CN109545424B - Conductive silver paste and preparation method and application thereof - Google Patents
Conductive silver paste and preparation method and application thereof Download PDFInfo
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- CN109545424B CN109545424B CN201811450637.5A CN201811450637A CN109545424B CN 109545424 B CN109545424 B CN 109545424B CN 201811450637 A CN201811450637 A CN 201811450637A CN 109545424 B CN109545424 B CN 109545424B
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- Prior art keywords
- silver paste
- conductive silver
- solar cell
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 22
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 36
- 229910052709 silver Inorganic materials 0.000 claims description 35
- 239000004332 silver Substances 0.000 claims description 35
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 claims description 30
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 claims description 30
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- 238000002161 passivation Methods 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052710 silicon Inorganic materials 0.000 abstract description 30
- 239000010703 silicon Substances 0.000 abstract description 30
- 239000011241 protective layer Substances 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 6
- -1 siloxane, siloxane Chemical class 0.000 description 39
- 239000010410 layer Substances 0.000 description 26
- 238000003466 welding Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 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
- 239000012535 impurity Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- XSTWLWOXFOTNMP-UHFFFAOYSA-N 2-propylsilylphenol Chemical class C(CC)[SiH2]C1=C(C=CC=C1)O XSTWLWOXFOTNMP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910017107 AlOx Inorganic materials 0.000 description 1
- YUKBKWUOVFAWHM-UHFFFAOYSA-N CCC[SiH2]C1=CC=CC=C1 Chemical class CCC[SiH2]C1=CC=CC=C1 YUKBKWUOVFAWHM-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 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
- 230000002411 adverse Effects 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- IJLKOVQDDDWMCM-UHFFFAOYSA-N butyl(propyl)silane Chemical class CCCC[SiH2]CCC IJLKOVQDDDWMCM-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- XWRLQRLQUKZEEU-UHFFFAOYSA-N ethyl(hydroxy)silicon Chemical compound CC[Si]O XWRLQRLQUKZEEU-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Development (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides conductive silver paste and a preparation method and application thereof. The raw material composition of the conductive silver paste comprises a conductive silver paste base material and an organic silicon compound, wherein the content of the organic silicon compound is 0.1-5 parts by weight and the total mass of the conductive silver paste is 100 parts by weight based on the weight of silicon dioxide, and the organic silicon compound is used for forming a silicon oxide protective layer. The conductive silver paste can be used for preparing a back electrode and a main gate electrode. The conductive silver paste can improve the bonding force to the silicon substrate on the basis of not damaging the passive film of the battery pole piece.
Description
Technical Field
The invention relates to conductive silver paste, in particular to conductive silver paste for a back electrode and a main gate electrode, and belongs to the technical field of solar cells.
Background
The biggest difference between a passivated emitter region and a back surface passivated cell (PERC) and a common silicon solar cell is that the back surface of the PERC is protected by thin layers of aluminum oxide, silicon nitride and the like, a back silver electrode and a back aluminum back field are not directly contacted with a silicon cell, the surface recombination rate is reduced, the open-circuit voltage of the silicon solar cell is improved, and finally the efficiency of the silicon solar cell is improved.
Due to the addition of the passivation layer on the back surface of the cell, the direct contact area of the back silver electrode and the silicon cell piece is greatly reduced, which results in the reduction of the adhesion between the back silver electrode and the silicon cell piece. The glass powder in the back silver paste corrodes the back passivation layer in the sintering process, although the adhesive force can be improved, the efficiency of the silicon solar cell is obviously reduced because the back passivation layer is damaged. The silver paste has high adhesive force on the basis of ensuring that the back passivation layer is not damaged, and is a technical difficulty of the back silver paste of the PERC solar cell.
Due to the special structure of the PERC battery, the conventional back electrode silver paste directly applied to the surface of the crystalline silicon can not meet the use requirement. Mainly because the conventional back electrode silver paste usually needs to corrode the surface of crystalline silicon in order to obtain higher tensile force, and the back surface of the PERC cell is an AlOx/SiNx laminated film which cannot be damaged, plays a role in passivation and can improve the open-circuit pressure and the efficiency. After the conventional back silver paste on the market is applied to the PERC battery, part of the conventional back silver paste can obtain high tensile force, but the passivation film is basically damaged, so that the effect of improving the passivation effect of the PERC battery is reduced. Therefore, it is imperative to develop a back electrode silver paste which can not only obtain high efficiency, but also provide high tension of the back electrode.
In addition, the main function of the main grid lines on the light receiving surface is to collect the current of the thin grid lines and provide welding points for component manufacturing, which needs to generate excellent welding bonding force with a welding strip and no resistance contact. The material of the main grid slurry is only combined with a passivation layer (such as silicon nitride, silicon oxide and the like) on the surface of the battery after being sintered, and excellent mechanical bonding force is provided. But does not generate metallized ohmic contact with P-N junction materials of the silicon cell, thereby effectively reducing the surface photoelectron recombination of the cell and improving the photoelectric conversion efficiency of the cell. Namely, the silver paste used for the main grid cannot damage the passivation layer on the surface layer of the cell and forms strong adhesive force.
The Chinese patent application 201610655793.X is a silver paste prepared by using silver powder, glass powder and an organic carrier in a limited proportion, wherein the silver powder comprises 55-70% of silver powder, 2-5% of glass powder and 25-43% of the organic carrier by taking the total amount as 100%, the silver powder is formed by mixing flake silver powder and spherical silver powder in proportion, and the glass powder comprises 5-20% of transition metal oxide, 1-10% of rare earth metal oxide, 30-50% of bismuth oxide, 5-15% of barium oxide, 5-10% of silicon oxide, 5-15% of strontium oxide and 5-15% of antimony oxide. The final slurry fineness is less than 10 mu m, the viscosity is 40-70Pa s, the tensile force is greater than 4N, the open pressure is increased by 1-2mv, the short flow is increased by 5-10mA, and the efficiency is increased by 0.05-0.12% compared with the conventional back silver slurry.
However, rare earth metals and oxides are introduced into a glass powder system to prepare glass powder, sintering corrosivity of the glass powder is adjusted only by blending the glass powder in a formula system, difficulty coefficient is large, matching performance with a battery piece is poor (passivation layers of the battery piece are different from manufacturers), and practical application is difficult.
Chinese patent application 201710001995.7 relates to a technical solution: the glass powder adopts PbO-SiO2-TiO2-B2O3-TeO2-Sc2O3Or Bi2O3-SiO2-TiO2-B2O3-TeO2-Sc2O3According to the system, elements such as Te, Ti and Sc are introduced into common glass, so that the using amount of glass powder in the silver paste on the back surface of the PERC silicon solar cell can be effectively reduced, the corrosivity of a back passivation layer is weakened, and the silver paste on the back surface of the PERC silicon solar cell has excellent weldability, welding resistance, welding tension and ageing resistance after being sintered. By adjusting the proportion of the components in the glass powder system, the network structure of the glass powder can be effectively adjusted, so that the glass powder is uniform and has a lower softening point, and the glass powder is more suitable for the process conditions of the solar cell.
However, by preparing the glass powder of a new system, the usage amount of the glass powder is reduced, and the corrosivity in the sintering process is reduced, so that the damage to the surface passivation layer of the solar cell is reduced, the control difficulty is high, and the bonding tension of the sintered silver paste is adversely affected due to the reduction of the usage amount of the glass powder.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a conductive silver paste which can improve the adhesion between the conductive silver paste and a silicon wafer without damaging a passivation layer, has strong aging resistance, and can further improve the photoelectric conversion efficiency of a solar cell.
In order to achieve the technical purpose, the invention firstly provides a conductive silver paste, which comprises the following raw materials: the conductive silver paste comprises a conductive silver paste base material and an organic silicon compound, wherein the content of the organic silicon compound (based on the weight of silicon dioxide) is 0.1-5 parts by weight based on 100 parts by weight of the total mass of the conductive silver paste; wherein the organosilicon compound is used to form a silicon oxide protective layer.
Here, in the conductive silver paste of the present invention, the content of the organic silicon compound is calculated based on the weight of silicon dioxide obtained by decomposing the organic silicon compound.
According to the conductive silver paste, the organic silicon compound with a specific structure is added into the conductive silver paste base material, so that a silicon oxide protective layer can be formed before the silver paste is sintered, and the silver paste is prevented from burning through a passivation layer (SiNx and/or Al) of a solar cell during sintering2O3) And the protective layer has strong adhesion with the silicon substrate, and the finally obtained electrode has large welding tension and strong aging resistance.
In the conductive silver paste of the invention, the organosilicon compound can decompose the silicon oxide protective layer at the temperature lower than 450 ℃.
Furthermore, the organosilicon compound can decompose the silicon oxide protective layer at 230-380 deg.C.
In one embodiment of the present invention, the organosilicon compounds employed decompose to form a protective layer of silica nanoparticles at a particular temperature.
In the conductive silver paste of the present invention, preferably, the molecular weight of the organosilicon compound used is 50 to 1500000.
Further, the molecular weight of the organosilicon compound used is 3000-50000.
The conductive silver paste can form a silicon oxide protective layer (specifically a silicon dioxide nano protective layer) on the surface of the passivation layer at the sintering temperature, and the protective layer has stable silicon-oxygen bond performance and strong temperature resistance, so that the passivation layer can be effectively prevented from being corroded by glass powder during subsequent high-temperature sintering, and the protective layer has good cohesiveness with a silicon substrate, so that the conductive silver paste has better welding tension and aging performance.
In the conductive silver paste of the present invention, the organosilicon compound used may be one or a combination of more of siloxane, siloxane resin, silane and polysilane.
Further, the organosilane compound used may be a siloxane resin and/or a siloxane.
In the conductive silver paste of the present invention, the siloxane used includes alkyl siloxane and/or alkoxy siloxane.
The siloxane may include one or more of methyl siloxane, ethyl siloxane, propyl siloxane, butyl siloxane, phenyl siloxane, methoxy siloxane, ethoxy siloxane, propoxy siloxane, butoxy siloxane and phenoxy siloxane.
In the conductive silver paste of the present invention, the siloxane resin used is a siloxane resin having an alkyl group, an aryl group, or an aralkyl group.
Specifically, the silicone resin used is a composition which can easily give a silicone-containing resin capable of forming a silicone oxide intermediate layer having excellent durability and filling a minute space.
In the conductive silver paste of the present invention, the alkyl group used in the siloxane resin is an alkyl group that facilitates silicon to form a silicon oxide protective layer having good heat resistance.
Further, the alkyl group used may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a tert-butyl group.
In the conductive silver paste of the present invention, the aryl group in the siloxane resin may be phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl, or pyrenyl.
In the conductive silver paste of the present invention, the aralkyl group contained in the siloxane resin may be a benzyl group or a phenethyl group.
In the conductive silver paste of the present invention, the silane to be used may be a methylsilane compound, an ethylsilane compound, a propylsilane compound, a butylsilane compound, a phenylsilane compound, a hydroxyphenylsilane compound, a naphthylsilane compound, a benzylsilane compound, a hydrosilane compound, a methylhydrosilane compound, an ethylhydrosilane compound, a propylhydrosilane compound, a butylhydrosilane compound, a phenylhydrosilane compound, a dimethylsilane compound, a diethylsilane compound, a dibutylsilane compound, a diphenylsilane compound, a methylethylsilane compound, a methylpropylsilane compound, a methylbutylsilane compound, a methylphenylsilane compound, a methyl (hydroxyphenyl) silane compound, an ethylpropylsilane compound, an ethylbutylsilane compound, an ethyl (hydroxyphenyl) silane compound, a propylsilyl compound, a butylsilyl compound, an ethylsilyl (hydroxyphenyl) silane compound, a butylsilyl compound, propyl (hydroxyphenyl) silane compounds, propylbutylsilane compounds, and propyl (phenyl) silane compounds.
It is to be noted that the above silane may be used in a small branch of the silane compound, which represents a silane compound having a certain group. For example, the methylsilane compound means a silane compound containing a methyl group.
In the conductive silver paste, the polysilane can be linear chain, branched chain, reticular or annular; polysilanes having a linear or branched chain structure are preferred.
Further, the polysilane used is a polysilane having a silanol group or an alkoxy group.
In the conductive silver paste, no special requirements are imposed on the raw material composition of the conductive silver paste base material. The adopted conductive silver paste base material contains silver powder, glass powder and an organic carrier.
Further, the adopted conductive silver paste base material comprises 30-85 parts by weight of silver powder, 1-5 parts by weight of glass powder and 10-50 parts by weight of organic carrier based on 100 parts by weight of the total mass of the conductive silver paste.
In the conductive silver paste of the present invention, there is no special requirement for the glass frit used, and any glass frit composition commonly used in the art can be used.
The glass powder composition is generally prepared by the procedures of mixing, melting, quenching, grinding, washing, filtering and drying.
In the conductive silver paste of the invention, the silver powder adopted has no special requirement, and can be conventional silver powder in the field.
In the conductive silver paste, no special requirements are imposed on the raw material composition of the organic carrier, and the organic carrier is conventional in the field. For example, the organic vehicle may comprise a cellulosic resin, a solvent, and additives.
Wherein the cellulose resin can be one or more of ethyl hydroxyethyl cellulose, nitrocellulose, ethyl cellulose, methyl cellulose and hydroxypropyl methyl cellulose.
Wherein, the solvent can be one or more of terpineol, butyl carbitol acetic acid, propylene glycol methyl ether acetate, ethylene glycol ethyl ether, ethylene glycol butyl ether acetate, petroleum ether and turpentine.
In order to achieve the above object, the present invention further provides a method for preparing a conductive silver paste, which comprises the following steps:
the method comprises the following steps: mixing silver powder, glass powder, an organic carrier and an organic silicon compound, and uniformly stirring;
alternatively, the first and second electrodes may be,
adding an organic silicon compound during the preparation of the organic carrier, stirring, then mixing with silver powder and glass powder, and stirring uniformly;
step two: grinding for 1-3 h, and filtering to obtain conductive silver paste with fineness less than or equal to 10 μm and viscosity of 30-100 Pa.S.
In the preparation method of the invention, the adopted organic silicon compound can be mixed with the conductive silver paste base material, or can be mixed with the raw material of the organic carrier during the preparation of the organic carrier and then mixed with other raw materials of the conductive silver paste base material.
In the preparation method of the present invention, the organic vehicle can be prepared by the following steps:
dissolving cellulose resin in a solvent at the temperature of 60-90 ℃, adding an additive, uniformly stirring and filtering to obtain the organic carrier.
When the organic silicon compound is added in the preparation process of the organic carrier, the organic silicon compound can be added in the preparation process and then mixed with other raw materials in the conductive silver paste base material to obtain the conductive silver paste.
The invention also provides an electrode which is prepared from the conductive silver paste. It should be noted here that the electrodes include, but are not limited to, a back electrode and a main gate electrode. Wherein the back electrode may be a back electrode of a back Passivated (PERC) cell; the main gate electrode may be the front side main gate electrode of conventional cells and PERC cells.
The electrode of the invention has good cohesive force, good aging resistance, low silver content and low cost.
The invention provides a solar cell comprising the above-described electrode of the invention. It should be noted here that the solar cell includes, but is not limited to, a PERC solar cell.
The solar cell has higher photoelectric conversion efficiency.
In one embodiment of the present invention, the PERC solar cell is a single crystal PERC solar cell or a polycrystalline PERC solar cell.
In one embodiment of the present invention, the PERC solar cell can be prepared by the following steps:
obtaining a PERC solar cell silicon wafer through texturing, diffusion, back polishing, etching and impurity removal of glass, back deposition of a passivation layer and front deposition of an antireflection layer;
and printing back silver paste and back field aluminum paste on the backlight surface of the silicon wafer in a screen printing mode, drying the front silver paste on the front surface of the silicon wafer by screen printing, putting the front silver paste into a tunnel furnace, drying at 150-200 ℃, and heating and sintering (forming a silicon oxide protective layer at 230-380 ℃, heating to 600-800 ℃ for sintering, wherein the peak sintering time is 1-3 s) to obtain the solar cell.
The front fine grid electrode silver paste and the back surface field aluminum paste are conventional pastes in the field and are not particularly limited. The back silver paste is the conductive silver paste of the invention, and the front main gate electrode is formed by the conductive silver paste of the invention.
After the conductive silver paste is printed on the surface of a battery through screen printing, drying is carried out, a solvent, a low molecular weight resin and the like are volatilized, an organic silicon compound generates a silicon oxide protective layer during low-temperature sintering, a protective layer can be formed on a silicon-based passivation layer, glass powder is dissolved along with further increase of temperature and is sintered with silver powder, the silicon oxide protective layer can effectively protect the passivation layer, the passivation layer is prevented from being burnt through, and meanwhile, better bonding force can be formed between the silicon oxide protective layer and a silicon wafer.
The conductive silver paste can be on a passivation layer (SiNx or Al) during silver paste sintering by adding the organic silicon compound2O3) A silicon oxide protective layer is formed on the silicon substrate to protect the passivation layer from being burnt through by silver paste; on the other hand, the adhesion between the sintered silver electrode and the silicon substrate can be enhanced, the welding tension is improved, and the photoelectric conversion efficiency is further improved.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
PERC refers to a Passivated Emitter region and a Passivated back surface battery (Passivated Emitter reactor Contact), and is a passivation layer made of aluminum oxide and silicon nitride on the back surface of a conventional battery. Impurities and defects in the silicon wafer and on the surface of the silicon wafer can cause negative influence on the performance of the solar cell, and the passivation process is to reduce the influence caused by the defects by reducing the recombination of surface carriers, so that the efficiency of the cell is ensured.
The positive electrode comprises a thin grid line arranged on the light receiving surface of the silicon wafer and a main grid line arranged above the thin grid line.
Examples
The embodiment provides a conductive silver paste, which is prepared through the following steps.
Preparing a glass powder composition: mixing raw materials (45 parts of bismuth oxide, 18 parts of silicon oxide, 20 parts of aluminum oxide, 15 parts of boron oxide, 2 parts of sodium oxide, potassium oxide, magnesium oxide, barium oxide and zinc oxide), and then carrying out melting, quenching, grinding and water washing processes to obtain a glass powder composition;
preparing an organic carrier: mixing a solvent (75 parts of butyl carbitol acetate), cellulose resin (10 parts of ethyl cellulose) and an additive (4 parts of oleic acid, 3 parts of polypropylene glycol and 8 parts of polyamide wax) to obtain an organic carrier;
preparing conductive silver paste, mixing silver powder, glass powder, an organic carrier and an organic silicon compound,
or mixing the conductive silver paste base material with the raw materials of the organic carrier during the preparation of the organic carrier, and then mixing the conductive silver paste base material with other raw materials of the conductive silver paste base material; the specific raw material compositions are shown in table 1;
stirring uniformly, transferring to a three-roll machine for grinding for 1-3 hours, controlling the fineness to be less than or equal to 10 mu m and the viscosity to be 30-100 Pa.S, and obtaining the conductive silver paste.
TABLE 1
The embodiment also provides a PERC solar cell, which can be prepared by the following steps:
obtaining a PERC solar cell silicon wafer through texturing, diffusion, back polishing, etching and impurity removal of glass, back deposition of a passivation layer and front deposition of an antireflection layer;
printing back silver paste and back field aluminum paste on the backlight surface of the silicon wafer in a screen printing mode, after drying, performing screen printing on front silver paste on the front surface of the silicon wafer, putting the front silver paste into a tunnel furnace, drying at 150-200 ℃, and performing heating sintering (forming a silicon oxide protective layer at 230-380 ℃, heating to 600-950 ℃ for sintering, wherein the peak sintering time is 1-3 s), so as to obtain the solar cell;
the front fine grid electrode silver paste and the back surface field aluminum paste are conventional pastes in the field and are not particularly limited. The back silver paste is the conductive silver paste of the present embodiment, and the front main gate electrode is formed by the conductive silver paste of the present embodiment.
The solar cell was subjected to performance tests, and the test results are shown in table 2.
Wherein, the electrical property of the solar cell is tested by using a solar simulation electrical efficiency tester under standard conditions (AM1.5, 1000W/m)2，25℃)。
The tensile force testing steps are as follows:
printing conductive silver paste on the back surface of a semi-finished solar cell, sintering, welding a back electrode by using a copper-tin welding strip, and carrying out a 180-degree stripping test to obtain a tensile test result; and (3) placing the welded battery piece into a 150-degree oven for 2h, taking out the battery piece, and testing to obtain a tensile force test result after aging.
TABLE 2
The above embodiments illustrate that the conductive silver paste of the present invention can improve the adhesion with a silicon substrate without damaging a passivation layer, has good aging resistance, and can improve the photoelectric conversion efficiency of a solar cell.
Claims (8)
1. The PERC solar cell comprises the following raw materials in percentage by weight: the conductive silver paste comprises a conductive silver paste base material and an organic silicon compound, wherein the conductive silver paste base material comprises silver powder, glass powder and an organic carrier; the content of the organic silicon compound is 0.1-5 parts by weight based on the weight of silicon dioxide obtained by decomposing the organic silicon compound, and the total mass of the conductive silver paste is 100 parts by weight, wherein the organic silicon compound is used for forming nano silicon oxide on the surface of a battery passivation layer; the molecular weight of the organosilicon compound is 1500-25000;
the organic silicon compound is siloxane resin and/or polysilane;
when the PERC solar cell is prepared, the silver paste on the back side is printed in a screen printing mode, nano silicon oxide is formed at 230-380 ℃, the temperature is increased to 600-800 ℃ for sintering, and the peak sintering time is 1-3 s, so that the PERC solar cell is obtained.
2. The PERC solar cell of claim 1, wherein said silicone resin is a silicone resin having an alkyl, aryl, or aralkyl group.
3. The PERC solar cell of claim 2, wherein said alkyl group is a methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl group.
4. The PERC solar cell of claim 2, wherein said aryl group is phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl, or pyrenyl.
5. The PERC solar cell of claim 2, wherein said aralkyl is benzyl or phenethyl.
6. The PERC solar cell of claim 1, wherein said polysilane is a polysilane having silanol or alkoxy groups.
7. The PERC solar cell of claim 1, wherein the conductive silver paste binder comprises 30 to 85 parts by weight of silver powder, 1 to 5 parts by weight of glass frit, and 10 to 50 parts by weight of organic vehicle, based on 100 parts by weight of the total mass of the conductive silver paste.
8. The PERC solar cell of claim 1, wherein said back side silver paste preparation method comprises the steps of:
the method comprises the following steps: mixing silver powder, glass powder, an organic carrier and the organic silicon compound, and uniformly stirring;
alternatively, the first and second electrodes may be,
adding an organic silicon compound during the preparation of the organic carrier, stirring, then mixing with silver powder and glass powder, and stirring uniformly;
step two: grinding for 1-3 h, and filtering to obtain conductive silver paste with fineness less than or equal to 10 μm and viscosity of 30-100 Pa.S.
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| CN103531658A (en) * | 2013-09-25 | 2014-01-22 | 北京七星华创电子股份有限公司 | Atomic layer deposition preparation method for aluminum oxide thin film |
| WO2018175167A1 (en) * | 2017-03-24 | 2018-09-27 | Heraeus Precious Metals North America Conshohocken Llc | Poly-siloxane containing organic vehicle for electroconductive pastes for perc solar cells |
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| CN1400610A (en) * | 2002-09-02 | 2003-03-05 | 广东风华高新科技集团有限公司 | Conducting slurry material |
| CN103531658A (en) * | 2013-09-25 | 2014-01-22 | 北京七星华创电子股份有限公司 | Atomic layer deposition preparation method for aluminum oxide thin film |
| WO2018175167A1 (en) * | 2017-03-24 | 2018-09-27 | Heraeus Precious Metals North America Conshohocken Llc | Poly-siloxane containing organic vehicle for electroconductive pastes for perc solar cells |
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