TWI667218B - PERC type aluminum paste composition for solar cells - Google Patents
PERC type aluminum paste composition for solar cells Download PDFInfo
- Publication number
- TWI667218B TWI667218B TW105113344A TW105113344A TWI667218B TW I667218 B TWI667218 B TW I667218B TW 105113344 A TW105113344 A TW 105113344A TW 105113344 A TW105113344 A TW 105113344A TW I667218 B TWI667218 B TW I667218B
- Authority
- TW
- Taiwan
- Prior art keywords
- paste composition
- aluminum
- glass frit
- solar cell
- component
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 165
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 63
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title abstract 4
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title abstract 4
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title abstract 4
- 239000011521 glass Substances 0.000 claims abstract description 89
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 38
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 22
- KODMFZHGYSZSHL-UHFFFAOYSA-N aluminum bismuth Chemical compound [Al].[Bi] KODMFZHGYSZSHL-UHFFFAOYSA-N 0.000 claims description 21
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 19
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 13
- 238000010248 power generation Methods 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011231 conductive filler Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- QNTVPKHKFIYODU-UHFFFAOYSA-N aluminum niobium Chemical compound [Al].[Nb] QNTVPKHKFIYODU-UHFFFAOYSA-N 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 43
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000010304 firing Methods 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 description 19
- -1 B 2 O 3 Chemical compound 0.000 description 17
- 229910052732 germanium Inorganic materials 0.000 description 16
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 229910052715 tantalum Inorganic materials 0.000 description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 9
- 238000002161 passivation Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000008012 organic excipient Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 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
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 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
- DRVLHCMOXCBPHN-UHFFFAOYSA-N aluminum ruthenium Chemical compound [Al].[Ru] DRVLHCMOXCBPHN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings 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
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Dispersion Chemistry (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
- Glass Compositions (AREA)
Abstract
本發明係提供一種PERC型太陽電池用鋁膏組成物，其可賦予PERC型太陽電池單元高轉換效率，且對於矽基板有優異之密著性，進一步，即使在高溫高濕環境下，亦可抑制電特性的降低及燒成後孔洞的產生。 The present invention provides a PERC type aluminum paste composition for a solar cell, which can impart high conversion efficiency to a PERC type solar cell unit, and has excellent adhesion to a ruthenium substrate, and further, even in a high temperature and high humidity environment, The reduction of electrical characteristics and the generation of voids after firing are suppressed.
其特徵為其係至少含有玻璃料作為構成成分之PERC型太陽電池用鋁膏組成物。前述玻璃料，不含Pb及鹼金屬，而係含B2O3成分者。 It is characterized in that it is a composition of an aluminum paste for a PERC type solar cell containing at least a glass frit as a constituent component. The glass frit contains no Pb or alkali metal but a B 2 O 3 component.
Description
本發明係關於一種在裏面具有鈍化膜(Passivation film)之結晶系太陽電池單元用之鋁膏組成物。 The present invention relates to an aluminum paste composition for a crystalline solar cell unit having a passivation film therein.
以提高結晶系太陽電池單元的轉換效率(發電效率)及信賴性等作為目的，目前實施了各種的研究開發，其中之一的PERC((射極鈍化太陽電池)Passivated emitter and rear cell)型高轉換效率單元已被習知。此PERC型高轉換效率單元，係在太陽電池單元之與受光面為相反側的裏面上，形成以氮化矽、氧化矽、氧化鋁等形成之反射防止膜。此反射防止膜藉由雷射光形成孔洞，並通過此孔洞與矽基板成為電氣接觸而形成鋁電極層。如此之PERC構造，存在有從上述之鋁電極層擴散鋁原子而形成之p+層。藉由此p+層的存在，從而得到可提高生成載子之收集效率的BSF((背面電場)Back Surface Field)効果。此外，由於上述反射防止膜，係作為所謂的鈍化膜而作用，故藉由抑制矽基板表面之電子的再結合，可減少產生之載流子的再結合率。其結果，可得到高電壓，從而提高太陽電池單元之轉換效率。 In order to improve the conversion efficiency (power generation efficiency) and reliability of crystalline solar cells, various research and developments have been carried out, one of which is PERC (Passivated emitter and rear cell) type high. Conversion efficiency units have been known. This PERC-type high conversion efficiency unit is formed on the inner side of the solar cell unit opposite to the light-receiving surface, and forms an anti-reflection film formed of tantalum nitride, hafnium oxide, aluminum oxide or the like. The anti-reflection film forms a hole by laser light, and electrically contacts the germanium substrate through the hole to form an aluminum electrode layer. In such a PERC structure, there is a p+ layer formed by diffusing aluminum atoms from the above-described aluminum electrode layer. By the presence of the p+ layer, a BSF (Back Surface Field) effect which can improve the collection efficiency of the generated carriers can be obtained. Further, since the anti-reflection film functions as a so-called passivation film, the recombination rate of generated carriers can be reduced by suppressing recombination of electrons on the surface of the ruthenium substrate. As a result, a high voltage can be obtained, thereby improving the conversion efficiency of the solar cell.
近年來，為了在上述PERC型高轉換效率單元之裏面側 形成鋁電極層(裏面電極)，鋁膏組成物有各種提案。PERC型高轉換效率單元用鋁膏組成物所必須之功能為：1)藉由形成均勻之BSF層而提高轉換效率、2)確保矽基板及鈍化膜之充分剝離強度、3)確保在高溫高濕環境中的長期信賴性。 In recent years, in order to be on the inside side of the above-mentioned PERC type high conversion efficiency unit There are various proposals for forming an aluminum electrode layer (back electrode) and an aluminum paste composition. The functions necessary for the aluminum paste composition of the PERC type high conversion efficiency unit are: 1) improving the conversion efficiency by forming a uniform BSF layer, 2) ensuring sufficient peel strength of the tantalum substrate and the passivation film, and 3) ensuring high temperature and high temperature Long-term reliability in a wet environment.
例如，專利文獻1係關於膏組成物所含玻璃料，其記載一種含有鉛30~70陽離子莫爾百分比、矽1~40陽離子莫爾百分比、硼10~65陽離子莫爾百分比、鋁1~25陽離子莫爾百分比之玻璃料。此外，專利文獻2記載一種膏組成物，其包含無PbO之玻璃料，該玻璃料含有0~12wt%之SiO2、0．3~10wt%之Al2O3、65~75wt%之Bi2O3。再者，專利文獻3記載一種鋁膏組成物，其係添加含有SiO、B2O3、ZnO及/或PbO、Al2O3的至少1種之鹼金屬氧化物之玻璃料者，從而，提高矽基板與電極的密著性。 For example, Patent Document 1 relates to a glass frit contained in a paste composition, which contains a percentage of lead 30 to 70 cationic moir, a percentage of cation 1 to 40 cationic moir, a percentage of boron 10 to 65 cationic moir, and aluminum 1 to 25 Glass frit with a percentage of cationic moir. Further, Patent Document 2 describes a paste composition comprising a Pb-free glass frit containing 0 to 12% by weight of SiO 2 , 0.3 to 10% by weight of Al 2 O 3 , and 65 to 75% by weight of Bi 2 . O 3 . Further, Patent Document 3 describes an aluminum paste composition in which a glass frit containing at least one alkali metal oxide of SiO, B 2 O 3 , ZnO, and/or PbO or Al 2 O 3 is added. Improve the adhesion between the substrate and the electrode.
【專利文獻1】日本特開2013-145865號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-145865
【專利文獻2】美國專利申請公開2013/0192670號 [Patent Document 2] US Patent Application Publication No. 2013/0192670
【專利文獻3】國際公開第2012/165167號 [Patent Document 3] International Publication No. 2012/165167
然而，即使將上述專利文獻1所記載之膏組成物適用於PERC型高轉換效率單元，仍無法斷言可得到充分之轉換效率，仍留有改善之餘地。此外，含Pb將產生影響環境面之問題。此外，上述專利文獻2所記載之膏組成物亦相同，仍留有變換效率上改善之餘地，此外，關於藉由燒成而形成之鋁電極的剝離強度亦須改善。專利文獻3所記載之膏組成物，雖確實可提升對於矽基板之密著性，但在高溫高濕環境下的信賴性方面，仍留有課題。此外，任一者之專利文獻所記載之膏組成物，藉由燒成而形成之Al-Si合金層皆係形成有孔洞者，有太陽電池單元之機械強度較低的問題。根據以上之觀點，目前須開發可解決上述問題點之膏組成物。 However, even if the paste composition described in Patent Document 1 is applied to the PERC type high conversion efficiency unit, it is not possible to conclude that sufficient conversion efficiency can be obtained, and there is still room for improvement. In addition, the inclusion of Pb will have problems affecting the environment. Further, the paste composition described in Patent Document 2 is also the same, and there is still room for improvement in conversion efficiency, and the peel strength of the aluminum electrode formed by firing must be improved. Although the paste composition described in Patent Document 3 can improve the adhesion to the ruthenium substrate, there is still a problem in terms of reliability in a high-temperature and high-humidity environment. Further, in the paste composition described in any of the patent documents, the Al-Si alloy layer formed by firing has pores formed, and the mechanical strength of the solar cell unit is low. From the above point of view, it is currently necessary to develop a paste composition that can solve the above problems.
本發明係鑑於上述技術背景而成，目的在於提供一種PERC型太陽電池用鋁膏組成物，其可賦予PERC型太陽電池單元高轉換效率，且對於矽基板有優異之密著性，並且，在高溫高濕環境下，仍可抑制電特性下降、或燒成後之孔洞的產生。 The present invention has been made in view of the above technical background, and an object of the invention is to provide a PERC-type aluminum paste composition for a solar cell, which can impart high conversion efficiency to a PERC-type solar cell unit, and has excellent adhesion to a ruthenium substrate, and In the high-temperature and high-humidity environment, the decrease in electrical characteristics or the generation of voids after firing can be suppressed.
本發明人等為達到上述目的而深入研究的結果，發現將鋁膏組成物所添加之玻璃料調整為特定之組成時，可達成上述目的，從而完成本發明。 As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be attained when the glass frit to which the aluminum paste composition is added is adjusted to a specific composition, thereby completing the present invention.
亦即，本發明係關於下述之PERC型太陽電池用鋁膏組成物。項1．一種膏組成物，其特徵為其係至少含有玻璃料作為構成成分之PERC型太陽電池用鋁膏組成物； 前述玻璃料，不含Pb及鹼金屬，而係含B2O3成分者。 That is, the present invention relates to the following aluminum paste composition for a PERC type solar cell. Item 1. A paste composition characterized in that it is a composition for a PERC-type aluminum paste for a solar cell containing at least a glass frit as a constituent component; and the glass frit contains no Pb or an alkali metal but a B 2 O 3 component.
項2．如上述項1項所記載之膏組成物，其中，前述玻璃料，係進一步包含選自Bi2O3、ZnO、SiO2、Al2O3、BaO、CaO、SrO、V2O5、Sb2O3、WO3、P2O5及TeO2所成群中至少1種成分者。 Item 2. The paste composition according to the above item 1, wherein the glass frit further comprises a material selected from the group consisting of Bi 2 O 3 , ZnO, SiO 2 , Al 2 O 3 , BaO, CaO, SrO, V 2 O 5 , and Sb. At least one component selected from the group consisting of 2 O 3 , WO 3 , P 2 O 5 and TeO 2 .
項3．如上述項1或2所記載之膏組成物，其中，前述玻璃料，係含有第1玻璃料及第2玻璃料，前述第1玻璃料係包含B2O3及Bi2O3成分；前述第2玻璃料係包含V2O5及BaO成分。 Item 3. The paste composition according to the above item 1 or 2, wherein the glass frit contains a first glass frit and a second glass frit, and the first frit contains B 2 O 3 and a Bi 2 O 3 component; 2 The frit system contains V 2 O 5 and BaO components.
項4．如上述項3所記載之膏組成物，其中，前述第1玻璃料中，B2O3成分與Bi2O3成分之莫爾比(B2O3/Bi2O3)係0．8以上4．0以下；前述第2玻璃料中，V2O5成分與BaO成分之莫爾比(V2O5/BaO)係1．0以上2．5以下。 Item 4. The paste composition according to the above item 3, wherein the first glass frit has a molar ratio of B 2 O 3 component to Bi 2 O 3 component (B 2 O 3 /Bi 2 O 3 ) 0.8. In the second glass frit, the Mo ratio (V 2 O 5 /BaO) of the V 2 O 5 component and the BaO component is 1.0 or more and 2.5 or less.
項5．如上述項1~4中任一項所記載之膏組成物，其中，其係進一步包含導電填料，前述導電填料係至少含鋁粉及鋁-矽合金粉。 Item 5. The paste composition according to any one of the items 1 to 4, further comprising a conductive filler, wherein the conductive filler contains at least aluminum powder and aluminum-bismuth alloy powder.
項6．如上述項5所記載之膏組成物，其中，前述鋁-矽合金粉中矽之含量，相對於前述鋁-矽合金粉中之鋁為100質量份，係3．0~30．0質量份；並且，前述膏組成物中矽之含量，相對於前述膏組成物中之鋁為100質量份，係3．0~15．0質量份。 Item 6. The paste composition according to the above item 5, wherein the content of the antimony in the aluminum-bismuth alloy powder is 3.0 to 30.0 parts by mass based on 100 parts by mass of the aluminum in the aluminum-bismuth alloy powder. Further, the content of bismuth in the paste composition is from 3.0 to 15.0 parts by mass based on 100 parts by mass of the aluminum in the paste composition.
項7．如上述項1~6中任一項所記載之膏組成物，其中，濕 熱試驗前後之發電效率(Eff)的降低率係5%以內。 Item 7. The paste composition according to any one of items 1 to 6, wherein the wet composition The rate of decrease in power generation efficiency (Eff) before and after the heat test is within 5%.
本發明之PERC型太陽電池用鋁膏組成物，至少含有玻璃料作為構成成分，該玻璃料並未含Pb及鹼金屬，而係含B2O3成分。藉此，只要將上述膏組成物適用於PERC型太陽電池單元，即可賦予該太陽電池單元高轉換效率。此外，藉由膏組成物的燒成而形成之電極(裏面電極)，與矽基板的密著性優異，且亦可抑制裏面電極與矽基板之間之孔洞的產生。並且，藉由將上述膏組成物適用於PERC型太陽電池，該PERC型太陽電池，即使在高溫高濕環境下，亦難以降低電特性。 The aluminum paste composition for a PERC solar cell of the present invention contains at least a glass frit as a constituent component, and the glass frit does not contain Pb and an alkali metal, but contains a B 2 O 3 component. Thereby, the solar cell unit can be imparted with high conversion efficiency by applying the above-described paste composition to the PERC type solar cell. Further, the electrode (back electrode) formed by the firing of the paste composition is excellent in adhesion to the ruthenium substrate, and the occurrence of voids between the back electrode and the ruthenium substrate can be suppressed. Further, by applying the above-described paste composition to a PERC-type solar cell, it is difficult to reduce electrical characteristics of the PERC-type solar cell even in a high-temperature and high-humidity environment.
1‧‧‧p型矽半導體基板 1‧‧‧p-type germanium semiconductor substrate
2‧‧‧n型雜質層 2‧‧‧n type impurity layer
3‧‧‧反射防止膜(鈍化膜) 3‧‧‧Anti-reflection film (passivation film)
4‧‧‧柵電極 4‧‧‧ gate electrode
5‧‧‧鋁電極層 5‧‧‧Aluminum electrode layer
6‧‧‧鋁-矽合金層 6‧‧‧Aluminum-bismuth alloy layer
7‧‧‧p+層 7‧‧‧p+ layer
8‧‧‧裏面電極 8‧‧‧ inside electrode
【圖1】表示PERC型太陽電池單元之斷面構造的一例之模式圖。 Fig. 1 is a schematic view showing an example of a cross-sectional structure of a PERC solar cell.
以下，詳細說明PERC型太陽電池用鋁膏組成物之實施型態。 Hereinafter, the embodiment of the aluminum paste composition for a PERC type solar cell will be described in detail.
本實施形態之PERC型太陽電池用鋁膏組成物(以下，簡稱為「膏組成物」)，可係為了形成PERC型高轉換效率單元之裏面電極而使用者。 The aluminum paste composition for a PERC solar cell of the present embodiment (hereinafter simply referred to as "paste composition") can be used to form a back electrode of a PERC type high conversion efficiency unit.
首先，說明本實施形態之膏組成物可適用之PERC型太 陽電池之單元的一例。 First, the PERC type to which the paste composition of the present embodiment is applicable is explained. An example of a unit of a positive battery.
圖1，係以模式圖表示PERC型太陽電池之單元的一般斷面構造。如圖1所示，太陽電池單元，例如，係使用厚180~250μm之p型矽半導體基板1而構成。矽半導體基板1之受光面側，係形成有厚0．3~0．6μm之n型雜質層2，且除此之外，形成有例如，氮化矽膜所成反射防止膜3(亦稱作所謂之鈍化膜3)及柵電極4等。 Fig. 1 is a schematic view showing a general sectional structure of a unit of a PERC type solar cell. As shown in FIG. 1, the solar cell unit is formed using, for example, a p-type germanium semiconductor substrate 1 having a thickness of 180 to 250 μm. An n-type impurity layer 2 having a thickness of 0.3 to 0.6 μm is formed on the light-receiving surface side of the semiconductor substrate 1, and an anti-reflection film 3 is formed, for example, by a tantalum nitride film. The so-called passivation film 3), the gate electrode 4, and the like are used.
此外，與矽半導體基板1之受光面為相反側之裏面，例如，形成有氮化矽膜所成反射防止膜3(亦稱作所謂之鈍化膜3)。且其形成有貫通此反射防止膜3並到達矽半導體基板1之表面的接觸孔、及通過該接觸孔與矽半導體基板1之表面接觸而沿著所定之圖型形狀所形成之鋁電極層5。 Further, on the inner side opposite to the light-receiving surface of the germanium semiconductor substrate 1, for example, an anti-reflection film 3 (also referred to as a so-called passivation film 3) formed of a tantalum nitride film is formed. Further, a contact hole penetrating through the anti-reflection film 3 and reaching the surface of the germanium semiconductor substrate 1 and an aluminum electrode layer 5 formed along the surface of the germanium semiconductor substrate 1 through the contact hole and formed along a predetermined pattern shape are formed. .
上述鋁電極層5，係藉由絲網印刷等塗佈後述之膏組成物，乾燥後，以超過660℃(鋁之熔點)之溫度進行短時間燒成而形成者。進行此燒成時，藉由鋁擴散至矽半導體基板1之內部，在鋁電極層5與矽半導體基板1之間形成鋁-矽(Al-Si)合金層6，同時藉由鋁原子之擴散而形成作為雜質層之p+層7(亦稱作BSF層7)。藉由此p+層7的存在，得到可防止電子的再結合、提高生成載子之收集效率的BSF効果。在矽半導體基板1之裏面側，形成有由上述之鋁電極層5與鋁-矽合金層6所構成之裏面電極8。藉由太陽電池單元具有上述構造，從而構成具備PERC構造之單元的背接觸型之太陽電池。 The aluminum electrode layer 5 is formed by applying a paste composition described later by screen printing or the like, and drying it at a temperature exceeding 660 ° C (melting point of aluminum) for a short period of time. At the time of this firing, aluminum is diffused into the interior of the germanium semiconductor substrate 1, and an aluminum-germanium (Al-Si) alloy layer 6 is formed between the aluminum electrode layer 5 and the germanium semiconductor substrate 1, while diffusing by aluminum atoms. On the other hand, a p+ layer 7 (also referred to as a BSF layer 7) as an impurity layer is formed. By the presence of the p+ layer 7, a BSF effect can be obtained which prevents recombination of electrons and improves the collection efficiency of the generated carriers. On the back side of the germanium semiconductor substrate 1, a back electrode 8 composed of the above-described aluminum electrode layer 5 and an aluminum-bismuth alloy layer 6 is formed. The solar battery cell has the above-described configuration, thereby constituting a back contact type solar cell having a unit of a PERC structure.
本實施形態之膏組成物，係為了形成上述之裏面電極8，而塗佈於反射防止膜3(鈍化膜3)之上的導電性膏。膏組成物，係塗佈 成為其通過形成於反射防止膜3之接觸孔而與矽半導體基板1之表面接觸。進一步詳細說明，本實施形態之膏組成物，可用於稱作LCO((雷射接點窗口)Laser contact opening)構造之太陽電池用的裏面電極。此時，膏組成物將與使用Laser等所設之開口部的矽反應，藉此，形成BSF層7。藉由形成BSF層，從而可實現太陽電池之電特性的提升。 The paste composition of the present embodiment is a conductive paste applied on the anti-reflection film 3 (passivation film 3) in order to form the above-described back electrode 8. Paste composition It is brought into contact with the surface of the tantalum semiconductor substrate 1 through a contact hole formed in the anti-reflection film 3. More specifically, the paste composition of the present embodiment can be used for a back electrode for a solar cell called an LCO (Laser contact opening) structure. At this time, the paste composition is reacted with ruthenium using an opening portion provided by Laser or the like, whereby the BSF layer 7 is formed. By forming the BSF layer, the electrical characteristics of the solar cell can be improved.
接著，對於本實施形態之膏組成物的構成進行詳述。 Next, the configuration of the paste composition of the present embodiment will be described in detail.
本實施形態之膏組成物，係至少含有玻璃料作為構成成分者。 The paste composition of the present embodiment contains at least a glass frit as a constituent component.
上述玻璃料，係不含Pb及鹼金屬，而含B2O3成分。 The above glass frit does not contain Pb and an alkali metal, but contains a B 2 O 3 component.
在此所述「不含Pb」，雖係指膏組成物不含有鉛(Pb)，惟並未排除作為不可避之雜質而含之鉛(Pb)。 As used herein, "without Pb" means that the paste composition does not contain lead (Pb), but does not exclude lead (Pb) contained as an unavoidable impurity.
此外，在此所述「不含鹼金屬」，雖係指膏組成物並不含鹼金屬，亦即，不含鋰、鈉、鉀、銣、銫及鈁，惟並未排除作為不可避之雜質而含之鹼金屬。 In addition, the term "alkali-free metal" as used herein means that the composition of the paste does not contain an alkali metal, that is, does not contain lithium, sodium, potassium, cesium, rubidium and cesium, but is not excluded as an unavoidable impurity. And the alkali metal contained.
又，以下敘述，係將上述之「玻璃料不含Pb」稱為「無Pb」、「玻璃料不含鹼金屬」稱為「無鹼金屬」。 In the following description, the above-mentioned "glass material does not contain Pb" is referred to as "no Pb", and "the glass frit does not contain alkali metal" is referred to as "alkali-free metal".
玻璃料，係含有B2O3作為必須之構成成分。藉此，膏組成物，可對於PERC型太陽電池形成良好之BSF層，從而提高太陽電池之發電效率。 The glass frit contains B 2 O 3 as an essential constituent. Thereby, the paste composition can form a good BSF layer for the PERC type solar cell, thereby improving the power generation efficiency of the solar cell.
玻璃料，係無Pb，並且，無鹼金屬，只要作為成分含有B2O3，則亦可包含其他成分。 The glass frit is Pb-free, and the alkali-free metal may contain other components as long as it contains B 2 O 3 as a component.
上述其他成分，除了B2O3，可例示如選自Bi2O3、SrO、BaO、Sb2O3、V2O5、P2O5、ZnO、SiO2、Al2O3、CaO、WO3、TeO2、TiO2、ZrO2、CuO、Ag2O、SnO及CeO2所成群中1種或2種以上。玻璃料係含有此等複數之金屬氧化物中1種以上作為構成成分時，可為各金屬氧化物彼此混合之混合物之型態存在，或者，複數種之金屬的氧化物所成，所謂複合氧化物之型態存在。此外，前述混合物及前述複合氧化物兩者在玻璃料中混在亦可，其形態並無限制。 The above other components, except for B 2 O 3 , may be exemplified by, for example, Bi 2 O 3 , SrO, BaO, Sb 2 O 3 , V 2 O 5 , P 2 O 5 , ZnO, SiO 2 , Al 2 O 3 , CaO. And one or more of WO 3 , TeO 2 , TiO 2 , ZrO 2 , CuO, Ag 2 O, SnO, and CeO 2 . When the glass frit contains one or more of the above-mentioned plural metal oxides as a constituent component, it may be in the form of a mixture in which the respective metal oxides are mixed, or in the form of oxides of a plurality of metals, so-called composite oxidation. The type of matter exists. Further, both the above mixture and the above composite oxide may be mixed in the glass frit, and the form thereof is not limited.
玻璃料，其構成亦可係包含：第1玻璃料，含有B2O3及Bi2O3成分；及第2玻璃料，含有V2O5及BaO成分。亦即，玻璃料，亦可係上述第1玻璃料與上述第2玻璃料之2種類的玻璃料之混合物。 The glass frit may further include a first glass frit containing B 2 O 3 and a Bi 2 O 3 component, and a second glass frit containing V 2 O 5 and a BaO component. That is, the glass frit may be a mixture of two types of glass frits of the first glass frit and the second glass frit.
如上所述之玻璃料，包含第1玻璃料、及第2玻璃料時，膏組成物對於PERC型太陽電池，可形成進一步良好之BSF層，從而可提高太陽電池之發電特性，特別係可提高發電效率(轉換效率)。除此之外，膏組成物所形成之電極與太陽電池之矽基板間的密著性亦可得到提升。 When the glass frit as described above includes the first glass frit and the second glass frit, the paste composition can form a further favorable BSF layer for the PERC type solar cell, thereby improving the power generation characteristics of the solar cell, and particularly improving the solar cell. Power generation efficiency (conversion efficiency). In addition, the adhesion between the electrode formed by the paste composition and the substrate of the solar cell can be improved.
玻璃料，包含第1玻璃料、及第2玻璃料時，在第1玻璃料及第2玻璃料之任一者中，各種玻璃料所含各成分之莫爾比並無限制。較佳係，第1玻璃料中，B2O3成分與Bi2O3成分之莫爾比(亦即，相對於Bi2O3成分之莫爾數，B2O3成分之莫爾數的比(B2O3之莫爾數/Bi2O3之莫爾數))為0．8以上4．0以下；第2玻璃料中，V2O 5成分與BaO成分之莫爾比(亦即，相對於BaO成分之莫爾數，V2O5成分之莫爾數的比(V2O5之莫爾數/BaO之莫爾數)為1．0以上2．5以下。此時，膏組成物，對於PERC型太陽電池，可形成進一步良好之BSF層，並可提高太陽電池之發電效率。除此之外，由膏組成物所形成之電極與太陽電池之矽基板之間的密著性可進一步提升。 When the glass frit includes the first glass frit and the second glass frit, the Mohr ratio of each component contained in each glass frit is not limited in any of the first glass frit and the second glass frit. Preferably, the Mohr ratio of the B 2 O 3 component and the Bi 2 O 3 component in the first glass frit (that is, the Moir number of the Bi 2 O 3 component and the Moir number of the B 2 O 3 component) The ratio (the Mohr number of B 2 O 3 / the Moir number of Bi 2 O 3 )) is 0.8 or more and 4.0 or less; in the second glass frit, the Mo 2 ratio of the V 2 O 5 component and the BaO component (That is, the ratio of the Moir number of the V 2 O 5 component (the Moir number of V 2 O 5 / the Moir number of BaO) to the Moir number of the BaO component is 1.0 or more and 2.5 or less. At this time, the paste composition can form a further good BSF layer for the PERC type solar cell, and can improve the power generation efficiency of the solar cell. In addition, the electrode formed by the paste composition and the substrate of the solar cell are The adhesion between them can be further improved.
第1玻璃料，亦可含有B2O3及Bi2O3成分以外之成分；第2玻璃料，亦可含有V2O5及BaO成分以外之成分。此時，第1玻璃料及第2玻璃料之任一者中，各成分可以上述混合物之狀態而存在，且各成分亦可以上述複合氧化物之狀態而存在。 The first glass frit may contain components other than the B 2 O 3 and Bi 2 O 3 components, and the second glass frit may contain components other than the V 2 O 5 and BaO components. In this case, in any of the first glass frit and the second glass frit, each component may exist in the state of the above mixture, and each component may exist in the state of the composite oxide.
玻璃料中，上述第1玻璃料與上述第2玻璃料的混合比例並無特別限定，可以任意之混合比例含有。較佳係，將第1玻璃料及第2玻璃料混合成為：第2玻璃料所含V2O5與第1玻璃料所含B2O3之莫爾比，亦即，V2O5之莫爾數/B2O3之莫爾數的值在1．0~10．0之範圍內。此時，膏組成物，對於PERC型太陽電池，可形成進一步良好之BSF層，並可提高太陽電池之發電效率。除此之外，由膏組成物所形成之電極與太陽電池之矽基板之間的密著性可進一步提升。 In the glass frit, the mixing ratio of the first glass frit and the second glass frit is not particularly limited, and may be contained in any mixing ratio. Preferred system, the first glass frit materials blended into the second: the second glass frit contained in the glass V 2 O 5 and 1 B 2 O 3 ratio of Moire contained material, i.e., of V 2 O 5 The Mohr number/B 2 O 3 Moire number has a value in the range of 1.0 to 10.0. At this time, the paste composition can form a further good BSF layer for the PERC type solar cell, and can improve the power generation efficiency of the solar cell. In addition, the adhesion between the electrode formed by the paste composition and the tantalum substrate of the solar cell can be further improved.
本實施形態之膏組成物，只要含有上述玻璃料，則可包含其他添加劑。例如，膏組成物，除了玻璃料之外，可含有導電填料、矽粉末及有機賦形劑。 The paste composition of the present embodiment may contain other additives as long as it contains the above glass frit. For example, the paste composition may contain, in addition to the glass frit, a conductive filler, a barium powder, and an organic vehicle.
膏組成物所含導電填料，係可使藉由燒成膏組成物而形成之鋁電極層發揮導電性。 The conductive filler contained in the paste composition is such that the aluminum electrode layer formed by firing the paste composition exhibits conductivity.
構成導電填料之材料並無特別限制。例如，導電填料，可 包含鋁粉及鋁-矽合金粉中至少一者，較佳係由鋁粉及鋁-矽合金粉所成。 The material constituting the conductive filler is not particularly limited. For example, a conductive filler, At least one of the aluminum powder and the aluminum-bismuth alloy powder is preferably made of aluminum powder and aluminum-bismuth alloy powder.
構成鋁粉末之鋁粒子的形狀並無特別限定。若鋁粒子的形狀特別係球狀，則將增大電極層中鋁粒子的充填性，藉此，可有效地降低電極之電阻。此外，鋁粒子的形狀為球狀時，矽半導體基板與鋁粒子之接點將會增加，從而可形成良好之BSF層。 The shape of the aluminum particles constituting the aluminum powder is not particularly limited. When the shape of the aluminum particles is particularly spherical, the filling property of the aluminum particles in the electrode layer is increased, whereby the electric resistance of the electrode can be effectively reduced. Further, when the shape of the aluminum particles is spherical, the junction of the germanium semiconductor substrate and the aluminum particles will increase, so that a good BSF layer can be formed.
構成鋁粉末之鋁粒子的平均粒徑係1μm以上10μm以下為佳，此時，可降低鋁粒子彼此凝集之疑慮，在膏組成物中較容易有良好之分散性，並且，較容易維持高反應性。鋁粉末之製造方法並無特別限定，例如，可藉由霧化法而製造。 The average particle diameter of the aluminum particles constituting the aluminum powder is preferably 1 μm or more and 10 μm or less. In this case, it is possible to reduce the agglomeration of the aluminum particles, and it is easy to have good dispersibility in the paste composition, and It is easy to maintain high reactivity. The method for producing the aluminum powder is not particularly limited, and for example, it can be produced by an atomization method.
作為導電填料，若將鋁粉末包含入膏組成物中，燒成膏組成物而形成裏面電極時，由於裏面電極與矽半導體基板之間會形成鋁-矽合金層與p+層，因此有可得到BSF効果之優點。 When the aluminum powder is contained in the paste composition and the paste composition is fired to form the inner electrode, an aluminum-niobium alloy layer and a p+ layer are formed between the inner electrode and the tantalum semiconductor substrate, so that it is available. The advantages of the BSF effect.
構成鋁-矽合金粉末之鋁-矽合金粒子的形狀並無特別限定。構成鋁-矽合金粉末之鋁-矽合金粒子的平均粒徑係1μm以上10μm以下為佳。此時，可降低鋁粒子彼此凝集之疑慮，在膏組成物中較容易有良好之分散性，並且，較容易維持高反應性。鋁-矽合金粉末之製造方法並無特別限定，例如，可藉由霧化法而製造。 The shape of the aluminum-bismuth alloy particles constituting the aluminum-bismuth alloy powder is not particularly limited. The aluminum-niobium alloy particles constituting the aluminum-bismuth alloy powder preferably have an average particle diameter of 1 μm or more and 10 μm or less. At this time, it is possible to reduce the agglomeration of the aluminum particles, and it is easy to have good dispersibility in the paste composition, and it is easier to maintain high reactivity. The method for producing the aluminum-niobium alloy powder is not particularly limited, and for example, it can be produced by an atomization method.
鋁-矽合金粉末，亦可使藉由燒成膏組成物而形成之鋁電極層發揮導電性。此外，除了鋁-矽合金粉末，膏組成物更包含後述之矽粉末時，藉由矽粉末中之矽與鋁-矽合金粉末中之矽，可易於控制膏組成物中之鋁與矽半導體基板中之矽的過剩反應。藉此，鋁電極層與矽半導體 基板之界面之孔洞(空洞)的產生可得到抑制。 The aluminum-niobium alloy powder can also exhibit electrical conductivity by the aluminum electrode layer formed by firing the paste composition. Further, in addition to the aluminum-bismuth alloy powder, when the paste composition further contains the cerium powder described later, the aluminum and ytterbium semiconductor substrates in the paste composition can be easily controlled by the ruthenium in the ruthenium powder and the ruthenium in the aluminum-ruthenium alloy powder. The excess reaction of Zhongzhi. Thereby, the aluminum electrode layer and the germanium semiconductor The generation of holes (voids) at the interface of the substrate can be suppressed.
又，本實施形態之膏組成物中所含鋁-矽合金粉末之含有比率，並無特別限定。例如，相對於鋁粉末100質量份，鋁-矽合金粉末係10質量份以上500質量份以下為佳。此時，可有效抑制膏組成物中之鋁與矽半導體基板中之矽的過剩反應。 Moreover, the content ratio of the aluminum-bismuth alloy powder contained in the paste composition of the present embodiment is not particularly limited. For example, the aluminum-bismuth alloy powder is preferably 10 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the aluminum powder. At this time, an excessive reaction of the aluminum in the paste composition with germanium in the germanium semiconductor substrate can be effectively suppressed.
膏組成物中包含矽粉末時，藉由上述之鋁-矽合金粉末中所含之矽與矽粉末中之矽，可控制膏組成物中之鋁與矽半導體基板中之矽的過剩反應。從而，可抑制鋁電極層與矽半導體基板之界面之孔洞(空洞)的產生。 When the bismuth powder is contained in the paste composition, the excess reaction in the aluminum and ruthenium semiconductor substrates in the paste composition can be controlled by the ruthenium in the ruthenium and osmium powder contained in the above-mentioned aluminum-bismuth alloy powder. Thereby, generation of voids (voids) at the interface between the aluminum electrode layer and the germanium semiconductor substrate can be suppressed.
構成矽粉末之矽粒子的形狀並無特別限定。構成矽粉末之矽粒子的平均粒徑係1μm以上10μm以下為佳。此時，可抑制矽粒子互相凝集，且維持膏組成物中具有良好之分散性，除此之外，亦可抑制反應性的降低。 The shape of the ruthenium particles constituting the ruthenium powder is not particularly limited. The average particle diameter of the cerium particles constituting the cerium powder is preferably 1 μm or more and 10 μm or less. At this time, it is possible to suppress aggregation of the ruthenium particles with each other, and to maintain good dispersibility in the paste composition, and to suppress the decrease in reactivity.
矽之含有量並無特別限制，可適宜地進行調節。例如，鋁-矽合金粉中矽之含量，相對於鋁-矽合金粉中之鋁100質量份，可係3．0~30．0質量份，並且，膏組成物中矽之含量，相對於膏組成物中之鋁100質量份，可係3．0~15．0質量份。此時，可藉由膏組成物形成良好之BSF層從而提升電特性，且鋁電極層與矽半導體基板之界面之孔洞(空洞)的產生亦可得到抑制。 The content of the mash is not particularly limited and can be appropriately adjusted. For example, the content of bismuth in the aluminum-bismuth alloy powder may be 3.0 to 30.0 parts by mass relative to 100 parts by mass of the aluminum in the aluminum-bismuth alloy powder, and the content of bismuth in the paste composition is relative to 100 parts by mass of aluminum in the paste composition may be 3.0 to 15.0 parts by mass. At this time, a good BSF layer can be formed by the paste composition to improve electrical characteristics, and generation of voids (voids) at the interface between the aluminum electrode layer and the germanium semiconductor substrate can be suppressed.
有機賦形劑，可使用以溶劑將因應必要之各種添加劑及樹脂溶解所成者。可使用習知者作為溶劑，具體而言，可列舉出：二甘醇單丁醚、二甘醇單丁醚乙酸酯、二丙二醇單甲醚等。各種添加劑，例如，可 使用抗氧化劑、腐蝕抑制劑、消泡劑、增稠劑、增黏劑(Tackifier)、偶聯劑、靜電賦予劑、聚合抑制劑、觸變劑、防沉降劑等。添加劑之具體例，可使用聚乙二醇酯化合物、聚乙二醇醚化合物、聚氧乙烯山梨醇酯化合物、山梨糖醇烷基酯化合物、脂肪族多元羧酸化合物、磷酸酯化合物、聚酯酸之醯胺胺鹽、氧化聚乙烯系化合物、脂肪酸脂肪酸醯胺蠟等。樹脂可使用習知者，可使用乙基纖維、硝化纖維、聚乙烯醇縮丁醛、酚醛樹脂、三聚氰胺甲醛樹脂、脲醛樹脂、二甲苯樹脂、醇酸樹脂、不飽和聚酯樹脂、丙烯酸樹脂、聚醯亞胺樹脂、呋喃樹脂、聚胺酯樹脂、異氰酸酯化合物、氰酸酯化合物等之熱硬化樹脂、聚乙烯、聚丙烯、聚苯乙烯、ABS樹脂、聚甲基丙烯酸甲酯、聚氯乙烯、聚偏二氯乙烯、聚乙酸乙烯酯、聚乙烯醇、聚縮醛、聚碳酸酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚苯醚、聚碸、聚醯亞胺、聚醚碸、聚芳酯、聚醚醚酮、聚四氟乙烯、矽樹脂等中之1種，抑或組合2種以上使用。有機賦形劑所含樹脂，亦可不以溶劑溶解直接使用。 As the organic vehicle, those obtained by dissolving various additives and resins necessary for the solvent can be used. A known solvent can be used, and specific examples thereof include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether. Various additives, for example, Antioxidants, corrosion inhibitors, antifoaming agents, thickeners, tackifiers, coupling agents, static electricity imparting agents, polymerization inhibitors, thixotropic agents, anti-settling agents, and the like are used. Specific examples of the additive include a polyethylene glycol ester compound, a polyethylene glycol ether compound, a polyoxyethylene sorbitan ester compound, a sorbitol alkyl ester compound, an aliphatic polycarboxylic acid compound, a phosphate compound, and a polyester. An acid amide amine salt, an oxidized polyethylene compound, a fatty acid fatty acid guanamine wax, or the like. The resin can be used, and ethyl cellulose, nitrocellulose, polyvinyl butyral, phenolic resin, melamine formaldehyde resin, urea resin, xylene resin, alkyd resin, unsaturated polyester resin, acrylic resin, Thermosetting resin such as polyimine resin, furan resin, polyurethane resin, isocyanate compound, cyanate compound, polyethylene, polypropylene, polystyrene, ABS resin, polymethyl methacrylate, polyvinyl chloride, poly Vinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyfluorene, polypyrene One of an amine, a polyether oxime, a polyarylate, a polyetheretherketone, a polytetrafluoroethylene, an anthracene resin, or the like, or a combination of two or more. The resin contained in the organic excipient may be used as it is without being dissolved in a solvent.
又，本實施形態之膏組成物中所含有機賦形劑之含有率，並無特別限定。例如，相對於鋁粉末100質量份，有機賦形劑之含有率係70質量份以上500質量份以下為佳。此時，較難發生膏組成物之印刷性的降低。 Further, the content ratio of the organic excipient contained in the paste composition of the present embodiment is not particularly limited. For example, the content of the organic excipient is preferably 70 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the aluminum powder. At this time, it is difficult to cause a decrease in the printability of the paste composition.
本實施形態之膏組成物，可藉由將所定量之各原料以適宜之方法混合而調製。混合方法並無特別限定，可使用分散機或三輥機等習知的混合機。 The paste composition of the present embodiment can be prepared by mixing a predetermined amount of each raw material in an appropriate manner. The mixing method is not particularly limited, and a conventional mixer such as a disperser or a three-roller can be used.
使用本實施形態之膏組成物，例如，可如圖1所示，形成 PERC型太陽電池單元之裏面電極。 The paste composition of the present embodiment can be formed, for example, as shown in FIG. The inner electrode of the PERC type solar cell unit.
上述膏組成物包含玻璃料，該玻璃料係無Pb及無鹼金屬，並且，包含B2O3成分。因此，將上述膏組成物適用於PERC型太陽電池單元時，可賦予該太陽電池單元高轉換效率。此外，膏組成物，特別係無鹼金屬(除了不可避而含有之鹼金屬)所構成，故藉由膏組成物之燒成而形成之裏面電極，與矽基板之間的密着性優異。並且，無鹼金屬時，即使在高溫高濕環境下亦難以發生電特性的降低，因此高溫高濕環境下之信賴性優異。此外，若將上述膏組成物適用於PERC型太陽電池單元，亦可抑制在太陽電池單元中裏面電極與矽半導體基板之間所形成之燒成後之孔洞的產生。除此之外，由於膏組成物係無Pb(除了不可避而含有之Pb)所構成，故對環境面之影響較小。 The above paste composition contains a glass frit which is free of Pb and alkali-free metals and contains a B 2 O 3 component. Therefore, when the above paste composition is applied to a PERC type solar cell unit, the solar cell unit can be given high conversion efficiency. Further, since the paste composition is particularly composed of an alkali-free metal (except for an alkali metal which is inevitably contained), the back electrode formed by firing of the paste composition is excellent in adhesion to the tantalum substrate. Further, in the case of an alkali-free metal, it is difficult to reduce electrical characteristics even in a high-temperature and high-humidity environment, and therefore, the reliability in a high-temperature and high-humidity environment is excellent. Further, when the paste composition is applied to a PERC type solar battery unit, generation of a hole after firing formed between the inner electrode and the tantalum semiconductor substrate in the solar battery cell can be suppressed. In addition, since the paste composition is composed of no Pb (except for Pb which is inevitably contained), the influence on the environmental surface is small.
使用本實施形態之膏組成物而形成之PERC型太陽電池單元，可抑制濕熱試驗前後之發電效率(以下，簡稱為「Eff」)的降低率，例如，濕熱試驗前後之Eff可被抑制在5%以內。因此，若使用本實施形態之膏組成物而形成PERC型太陽電池單元，可提高該太陽電池單元之長期信賴性。 The PERC type solar cell formed by using the paste composition of the present embodiment can suppress the rate of decrease in power generation efficiency (hereinafter, simply referred to as "Eff") before and after the damp heat test. For example, the Eff before and after the damp heat test can be suppressed to 5 Less than %. Therefore, when the PERC solar cell is formed by using the paste composition of the present embodiment, the long-term reliability of the solar cell can be improved.
以下，藉由實施例更具體說明本發明，惟本發明並非限定為此等實施例之態樣。 Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the embodiments.
(實施例1) (Example 1)
準備由B2O3-Bi2O3-SrO-BaO-Sb2O3以43/22 /18/12/5(mol%)之組成比例所構成之第1玻璃料、及由V2O5-BaO-P2O5-B2O3-SrO以39/26/18/10/7(mol%)之組成比例所構成之第2玻璃料。 Preparing a first glass frit composed of B 2 O 3 -Bi 2 O 3 -SrO-BaO-Sb 2 O 3 at a composition ratio of 43/22 /18/12/5 (mol%), and from V 2 O 5 -BaO-P 2 O 5 -B 2 O 3 -SrO The second glass frit composed of a composition ratio of 39/26/18/10/7 (mol%).
將上述第1玻璃料1．0質量份、第2玻璃料2．0質量份、以霧化法生成之D50為6．0μm的鋁粉100質量份、以霧化法生成之D50為6．0μm的鋁-15%矽合金粉25質量份、及以丁基二甘醇溶解乙基纖維所成樹脂液35質量份，使用分散機或三輥機等習知的混合機混合而調製膏組成物。此膏組成物中係調製成含有之矽(Si)的含量，相對於此膏組成物中之鋁100質量份，係3．0質量份(Si/Al量為3．0wt%)者。 1.0 part by mass of the first glass frit, 2.0 parts by mass of the second glass frit, 100 parts by mass of aluminum powder having a D50 of 6.0 μm by the atomization method, and a D50 of 4. 25 parts by mass of aluminum- 15% bismuth alloy powder of 0 μm and 35 parts by mass of a resin liquid obtained by dissolving ethyl fibers with butyl diglycol, and mixing with a conventional mixer such as a disperser or a three-roller to prepare a paste composition Things. The content of the cerium (Si) contained in the paste composition is 3.0 parts by mass (the amount of Si/Al is 3.0% by weight) based on 100 parts by mass of the aluminum in the paste composition.
另一方面，太陽電池單元係如以下所述而製作。首先，準備電阻值3Ω．cm的裏面鈍化型單晶矽基板，且其已預先使用雷射等設置開口部。並且，將如上述所調製之膏組成物，在上述矽基板之裏面側(與受光面係相反之面)印刷為1．0-1．1g/pc。接著，對於上述矽基板之受光面，印刷上藉由習知技術所預先調製的Ag膏。之後，藉由對於上述處理後之矽基板使用設定為800℃之紅外線爐，從而在矽基板之受光面及裏面側形成電極，得到太陽電池單元。 On the other hand, the solar cell unit was fabricated as described below. First, prepare a resistance value of 3Ω. The inner passivation type single crystal germanium substrate of cm is provided with an opening in advance using a laser or the like. Further, the paste composition prepared as described above is printed on the back side of the crucible substrate (the surface opposite to the light receiving surface) to 1.0 to 1.1 g/pc. Next, an Ag paste prepared in advance by a conventional technique is printed on the light-receiving surface of the above-mentioned ruthenium substrate. Thereafter, an infrared furnace set to 800 ° C was used for the above-mentioned treated ruthenium substrate to form electrodes on the light-receiving surface and the back surface side of the ruthenium substrate, thereby obtaining a solar battery cell.
(實施例2) (Example 2)
除了藉由調節鋁粉之使用量而調製為膏組成物中所含矽(Si)之含量，相對於膏組成物中鋁100質量份，係7．0質量份以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 The content of cerium (Si) contained in the paste composition was adjusted by adjusting the amount of use of the aluminum powder, and was 7.0 parts by mass with respect to 100 parts by mass of aluminum in the paste composition, by using Example 1 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例3) (Example 3)
除了藉由調節鋁粉之使用量而調製為膏組成物中所含矽(Si)之含量，相對於膏組成物中鋁100質量份，係15．0質量份以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 The content of cerium (Si) contained in the paste composition was adjusted by adjusting the amount of use of the aluminum powder, and was 15.0 parts by mass with respect to 100 parts by mass of aluminum in the paste composition, by using Example 1 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例4) (Example 4)
除了使用鋁-3%矽合金粉取代鋁-15%矽合金粉，相對於膏組成物中鋁100質量份，使膏組成物中所含矽(Si)之含量為3．0質量份而調製以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 In addition to using aluminum-3% niobium alloy powder instead of aluminum-15% niobium alloy powder, the content of niobium (Si) contained in the paste composition is 3.0 parts by mass relative to 100 parts by mass of aluminum in the paste composition. The paste composition was prepared in the same manner as in Example 1 except that the solar cell was obtained.
(實施例5) (Example 5)
使用鋁-20%矽合金粉取代鋁-15%矽合金粉，調節鋁粉之使用量以使相對於膏組成物中鋁100質量份，膏組成物中所含矽(Si)之含量成為7．0質量份而調製以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 The aluminum-15% niobium alloy powder is used in place of the aluminum-15% niobium alloy powder, and the amount of the aluminum powder is adjusted so that the content of niobium (Si) in the paste composition becomes 7 with respect to 100 parts by mass of the aluminum in the paste composition. The paste composition was prepared by the same method as in Example 1 except that the amount was adjusted to 0 parts by mass to obtain a solar cell.
(實施例6) (Example 6)
使用鋁-30%矽合金粉取代鋁-15%矽合金粉，調節鋁粉之使用量以使相對於膏組成物中鋁100質量份，膏組成物中所含矽(Si)之含量成為7．0質量份而調製以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 The aluminum-15% niobium alloy powder is used in place of the aluminum-15% niobium alloy powder, and the amount of the aluminum powder is adjusted so that the content of niobium (Si) in the paste composition becomes 7 with respect to 100 parts by mass of the aluminum in the paste composition. The paste composition was prepared by the same method as in Example 1 except that the amount was adjusted to 0 parts by mass to obtain a solar cell.
(實施例7) (Example 7)
除了將第1玻璃料之B2O3-Bi2O3-SrO-BaO-Sb2O3的組成比例變更為40/40/10/5/5(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 In addition to changing the composition ratio of B 2 O 3 -Bi 2 O 3 -SrO-BaO-Sb 2 O 3 of the first glass frit to 40/40/10/5/5 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例8) (Example 8)
除了將第1玻璃料之B2O3-Bi2O3-SrO-BaO-Sb2O3的組成比例變更為58/15/9/13/5(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 In addition to changing the composition ratio of B 2 O 3 -Bi 2 O 3 -SrO-BaO-Sb 2 O 3 of the first glass frit to 58/15/9/13/5 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例9) (Example 9)
除了將第2玻璃料之V2O5-BaO-P2O5-B2O3-SrO的組成比例變更為37/18/24/15/6(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 Except that the composition ratio of V 2 O 5 -BaO-P 2 O 5 -B 2 O 3 -SrO of the second glass frit was changed to 37/18/24/15/6 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例10) (Embodiment 10)
除了將第2玻璃料之V2O5-BaO-P2O5-B2O3-SrO的組成比例變更為30/30/20/15/5(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 In addition to changing the composition ratio of V 2 O 5 —BaO—P 2 O 5 —B 2 O 3 —SrO of the second glass frit to 30/30/20/15/5 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例11) (Example 11)
除了調製為膏組成物中所含矽(Si)之含量，相對於膏組成物中鋁100質量份，係0質量份(亦即，導電填料僅有鋁粉末)以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 In addition to the content of cerium (Si) contained in the paste composition, with respect to 100 parts by mass of aluminum in the paste composition, 0 parts by mass (that is, the conductive filler has only aluminum powder), and Example 1 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例12) (Embodiment 12)
除了藉由調節鋁粉之使用量而調製為膏組成物中所含矽(Si)之含量，相對於膏組成物中鋁100質量份，係1．5質量份以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 The content of cerium (Si) contained in the paste composition was adjusted by adjusting the amount of use of the aluminum powder, and was 1.5 parts by mass with respect to 100 parts by mass of aluminum in the paste composition, by using Example 1 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例13) (Example 13)
除了藉由調節鋁粉之使用量而調製為膏組成物中所含矽(Si)之含 量，相對於膏組成物中鋁100質量份，係20．0質量份以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 In addition to adjusting the amount of strontium (Si) contained in the paste composition by adjusting the amount of aluminum powder used The amount of the paste composition was adjusted in the same manner as in Example 1 except that 100 parts by mass of aluminum in the paste composition was 20.0 parts by mass to obtain a solar battery cell.
(實施例14) (Example 14)
除了使用鋁-35%矽合金粉取代鋁-15%矽合金粉，並調節鋁粉之使用量而調製為膏組成物中所含矽(Si)之含量，相對於膏組成物中鋁100質量份，為7．0質量份以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 In addition to using aluminum-35% niobium alloy powder instead of aluminum-15% niobium alloy powder, and adjusting the amount of aluminum powder used to prepare the content of niobium (Si) contained in the paste composition, relative to the mass of aluminum 100 in the paste composition The paste composition was prepared in the same manner as in Example 1 except that the amount was 7.0 parts by mass to obtain a solar cell.
(實施例15) (Example 15)
除了未使用第2玻璃料以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 A paste composition was prepared by the same method as in Example 2 except that the second glass frit was not used, thereby obtaining a solar cell.
(實施例16) (Embodiment 16)
除了未使用第1玻璃料以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 A paste composition was prepared by the same method as in Example 2 except that the first glass frit was not used, and a solar cell was obtained.
(實施例17) (Example 17)
除了將第1玻璃料之B2O3-Bi2O3-SrO-BaO-Sb2O3的組成比例變更為40/8/25/15/12(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 In addition to changing the composition ratio of B 2 O 3 -Bi 2 O 3 -SrO-BaO-Sb 2 O 3 of the first glass frit to 40/8/25/15/12 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例18) (Embodiment 18)
除了將第1玻璃料之B2O3-Bi2O3-SrO-BaO-Sb2O3的組成比例變更為25/50/12/8/5(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 In addition to changing the composition ratio of B 2 O 3 -Bi 2 O 3 -SrO-BaO-Sb 2 O 3 of the first glass frit to 25/50/12/8/5 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例19) (Embodiment 19)
除了將第2玻璃料之V2O5-BaO-P2O5-B2O3-SrO的組成比例變更為65/20/5/5/5(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 Except that the composition ratio of V 2 O 5 -BaO-P 2 O 5 -B 2 O 3 -SrO of the second glass frit was changed to 65/20/5/5/5 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(實施例20) (Embodiment 20)
除了將第2玻璃料之V2O5-BaO-P2O5-B2O3-SrO的組成比例變更為25/35/25/10/5(mol%)以外，藉由與實施例2相同之方法而調製膏組成物，得到太陽電池單元。 In addition to changing the composition ratio of V 2 O 5 -BaO-P 2 O 5 -B 2 O 3 -SrO of the second glass frit to 25/35/25/10/5 (mol%), 2 The paste composition was prepared in the same manner to obtain a solar cell unit.
(比較例1) (Comparative Example 1)
變更為第1玻璃料之組成B2O3-SiO2-Al2O3-K2O-Na2O係40/15/15/15/15(mol%)的組成比例所構成之玻璃料，並且，未使用第2玻璃料，進一步，相對於膏組成物中鋁100質量份，係0質量份(亦即，導電填料僅有鋁粉末)而調製以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 The glass frit composed of the composition ratio of the composition of the first glass frit B 2 O 3 -SiO 2 -Al 2 O 3 -K 2 O-Na 2 O system 40/15/15/15/15 (mol%) Further, the second glass frit is not used, and further, the same as in the first embodiment, except that 100 parts by mass of aluminum in the paste composition is 0 parts by mass (that is, the conductive filler has only aluminum powder). The paste composition is prepared to obtain a solar cell unit.
(比較例2) (Comparative Example 2)
變更為第1玻璃料之組成PbO-B2O3-Al2O3-SiO2係57/24/4/15(mol%)的組成比例所構成之玻璃料，並且，未使用第2玻璃料，進一步，相對於膏組成物中鋁100質量份，係0質量份(亦即，導電填料僅有鋁粉末)而調製以外，藉由與實施例1相同之方法而調製膏組成物，得到太陽電池單元。 Change to the composition of the first frit a glass frit composed of a composition ratio of PbO-B 2 O 3 -Al 2 O 3 -SiO 2 system of 57/24/4/15 (mol%), and the second glass frit is not used, and further, relative to the paste composition The paste composition was prepared in the same manner as in Example 1 except that 100 parts by mass of aluminum was used in an amount of 0 parts by mass (that is, the conductive filler was only aluminum powder) to obtain a solar cell.
<發電效率(Eff)之測定> <Measurement of power generation efficiency (Eff)>
對於各實施例及比較例所得太陽電池單元，使用Wacom電創之太陽模擬器：WXS-156S-10及I-V測定裝置：IV15040-1 0，實施I-V測定。以I-V測定所計量之Isc(A)、Voc(V)及FF值作為基準，藉由下述算式，算出發電效率(Eff)發電效率Eff(%)=(Isc×Voc×FF)/單元面積。 For the solar cell units obtained in the respective examples and comparative examples, Wacom Electric's solar simulator was used: WXS-156S-10 and I-V measuring device: IV15040-1 0, I-V measurement was performed. The Isc (A), Voc (V), and FF values measured by IV measurement were used as a reference, and the power generation efficiency (Eff) power generation efficiency Eff (%) = (Isc × Voc × FF) / unit area was calculated by the following formula .
<密著性評估> <Adhesion evaluation>
由膏組成物形成之裏面電極與矽基板之間的密著性，係使用3M社製之隱形膠帶(CAT NO．810-1-18)而實施。具體而言，隱形膠帶貼附由膏組成物所形成之裏面電極後，剝離該膠帶，目測確認剝離後之膠帶的黏著面，根據下述判斷基準進行密著性之評估。 The adhesion between the back electrode formed of the paste composition and the tantalum substrate was carried out using an invisible tape (CAT NO. 810-1-18) manufactured by 3M. Specifically, after attaching the inner electrode formed of the paste composition to the invisible tape, the tape was peeled off, and the adhesive surface of the tape after peeling was visually confirmed, and the adhesion was evaluated based on the following criteria.
◎：膠帶整面之附著全部消失，未觀察到電極之剝離。 ◎: The adhesion of the entire surface of the tape disappeared, and peeling of the electrode was not observed.
○：相對於膠帶整面有未達30%之附著，觀察到電極之稍微剝離。 ○: There was less than 30% adhesion to the entire surface of the tape, and slight peeling of the electrode was observed.
△：相對於膠帶整面有30%以上未達60%之附著，觀察到電極之剝離。 △: 30% or more of the entire surface of the tape was not adhered to 60%, and peeling of the electrode was observed.
×：相對於膠帶整面有60%以上之附著，觀察到電極之多數剝離。 ×: 60% or more of the entire surface of the tape was adhered, and most of the peeling of the electrode was observed.
<孔洞評估> <hole evaluation>
將膏組成物塗佈並燒成後，藉由光學顯微鏡(200倍)觀察矽基板之斷面，觀察任意決定之20處，根據下述判定基準進行評估矽基板與裏面電極層之界面上孔洞之有無。 After the paste composition was applied and fired, the cross section of the ruthenium substrate was observed by an optical microscope (200 times), and 20 arbitrary points were observed, and the holes at the interface between the ruthenium substrate and the back electrode layer were evaluated according to the following criteria. Whether there is.
○：完全無形成孔洞。 ○: No holes were formed at all.
△：形成1~9個孔洞。 △: 1 to 9 holes are formed.
×：形成10~20個孔洞。 ×: 10 to 20 holes are formed.
<高溫高濕環境下之耐久性> <Durability in high temperature and high humidity environment>
高溫高濕環境下之耐久性，係根據濕熱試驗後(以下，記載為「DH 後」)之Eff的降低率判斷。濕熱試驗，係根據IEC-61215/JIS C 8990 10．13之規格為基準，在溫度85℃、濕度85%RH、試驗時間1000下進行。 The durability in a high-temperature and high-humidity environment is based on the damp heat test (hereinafter, it is described as "DH". After the "), the Eff reduction rate is judged. The damp heat test was carried out in accordance with the specifications of IEC-61215/JIS C 8990 10.13 at a temperature of 85 ° C, a humidity of 85% RH, and a test time of 1000.
表1係表示：各實施例及比較例之玻璃料的組成，相對於鋁-矽合金粉中之鋁，矽之含量(Al-Si合金粉末)；相對於膏組成物中之鋁，矽之含量(Si/Al量)及評估結果(Eff、密著性評估、孔洞評估、DH後之Eff的降低率)。又，鋁-矽合金粉中矽之含量及膏組成物中矽之含量係以重量%(wt%)記載。 Table 1 shows the composition of the glass frit of each of the examples and the comparative examples, the content of bismuth (Al-Si alloy powder) relative to the aluminum in the aluminum-bismuth alloy powder; and the aluminum in the paste composition, Content (Si/Al amount) and evaluation results (Eff, adhesion evaluation, hole evaluation, Eff reduction rate after DH). Further, the content of cerium in the aluminum-bismuth alloy powder and the content of cerium in the paste composition are described by weight % (wt%).
各實施例所得太陽電池單元，使用之膏組成物的玻璃料係無Pb及無鹼金屬，並且至少含有B2O3成分，故發電效率高、裏面電極與矽基板之間的密著性優異，此外，孔洞的產生亦被抑制。藉此，其在高溫高濕環境下之耐久性亦非常優異。 In the solar battery unit obtained in each of the examples, the glass frit of the paste composition used has no Pb and no alkali metal, and contains at least a B 2 O 3 component, so that the power generation efficiency is high, and the adhesion between the back electrode and the tantalum substrate is excellent. In addition, the generation of holes is also suppressed. Thereby, its durability in a high-temperature and high-humidity environment is also excellent.
另一方面，比較例1所使用之膏組成物的玻璃料含有鹼金屬，故裏面電極與矽基板之間的密著性低，且其係產生多數孔洞者。此外，比較例1在高溫高濕環境下之耐久性亦低。比較例2所使用之膏組成物的玻璃料含有Pb，故裏面電極與矽基板之間的密著性低，且產生多數孔洞，係電特性之長期信賴性較低者。 On the other hand, since the glass frit of the paste composition used in the comparative example 1 contains an alkali metal, the adhesion between the inner electrode and the tantalum substrate is low, and a large number of pores are generated. Further, Comparative Example 1 was also low in durability in a high-temperature and high-humidity environment. Since the glass frit of the paste composition used in Comparative Example 2 contains Pb, the adhesion between the back electrode and the ruthenium substrate is low, and a large number of pores are generated, and the long-term reliability of the electric characteristics is low.
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| JP6825948B2 (en) * | 2017-03-17 | 2021-02-03 | 東洋アルミニウム株式会社 | Paste composition for solar cells |
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| JP6885188B2 (en) * | 2017-04-28 | 2021-06-09 | 住友金属鉱山株式会社 | Method for manufacturing conductive composition and terminal electrode |
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| CN110663119B (en) * | 2017-05-31 | 2023-08-29 | 东洋铝株式会社 | Paste composition for solar cell |
| JP2019009401A (en) * | 2017-06-28 | 2019-01-17 | 東洋アルミニウム株式会社 | Solar cell electrode |
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