste.
[12] The electroconductive paste according to [11], wherein the glass composition has a temperature difference (Ts-Tg) between a glass softening temperature (Ts) and a glass transition temperature (Tg) of 45 ℃ or more and 78 ℃ or less.
[13]As described above [11]Or [12]]The electroconductive paste, wherein D represents a volume-based 50% particle diameter in a cumulative particle size distribution of the glass powder50D of the glass powder500.3 to 3.0 μm.
[14] The electroconductive paste according to any one of the above [11] to [13], wherein the metal contains Ag.
[15] The conductive paste according to any one of the above [11] to [14], wherein the organic vehicle is an organic resin binder solution obtained by dissolving an organic resin binder in a solvent, the organic resin binder contains at least one of an acrylic resin and a cellulosic resin, and the solvent contains at least one selected from the group consisting of diethylene glycol monobutyl ether, terpineol, diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol diacetate, and methyl ethyl ketone.
Effects of the invention
The glass composition and the glass powder containing the glass composition of the present invention can be mixed with a conductive metal powder and an organic vehicle and slurried to obtain a conductive paste having high burnthrough property.
In addition, the conductive paste of the present invention has high burnthrough properties.
By using such a conductive paste having high burnthrough properties, a solar cell having high conversion efficiency can be manufactured with excellent production efficiency.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of an n-type Si substrate double-sided light receiving type solar cell in which an electrode is formed using the conductive paste of the present embodiment.
FIG. 2 is a view showing an electrode pattern formed on an Si substrate used for evaluating the contact resistance Rc [ omega ].
Description of the reference symbols
10.. solar cell, 1.. n-type Si semiconductor substrate, 1a.. n-type layer, 1b.. p-type layer, 2a.. antireflection film (silicon nitride/aluminum oxide), 2b.. antireflection film (silicon nitride/aluminum oxide), 3a.. Ag electrode, 3b.. Ag-Al electrode, s1.. light receiving face, s2.. non-light receiving face
Detailed Description
Hereinafter, embodiments of the present invention will be described.
< glass composition >
The glass composition of the present embodiment is characterized by containing 0.1 to 30% of SiO in mol% in terms of oxide20.1 to 30 percent of B2O345 to 70 percent of PbO and 0.1 to 10 percent of Al2O30.1% -8% of V2O50.1 to 8 percent of Nb2O5And 0 to 5% of Y2O3. In the following description, unless otherwise specified, "%" in the content of each component of the glass composition represents mol% in terms of oxides. In the present specification, "to" indicating a numerical range indicates upper and lower limits.
The content of each component in the glass composition of the present embodiment is determined from the result of InductiVely Coupled Plasma (ICP-AES: InductiVely Coupled Plasma-Atomic Emission Spectroscopy) analysis or Electron Probe microanalyzer (EPMA: Electron Probe Micro Analyzer) analysis of the obtained glass composition.
The glass composition of the present embodiment contains the above-mentioned specific amount of SiO2、B2O3、PbO、Al2O3、V2O5And Nb2O5. In addition, Y2O3May be 0%, that is, may contain no optional component.
When such a glass composition is slurried by mixing a metal and an organic vehicle, a conductive paste having high burnthrough property can be obtained. More specifically, when the conductive paste including the glass composition of the present embodiment is baked, the glass composition flows and reacts with the insulating film at a relatively early stage, thereby penetrating the insulating film. When the conductive paste containing the glass composition of the present embodiment is used in this manner, an electrode can be formed satisfactorily even in a solar cell composed of two insulating films, and the electrical characteristics of the solar cell can be improved.
In the glass composition of the present embodiment, SiO2Is an essential component. SiO 22The glass composition is a component for improving the weather resistance and stability of the glass composition, and is a component for adjusting the reactivity with an insulating film or a silicon substrate. The glass composition of the present embodiment contains SiO in a proportion of 0.1% to 30%2。SiO2When the content of (b) is less than 0.1%, vitrification cannot be achieved and formation of an electrode is difficult. SiO 22The content of (b) is preferably 5% or more, more preferably 7% or more. SiO 22When the content of (b) is more than 30%, the glass transition temperature becomes high, the fluidity is lowered, and the reactivity with the insulating film and the silicon substrate is lowered. SiO 22The content of (b) is preferably 25% or less, more preferably 23% or less.
In the glass composition of the present embodiment, B2O3Is an essential component. B is2O3The component is a component for improving the fluidity of the glass composition at the time of softening and improving the adhesive strength with the semiconductor substrate. In addition, B2O3Is a network structure forming component of the glass, or is a component contributing to stabilization of the glass composition. The glass composition of the present embodiment contains B in a proportion of 0.1% to 30%2O3。B2O3When the content of (b) is less than 0.1%, the stability of the glass composition is lowered and vitrification may not be possible. Further, the fluidity is insufficient, and the effect of promoting the reaction between the semiconductor substrate and the glass composition may not be sufficiently obtained. B is2O3The content of (b) is preferably 5% or more, more preferably 11% or more. B is2O3When the content of (b) is more than 30%, the weather resistance of the glass composition may be deteriorated. B is2O3The content of (b) is preferably 28% or less, more preferably 27% or less.
In the glass composition of the present embodiment, PbO is an essential component. PbO is reactive with an insulating film and a silicon substrate, and has a function of improving the softening fluidity of the glass composition. Thus, for example, when an electrode is formed on a semiconductor substrate or the like using a conductive paste containing the glass composition of the present embodiment, the resistance between the electrode and the substrate or the like can be reduced or the adhesion strength can be improved.
The glass composition of the present embodiment contains PbO in a proportion of 45% to 70%. When the content of PbO is less than 45%, reactivity with an insulating film and a silicon substrate is reduced and fluidity is reduced as the glass transition temperature becomes high. In this case, for example, when the electrode is formed as described above, the resistance between the electrode and the semiconductor substrate or the like increases, or the adhesive strength becomes insufficient. The content of PbO is preferably 50% or more, more preferably 55% or more. On the other hand, when the content of PbO is more than 70%, the glass composition cannot be obtained due to crystallization. The content of PbO is preferably 65% or less, more preferably 61% or less.
In the glass composition of the present embodiment, Al2O3Is an essential component. Al (Al)2O3Is a component for improving the weather resistance of the glass composition. The glass composition of the present embodiment contains a1 in a proportion of 0.1% to 10%2O3。Al2O3When the content of (b) is less than 0.1%, the glass has insufficient weather resistance. Al (Al)2O3The content of (b) is preferably 1.0% or more, more preferably 2.0% or more. Al (Al)2O3When the content of (b) is more than 10%, crystals precipitate and vitrification may not be achieved. Al (Al)2O3The content of (b) is preferably 7% or less, more preferably 5% or less.
In the glass composition of the present embodiment, V2O5Is an essential component. V2O5Has the functions of improving conductivity and improving fluidity and reactivity. The glass composition of the present embodiment contains V in a proportion of 0.1% to 8%2O5。V2O5When the content of (b) is less than 0.1%, the interval between the glass transition temperature and the softening temperature of the glass becomes narrow, and thus the fluidity is lowered. V2O5The content of (b) is preferably 1.0% or more, more preferably 2.0% or more. On the other hand, V2O5When the content of (b) is more than 8%, a glass composition may not be obtained due to crystallization. V2O5The content of (A) is preferably 7% or less, more preferably 5% or lessThe following steps.
In the glass composition of the present embodiment, Nb2O5Is an essential component. Nb2O5Has the function of improving the weatherability of the glass composition and improving the fluidity and reactivity. The glass composition of the present embodiment contains Nb in a proportion of 0.1% to 8%2O5。Nb2O5When the content of (b) is less than 0.1%, the reactivity is lowered, and thus the electrical characteristics of the solar cell cannot be improved. Nb2O5The content of (b) is preferably 1.0% or more, more preferably 1.5% or more. Nb2O5When the content of (b) is more than 8%, a glass composition may not be obtained due to crystallization. Nb2O5The content of (b) is preferably 7% or less, more preferably 5% or less.
V of the glass composition of the present embodiment2O5And Nb2O5Total content (V) of2O5+Nb2O5) Preferably 0.2% or more, and preferably 10% or less. Simultaneous presence of V2O5And Nb2O5The resulting mixing effect further improves the weatherability of the glass composition. By mixing V2O5And Nb2O5Total content (V) of2O5+Nb2O5) It is preferable to set the content to 0.2% or more because the above-mentioned mixing effect can be more suitably exhibited. V2O5And Nb2O5Total content (V) of2O5+Nb2O5) More preferably 0.5% or more, and still more preferably 4% or more.
On the other hand, by mixing V2O5And Nb2O5Total content (V) of2O5+Nb2O5) Setting to 10% or less is preferable because crystallization can be suppressed appropriately. V2O5And Nb2O5Total content (V) of2O5+Nb2O5) More preferably 8% or less, and still more preferably 7% or less.
Glass of the present embodimentNb of the composition2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) ) is preferably 0.1 or more, and further preferably 0.8 or less. Known as V2O5Easily changed in valence number in the glass, but by the simultaneous presence of Nb2O5Such a change in valence is not easily caused. By adding Nb2O5Relative to V2O5And Nb2O5Total ratio of (B)/(B)2Os/(V2O5+Nb2O5) 0.1 or more) can more suitably obtain Nb2O5Preventing V2O5The valence of (c). Nb2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) Is more preferably 0.2 or more, and still more preferably 0.3 or more.
On the other hand, Nb2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) Too much), from V2O5The effect of improving the conductivity may be small. Thus, Nb2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) ) is preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.
The glass composition of the present embodiment preferably further comprises WO3。WO3Has the function of improving the conductivity of the glass composition. WO3The content of (b) is preferably 0.1% or more, and more preferably 10% or less. WO3When the content of (b) is 0.1% or more, sufficient conductivity can be easily obtained. WO3The content of (b) is more preferably 0.3% or more, and still more preferably 0.5% or more. WO3When the content of (b) is 10% or less, vitrification becomes particularly easy. WO3The content of (b) is more preferably 7% or less, and still more preferably 4% or less.
The glass composition of the present embodiment preferably further contains Y2O3。Y2O3Has a function of improving the weatherability of the glass composition and a function of adjusting the reactivity. Y is2O3The content of (b) is preferably 0% to 5%, more preferably 0.1% to 5%. Y is2O3When the content of (b) is 0.1% or more, sufficient weather resistance can be easily obtained. Y is2O3The content of (b) is more preferably 0.5% or more, and still more preferably 1.0% or more. Y is2O3When the content of (b) is 5% or less, sufficient reactivity can be easily obtained. Y is2O3The content of (b) is more preferably 3% or less, and still more preferably 2% or less.
The glass composition of the present embodiment may further contain other optional components. As examples of other optional components, Ag may be mentioned2O、As2O5、Sb2O5、Ga2O3、In2O3、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、FeO、Fe2O3、CuO、Sb2O3、SnO、SnO2、MnO、MnO2、CeO2、Cr2O3、TiO2And various oxide components used in general glass compositions.
The other optional components may be used singly or in combination of two or more, depending on the purpose. The content of each of the other optional components is preferably 50% or less, and more preferably 40% or less. The total content of other optional components is preferably 50% or less, and more preferably 40% or less.
The method for producing the glass composition of the present embodiment is not particularly limited. For example, the production can be carried out by the following method.
First, a raw material mixture is prepared. The raw materials are not particularly limited as long as they are used for the production of a usual oxide glass composition, and oxides, carbonates, and the like can be used. The kind and the ratio of the raw materials are appropriately adjusted so that the resulting glass composition is within the above-described composition range, thereby making a raw material mixture.
Next, the raw material mixture is heated by a known method to obtain a melt. The temperature for heating and melting (melting temperature) is preferably 800 ℃ or higher, more preferably 900 ℃ or higher, and further preferably 1400 ℃ or lower, more preferably 1300 ℃ or lower. The time for heating and melting is preferably 30 to 300 minutes.
Then, the melt is cooled and solidified, whereby the glass composition of the present embodiment can be obtained. The cooling method is not particularly limited. For example, a rolling mill (rolling machine) or a press may be used, and a method of quenching by dropping the cooling liquid or the like may be employed. The glass composition obtained is preferably completely amorphous, i.e., has a crystallinity of 0%. However, the crystallized portion may be contained within a range not to impair the effects of the present invention.
The glass composition of the present embodiment obtained in this manner may be in any form. For example, the material may be in the form of a block, a plate, a sheet (flake), a powder, or the like.
The glass composition of the present embodiment has a function as a binder and conductivity, and is preferably used for a conductive paste. The conductive paste containing the glass composition of the present embodiment has high conductivity and is suitable for forming an electrode of a solar cell, for example. When the glass composition of the present embodiment is contained in the conductive paste, the glass composition is preferably contained in the form of glass powder.
< glass powder >
The glass powder of the present embodiment contains the above<Glass composition>The glass composition as described in (1). Glass powder D of the present embodiment50Preferably 0.3 μm or more and 3.0 μm or less. The D50Is particularly preferable for the electroconductive pasteAnd (3) a range. By D50The particle size is 0.3 μm or more, and the dispersibility in the conductive paste is further improved. In addition, by D50Being 3.0 μm or less, a portion where no glass powder is present around the conductive metal powder is less likely to be generated in the conductive paste, and thus the adhesiveness between the electrode and the semiconductor substrate or the like is further improved. Glass powder D of the present embodiment50More preferably 0.5 μm or more. In addition, D of the glass powder of the present embodiment50More preferably 2.7 μm or less.
In the present specification, "D" means50"represents the volume-based 50% particle diameter in the cumulative particle size distribution. Specifically, the particle size is the particle size at which the cumulative amount is 50% on a volume basis in a cumulative particle size curve of a particle size distribution measured by a laser diffraction/scattering particle size distribution measuring apparatus.
The glass powder of the present embodiment can be obtained by, for example, pulverizing the glass composition to a desired particle size distribution by a dry pulverization method or a wet pulverization method.
The method of grinding glass for obtaining the glass powder of the present embodiment is preferably a method of dry grinding and then wet grinding a glass composition having an appropriate shape. The dry grinding and the wet grinding can be performed using a grinder such as a roll mill, a ball mill, or a jet grinder, for example. The particle size distribution can be adjusted by adjusting the pulverizer, for example, the pulverizing time in each pulverization, the size of the ball mill, and the like. In the case of the wet pulverization method, water is preferably used as a solvent. After wet grinding, the glass powder is obtained by removing water by drying or the like. In order to adjust the particle size of the glass powder, classification may be performed as necessary in addition to pulverization of the glass.
< evaluation of thermal Properties of glass composition >
When the softening point (glass softening temperature) of the glass composition is Ts and the glass transition temperature is Tg, the temperature difference represented by (Ts-Tg) of the glass composition of the present embodiment is preferably 45 ℃ or more, and is preferably less than 78 ℃. When the (Ts-Tg) is less than 78 ℃, the pulverized glass composition can exhibit high fluidity when baked. When the temperature (Ts-Tg) is 45 ℃ or higher, the decrease in fluidity associated with crystallization can be suppressed.
The temperature difference represented by (Ts-Tg) of the glass composition of the present embodiment is more preferably 50 ℃ or more and less than 74 ℃.
The glass transition temperature Tg and the softening point Ts can be determined as follows: a Differential Thermal Analysis (DTA) apparatus TG8110 manufactured by japan physical corporation was used at a temperature increase rate: the first inflection point of the DTA graph obtained by measurement at 10 ℃/min was Tg and the fourth inflection point was Ts.
< conductive paste >
The conductive paste of the present embodiment contains a metal, the glass composition described in the above < glass composition >, and an organic vehicle.
As the metal contained in the conductive paste of the present embodiment, for example, a conductive metal powder is used. As the conductive metal powder, a powder of a metal generally used for an electrode formed on a circuit substrate such as a semiconductor substrate or an insulating substrate can be used without particular limitation. The circuit board is a concept including a laminated electronic component.
The metal preferably contains at least one selected from the group consisting of Al, Ag, Cu, Au, Pd, and Pt, for example, which are conductive metals, and their powders may be more preferably used. Among these, Ag powder is preferable from the viewpoint of productivity.
D of the conductive metal powder from the viewpoint of suppressing aggregation and obtaining uniform dispersibility50Preferably 0.3 μm or more, and preferably 10 μm or less.
The content of the metal in the conductive paste of the present embodiment is preferably 63.0 mass% or more, and more preferably 97.9 mass% or less, with respect to the total mass of the conductive paste.
When the content of the metal is 63.0 mass% or more with respect to the total mass of the conductive paste, the resistance of the conductive paste can be prevented from increasing while the conductivity of the metal is maintained. The content of the metal is more preferably 70.0 mass% or more with respect to the total mass of the conductive paste.
In addition, when the content of the metal is 97.9 mass% or less with respect to the total mass of the conductive paste, the content of the glass composition in the conductive paste can be sufficiently secured, and thus the conductive paste can be favorably adhered as an electrode to a circuit board such as a semiconductor substrate or an insulating substrate. The content of the metal is more preferably 95.0 mass% or less with respect to the total mass of the conductive paste.
The glass composition of the present embodiment contained in the conductive paste is preferably the glass powder described in the above < glass powder >.
For example, the content of the glass composition in the conductive paste is preferably 0.1 parts by mass or more and 9.8 parts by mass or less with respect to 100 parts by mass of the metal. When the content of the glass composition is 0.1 parts by mass or more per 100 parts by mass of the metal, the periphery of the metal is easily covered with the glass composition. Further, the adhesiveness between the electrode and a circuit board such as a semiconductor substrate or an insulating substrate is improved. On the other hand, when the content of the glass composition is 9.8 parts by mass or less based on 100 parts by mass of the metal, the glass is less likely to bulge due to excessive sintering of the metal
And the like. The content of the glass composition is more preferably 0.5 parts by mass or more and further more preferably 5 parts by mass or less with respect to 100 parts by mass of the metal.
As the organic vehicle contained in the conductive paste, an organic resin binder solution obtained by dissolving an organic resin binder in a solvent can be preferably used.
As the organic resin binder used in the organic vehicle, at least one of an acrylic resin and a cellulose resin is preferably used. More specifically, for example, cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose; and organic resins such as acrylic resins obtained by polymerizing at least one acrylic monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-hydroxyethyl acrylate. As the organic resin binder, these resins may be used alone or in combination.
The solvent used in the organic vehicle is not particularly limited as long as it dissolves the binder of the organic resin composition and can be removed by volatilization, decomposition, or the like at the time of baking or the like at the time of forming the electrode. When the organic resin binder is a cellulose resin, a solvent such as diethylene glycol monobutyl ether, terpineol, diethylene glycol monobutyl ether acetate, diethylene glycol ethyl ether acetate, and propylene glycol diacetate is preferably used, and when the organic resin binder is an acrylic resin, a solvent such as diethylene glycol monobutyl ether, methyl ethyl ketone, terpineol, diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, and propylene glycol diacetate is preferably used. These solvents may be used alone or in combination of two or more.
The ratio of the organic resin binder to the solvent in the organic vehicle is not particularly limited, and is selected so that the obtained organic resin binder solution has a viscosity capable of adjusting the viscosity of the conductive paste. Specifically, the mass ratio expressed by the organic resin binder to the solvent is preferably about 3: 97 to about 15: 85.
The content of the organic vehicle in the conductive paste is preferably 2 mass% or more and 30 mass% or less with respect to the total amount of the conductive paste. When the content of the organic vehicle is 2% by mass or more, the viscosity of the conductive paste is likely to fall within an appropriate range, and the coatability of the conductive paste such as printing is likely to be improved, thereby forming a good conductive layer (electrode). When the content of the organic vehicle is 30% by mass or less, the content ratio of the solid content in the conductive paste becomes high, and thus a sufficient coating film thickness can be easily obtained.
In the conductive paste of the present embodiment, in addition to the glass composition, the metal, and the organic vehicle, a known additive may be blended as needed within a limit not departing from the object of the present invention.
Examples of the additives includeAn inorganic oxide. Specific examples of the inorganic oxide include B2O3、SiO2、Al2O3、TiO2、MgO、ZrO2、Sb2O3And composite oxides thereof. These inorganic oxides have an effect of moderating sintering of the metal at the time of baking of the conductive paste, thereby having an effect of adjusting the bonding strength after baking. The size of the additive containing these inorganic oxides is not particularly limited, and for example, D can be preferably used50An additive having a particle size of 10 μm or less.
The content of the inorganic oxide in the conductive paste is appropriately set according to the purpose, and is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less, with respect to 100 parts by mass of the glass composition. When the content of the inorganic oxide is 10 parts by mass or less with respect to 100 parts by mass of the glass composition, the fluidity of the conductive paste in forming the electrode is likely to be good, and thus the adhesive strength between the electrode and a circuit board such as a semiconductor substrate or an insulating substrate is likely to be high. In order to obtain a practical compounding effect, i.e., to adjust the adhesion strength after baking, the content of the inorganic oxide is preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more.
Additives known in the conductive paste, such as an antifoaming agent and a dispersant, may be added to the conductive paste. The organic vehicle and the additives are generally components that disappear during the formation of the electrode. For the preparation of the electroconductive paste, a known method using a rotary mixer having an agitating blade, a masher (milling), a roll mill, a ball mill or the like can be used.
The conductive paste can be applied and baked to a circuit board such as a semiconductor substrate or an insulating substrate by the same method as that for conventional electrode formation. Examples of the coating method include screen printing and dot coating (discrete) method. The baking temperature depends on the kind, surface state, and the like of the conductive metal powder contained, and a temperature of about 500 to about 1000 ℃ can be exemplified. The baking time may be appropriately adjusted according to the shape, thickness, and the like of the electrode to be formed. Further, a drying treatment at about 80 to about 200 ℃ may be provided between the application and baking of the conductive paste.
< solar cell >
The solar cell of the present embodiment has an electrode formed using the conductive paste described in the < conductive paste >, specifically an electrode fired (fired け) on a semiconductor substrate. In the solar cell of the present embodiment, at least one of the electrodes is preferably an electrode provided so as to partially penetrate the insulating film by burning through using the conductive paste and to be in contact with the semiconductor substrate.
Examples of the electrode penetrating through the insulating film included in the solar cell include: an electrode on a light receiving surface of a solar cell as a semiconductor substrate using a pn junction type, and an electrode provided so as to partially penetrate an insulating film as an antireflection film and to be in contact with the semiconductor substrate. As the insulating material constituting the insulating film as the antireflection film, there can be mentioned: silicon nitride, titanium dioxide, silicon dioxide, aluminum oxide, etc., the insulating material preferably comprises two layers. In this case, the light receiving surface may be a single surface or both surfaces of the semiconductor substrate, and the semiconductor substrate may be either an n-type or a p-type semiconductor substrate. Such an electrode provided on the light-receiving surface of the solar cell may be formed by firing through using the above-described conductive paste.
Hereinafter, a configuration example of the solar cell of the present embodiment will be described, but the configuration of the solar cell of the present embodiment is not limited to this configuration example.
The solar cell of this configuration example has: a silicon substrate having a sunlight-receiving surface (hereinafter also simply referred to as "surface"); a first insulating film provided on a light-receiving surface of a silicon substrate; a second insulating film provided on a surface of the silicon substrate on the opposite side to the light-receiving surface (hereinafter also simply referred to as "back surface") and having at least one opening portion; a first electrode penetrating a part of the first insulating film and contacting the silicon substrate; and a second electrode partially in contact with a silicon substrate via the opening portion of the second insulating film.
More specifically, for example, as shown in fig. 1, the solar cell 10 is provided with the p-type layer 1b on the light receiving surface S1 of the n-type Si semiconductor substrate 1. An antireflection film (silicon nitride/aluminum oxide) 2b is also formed on the surface thereof, but in a part of the area, an Ag — Al electrode 3b is formed so as to penetrate through the antireflection film (silicon nitride/aluminum oxide) 2b and to be in contact with the p-type layer 1b.
An n-type layer 1a is similarly provided on the non-light-receiving surface S2 of the n-type Si semiconductor substrate 1, and an antireflection film (silicon nitride/alumina) 2a is also formed on the surface thereof, but in a part of the region, an Ag electrode 3a is formed so as to penetrate through the antireflection film (silicon nitride/alumina) 2a and be in contact with the n-type layer 1a.
The Ag — Al electrode 3b and the Ag electrode 3a can be formed by coating and baking the Ag — Al electrode 3b or the Ag electrode 3a via the above-described conductive paste in a partial region on the surface of the antireflection film (silicon nitride/aluminum oxide) 2b, 2a.
In this configuration example, the first electrode and the second electrode are electrodes formed by firing using the conductive paste of the present embodiment, and preferably include a metal containing at least one selected from the group consisting of Al, Ag, Cu, Au, Pd, and Pt and the glass composition of the present embodiment.
The first electrode more preferably contains 90 mass% to 99.9 mass% of the metal, and 0.1 mass% to 10 mass% of the glass composition of the present embodiment. In addition, the first electrode more preferably contains at least Ag.
In this configuration example, the first insulating film and the second insulating film more preferably have a metal oxide film in contact with both sides of the silicon substrate and a silicon nitride film on the metal oxide film. The metal oxide film more preferably contains alumina or silica.
[ examples ]
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples. Examples 1 to 9 are examples, and examples 10 to 13 are comparative examples.
(examples 1 to 13)
A thin plate-shaped glass composition was produced by the following method, a glass powder was produced from the glass composition, and the particle size distribution of the glass powder was measured.
< production of glass composition (sheet glass) >
Raw material powders were mixed and mixed so as to have the compositions shown in table 1, and melted in an electric furnace at 900 to 1200 ℃ for 30 minutes to 1 hour using a crucible, and formed into sheet-like glass including a glass composition. In examples 12 and 13, devitrification (crystallization) occurred, and a glass composition could not be obtained. In table 1, the blank column in the column of each component of the glass composition indicates that the content is 0%, that is, less than the detection limit.
< production of glass powder >
In examples 1 to 11, the obtained sheet-like glass was pulverized by a combination of dry pulverization and wet pulverization as follows, and the particle size distribution was adjusted.
The resulting mixture was dry-ground for 6 hours in a ball mill, and coarse particles were removed by a 150-mesh sieve. Then, the glass powder obtained by dry grinding and removing coarse particles is treated with D50The glass powder having a desired particle size distribution was produced by wet-grinding with water using a ball mill so as to fall within a predetermined range. In the wet grinding, a predetermined D value is obtained50Alumina balls of 5mm diameter were used. Then, the slurry obtained by wet grinding was filtered and dried at 130 ℃ by a dryer to remove water, thereby producing a glass powder.
< evaluation >
The glass transition temperature Tg, the softening points Ts and D of the glass compositions and the glass powders of examples 1 to 11 were measured by the following methods50. The results are shown in table 1.
(Tg、Ts、Ts-Tg)
Using a Differential Thermal Analysis (DTA) apparatus TG8110 manufactured by japan, inc: thermal analysis of the glass composition was performed at 10 deg.C/min. The first inflection point of the obtained DTA graph is denoted by Tg, the fourth inflection point is denoted by Ts, and Ts-Tg is calculated from the values of these.
(D50)
0.02g of glass powder was mixed with 60mL of IPA (Isopropyl Alcohol) and dispersed for 1 minute by ultrasonic dispersion. Then, the resultant was put into a Microtrack (laser diffraction/scattering particle size distribution measuring apparatus) to measure D50。
< production of conductive paste >
Conductive pastes for forming Ag-Al electrodes, each containing the glass powders of examples 1 to 11 prepared above, were prepared by the following method.
First, 95 parts by mass of diethylene glycol butyl ether acetate was mixed with 5 parts by mass of ethyl cellulose, and the mixture was stirred at 85 ℃ for 2 hours to prepare an organic vehicle. Next, 15 parts by mass of the obtained organic vehicle was mixed with 82 parts by mass of Ag powder (manufactured by DOWA Electronics Co., Ltd., spherical silver powder: AG-4-8F) and 3 parts by mass of Al powder (manufactured by Maruko Co., atomized aluminum powder: #600F), followed by kneading for 10 minutes by a kneader. Then, the glass powders of examples 1 to 11 were mixed in an amount of 2 parts by mass based on 100 parts by mass of the total of the Ag powder and the Al powder as the metal powder, and further kneaded by a kneader for 90 minutes, thereby obtaining an electroconductive paste for forming an Ag — Al electrode.
< measurement of contact resistance >
Using the conductive pastes for forming Ag — Al electrodes prepared above, Ag — Al electrodes were formed on a semiconductor substrate with an insulating film interposed therebetween in the following manner, and the penetration of the insulating film, i.e., the burnthrough property at that time was evaluated. The insulating film is a two-layer film including a silicon nitride layer and an aluminum oxide layer.
With reference to fig. 1, an n-type crystal Si semiconductor substrate cut to a thickness of 160 μm was used, and etching treatment was performed on the front surface and the back surface with hydrofluoric acid to a very small amount in order to clean the cut surface of the Si semiconductor substrate. Then, an uneven structure (not shown in fig. 1) that reduces the light reflectance and the like is formed on the light receiving surface S1 of the n-type Si semiconductor substrate 1 by a wet etching method. Next, a p-type layer 1b is formed on the light receiving surface S1 of the n-type Si semiconductor substrate 1 by diffusion. B (boron) is used as a doping element for p-type doping. Next, an antireflection film 2b is formed on the surface of the p-type layer 1b on the light receiving surface S1 side of the n-type Si semiconductor substrate 1. As the material of the antireflection film 2b, silicon nitride and aluminum oxide are used. The silicon nitride was formed to a thickness of 80nm by plasma CVD. Alumina was formed to a thickness of 10nm by ALD (Atomic Layer Deposition). Next, with respect to the back surface of the n-type Si semiconductor substrate 1, that is, the non-light-receiving surface S2, the antireflection film 2a is formed in the same manner after the n-type layer 1a is diffused.
Next, the Ag — Al electrode-forming conductive paste obtained using the glass powders of examples 1 to 11 described above was applied in a line form on the surface of the obtained Si semiconductor substrate with an antireflection film on the light-receiving surface S1 side by screen printing, and dried at 120 ℃.
Subsequently, the surface Ag — Al electrode 3b was formed by baking for 100 seconds at a peak temperature of 750 ℃ in an infrared heating furnace, and the single-sided battery for measuring contact resistance was completed. By baking, the Ag — Al electrode 3b is formed so as to penetrate through the antireflection film 2b and to be in contact with the p-type layer 1b of the n-type Si semiconductor substrate 1.
The contact resistance of the single-sided batteries produced using the conductive pastes for Ag — Al electrode formation each containing the glass powder of the above examples was measured by the TLM Method (Transfer length Method). Specifically, the contact resistance Rc Ω between an n-type Si semiconductor substrate having an Ag — Al electrode formed as an antireflection film of two films including a silicon nitride layer and an aluminum oxide layer with the insulating film on the p-type layer side obtained in the above manner interposed therebetween and the Ag — Al electrode was evaluated.
The contact resistance Rc [ Ω ] is determined as follows: the anode side of the tester was fixed to the pattern P1 of fig. 2, and the cathode side of the tester was placed at each position of the patterns P2, P3, P4, and P5 to measure the resistance.
In examples 1 to 9, Rc was low and the insulating film penetration was excellent. On the other hand, examples 10 and 11 had large Rc and insufficient penetration of the insulating film.
As is clear from table 1, the glass compositions and glass powders of examples 1 to 9 are suitable for forming electrodes of solar cells, as compared with the glass compositions and glass powders of examples 10 to 13, which are comparative examples.
Claims (15)
1. A glass composition, wherein the glass composition comprises, in mol% on an oxide basis:
0.1 to 30 percent of SiO2、
0.1 to 30 percent of B2O3、
45 to 70 percent of PbO,
0.1 to 10 percent of Al2O3、
0.1% -8% of V2O5、
0.1 to 8 percent of Nb2O5And, and
0 to 5% of Y2O3。
2. The glass composition according to claim 1, wherein V is represented by mol% in terms of oxide2O5And Nb2O5Total content (V) of2O5+Nb2O5) 0.2 to 10 percent.
3. The glass composition according to claim 2, wherein V is represented by mol% in terms of oxide2O5And Nb2O5Total content (V) of2O5+Nb2O5) 0.5 to 8 percent.
4. The glass composition according to any one of claims 1 to 3, wherein Nb is contained in a molar percentage in terms of oxide2O5Of (1) containsAmount relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) 0.1 to 0.8.
5. The glass composition according to any one of claims 1 to 4, wherein Nb is contained in a molar percentage in terms of oxide2O5Relative to V2O5And Nb2O5(ii) ratio of the total content of (Nb)2O5/(V2O5+Nb2O5) ) is 0.2 to 0.7.
6. The glass composition according to any one of claims 1 to 5, further comprising 0.1 to 10% of WO in mol% on an oxide basis3。
7. The glass composition of any of claims 1-6, wherein the glass composition has a temperature difference (Ts-Tg) between a glass softening temperature (Ts) and a glass transition temperature (Tg) of greater than or equal to 45 ℃ and less than 78 ℃.
8. A glass powder comprising the glass composition according to any one of claims 1 to 7, wherein a volume-based 50% particle diameter in a cumulative particle size distribution of the glass powder is defined as D50D of the glass powder500.3 to 3.0 μm.
9. An electroconductive paste comprising the glass powder according to claim 8, an electroconductive metal powder and an organic vehicle.
10. A solar cell having an electrode formed using the conductive paste of claim 9.
11. A conductive paste comprising a metal, a glass powder comprising a glass composition, and an organic vehicle, wherein,
the conductive paste includes 63.0 to 97.9 mass% of the metal with respect to a total mass of the conductive paste, and the metal includes at least one selected from the group consisting of Al, Ag, Cu, Au, Pd, and Pt,
the conductive paste contains 0.1 to 9.8 parts by mass of the glass composition per 100 parts by mass of the metal, and the glass composition contains, expressed in terms of mole% on an oxide basis: 0.1 to 30 percent of SiO20.1 to 30 percent of B2O345 to 70 percent of PbO and 0.1 to 10 percent of Al2O30.1% -8% of V2O50.1 to 8 percent of Nb2O5And 0 to 5% of Y2O3And is and
the conductive paste includes the organic vehicle in an amount of 2 to 30 mass% with respect to the total mass of the conductive paste.
12. The conductive paste according to claim 11, wherein a temperature difference (Ts-Tg) between a glass softening temperature (Ts) and a glass transition temperature (Tg) of the glass composition is 45 ℃ or more and less than 78 ℃.
13. The electroconductive paste according to claim 11 or 12, wherein the volume-based 50% particle diameter in the cumulative particle size distribution of the glass powder is set as D50D of the glass powder500.3 to 3.0 μm.
14. The electroconductive paste of any one of claims 11-13, wherein said metal comprises Ag.
15. The electroconductive paste according to any one of claims 11 to 14, wherein the organic vehicle is an organic resin binder solution obtained by dissolving an organic resin binder in a solvent,
the organic resin binder contains at least one of an acrylic resin and a cellulosic resin, and
the solvent includes at least one selected from the group consisting of diethylene glycol monobutyl ether, terpineol, diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol diacetate, and methyl ethyl ketone.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019154893 | 2019-08-27 | ||
| JP2019-154893 | 2019-08-27 | ||
| JP2020-100922 | 2020-06-10 | ||
| JP2020100922A JP2021040123A (en) | 2019-08-27 | 2020-06-10 | Glass composition, glass powder and conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112441738A true CN112441738A (en) | 2021-03-05 |
Family
ID=74733461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010866654.8A Pending CN112441738A (en) | 2019-08-27 | 2020-08-25 | Glass composition, glass powder and conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112441738A (en) |
-
2020
- 2020-08-25 CN CN202010866654.8A patent/CN112441738A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI778207B (en) | Glass, glass powder, conductive paste and solar cells | |
| EP3405961B1 (en) | Conductive paste, method, electrode and solar cell | |
| KR101706539B1 (en) | Glass frit composition for forming solar cell electrode, solar cell electrode formed by using the same glass composition, and solar cell including the same electrode | |
| JP6966950B2 (en) | Glass, glass manufacturing methods, conductive pastes and solar cells | |
| CN108352212B (en) | Method for forming conductor rails or coatings | |
| JP6958257B2 (en) | Glass compositions, glass powders, conductive pastes and solar cells | |
| JP2020083670A (en) | Glass composition, glass powder, conductive paste, and solar battery | |
| JP2017218335A (en) | Glass, conductive paste and solar battery | |
| JP6720712B2 (en) | Glass powder, conductive paste and solar cell | |
| CN112441738A (en) | Glass composition, glass powder and conductive paste | |
| KR102183618B1 (en) | Glass frit composition for forming solar cell electrode, and paste composition including the same | |
| JP2014078594A (en) | Paste composition and solar battery | |
| JP7444552B2 (en) | Glass composition, method for producing glass composition, conductive paste, and solar cell | |
| CN112028494B (en) | Glass composition, method for producing glass composition, conductive paste, and solar cell | |
| KR20210025483A (en) | Glass composition, glass powder and conductive paste | |
| JP7088811B2 (en) | Glass, glass powder, conductive paste and solar cells | |
| CN115521064A (en) | Glass, glass powder, conductive paste and solar cell | |
| JP2023004853A (en) | Glass, glass powder, conductive paste and solar cell | |
| CN116332500A (en) | Glass, conductive paste and solar cell | |
| CN116332501A (en) | Glass, conductive paste and solar cell | |
| JP2023097338A (en) | Glass, conductive paste and solar cell | |
| JP7027719B2 (en) | Glass composition and glass powder | |
| JP6702011B2 (en) | Glass powder, conductive paste and solar cell | |
| KR101981660B1 (en) | Glass frit for forming solar cell electrode, paste composition including the same glass frit | |
| KR20230055847A (en) | Glass frit composition for forming solar cell electrode, solar cell electrode formed by using the same glass composition, and solar cell including the same electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210305 |