CN116332518A - Glass powder composition, glass powder, conductive silver paste and solar cell - Google Patents
Glass powder composition, glass powder, conductive silver paste and solar cell Download PDFInfo
- Publication number
- CN116332518A CN116332518A CN202111589514.1A CN202111589514A CN116332518A CN 116332518 A CN116332518 A CN 116332518A CN 202111589514 A CN202111589514 A CN 202111589514A CN 116332518 A CN116332518 A CN 116332518A
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- CN
- China
- Prior art keywords
- glass frit
- silver paste
- conductive silver
- glass
- solar cell
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 97
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000843 powder Substances 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000002161 passivation Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 238000009792 diffusion process Methods 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- -1 fatty acid amine Chemical class 0.000 claims description 17
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000007639 printing Methods 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910004205 SiNX Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000003906 humectant Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000013008 thixotropic agent Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010344 co-firing Methods 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005323 carbonate salts Chemical class 0.000 claims description 2
- 239000012461 cellulose resin Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052752 metalloid Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 238000001816 cooling Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 5
- 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 5
- 229910000831 Steel Inorganic materials 0.000 description 5
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- 239000010959 steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 230000009969 flowable effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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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
- C03C12/00—Powdered glass; Bead compositions
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a glass powder composition, glass powder, conductive silver paste and a solar cell. The glass frit composition contains GeO 1-20wt% 2 20-30wt% of TeO 2 . The invention also provides glass powder, conductive silver paste and a solar cell which are prepared from the glass powder composition. The invention providesFor the glass system Ge-Te, geO 2 Has a low coefficient of thermal expansion while providing free oxygen, and TeO 2 A stable network structure can be formed. Compared with the conventional slurry, the conductive silver slurry containing the Ge-Te glass system has relatively weak corrosion capability and weak corrosion to the passivation layer, so that the passivation layer is less damaged by metal, and the quantity and particle size of glass entering silicon are reduced due to the weak corrosion capability, so that the recombination brought by the conductive slurry is reduced, the open-circuit voltage is improved, and the photoelectric conversion efficiency of the solar cell is further improved.
Description
Technical Field
The invention relates to a glass powder composition, glass powder, conductive silver paste and a solar cell, and belongs to the technical field of solar cells.
Background
Solar cells generate electricity using the photovoltaic effect, with the most central structure being the PN junction. At present, PN junctions of commercial solar cells are formed through diffusion, and in order to further improve the conversion efficiency of the cell, a SE (selective emitter) process is adopted for diffusion, and the SE process is heavily doped under metallization and lightly doped elsewhere. The existing SE technology mainly carries out light doping through diffusion, and then carries out doping treatment on a metalized area by taking PSG formed after diffusion as a doping source through laser. During the manufacture of the solar cell, some antireflection and passivation film layers such as Si are coated on the front surface 3 N 4 ，SiO 2 And the like, the film layers not only can reduce light reflection, but also can passivate the defects on the surface of the silicon wafer, so that the carrier recombination on the surface of the battery is reduced, and the conversion efficiency of the battery is improved. The metallization of solar cells is typically formed by printing a conductive silver paste on the front side, by sintering. In the case of SE process for diffusion, the metal will contact the heavily doped semiconductor, so a good contact resistance is easily formed, and the damage degree of the metal paste to the passivation layer and the effect of the recombination of the metal material itself on the battery performance will be greater.
The contact performance of the conductive paste and silicon and the shape of the thin grid line after printing are mainly considered in the prior conductive paste. The contact resistance and the shading area are reduced as much as possible, so that the short-circuit current and the filling factor of the battery are improved. As disclosed in chinese application 202010371818.X, a glass frit composition and a conductive paste prepared therefrom are disclosed, which have the main effects of reducing contact resistance and improving the morphology of a grid line; chinese application 201910944685.8 discloses a conductive paste that addresses mass-produced fine line printing processes. However, the technical solutions disclosed in the above two patent applications do not consider the influence of glass on the passivation layer and the composite caused by the conductive paste, and do not consider the influence of corrosion of glass on the passivation layer and the metal composite of the paste on the solar cell performance.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a novel glass system and a conductive paste based on the glass system, wherein the conductive paste can be better matched with a diffusion SE process, so that damage to a passivation layer is reduced under the condition of forming good contact resistance, the quantity and the size of metal entering silicon are reduced, the recombination is reduced, and the open-circuit voltage and the conversion efficiency of a solar cell are improved.
To achieve the above object, the present invention provides a glass frit composition, wherein the glass frit composition comprises 1 to 20wt% of GeO 2 20-30wt% of TeO 2 . If the proportion of Ge is too high, the glass is not flowable, is liable to accumulate, and the contact resistance becomes poor. If the Te content is too low, the formed glass network structure is unstable, the content is too high, the glass fluidity is good, and the damage to the passivation layer is large.
According to a specific embodiment of the present invention, preferably, the GeO 2 The content of (C) is 5-15wt%.
According to a specific embodiment of the present invention, preferably, the glass frit composition further comprises WO 3 、Bi 2 O 3 、Li 2 O、ZnO、SnO 2 One or a combination of two or more of CuO, caO, pbO, mgO.
According to a specific embodiment of the present invention, preferably, the glass frit composition further comprises 10 to 15wt% of WO 3 15-20wt% Bi 2 O 3 1-5wt% of Li 2 O, 0-3wt% (preferably 3wt% or less) ZnO, 0-3wt% (preferably 3wt% or less) SnO 2 0-3wt% (preferably 3wt% toThe following) CuO, 0-3wt% (preferably 3wt% or less) CaO, 25% -30% PbO, 0-3wt% (preferably 3wt% or less) MgO.
According to a specific embodiment of the present invention, preferably, the glass frit composition contains GeO in an amount of 5 to 20wt% 2 21-26wt% of TeO 2 WO 11-11.5wt% 3 18-19wt% Bi 2 O 3 2-6wt% of Li 2 O, less than 3wt% of ZnO, less than 3wt% of CuO, and 22-32.5wt% of PbO.
According to a specific embodiment of the present invention, preferably, in the glass frit composition, geO 2 、TeO 2 、WO 3 、Bi 2 O 3 、Li 2 O、ZnO、SnO 2 One or a combination of two or more of CuO, caO, pbO, mgO is replaced by a carbonate salt of a corresponding metallic or metalloid element capable of providing a molar amount, for example: according to WO 3 The mass of (2) is calculated to give the number of moles of W, assuming Xmol, from which Xmol of W (CO 3 ) 3 The mass of (2) is taken as W (CO) 3 ) 3 The amount to be added to the glass frit composition. Wherein "carbonate" includes not only various elements and Carbonate (CO) 3 2- ) Salts formed, also including bicarbonate (acid carbonate), basic carbonate.
The invention also provides glass powder which is prepared from the glass powder composition provided by the invention.
According to a specific embodiment of the present invention, the glass frit may be prepared by the steps of: mixing the glass powder composition, and heating and melting at 750-1000 ℃ for 30-120 min; cooling to obtain fragments; the fragments are further crushed and then ball-milled to obtain the glass powder with the required particle size distribution.
According to a specific embodiment of the present invention, it is preferable that the fineness of the particle diameter of the glass frit composition satisfies D50. Ltoreq.10. Mu.m.
According to a specific embodiment of the present invention, preferably, the glass frit is one or a combination of two or more of amorphous glass frit, crystalline glass frit, partially amorphous glass frit.
The invention also provides conductive silver paste, wherein the conductive silver paste contains 1-4% of glass powder by weight percent, and the glass powder is the glass powder provided by the invention.
According to a specific embodiment of the present invention, preferably, the conductive silver paste further contains silver powder (conductive phase) and an organic carrier; more preferably, the silver powder is contained in an amount of 85 to 92% by weight and the organic vehicle is contained in an amount of 5 to 12% by weight.
According to a specific embodiment of the present invention, preferably, the silver powder has a particle diameter of 1 to 5 μm and a tap density of 5 to 9g/cm 2 。
According to a specific embodiment of the present invention, in the conductive silver paste: the glass powder is mainly used for wetting silver powder, corroding a passivation layer and bonding silver silicon in the sintering process, and has a main influence on the contact resistance of the conductive silver paste and the battery; silver powder is used as a conductive phase and mainly plays a role in conduction, and is used for collecting photo-generated carriers after sintering; the organic carrier is mainly used for dispersing silver powder, so that the slurry has good rheological property and can be well subjected to screen printing.
According to a specific embodiment of the present invention, preferably, the silver powder is a surface-treated silver powder, and the dispersion stability of the silver powder in the conductive silver paste can be improved by modification; more preferably, the modifier used for the surface treatment of the silver powder comprises one or more of oleic acid, linoleic acid, linolenic acid, a silane coupling agent, hard fatty acid, fatty acid amine, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether, a block macromolecular surfactant and the like. The surface treatment for the silver powder may be performed in a conventional manner in the art.
According to a specific embodiment of the present invention, preferably, the organic carrier includes a resin, an organic solvent and an auxiliary agent, and the addition amounts of the three are 1-20%, 75-95% and 0.1-4%, respectively.
According to a specific embodiment of the present invention, preferably, the resin is one or a combination of two or more of a cellulose resin, an epoxy resin, and an acrylic resin.
According to a specific embodiment of the present invention, preferably, the organic solvent is one or a combination of two or more of terpineol, butyl carbitol acetate, and dodecanol ester.
According to a specific embodiment of the present invention, preferably, the auxiliary agent includes one or a combination of two or more of a dispersant, a thixotropic agent, a lubricant, a humectant and a plasticizer. Wherein the dispersant is preferably a macromolecular dispersant such as polyether, polyester, polyamide or polysilicone; the lubricant is preferably surfactant and/or silicone oil; the thixotropic agent is preferably one or more than two of hydrogenated castor oil, polyamide, fumed silica and the like; the humectant is preferably one or more of diethylene glycol, triethylene glycol, PEG400, glycerol, ethylene glycol, sorbitol, 1, 2-propylene glycol, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone, condensate of polyalcohol and ethylene oxide, xylitol, etc.; the plasticizer is preferably one or more of aliphatic dibasic acid ester, phthalic acid ester, terephthalic acid ester, benzene polyacid ester, benzoate, polyol ester epoxy, citric acid ester, polyester and the like.
According to a specific embodiment of the present invention, it is preferable that the average blade fineness of the conductive silver paste is 10 μm or less, more preferably 5 μm or less.
The conductive silver paste can be prepared by the following steps:
1) Preparation of organic vehicle body: mixing resin and organic solvent in proportion, and stirring at room temperature or under heating;
2) And (3) preparing slurry: mixing silver powder, glass powder composition and organic carrier, stirring, and grinding and dispersing with a three-roller machine to obtain conductive silver paste with average scraper fineness below 10 μm, preferably below 5 μm.
In the preparation process of the conductive silver paste, the auxiliary agent can be added in the step 1) of preparing the organic carrier, can also be added in the step 2) of preparing the paste, or can be added in part in the step 1) and in part in the step 2).
The invention also provides a solar cell, wherein the front electrode of the solar cell is made of the conductive silver paste containing the glass powder composition and/or the conductive silver paste provided by the invention. More preferably, the solar cell is a solar cell manufactured by a SE process.
The invention also provides a preparation method of the solar cell, which is an SE process and comprises the following steps:
firstly, preparing an anti-reflection suede on one side surface of a silicon substrate, for example, corroding by using alkali solution or acid solution to form a pyramid-shaped (single crystal) or rugged (polycrystal) anti-reflection suede;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, forming the N-type diffusion layer (preferably using phosphorus oxychloride as a diffusion source) by adopting a gas phase thermal diffusion method, doping the N-type diffusion layer by laser SE (selective laser) to ensure that the diffused sheet resistance is 120-160 omega/sq, and removing phosphorus at the edge, such as wet etching or dry etching, from the heavily doped region after laser SE doping to ensure that the sheet resistance is 60-100 omega/sq;
thirdly, performing thermal diffusion on the N surface to form SiO 2 Then plating a SiNx antireflection layer (or similar other coating with good antireflection and passivation effects) on the P surface 2 O 3 And a passivation layer of SiNx, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
and fourthly, forming a vertical and horizontal main grid and a fine grid on the anti-reflection film on one side of the N-type silicon substrate by using conductive silver paste in a screen printing mode, printing a back electrode and an aluminum back field on one side of the P-type silicon substrate, and co-firing at a sintering temperature of 700-900 ℃ to form an electrode body.
The glass powder composition and silver paste formed by the glass powder composition can be used in a solar cell of SE technology.
The invention provides a Ge-Te glass system, geO 2 Has a low coefficient of thermal expansion while providing free oxygen, and TeO 2 A stable network structure can be formed. Compared with the conventional sizing agent, the conductive material containing the Ge-Te glass system of the inventionThe corrosion capability of the silver paste is relatively weak, and the corrosion to the passivation layer is weak, so that the damage of metal to the passivation layer is small, and meanwhile, the quantity and particle size of glass entering silicon are small due to the weak corrosion capability (as shown in fig. 1 and a comparison group as shown in fig. 2), so that the recombination brought by the conductive paste is reduced, the open-circuit voltage is improved, and the photoelectric conversion efficiency of the solar cell is further improved.
Drawings
Fig. 1 is a scanning electron microscope image of a solar cell electrode and silicon interface made of the conductive paste of example 1.
Fig. 2 is a scanning electron microscope image at the interface of the solar cell electrode and silicon fabricated with the conductive paste of comparative example 1.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a conductive paste for solar energy, which comprises 89.2 parts of silver powder, 2.4 parts of glass powder and 8.4 parts of organic carrier according to 100 parts of total weight.
Wherein, the glass powder comprises the following components in percentage by weight: geO (GeO) 2 5％、TeO 2 26％、Bi 2 O 3 19％、Li 2 CO 3 6％、WO 3 11.5%, cuO 0.5%, znO 2% and PbO 30%. The glass powder is prepared by the following steps: mixing the raw materials, heating in a muffle furnace at 900-1100 ℃ for 45-90 min, quenching with water, cooling with a steel plate to obtain glass powder composition fragments, further crushing the fragments, and ball milling with a planetary ball mill to obtain the required particle size distribution (D50:0.1-5 μm).
The organic carrier comprises 78% of solvent, 20% of resin and 2% of auxiliary agent in percentage by weight, wherein the solvent is prepared from the following components in percentage by weight: 4:1, butyl carbitol acetate and dodecyl ester, wherein the mass ratio of the resin is 1:4, the mass ratio of the auxiliary agent to the mixture of the ethyl cellulose and the acrylic acid is 1:5, hydrogenated castor oil and silicone oil. The organic carrier is prepared by the following steps: adding resin into solvent, stirring thoroughly under heating condition of 70-100deg.C, adding adjuvant after resin is completely dissolved, and obtaining organic carrier.
Silver powder requires particle size: 1-5 μm (D50), tap density: 5-9g/cm 3 。
The conductive paste is prepared according to the following steps: mixing the silver powder, the glass powder and the organic powder, uniformly stirring, and carrying out three-roller grinding and dispersing to obtain the conductive paste, wherein the average scraping plate fineness is less than 5 mu m.
Example 2
The embodiment provides a conductive paste for solar energy, which comprises 89.2 parts of silver powder, 2.4 parts of glass powder and 8.4 parts of organic carrier according to 100 parts of total weight.
Wherein, the glass powder comprises the following components in percentage by weight: geO (GeO) 2 10％、TeO 2 23％、Bi 2 O 3 19％、Li 2 CO 3 6％、WO 3 11.5%, cuO 0.5%, znO 1.5% and PbO 28.5%. The glass powder is prepared by the following steps: mixing the raw materials, heating in a muffle furnace at 900-1100 ℃ for 45-90 min, quenching with water, cooling with a steel plate to obtain glass powder composition fragments, further crushing the fragments, and ball milling with a planetary ball mill to obtain the required particle size distribution (D50:0.1-5 μm).
The organic carrier comprises 78% of solvent, 20% of resin and 2% of auxiliary agent in percentage by weight, wherein the solvent is prepared from the following components in percentage by weight: 4:1, butyl carbitol acetate and dodecyl ester, wherein the mass ratio of the resin is 1:4, the mass ratio of the auxiliary agent to the mixture of the ethyl cellulose and the acrylic acid is 1:5, hydrogenated castor oil and silicone oil. The organic carrier is prepared by the following steps: adding resin into solvent, stirring thoroughly under heating condition of 70-100deg.C, adding adjuvant after resin is completely dissolved, and obtaining organic carrier.
Silver powder requires particle size: 1-5 μm (D50)Tap density: 5-9g/cm 3 。
The conductive paste is prepared according to the following steps: mixing the silver powder, the glass powder and the organic powder, uniformly stirring, and carrying out three-roller grinding and dispersing to obtain the conductive paste, wherein the average scraping plate fineness is less than 5 mu m.
Example 3
The embodiment provides a conductive paste for solar energy, which comprises 89.2 parts of silver powder, 2.4 parts of glass powder and 8.4 parts of organic carrier according to 100 parts of total weight.
Wherein, the glass powder comprises the following components in percentage by weight: geO (GeO) 2 15％、TeO 2 22％、Bi 2 O 3 18％、Li 2 CO 3 6％、WO 3 11%, cuO 0.5%, znO 1.5% and PbO 26%. The glass powder is prepared by the following steps: mixing the raw materials, heating in a muffle furnace at 900-1100 ℃ for 45-90 min, quenching with water, cooling with a steel plate to obtain glass powder composition fragments, further crushing the fragments, and ball milling with a planetary ball mill to obtain the required particle size distribution (D50:0.1-5 μm).
The organic carrier comprises 78% of solvent, 20% of resin and 2% of auxiliary agent in percentage by weight, wherein the solvent is prepared from the following components in percentage by weight: 4:1, butyl carbitol acetate and dodecyl ester, wherein the mass ratio of the resin is 1:4, the mass ratio of the auxiliary agent to the mixture of the ethyl cellulose and the acrylic acid is 1:5, hydrogenated castor oil and silicone oil. The organic carrier is prepared by the following steps: adding resin into solvent, stirring thoroughly under heating condition of 70-100deg.C, adding adjuvant after resin is completely dissolved, and obtaining organic carrier.
Silver powder requires particle size: 1-5 μm (D50), tap density: 5-9g/cm 3 。
The conductive paste is prepared according to the following steps: mixing the silver powder, the glass powder and the organic powder, uniformly stirring, and carrying out three-roller grinding and dispersing to obtain the conductive paste, wherein the average scraping plate fineness is less than 5 mu m.
Example 4
The embodiment provides a conductive paste for solar energy, which comprises 89.2 parts of silver powder, 2.4 parts of glass powder and 8.4 parts of organic carrier according to 100 parts of total weight.
Wherein, the glass powder comprises the following components in percentage by weight: geO (GeO) 2 18％、TeO 2 21％、Bi 2 O 3 18％、Li 2 CO 3 5％、WO 3 11%, cuO 0.5%, znO 1.5% and PbO 25%. The glass powder is prepared by the following steps: mixing the raw materials, heating in a muffle furnace at 900-1100 ℃ for 45-90 min, quenching with water, cooling with a steel plate to obtain glass powder composition fragments, further crushing the fragments, and ball milling with a planetary ball mill to obtain the required particle size distribution (D50:0.1-5 μm).
The organic carrier comprises 78% of solvent, 20% of resin and 2% of auxiliary agent in percentage by weight, wherein the solvent is prepared from the following components in percentage by weight: 4:1, butyl carbitol acetate and dodecyl ester, wherein the mass ratio of the resin is 1:4, the mass ratio of the auxiliary agent to the mixture of the ethyl cellulose and the acrylic acid is 1:5, hydrogenated castor oil and silicone oil. The organic carrier is prepared by the following steps: adding resin into solvent, stirring thoroughly under heating condition of 70-100deg.C, adding adjuvant after resin is completely dissolved, and obtaining organic carrier.
Silver powder requires particle size: 1-5 μm (D50), tap density: 5-9g/cm 3 。
The conductive paste is prepared according to the following steps: mixing the silver powder, the glass powder and the organic powder, uniformly stirring, and carrying out three-roller grinding and dispersing to obtain the conductive paste, wherein the average scraping plate fineness is less than 5 mu m.
Comparative example 1
The comparative example 1 provides a conductive silver paste as a control group, using a Pb-Te-Si glass system, comprising 89.2 parts of silver powder, 2.4 parts of glass frit, and 8.4 parts of an organic vehicle, based on 100 parts by weight of the total weight.
Wherein, the glass powder comprises the following components in percentage by weight: pbO 30%, teO 2 40％、SiO 2 9％、Bi 2 O 3 7％、Li 2 O 11％、Na 2 O3%. The glass powder is prepared by the following steps: mixing the raw materials, heating in a muffle furnace at 900-1100 ℃ for 45-90 min, quenching with water, cooling with a steel plate to obtain glass powder composition fragments, further crushing the fragments, and ball milling with a planetary ball mill to obtain the required particle size distribution (D50:0.1-5 μm).
The organic carrier comprises 78% of solvent, 20% of resin and 2% of auxiliary agent in percentage by weight, wherein the solvent is a mixture of terpineol, butyl carbitol acetate and dodecanol ester in a mass ratio of 1:4:1, the resin is a mixture of ethyl cellulose and acrylic acid in a mass ratio of 1:4, and the auxiliary agent is a mixture of hydrogenated castor oil and silicone oil in a mass ratio of 1:5. The organic carrier is prepared by the following steps: adding resin into solvent, stirring thoroughly under heating condition of 70-100deg.C, adding adjuvant after resin is completely dissolved, and obtaining organic carrier.
Silver powder requires particle size: 1-5 μm (D50), tap density: 5-9g/cm 3 。
The conductive paste is prepared according to the following steps: mixing the silver powder, the glass powder and the organic powder, uniformly stirring, and carrying out three-roller grinding and dispersing to obtain the conductive paste, wherein the average scraping plate fineness is less than 5 mu m.
Example 5
The embodiment provides a solar cell, which is prepared by the following steps:
the semiconductor substrate is a P-type silicon substrate doped with boron or gallium, the P-type silicon substrate is a silicon wafer with the thickness of 150-200 mu m and the side length of 156-210 mm;
etching one side of a silicon substrate by using alkali solution or acid solution to prepare pyramid (single crystal) or rugged (polycrystal) anti-reflection suede;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, wherein the N-type diffusion layer can be a gas-phase thermal diffusion method by taking phosphorus oxychloride as a diffusion source, the diffused sheet resistance is 120-170 omega/sq, then doping the N-type diffusion layer by laser SE, the sheet resistance of a heavily doped region after laser is 70-110 omega/sq, and removing the phosphorus at the edge by wet etching or dry etching;
thirdly, performing thermal diffusion on the N surface to form a layer of SiO 2 Then plating a SiNx antireflection layer, or similar other coating with good antireflection and passivation effects, plating Al on the P surface 2 O 3 And a passivation layer of SiNx, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
and fourthly, forming a vertical and horizontal main grid and a fine grid on the anti-reflection film on one side of the N-type silicon substrate by using conductive silver paste in a screen printing mode, printing a back electrode and an aluminum back field on one side of the P-type silicon substrate, and co-firing at a sintering temperature of 700-900 ℃ to form an electrode body.
The electrical performance test is carried out on the solar cell, specifically: test under standard conditions (atmospheric quality AM 1.5, illumination intensity 1000W/m using a solar simulated electrical efficiency tester 2 Test temperature 25 ℃).
The open circuit voltage and conversion efficiency of the solar cell prepared with the above conductive paste were measured by an electrical property test as shown in table 1 below:
TABLE 1
| Uoc(mV) | Efficiency of | |
| Example 1 | 689.5 | 23.14％ |
| Example 2 | 689.3 | 23.12％ |
| Example 3 | 689.8 | 23.17％ |
| Example 4 | 689.2 | 23.12％ |
| Comparative example 1 | 685.2 | 22.87％ |
From the data, the glass system of Ge-Te has weak corrosion capability to the passivation layer, reduces damage to the passivation layer, reduces the quantity and size of metal entering silicon, reduces the recombination brought by the metal in the slurry, has good open-circuit voltage and battery conversion efficiency, and improves the product competitiveness of the corresponding solar cell.
Claims (13)
1. A glass frit composition, wherein the glass frit composition comprises 1-20wt% of GeO 2 20-30wt% of TeO 2 。
2. The glass frit composition of claim 1, wherein the GeO 2 The content of (C) is 5-15wt%.
3. The glass frit composition according to claim 1 or 2, wherein the glass frit composition further comprises 10-15wt% of WO 3 15-20wt% Bi 2 O 3 1-5wt% of Li 2 O, 0-3wt% (preferably 3wt% or less) ZnO, 0-3wt% (preferably 3wt% or less) SnO 2 0-3wt% (preferably less than 3 wt%) of CuO, 0-3wt% (preferably less than 3 wt%) of CaO, 25-30wt% of PbO, 0-3wt% (preferably less than 3 wt%) ofOne or a combination of two or more of the following) MgO.
4. A glass frit composition according to any of claims 1 to 3, wherein the glass frit composition comprises 5 to 20wt% GeO 2 21-26wt% of TeO 2 WO 11-11.5wt% 3 18-19wt% Bi 2 O 3 1-5wt% of Li 2 O, less than 3wt% of ZnO, less than 3wt% of CuO, and 22-32.5wt% of PbO.
5. The glass frit composition of any of claims 1-4, wherein the GeO 2 、TeO 2 、WO 3 、Bi 2 O 3 、Li 2 O、ZnO、SnO 2 One or a combination of two or more of CuO, caO, pbO, mgO is replaced by a carbonate salt of a corresponding metal element or metalloid element capable of providing the same molar amount.
6. A glass frit made from the glass frit composition of any of claims 1-5;
preferably, the fineness of the particle diameter of the glass frit composition satisfies D50. Ltoreq.10 μm;
more preferably, the glass frit is one or a combination of two or more of an amorphous glass frit composition, a crystalline glass frit composition, a partially crystalline glass frit composition, and a partially amorphous glass frit composition.
7. A conductive silver paste, wherein the conductive silver paste contains 1% -4% by weight of glass powder, and the glass powder is the glass powder of claim 6.
8. The conductive silver paste of claim 7, wherein the conductive silver paste further comprises silver powder and an organic carrier; preferably, the silver powder is 85-92% by weight, and the organic carrier is 5-12% by weight;
preferably, the silver powder has a particle diameter of 1-5 μm,Tap density of 5-9g/cm 2 。
9. The conductive silver paste of claim 8, wherein the silver powder is a surface-treated silver powder;
preferably, the modifier used for the surface treatment of the silver powder comprises one or more than two of oleic acid, linoleic acid, linolenic acid, silane coupling agent, hard fatty acid, fatty acid amine, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether and block macromolecular surfactant.
10. The conductive silver paste according to any one of claims 7 to 9, wherein the organic carrier comprises resin, an organic solvent and an auxiliary agent, and the addition amounts of the three are 1 to 20%, 75 to 95% and 0.1 to 4%, respectively;
preferably, the resin is one or a combination of more than two of cellulose resin, epoxy resin and acrylic resin;
preferably, the organic solvent is one or a combination of more than two of terpineol, butyl carbitol acetate and dodecanol ester;
preferably, the auxiliary agent comprises one or a combination of more than two of dispersing agent, thixotropic agent, lubricant, humectant and plasticizer;
more preferably, the dispersant is a macromolecular dispersant, such as a polyether, polyester, polyamide or polysilicone; the lubricant is surfactant and/or silicone oil; the thixotropic agent is one or the combination of more than two of hydrogenated castor oil, polyamide and fumed silica; the humectant is one or more than two of diethylene glycol, triethylene glycol, PEG400, glycerol, ethylene glycol, sorbitol, 1, 2-propylene glycol, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone, condensate of polyalcohol and ethylene oxide and xylitol; the plasticizer is one or more than two of aliphatic dibasic acid ester, phthalic acid ester, terephthalic acid ester, benzene polyacid ester, benzoate, polyol ester epoxy, citric acid ester and polyester.
11. The conductive silver paste according to claim 10, wherein the conductive silver paste has an average blade fineness of 10 μm or less, preferably 5 μm or less.
12. A solar cell, wherein the front electrode of the solar cell is made of the conductive silver paste comprising the glass frit of claim 6 and/or the conductive silver paste of any one of claims 7 to 11; preferably, the solar cell is a solar cell manufactured by a SE process.
13. The method for manufacturing a solar cell according to claim 12, comprising the steps of:
firstly, manufacturing an antireflection suede on one side surface of a silicon substrate;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, forming the N-type diffusion layer by adopting a gas phase thermal diffusion method, doping the N-type diffusion layer by laser SE, enabling the sheet resistance of a heavily doped region after laser SE to be 60-100 ohm/sq, and removing phosphorus at the edge;
thirdly, performing thermal diffusion on the N surface to form SiO 2 Then plating a SiNx antireflection layer, plating Al on the P surface 2 O 3 And a passivation layer of SiNx, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
and fourthly, forming a vertical and horizontal main grid and a fine grid on the anti-reflection film on one side of the N-type silicon substrate by using conductive silver paste in a screen printing mode, printing a back electrode and an aluminum back field on one side of the P-type silicon substrate, and co-firing at a sintering temperature of 700-900 ℃ to form an electrode body.
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