CN102365688A - Metal pastes and use thereof in the production of silicon solar cells - Google Patents
Metal pastes and use thereof in the production of silicon solar cells Download PDFInfo
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- CN102365688A CN102365688A CN2010800158640A CN201080015864A CN102365688A CN 102365688 A CN102365688 A CN 102365688A CN 2010800158640 A CN2010800158640 A CN 2010800158640A CN 201080015864 A CN201080015864 A CN 201080015864A CN 102365688 A CN102365688 A CN 102365688A
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- Prior art keywords
- metal paste
- weight
- arc layer
- silicon chip
- silver
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 82
- 239000002184 metal Substances 0.000 title claims abstract description 82
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 56
- 229910052710 silicon Inorganic materials 0.000 title claims description 56
- 239000010703 silicon Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 238000007639 printing Methods 0.000 claims description 14
- 239000005308 flint glass Substances 0.000 claims description 13
- 238000007650 screen-printing Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 239000002002 slurry Substances 0.000 description 23
- 239000004411 aluminium Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008521 reorganization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-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
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 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
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 alcohol ester Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood 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
- H01B1/14—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
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
-
- 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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- 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
- C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Sustainable Development (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Metal pastes comprising (a) at least one electrically conductive metal powder selected from the group consisting of silver, copper and nickel, (b) at least one lead-containing glass frit with a softening point temperature in the range of 571 to 636 DEG C and containing 53 to 57 wt.-% of PbO, 25 to 29 wt.-% of SiO2, 2 to 6 wt.-% of Al2O3 and 6 to 9 wt.-% of B2O3 and (c) an organic vehicle.
Description
Invention field
The present invention relates to metal paste and the purposes in silicon solar cell is produced thereof.
Background of invention
The conventional solar battery structure with p type substrate has front or the negative pole on the plane of illumination that is usually located at battery and is positioned at the positive pole on the back side.As everyone knows, serve as the extra power that in this semiconductor, produces electron-hole pair in the radiation of the suitable wavelength of incident on the semi-conductive p-n junction.There is electrical potential difference in the place at p-n junction, and this causes hole and electronics to stride across this knot with opposite direction moving, thereby produces the electric current that can transmit electric power to external circuit.Most of solar cell is metallized silicon chip form,, has the hard contact of conduction that is.
Used solar power generation cell is silicon solar cell mostly at present.Specifically, electrode is prepared by metal paste through using the method such as silk screen printing.
The production of silicon solar cell begins from the p type silicon substrate of silicon chip form usually, and the thermal diffusion through phosphorus (P) etc. forms reverse conductance n type diffusion layer on substrate then.Usually with phosphorous oxychloride (POCl
3) as the gaseous state phosphorous diffusion source, other fluid supplies are phosphoric acid etc.Having no under the situation of concrete modification, diffusion layer forms on the whole surface of silicon substrate.At the position that forms p-n junction, the concentration of p type dopant equals the concentration of n type dopant; The conventional batteries that has near the p-n junction of plane of illumination has the junction depth between 0.05 and 0.5 μ m.
After having formed this diffusion layer, unnecessary watch crystal is removed from the remainder on surface through carrying out etching with certain acid such as hydrofluoric acid.
Then through forming the TiO of thickness between 0.05 and 0.1 μ m on the n type diffusion layer such as plasma CVD methods such as (chemical vapour deposition (CVD)s)
x, SiO
x, TiO
x/ SiO
x, or SiN specifically
xOr Si
3N
4ARC layer (ARC).
The conventional solar battery structure with p type substrate has the negative grid electrode that is positioned on battery front side or the plane of illumination usually and is positioned at the positive pole on the back side.Usually apply gate electrode through silk screen printing on the ARC of battery front side layer and dry front side silver paste (forming the silver slurry of front electrode).Usually carry out silk screen printing with so-called H pattern frontal gate electrode, said H pattern comprises (i) thin parallel fingers (gatherer line) and two buses that (ii) intersect with right angle and fingers.In addition, back silver slurry or silver/aluminium paste and aluminium paste silk screen printing (or certain other application processes) on the back side of substrate, and are carried out drying successively.Usually at first back silver slurry or silver/aluminium paste are screen-printed on the silicon chip back, form two parallel buses or form rectangle (lug), be used for solder interconnections line (copper strips that prewelding connects).Then aluminium paste is printed onto in the exposed region, overlapping slightly with back silver or silver/aluminium.In some cases, after having printed aluminium paste, carry out the printing of silver slurry or silver/aluminium paste.Usually in band oven, carry out roasting then, continue 1 to 5 minute time, make silicon chip reach 700 to 900 ℃ of peak temperatures in the scope.Positive gate electrode and backplate be roasting or roasting simultaneously in order.
Usually the aluminium paste silk screen printing is also dry on silicon chip back.With silicon chip at the roasting temperature that is higher than the aluminium fusing point to form the aluminium silicon melt, during cooling stage, form the epitaxially grown silicon layer that is mixed with aluminium subsequently.This layer is commonly referred to back of the body surface field (BSF) layer.Aluminium paste is converted into the aluminium backplate through roasting from drying regime.Simultaneously, back silver slurry or silver/aluminium paste roasting are become silver or silver/aluminium backplate.During roasting, the border between back side aluminium and back silver or the silver/aluminium presents alloy state, and realizes being electrically connected.The aluminium electrode accounts for most zones of backplate, and part is owing to the needs that form the p+ layer.Part overleaf (usually as 2 to 6mm wide buses) goes up and forms silver or silver/aluminium backplate, with as the electrode that is used for waiting through the copper strips that prewelding connects interconnect solar cells.In addition, in roasting process, pass the ARC layer as the front side silver paste sintering and the infiltration of positive gate electrode printing, thereby can be electrically connected with n type layer.This process is commonly referred to " grilling thoroughly ".
WO 92/22928 discloses a kind of method, and wherein positive gate electrode is through the printing of two steps; The printing of fingers and the printing of bus are separately carried out.Yet fingers is formed by the silver slurry printing that can grill thoroughly the ARC coating, and the silver slurry that is used for printed busbar but is not quite similar.The silver slurry that is used for printed busbar does not have the ability of grilling thoroughly.Obtain after the roasting by grilling thoroughly the gate electrode that fingers and so-called contactless bus (bus of floating, the bus of insufficient burnt ARC layer) are formed.The advantage that the gate electrode that fingers grilled thoroughly is only arranged is that it has reduced hole and electronics in metal/semiconductor reorganization at the interface.The minimizing of reorganization causes open circuit voltage to increase, thereby improves the electricity productioin of the silicon solar cell with this type of positive gate electrode.
Be desirable to provide the ability of grilling thoroughly a little less than having or even do not grill thoroughly the thick film conductive composition of ability; Said composition can generate the bus that does not contact or have only few contact with silicon substrate, said bus have improvement soldering resistance and with the silicon solar cell front on the good adhesion of ARC layer.Good adhesiveness means that silicon solar cell has long durability or useful life.
Summary of the invention
The present invention relates to thick film conductive composition; It comprises (a) at least a conductive metal powder that is selected from silver, copper and mickel; (b) at least a flint glass material; This frit has the softening point temperature (glass transition temperature is measured under the heating rate of 10K/min through differential thermal analysis DTA) in 571 to 636 ℃ of scopes, and contains the PbO of 53 to 57 weight %, the SiO of 25 to 29 weight %
2, 2 to 6 weight % Al
2O
3B with 6 to 9 weight %
2O
3, and (c) organic carrier.
Detailed Description Of The Invention
Thick film conductive composition of the present invention shows as can be through printing, the metal paste form of using through silk screen printing specifically.In following description and claims, thick film conductive composition is also referred to as " metal paste ".
Metal paste of the present invention comprises at least a conductive metal powder that is selected from silver, copper and mickel.Silver powder preferably.Metal dust or silver powder can be the uncoated powder that has or be coated with surfactant at least in part.Surfactant can be selected from but be not limited to stearic acid, palmitic acid, laurate, oleic acid, capric acid, myristic acid and linoleic acid and their salt, for example ammonium salt, sodium salt or sylvite.
Conductive metal powder, or specifically, the particle mean size of silver powder is in 0.5 to 5 mu m range for example.In metal paste of the present invention, conductive metal powder or specifically the total content of silver powder be for example 50 to 92 weight %, or be 65 to 84 weight % in one embodiment.
In this specification and claims, use a technical term " particle mean size ".This means through the laser diffraction method and measure average grain diameter (d50).All statements of doing about particle mean size in this specification and claims all relate to as being present in the particle mean size of the associated materials in the metal paste.
In general, metal paste of the present invention only comprises at least a conductive metal powder that is selected from silver, copper and mickel.Yet, can the sub-fraction of the conducting metal that is selected from silver, copper and mickel be replaced with one or more other metallic particles.By the total weight of the metallic particles that comprises in the conductive metal slurry, the ratio of these type of other metallic particles is for example 0 to 10 weight %.
Metal paste of the present invention comprises one or more flint glass material as inorganic bond.Said at least a flint glass material has 571 to 636 ℃ of softening point temperatures in the scope, and comprises the PbO of 53 to 57 weight %, the SiO of 25 to 29 weight %
2, 2 to 6 weight % Al
2O
3B with 6 to 9 weight %
2O
3PbO, SiO
2, Al
2O
3And B
2O
3Percentage by weight summation can for or can not be 100 weight %.In summation is not under the situation of 100 weight %, and remaining percentage by weight can specifically be made up of one or more other oxides, and for example alkali metal oxide is (like Na
2O), alkaline earth oxide (like MgO) and metal oxide are (like TiO
2And ZnO).
In one embodiment, except that said at least a flint glass material, metal paste of the present invention also comprises one or more lead-less glasses materials.In this embodiment; Metal paste of the present invention comprises (a) at least a conductive metal powder that is selected from silver, copper and mickel; (b) at least a flint glass material; Said flint glass material has the softening point temperature in 571 to 636 ℃ of scopes, and comprises the PbO of 53 to 57 weight %, the SiO of 25 to 29 weight %
2, 2 to 6 weight % Al
2O
3B with 6 to 9 weight %
2O
3, (c) at least a lead-less glasses material, said lead-less glasses material have the softening point temperature in 550 to 611 ℃ of scopes, and comprise the SiO of 11 to 33 weight %
2,＞0 is specially the Al of 5 to 6 weight % to 7 weight %
2O
3B with 2 to 10 weight %
2O
3, and (d) organic carrier.Under the situation of using lead-less glasses material, SiO
2, Al
2O
3And B
2O
3The summation of percentage by weight be not 100 weight %, remaining percentage by weight specifically is made up of one or more other oxides, for example alkali metal oxide is (like Na
2O), alkaline earth oxide (like MgO) and metal oxide are (like Bi
2O
3, TiO
2And ZnO).
In one embodiment, said at least a lead-less glasses material comprises 40 to 73 weight %, the Bi of 48 to 73 weight % specifically
2O
3In this embodiment; Metal paste of the present invention comprises (a) at least a conductive metal powder that is selected from silver, copper and mickel; (b) at least a flint glass material; Said flint glass material has the softening point temperature in 571 to 636 ℃ of scopes, and comprises the PbO of 53 to 57 weight %, the SiO of 25 to 29 weight %
2, 2 to 6 weight % Al
2O
3B with 6 to 9 weight %
2O
3, (c) at least a lead-less glasses material, said lead-less glasses material have the softening point temperature in 550 to 611 ℃ of scopes, and comprise the Bi of 40 to 73 weight %
2O
3, 11 to 33 weight % SiO
2,＞0 is specially the Al of 5 to 6 weight % to 7 weight %
2O
3B with 2 to 10 weight %
2O
3, and (d) organic carrier.Comprise Bi in use
2O
3Lead-less glasses material the time, Bi
2O
3, SiO
2, Al
2O
3And B
2O
3Percentage by weight summation can for or can not be 100 weight %.In summation is not under the situation of 100 weight %, and remaining percentage by weight can specifically be made up of one or more other oxides, and for example alkali metal oxide is (like Na
2O), alkaline earth oxide (like MgO) and metal oxide are (like TiO
2And ZnO).
If metal paste of the present invention not only comprises at least a flint glass material, but also comprise at least a lead-less glasses material, the ratio of this frit of two types can be an arbitrary ratio so, in other words, and can be to infinitely-great scope＞0.
The particle mean size of frit is in the scope of for example 0.5 to 4 μ m.The total content of frit in the metal paste of the present invention (at least a flint glass material and the optional at least a lead-less glasses material sum that exists) is for example 0.25 to 8 weight %, perhaps in one embodiment, is 0.8 to 3.5 weight %.
The preparation of frit is known, and for example comprises that glass ingredient with the oxide component form is fused together and this type of melt composition is injected water to form frit.As known in the art, can be heated to peak temperature and keep a period of time, make melt become liquid and evenly fully.
Can glass low viscosity low boiling organic liquids of water or inertia in ball mill be ground with the granularity that reduces frit and obtained size frit uniformly basically.Can it be deposited in water or the said organic liquid to isolate fines and can remove the supernatant that comprises fines then.Also can use other sorting techniques.
Metal paste of the present invention comprises organic carrier.Can be with diversified inert viscous materials as organic carrier.Organic carrier can be following carrier: wherein granular component (conductive metal powder, frit) is dispersible, and has enough stabilitys.The characteristic of organic carrier (especially rheological characteristic) can make them to metal paste the good characteristic of using is provided; Comprise: the stable dispersion property of undissolved solid, for using ARC layer and the suitable wettability of slurry solids on (especially for silk screen printing) suitable viscosity and thixotropy, the silicon chip front, good rate of drying, and good roasting performance.The organic carrier that is used for metal paste of the present invention can be non-aqueous inert fluid.Organic carrier can be organic solvent or ORGANIC SOLVENT MIXTURES; In one embodiment, organic carrier can be one or more organic polymers and is dissolved in the solution that forms in one or more organic solvents.Can use in the multiple organic carrier any, said carrier can comprise or not comprise thickener, stabilizer and/or other typical additives.In one embodiment, the polymer as the organic carrier component can be ethyl cellulose.What other instances of the polymer that can use separately or use with compound mode comprised ethylhydroxyethylcellulose, wood rosin, phenolic resins and lower alcohol gathers (methyl) acrylic acid ester.The instance of appropriate organic solvent comprises alcohol ester and terpenes such as α-or the mixture of β-terpineol or they and other solvents such as kerosene, dibutyl phthalate, diethylene glycol butyl ether, butyl carbitol acetate, hexylene glycol and high-boiling point alcohol.In addition, in organic carrier, also can comprise volatile organic solvent, to be used to promote the quick-hardening of metal paste after using.The various combinations that can prepare these solvents and other solvents are to reach desired viscosity and volatility requirement.
The ratio of organic carrier in the metal paste of the present invention and inorganic component (conductive metal powder, frit and optional other inorganic additive sums that exist) depends on the application process of metal paste and the kind of used organic carrier, and this ratio can change.Usually, metal paste of the present invention can comprise the inorganic component of 58 to 95 weight % and the organic carrier of 5 to 42 weight %.
Metal paste of the present invention is a viscous composition, and it can make through conductive metal powder and frit and organic carrier are carried out mechanical mixture.In one embodiment, but the working power mixed production method, and it is a kind of dispersion technology that is equal to the conventional roll mill; Also can use roller mill or other hybrid technologies.
Metal paste of the present invention can in statu quo use or can (for example) through adding one or more extra organic solvents it be diluted; Therefore, the percentage by weight of every other component can reduce in the metal paste.
Metal paste of the present invention can be used for producing the positive gate electrode of silicon solar cell, or is respectively applied for the production silicon solar cell.Therefore, the positive gate electrode and the silicon solar cell that the invention still further relates to this type of production method and make through said production method.
Producing the method for positive gate electrode can implement through following steps: (1) provides the front to have the silicon chip of ARC layer; (2) with metal paste printing of the present invention, be screen-printed on the ARC layer on the silicon chip front specifically and drying, form two or more parallel buses; (3) will have the metal paste printing of the ability of grilling thoroughly; Be screen-printed on the ARC layer specifically and drying, form the thin parallel fingers that intersects with right angle and bus, and (4) roasting has been printed and dry metal paste.Can obtain by grilling thoroughly the positive gate electrode that fingers and contactless bus are formed according to this method.
Yet; Produce the method for this type of positive gate electrode and also can implement with reverse order, that is: (1) provides the silicon chip that the front has the ARC layer, and (2) will have the metal paste printing of the ability of grilling thoroughly; Be screen-printed on the ARC layer on the silicon chip front specifically and drying; Form thin parallel fingers, (3) are screen-printed on the ARC layer metal paste printing of the present invention and drying specifically; Two or more parallel buses that formation is intersected with right angle and fingers, and (4) roasting has been printed and dry metal paste.Can obtain by grilling thoroughly the positive gate electrode that fingers and contactless bus are formed according to this method.
In the step (1) of preceding two sections disclosed methods, provide the front to have the silicon chip of ARC layer.Silicon chip is conventional monocrystalline or the polysilicon chip that is usually used in producing silicon solar cell, that is, it has p type zone, n type zone and p-n junction usually.Silicon chip has (for example) TiO in its front
x, SiO
x, TiO
x/ SiO
x, or SiN specifically
xOr Si
3N
4The ARC layer.This type of silicon chip is that the technical staff knows; For for simplicity, can be with reference to " background of invention " part.Of preceding text " background of invention " part, silicon chip can have conventional back side metallisation, i.e. back side aluminium paste and back silver slurry or back silver/aluminium paste.Using of back metal slurry can be implemented after positive gate electrode form preceding or form.Back side slurry is roasting or common roasting separately, or even with step (2) and (3) in be printed on the common roasting of front metal slurry on the ARC layer.
In specification and claims part, " metal paste with the ability of grilling thoroughly " uses a technical term.This means that the common metal slurry is electrically connected with the formation of silicon substrate surface after grilling thoroughly the ARC layer, on the contrary, metal paste of the present invention can be not like this.Specifically, this type of metal paste comprises the silver slurry with the ability of grilling thoroughly; They are that the technical staff is known, and in various patent documentations (for example US 2006/0231801 A1), all describe to some extent.
After in step (2) and (3), using metal paste, be dried for example a period of time of 1 to 100 minute, make silicon chip reach 100 to 300 ℃ of peak temperatures in the scope.Dry for example belt capable of using, rotary or state type drying machine, IR (infrared ray) band drier carries out specifically.
Step (2) and (3) calcination steps (4) afterwards is common calcination steps.Yet,, also can between step (2) and (3), carry out extra calcination steps though be not preferred.In any case, according to the preparation method who comprises step (1) to (4), on the ARC layer on the silicon chip front, prepared by grilling thoroughly the gate electrode that fingers and contactless bus are formed.The parallel fingers of grilling thoroughly has for example 2 to 5mm spacing, the for example layer thickness of 3 to 30 μ m and the for example width of 50 to 150 μ m.Through roasting but contactless bus has for example layer thickness and for example 1 to 3mm the width of 20 to 50 μ m.
Sustainable for example a period of time of 1 to 5 minute of the roasting of step (4), make silicon chip reach 700 to 900 ℃ of peak temperatures in the scope.Roasting for example single section capable of using or multi-region section band oven especially multi-region section IR band oven carry out.Roasting can or exist under inert gas atmosphere under the oxygen situation of (for example having air) and takes place.In roasting process, organic substance comprises that unevaporated organic moiety can be removed in non-volatile organic material and the dry run, is promptly burnouted and/or carbonization, burnouted specifically, and frit and conductive metal powder sintering is together.Yet the metal paste that is used to print parallel thin fingers can etching and is grilled thoroughly the ARC layer, causes the formation of fingers and silicon substrate to electrically contact, and the situation that is used for the metal paste of the present invention of printed busbar is not like this.Bus still is " contactless " bus after the roasting, and promptly the ARC layer remains between bus and silicon substrate at least basically.
The gate electrode or the silicon solar cell of the method preparation of the application of the invention metal paste show favourable electrical property, and this electrical property is associated with contactless bus or with respect to grilling thoroughly the only few bus that partly contacts silicon substrate of bus.Bus advantage through method of the present invention preparation is to have good soldering resistance, and with positive or more properly say the good adhesion of the ARC layer on the silicon solar cell front.
Embodiment
But embodiment as herein described relates to the metal paste of roasting to the conventional solar cell, and said solar cell has p type silicon substrate and silicon nitride ARC layer on positive n type emitter.
Below discussion described and how to utilize composition of the present invention to form solar cell and how to test its technical characteristic.
(1) manufacturing of solar cell
The following solar cell that forms:
(i) (area that 200 μ m are thick is 243cm at silicon substrate
2Polysilicon chip, p type (boron) piece silicon has the POCl of n type diffusion
3Emitter, sour veining is used on the surface, has through chemical vapour deposition (CVD) to be applied in the SiN on the silicon chip emitter
xThe ARC layer) silk screen printing front side silver paste (PV142 on the front; Can be purchased acquisition from E.I.Du Pont de Nemours and Company) and dry; Form that 100 μ m are wide, 20 μ m are thick, to each other apart from being the thin parallel fingers of 2.2mm; Wherein has the wide bus of the thick aluminium electrode of 30 μ m (by obtaining) and two 5mm on the back surfaces of silicon substrate (by obtaining from the silver composition PV505 silk screen printing that E.I.Du Pont de Nemours and Company is purchased acquisition from the PV381 aluminum composition silk screen printing that E.I.Du Pont de Nemours and Company is purchased acquisition; And each edge all with the overlapping 1mm of aluminium film, be electrically connected guaranteeing).Silk screen printing front bus silver slurry then forms two 2mm is wide, 25 μ m are thick, with right angle and the crossing parallel bus of fingers.All metal pastes had all carried out drying before common roasting.
Exemplary front bus silver slurry comprises the silver powder (particle mean size 2 μ m) of 81 weight %, organic carrier (organic polymer resin and organic solvent) and the frit (particle mean size 0.8 μ m) of 19 weight %.Table l provides the composition data of employed frit type.
The silicon chip that (ii) will print is then put into the Despatch stove and is carried out roasting with the belt speed of 3000mm/min; Wherein zone temperatures is restricted to section 1=500 ℃, and section 2=525 ℃, section 3=550 ℃; Section 4=600 ℃; Section 5=925 ℃, last section is set at 890 ℃, so silicon chip reaches 800 ℃ peak temperature.After the roasting, the metallization wafer becomes the function photovoltaic device.
Measure electrical property and front bus and SiN
xRoasting adhesiveness between the ARC layer.In addition, measured the ability of grilling thoroughly.
(2) testing procedure
Efficient
To place commercial I-V tester (providing) with the measuring light conversion efficiency according to the solar cell that said method forms by h.a.l.m.elektronik GmbH.(about 1000W/m has been simulated and had known strength to lamp in this I-V tester
2) daylight and the irradiation battery emitter.Make the metallisation on the electric probe contact battery subsequently.Photoelectric current (Voc, i.e. open circuit voltage that these solar cells produce have been measured on a series of resistance; Isc, i.e. short circuit current) to calculate the I-V response curve.
Grill thoroughly ability
Front bus silver slurry is carried out silk screen printing and roasting by above-mentioned H pattern, and said H pattern comprises that fingers and bus (do not use the PVl42 front side silver paste to be used for the fingers printing! ).Measure the efficient of battery then.If it is very low that front bus slurry does not have the ability of grilling thoroughly or grills thoroughly ability, then the electrical efficiency of solar cell (that is, does not have or has only the limited ability of grilling thoroughly) in 0 to 4% scope.
The adhesiveness test
When carrying out the adhesiveness test,, and use manual soldering iron to move along whole silicon wafer length and weld with constant rate of speed with wetting band of liquid soldering flux and front bus.The soldering iron tip is adjusted to 325 ℃ of assigned temperatures.Scaling powder does not carry out predrying or preheating before welding.
Scaling powder and the scolder band that is used for this test is respectively Kester
952S and 62Sn-36Pb-2Ag (metal alloy of being made up of the silver plumbous and 2 weight % of the tin of 62 weight %, 36 weight %).
Through with the stretching angle of the speed of 100mm/s and 90 ° a plurality of some stretching scolder bands, use the Mecmesin adhesion tester to measure adhesion along bus.With the gram is that the unit measurement removes the required power of bus.
Listed embodiment A shows ratio and the functional relation of composition of the electrical property frit contained with it of front bus silver slurry in the table 2 to D.Data in the table 2 show, compare with using the solar cell that makes according to the silver-colored slurry of the front bus of comparing embodiment E, use the electrical property of the solar cell that makes according to the silver-colored slurry of embodiment A to the front bus of D to significantly improve.Open circuit voltage Voc increases, and adhesiveness is stronger, and resistivity is lower.
Table 1
Table 2
*), according to the present invention
*), comparing embodiment
Claims (15)
1. metal paste; Said metal paste comprises (a) at least a conductive metal powder that is selected from silver, copper and mickel; (b) at least a flint glass material, said flint glass material have the softening point temperature in 571 to 636 ℃ of scopes and comprise the PbO of 53 to 57 weight %, the SiO of 25 to 29 weight %
2, 2 to 6 weight % Al
2O
3, and the B of 6 to 9 weight %
2O
3, and (c) organic carrier.
2. the metal paste of claim 1, said metal paste comprises at least a lead-less glasses material, and said lead-less glasses material has the softening point temperature in 550 to 611 ℃ of scopes and comprises the SiO of 11 to 33 weight %
2,＞0 is to the Al of 7 weight %
2O
3, and the B of 2 to 10 weight %
2O
3
3. the metal paste of claim 2, wherein said lead-less glasses material comprises the Bi of 40 to 73 weight %
2O
3
4. claim 1,2 or 3 metal paste, the total content of wherein said conductive metal powder is 50 to 92 weight %.
5. the metal paste of aforementioned each claim, wherein said at least a conductive metal powder is a silver powder.
6. the metal paste of aforementioned each claim, the total content of wherein said frit is 0.25 to 8 weight %.
7. each metal paste in the claim 2 to 6, the ratio of wherein said at least a flint glass material and said at least a lead-less glasses material＞0 to infinitely-great scope.
8. the metal paste of aforementioned each claim, said metal paste comprises the inorganic component of 58 to 95 weight % and the organic carrier of 5 to 42 weight %.
9. prepare the method for positive gate electrode, said method comprising the steps of:
(1) be provided at the silicon chip that its front has the ARC layer,
(2) each metal paste in the claim 1 to 8 is printed onto on the ARC layer on the front of said silicon chip and dry forming two or more parallel buses,
The metal paste that (3) will have an ability of grilling thoroughly is printed onto on the said ARC layer and is dry forming with right angle and the crossing thin parallel fingers of said bus, and
(4) said printing of roasting and dry metal paste.
10. prepare the method for positive gate electrode, said method comprising the steps of:
(1) be provided at the silicon chip that its front has the ARC layer,
The metal paste that (2) will have an ability of grilling thoroughly is printed onto on the ARC layer on the front of said silicon chip and is dry forming thin parallel fingers,
(3) be printed onto on the said ARC layer each metal paste in the claim 1 to 8 and dry two or more parallel buses that intersect with right angle and said fingers with formation, and
(4) said printing of roasting and dry metal paste.
11. the method for claim 9 or 10, wherein said ARC layer is selected from TiO
x, SiO
x, TiO
x/ SiO
x, SiN
xOr Si
3N
4The ARC layer.
12. claim 9,10 or 11 method are wherein carried out extra calcination steps between step (2) and (3).
13. each method in the claim 9 to 12 wherein is printed as silk screen printing in step (2) and (3).
14. positive gate electrode according to each method preparation in the claim 9 to 13.
15. comprise the silicon solar cell of silicon chip, said silicon chip has the positive gate electrode of ARC layer and claim 14 on its front.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16456609P | 2009-03-30 | 2009-03-30 | |
| US61/164,566 | 2009-03-30 | ||
| PCT/US2010/029181 WO2010117773A1 (en) | 2009-03-30 | 2010-03-30 | Metal pastes and use thereof in the production of silicon solar cells |
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| Publication Number | Publication Date |
|---|---|
| CN102365688A true CN102365688A (en) | 2012-02-29 |
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ID=42470577
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|---|---|---|---|
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| Country | Link |
|---|---|
| EP (1) | EP2417608A1 (en) |
| JP (1) | JP2012522355A (en) |
| KR (1) | KR20120014131A (en) |
| CN (1) | CN102365688A (en) |
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| CN105263876A (en) * | 2012-12-28 | 2016-01-20 | 赫劳斯德国有限两和公司 | Binary glass frits used in n-type solar cell production |
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| US20130192671A1 (en) | 2011-08-11 | 2013-08-01 | E I Du Pont De Nemours And Company | Conductive metal paste and use thereof |
| KR101350960B1 (en) * | 2012-01-13 | 2014-01-16 | 한화케미칼 주식회사 | Glass frits, conductive paste composition comprising the same and solar cell |
| US20130183795A1 (en) * | 2012-01-16 | 2013-07-18 | E I Du Pont De Nemours And Company | Solar cell back side electrode |
| US8952245B2 (en) * | 2012-01-23 | 2015-02-10 | Heraeus Precious Metals North America Conshohocken Llc | Conductive thick film paste for solar cell contacts |
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| EP2025435A2 (en) * | 2007-07-24 | 2009-02-18 | Ferro Corporation | Ultra low-emissivity (Ultra Low E) silver coating |
-
2010
- 2010-03-30 EP EP10723425A patent/EP2417608A1/en not_active Withdrawn
- 2010-03-30 WO PCT/US2010/029181 patent/WO2010117773A1/en active Application Filing
- 2010-03-30 JP JP2012503601A patent/JP2012522355A/en active Pending
- 2010-03-30 TW TW099109691A patent/TW201044415A/en unknown
- 2010-03-30 KR KR1020117025474A patent/KR20120014131A/en not_active Application Discontinuation
- 2010-03-30 CN CN2010800158640A patent/CN102365688A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178685A (en) * | 1991-06-11 | 1993-01-12 | Mobil Solar Energy Corporation | Method for forming solar cell contacts and interconnecting solar cells |
| US5279682A (en) * | 1991-06-11 | 1994-01-18 | Mobil Solar Energy Corporation | Solar cell and method of making same |
| EP1713091A2 (en) * | 2005-04-14 | 2006-10-18 | E.I.Du pont de nemours and company | Method of manufacture of semiconductor device and conductive compositions used therein |
| EP1993144A1 (en) * | 2006-03-07 | 2008-11-19 | Murata Manufacturing Co. Ltd. | Conductive paste and solar cell |
| EP2025435A2 (en) * | 2007-07-24 | 2009-02-18 | Ferro Corporation | Ultra low-emissivity (Ultra Low E) silver coating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102855961A (en) * | 2012-08-24 | 2013-01-02 | 西安交通大学苏州研究院 | Paste for formation of solar cell back electrodes and preparation method thereof |
| CN105263876A (en) * | 2012-12-28 | 2016-01-20 | 赫劳斯德国有限两和公司 | Binary glass frits used in n-type solar cell production |
| CN105263876B (en) * | 2012-12-28 | 2019-03-26 | 赫劳斯德国有限两和公司 | It is used to prepare the binary glass material of N-shaped solar battery |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2417608A1 (en) | 2012-02-15 |
| JP2012522355A (en) | 2012-09-20 |
| WO2010117773A1 (en) | 2010-10-14 |
| KR20120014131A (en) | 2012-02-16 |
| TW201044415A (en) | 2010-12-16 |
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