JP4743350B1 - Solar cell electrode paste and solar cell - Google Patents
Solar cell electrode paste and solar cell Download PDFInfo
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- JP4743350B1 JP4743350B1 JP2011505288A JP2011505288A JP4743350B1 JP 4743350 B1 JP4743350 B1 JP 4743350B1 JP 2011505288 A JP2011505288 A JP 2011505288A JP 2011505288 A JP2011505288 A JP 2011505288A JP 4743350 B1 JP4743350 B1 JP 4743350B1
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- solar cell
- electrode
- silver
- fatty acid
- silver powder
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- 239000002003 electrode paste Substances 0.000 title claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 46
- 239000000194 fatty acid Substances 0.000 claims abstract description 46
- 229930195729 fatty acid Natural products 0.000 claims abstract description 46
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 46
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052710 silicon Inorganic materials 0.000 abstract description 27
- 239000010703 silicon Substances 0.000 abstract description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 39
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 38
- 229910001923 silver oxide Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000010304 firing Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 4
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 4
- 229940088601 alpha-terpineol Drugs 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic monocarboxylic acid Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- XDOAWJXSYHDYFN-UHFFFAOYSA-M silver;2-methylbutanoate Chemical compound [Ag+].CCC(C)C([O-])=O XDOAWJXSYHDYFN-UHFFFAOYSA-M 0.000 description 2
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-BYPYZUCNSA-N 2-Methylbutanoic acid Natural products CC[C@H](C)C(O)=O WLAMNBDJUVNPJU-BYPYZUCNSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- ZAMLDSWLRHVSSA-UHFFFAOYSA-M silver;2-ethylbutanoate Chemical compound [Ag+].CCC(CC)C([O-])=O ZAMLDSWLRHVSSA-UHFFFAOYSA-M 0.000 description 1
- GYEMIEGAEOIJQR-UHFFFAOYSA-M silver;2-methylpropanoate Chemical compound [Ag+].CC(C)C([O-])=O GYEMIEGAEOIJQR-UHFFFAOYSA-M 0.000 description 1
- RQZVTOHLJOBKCW-UHFFFAOYSA-M silver;7,7-dimethyloctanoate Chemical compound [Ag+].CC(C)(C)CCCCCC([O-])=O RQZVTOHLJOBKCW-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
- H01L31/02—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—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
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/121—Metallo-organic compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
本発明の目的は、体積抵抗率を低く、かつ、アスペクト比を高くすることができ、また、シリコン基板との密着性にも優れ、配線として形成した際に断線が生じない電極を形成することができる太陽電池電極用ペーストおよびそれを用いた太陽電池セルを提供することである。本発明の太陽電池電極用ペーストは、所定の平均粒子径を有する球状の銀粉と、所定の式で表される脂肪酸銀塩と、溶媒とを含有する太陽電池電極用のペーストである。
【選択図】なしAn object of the present invention is to form an electrode that can have a low volume resistivity and a high aspect ratio, has excellent adhesion to a silicon substrate, and does not break when formed as a wiring. It is providing the solar cell electrode paste which can carry out, and a solar cell using the same. The solar cell electrode paste of the present invention is a solar cell electrode paste containing spherical silver powder having a predetermined average particle diameter, a fatty acid silver salt represented by a predetermined formula, and a solvent.
[Selection figure] None
Description
本発明は、太陽電池電極用ペーストおよび太陽電池セルに関する。 The present invention relates to a solar battery electrode paste and a solar battery cell.
太陽光のような光エネルギーを電気エネルギーに変換する太陽電池は、地球環境問題に対する関心が高まるにつれ、積極的に種々の構造・構成のものが開発されている。その中でも、シリコンなどの半導体基板を用いた太陽電池は、その変換効率、製造コストなどの優位性により最も一般的に用いられている。 Solar cells that convert light energy such as sunlight into electrical energy have been actively developed in various structures and configurations as interest in global environmental issues increases. Among them, solar cells using a semiconductor substrate such as silicon are most commonly used due to advantages such as conversion efficiency and manufacturing cost.
このような太陽電池の電極を形成する材料としては、樹脂系のペースト材料が知られている。
例えば、特許文献１には、「銀粉末、ガラスフリット、樹脂および有機溶剤を少なくとも含み、ガラスフリットが、開口径２４〜１００μｍの篩で分級した残留分であることを特徴とする銀電極用ペースト。」が記載されている。
また、特許文献２には、「結晶子径が５８ｎｍ以上である第１銀粉末、前記銀粉末と結晶子径の異なる第２銀粉末、ガラスフリット、および樹脂バインダーを含む、太陽電池電極用ペースト。」が記載されている。
また、特許文献３には、「比表面積が０．２０〜０．６０ｍ2／ｇである銀粒子、ガラスフリット、樹脂バインダー、およびシンナー、を含む、太陽電池受光面電極用ペースト。」が記載されている。As a material for forming such an electrode of a solar cell, a resin-based paste material is known.
For example, Patent Document 1 discloses that “a silver electrode paste comprising at least silver powder, glass frit, a resin and an organic solvent, wherein the glass frit is a residue classified by a sieve having an opening diameter of 24 to 100 μm. Is described.
Patent Document 2 discloses that “a first silver powder having a crystallite diameter of 58 nm or more, a second silver powder having a crystallite diameter different from that of the silver powder, a glass frit, and a resin binder, and a solar cell electrode paste. Is described.
Patent Document 3 describes “a paste for solar cell light-receiving surface electrode containing silver particles having a specific surface area of 0.20 to 0.60 m 2 / g, glass frit, a resin binder, and thinner.” Has been.
しかしながら、特許文献１〜３に記載されたような樹脂系のペースト材料を用いて電極を形成した場合、電極自体の体積抵抗率（比抵抗）が高くなる場合があり、また、電極の断面の高さと幅の比率（高さ／幅）（以下、「アスペクト比」という。）が小さく、電極とシリコン基板との密着性が劣ることが明らかとなった。 However, when an electrode is formed using a resin-based paste material as described in Patent Documents 1 to 3, the volume resistivity (specific resistance) of the electrode itself may increase, and the cross-section of the electrode It became clear that the ratio of height to width (height / width) (hereinafter referred to as “aspect ratio”) was small, and the adhesion between the electrode and the silicon substrate was poor.
また、本発明者は、特許文献１〜３に記載された樹脂系の導電性ペーストに代えて、本出願人が提案した「酸化銀（Ａ）と、沸点が２００℃以下の２級脂肪酸を用いて得られる２級脂肪酸銀塩（Ｂ）と、を含有する導電性組成物。」や「酸化銀（Ａ）と、水酸基を１個以上有する脂肪酸銀塩（Ｂ）と、を含有する導電性組成物。」等の導電性組成物（例えば、特許第３９９０７１２号公報、特開２００９−１０５０３４号公報等参照）を適用してみたところ、電極として形成される配線に断線が生じる場合があることが明らかとなった。 In addition, the present inventor, instead of the resin-based conductive paste described in Patent Documents 1 to 3, proposes “silver oxide (A) proposed by the present applicant and a secondary fatty acid having a boiling point of 200 ° C. or less. A conductive composition containing a secondary fatty acid silver salt (B) obtained by using a conductive composition containing silver oxide (A) and a fatty acid silver salt (B) having one or more hydroxyl groups. As a result of applying a conductive composition (for example, see Japanese Patent No. 3990712, Japanese Patent Application Laid-Open No. 2009-105034, etc.), a wire formed as an electrode may be disconnected. It became clear.
そこで、本発明は、体積抵抗率を低く、かつ、アスペクト比を高くすることができ、また、シリコン基板との密着性にも優れ、配線として形成した際に断線が生じない電極を形成することができる太陽電池電極用ペーストおよびそれを用いた太陽電池セルを提供することを課題とする。 Therefore, the present invention is to form an electrode that can have a low volume resistivity and a high aspect ratio, has excellent adhesion to a silicon substrate, and does not break when formed as a wiring. It is an object of the present invention to provide a solar cell electrode paste and a solar cell using the same.
本発明者は、上記課題を解決するため鋭意検討した結果、所定の式で表される脂肪酸銀塩に対して、特定粒径・形状の銀粉末を用いる太陽電池電極用ペーストが、体積抵抗率を低く、かつ、アスペクト比を高くすることができ、また、シリコン基板との密着性にも優れ、配線として形成した際に断線が生じない電極を形成することができることを見出し、本発明を完成させた。即ち、本発明は、下記（１）〜（４）を提供する。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a paste for a solar cell electrode using a silver powder having a specific particle size and shape with respect to a fatty acid silver salt represented by a predetermined formula has a volume resistivity. And an aspect ratio can be made high, and it has excellent adhesiveness with a silicon substrate, and an electrode that does not break when formed as a wiring can be formed, and the present invention is completed. I let you. That is, the present invention provides the following (1) to (4).
（１）銀粉（Ａ）と、下記式（Ｉ）で表される脂肪酸銀塩（Ｂ）と、溶媒（Ｃ）とを含有し、
上記銀粉（Ａ）が、平均粒子径が０．５〜５μｍの球状の銀粉末である太陽電池電極用ペースト。
The solar cell electrode paste, wherein the silver powder (A) is a spherical silver powder having an average particle diameter of 0.5 to 5 µm.
（２）上記脂肪酸銀塩（Ｂ）の含有量が、上記銀粉（Ａ）１００質量部に対して１〜１００質量部である上記（１）に記載の太陽電池電極用ペースト。 (2) The paste for solar cell electrodes according to (1), wherein the content of the fatty acid silver salt (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the silver powder (A).
（３）更に、ガラスフリットを含有する上記（１）または（２）に記載の太陽電池電極用ペースト。 (3) The solar cell electrode paste according to (1) or (2), further comprising glass frit.
（４）受光面側の表面電極、半導体基板および裏面電極を具備し、
上記表面電極および／または上記裏面電極が、上記（１）〜（３）のいずれかに記載の太陽電池電極用ペーストを用いて形成される太陽電池セル。(4) It comprises a surface electrode on the light receiving surface side, a semiconductor substrate and a back electrode,
The solar cell in which the surface electrode and / or the back electrode are formed using the solar cell electrode paste according to any one of (1) to (3).
以下に示すように、本発明によれば、体積抵抗率が低く、アスペクト比が高く、また、シリコン基板との密着性にも優れた電極を形成することができる太陽電池電極用ペーストおよびそれを用いた太陽電池セルを提供することができる。
また、本発明の太陽電池電極用ペーストを用いれば、断線の発生を抑制して配線（電極）を形成することができるため非常に有用である。As shown below, according to the present invention, a solar cell electrode paste capable of forming an electrode having a low volume resistivity, a high aspect ratio, and excellent adhesion to a silicon substrate, and The used solar battery cell can be provided.
Moreover, if the solar cell electrode paste of the present invention is used, it is very useful because wiring (electrode) can be formed while suppressing occurrence of disconnection.
本発明の太陽電池電極用ペーストは、銀粉（Ａ）と、上記式（１）で表される脂肪酸銀塩（Ｂ）と、溶媒（Ｃ）とを含有し、上記銀粉（Ａ）が、平均粒子径が０．５〜５μｍの球状の銀粉末である太陽電池電極用のペーストである。
以下に、銀粉（Ａ）、脂肪酸銀塩（Ｂ）および溶媒（Ｃ）について詳述する。The solar cell electrode paste of the present invention contains silver powder (A), a fatty acid silver salt (B) represented by the above formula (1), and a solvent (C), and the silver powder (A) is an average. It is a paste for solar cell electrodes which is a spherical silver powder having a particle diameter of 0.5 to 5 μm.
Below, silver powder (A), fatty-acid silver salt (B), and a solvent (C) are explained in full detail.
＜銀粉（Ａ）＞
本発明の太陽電池電極用ペーストで用いる銀粉（Ａ）は、平均粒子径が０．５〜５μｍの球状の銀粉末である。
ここで、球状とは、長径／短径の比率が２以下の粒子の形状をいう。
また、平均粒子径とは、球状の銀粉末の粒子径の平均値をいい、レーザー回折式粒度分布測定装置を用いて測定された５０％体積累積径（Ｄ５０）をいう。なお、平均値を算出する基になる粒子径は、球状の銀粉末の断面が楕円形である場合はその長径と短径の合計値を２で割った平均値をいい、正円形である場合はその直径をいう。
例えば、後述する実施例で使用する銀粉（ＡｇＣ−１０３、福田金属箔社製）の写真（図２）で示されるものは球状の銀粉末に該当するが、比較例で使用する銀粉（ＡｇＣ−２０１１、福田金属箔社製）の写真（図３）で示されるものは球状の銀粉末には該当せず、フレーク（鱗片）状の銀粉末に該当するものである。<Silver powder (A)>
The silver powder (A) used in the solar cell electrode paste of the present invention is a spherical silver powder having an average particle diameter of 0.5 to 5 μm.
Here, the term “spherical” refers to the shape of particles having a major axis / minor axis ratio of 2 or less.
Moreover, an average particle diameter means the average value of the particle diameter of spherical silver powder, and means the 50% volume cumulative diameter (D50) measured using the laser diffraction type particle size distribution measuring apparatus. In addition, when the cross section of the spherical silver powder is elliptical, the particle diameter that is the basis for calculating the average value is the average value obtained by dividing the total value of the major axis and the minor axis by 2, and is a regular circle Refers to its diameter.
For example, what is shown in the photograph (FIG. 2) of silver powder (AgC-103, manufactured by Fukuda Metal Foil Co., Ltd.) used in Examples described later corresponds to spherical silver powder, but silver powder (AgC- 2011 (produced by Fukuda Metal Foil Co., Ltd.) (FIG. 3) does not correspond to spherical silver powder, but corresponds to flake (scalar) silver powder.
本発明においては、上記銀粉（Ａ）の平均粒子径は、印刷性が良好となる理由から、０．７〜５μｍであるのが好ましく、焼結速度が適当となり作業性に優れる理由から、１〜３μｍであるのがより好ましい。
また、上記銀粉（Ａ）の含有量は、印刷性が良好となり、比抵抗のより小さい電極を形成することができる理由から、後述する溶媒（Ｃ）１００質量部に対して３００〜７００質量部であるのが好ましく、４００〜６００質量部であるのがより好ましい。In the present invention, the average particle diameter of the silver powder (A) is preferably 0.7 to 5 μm because the printability is good, and the reason is that the sintering speed is appropriate and the workability is excellent. More preferably, it is ˜3 μm.
Further, the content of the silver powder (A) is 300 to 700 parts by mass with respect to 100 parts by mass of the solvent (C) described later, because the printability is improved and an electrode having a smaller specific resistance can be formed. It is preferable that it is 400-600 mass parts.
また、本発明においては、上記銀粉（Ａ）として市販品を用いることができ、その具体例としては、ＡｇＣ−１０２（平均粒子径：１．５μｍ、福田金属箔粉工業社製）、ＡｇＣ−１０３（平均粒子径：１．５μｍ、福田金属箔社製）、ＡＧ４−８Ｆ（平均粒子径：２．２μｍ、ＤＯＷＡエレクトロニクス社製）、ＡＧ２−１Ｃ（平均粒子径：１．０μｍ、ＤＯＷＡエレクトロニクス社製）、ＡＧ３−１１Ｆ（平均粒子径：１．４μｍ、ＤＯＷＡエレクトロニクス社製）、ＥＨＤ（形状：球状、平均粒子径：０．５μｍ、三井金属社製）等が挙げられる。 Moreover, in this invention, a commercial item can be used as said silver powder (A), As a specific example, AgC-102 (average particle diameter: 1.5 micrometer, Fukuda metal foil powder industry company make), AgC- 103 (average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Co., Ltd.), AG4-8F (average particle size: 2.2 μm, manufactured by DOWA Electronics), AG2-1C (average particle size: 1.0 μm, DOWA Electronics Co., Ltd.) Manufactured), AG3-11F (average particle size: 1.4 μm, manufactured by DOWA Electronics), EHD (shape: spherical, average particle size: 0.5 μm, manufactured by Mitsui Kinzoku Co., Ltd.), and the like.
更に、本発明においては、後述する実施例４にも示すように、上記銀粉（Ａ）とともに、フレーク状の銀粉末を併用することができる。
ここで、フレーク状の銀粉末を併用する場合の含有量は、上記銀粉（Ａ）との合計の質量に対して５０質量％以下であるのが好ましい。
なお、フレーク状の銀粉末を併用する場合、本段落以外で言及する上記銀粉（Ａ）の含有量に関する記載は、上記銀粉（Ａ）とフレーク状の銀粉末との合計の含有量のことをいう。Furthermore, in this invention, as shown also in Example 4 mentioned later, flaky silver powder can be used together with the said silver powder (A).
Here, it is preferable that content when using together flaky silver powder is 50 mass% or less with respect to the total mass with the said silver powder (A).
In addition, when using together flaky silver powder, the description regarding content of the said silver powder (A) mentioned other than this paragraph is the total content of the said silver powder (A) and flaky silver powder. Say.
＜脂肪酸銀塩（Ｂ）＞
本発明の太陽電池電極用ペーストで用いる脂肪酸銀塩（Ｂ）は上記式（１）で表される化合物であれば特に限定されず、具体的には、以下に示す脂肪酸と酸化銀とを反応させて得られるものである。<Fatty acid silver salt (B)>
The fatty acid silver salt (B) used in the solar cell electrode paste of the present invention is not particularly limited as long as it is a compound represented by the above formula (1), and specifically, the following fatty acid and silver oxide are reacted. Can be obtained.
本発明においては、上記脂肪酸銀塩（Ｂ）の反応に用いられる脂肪酸は、下記式（１）で表される脂肪酸、即ち、２−メチルプロパン酸（別名：イソ酪酸）である。このような脂肪酸を用いると、得られる脂肪酸銀塩（Ｂ）を含有する本発明の太陽電池電極用ペーストの流動性およびチクソ性が良好となるため印刷性が向上し、また、版離れ性も良好となるため電極（印刷パターン）に断線やニジミが生じにくくなり、更に、スクリーン印刷による目詰まりも生じにくくなる。 In the present invention, the fatty acid used in the reaction of the fatty acid silver salt (B) is a fatty acid represented by the following formula (1), that is, 2-methylpropanoic acid (also known as isobutyric acid). When such a fatty acid is used, the fluidity and thixotropy of the solar cell electrode paste of the present invention containing the resulting fatty acid silver salt (B) are improved, so that the printability is improved, and the release property is also improved. As a result, the electrode (printing pattern) is less likely to be broken or blurred, and clogging due to screen printing is less likely to occur.
また、本発明においては、チクソ性の観点から、上記式（１）で表される脂肪酸とともに、炭素数８以上の脂肪族モノカルボン酸や３級脂肪酸銀塩を併用するのが好ましい。
上記脂肪族モノカルボン酸としては、具体的には、例えば、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等が好適に挙げられる。
また、上記３級脂肪酸銀塩としては、具体的には、例えば、ネオデカン酸等が挙げられる。
ここで、脂肪族モノカルボン酸や３級脂肪酸銀塩を併用する場合の含有量は、上記脂肪酸銀塩（Ｂ）との合計の質量に対して５０質量％以下であるのが好ましい。In the present invention, from the viewpoint of thixotropy, it is preferable to use an aliphatic monocarboxylic acid having 8 or more carbon atoms or a tertiary fatty acid silver salt together with the fatty acid represented by the above formula (1).
Specific examples of the aliphatic monocarboxylic acid include capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid.
Specific examples of the tertiary fatty acid silver salt include neodecanoic acid.
Here, the content in the case of using an aliphatic monocarboxylic acid or a tertiary fatty acid silver salt in combination is preferably 50% by mass or less based on the total mass with the fatty acid silver salt (B).
一方、上記脂肪酸銀塩（Ｂ）の反応に用いられる酸化銀は、酸化銀（Ｉ）、即ち、Ａｇ2Ｏである。On the other hand, the silver oxide used for the reaction of the fatty acid silver salt (B) is silver (I), that is, Ag 2 O.
本発明の太陽電池電極用ペーストで用いる脂肪酸銀塩（Ｂ）は、上述した脂肪酸と酸化銀とを反応させて得られ、以下に示す反応式中の下記式（Ｉ）で表される化合物である。
この反応は、例えば、以下に示す反応式で表される反応が進行するものであれば特に限定されないが、上記酸化銀を粉砕しつつ進行させる方法や、上記酸化銀を粉砕した後に上記脂肪酸を反応させる方法が好ましい。前者の方法としては、具体的には、上記酸化銀と、溶剤により上記脂肪酸を溶液化したものとを、ボールミル等により混練し、固体である上記酸化銀を粉砕させながら、室温で、１〜２４時間程度、好ましくは２〜８時間反応させるのが好ましい。The fatty acid silver salt (B) used in the solar cell electrode paste of the present invention is obtained by reacting the above-described fatty acid and silver oxide, and is a compound represented by the following formula (I) in the reaction formula shown below. is there.
This reaction is not particularly limited as long as the reaction represented by the following reaction formula proceeds, for example, a method of proceeding while pulverizing the silver oxide, or the fatty acid after pulverizing the silver oxide. A reaction method is preferred. Specifically, as the former method, the above silver oxide and a solution obtained by dissolving the above fatty acid with a solvent are kneaded with a ball mill or the like, and the above solid silver oxide is pulverized at room temperature, The reaction is preferably performed for about 24 hours, preferably 2 to 8 hours.
上記脂肪酸を溶液化する溶媒としては、具体的には、例えば、ブチルカルビトール、メチルエチルケトン、イソホロン、α−テルピネオール等が挙げられ、これらを１種単独で用いても２種以上を併用してもよい。
これらの溶媒を用いて脂肪酸銀塩（Ｂ）を調製した場合、脂肪酸銀塩（Ｂ）を結晶として取り出した後に後述する溶媒（Ｃ）に溶解させるのが好ましい。Specific examples of the solvent for dissolving the fatty acid include butyl carbitol, methyl ethyl ketone, isophorone, α-terpineol, and the like. These may be used alone or in combination of two or more. Good.
When the fatty acid silver salt (B) is prepared using these solvents, the fatty acid silver salt (B) is preferably taken out as crystals and then dissolved in the solvent (C) described later.
上記脂肪酸銀塩（Ｂ）の含有量は、印刷性が良好となり、比抵抗のより小さい電極を形成することができる理由から、上記銀粉（Ａ）１００質量部に対して１〜１００質量部であるのが好ましく、５〜８０質量部であるのがより好ましい。 The content of the fatty acid silver salt (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the silver powder (A) because the printability is good and an electrode having a smaller specific resistance can be formed. It is preferable that it is 5 to 80 parts by mass.
本発明においては、上述した銀粉（Ａ）および脂肪酸銀塩（Ｂ）を含有する太陽電池電極用ペーストを用いることにより、体積抵抗率を低く、かつ、アスペクト比を高くすることができ、また、シリコン基板との密着性にも優れ、配線として形成した際に断線が生じない電極を形成することができる。
これは、熱処理により脂肪酸銀塩（Ｂ）から分解される銀が融解する際に銀粉（Ａ）を連結することにより、断線の発生を抑制して高い導電性を発現すると考えられる。また、熱処理により脂肪酸銀塩（Ｂ）から分解される銀が融解する際にシリコン基板に適度に濡れ広がるため、シリコン基板との密着性が向上すると考えられる。更に、脂肪酸銀塩（Ｂ）が太陽電池電極用ペーストに適度なチクソ性を付与し、印刷時の流動性を確保しつつ塗布面の広がりを抑制できるため、アスペクト比を高くすることができると考えられる。In the present invention, by using the solar cell electrode paste containing the silver powder (A) and the fatty acid silver salt (B) described above, the volume resistivity can be lowered and the aspect ratio can be increased, An electrode that is excellent in adhesiveness with a silicon substrate and does not cause disconnection when formed as a wiring can be formed.
It is considered that this is because the silver powder (A) is connected when the silver decomposed from the fatty acid silver salt (B) is melted by heat treatment, thereby suppressing the occurrence of disconnection and expressing high conductivity. In addition, when silver decomposed from the fatty acid silver salt (B) is melted by heat treatment, the silicon substrate is appropriately wetted and spread, so that the adhesion to the silicon substrate is considered to be improved. Furthermore, since the fatty acid silver salt (B) imparts an appropriate thixotropy to the solar cell electrode paste and can suppress the spread of the coated surface while ensuring fluidity during printing, the aspect ratio can be increased. Conceivable.
また、本発明においては、太陽電池電極用ペーストのチクソ性がより良好となり、アスペクト比をより高くすることができる理由から酸化銀の含有量は後述する溶媒（Ｃ）１００質量部に対して１０質量部以下であるのが好ましく、５質量部以下であるのがより好ましく、１質量部以下であるのが更に好ましく、実質的に酸化銀を含有していない態様が最も好ましい。 In the present invention, the thixotropy of the solar cell electrode paste becomes better and the aspect ratio can be increased, so that the silver oxide content is 10 with respect to 100 parts by mass of the solvent (C) described later. It is preferably no greater than 5 parts by mass, more preferably no greater than 5 parts by mass, even more preferably no greater than 1 part by mass, and most preferably an embodiment containing substantially no silver oxide.
＜溶媒（Ｃ）＞
本発明の太陽電池電極用ペーストで用いる溶媒（Ｃ）は、本発明の太陽電池電極用ペーストを基材上に塗布することができるものであれば特に限定されない。
上記溶媒（Ｃ）としては、具体的には、例えば、ブチルカルビトール、メチルエチルケトン、イソホロン、α−テルピネオール等が挙げられ、これらを１種単独で用いても２種以上を併用してもよい。<Solvent (C)>
The solvent (C) used in the solar cell electrode paste of the present invention is not particularly limited as long as the solar cell electrode paste of the present invention can be applied onto a substrate.
Specific examples of the solvent (C) include butyl carbitol, methyl ethyl ketone, isophorone, α-terpineol, and the like. These may be used alone or in combination of two or more.
＜ガラスフリット＞
本発明の太陽電池電極用ペーストは、形成される電極とシリコン基板との密着性がより良好となる理由から、ガラスフリットを含有するのが好ましい。<Glass frit>
The solar cell electrode paste of the present invention preferably contains glass frit because the adhesion between the electrode to be formed and the silicon substrate becomes better.
本発明においては、上記ガラスフリットを配合する場合、軟化温度が３００℃以上で、焼成温度（熱処理温度）以下のものを用いるのが好ましい。
このようなガラスフリットとしては、具体的には、例えば、軟化温度３００〜８００℃のホウケイ酸ガラスフリット等が挙げられる。In the present invention, when blending the glass frit, it is preferable to use one having a softening temperature of 300 ° C. or higher and a firing temperature (heat treatment temperature) or lower.
Specific examples of such a glass frit include a borosilicate glass frit having a softening temperature of 300 to 800 ° C.
本発明においては、上記ガラスフリットの形状は特に限定されず、球状でも破砕粉状でもよい。
また、球状のガラスフリットの平均粒子径（Ｄ５０）は、０．１〜２０μｍであることが好ましく、１〜３μｍであることがより好ましい。
更に、１０μｍ以上の粒子を除去した、シャープな粒度分布を持つガラスフリットを用いることが好ましい。In the present invention, the shape of the glass frit is not particularly limited, and may be spherical or crushed powder.
Moreover, it is preferable that the average particle diameter (D50) of a spherical glass frit is 0.1-20 micrometers, and it is more preferable that it is 1-3 micrometers.
Furthermore, it is preferable to use a glass frit having a sharp particle size distribution from which particles of 10 μm or more are removed.
本発明においては、上記ガラスフリットを配合する場合、その含有量は、上記銀粉（Ａ）１００質量部に対して０．１〜１０質量部であるのが好ましく、１〜５質量部であるのがより好ましい。 In this invention, when mix | blending the said glass frit, it is preferable that the content is 0.1-10 mass parts with respect to 100 mass parts of said silver powder (A), and is 1-5 mass parts. Is more preferable.
＜ビヒクル＞
本発明の太陽電池電極用ペーストは、必要に応じて、バインダー機能を有する樹脂を有機溶剤に溶解したビヒクルを含有していてもよい。
上記樹脂としては、具体的には、例えば、エチルセルロース樹脂、ニトロセルロース樹脂、アルキド樹脂、アクリル樹脂、スチレン樹脂、フェノール樹脂等が挙げられ、これらを１種単独で用いても２種以上を併用してもよい。これらのうち、熱分解性の観点から、エチルセルロース樹脂を用いるのが好ましい。
また、上記有機溶剤としては、具体的には、例えば、α−テルピネオール、ブチルカルビトール、ブチルカルビトールアセテート、ジアセトンアルコール、メチルイソブチルケトン等が挙げられ、これらを１種単独で用いても２種以上を併用してもよい。<Vehicle>
The solar cell electrode paste of the present invention may contain a vehicle in which a resin having a binder function is dissolved in an organic solvent, if necessary.
Specific examples of the resin include ethyl cellulose resin, nitrocellulose resin, alkyd resin, acrylic resin, styrene resin, phenol resin and the like, and these may be used alone or in combination of two or more. May be. Among these, it is preferable to use ethyl cellulose resin from the viewpoint of thermal decomposability.
Specific examples of the organic solvent include α-terpineol, butyl carbitol, butyl carbitol acetate, diacetone alcohol, methyl isobutyl ketone, and the like. More than one species may be used in combination.
本発明の太陽電池電極用ペーストは、必要に応じて、上述した銀粉（Ａ）以外の金属粉、還元剤等の添加剤を含有していてもよい。
上記金属粉としては、具体的には、例えば、銅、アルミニウム等が挙げられ、中でも、銅であるのが好ましい。また、０．０１〜１０μｍの粒径の金属粉であるのが好ましい。
上記還元剤としては、具体的には、例えば、エチレングリコール類等が挙げられる。The solar cell electrode paste of the present invention may contain additives such as a metal powder other than the above-described silver powder (A) and a reducing agent, if necessary.
Specific examples of the metal powder include copper and aluminum. Among them, copper is preferable. Moreover, it is preferable that it is a metal powder with a particle size of 0.01-10 micrometers.
Specific examples of the reducing agent include ethylene glycols.
本発明の太陽電池電極用ペーストの製造方法は特に限定されず、上記銀粉（Ａ）、上記脂肪酸銀塩（Ｂ）および上記溶媒（Ｃ）ならびに所望により含有していてもよい添加剤（ガラスフリット、ビヒクルを含む。）を、ロール、ニーダー、押出し機、万能かくはん機等により混合する方法が挙げられる。 The method for producing the solar cell electrode paste of the present invention is not particularly limited, and the silver powder (A), the fatty acid silver salt (B), the solvent (C), and an additive (glass frit which may be optionally contained). , Including a vehicle) by a roll, a kneader, an extruder, a universal agitator, or the like.
本発明の太陽電池セルは、受光面側の表面電極、半導体基板および裏面電極を具備し、上記表面電極および／または上記裏面電極が、上述した本発明の太陽電池電極用ペーストを用いて形成される太陽電池セルである。
ここで、本発明の太陽電池セルは、上述した本発明の太陽電池電極用ペーストが全裏面電極型（いわゆるバックコンタクト型）太陽電池の裏面電極の形成にも適用することができるため、全裏面電極型の太陽電池にも適用することができる。
以下に、本発明の太陽電池セルの構成について図１を用いて説明する。The solar cell of the present invention comprises a light-receiving surface-side surface electrode, a semiconductor substrate, and a back electrode, and the surface electrode and / or the back electrode is formed using the solar cell electrode paste of the present invention described above. It is a solar battery cell.
Here, since the solar cell electrode of the present invention described above can be applied to the formation of the back electrode of the all back electrode type (so-called back contact type) solar cell, The present invention can also be applied to an electrode type solar cell.
Below, the structure of the photovoltaic cell of this invention is demonstrated using FIG.
図１に示すように、本発明の太陽電池セル１は、受光面側の表面電極４と、ｐ層５およびｎ層２が接合したｐｎ接合シリコン基板７と、裏面電極６とを具備するものである。
また、図１に示すように、本発明の太陽電池セル１は、反射率低減のため、例えば、ウェハー表面にエッチングを施して、ピラミッド状のテクスチャを形成し、反射防止膜３を具備するのが好ましい。As shown in FIG. 1, a solar cell 1 of the present invention includes a surface electrode 4 on the light-receiving surface side, a pn junction silicon substrate 7 in which a p layer 5 and an n layer 2 are joined, and a back electrode 6. It is.
Further, as shown in FIG. 1, the solar battery cell 1 of the present invention is provided with an antireflection film 3 by, for example, etching the wafer surface to form a pyramidal texture in order to reduce the reflectance. Is preferred.
＜表面電極／裏面電極＞
本発明の太陽電池セルが具備する表面電極および裏面電極は、いずれか一方または両方が本発明の太陽電池電極用ペーストを用いて形成されていれば、電極の配置（ピッチ）、形状、高さ、幅等は特に限定されない。なお、電極の高さは、通常、数〜数十μｍに設計されるが、本発明の太陽電池電極用ペーストを用いて形成した電極のアスペクト比は、０．４以上となる。
ここで、表面電極および裏面電極は、図１に示すように、通常、複数個有するものであるが、本発明においては、例えば、複数の表面電極の一部のみが本発明の太陽電池電極用ペーストで形成されたものであってもよく、複数の表面電極の一部と複数の裏面電極の一部が本発明の太陽電池電極用ペーストで形成されたものであってもよい。<Front electrode / Back electrode>
If either one or both of the front electrode and the back electrode provided in the solar battery cell of the present invention are formed using the solar cell electrode paste of the present invention, the arrangement (pitch), shape, and height of the electrodes The width and the like are not particularly limited. In addition, although the height of an electrode is normally designed by several to several dozen micrometer, the aspect ratio of the electrode formed using the solar cell electrode paste of this invention will be 0.4 or more.
Here, as shown in FIG. 1, the front surface electrode and the back surface electrode usually have a plurality, but in the present invention, for example, only a part of the plurality of front surface electrodes is for the solar cell electrode of the present invention. It may be formed of a paste, or part of the plurality of front surface electrodes and part of the plurality of back surface electrodes may be formed of the solar cell electrode paste of the present invention.
＜反射防止膜＞
本発明の太陽電池セルが具備していてもよい反射防止膜は、受光面の表面電極が形成されていない部分に形成される膜（膜厚：０．０５〜０．１μｍ程度）であって、例えば、シリコン酸化膜、シリコン窒化膜、酸化チタン膜、これらの積層膜等から構成されるものである。<Antireflection film>
The antireflection film that the solar battery cell of the present invention may have is a film (film thickness: about 0.05 to 0.1 μm) formed on a portion of the light receiving surface where the surface electrode is not formed. For example, a silicon oxide film, a silicon nitride film, a titanium oxide film, or a laminated film thereof.
＜シリコン基板＞
本発明の太陽電池セルが具備するシリコン基板は特に限定されず、太陽電池を形成するための公知のシリコン基板（板厚：１００〜４５０μｍ程度）を用いることができ、また、単結晶または多結晶のいずれのシリコン基板であってもよい。<Silicon substrate>
The silicon substrate included in the solar battery cell of the present invention is not particularly limited, and a known silicon substrate (plate thickness: about 100 to 450 μm) for forming a solar battery can be used, and a single crystal or polycrystal Any silicon substrate may be used.
また、上記シリコン基板はｐｎ接合を有するが、これは、第１導電型の半導体基板の表面側に第２導電型の受光面不純物拡散領域が形成されていることを意味する。なお、第１導電型がｎ型の場合には、第２導電型はｐ型であり、第１導電型がｐ型の場合には、第２導電型はｎ型である。
ここで、ｐ型を与える不純物としては、ホウ素、アルミニウム等が挙げられ、ｎ型を与える不純物としては、リン、砒素などが挙げられる。The silicon substrate has a pn junction, which means that a second conductivity type light-receiving surface impurity diffusion region is formed on the surface side of the first conductivity type semiconductor substrate. When the first conductivity type is n-type, the second conductivity type is p-type. When the first conductivity type is p-type, the second conductivity type is n-type.
Here, examples of the impurity imparting p-type include boron and aluminum, and examples of the impurity imparting n-type include phosphorus and arsenic.
本発明の太陽電池セルは、表面電極および／または裏面電極が本発明の太陽電池電極用ペーストを用いて形成されているため、電極のアスペクト比が０．４以上となり、受光により発生した起電力を電流として効率良く取り出すことができる。 In the solar cell of the present invention, since the front electrode and / or the back electrode is formed using the solar cell electrode paste of the present invention, the electrode has an aspect ratio of 0.4 or more, and the electromotive force generated by light reception Can be efficiently extracted as a current.
本発明の太陽電池セルの製造方法は特に限定されないが、本発明の太陽電池電極用ペーストをシリコン基板上に塗布して配線を形成する配線形成工程と、得られた配線を熱処理して電極（表面電極および／または裏面電極）を形成する電極形成工程とを有する方法が挙げられる。
なお、本発明の太陽電池セルが反射防止層を具備する場合、反射防止膜は、プラズマＣＶＤ法等の公知の方法により形成することができる。
以下に、配線形成工程、熱処理工程について詳述する。Although the manufacturing method of the photovoltaic cell of this invention is not specifically limited, The wiring formation process which apply | coats the solar cell electrode paste of this invention on a silicon substrate, and forms wiring, heat-treats the obtained wiring, and an electrode ( And an electrode forming step of forming a front electrode and / or a back electrode).
In addition, when the photovoltaic cell of this invention comprises an antireflection layer, an antireflection film can be formed by well-known methods, such as a plasma CVD method.
Below, a wiring formation process and a heat treatment process are explained in full detail.
＜配線形成工程＞
上記配線形成工程は、本発明の太陽電池電極用ペーストをシリコン基材上に塗布して配線を形成する工程である。
ここで、塗布方法としては、具体的には、例えば、インクジェット、スクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷等が挙げられる。<Wiring formation process>
The said wiring formation process is a process of apply | coating the paste for solar cell electrodes of this invention on a silicon base material, and forming wiring.
Here, specific examples of the coating method include inkjet, screen printing, gravure printing, offset printing, letterpress printing, and the like.
＜熱処理工程＞
上記熱処理工程は、上記配線形成工程で得られた塗膜を熱処理して導電性の配線（電極）を得る工程である。
配線を熱処理することにより、脂肪酸銀塩（Ｂ）から分解される銀が融解する際に銀粉（Ａ）が連結され、電極（銀膜）が形成される。<Heat treatment process>
The heat treatment step is a step of obtaining a conductive wiring (electrode) by heat-treating the coating film obtained in the wiring forming step.
By heat-treating the wiring, when the silver decomposed from the fatty acid silver salt (B) melts, the silver powder (A) is connected to form an electrode (silver film).
本発明においては、上記熱処理は特に限定されないが、５００〜８５０℃の温度で、数秒〜数十分間、加熱（焼成）する処理であるのが好ましい。温度および時間がこの範囲であると、シリコン基板上に反射防止膜を形成した場合であっても、ファイヤースルー法により容易に電極を形成することができる。 In the present invention, the heat treatment is not particularly limited, but is preferably a treatment of heating (firing) at a temperature of 500 to 850 ° C. for several seconds to several tens of minutes. When the temperature and time are within this range, even when an antireflection film is formed on the silicon substrate, the electrode can be easily formed by the fire-through method.
なお、本発明においては、上記配線形成工程で得られた配線は、紫外線または赤外線の照射でも電極を形成することができるため、上記熱処理工程は、紫外線または赤外線の照射によるものであってもよい。 In the present invention, since the wiring obtained in the wiring formation step can form electrodes even by irradiation with ultraviolet rays or infrared rays, the heat treatment step may be performed by irradiation with ultraviolet rays or infrared rays. .
以下、実施例を用いて、本発明の太陽電池電極用ペーストについて詳細に説明する。ただし、本発明はこれに限定されるものではない。 Hereinafter, the solar cell electrode paste of the present invention will be described in detail with reference to Examples. However, the present invention is not limited to this.
（実施例１〜６、比較例１〜６）
ボールミルに、下記第１表に示す銀粉等を下記第１表中に示す組成比となるように添加し、これらを混合することにより太陽電池電極用ペーストを調製した。
調製した太陽電池電極用ペーストをシリコン基板（単結晶シリコンウェハー、ＬＳ−２５ＴＶＡ、１５６ｍｍ×１５６ｍｍ×２００μｍ、信越化学工業社製）上に、スクリーン印刷で塗布して配線を形成した。
その後、オーブンにて７００℃で１０分間乾燥し、導電性の配線（電極）を形成させた太陽電池セルのサンプルを作製した。(Examples 1-6, Comparative Examples 1-6)
The silver powder shown in the following Table 1 was added to the ball mill so as to have the composition ratio shown in the following Table 1, and these were mixed to prepare a solar cell electrode paste.
The prepared solar cell electrode paste was applied on a silicon substrate (single crystal silicon wafer, LS-25TVA, 156 mm × 156 mm × 200 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) by screen printing to form a wiring.
Then, it dried for 10 minutes at 700 degreeC in oven, and produced the sample of the photovoltaic cell in which the electroconductive wiring (electrode) was formed.
＜断線＞
スクリーン印刷で形成した乾燥（焼成）前の配線を光学顕微鏡で観察し、断線の有無を確認した。その結果を下記第１表に示す。<Disconnection>
Wiring before drying (firing) formed by screen printing was observed with an optical microscope to confirm the presence or absence of disconnection. The results are shown in Table 1 below.
＜アスペクト比（焼成前）＞
スクリーン印刷で形成した乾燥（焼成）前の配線を共焦点顕微鏡で観察し、高さと幅とを測定し、アスペクト比（高さ／幅）を求めた。
アスペクト比０．６以上を、アスペクト比が十分に高い（十分満足できる）として「◎」と評価し、０．４以上０．６未満を、アスペクト比が高い（満足できる）として「○」と評価し、０．４未満を、アスペクト比が低い（満足できない）として「×」と評価した。
これらの結果を下記第１表に示す。<Aspect ratio (before firing)>
The wiring before drying (firing) formed by screen printing was observed with a confocal microscope, the height and width were measured, and the aspect ratio (height / width) was determined.
An aspect ratio of 0.6 or more is evaluated as “◎” as the aspect ratio is sufficiently high (sufficiently satisfactory), and an aspect ratio of 0.4 or more and less than 0.6 is evaluated as “◯” as the aspect ratio is high (satisfied). Evaluation was evaluated as “x” as the aspect ratio was low (unsatisfactory) when less than 0.4.
These results are shown in Table 1 below.
＜体積抵抗率（比抵抗）＞
作製した各太陽電池セルのサンプルについて、電極の体積抵抗率を抵抗率計（ロレスターＧＰ、三菱化学社製）を用いた４端子４探針法により測定した。その結果を下記第１表に示す。<Volume resistivity (specific resistance)>
About the sample of each produced photovoltaic cell, the volume resistivity of the electrode was measured by a 4-terminal 4-probe method using a resistivity meter (Lorestar GP, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1 below.
＜密着性＞
作製した各太陽電池セルのサンプルの表面上にセロハン粘着テープ（幅１８ｍｍ）を完全に付着させた後、直ちにテープの一端を直角に保ち、瞬間的に引き離し、電極（印刷パターン）が剥がれるか否かを調べた。
電極に剥がれが確認できたものを密着性に劣るものとして「×」と評価し、電極に剥がれが確認できなかったものを密着性に優れるものとして「○」と評価した。その結果を下記第１表に示す。<Adhesion>
After the cellophane adhesive tape (width 18 mm) is completely attached on the surface of each solar cell sample produced, immediately hold one end of the tape at a right angle and pull it away instantaneously to see if the electrode (print pattern) is peeled off I investigated.
The case where peeling was confirmed on the electrode was evaluated as “x” as being poor in adhesion, and the case where peeling was not confirmed on the electrode was evaluated as “◯” as being excellent in adhesion. The results are shown in Table 1 below.
＜アスペクト比（焼成後）＞
作製した各太陽電池セルのサンプルについて、電極をレーザー顕微鏡で観察し、高さと幅とを測定し、アスペクト比（高さ／幅）を求めた。
アスペクト比０．６以上を、アスペクト比が十分に高い（十分満足できる）として「◎」と評価し、０．４以上０．６未満を、アスペクト比が高い（満足できる）として「○」と評価し、０．４未満を、アスペクト比が低い（満足できない）として「×」と評価した。
これらの結果を下記第１表に示す。<Aspect ratio (after firing)>
About the sample of each produced photovoltaic cell, the electrode was observed with the laser microscope, height and width were measured, and the aspect ratio (height / width) was calculated | required.
An aspect ratio of 0.6 or more is evaluated as “◎” as the aspect ratio is sufficiently high (sufficiently satisfactory), and an aspect ratio of 0.4 or more and less than 0.6 is evaluated as “◯” as the aspect ratio is high (satisfied). Evaluation was evaluated as “x” as the aspect ratio was low (unsatisfactory) when less than 0.4.
These results are shown in Table 1 below.
＜光電変換効率＞
作製した各太陽電池セルのうち、実施例２および比較例６について、光源としてソーラーシミュレーターを用い、ＡＭ１．５の擬似太陽光を１００ｍＷ／ｃｍ2の光強度で光電極側から照射し、電流電圧測定装置（ケースレーインスツルメンツ社製デジタルソースメーター２４００）を用いて変換効率を求めた。その結果を下記第１表に示す。<Photoelectric conversion efficiency>
Among the produced solar cells, for Example 2 and Comparative Example 6, a solar simulator was used as a light source, and AM1.5 pseudo-sunlight was irradiated from the photoelectrode side with a light intensity of 100 mW / cm 2. Conversion efficiency was determined using a measuring device (Digital Source Meter 2400 manufactured by Keithley Instruments). The results are shown in Table 1 below.
第１表中の各成分は、以下のものを使用した。
・銀粉１：ＡｇＣ−１０３（形状：球状、平均粒子径：１．５μｍ、福田金属箔社製）
・銀粉２：Ａｇ−４−８Ｆ（形状：球状、平均粒子径：２．２μｍ、ＤＯＷＡエレクトロニクス社製）
・銀粉３：ＡｇＣ−２０１１（形状：フレーク状、平均粒子径：２〜１０μｍ、福田金属箔社製）The following were used for each component in Table 1.
Silver powder 1: AgC-103 (shape: spherical, average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Co., Ltd.)
Silver powder 2: Ag-4-8F (shape: spherical, average particle size: 2.2 μm, manufactured by DOWA Electronics)
Silver powder 3: AgC-2011 (shape: flake shape, average particle size: 2 to 10 μm, manufactured by Fukuda Metal Foil Co., Ltd.)
・２−メチルプロパン酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、２−メチルプロパン酸（関東化学社製）３８ｇおよびメチルエチルケトン（ＭＥＫ）３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、２−メチルプロパン酸銀塩を調製した。
・２−メチルブタン酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、２−メチルブタン酸（関東化学社製）４４ｇおよびＭＥＫ３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、２−メチルブタン酸銀塩を調製した。
・２−エチル酪酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、２−エチル酪酸（関東化学社製）５０．２ｇおよびＭＥＫ３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、２−エチル酪酸銀塩を調製した。
・ネオデカン酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、ネオデカン酸（東洋合成社製）７４．３ｇおよびＭＥＫ３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、ネオデカン酸銀塩を調製した。
・ステアリン酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、ステアリン酸（関東化学社製）１２３ｇおよびＭＥＫ３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、ステアリン酸銀塩を調製した。-Silver salt of 2-methylpropanoic acid: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 38 g of 2-methylpropanoic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are put into a ball mill, and are kept at room temperature for 24 hours. The reaction was allowed to stir. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-methylpropanoate.
Silver 2-methylbutanoate: First, 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 44 g of 2-methylbutanoic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were put into a ball mill and reacted by stirring at room temperature for 24 hours. It was. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-methylbutanoate.
-Silver 2-ethylbutyrate: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 50.2 g of 2-ethylbutyric acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK are put into a ball mill and stirred at room temperature for 24 hours. Reacted. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-ethylbutyrate.
-Neodecanoic acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Kagaku Co., Ltd.), 74.3 g of neodecanoic acid (manufactured by Toyo Gosei Co., Ltd.) and 300 g of MEK were charged into a ball mill and reacted by stirring at room temperature for 24 hours. Next, MEK was removed by suction filtration, and the obtained powder was dried to prepare a silver neodecanoate.
Silver stearate: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 123 g of stearic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare a silver stearate salt.
・酸化銀：酸化銀（Ｉ）（東洋化学工業社製）
・α−テルピネール：溶剤
・ガラスフリット：硼珪酸鉛ガラス粉末
・銀ペースト：樹脂系銀ペースト（ＤＷＰ−０２５、東洋紡績社製）Silver oxide: Silver oxide (I) (manufactured by Toyo Chemical Industry Co., Ltd.)
Α-terpineol: solvent glass frit: lead borosilicate glass powder silver paste: resin-based silver paste (DWP-025, manufactured by Toyobo Co., Ltd.)
第１表に示す結果から、従来公知の樹脂系の銀ペーストで調製した比較例１は、断線がなかったが、電極の体積抵抗率が若干高く、シリコン基板との密着性に劣り、また、焼成前後のいずれにおいてもアスペクト比が低いことが分かった。
また、銀粉の代わりに酸化銀を含有するペーストで調製した比較例２は、断線があり、電極の体積抵抗率も高くなり、また、シリコン基板との密着性にも劣り、更に、焼成前後のいずれにおいてもアスペクト比が低いことが分かった。
また、銀粉（Ａ）に該当しないフレーク状の銀粉を用いて調製した比較例３は、断線があり、電極の体積抵抗率も高くなり、また、シリコン基板との密着性に劣り、更に、焼成前後のいずれにおいてアスペクト比が低いことが分かった。
また、脂肪酸銀塩（Ｂ）に該当しない脂肪酸銀塩を用いて調製した比較例４および６は、断線がなく、電極の体積抵抗率が十分に低く、また、シリコン基板との密着性にも優れていたが、焼成後のアスペクト比が低いことが分かった。
また、脂肪酸銀塩（Ｂ）に該当しない脂肪酸銀塩を用いて調製した比較例５は、電極の体積抵抗率が十分に低く、また、シリコン基板との密着性にも優れていたが、断線があり、焼成後のアスペクト比が低いことが分かった。From the results shown in Table 1, in Comparative Example 1 prepared with a conventionally known resin-based silver paste, there was no disconnection, but the volume resistivity of the electrode was slightly high and the adhesion to the silicon substrate was poor, It was found that the aspect ratio was low both before and after firing.
Further, Comparative Example 2 prepared with a paste containing silver oxide instead of silver powder has a disconnection, the electrode has a high volume resistivity, is inferior in adhesion to the silicon substrate, and before and after firing. In both cases, the aspect ratio was found to be low.
Further, Comparative Example 3 prepared using flaky silver powder not corresponding to silver powder (A) has a disconnection, the electrode has a high volume resistivity, is inferior in adhesion to the silicon substrate, and is further fired. It was found that the aspect ratio was low before and after.
Further, Comparative Examples 4 and 6 prepared using a fatty acid silver salt not corresponding to the fatty acid silver salt (B) have no disconnection, the volume resistivity of the electrode is sufficiently low, and the adhesion to the silicon substrate is also good. Although it was excellent, it was found that the aspect ratio after firing was low.
Further, Comparative Example 5 prepared using a fatty acid silver salt not corresponding to the fatty acid silver salt (B) had a sufficiently low volume resistivity of the electrode and excellent adhesion to the silicon substrate. It was found that the aspect ratio after firing was low.
これに対し、銀粉（Ａ）および脂肪酸銀塩（Ｂ）を用いた実施例１〜６は、断線がなく、電極の体積抵抗率が十分に低く、また、シリコン基板との密着性に優れ、更に、焼成前後のいずれにおいてもアスペクト比も高いことが分かった。
また、実施例２および比較例６の光電変換効率の結果から、３級脂肪酸銀塩よりも２級脂肪酸銀塩の方が、太陽電池電極用途に適していることが分かった。なお、実施例２の光電変換効率（１４．０１）と比較例６の光電変換効率（１３．２０）との相違は、電極材料のみの相違として現れる差としては顕著なものである。On the other hand, Examples 1-6 using silver powder (A) and fatty acid silver salt (B) have no disconnection, the volume resistivity of an electrode is low enough, and is excellent in adhesiveness with a silicon substrate, Further, it was found that the aspect ratio was high both before and after firing.
Moreover, it turned out that the secondary fatty acid silver salt is more suitable for a solar cell electrode use than the tertiary fatty acid silver salt from the result of the photoelectric conversion efficiency of Example 2 and Comparative Example 6. In addition, the difference between the photoelectric conversion efficiency (14.01) of Example 2 and the photoelectric conversion efficiency (13.20) of Comparative Example 6 is remarkable as a difference that appears as a difference of only the electrode material.
１ 太陽電池セル
２ ｎ層
３ 反射防止膜
４ 表面電極
５ ｐ層
６ 裏面電極
７ シリコン基板DESCRIPTION OF SYMBOLS 1 Solar cell 2 N layer 3 Antireflection film 4 Surface electrode 5 P layer 6 Back electrode 7 Silicon substrate
Claims (4)
前記銀粉（Ａ）が、平均粒子径が０．５〜５μｍの球状の銀粉末である太陽電池電極用ペースト。
The solar cell electrode paste, wherein the silver powder (A) is a spherical silver powder having an average particle diameter of 0.5 to 5 µm.
前記表面電極および／または前記裏面電極が、請求項１〜３のいずれかに記載の太陽電池電極用ペーストを用いて形成される太陽電池セル。It comprises a surface electrode on the light receiving surface side, a semiconductor substrate and a back electrode
The photovoltaic cell in which the said surface electrode and / or the said back surface electrode are formed using the paste for solar cell electrodes in any one of Claims 1-3.
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| PCT/JP2010/071984 WO2011071066A1 (en) | 2009-12-09 | 2010-12-08 | Paste for solar cell electrode and solar cell |
| JP2011505288A JP4743350B1 (en) | 2009-12-09 | 2010-12-08 | Solar cell electrode paste and solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007019106A (en) * | 2005-07-05 | 2007-01-25 | Kyocera Chemical Corp | Conductive paste for forming electrode, and photovoltaic cell |
| JP2007280881A (en) * | 2006-04-11 | 2007-10-25 | Yokohama Rubber Co Ltd:The | Conductive composition, formation method of conductive coating, and conductive coating |
| JP2007317535A (en) * | 2006-05-26 | 2007-12-06 | Yokohama Rubber Co Ltd:The | Conductive composition, method for forming conductive film, and conductive film |
| JP2008198595A (en) * | 2007-01-16 | 2008-08-28 | Mitsubishi Chemicals Corp | Metal particulate ink paste and organic acid treated metal particulate |
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| JP4126215B2 (en) | 2002-10-23 | 2008-07-30 | シャープ株式会社 | Method for manufacturing solar battery cell |
| JP5323307B2 (en) | 2005-12-21 | 2013-10-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Solar cell electrode paste |
| JP2007235082A (en) | 2006-02-02 | 2007-09-13 | E I Du Pont De Nemours & Co | Paste for solar battery electrode |
| DE102007017005B4 (en) * | 2006-04-11 | 2009-12-31 | The Yokohama Rubber Co., Ltd. | Electrically conductive composition, process for producing an electrically conductive film |
| JP4339919B2 (en) | 2007-10-02 | 2009-10-07 | 横浜ゴム株式会社 | Conductive composition, method for forming conductive film, and conductive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007019106A (en) * | 2005-07-05 | 2007-01-25 | Kyocera Chemical Corp | Conductive paste for forming electrode, and photovoltaic cell |
| JP2007280881A (en) * | 2006-04-11 | 2007-10-25 | Yokohama Rubber Co Ltd:The | Conductive composition, formation method of conductive coating, and conductive coating |
| JP2007317535A (en) * | 2006-05-26 | 2007-12-06 | Yokohama Rubber Co Ltd:The | Conductive composition, method for forming conductive film, and conductive film |
| JP2008198595A (en) * | 2007-01-16 | 2008-08-28 | Mitsubishi Chemicals Corp | Metal particulate ink paste and organic acid treated metal particulate |
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| CN102349162B (en) | 2013-03-27 |
| JPWO2011071066A1 (en) | 2013-04-22 |
| WO2011071066A1 (en) | 2011-06-16 |
| CN102349162A (en) | 2012-02-08 |
| KR101179113B1 (en) | 2012-09-10 |
| DE112010004746T5 (en) | 2013-03-07 |
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