WO2020238367A1 - 一种导电性浆料及由其制备的太阳能电池及制造方法 - Google Patents
一种导电性浆料及由其制备的太阳能电池及制造方法 Download PDFInfo
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- WO2020238367A1 WO2020238367A1 PCT/CN2020/080999 CN2020080999W WO2020238367A1 WO 2020238367 A1 WO2020238367 A1 WO 2020238367A1 CN 2020080999 W CN2020080999 W CN 2020080999W WO 2020238367 A1 WO2020238367 A1 WO 2020238367A1
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- WIPO (PCT)
- Prior art keywords
- glass
- tellurium
- lead
- conductive paste
- semiconductor substrate
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 206
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 103
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 238000007639 printing Methods 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims description 93
- 239000000758 substrate Substances 0.000 claims description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- ZGUQQOOKFJPJRS-UHFFFAOYSA-N lead silicon Chemical compound [Si].[Pb] ZGUQQOOKFJPJRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002503 electroluminescence detection Methods 0.000 abstract description 25
- 239000010410 layer Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 39
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- 230000000694 effects Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- 239000005368 silicate glass Substances 0.000 description 12
- 239000002003 electrode paste Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000011241 protective layer Substances 0.000 description 8
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000005355 lead glass Substances 0.000 description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- -1 tackifiers Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 238000005401 electroluminescence Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000007130 inorganic reaction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 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
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 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
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide 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
- 238000002834 transmittance Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
- H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
- H01L31/0516—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module specially adapted for interconnection of back-contact 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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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
- Y02E10/52—PV systems with concentrators
Definitions
- the present invention mainly relates to a slurry composition for solar cell electrodes that is suitable for manufacturing defect-free and highly stable solar cell electrodes under EL inspection, and a solar cell using the slurry and a manufacturing method thereof.
- Electrodes Conventional solar cells are on a conductive semiconductor substrate, a semiconductor layer of opposite conductivity is provided, and an anti-reflection film and a light-receiving surface electrode are provided on the semiconductor layer, and a back electrode structure (hereinafter When the front and back sides are not distinguished, they are collectively referred to as “electrodes”), and the electrical energy generated by the semiconductor pn junction after light is exported through the electrodes.
- the above-mentioned anti-reflection film maintains sufficient visible light At the same time as the transmittance, it can reduce the surface reflectivity and increase the light receiving rate, so it is generally composed of thin films such as silicon nitride, titanium dioxide, and silicon dioxide.
- Solar cells with multi-layer structures are now also in widespread use, such as cell structures with protective layers (passivation layers, generally composed of aluminum oxide, silicon oxide, etc.) that improve efficiency by protecting the semiconductor layer under the anti-reflection film, and
- a battery structure called TOPCON (Tunneling Oxide Passivated Contact) has a conductive layer under the semiconductor layer.
- the above-mentioned anti-reflection film (with or without a protective layer if not specifically labeled) has a large resistance value, and in order to more fully derive the power generated by the semiconductor pn junction, it needs to be formed Remove the anti-reflection film on the light-receiving surface electrode. Therefore, assuming that the light-receiving surface electrode of the solar cell is formed by the burn-through method, first form the above-mentioned anti-reflection film on the n+ layer, and then use the screen printing method to print a conductive paste on the anti-reflection film, which is The paste-like electrode material is coated and printed in an appropriate shape, and then sintered.
- the anti-reflection film that touches the electrode material will also melt, so that the light-receiving surface A contact is formed between the electrode and the semiconductor substrate.
- the main components of the above conductive paste are silver powder, glass (after the glass material is melted and quenched, it is made into flake or powdered glass after ball milling as needed), organic phase and organic solvent.
- the glass component in the conductive paste will destroy the anti-reflection film, and the conductor component in the conductive paste will form an ohmic contact through the n+ layer. Therefore, compared with removing part of the anti-reflection film before forming the electrode, the process is simpler, and there is no problem of alignment deviation between the part where the anti-reflection film is removed and the part where the electrode is formed.
- tellurium in the glass composition is a network forming body, which can increase the amount of silver dissolved in the glass and reduce the contact resistance. In the cooling stage of sintering, it can inhibit the precipitation of silver, thereby widening the sintering window while suppressing the semiconductor substrate The effect of being excessively corroded.
- the anti-reflection film (also called insulating film) can be sufficiently corroded to ensure good contact between the light-receiving surface electrode and the substrate, and at the same time, since the electrode material entering the semiconductor layer region such as pn junction can be suppressed, It will be easier to form a good ohmic contact, and because the conductivity has also been improved, the electrical performance should also be improved.
- the burn-through can be controlled more easily, which is also helpful for thinning the semiconductor layer on the light-receiving surface side.
- Patent Document 1 mentions the use of lead-tellurium-based glass, the purpose of which is to form a penetration between the electrode paste and the anti-reflection film under low-temperature sintering, thereby forming good contact with the semiconductor substrate.
- Patent Document 2 also mentions electrode pastes using lead-based glass containing tellurium. It can be seen from paragraph [0076] that as the amount of PbO in the glass increases, the bonding strength between the electrode and the substrate will weaken. This effect on bonding strength can be considered to be related to the morphology of the substrate/electrode interface. In other words, if PbO is contained in the glass, even if it does not contain a hard SiO 2 component, the glass will corrode the substrate, and a good contact will be formed between the substrate and the electrode. However, if the composition of PbO is excessive, the substrate will be corroded more uniformly and the corroded surface will become smoother. As a result, the bonding strength will be weakened. The bonding strength of the electrode paste using lead-tellurium glass will also be Weaken.
- Patent Document 3 Japanese Patent Publication No. 5559509
- a conductive paste for solar cell electrodes made of conductive powder whose main component is silver, glass, an organic phase, and a solvent is used to contain tellurium oxide as a conductive paste.
- the conductive paste of tellurium-based glass in the network formation reduces the contact resistance between the light-receiving surface electrode and the semiconductor substrate.
- the contact resistance is mainly related to the composition of the glass. In other words, the contact resistance is affected by tellurium oxide and other glass components (tungsten oxide, molybdenum oxide, etc.), so it is difficult to maintain a low contact resistance all the time.
- the lead-free conductive paste with lead content below 0.1 (wt%) in order to obtain good solar cell performance, it has been proposed to add at least one of the additives in the glass and the conductive paste
- One of Mg, Ca, Sr, and Ba, and the added content is: for a conductive powder with a weight of 100, the content range is preferably about 0.1 to 10 weight (for example, refer to the Japanese Patent Publication 2009-194141 (Patent Document 5)).
- Patent Document 6 Japanese Patent Publication No. 5856277 (Patent Document 6), it is mentioned that lead-free glass containing tellurium, bismuth, zinc, and lithium as essential elements is recommended.
- Patent Document 6 the composition in Patent Documents 3 to 5 is summarized, that is, "The solar cell sheet using the conductive paste of lead-free glass mentioned above to form the light-receiving surface electrode is It is hoped to be able to achieve high bonding strength between the substrate and the electrodes at the same time, as well as to improve battery performance (especially to achieve low contact resistance and low line resistance), but no particularly satisfactory results have been obtained.”
- the characteristics of the paste for solar cell electrodes using lead-free glass are explained: “Although the bonding strength can be achieved by adjusting the softening point of the glass relatively easily, it is more difficult to control the lead-free glass than lead glass. The degree of corrosion is difficult to control the conditions for achieving good contact”.
- the so-called high stability refers to the power generation capacity that can ensure long-term stability after the manufactured solar cells are arranged in series to form a module. Recently, it has been able to maintain 25 years.
- the new detection item is EL detection (Electro Luminescence).
- EL detection is to apply an electric field on the solar cell, recombine the electrons and holes that enter the semiconductor, take a picture of the light-emitting part, and then analyze the taken picture. After the electric field is applied, the part where the charge flows will emit light, and the part where no charge passes will be dark. Using this feature, it is possible to clarify in advance defects and problems that cannot be seen in the appearance of the battery, thereby ensuring its high stability.
- Figure 1 includes the case detection results of four solar cells. (1)-(3) all show poor EL detection performance, and (4) are normal EL detection performance cases. But (4) has poor tensile properties and low bonding strength.
- the present invention provides a conductive paste, a solar cell printed with the conductive paste as a surface electrode, and a method for manufacturing the solar cell.
- the prepared solar cell has normal EL performance detection and high stability , And the battery has excellent ohmic contact, thus the battery efficiency is high, and at the same time, the bonding performance is taken into account, and the bonding strength is excellent.
- a conductive paste used to form surface electrodes of solar cells which contains conductive powder, mixed glass, and organic phase; wherein, the mixed glass contains the following two types of glass components: the first type of glass is selected from substantially At least one kind of tellurium-based glass containing no lead and containing lithium bismuth tellurium as an essential component; and the second type of glass is selected from at least one kind of lead silicate-based glass containing lead and silicon as essential components and substantially containing no tellurium.
- the tellurium-based glass may also contain any one or more of oxides of tungsten, zinc, silicon, sodium, aluminum, and copper.
- the lead silicate glass may further contain any one or more of zinc, tungsten, sodium, lithium, aluminum, and copper, and the lead silicate glass is converted into For oxides, 39 to 70 mol% of lead, 20 to 43 mol% of silicon, and 0 to 20 mol% of zinc, tungsten, sodium, lithium, aluminum, and copper.
- the mixed glass may also contain other types of glass.
- the total mass of the first type of glass and the second type of glass exceeds 50%.
- the content of the mixed glass is preferably controlled to a mass of about 0.1-10.
- the present invention also provides a solar cell having a semiconductor substrate, a first region anti-reflection film provided on the surface of the semiconductor substrate, and a surface electrode provided on the second region on the surface of the semiconductor substrate , Wherein the surface electrode is made by printing any of the above conductive pastes.
- the above-mentioned surface refers to the front and/or back of the semiconductor substrate.
- the present invention also provides a method for manufacturing a solar cell, the solar cell having a semiconductor substrate, a first region anti-reflection film provided on the surface of the semiconductor substrate, and a semiconductor substrate provided on the surface of the semiconductor substrate.
- the surface electrode of the second area wherein the manufacturing method is mainly divided into the following three steps:
- the first process is: forming an anti-reflection film on the surface of the semiconductor substrate;
- the second step process is: printing a conductive paste containing conductive powder, mixed glass, and organic phase on the anti-reflection film formed in the first step, wherein the mixed glass is mainly made of a type of substantially lead-free, A mixture of tellurium-based glass with lithium bismuth tellurium as an essential component and a type of lead silicate-based glass with lead-silicon as an essential component and substantially free of tellurium;
- the third step of the process is: sintering the conductive paste. During the sintering process, the part of the anti-reflection film under the conductive paste is removed, so that the first area of the semiconductor substrate is finally formed. The anti-reflection film forms the surface electrode in the second region of the semiconductor substrate.
- the above-mentioned surface refers to the front and/or back of the semiconductor substrate.
- the first type of glass may include one or more tellurium-based glasses that are substantially free of lead and contain lithium bismuth telluride as an essential component;
- the second type of glass may include one Or a variety of lead silicate-based glasses containing lead and silicon as essential components and substantially free of tellurium.
- the present invention also claims a glass frit for solar cells, which is any of the above-mentioned mixed glass.
- the EL performance test of the solar cell prepared by the conductive paste of the present invention is normal, so the high stability of the module can be ensured, and the ohmic contact of the battery is excellent, so the cell has high efficiency and long life, and at the same time, the adhesion performance is taken into account. Excellent bonding strength.
- Fig. 1 is a photo of EL detection of several solar cells in the prior art
- FIG. 2 is a cross-sectional view of important parts of an embodiment of a solar cell manufactured by using the conductive paste related to the present invention
- Figure 3 is an enlarged plan view of the electrode side of the light-receiving surface
- Fig. 4 is a schematic view of the enlarged bottom surface on the side of the back electrode
- Figure 5 is a photo of EL detection results of samples with slurry numbers 1-13 in the embodiment
- Figure 6 is a photograph of EL detection results of samples with slurry numbers 31-38 in the examples.
- 1 semiconductor substrate
- 1a n-type semiconductor layer
- 1b p-type semiconductor layer
- 2-anti-reflection film including or excluding protective layer
- 3-light-receiving surface electrode 4-back electrode
- 5a, 5b...5n-fine grid electrode 6-main grid electrode
- 7-collector electrode 8-lead-out electrode.
- the present invention provides a conductive paste for solar cells, a solar cell using the conductive paste, and a method for manufacturing the solar cell.
- the present inventors studied existing lead-free tellurium-based glasses.
- the lead-free tellurium-based glasses disclosed in Patent Documents 4 to 6 mentioned in the background art of the present invention all have bismuth as an essential component.
- the inventor believes that the bismuth component in the lead-free tellurium-based glass can appropriately weaken the strong corrosion inhibitory effect of tellurium, thereby improving the corrosiveness of the lead-free tellurium-based glass.
- the lead-free tellurium-based glass containing bismuth tends to separate into phases during heating and melting, and the high-fluidity part and the low-fluidity part will separate, resulting in excessive corrosion of the high-fluidity part.
- the inventor believes that it is also for this reason that uneven ohmic contact is formed between the semiconductor substrate and the electrode paste.
- the present invention provides an electrode paste that can ensure both electrical performance and bonding strength, and also exhibits good contact under EL detection, that is, an electrode paste for printing surface electrodes on solar cells. Slurry.
- the inventors conducted a lot of research and finally confirmed that the electrode paste using only lead-free glass containing tellurium is more prone to battery black spots caused by poor ohmic contact during EL detection.
- the sintering temperature is usually increased, but it will cause cloud-like black spots due to over-burning, that is, the optimal burning temperature window is very narrow and difficult to operate.
- the inventor found through a lot of research and analysis that if a tellurium-based lead-free glass containing a specific composition and ratio is used together with a lead glass that does not contain tellurium but contains a specific composition and ratio, the electrode paste will be sintered. No EL defect can be seen during the EL test.
- the conductive paste involved in the present invention is a conductive paste used to form solar cell electrodes. It is characterized by the use of at least conductive powder, and the use of lead-free glass, which is mainly composed of lithium bismuth telluride and substantially free of lead, And lead silicate-based glass whose main component is lead-silicon but does not contain tellurium substantially.
- Patent Document 7 conductive paste for surface electrodes of solar cells is mentioned. It is composed of conductive powder, mixed glass and organic phase.
- Mixed glass refers to It is a combination of tellurium-based glass with tellurium, tungsten, and bismuth as essential components, and a mixture of lead-bismuth-based glass with lead-bismuth as essential components and substantially no tellurium.
- the glass composition disclosed in Patent Document 7 does not achieve the purpose of the present invention, that is, it does not solve the problem of poor ohmic contact found in EL detection. Therefore, it can be seen that not all combinations of tellurium-based glass and lead glass can achieve the good effect of the EL detection of the present invention, but only the specific glass combination of the present invention can achieve the effect of good EL detection and good adhesion performance.
- Patent Document 8 discloses an inorganic reaction system in a conductive paste for a surface electrode of a solar cell, that is, a mixture of lead-based glass and tellurium-based glass.
- Patent Document 8 and Patent Document 7 fail to solve the problem of appearance during EL detection that is emphasized in the present invention.
- FIG. 2 is a cross-sectional view of an important part of the morphology of a solar cell manufactured using the conductive paste related to the present invention.
- the composition of the solar cell includes: a semiconductor substrate 1 with silicon as the main component, an anti-reflection film 2 and a light-receiving surface electrode 3 formed on one surface of the semiconductor substrate 1, and a semiconductor substrate 1 formed on the other surface The back electrode 4.
- the semiconductor substrate 1 has a p-type semiconductor layer 1b and an n-type semiconductor layer 1a, and the n-type semiconductor layer 1a is formed on the p-type semiconductor layer 1b.
- the semiconductor substrate 1 can be obtained by diffusing impurities on one surface of the p-type semiconductor layer 1b of single crystal silicon or polycrystalline silicon and forming a thin n-type semiconductor layer 1a.
- the n-type semiconductor layer 1a can be formed on the p-type semiconductor layer 1b, and there are no particular restrictions and requirements regarding its structure and manufacturing method.
- the semiconductor substrate 1 may also use a structure in which a thin p-type semiconductor layer is formed on one surface of an n-type semiconductor layer, or it may also be used to form a p-type semiconductor layer and an n-type semiconductor simultaneously on one surface of the semiconductor substrate 1. Layer structure. Regardless of the structure, as long as it is on the surface of the semiconductor substrate 1 on which the anti-reflection film 2 is formed, the conductive paste according to the present invention can be used.
- the surface of the semiconductor substrate 1 is flat, but in order to confine the sunlight in the semiconductor substrate as efficiently as possible, the surface is actually a structure with small concavities and convexities.
- the anti-reflection film 2 is made of insulating materials such as silicon nitride (SiNx), and is used to suppress the reflection of sunlight on the light-receiving surface as shown by arrow A, and then quickly and efficiently transmit sunlight to the semiconductor substrate 1 in.
- the constituent material of the anti-reflection film 2 is not limited to the above-mentioned silicon nitride, and other insulating materials may be used.
- silicon oxide and titanium oxide may be used, or two or more insulating materials may be used at the same time.
- the semiconductor substrate as long as it is a crystalline silicon system, either single crystal silicon or polycrystalline silicon can be used.
- the anti-reflection film 2 may or may not include a protective layer (a passivation layer that improves efficiency by protecting the semiconductor layer under the anti-reflection film, and is generally composed of aluminum oxide, silicon oxide, etc.).
- the light-receiving surface electrode 3 is formed by penetrating the anti-reflection film 2 on the semiconductor substrate 1.
- the light-receiving surface electrode 3 is formed by applying the conductive paste of the present invention described later on the semiconductor substrate 1 to form a conductive film using a method such as screen printing, and then sintering. In other words, during the sintering process for forming the light-receiving surface electrode 3, the anti-reflection film 2 under the conductive film will be decomposed, removed, and burned through, so that the conductive paste and the anti-reflection film 2 are penetrated together.
- a light-receiving surface electrode 3 is formed on the upper surface of the substrate 1, and the light-receiving surface electrode 3 is electrically connected to the semiconductor substrate 1.
- the specific structure of the light-receiving surface electrode 3 can be as shown in Fig. 3, a lot of fine grid electrodes 5a, 5b, ... 5n are arranged together like comb teeth, while the main grid electrode 6 and the fine grid electrodes 5a, 5b, ... ...5n is arranged in a cross shape, and the fine gate electrodes 5a, 5b, ...5n and the main gate electrode 6 are electrically conductive.
- an anti-reflection film 2 is formed in a region other than the light-receiving surface electrode 3. In this way, the electric energy generated by the semiconductor substrate 1 is collected by the thin gate electrodes 5a, 5b,... 5n, and at the same time is discharged to the outside through the main gate electrode 6.
- the back electrode 4, as specifically shown in FIG. 4, is a current collecting electrode 7 made of Al or the like formed on the back surface of the p-type semiconductor layer 1b, and a lead-out electrode 8 composed of Ag or the like that is electrically connected to the current collecting electrode 7 And composed. Among them, the electric energy generated by the semiconductor substrate 1 is collected by the collector electrode 7, and then the electric energy is exported through the lead-out electrode 8.
- the conductive paste mentioned in the present invention is mainly composed of conductive powder, mixed glass and organic phase.
- the mixed glass contains two types of glass frit, one of which is substantially free of lead and contains lithium bismuth telluride as an essential component. At least one type of tellurium-based glass, and the other type is at least one type of lead silicate-based glass containing lead silicon as an essential component and substantially free of tellurium.
- the first type of glass may include one or more tellurium-based glasses that are substantially free of lead and contain lithium bismuth telluride as an essential component; and the second type of glass may include One or more lead silicate-based glasses containing lead and silicon as essential components and substantially free of tellurium.
- the specific constituent components of each element of each glass are not recorded, the element is contained in the glass as an oxide. Therefore, to say "substantially not contain" a certain component X means that a small amount of component X is actually unavoidable, or it does not exclude that a small amount of component X will be included in order to utilize the essence of the present invention without affecting the realization of the purpose of the present invention. Add ingredient X.
- the conductive paste forming the light-receiving surface electrode 3 contains the above-mentioned conductive powder, mixed glass, an appropriate amount of additives, and an organic phase.
- This conductive paste may also be a rheological paste, paint, or ink-like composition suitable for printing methods other than screen printing.
- the content of the mixed glass in the conductive paste can refer to the usual usage in the conductive paste for solar cell electrodes, but here is an example.
- the content of the mixed glass is best controlled at The quality is about 0.1-10.
- the mass of the mixed glass if the mass of the mixed glass is 0.1 or more, the required sealing properties and electrode strength can be obtained.
- the mass of the mixed glass if the mass of the mixed glass is less than 10, glass will float on the electrode surface, and the glass flowing into the interface between the electrode and the diffusion layer of the semiconductor substrate can help reduce the contact resistance The increase.
- the average particle diameter of the tellurium-based glass and the lead silicate-based glass in the conductive paste in this embodiment is most suitable to be 0.5-3.0 ⁇ m.
- the main component is silver. Its shape can be spherical, flake, dendritic, etc., and silver powder that has been used before can be used.
- a silver-coated composite powder whose surface is at least a silver layer, or an alloy containing silver as a main component may be used.
- Conductive powders such as silver powder preferably have an average particle size of 0.1-10 ⁇ m.
- two or more kinds of conductive powders different in average particle size, particle size distribution, shape, etc. may be mixed and used, and silver powder and conductive powder other than silver may be mixed and used together.
- main component refers to a component whose mass exceeds 50%, and preferably refers to a component whose mass exceeds 70%.
- metals that are compounded, alloyed, or mixed with silver powder such as aluminum, gold, palladium, copper, nickel, etc., are not limited as long as they do not impair the effects of the present invention and its embodiments. However, from the viewpoint of conductivity, silver powder is the most recommended.
- organic phase there are no special restrictions. Generally, organic resins and organic solvents commonly used in the organic phase of silver paste will be used reasonably. In addition, as the organic resin, cellulose, acrylic resin, phenol resin, alkyd resin, or rosin resin can be used. As the organic solvent, organic solvents such as alcohols, ethers, esters, and hydrocarbons, or water, and mixed solvents of these can be used. Therefore, there is no special requirement for the ratio of the organic phase, as long as the appropriate amount is taken, it can form a slurry with the conductive powder and mixed glass and other inorganic components, and then it can be adjusted reasonably by coating and other methods. In spite of this, generally for a conductive powder with a mass of 100, the mass of the organic phase is about 5-40.
- ingredients can be added as needed, as long as they do not impair the effects of the present invention and its embodiments, and appropriate amounts of conventional additives, such as plasticizers, tackifiers, surfactants, oxidants, and metal oxides, can be added.
- plasticizers such as plasticizers, tackifiers, surfactants, oxidants, and metal oxides
- metal oxides Compounds, metal organic compounds, etc.
- silver compounds such as silver carbonate, silver oxide, and silver acetate can also be used.
- an appropriate amount of copper oxide, zinc oxide, tungsten oxide, and titanium oxide can also be added.
- tellurium-based glass for example, when converted into an oxide, tellurium is 44 to 76 mol%, bismuth is 7 to 51 mol%, and lithium is 2 to 14 mol%.
- tellurium acts as a network forming body. Like the above, it can increase the amount of silver dissolved in the glass and reduce the contact resistance. In the cooling stage of sintering, it can suppress the precipitation of silver and widen the sintering window. , And also inhibit the corrosion of the semiconductor substrate. Through these effects, the insulating film can be fully corroded to ensure good contact between the electrode material and the substrate. At the same time, since the electrode material entering the semiconductor layer region such as the pn junction can be prevented, it will be easier to form a good ohmic contact and conduct electricity. Performance has also been improved, and electrical performance can also be improved.
- bismuth is a component that increases the softening point of glass, and can be added when adjusting the softening point while ensuring the low viscosity of tellurium-based glass. In addition, it can also impart a corrosive effect to the glass. Although the aforementioned tellurium has a strong inhibitory effect on corrosion, the corrosiveness can be controlled to the right degree by appropriately adjusting the content of bismuth. However, if the bismuth content exceeds 52 (mol%), the glass will easily crystallize.
- lithium has the effect of lowering the softening point of glass and is also a donor.
- the semiconductor substrate such as a silicon substrate
- the electrode material through the mutual diffusion between the semiconductor substrate (such as a silicon substrate) and the electrode material, the donor concentration near the interface will decrease, and lithium can Play the role of supply. If the lithium content is less than 1 (mol%), it will not play a good replenishment effect, but if it exceeds 14 (mol%), the corrosion effect will be too strong, and the stability of the glass will decrease.
- alkali metal components have a bad influence on the characteristics of solar cells, so it is best not to use them. For example, Na will cause the opening voltage Voc to decrease, and K will cause the decrease of FF and increase the contact resistance. Moreover, Na and K will not form a donor, so there is no advantage to use. Lithium has a replenishment effect. In the formation of n-type semiconductor electrodes, better solar cell characteristics can be obtained, so it is very useful.
- the tellurium-based glass may contain any one or more of oxides of tungsten, zinc, silicon, sodium, aluminum, and copper in addition to lithium bismuth tellurium.
- lead silicon is an essential component, and it may also contain any one or more of zinc, tungsten, sodium, lithium, aluminum, and copper.
- lead silicate glass can also contain any one or more of zinc, tungsten, sodium, lithium, aluminum, and copper.
- the elements are converted into oxides, and the content is: lead is 39-70 mol%, silicon 20-43 mol%, zinc, tungsten, sodium, lithium, aluminum, and copper total 0-20 mol%.
- Lead is mainly used as a component of mesh formation to form a network of lead silicate glass.
- Lead has the ability to form glass alone, and the content is preferably between 39 and 70 mol%. If the content is within this range, the burn-through property will be improved.
- Silicon especially in the above-mentioned lead silicate-based glass, can help form a glass network, making it easier to adjust the softening point. Converted into oxides, if the content of silicon is 1-50 mol%, it will be easier to form glass, and the best content range is 20-43 mol%. When the content exceeds 50 mol%, the softening point becomes too high, and at the same time, it is a mesh-forming component of lead, which may hinder the formation of the network.
- the lead silicate glass may also contain any one or more of zinc, tungsten, sodium, lithium, aluminum, and copper.
- the content of these elements, when converted into oxides, is preferably 20 mol% or less in total.
- the mixed glass is at least a mixture of tellurium-based glass and lead silicate-based glass, and may additionally contain other glasses without substantially affecting the effects of the present invention.
- the conductive paste can balance good ohmic contact and bonding strength at the same time, and can also form surface electrodes without EL problems.
- this effect cannot be achieved by using tellurium-based glass alone or by using lead silicate-based glass alone, and at the same time using lead-tellurium-based glass alone cannot be achieved.
- TeO 2 , Bi 2 O 3 , WO 3 , ZnO, Al 2 O 3 , LiO 2 , B 2 O 3 etc. are prepared, as shown in Table 1-1, Table 1-2, and Table 1-3 These glass materials were weighed and prepared at the ratio shown, and finally glass samples A-1 to A-5 were made.
- A-4 is an example of a tellurium-based glass defined by the present invention that is substantially free of lead and uses lithium bismuth telluride as an essential component.
- the rest are comparative examples, specifically,
- A-1 is tellurium bismuth tungsten glass (the formula in Patent Document 7);
- A-2 is a glass with zinc, bismuth and tellurium as the main component and aluminum added.
- A-3 is a glass with zinc, bismuth and tellurium as the main component and aluminum added.
- A-5 is telluride glass (the formula in Patent Document 8)
- B-2 to B-6 and B-8 are examples of lead silicate-based glasses that take lead silicon as an essential component and do not substantially contain tellurium. Among them, B-2 is also the formula in Patent Document 8;
- B-1 and B-7 are comparative examples, which do not belong to lead silicate glass with lead-silicon as an essential ingredient and substantially free of tellurium.
- B-1 is a lead-bismuth-based glass containing lead-bismuth as an essential component and substantially free of tellurium (the formula in Patent Document 7);
- B-3 to B-8 are a series that specifically investigated the necessity of the presence of zinc, tungsten, silicon, sodium, and lithium in lead glass; among them,
- B-3 is an embodiment where zinc, tungsten, silicon, sodium, and lithium are all present
- B-4 is an embodiment in which tungsten is removed
- B-5 is an example of removing sodium
- B-6 is an example of removing zinc element
- B-7 is lead glass with silicon removed
- B-8 is an example in which lithium is removed.
- spherical silver powder with an average particle diameter of 2.0 ⁇ m was prepared in advance.
- the organic phase is prepared: 10wt% ethyl cellulose is used as the resin, and 90wt% octanol is used as the organic solvent, and the two are mixed to form the organic phase.
- I also purchased a single-crystal silicon solar cell Si-based semiconductor substrate (156mm square) from Tongwei Company in China.
- the silicon semiconductor substrate is also surface-textured and has a square resistance of 90 ⁇ /sq. It has protection on the phosphorous diffused emitter layer.
- the screen used in printing is a 5 main grid screen.
- the sintered solar cells are tested with an EL inspection device (produced by Geonic Automation), and the photos are inspected without black spots (black spots represent poor EL), and an IV tester (produced by Pasan) is used to test the cell conversion efficiency . If there is no chip damage during the preparation process, 10 chips will be tested for each sample.
- an EL inspection device produced by Geonic Automation
- an IV tester produced by Pasan
- the bonding strength is tested by a self-made automatic tensile testing machine and the 180-degree peeling method.
- Table 4 and Figure 5 show the glass ratio and test results in the slurry.
- B-1 the lead-bismuth-based lead-bismuth-based glass disclosed in Patent Document 7 as an essential component and substantially free of tellurium
- a combination of lead-free tellurium-based glass from any one of A-1 to A-4 No. 5- 8
- the EL test results were all bad.
- B-2 lead-borosilicate glass disclosed in Patent Document 8
- A-5 tellurium-based glass disclosed in Patent Document 8
- the EL detection result was poor. It proves that the lead silicate-based glass can not be combined with any tellurium-based glass to obtain good results in EL detection.
- Paste numbers 1 to 4 are the results when lead-free tellurium-based glass is used alone. among them,
- A-1 is sample 7 on page 9 of Patent Document 7.
- A-2 and A-3 are samples No. 1 and No. 7 on page 10 of Patent Document 4.
- A-4 is a lead-free tellurium-based glass invented by the inventor himself.
- Paste numbers 5 to 8 are the lead-free tellurium glasses A-1 to A-4 and the lead glass shown in B-1 in Table 2 (Patent Document 7, page 12, B6 in Table 2) Made of mixed use.
- Paste No. 9 was prepared using the same glass in Example Paste 1 shown on page 13 of Patent Document 8.
- the glass composition used is shown in Table 1-3 and Table 2-2, which are lead-borosilicate glass (glass A) on page 12 of Patent Document 8, and tellurium-based glass (glass B) on page 13 Glass of the same composition.
- the paste numbers 10 to 13 are for verifying the result of the combination with the lead silicate glass compound invented by the inventor. Among them, only the EL situation of slurry number 13 has been improved. Therefore, it can be confirmed that even in the same lead-free bismuth tellurium-based glass, lithium is an essential component. Only when lithium is present, the combination with lead silicate-based glass has a good effect.
- the paste numbers 14-17 are mainly to find the essential elements that function in glass B-3.
- the verification method is to remove the oxides of B-4 to B-8 alternatively.
- the verification result is that, including glass, lead and silicon are essential elements.
- Table 5 shows a part of the working range of the combination of lead-free tellurium-based glass and lead silicate-based glass in the present invention.
- Figure 6 shows the EL detection photos of the samples with slurry numbers 31-38 in Table 7. It can be seen from Figure 6 that there are no black spots in each photo, which proves that the EL test results of the samples with paste numbers 31-38 are good.
- the samples with paste numbers 31-37 in Table 7 are a combination of A-15 and B-17, but the contents and relative ratios of the two are different, which proves that these contents and ratios can obtain high-stability solar cells.
- the paste number 31 is an experimental result obtained by using a single crystal silicon solar cell Si-based semiconductor substrate having a protective layer under the anti-reflection film.
- the remaining numbered pastes are the results of experiments using a single crystal silicon solar cell Si-based semiconductor substrate with an anti-reflection film.
- the paste of the present invention is suitable for both semiconductor substrates containing a protective layer and semiconductor substrates that do not contain a protective layer.
- the conductive paste provided by the present invention can be applied in a wide content range.
- the conductive paste of the present invention is used as an electrode paste to produce solar cells that have good electrical properties (cell conversion efficiency) and bonding strength, and EL detection shows that they have good contact and high stability.
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Abstract
一种用来形成太阳能电池表面电极的导电性浆料,其含有导电性粉末、混合玻璃、以及有机相;其中,所述混合玻璃包含以下两类玻璃组分:第一类玻璃是选自实质上不含铅、以碲铋锂为必需成分的碲系玻璃的至少一种;第二类玻璃是选自以铅和硅为必需成分、实质上不含碲的硅酸铅系玻璃的至少一种。还提供了使用上述导电性浆料印刷为表面电极制备的太阳能电池及该太阳能电池的制造方法。由上述导电性浆料所制得的太阳能电池的EL性能检测良好,电池欧姆接触优良,电池效率高,稳定性高,并且附着力强,在提高稳定性和欧姆接触的同时兼顾了粘接性能。
Description
本发明主要涉及一种适用于用来制造EL检测下无缺陷的、具有高稳定性的太阳能电池电极用浆料组成以及使用该浆料的太阳能电池及其制造方法。
常规的太阳能电池是在呈导电型的半导体基板上面,设置电性相反的导电型的半导体层,并在该半导体层上设置防反射膜和受光面电极,同时在背面设置背面电极结构(下文在不区分正面、背面的时候,会统称为“电极”),受光后半导体的pn结产生的电能通过电极导出。假设上述的半导体基板是p型多晶半导体硅基板,受光面一侧的半导体层是n+层,同时,假设背面一侧的半导体层是p+层,上述的防反射膜在保持充分的可视光透过率的同时,可以降低表面反射率、提高受光率,因此一般是由氮化硅、二氧化钛、二氧化硅等薄膜组成的。具有多层结构的太阳能电池现在也在大量普及,例如通过保护防反射膜下面的半导体层来提高效率的具有保护层(钝化层,一般由氧化铝、氧化硅等构成)的电池构造、以及在半导体层下面具有导电层的被称为TOPCON(Tunneling oxide passivated contact,隧穿氧化钝化)的电池构造等。
同时,还有背面也能像正面一样,具有吸收太阳光功能的双面构造太阳能电池(Bifacial solar cells)。
上述的防反射膜(没有特别标注的情况下,包括具有保护层或不具有保护层两种情况)电阻值很大,而为了更充分的将半导体pn结产生的电能导出来,就需要在形成受光面电极的部分除去防反射膜。因此,假设太阳能电池的受光面电极是通过烧穿法形成的,那么首先在n+层上形成上述的防反射膜,再用丝网印刷法,在防反射膜上印刷导电性浆料,也就是以适宜的形状将呈浆料状的电极材料进行涂布印刷,再烧结,在烧结过程中,电极材料在加热 熔融的同时,接触到该电极材料的防反射膜也会熔融,从而在受光面电极和半导体基板之间形成接触。假设上面的导电性浆料的主要成分是银粉、玻璃(将玻璃原料熔融骤冷后,根据需要将其做成球磨后是片状或是粉末状的玻璃)、有机相和有机溶剂,在烧结过程中,这种导电性浆料中的玻璃成分会破坏防反射膜,导电性浆料中的导体成分就会通过n+层形成欧姆接触。因此,这与在形成电极之前先除去部分的防反射膜相比,工艺更简单,同时除去防反射膜的部分和形成电极的部分也不会有对位偏差的问题。
在形成上述所说的太阳能电池受光面电极时,需要在保证半导体基板和电极之间的粘结强度的同时,降低接触电阻,保证良好的欧姆接触,还需要提高电池的转换效率。针对太阳能电池电极的这些要求,从很久以前,就有很多针对改善粘结强度和接触电阻的提案和建议。其中,最有效的就是使用碲系玻璃的方案。
碲在玻璃成分中的作用是网络形成体,可以增大玻璃中银的溶解量,降低接触电阻,在烧结的降温段,可以抑制银的析出,从而在拓宽烧结窗口的同时,还有抑制半导体基板被过度腐蚀的作用。
通过上述的这些作用,可以充分的腐蚀防反射膜(也称之为绝缘膜),确保受光面电极和基板之间的良好接触,同时由于可以抑制进入到pn结等半导体层区域的电极材料,就会更容易形成良好的欧姆接触,而且因为导电性也得到提高,那么电性能方面应该也可以得到提高。另外,也能更容易的控制烧穿,这对于受光面一侧的半导体层的薄层化也有帮助。
关于使用碲系玻璃的太阳能电池,有如下的一些专利文献:
例如在日本专利公报第5782112号(专利文献1)中提到了使用铅碲系玻璃,其目的是在低温烧结下,形成电极浆料与防反射膜的贯通,从而与半导体基板形成良好的接触。
另外在日本专利公报第6074483号(专利文献2)中,同样的也提到了使用含碲的铅系玻璃的电极浆料。从其【0076】段中可以看到,随着玻璃中PbO的量增多,电极和基板之间的粘结强度就会减弱。这种对粘结强度的影响可以认为是与基板/电极界面的形态相关的。也就是说,玻璃中如果含有PbO, 即使不含有硬质的SiO
2成分,玻璃也会腐蚀基板,基板和电极之间也会形成良好的接触。然而,如果PbO的成分过量的话,基板会被腐蚀的更均一,腐蚀面就会变得更光滑,结果就会导致粘结强度减弱,使用铅碲系玻璃的电极浆料的粘结强度也会减弱。
为了解决这个问题,大家在致力于使用无铅玻璃来进行电极浆料的开发。
在日本专利公报第5559509号(专利文献3)中提到,由主要成分为银的导电性粉末、玻璃、有机相、溶剂做成的太阳能电池电极用导电浆料,通过使用含有以氧化碲为网络形成体的碲系玻璃的导电性浆料,来降低受光面电极和半导体基板之间的接触电阻。但是接触电阻主要与玻璃的组成相关。也就是说,接触电阻会受到氧化碲和其他玻璃成分(氧化钨和氧化钼等)的影响,因此很难去一直维持很低的接触电阻。
基于同样的目的,在无铅体系中,为了同时降低电极和半导体基板之间的接触电阻和电极的线电阻,有人提出使用将Te、Bi、Zn的摩尔总量换算成氧化物后为95(mol%)以上的玻璃的导电性浆料(例如可以参照日本专利公报第5937689号)(专利文献4))。另外,在该专利文献中也提到,将各个成分换算成对应的氧化物后的最佳范围为,Te 40~90(mol%)、Bi1~20(mol%)、Zn5~50(mol%),同时玻璃中的Si、B、Al、Zr、Ba、Mo以及La的总量在5(mol%)以下最为合适。
另外,含铅量在0.1(wt%)以下的无铅导电性浆料中,为了获得良好的太阳能电池性能,有人提出要在玻璃和导电浆料中的添加物的至少一种里,至少加入Mg、Ca、Sr和Ba中的一种,而加入的含量为:对于重量为100的导电性粉末,按照元素换算后,含量范围最好在0.1~10重量左右(例如可以参照日本公开专利公报2009-194141号(专利文献5))。在该专利文献中,没有对玻璃提出特别的要求限制,而是举例展示了Bi
2O
3-B
2O
3-SiO
2-CeO
2-LiO
2-NaO
2系玻璃和SiO
2-B
2O
3-Li
2O系等无铅玻璃。
在日本专利公报第5856277号(专利文献6)中,提到了推荐使用以碲、铋、锌、锂为必需元素的无铅玻璃。
在专利文献6的【0010】段落中,针对专利文献3到5中的组成进行了 总结,即“使用上述所说的无铅玻璃的导电性浆料来形成受光面电极的太阳能电池片,是希望能够同时能够实现基板和电极之间的高粘结强度,以及改善电池性能(尤其是实现低接触电阻和低线电阻),但是未能得到特别满意的结果”。另外也阐述了使用无铅玻璃的太阳能电池电极用浆料的特征:“虽然粘结强度是可以比较容易的通过调整玻璃软化点来实现的,但是和铅玻璃相比,无铅玻璃更难控制腐蚀程度,很难控制实现良好接触的条件”。
如上面所述,相对比较容易的可以获得较理想的粘结强度,这刚好符合以前在太阳能电池中占主流的多晶硅片对高粘结强度的要求,因此在太阳能电池市场中,使用无铅玻璃制备的导电性浆料开始被大家广为使用。
另一方面,在太阳能电池市场中,电池制造厂在拼命提高电池的转换效率的同时,也在急于实现其高稳定性。
所谓的高稳定性指的是,将制造好的太阳能电池串联排列,做成组件后能保证长时间的稳定性的发电能力,最近已经有能维持25年的。
提高太阳能电池稳定性的研究一直不断,同时也在讨论各种对稳定性有损害的不良因素,相关研究例如International Energy Agency、IEA,PHOTOVOLTAIC POWER SYSTEMS PROGRAMME、Reviewing the practicality and utility of electroluminescence and thermography images,M.
Institute for Solar Energy Research Hamelin。
为了确保组件的高稳定性,在太阳能电池领域引进了一种以前没有的新型检测项目,这也对浆料提出了新的要求。新型的检测项目是EL检测(Electro Luminescence)。
EL检测是在太阳能电池上施加电场,进入半导体内的电子和空穴再结合,将发光的部分拍摄下来,再分析这个拍摄的照片。施加电场后,电荷流过的部分就会发光,没有电荷通过的部分就会是暗的。利用这个特性,就可以提前明确在电池外观上无法看出的缺陷和问题,从而能够确保其高稳定性。
通过这种新型检测项目,太阳能电池的研究者开始了解,在使用无铅的碲系玻璃的电极浆料的太阳能电池中,其实会经常发生黑点或云雾状黑斑,影响太阳能电池的性能。EL检测照片的案例如图1所示,图1包括四种太阳 能电池的案例检测结果,其中(1)-(3)均显示为EL检测性能不佳,(4)为EL检测性能正常案例,但(4)的拉力性能不好,粘接强度低。
发明内容
本发明提供一种导电性浆料,及使用所述导电性浆料印刷为表面电极的太阳能电池以及所述太阳能电池的制造方法,所制得的太阳能电池的EL性能检测正常,因而稳定性高,且电池欧姆接触优良,进而电池效率高,并同时兼顾了粘接性能,粘接强度优良。
本发明的技术方案如下:
一种用来形成太阳能电池表面电极的导电性浆料,其含有导电性粉末、混合玻璃、以及有机相;其中,所述混合玻璃包含以下两类玻璃组分:第一类玻璃选自实质上不含铅、以碲铋锂为必需成分的碲系玻璃的至少一种;第二类玻璃选自以铅和硅为必需成分、实质上不含碲的硅酸铅系玻璃的至少一种。
如上所述的导电性浆料,其中,所述第一类玻璃可包含一种或多种实质上不含铅、以碲铋锂为必需成分的碲系玻璃;所述第二类玻璃可包含一种或多种以铅和硅为必需成分、实质上不含碲的硅酸铅系玻璃。
如上所述的导电性浆料,其中,所述的混合玻璃中,所述碲系玻璃的总量与所述硅酸铅系玻璃的总量的质量比为2:8~8:2。
如上所述的导电性浆料,其中,所述碲系玻璃换算成氧化物,碲为44~76%,铋为7~51mol%,锂为2~14mol%。
在本发明的一些实施例中,所述碲系玻璃还可以含有钨、锌、硅、钠、铝、铜的氧化物中的任何一种或几种。
如上所述的导电性浆料,其中,所述硅酸铅系玻璃还可以含有锌、钨、钠、锂、铝、铜中的任何一个或任何几个,所述硅酸铅系玻璃换算成氧化物,铅为39~70mol%,硅为20~43mol%,锌、钨、钠、锂、铝、铜总计为0~20mol%。
如上所述的导电性浆料,其中,在不影响本发明目的实现的前提下,例如作为本发明的主要实施方案的可替换实施例,所述混合玻璃还可以含有其它种类的玻璃,在这种情况下,对于质量为100%的混合玻璃,所述第一类玻璃和第二类玻璃的质量总量超过50%。
如上所述的导电性浆料,其中,对于质量为100的导电性粉末,混合玻璃的含量最好控制在质量为0.1~10左右。
本发明还提供一种太阳能电池,其具有半导体基板、设置于所述半导体基板的表面上的第一区域的防反射膜、设置于所述半导体基板的所述表面上的第二区域的表面电极,其中,所述表面电极为上述任一的导电性浆料印刷制得。上述的表面指所述半导体基板的正面和/或背面。
本发明还提供一种太阳能电池的制造方法,所述太阳能电池具有半导体基板、设置于所述半导体基板的表面上的第一区域的防反射膜、设置于所述半导体基板的所述表面上的第二区域的表面电极,其中,所述制造方法主要分为以下三步工艺:
第一步工艺为:在所述半导体基板的所述表面上形成防反射膜;
第二步工艺为:将含有导电性粉末、混合玻璃、有机相的导电性浆料印刷在第一步形成的防反射膜上,其中所述混合玻璃主要是由一类实质上不含铅、以碲铋锂为必需成分的碲系玻璃和一类以铅硅为必需成分、实质上不含碲的硅酸铅系玻璃混合组成的;
第三步工艺为:对所述导电性浆料进行烧结,烧结过程中除去了位于所述导电性浆料下面的防反射膜部分,从而最终在所述半导体基板的所述第一区域形成所述防反射膜、在所述半导体基板的所述第二区域形成所述表面电极。
上述的表面指所述半导体基板的正面和/或背面。
如上所述的导电性浆料,所述第一类玻璃可包含一种或多种实质上不含铅、以碲铋锂为必需成分的碲系玻璃;所述第二类玻璃可包含一种或多种以铅和硅为必需成分、实质上不含碲的硅酸铅系玻璃。
本发明还请求保护一种用于太阳能电池的玻璃料,其为上述任一的混合玻璃。
与现有技术相比,本发明的有益效果如下:
由本发明的导电性浆料所制得的太阳能电池的EL性能检测正常,因而能确保组件的高稳定性,且电池欧姆接触优良,所以电池效率高、寿命长,并同时兼顾了粘接性能,粘接强度优良。
图1是现有技术中几种太阳能电池EL检测的照片;
图2是使用与本发明相关的导电性浆料生产制造的太阳能电池的实施方式的重要部分截面图;
图3是受光面电极一侧的扩大平面模式图;
图4是背面电极一侧的扩大底面模式图;
图5是实施例中浆料编号为1-13的样品的EL检测结果照片;
图6是实施例中浆料编号为31-38的样品的EL检测结果照片。
图中标号含义如下:1—半导体基板;1a—n型半导体层;1b—p型半导体层;2—防反射膜(包括或不包括保护层);3—受光面电极;4—背面电极;5a、5b…5n—细栅电极;6—主栅电极;7—集电电极;8—导出电极。
本发明提供一种太阳能电池用导电性浆料,及使用该导电性浆料的太阳能电池,及该太阳能电池的制造方法。
本发明人研究了现有的无铅碲系玻璃,其中,在本发明的背景技术中提到的专利文献4至6中公开的无铅碲系玻璃都是以铋作为其必需成分的。本发明人认为,无铅碲系玻璃中的铋成分虽然可以适当减弱碲较强的抑制腐蚀的作用,从而可以提高无铅碲系玻璃的腐蚀性。但是,含铋的无铅碲系玻璃在加热熔融时容易分相,高流动性部分和低流动性部分会分开,导致高流动 性部分会过度的腐蚀。本发明人通过研究认为,也正是因为这个原因,半导体基板和电极浆料之间会形成不均一的欧姆接触。
在以前,这种不均一的欧姆接触并不为人所知,但是导入了上述EL检测后,这个问题开始显现出来。
这个问题的出现对导电性浆料提出了新的要求,即在保证良好的粘结强度的同时,欧姆接触也要较均一,也就是需要研发一种能在EL检测下实现良好接触、且粘接强度良好的电极浆料。
针对此问题,本发明提供了一种既能保证电性能又能保证粘结强度、而且EL检测下也是呈现良好接触的电极浆料,即一种用于在太阳能电池上印刷表面电极的导电性浆料。
为了实现上述目的,本发明者进行了大量的研究,最终确认:只使用含碲的无铅玻璃的电极浆料在EL检测时会更容易发生由于欧姆接触不好而导致的电池黑斑现象,为了确保良好的欧姆接触,通常会提高烧结温度,但又会由于过烧造成云雾状的黑斑,即最佳的烧温窗口特别窄,难以操作。为了解决此问题,发明人经大量研究和分析发现,如果使用含有特定成分和比例的碲系无铅玻璃和不含碲但含有特定成分和比例的铅玻璃同时配合使用,电极浆料在烧结后的EL检测时看不见EL不良。
本发明方案的提出就是基于发明人的上述发现。本发明中涉及到的导电性浆料是形成太阳能电池电极用的导电性浆料,特点是至少使用导电性粉末,以及同时使用主成分为碲铋锂而实质上不含铅的无铅玻璃、和主成分为铅硅但实质上不含碲的硅酸铅系玻璃。
在日本专利公报第6175392号(专利文献7)中,和本发明一样提到了太阳能电池片表面电极用导电性浆料,它是由导电性粉末、混合玻璃和有机相组成的,混合玻璃指的是碲、钨、铋为必需成分的碲系玻璃,和铅铋为必需成分、实质上不含碲的铅铋系玻璃混合使用的。但是通过本发明后面叙述的结果可知,在专利文献7中公开的玻璃组成,并未达到本发明的目的,即没有解决EL检测时发现的欧姆接触不良的问题。因此可见,并不是所有的碲系玻璃与铅玻璃的组合都能实现本发明的EL检测良好的效果,而是只有本发明 的特定玻璃组合才能达到EL检测良好、同时粘接性能佳的效果。
另外,在中国专利文献第103377752B号(专利文献8)中,公开了太阳能电池片表面电极用导电性浆料中的无机反应体系,即混合使用铅系玻璃和碲系玻璃。但是本发明人经过后述的测试结果可以确认,专利文献8和专利文献7一样,均未能解决本篇发明中重点强调的EL检测时的外观问题。
在本文中,由「一数值至另一数值」表示的范围,是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此,某一特定数值范围的记载,涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围,如同在说明书中明文写出该任意数值和该较小数值范围一样。
以下会详细说明本发明的实施方式。应该理解,这些实施方式和实施例仅用于说明本发明,而不用于限定本发明的保护范围。在实际应用中本领域技术人员根据本发明做出的改进和调整,仍属于本发明的保护范围。
图2是使用与本发明相关的导电性浆料生产制造的太阳能电池的形貌的重要部分的截面图。
该太阳能电池的组成包括:以硅为主要成分的半导体基板1,以及在半导体基板1的一个表面上形成的防反射膜2以及受光面电极3,和在该半导体基板1的另一个表面上形成的背面电极4。
更具体地,半导体基板1具有p型半导体层1b和n型半导体层1a,p型半导体层1b的上面形成n型半导体层1a。
具体地例如,在单晶硅或多晶硅的p型半导体层1b的一个表面上扩散杂质,通过形成薄薄的n型半导体层1a,就可以得到该半导体基板1,但是对于本发明而言,只要能在p型半导体层1b的上面形成n型半导体层1a即可,关于它的结构和制造方法都没有特别的限定和要求。另外,半导体基板1还可以使用在n型半导体层的一个表面上形成薄薄的p型半导体层的构造,或者也可以使用在半导体基板1的一个表面上同时形成p型半导体层和n型半导体层的构造。无论是哪种构造,只要是形成了防反射膜2的半导体基板1的表面上,都可以使用本发明中涉及到的导电性浆料。
另外,在图2中,半导体基板1的表面是平平的,但是为了将太阳光尽可能高效的封闭在半导体基板里,其表面其实是呈微小凹凸状的结构。
防反射膜2,是由氮化硅(SiNx)等绝缘性材料形成的,用来抑制箭头A所显示的太阳光在受光面的反射,进而快速而又高效的将太阳光传导到半导体基板1中。防反射膜2的构成材料,不仅仅限于上述的氮化硅,也可以使用其他的绝缘性材料,例如可以使用氧化硅、氧化钛,也可以同时使用两种以上的绝缘性材料。另外,对于半导体基板而言,只要是晶体硅系,无论是单晶硅还是多晶硅都可以使用。在本发明中,防反射膜2可以包括或不包括保护层(通过保护防反射膜下面的半导体层来提高效率的一种钝化层,一般由氧化铝、氧化硅等构成)。
受光面电极3,是在半导体基板1上贯通防反射膜2而形成的。受光面电极3,是使用丝网印刷等方法,将后面所述的本发明的导电性浆料涂布在半导体基板1上形成导电膜,然后通过烧结而形成的。也就是说,在形成受光面电极3的烧结过程中,导电膜下层的防反射膜2会被分解、除去、烧穿,从而导电性浆料与防反射膜2贯通在一起的方式,在半导体基板1的上面形成了受光面电极3,其中,受光面电极3与半导体基板1导通。
受光面电极3的具体结构可以如图3所示,很多的细栅电极5a、5b、……5n像梳子的齿状一样排在一起,同时主栅电极6和细栅电极5a、5b、……5n呈交叉状设置,细栅电极5a、5b、……5n和主栅电极6是电导通的。另外,在受光面电极3之外的区域,形成防反射膜2。像这样,半导体基板1产生的电能通过细栅电极5a、5b、……5n进行收集,同时通过主栅电极6导出到外面。
背面电极4,具体如图4所示,是由在p型半导体层1b背面形成的由Al等构成的集电电极7、和与该集电电极7电流导通的Ag等构成的导出电极8而组成的。其中,半导体基板1产生的电能通过集电电极7进行收集,再通过导出电极8将电能导出去。
下面,将就本发明中形成受光面电极3的导电性浆料进行详细叙述。
本发明中所说的导电性浆料主要由导电性粉末、混合玻璃以及有机相组 成,其中混合玻璃含有两类玻璃料,其中一类是实质上不含铅、以碲铋锂为必需成分的碲系玻璃的至少一种,另一类为以铅硅为必需成分、实质上不含碲的硅酸铅系玻璃的至少一种。
如上所述的导电性浆料,其中,所述第一类玻璃可包含一种或多种实质上不含铅、以碲铋锂为必需成分的碲系玻璃;所述第二类玻璃可包含一种或多种以铅和硅为必需成分、实质上不含碲的硅酸铅系玻璃。在以下明细表中,如果没有记载各个玻璃的每种元素的具体构成组分,那么该元素就是作为氧化物包含在玻璃中了。因此,说“实质上不含有”某种成分X,意思是其实不可避免的会含有少量成分X,或者说也不排除会为了利用本发明的实质而在不影响实现本发明目的的前提下少量添加成分X。
另外,形成受光面电极3的导电性浆料,含有上述的导电性粉末、混合玻璃、适量的添加剂以及有机相。这种导电性浆料还可以是适合丝网印刷之外的其他印刷方法的流变浆料、涂料、或者油墨状的组成物。
导电性浆料中混合玻璃的含量,可以参考太阳能电池电极用导电性浆料中通常的使用量,但是在这里可以举一例,对于质量为100的导电性粉末,混合玻璃的含量最好控制在质量为0.1~10左右。对于质量为100的导电性粉末,混合玻璃的质量如果在0.1以上,就可以得到所规定的密封性和电极强度。另外,对于质量为100的导电性粉末,如果混合玻璃的质量在10以下,那么电极表面就会浮出玻璃,而通过流入到电极和半导体基板的扩散层的界面的玻璃,可以帮助降低接触电阻的增加。虽然没有什么特别的限制要求,但是在本篇实施方式中的导电性浆料中的碲系玻璃和硅酸铅系玻璃,平均粒径在0.5~3.0μm最为合适。
对于导电性粉末,除了主要成分为银这个要求外,其他没有什么限制,它的形状可以为球状、片状、树枝状等,以前一直在用的银粉都可以。另外,除了纯银粉末之外,至少表面是银层的银包覆复合粉末,或者是以银为主要成分的合金等都可以。银粉末等导电性粉末,平均粒径最好在0.1~10μm。另外平均粒径、粒度分布、形状等不同的两种以上的导电性粉末混合使用也可以,甚至可以将银粉末和银以外的导电性粉末一起混合使用也可以。上述 的“主要成分”指的是质量超过50%的成分,最好是指质量超过70%的成分。另外,和银粉末复合、合金、或者混合的金属,只要对于本发明及其实施方式中所说的作用效果没有损害,就没有其他的限制,例如铝、金、钯、铜、镍等。不过,从导电性的角度来看,还是最推荐使用银粉末。
对于有机相,也没有特别的限定要求,一般会合理的使用银浆有机相中通常被使用的有机树脂和有机溶剂等。另外有机树脂可使用纤维素类、丙烯酸树脂类、苯酚树脂类、醇酸树脂、或者是松香树脂等。有机溶剂可使用醇类、醚类、酯类、烃类等有机溶剂,或者是水,以及上述这些的混合溶剂。因此对于有机相的比例没有特别的要求,只要取适量,然后能和导电性粉末以及混合玻璃等无机成分形成浆料,之后可通过涂布等方法再合理调整。虽说如此,但一般对于质量为100的导电性粉末来说,有机相的质量为5~40左右。
其他的成分可以根据需要,只要在不有损本发明及其实施方式的作用效果的范围内,可以适量的添加常规使用的添加剂,例如可塑剂、调粘剂、界面活性剂、氧化剂、金属氧化物、金属有机化合物等。另外,也可以使用碳酸银、氧化银、醋酸银等银化合物,为了优化烧结温度,改善太阳能电池的特性,也可以适量添加氧化铜、氧化锌、氧化钨、氧化钛等。
上述碲系玻璃,例如换算成氧化物的话,碲为44~76mol%,铋为7~51mol%,锂为2~14mol%。
上述碲系玻璃中,碲起到网络形成体的作用,像上述一样,它可以增大玻璃中银的溶解量、降低接触电阻,在烧结的降温段,可以抑制银的析出,拓宽烧结窗口的同时,还有抑制对半导体基板腐蚀的作用。通过这些作用,可以充分的腐蚀绝缘膜,确保电极材料和基板之间的良好接触,同时由于可以抑制进入到pn结等半导体层区域的电极材料,就会更容易形成良好的欧姆接触,而且导电性也得到提高,电性能方面也可以得到提高。另外,也更容易控制烧穿,这对于受光面一侧的半导体层的薄层化也有帮助。碲的含量如果不足44(mol%),就无法充分增大玻璃中银的溶解量,而超过76(mol%)的话,抑制腐蚀的作用就会过强,从而无法充分烧穿。
另外,铋是提高玻璃软化点的成分,在保证碲系玻璃低粘性的同时调整软化点时可以添加该成分。另外,还可以赋予玻璃腐蚀作用。上述的碲虽然抑制腐蚀作用很强,但是通过适宜的调整铋的含量,也可以将腐蚀性控制的恰到好处。但铋的含量如果超过52(mol%),玻璃就会容易结晶。
另外,锂有降低玻璃软化点的作用,同时也是施主,对于n型半导体来说,通过半导体基板(例如硅基板)和电极材料之间的相互扩散,界面旁的施主浓度会下降,而锂可以起到补给的作用。如果锂的含量不足1(mol%),就无法起到很好的补给作用,但是超过14(mol%)腐蚀作用就会过强,玻璃的稳定性就会下降。另外,一般来说碱金属成分对太阳能电池特性会有不好的影响,因此最好不要使用。例如Na会导致开压Voc降低,K会导致FF降低的同时提高接触电阻。而且,Na、K不会形成施主,因此没有使用的利处。而锂则有补给的作用,在n型半导体的电极形成中,可以获得更优的太阳能电池特性,因此很有用。
另外,碲系玻璃除碲铋锂之外,还可以含有钨、锌、硅、钠、铝、铜的氧化物中的任何一种或几种。
上述的硅酸铅系玻璃,铅硅为必需成分,另外还可以含有锌、钨、钠、锂、铝、铜中的任何一种或几种。
对于硅酸铅系玻璃除铅硅之外,还可以含有锌、钨、钠、锂、铝、铜中的任何一种或几种的情况,各元素换算成氧化物,含量分别为:铅为39~70mol%,硅为20~43mol%,锌、钨、钠、锂、铝、铜总计为0~20mol%。
铅主要是作为网目形成的成分,用来形成硅酸铅系玻璃的网络。铅具有单独形成玻璃的能力,含量最好在39~70mol%之间,含量在这个范围内,烧穿性会得到改善。
硅,尤其是在上述硅酸铅系玻璃中,可以帮助形成玻璃网络,更容易调整软化点。换算成氧化物,如果硅的含量在1~50mol%的话,会更容易成玻,最好含量范围在20~43mol%。一旦含量超过50mol%,软化点就会变得过高,同时作为铅的网目形成成分,担心会阻碍网络的形成。
在上述硅酸铅系玻璃中,还可以含有锌、钨、钠、锂、铝、铜中的任何 一种或几种。这些元素的含量,换算成氧化物后,最好总量在20mol%以下。
在EL检测中为了获得良好的外观,以及高稳定性的表面电极,最好控制混合玻璃中碲系玻璃和硅酸铅系玻璃的质量比为2:8~8:2。另外,混合玻璃至少是混合使用碲系玻璃和硅酸铅系玻璃,也可以在基本不影响本发明效果的前提下额外含有其他玻璃。
如上述所说,使用主要由实质上不含铅、以碲铋锂为必需成分的碲系玻璃和以铅硅为必需成分、实质上不含碲的硅酸铅系玻璃构成的混合玻璃制作的导电浆料,可以同时平衡良好的欧姆接触和粘结强度,同时也可以形成没有EL问题的表面电极。而这种作用效果,是单独使用碲系玻璃或单独使用硅酸铅系玻璃达不到的,并且同时单独使用铅碲系玻璃也是达不到的。
下面会具体描述本发明的实施例。
实施例1
〔小样制作〕
制作碲系玻璃:准备了TeO
2、Bi
2O
3、WO
3、ZnO、Al
2O
3、LiO
2、B
2O
3等,如表1-1、表1-2、表1-3中所示的配比,将这些玻璃原材料进行称量调制,最后做成了小样玻璃A-1~A-5。
表1-1
表1-2
表1-3
A-5 | TeO2 | B2O3 |
重量% | 93 | 7 |
Mol% | 85.3 | 14.7 |
其中,
A-4为本发明定义的实质上不含铅、以碲铋锂为必需成分的碲系玻璃的实施例,
其余为对比例,具体地,
A-1为碲铋钨玻璃(专利文献7中的配方);
A-2为碲铋锌为主要组分且添加铝元素的玻璃。
A-3为碲铋锌为主要组分并添加铝元素的玻璃。
A-5为碲硼玻璃(专利文献8中的配方)
制作硅酸铅系玻璃:准备了PbO、Bi
2O
3、WO
3、ZnO、SiO
2、Na
2O、B
2O
3、Al
2O
3、LiO
2、TiO
2等,如表2-1、表2-2、表2-3所示的配比,将这些玻璃原材料称量调制,最后做成了小样玻璃B-1~B-8。
表2-1
表2-2
B-2 | PbO | B2O3 | SiO2 | Al2O3 | TiO2 |
重量% | 79.03 | 4.11 | 7.09 | 6.01 | 3.77 |
Mol% | 55.56 | 9.26 | 18.52 | 9.26 | 7.41 |
表2-3
其中:
B-2至B-6、B-8为以铅硅为必需成分、实质上不含碲的硅酸铅系玻璃的实例,其中B-2也是专利文献8中的配方;
B-1、B-7为对比例,不属于以铅硅为必需成分、实质上不含碲的硅酸铅系玻璃,
其中B-1为铅铋为必需成分的、实质上不含碲的铅铋系玻璃(专利文献7中配方);
B-3至B-8为一个系列,具体考察了铅玻璃中锌、钨、硅、钠、锂元素存在的必要性;其中,
B-3为锌、钨、硅、钠、锂元素均存在的实施例;
B-4为去掉钨元素的实施例;
B-5为去掉钠元素的实施例;
B-6为去掉锌元素的实施例;
B-7为去掉硅元素的铅玻璃;
B-8为去掉锂元素的实施例。
另外,对于导电性粉末,提前准备了平均粒径在2.0μm的球形银粉。
制作有机相:树脂使用10wt%的乙基纤维素,而有机溶剂使用90wt%的辛醇,将二者混合,制成有机相。
然后,取银粉末为88.0wt%,玻璃总量为2.6wt%,将这些和脂肪酸酰胺、脂肪酸等流变调整剂,以及上述有机相等共同混合,行星搅拌机进行混合后,三辊机进行混合压制,从而做成导电浆料。
使用上述制得的各导电浆料制作太阳能电池方法如下:
从中国的华昌公司购买了单晶硅太阳能电池Si系半导体基板(156mm的正方形),该硅半导体基板为表面制绒,方阻为90Ω/sq、在磷扩散发射极层上具有SiNx防反射膜。
也从中国的通威公司购买了单晶硅太阳能电池Si系半导体基板(156mm的正方形),该硅半导体基板同样为表面制绒、方阻为90Ω/sq,在磷扩散发射极层上具有保护层atomic layer deposited aluminum oxide(ALD-Al2O3), 在保护层上具有SiNx防反射膜。
接下来要准备以Al为主成分的铝浆,以及Ag为主成分的银浆。然后在上述Si系半导体基板的背面涂覆适量的铝浆和银浆,然后干燥烘干,就会形成背面电极用导电膜。
接下来使用上述导电性浆料进行丝网印刷,在Si系半导体基板的表面上涂布导电性浆料,做成受光面电极用导电膜。
印刷时使用的网版为5主栅的网版。
印刷结束后,使用带式近红外炉(despatch公司生产,烘干烧结一体式),按照下表3的条件完成烘干烧结。
【表3】
〔小样评估〕
烧结好的太阳能电池,使用EL检测装置(Geonic automation公司产)检测,并将照片检测时没有黑点(黑点代表EL不良)的电池片,使用I-V测试仪(Pasan公司生产)测试电池转换效率。如果在准备过程中没有片子破损,会每个样品测试10片。
粘结强度通过自制的自动拉力测试机,采用180度剥离法来测试粘度强度。
表4和图5为浆料中的玻璃配比和测试结果。
表4
浆料编号 | 无铅的碲系玻璃 | 比例(wt%) | 硅酸铅系玻璃 | 比例(wt%) | EL检测结果 | 池转换效率(% |
1 | A-1 | 2.6 | NG | 未测 | ||
2 | A-2 | 2.6 | NG | 未测 | ||
3 | A-3 | 2.6 | NG | 未测 | ||
4 | A-4 | 2.6 | NG | 未测 | ||
5 | A-1 | 1.625 | B-1 | 0.975 | NG | 未测 |
6 | A-2 | 1.625 | B-1 | 0.975 | NG | 未测 |
7 | A-3 | 1.625 | B-1 | 0.975 | NG | 未测 |
8 | A-4 | 1.625 | B-1 | 0.975 | NG | 未测 |
9 | A-5 | 2.79 | B-2 | 0.9 | NG | 未测 |
10 | A-1 | 1.625 | B-3 | 0.975 | NG | 未测 |
11 | A-2 | 1.625 | B-3 | 0.975 | NG | 未测 |
12 | A-3 | 1.625 | B-3 | 0.975 | NG | 未测 |
13 | A-4 | 1.625 | B-3 | 0.975 | OK | 19.98 |
14 | A-4 | 1.625 | B-4 | 0.975 | OK | 19.98 |
15 | A-4 | 1.625 | B-5 | 0.975 | OK | 20.05 |
16 | A-4 | 1.625 | B-6 | 0.975 | OK | 20.03 |
17 | A-4 | 1.625 | B-8 | 0.975 | OK | 20.02 |
表4中,EL检测结果一列中,NG代表检测结果不良。
从表4可以看出,
单独的无铅碲系玻璃(编号1-4)EL检测结果不良;
B-1(专利文献7中公开的铅铋为必需成分的、实质上不含碲的铅铋系玻璃)与A-1至A-4中任何一种无铅碲系玻璃组合(编号5-8)后,EL检测结果均不良。B-2(专利文献8中公开的铅-硼-硅酸盐玻璃)与A-5(专利文献8中公开的碲系玻璃)组合(编号9)后,EL检测结果不良。证明硅酸铅系玻璃并不是与任一种碲系玻璃组合后都能够得到EL检测良好的效果。
B-3(本发明的硅酸铅系玻璃)与A-4(本发明的碲铋锂无铅玻璃)组合(编号13)后EL检测效果良好,而与A-1至A-3(其他碲系玻璃)分别组合(编号10-12)后,EL检测结果不良。
A-4与B-3、B-4、B-5、B-6、B-8分别组合(编号13-17)后,EL检测结果良好。可见,B系列代表的硅酸铅系玻璃,硅元素和铅元素为必不可少的,而锌、钨、钠、锂中任一元素去除仍能够得到EL检测良好的结果。
由于B-7不能成玻,因此未进行组合实验。
图5中,
浆料编号1~4,是单独使用无铅的碲系玻璃时的结果。其中,
A-1是专利文献7中第9页的小样7。
A-2,A-3是专利文献4第10页的小样No.1和No.7。
A-4是本发明人自己发明的无铅的碲系玻璃。
通过上述结果可知,单独使用无铅的碲系玻璃,所有的电池都会在EL检测时出现黑斑(EL不良)。
浆料编号5~8,是将上述的无铅的碲系玻璃A-1至A-4和表2中B-1所示的铅玻璃(专利文献7第12页,表2中的B6)混合使用做成的。
在这种情况下,发现所有的组合也都会在EL检测时出现黑斑(EL不良)。
因此可以确认,专利文献7中提到的用碲、钨、铋为必需成分的碲系玻璃,和铅铋为必需成分、实质上不含碲的铅铋系玻璃复配混合的方法,是对EL改善没有效果的。
浆料编号9是使用专利文献8第13页所示的实施例浆料1中相同的玻璃制备的。
使用的玻璃组成如表1-3和表2-2所示,是和专利文献8第12页的铅-硼-硅酸盐玻璃(玻璃A)、第13页的碲系玻璃(玻璃B)具有相同组成的玻璃。
经确认,该浆料在EL检测时会出现黑斑(EL不良)。
经过以上结果,可以确认,专利文献8中提出的无机反应体系对EL改善没有效果,和本篇发明具有本质性的差异。
浆料编号10~13是为了验证和本发明人自己发明的硅酸铅系玻璃复配组合的结果。其中只有浆料编号13的EL情况得到了改善。因此从中可确认,即使是相同的无铅的碲铋系玻璃,锂是必需成分,只有在锂存在的情况下,和硅酸铅系玻璃组合使用才有好的效果。
对比浆料编号8和13,可以发现由于玻璃B-1和B-3的差异造成了效果的差异。因此,浆料编号14~17,主要是为了找出玻璃B-3中起作用的必需元素。验证方法为,将B-4~B-8的氧化物择一除去。验证结果为,包括成玻在内,铅和硅是必需元素。
下表5,表6,表7中对本发明中的无铅的碲系玻璃和硅酸铅系玻璃组合起作用的范围,进行了实施例中的一部分展示。
表5
从表5的A-11、A-12、A-13可以看出,当无铅的碲系玻璃中氧化碲的含量小于40mol%、氧化铋的含量大于55%时,不能成玻或熔制不均一。
表6
从表6的B-10、B-12、B-15可以看到,即使只含有铅硅两种元素,也存在能够良好成玻的方案。
从表6的B-11、B-14、B-16可见,当硅酸铅系玻璃中氧化铅的含量小于等于30%、氧化硅的含量大于等于70%时,不能成玻。
表7
从表7的编号18(A-4+B-12)样品可以看出,当硅酸铅系玻璃中氧化铅的含量大于80mol%时,EL检测结果不佳。
从表8的编号23(A-9+B-3)样品可以看出,当无铅的碲系玻璃中去掉氧化铋时,EL检测结果不佳。
从表8的编号24(A-10+B-3)样品可以看出,当无铅的碲系玻璃中氧化碲的含量大于80mol%、且氧化锂的含量小于2mol%时,EL检测结果不佳。
图6展示了表7中的浆料编号为31-38的样品的EL检测照片。从图6中可见,各照片均无黑点,证明浆料编号为31-38的样品EL检测结果良好。
表7中的浆料编号为31-37的样品是A-15和B-17的组合,但两者的含量及相对比例不同,证明这些含量及比例均能够得到高稳定性的太阳能电池。
其中,浆料编号31,是使用在防反射膜下面具有保护层的单晶硅太阳能电池Si系半导体基板,得到的实验结果。
其余编号的浆料,是使用具有防反射膜的单晶硅太阳能电池Si系半导体基板的实验结果。
这证明本发明的浆料既适用于含有保护层的半导体基板,也适用于不含有保护层的半导体基板。
根据上述所有结果可知,本发明提供的导电性浆料在很宽的含量范围内都可 以适用。
【产业上的可利用性】
本发明的导电性浆料作为电极浆料制造得到的太阳能电池片具有良好的电性能(电池转换效率)和粘结强度,同时EL检测显示具有良好接触,具有高稳定性。
在本发明及上述实施例的教导下,本领域技术人员很容易预见到,本发明所列举或例举的各原料或其等同替换物、各加工方法或其等同替换物都能实现本发明,以及各原料和加工方法的参数上下限取值、区间值都能实现本发明,在此不一一列举实施例。
Claims (8)
- 一种用来形成太阳能电池表面电极的导电性浆料,其特征在于,含有导电性粉末、混合玻璃、以及有机相;其中,所述混合玻璃包含以下两类玻璃组分:第一类玻璃选自实质上不含铅、以碲铋锂为必需成分的碲系玻璃的至少一种;第二类玻璃选自以铅和硅为必需成分、实质上不含碲的硅酸铅系玻璃的至少一种。
- 如权利要求1所述的导电性浆料,其特征在于,所述的混合玻璃中,所述碲系玻璃的总量与所述硅酸铅系玻璃的总量的质量比为2:8~8:2。
- 如权利要求1所述的导电性浆料,其特征在于,所述碲系玻璃换算成氧化物,碲为44~76mol%,铋为7~51mol%,锂为2~14mol%。
- 如权利要求1或2或3所述的导电性浆料,其特征在于,所述硅酸铅系玻璃换算成氧化物,铅为39~70mol%,硅为20~43mol%,锌、钨、钠、锂、铝、铜总计为0~20mol%。
- 如权利要求1或2所述的导电性浆料,其特征在于,对于质量为100的导电性粉末,所述混合玻璃的含量控制在质量为0.1~10。
- 一种太阳能电池,具有半导体基板、设置于所述半导体基板的表面上的第一区域的防反射膜、设置于所述半导体基板的所述表面上的第二区域的表面电极,其特征在于,所述表面电极由权利要求1-5中任一所述的导电性浆料印刷制得。
- 一种太阳能电池的制造方法,所述太阳能电池具有半导体基板、设置于所述半导体基板的表面上的第一区域的防反射膜、设置于所述半导体基板的所述表面上的第二区域的表面电极,其特征在于,所述制造方法主要分为以下三步工艺:第一步工艺为:在所述半导体基板的所述表面上形成防反射膜;第二步工艺为:将含有导电性粉末、混合玻璃、有机相的导电性浆料印刷在第一步形成的防反射膜上,其中所述混合玻璃主要是由一类实质上不含铅、以碲铋锂为必需成分的碲系玻璃和一类以铅硅为必需成分、实质上不含碲的硅酸铅系玻璃混合组成的;第三步工艺为:对所述导电性浆料进行烧结,烧结过程中除去了位于所述导电性浆料下面的防反射膜部分,从而最终在所述半导体基板的所述第一区域形成所述防反射膜、在所述半导体基板的所述第二区域形成所述表面电极。
- 一种用于太阳能电池的玻璃料,其特征在于,为权利要求1-5中任一所述的混合玻璃。
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