TW201250716A - Solar cell and paste composition for forming aluminum electrode of solar cell - Google Patents
Solar cell and paste composition for forming aluminum electrode of solar cell Download PDFInfo
- Publication number
- TW201250716A TW201250716A TW101117083A TW101117083A TW201250716A TW 201250716 A TW201250716 A TW 201250716A TW 101117083 A TW101117083 A TW 101117083A TW 101117083 A TW101117083 A TW 101117083A TW 201250716 A TW201250716 A TW 201250716A
- Authority
- TW
- Taiwan
- Prior art keywords
- mol
- electrode
- glass
- solar cell
- aluminum
- Prior art date
Links
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 239000011521 glass Substances 0.000 claims abstract description 115
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 65
- 239000000463 material Substances 0.000 claims description 50
- 239000004065 semiconductor Substances 0.000 claims description 26
- 239000002313 adhesive film Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- -1 B 2 〇 3 Inorganic materials 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 40
- 239000010408 film Substances 0.000 description 33
- 239000002245 particle Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 13
- 239000004332 silver Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-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
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-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
- 239000004838 Heat curing adhesive Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003930 SiCb Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920003174 cellulose-based polymer Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy 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
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
Description
201250716 六、發明說明： 【發明所屬^技術領】 發明領域 本發明係有關於一種太陽電池(cell)及其製造方法，以 及用於該製造方法之鋁電極形成用糊組成物。 又’本申請案依據2011年6月3日申請之日本專利申請 案2011-125062號主張優先權，且該申請案之全部内容加入 本說明書中作為參考。201250716 VI. Description of the Invention: [Technical Field] The present invention relates to a solar cell and a method of manufacturing the same, and a paste composition for forming an aluminum electrode used in the manufacturing method. Further, the present application claims priority to Japanese Patent Application No. 2011-125062, filed on Jun. 3, 2011, the entire content of
C 'J 以往，以如結晶矽、非晶矽之矽（半導體基板）為主體之 太陽電池（以下亦稱為「石夕系太陽電池」）的一典型例已知的 是如第7圖所示之單面受光型太陽電池1〇〇〇(例如，請參照 由專利文獻1至4)。 該太陽電池1000具有藉由pn接合形成在矽半導體基板 111 (Si晶圓）之p-Si層（p型結晶矽）118之受光面側形成的n-Si 層116’且在其表面上具有由藉由cvD等形成之氧化鈦或氮 化矽形成之抗反射膜114，及典型地藉由網版印刷且燒成以 報(Ag)為主體之糊組成物（以下亦稱為「銀糊」）而形成的由 八§形成之表面電極（受光面電極）112。 另一方面，在p-Si層118之背面（所謂受光面之相反側的 面。以下相同。）側具有與表面電極同樣地藉由網版印刷且 繞成銀糊而形成之由Ag形成之背面側外部連接用電極 122 ’及具有所謂背面電場(BSF ; Back Surface Field)效果的 叙電極120。 3 201250716 6玄#呂電極120藉印刷 '燒成以紹㈣粉末為主體之糊組 成物（以下亦稱為「IS糊」）形成在f面之大致全面上。該燒 成時形成未圖示之Al-Si合金層，且㈣散至p_Si層118而形 成p層m。由於形成該p+層丨24,即BSF層，可防止光生成 之載子在背面電極附近再結合，可實現例如短路電流或開 路電壓(Voc)之提高。 先前技術文獻 專利文獻 專利文獻1 :曰本專利申請案公開2010_10495號公報 專利文獻2 :日本專利申請案公開2011_23598號公報 專利文獻3 :日本專利申請案公開2〇1〇_19248〇號公報 專利文獻4 :日本專利申請案公開2007_59380號公報 t發明内容3 發明概要 如第7圖所示，習知之太陽電池1〇〇〇係在受光面側形成 有用以取出電流之Ag表面電極（受光面電極）ιΐ2，且在背面 側形成有用以防止電子再結合之BSF層124。用以形成Ag表 面電極112及BSF層124之鋁電極120係典型地藉由網版印刷 法形成，且藉由在兩面同時燒結而形成。 又，如此地在兩面形成電極（112、120、122；)之太陽電 池1000上焊接電流取出用之導線（引線框：未圖示）。此外， 藉由使用該導線而串聯連接多數片太陽電池1000可模組 化，且可在如此模組化之狀態下供給預定之電力。 在此，在第7圖顯示之構造中，由於在用於背面之鋁電 201250716 極120上未使用焊料，所以在焊接部份形成有Ag電極122。 結果，因形成Ag電極122妨礙BSF層124之均一化，又，形 成Ag電極122時’由於使用比鋁昂貴之貴金屬銀作為導電成 分，所以成為局成本之主要原因。 本發明人檢討不使用焊料’而使用導電性接著薄膜 (即’含有接著材及導電性粒子之薄膜），且加熱加壓附著導 線之方法，作為以鋁電極覆蓋背面全面之嘗試。具體而言， 藉由加熱加壓附著導線，不使用焊料實行連接。 但是，已知的是藉由使用該導電性接著薄膜之方法無 法在由鋁形成之電極122上得到充分之接著強度。即，經本 發明人檢討後，認為一旦剝下透過導電性接著薄膜接著導 線（導電帶狀線)之接著部份，由鋁形成之電極122中之鋁膜 内產生剝離，且這是無法得到充分接著強度之原因。進一 步來說，發現原因是形成鋁之鋁粒子間彼此燒成後之接著 強度減弱而不是由鋁形成之電極122中之鋁膜内本身的強 度減弱。 另方面，如果可以在太陽電池晶圓之鋁電極上接著 導線’則不但可得到可於全面形成BSF層以之好處，而且 由於不需要❹銀，因此亦可達成相當於銀齡之材料價 格差之大幅成本下降。 本發明係有鑑於這方面而創出者，且一目的在於提供 種用以形成提高接著強度之紹電極(特別是背面側外部 連接用電極)之糊組成物。又，另—目的在於提供一種具有 用X糊、’且成物形成之鋁電極（特別是背面側外部連接用 201250716 電極)及其製法。 藉由本發明提供之糊組成物（即所謂調製成糊狀之組 成物）係用以形成太陽電池之鋁電極的糊組成物。 又’在此揭示之太陽電池之鋁電極用糊組成物包含紹 粉末，玻料及有機載體。又，其特徵在於玻料具有以下條件： (1) 玻璃軟化點為4〇〇°c以上且600°C以下； (2) 熱膨脹係數為6〇xl〇-7/°c以上且8〇χ1〇-7/<^以下·， (3) 含有Si〇2、β2〇3、Ζη〇及/或Pb〇、八丨2〇3、及至少一 種鹼金屬氧化物作為必須構成成分。 在上述構成之糊組成物（鋁糊）中，由於具有上述（1)〜（3) 所不條件之性狀的玻料(玻璃粉末），因此可提高在矽半導體 基材中賦予該糊組成物而形成之鋁電極的接著強度。因 此例如，可女疋地維持由該糊組成物形成之紹電極(例如 背面側外部連接料極)與其他連制構件(例如含有接著 材及導電性粒子之導電性接著薄膜)之接合。結果，可將以 往使用Ag電極之部位，例如外部連接用電極之導電成分由 銀等貴金屬置換為便宜之紹，且可實現相當於銀與紹之材 料價格差之大幅成本下降。又’如果可以將背面側外部連 接用之Ag電極置換為铭電極，則可在石夕半導體基板之背面 側的全面上均一地形成BSF層。 20〜35mol%， 在此揭示之糊組成物（鋁糊）之—較佳態樣之特徵在於 上述玻料為當令以下之各成分全體為⑽咖1%，各成分之 莫耳含有率為 Si02 6 201250716 5〜30mol%， 25〜45mol%， 2〜lOmol%， 5〜15mol%， 0〜lOmol%， 0〜5mol0/〇， B2O3C 'J In the past, a typical example of a solar cell (hereinafter also referred to as "Stone solar cell") mainly composed of a germanium (a semiconductor substrate) such as a crystalline germanium or an amorphous germanium is known as Fig. 7 One-sided light-receiving type solar cell 1 〇〇〇 (for example, refer to Patent Documents 1 to 4). The solar cell 1000 has an n-Si layer 116' formed on the light-receiving surface side of a p-Si layer (p-type crystalline germanium) 118 of a germanium semiconductor substrate 111 (Si wafer) by pn bonding and has a surface thereof An anti-reflection film 114 formed of titanium oxide or tantalum nitride formed by cvD or the like, and a paste composition which is typically screen-printed and fired to report (Ag) (hereinafter also referred to as "silver paste" The surface electrode (light-receiving surface electrode) 112 formed by VIII is formed. On the other hand, on the back surface of the p-Si layer 118 (the surface on the opposite side of the light-receiving surface, the same applies hereinafter), the side is formed of Ag which is formed by screen printing and wound into a silver paste in the same manner as the surface electrode. The back side external connection electrode 122' and the reference electrode 120 having a so-called back surface field effect (BSF). 3 201250716 6 Xuan #吕电极120 by printing The composition of the paste (hereinafter also referred to as "IS paste") which is based on the powder of the Shao (4) powder is formed on the entire surface of the f-plane. At the time of the firing, an Al-Si alloy layer (not shown) is formed, and (4) is dispersed to the p-Si layer 118 to form a p-layer m. Since the p+ layer 24, i.e., the BSF layer, is formed, it is possible to prevent the photo-generated carriers from recombining in the vicinity of the back surface electrode, for example, to improve the short-circuit current or the open-circuit voltage (Voc). PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1 Patent Publication No. 2010_10495 Patent Document 2: Japanese Patent Application Publication No. 2011-23598 Patent Publication No.: Japanese Patent Application Publication No. Hei. 4: SUMMARY OF THE INVENTION As shown in Fig. 7, a conventional solar cell 1 is formed on the light-receiving surface side to form an Ag surface electrode (light-receiving surface electrode) for taking out a current. ΐ 2, and a BSF layer 124 useful to prevent electron recombination is formed on the back side. The aluminum electrode 120 for forming the Ag surface electrode 112 and the BSF layer 124 is typically formed by a screen printing method and formed by simultaneous sintering on both sides. Further, in the solar cell 1000 in which the electrodes (112, 120, 122; are formed on both sides), a lead wire for drawing current is drawn (lead frame: not shown). Further, by connecting the plurality of solar cells 1000 in series by using the wires, the solar cells 1000 can be modularized, and predetermined power can be supplied in such a modular state. Here, in the structure shown in Fig. 7, since the solder is not used on the aluminum electric 201250716 pole 120 for the back surface, the Ag electrode 122 is formed in the welded portion. As a result, the formation of the Ag electrode 122 hinders the uniformization of the BSF layer 124, and when the Ag electrode 122 is formed, the use of noble metal silver which is more expensive than aluminum is used as a conductive component, which is a major factor in the cost. The inventors of the present invention have tried to use a conductive adhesive film (i.e., a film containing a backing material and conductive particles) without using solder, and a method of heating and pressing a conductive wire as an attempt to cover the back surface with an aluminum electrode. Specifically, the wires are attached by heating and pressing, and the bonding is performed without using solder. However, it is known that a sufficient adhesive strength cannot be obtained on the electrode 122 formed of aluminum by using the conductive adhesive film. That is, after review by the present inventors, it is considered that peeling occurs in the aluminum film in the electrode 122 formed of aluminum once the conductive portion is peeled off and the subsequent portion of the conductive wire (conductive strip line) is peeled off, and this is not sufficiently obtained. Then the reason for the intensity. Further, it was found that the reason was that the strength of the aluminum-forming aluminum particles after firing with each other was weakened, and the strength of the aluminum film itself in the electrode 122 formed of aluminum was weakened. On the other hand, if the wire can be attached to the aluminum electrode of the solar cell wafer, the benefits of forming the BSF layer can be obtained, and since the silver is not required, the price difference of the material equivalent to the silver age can be achieved. The substantial cost has dropped. The present invention has been made in view of the above, and an object thereof is to provide a paste composition for forming an electrode for improving the adhesion strength (particularly, an electrode for backside external connection). Further, another object is to provide an aluminum electrode (especially a 201250716 electrode for backside external connection) having an X paste and a composition, and a method for producing the same. The paste composition provided by the present invention (i.e., a composition prepared as a paste) is used to form a paste composition of an aluminum electrode of a solar cell. Further, the paste composition for an aluminum electrode of a solar cell disclosed herein contains a powder, a glass material and an organic vehicle. Further, it is characterized in that the glass material has the following conditions: (1) The glass softening point is 4 〇〇 ° C or more and 600 ° C or less; (2) The thermal expansion coefficient is 6 〇 x l 〇 -7 / ° c or more and 8 〇χ 1 〇-7/<^以下, (3) Contains Si〇2, β2〇3, Ζη〇 and/or Pb〇, 丨2丨3, and at least one alkali metal oxide as essential constituents. In the paste composition (aluminum paste) having the above configuration, since the glass material (glass powder) having the properties unconditionally described in the above (1) to (3) is provided, the paste composition can be provided in the tantalum semiconductor substrate. The subsequent strength of the formed aluminum electrode. Therefore, for example, the bonding of the electrode formed of the paste composition (e.g., the back side external connection material) to other bonding members (e.g., the conductive bonding film containing the bonding material and the conductive particles) can be maintained. As a result, it is possible to replace the conductive component of the electrode using the Ag electrode, for example, the electrode for external connection, with a noble metal such as silver, and it is possible to achieve a significant cost reduction corresponding to the price difference between the material of silver and the material. Further, if the Ag electrode for external connection on the back side can be replaced with the electrode, the BSF layer can be uniformly formed on the entire back side of the stone substrate. 20 to 35 mol%, the paste composition (aluminum paste) disclosed herein is characterized in that the glass material is such that the following components are all (10) coffee 1%, and the molar content of each component is SiO 2 . 6 201250716 5~30mol%, 25~45mol%, 2~lOmol%, 5~15mol%, 0~lOmol%, 0~5mol0/〇, B2O3
ZnO及 / 或 PbO ai2o3ZnO and / or PbO ai2o3
Li20、Na20及K20中之至少1種 CaO、SrO及BaO中之至少1種 Bi203 且該等成分之合計係該玻料全體之9 5 m 01 %以上（例如 lOOmol%)。 藉由採用如此之組成之玻料，可進一步提高由該糊組 成物形成之鋁電極（例如背面側外部連接用電極）之接著強 度（剝離強度）。 在此揭示之糊組成物（鋁糊）之一更佳態樣之特徵在於 上述玻料為當令以下之各成分全體為lOOmol%，各成分之 莫耳含有率為At least one of Li20, Na20 and K20, at least one of CaO, SrO and BaO, and the total of the components is 9 5 m 01 % or more (for example, 100 mol%) of the entire glass. By using the glass material having such a composition, the adhesion strength (peeling strength) of the aluminum electrode (e.g., the electrode for rear side external connection) formed of the paste composition can be further improved. A more preferable aspect of the paste composition (aluminum paste) disclosed herein is characterized in that the glass material is 100% by mol of the following components, and the molar content of each component is
Si02 20〜30mol〇/〇， B2O3Si02 20~30mol〇/〇, B2O3
ZnO 20〜30mol〇/〇， 25〜35mol0/〇，ZnO 20~30mol〇/〇, 25~35mol0/〇,
Al2〇3 3 〜7mol%，Al2〇3 3 to 7 mol%,
Li20、Na20及K20 中之至少 1種 10〜15mol%，At least one of Li20, Na20 and K20 is 10 to 15 mol%,
CaO、SrO及BaO中之至少1種 2〜lOmol%， 且該等成分之合計係該玻料全體之9 5 m 01 %以上（例如 lOOmol%)。 藉由採用如此之組成之玻料，可更進一步提高由該糊 組成物形成之背面側外部連接用電極等之鋁電極的接著強 201250716 度(剝離強度）。x，可無純實現如此之高接著強度。 又’在此揭示之糊組成物（紹糊）之另一較佳態樣之特徵 在於上述玻料之玻璃軟化點為500<t以上且6〇(rc以下。藉 线用在如此之溫度範_具妹化點之玻料可形成高 接著強度（剝離強度)之鋁電極。 又’在此揭示之糊組成物（鋁糊）之另一較佳態樣之特徵 在於令糊組成物全體為·f4%，上述歸末之含有率為 60 80質/〇’且，上述玻料之含有率為2〜丄〇質量％。糊 組成物之SI形體為域含有料，麵半導縣板上容易 (典型地為難)均—地賦予含有該固㈣之她成物，且藉 由燒成經断糊組成物之絲，可形纽好外觀之接著強 度強的鋁電極。 如上所述’藉由使用在此揭示之任一糊組成物（銘糊）， 可在石夕半導體基板上料高接著㈣之铭電極。 因此，依據本發明，可提供一種太陽電池，其具有矽 半導體基板、在該基板之其中—面之受光面側上形成之受 光面電極、及在該基板之另一面之背面側上形成之鋁電 極’其特徵在於上述鋁電極之至少一部份含有具有以下條 件之玻璃組成物： (1) 玻璃軟化點為4〇〇〇c以上且6〇〇。〇以下； (2) 熱膨脹係數為60χ1〇-7Λ：以上且80x1 〇-7/。(：以下； (3) 含有Si02、β2〇3、Ζη〇及/或pb〇、α1203、及至少 _ 種鹼金屬氧化物作為必須構成成分。 該構成之太陽電池可就含有上述性狀之玻璃組成物 201250716 (玻璃成分)之铭電極實現南接著強度（剝離強度）。因此，在 此揭示之太陽電池（矽系太陽電池）可將以往使用Ag電極之 部位，例如外部連接用電極之導電成分由銀等貴金屬置換 為便宜之鋁，且可實現電極製造成本之降低（由Ag電極置換 為IS電極）。 又，依據本發明，可提供在背面側外部連接用Ag電極 置換成銘電極之石夕半導體基板之背面側的全面上形成BSF 層之太陽電池。 在此揭示之一較佳態樣之太陽電池之特徵在於上述玻 璃組成物為當令以下之各成分全體為lOOmol%，各成分之 莫耳含有率為 20〜35mol%， 5〜30mol%， 25〜45mol%， 2〜10mol0/〇， 5 〜15mol%， 0〜10mol〇/〇， 0〜5mol%，At least one of CaO, SrO and BaO is 2 to 10 mol%, and the total of the components is 9 5 m 01 % or more (for example, 100 mol%) of the entire glass. By using the glass frit having such a composition, the adhesion strength of the aluminum electrode such as the back side external connection electrode formed of the paste composition can be further increased to 201250716 degrees (peel strength). x, can achieve such high high strength without pure. Further, another preferred aspect of the paste composition disclosed herein is characterized in that the glass softening point of the glass material is 500 < t or more and 6 〇 (rc or less. The borrowing line is used in such a temperature range) The glass material having the masculine point can form an aluminum electrode having a high strength (peel strength). Another preferred aspect of the paste composition (aluminum paste) disclosed herein is characterized in that the paste composition is made entirely · f4%, the content of the above-mentioned finalization is 60 80 mass / 〇 ', and the content of the glass material is 2 to 丄〇 mass %. The SI shape of the paste composition is a domain-containing material, and the surface of the semi-conducting county plate It is easy (typically difficult) to uniformly impart an aluminum electrode containing the solid (four), and by firing the filament of the broken paste composition, the aluminum electrode having a strong bonding strength can be formed as described above. By using any of the paste compositions disclosed herein, it can be coated on the Shishi semiconductor substrate with the electrode of (4). Therefore, according to the present invention, a solar cell having a germanium semiconductor substrate can be provided. a light-receiving surface electrode formed on the light-receiving surface side of the substrate, and The aluminum electrode formed on the back side of the other side of the substrate is characterized in that at least a portion of the aluminum electrode contains a glass composition having the following conditions: (1) The glass softening point is 4 〇〇〇c or more and 6 〇〇. (2) The coefficient of thermal expansion is 60χ1〇-7Λ: above and 80x1 〇-7/. (: below; (3) Contains SiO 2 , β 2 〇 3 , Ζ 〇 〇 and / or pb 〇, α 1203, and at least _ The alkali metal oxide is an essential component. The solar cell of the above configuration can achieve the south strength (peel strength) of the electrode of the glass composition 201250716 (glass component) containing the above properties. Therefore, the solar cell disclosed herein ( In the conventional solar cell, the conductive component of the electrode for external connection, for example, the electrode for external connection can be replaced with a noble metal such as silver, and the cost of manufacturing the electrode can be reduced (the electrode is replaced by an Ag electrode). Moreover, according to the present invention, it is possible to provide a solar cell in which a BSF layer is formed on the back side of the back side of the Shih-Side semiconductor substrate in which the Ag electrode is replaced by an Ag electrode on the back side. A preferred aspect of the solar cell is characterized in that the glass composition is 100% by mole of each of the following components, and the molar content of each component is 20 to 35 mol%, 5 to 30 mol%, 25 to 45 mol%, 2 ~10mol0/〇, 5~15mol%, 0~10mol〇/〇, 0~5mol%,
Si02 B2O3Si02 B2O3
ZnO及 / 或 PbO AI2O3ZnO and / or PbO AI2O3
Li2〇、Na20及K20中之至少1種 CaO、SrO及BaO中之至少1種 Bi203 且該等成分之合計係該玻璃組成物全體之9 5 m 0丨％以 上(典型的是1 〇〇mol°/0)。 又，較佳地，上述玻璃組成物為當令以下之各成分全 體為lOOmol% ’各成分之莫耳含有率為At least one of Ca2, SrO, and BaO of Li2〇, Na20, and K20 is at least one of Bi203, and the total of the components is more than 95% by weight of the entire glass composition (typically 1 〇〇mol) °/0). Further, preferably, the glass composition is such that the following components are all in a total amount of 100% by mass.
Si〇2 20〜30mol%， B2O3 20〜30mol%， 201250716Si〇2 20~30mol%, B2O3 20~30mol%, 201250716
ZnO 25〜35mol%， AI2O3 3 〜7mol%，ZnO 25~35mol%, AI2O3 3~7mol%,
Li20，Na20及K20 中之至少 1種 10〜15mol〇/0，Li20, at least one of Na20 and K20, 10~15mol〇/0,
CaO，SrO及BaO中之至少1種 2〜lOmol%， 且該等成分之合計係該玻璃組成物全體之95mol°/〇以 上（典型的是lOOmol%)。 又，較佳地，上述玻璃組成物之玻璃軟化點為500°C以 上且600°C以下。 依據本發明，可在矽半導體基板上形成接著強度（剝離 強度）等於或大於習知Ag電極之鋁電極，作為外部連接用電極。 因此，作為在此揭示之太陽電池，一特佳之態樣之特 徵在於其在石夕半導體基板之背面側上形成有外部連接用電 極’在此該外部連接用電極係由含有上述玻璃組成物之鋁 電極所構成。 又，一較佳態樣之特徵在於其在構成外部連接用電極 之含有上述玻璃組成物之鋁電極上黏貼有導電性接著薄 膜。 又，本發明實現上述目&之另一方面係独一種製造 具備下述70件之太陽電池之方法：⑪半導體基板、在該基 板之其中-面之受光面側上形成之受光面電極、及在該基 板之另一面之背面側上形成之鋁電極。 即，在此揭不之太陽電池製造方法之特徵在於使用由 本發明所提供之任-糊組成物，來形成在背面側上形成之 紹電極之至少一部份。 10 201250716 圖式簡單說明 第1圖是模式地顯示本發明一實施形態之太陽電池100 之構造一例的戴面圖。 第2(a)及（b)圖分別是模式地顯示太陽電池1〇〇中之基 板11之背面側之構成的俯視圖及截面圖。 第3圖是模式地顯示在太陽電池1 〇 〇之背面側外部連接 用鋁電極22上’配置有導電性接著薄膜3〇之構成的立體圖。 第4(a)及(b)圖係顯示在外部連接用鋁電極22上，透過 導電性接著薄膜30配置有導線（片狀線)35之構造的戴面圖。 第5圖是模式地顯示實行接著強度評價之強度測量裝 置300之構成的戴面圖。 第6圖是顯示接著強度與玻料軟化點之關係的圖表。 第7圖是模式地顯示習知太陽電池1000構造之一例的 截面圖。 用以實施發明之形態 以下，說明本發明之較佳實施形態。又，在本說明書 中特別提及之事項(例如⑽末或玻料之形態、組成、混合 比率等）以外之事情之本發明實施所需事情(例如糊之調合 法/又有本發明特徵之太陽電池(ce⑴之—般製造程序)可依 H頁域巾之習知技術作為所屬技術領域巾具有通常知識 者U事項來掌握。本發明可依據本說明書揭示之内容 及該領域巾q術常識來實施。 首先就由本發明所提供之㉟電極形成用糊組成物詳 201250716 細地說明。 在此揭示之鋁電極形成用糊組成物係用於形成太陽電 池申之鋁電極用途的鋁糊，且係經調製成含有鋁粉末、玻 料及有機載體之糊狀（包含呈現為墨水狀時）的電極形成用 材料並且只要可實現本發明之目的，關於其他構成成分 並無特別限制。 在本說明書中鋁粉末係指以鋁(A1)為主體之粒子的集 合體，且典型的是由A1單體形成之粒子的集合體，但是亦 為可含有微量A1以外之不純物或八丨主體之合金者，只要全 體是紹主體之粒子集合體，在此就可包含於所謂「銘粉末 中。又，鋁粉末本身可為依據以往公知之製造方法製造者， 並非要求特別製造手段者。構成使用之鋁粉末的粒子典型 是球狀，但是不限於所謂真球狀者。亦可包含薄片形狀戋 不規則形狀之粒子。 使用之鋁粉末最好是粒徑分布比較窄（換言之，粒秤均 一）之粉末。該指標可採用累積體積10%時之粒徑(Di〇)與累 積體積90%時之粒徑(D90)之比（D10/D90)。構成粉末之粒斤 全部相等時D10/D90之值為1 ’相反地，粒徑分布越廣， D10/D90之值越接近1。使用如D10/D90之值為0.2以上（例士 0.2〜0.5)之較窄粒徑分布的粉末是理想的。 在此揭不之铭電極形成用糊組成物含有之雀呂粉本係下 均20μπι以下為適當’例如可較佳地使用平均敉徑丨 ΙΟμηι左右者。 在本說明書中平均粒徑是指粉末之粒徑分布中累積體 12 201250716 積 寺之粒，即D50(中徑）。該D50可依據雷射繞射法 藉由粒徑分布測量裝置輕易地測量。 雖無特別限制，但是鋁粉末之含量係令糊組成物全體 為100質售〇/ ^ 0，其大致成為55〜85質量。/。之量為適當，且60 80貝里。/〇之量更佳。鋁粉末之含量係如上述之情形時， 〇夕半導體基板上適合地形成進一步提高緻密性之紹電 ° 膜厚l〇〇^m以下，例如膜厚ΙΟμηι〜ΙΟΟμηι之外部連 接用I呂電極）。 在此揭示之紹電極形成用糊組成物中之固形物中，玻 料(玻螭粉末)係提高鋁電極之接著強度的無機添加物。特別 地，在藉由本發明所提供之糊組成物(鋁糊）十，由於玻料具 有上述（1)〜（3)之條件，因此可對形成之鋁電極賦予高接著 強度(剝離強度）。 即，在此揭示之鋁電極形成用糊組成物含有之玻料(玻 璃粉末)係，例如，熱膨脹係數(線熱膨脹係數)為60χ10·7/\： 以上且80χ1〇·7/°(：以下者為適當，且該熱膨脹係數（線熱膨 脹係數）為65x10 7/°C以上且75xl〇-7/°C以下者更佳。 又，在本說明書中「熱膨脹係數」係算出為依據一般 之示差膨脹方式藉熱機械分析裝置(τ M A )測量之室溫(2 5它） 〜玻璃軟化點以下之溫度（例如4〇〇°c或5〇(rc )之間的平均 值。 又，在此揭示之銘電極形成用糊組成物含有之玻料係 玻璃軟化點（與上述熱膨脹係數同樣地藉由一般熱機械分 析裝置（TMA)測量而算出之玻璃軟化點）為々^^以上且 13 201250716 600°C以下者為適當。又，玻璃軟化點為500°C以上且600°C 以下者特佳。 具有上述較佳熱膨脹係數以及玻璃軟化點之玻料（玻 璃組成物）宜含有Si02、B2〇3、ZnO及/或PbO、Al2〇3、及至 少一種驗金屬氧化物(例如由Li20、Na2〇、K20中選擇)作為 必須構成成分。 在此揭示之铭電極形成用糊組成物中含有之玻料（玻 璃組成物）之適當例可舉例如：令以下之各成分全體為 lOOmol%，各成分之莫耳含有率為At least one of CaO, SrO and BaO is 2 to 10 mol%, and the total of the components is 95 mol% or more (typically 100 mol%) of the entire glass composition. Further, preferably, the glass composition has a glass softening point of 500 ° C or more and 600 ° C or less. According to the present invention, an aluminum electrode having a bonding strength (peeling strength) equal to or larger than that of a conventional Ag electrode can be formed on a germanium semiconductor substrate as an external connection electrode. Therefore, as a solar cell disclosed herein, a particularly preferable feature is that an electrode for external connection is formed on the back side of the stone substrate. Here, the electrode for external connection is composed of the glass composition. Made up of aluminum electrodes. Further, a preferred aspect is characterized in that a conductive adhesive film is adhered to the aluminum electrode containing the glass composition constituting the external connection electrode. Further, the present invention achieves the above-described object and another method for producing a solar cell having the following 70 pieces: a semiconductor substrate, a light-receiving surface electrode formed on the light-receiving surface side of the substrate, And an aluminum electrode formed on the back side of the other side of the substrate. That is, the solar cell manufacturing method disclosed herein is characterized in that at least a portion of the electrode formed on the back side is formed using the any-paste composition provided by the present invention. 10 201250716 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view schematically showing an example of a structure of a solar cell 100 according to an embodiment of the present invention. Figs. 2(a) and 2(b) are a plan view and a cross-sectional view, respectively, schematically showing a configuration of the back side of the substrate 11 in the solar cell. Fig. 3 is a perspective view schematically showing a configuration in which a conductive adhesive film 3 is disposed on the aluminum electrode 22 on the back side of the solar cell 1 外部. 4(a) and 4(b) are views showing a structure in which a wire (sheet line) 35 is disposed on the external connection aluminum electrode 22 through the conductive adhesive film 30. Fig. 5 is a front view schematically showing the configuration of the intensity measuring device 300 for performing the subsequent strength evaluation. Figure 6 is a graph showing the relationship between the strength of the bond and the softening point of the glass. Fig. 7 is a cross-sectional view schematically showing an example of a structure of a conventional solar cell 1000. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described. Further, in the matter specifically mentioned in the present specification (for example, (10) or the form, composition, mixing ratio, etc. of the glass material), the present invention requires the implementation of the matter (for example, the paste method/there is a feature of the present invention. The solar cell (the general manufacturing procedure of ce(1)) can be grasped according to the conventional technology of the H-page domain towel as the general knowledge of the technical field. The invention can be based on the contents disclosed in the present specification and the knowledge of the field towel. First, the paste composition for forming an electrode for 35 electrodes provided by the present invention is described in detail in 201250716. The paste composition for forming an aluminum electrode disclosed herein is used for forming an aluminum paste for use in a solar cell of a solar cell. It is prepared into an electrode forming material containing a paste of aluminum powder, a glass material, and an organic vehicle (including when it is in the form of an ink), and as long as the object of the present invention can be achieved, the other constituent components are not particularly limited. Aluminum powder refers to an aggregate of particles mainly composed of aluminum (A1), and is typically an aggregate of particles formed of A1 monomers, but may also contain trace A. The alloy of the impurity other than the one or the alloy of the gossip body may be included in the so-called "Ming powder" as long as the whole is the aggregate of the particles of the main body. Further, the aluminum powder itself may be manufactured according to a conventionally known manufacturing method. The particles constituting the aluminum powder to be used are typically spherical, but are not limited to the so-called true spherical shape. They may also include particles having an irregular shape in the shape of a sheet. The aluminum powder used is preferably a particle size distribution. A powder that is narrower (in other words, uniform). This index can be used as the ratio of the particle size (Di〇) at a cumulative volume of 10% to the particle size (D90) at a cumulative volume of 90% (D10/D90). When the granules are all equal, the value of D10/D90 is 1'. Conversely, the wider the particle size distribution, the closer the value of D10/D90 is to 1. The value of D10/D90 is 0.2 or more (example: 0.2 to 0.5). It is preferable that the powder having a narrow particle size distribution is contained in the composition of the paste for forming an electrode of the present invention, and that it is suitably 20 μm or less in the present system, for example, the average diameter 丨ΙΟμηι can be preferably used. Average in this manual The particle size refers to the particle size distribution of the powder in the 2012 20121616 temple, ie D50 (medium diameter). The D50 can be easily measured by the laser diffraction method by the particle size distribution measuring device. However, the content of the aluminum powder is such that the entire paste composition is 100 mass sold 〇 / ^ 0, which is approximately 55 to 85 mass. The amount is appropriate, and 60 80 Berry. / The amount of bismuth is better. When the content of the powder is as described above, the thickness of the film is further increased to a thickness of 1 以下^m, for example, the thickness of the film is 外部μηι~ΙΟΟμηι, and the external connection is Ilu electrode. In the solid matter in the paste composition for electrode formation disclosed herein, the glass frit (glass matte powder) is an inorganic additive which increases the bonding strength of the aluminum electrode. In particular, in the paste composition (aluminum paste) provided by the present invention, since the glass material has the above conditions (1) to (3), it is possible to impart high adhesion strength (peel strength) to the formed aluminum electrode. In other words, the glass frit (glass powder) contained in the paste composition for forming an aluminum electrode disclosed herein has a coefficient of thermal expansion (linear thermal expansion coefficient) of, for example, 60 χ 10·7/\: or more and 80 χ 1 〇 · 7 / ° (: It is suitable, and the coefficient of thermal expansion (linear thermal expansion coefficient) is preferably 65 x 10 7 / ° C or more and 75 x l 〇 -7 / ° C or less. Further, in the present specification, "thermal expansion coefficient" is calculated as a general basis. The expansion mode is measured by the thermomechanical analysis device (τ MA ) at room temperature (2 5 it) ~ the temperature below the glass softening point (for example, the average value between 4 〇〇 ° c or 5 〇 (rc ). Again, here The softening point of the glass-based glass contained in the composition for forming an electrode for electrode formation (the glass softening point calculated by a general thermomechanical analyzer (TMA) as in the above-described thermal expansion coefficient) is 々^^ and 13 201250716 600 ° C or less is suitable. Further, the glass softening point is preferably 500 ° C or more and 600 ° C or less. The glass material (glass composition) having the above preferred thermal expansion coefficient and glass softening point should preferably contain SiO 2 , B 2 . 〇3, ZnO and/or PbO, Al2〇3, and A metal oxide (for example, selected from Li20, Na2, and K20) is an essential component. Suitable examples of the glass material (glass composition) contained in the paste composition for forming an electrode disclosed herein include, for example: Let all of the following components be 100 mol%, and the molar content of each component is
Si〇2 20〜35mol%， B2O3 5〜30mol%， 25〜45mol%，Si〇2 20~35mol%, B2O3 5~30mol%, 25~45mol%,
ZnO及 / 或 PbO AI2O3 2〜lOmol%，ZnO and / or PbO AI2O3 2~lOmol%,
Li20，Na20及K20 中之至少 1種 5〜15mol0/〇，At least one of Li20, Na20 and K20 5~15mol0/〇,
CaO ’ SrO及BaO中之至少1種 0〜lOmol%，At least one of CaO ' SrO and BaO 0 to 10 mol%,
Bi2〇3 0〜5mol%， 且該等成分之合計係玻料（玻璃組成物）全體之95m〇i% 以上(典型的是lOOmol%)者。 又，特佳之組成的玻料可舉例如：令以下之各成分全 體為lOOmol%，各成分之莫耳含有率為Bi2〇3 0~5 mol%, and the total amount of these components is 95 m〇i% or more (typically 100 mol%) of the entire glass (glass composition). Further, the glass material of a particularly preferable composition is, for example, such that the following components are all in a total amount of 100% by mol, and the molar content of each component is
Si02 B2O3Si02 B2O3
ZnO 20〜30m〇l%， 20〜3〇m〇l0/0， 25〜35m〇l%， AI2O3 3 〜7mol%， 14 201250716ZnO 20~30m〇l%, 20~3〇m〇l0/0, 25~35m〇l%, AI2O3 3~7mol%, 14 201250716
Li20 ’ Na20及Κ20 中之至少 1種 l〇〜15mol0/。，At least one of Li20 'Na20 and Κ20 l〇~15mol0/. ,
CaO，SrO及BaO中之至少1種 2〜l〇m〇i〇/0， 且該等成分之合計係玻料(玻璃組成物）全體之95m〇1% 以上(典型的是lOOmol%)者。 藉由含有如上述組成之玻料’可進一步提高形成之鋁 電極之接著強度（剝離強度）。 例如’必須構成成分之SiCb係構成玻璃骨架之主成 分。Si〇2含有率過高時玻璃軟化點變得過高而不理想。另 —方面，Si〇2含有率過低時由於耐化學性或耐水性下降故 不理想。 又’ B2〇3係使軟化點以及玻料之熔融溫度降低之效果 為尚之成分。B2〇3含有率過低時無法得到使軟化點以及玻 料之熔融溫度降低之效果。另一方面，B2〇3含有率過高時 由於有招致财水性降低之虞故不理想。 又’ ZnO或PbO係可降低玻料(玻璃組成物）之軟化點或 可進彳于熱膨服係數之調整的成分，且宜在上述含有率範圍 内含有ZnO及PbO中之任一種或兩種。該等成分之含有率過 向時由於玻璃軟化點過低故不理想。又，無pb〇者是理想的。 又，Al2〇3係控制玻料‘熔融時之流動性，且與銘電極形 成時之附著安定性有關的成分b Αία;含有率過低時由於附 著安定性降低故不理想，而八丨2〇3含有率過高時有使玻璃之 耐化學性降低之虞且不理想。 又，Li2〇、Na2〇、K2〇等之鹼金屬氧化物成分係提高 熱膨脹係數之成分。s亥專驗金屬氧化物成分之含有率過低 15 201250716 時有熱膨脹係數變得過低之虞。另一方面，該等含有率過 高時由於熱膨脹係數過度地高故不理想。 玻料中除了上述必須構成成分以外，可含有任意成分。 例如’宜以lOmol%以下之含有率含有CaO、SrO、BaO 等之鹼土族金屬之氧化物成分》藉由含有至少1種鹼土族金 屬氧化物，可更容易地進行熱膨脹係數之調整，並且藉由 玻璃組成之多樣化（構成金屬元素之多種類化）提高耐化學 性等，且可提高玻璃之安定性因此是理想的。宜以例如 lmol%以上且l〇mol❶/。以下（例如2〜l〇mol%，特別是5〜 10m〇l%)之含有率有CaO、SrO、BaO等之驗土族金屬之氧 化物成分。 又，為達成提高燒成後之玻璃（進而燒成後之鋁電極） 之安定性的目的，亦可以例如l〇m〇l%以下（較佳為5111〇1%以 下）之比例含有適當量Bi2〇3。 又，亦可以玻璃組成物全體之5m〇I%以下（例如〇」〜 5mol%左右）的比例適當含有zr、Ti、V、Nb、La、Ce、Sn、 P等氧化物成分。 為了安㈣燒成、固定附著(燒結)料切半導體基板 上之糊組成物（塗布膜），該糊組成物中含有之玻料係依據 BET法比表面積宜為大約Q 5m2/g以上且5如％以上左右， 立平均粒雖0)宜騎祕下_是_左右或_以下） 者。 又’該玻璃粉末之上述糊级成物中之含量並無特別限 制，但是令該她成物為刚質量％>1〜呵量％左右是適 16 201250716 當的，且2〜10質量％左右是理想的。藉由以該程度之含有 率含有如上述之元素組成之玻料的糊組成物，可適當地形 成接著強度高之鋁電極(例如背面側之外部連接用鋁電極）。 在此揭示之糊組成物包含如上述之鋁粉末、玻料（玻璃 粉末)作為固形物，並且包含用以分散該固形物之液狀媒體 (有機載體）。 構成該載體之有機溶劑只要是可良好地分散鋁粉末或 玻料者即可，且可無特別限制地使用用於習知這種糊者。 例如，構成載體之有機溶劑可使用乙二醇及二乙二醇衍生 物（系溶劑）、甲苯、二曱苯、丁卡必醇(BC)、二乙二醇丁醚 醋酸酯（BDGA)、松香醇等高沸點有機溶劑之一種或組合使 用多數種。 又，構成載體之有機黏結劑可含有種種之樹脂成分。 該樹脂成分只要是可賦予在此揭示之糊組成物良好黏性及 塗肚形成能力（對矽基板之附著性)者即可，且可無特別限制 地使用用於習知這種糊者。例如，可舉例如：以丙稀酸樹 脂，環氧樹脂，紛樹脂，醇酸樹脂，纖維素系高分子，聚 乙烯醇、松香樹脂等為主體者。其中，特佳的是乙基纖維 素等之纖維素系高分子。 雖然沒有特別限定，但是有機載體含量為糊全體之大致 10〜30質量％之量是適當的，且大致15〜25質量％之量更佳。 在此揭示之糊組成物係，與習知太陽電池用鋁糊同樣 地，可典型地藉由混合鋁粉末、玻料(玻璃粉末）、及適當之 有機載體輕易地調製。例如，可使用三個輥軋機及其他混 17 201250716 練機，且以預定混合比與有機載體一起混合、攪拌預定混 合比之鋁粉末及玻料。 在此揭示之糊組成物為了在基板上形成作為背面電極 之鋁電極（進一步是P+層，即BSF層），可與習知使用的鋁糊 同樣地處理’且可沒有特別限制地採用公知之方法。典型 地’藉由網版印刷法、分配法、浸塗法等，賦予（塗布)石夕半 導體基板糊組成物，使其成為所希望之膜厚度或塗膜圖 案。这基板之厚度可考慮所希望之太陽電池尺寸、在該基 板上形成之鋁電極膜厚、該基板之強度(例如破壞強度）等來 設定。雖然並無特別限制，但是5μηι〜300μηι左右是適當 的，且5μηι〜200μηι左右(特別是i〇ym〜 i〇〇gm左右)是理想的。 接著，以適當之溫度（例如室溫以上且典型的是1 左右）乾燥糊塗布物。乾燥後，在適當之燒成爐(例如高速燒 成爐）中以適當之加熱條件（例如6〇〇°c以上且9〇〇°c以下，且 較佳為700 C以上且800°C以下）加熱預定時間，藉此進行乾 燥塗臈之燒成。因此，上述糊塗布物燒結在基板上，且可 形成如後述第1圖所示之外部連接用鋁電極22。 第1圖是顯示本發明實施形態之太陽電池1〇〇之構成的 截面圖。本實施形態之太陽電池1〇〇係由矽半導體基板(Si B曰圓）U ’在基板11之其中一面側（表面側）形成之受光面電 極U ’及在基板11之另一面側（背面側)形成之紹電極(2〇、 22)構成。 本實施形態之石夕半導體基板⑽由如結晶石夕，非晶石夕 之砂構成。在本實絲態之構射，藉由pn接合形成而形 18 201250716 成之n-Si層16係位在基板11之p-Si層（p型結晶石夕）18之受光 面側。又，藉由一般化學蒸氣沈積法(CVD)等形成之由氧化 鈦或氮化矽形成之抗反射膜14係位於η-Si層16之表面。另 外，在抗反射膜14之表面上，設有典型地藉由網版印刷燒 成銀糊而形成之由Ag形成的表面電極（受光面電極）12。 在本實施形態之構成中，在P-Si層18之背面側上，設有 以在此揭示之鋁電極形成用糊組成物（以下，為了方便有時 稱為「第1鋁糊」）為材料形成之鋁電極22。該鋁電極22係 相當於如例如導線（導電帶狀線）等與其他外部連接用構件 電連接之背面側的外部連接用電極22。 本實施形態之外部連接用鋁電極22係，與習知之形成 這種電極之情形（例如，以銀糊為材料形成外部連接用Ag 電極之情形）同樣地’藉由網版印刷、燒成預定組成之第j 鋁糊而形成。 在p-Si層18之背面側上’與外部連接用鋁電極22 —起形 成有由另一鋁糊（以下，為了方便有時稱為「第2鋁糊」）形 成之鋁電極20。該鋁電極20係形成在p-Si層18之背面的全面 上，且係具有背面電場(BSF ; Back Surface Field)效果之紹 電極（以下，稱為「背面大範圍鋁電極」）。在本實施形態之 構成中，外部連接用鋁電極22係線狀地形成在p_Si層18之背 面側，又，背面大範圍鋁電極20係設置在p_Si層18之背面 側，且大致全面地形成在形成有該外部連接用鋁電極22之區 域以外。 又，在本實施形態之構成中，背面大範圍鋁電極20覆 19 201250716 蓋背面大範_電㈣之-部份（具體而言，線狀構造之兩 邊緣部），並且以具有露出外部連接祕電極22之開口部23 之狀態形成。此外，背面大範園飽電極20除了呈覆蓋外部 連接用紹電極22之兩邊緣部之狀態以外，亦可以背面大範 _電極20之侧面與外部熟心電㈣之側面連接之狀 態形成兩者。 另外，在本實施形態中，該背面大範圍銘電極2〇包含 形成铭粉末、玻料及有機魏，且只要是用於形成習知太 陽電池之!S電極之用途的-般㈣即可，其内容並無特別 限制。因此，由於沒有本發明之特徵，故省略詳細之說明。 在本實施形態中，典型地，藉由網版印·、分配法、 浸塗法等’將第1紹糊塗布在矽半導體基板（晶圓川上，使 其成為所希望之膜厚度或塗膜圖案。接著，以適當溫度（室 溫〜100°C左右）乾燥塗布物。又，在矽半導體基板u上塗 布第2鋁糊，以形成露出外部連接用紹電極22之開口部23。 接著，以適當溫度（室溫〜100°C左右）乾燥塗布物。然後， 在適當之燒成爐（例如向速燒成爐）中以適當之加熱條件（例 如7〇〇 C〜8〇〇 C)加熱預定時間’藉此進行乾燥塗膜之燒 成。因此，塗布物燒結在基板上，且形成如第i圖所示之外 部連接用銘電極22及责面大範圍铭電極20。在本實施形，離 中，外部連接用鋁電極22及背面大範圍鋁電極2〇燒成，並 且玎形成P+層（BSF層）24。 第2(a)及(b)圖是模式地顯示本實施形態之矽系太陽電 池100之基板11中之背面側之構成的俯視圖及截面圖。在第 20 201250716 2(a)及(b)圖中’為了方便，顯示基板u之背面側位於上方。 外部連接用鋁電極22係形成在第7圖所示之構成中外 部連接用電極(Ag電極)所在之位置。在第2(a)及(b)圖顯示之 例子中’外部連接用鋁電極22可具有作為例如2〜6mm寬度 之電極的機能。一般來說，鋁與焊料之接合是困難的。因 此，在本實施形態之構成中，以加壓附著在外部連接用鋁 電極22上之狀態黏貼導電性接著薄膜3〇(請參照後述第3 圖）V電性接著薄膜3 0(第3圖）典型地是異向性導電性接著 薄膜，例如，接著材成分可採用環氧樹脂、苯氧基樹脂、 丙烯酸樹脂、聚醯亞胺樹脂、聚醯胺樹脂 '聚碳酸醋樹脂 及其他熱硬化型樹脂或熱可塑性樹脂。然後，作成在該樹 =(接著材)成分中分散種種導電性粒子(典型的是錄 '銅、 貴金屬等之金屬粒子)之構成，且藉由加熱、加壓導電性接 著薄膜30，可將導電性接著薄膜3〇黏貼在預定之部位上， =可藉由該導電性粒子確保導通。又，使狀導電性接 無特別限制’可無特別限制地採用市售這種用途 的導電性接著薄膜。 第3圖是模式地顯示在 用銘電極22上，配置如上过之導電雷也1〇0之背面側外部連接 立體圖。如第3圖所示接卿 用銘電極22之以上 者_3G配置在外部連接 配置在導電性购電帶狀線- 第4(a)及（b)圖顯示在 邮上，透過導電性接著薄蘭己置;電 21 201250716 首先，如第4(a)圖所示，形成在基板11上之外部連接用 铭電極22上積科雜接著薄卿，且在科電性接著薄 膜3〇上積層片狀線35。導·接著薄咖具有在導電粒子 3U例如，鍵金之錄粒子)均一地分散在由例如環氧系熱硬化 型樹脂形成之接著材成分32中。 接著，如第4(b)圖所示，以導電性接著薄膜如作為片狀 線接合材料’且藉由加壓、加熱外部連接㈣電肋，導 電性接著薄膜3G及片狀線35(請參照箭號％)，導電性接著薄 膜30中之導電粒子料料料接⑽電肋及片狀線 35(请參照箭號55)。同時，藉由導電性接著薄卿中之接著 材成分(在此為熱硬化_脂)32熱魏，可實現與焊料接合 同樣程度之確實導通。又，焊接片狀線35時，必須施加2〇代 以上之高溫，但是導電性接著薄膜3G之接合可實行18代左 右之低溫接合。因此，可減低或事先防止因加熱對太陽電 池（電池）100之影響（例如因熱產生應變）。 在以上說明之實施形態中顯示以由第丨鋁糊構成之外 部連接肋電極22,及由第2紹糊構成之背面大範圍紹電極 20作為背面鋁電極之構成，但是不限於此。 例如，包含背面大範圍鋁電極2〇之部份在内，可藉由 第1紹糊形成全部之背面鋁電極。 以下說明有關本發明之幾個實驗例，但是不是意圖將 本發明限制於顯示之試驗例。 在以下之試驗中’就鋁電極形成用糊組成物（鋁糊）之固 形成分之玻料性狀互相不同時之接著強度的差異進行評價。 22 201250716 本試驗中使用在以下表1中顯示之玻璃組成（mol%)，玻 璃軟化點（°C)及熱膨脹率（熱膨脹係數）之共計8種玻璃樣本 (樣本1〜樣本8)。 23 201250716 【表1】 组成（moiS) 软im 仇切賬痒Γ Si02 B2〇j bi2o3 2nO PbO AI2〇a CaO SrO BoO ϋ,Ο Na20 K2〇 (°C) 樣本1 15 24.9 60.1 644 45 樣本2 29 36 β 4 to 13 690 67 樣本3 33.6 33.6 7.5 3.7 9.3 12.1 716 66 樣本4 14.5 29.2 15.3 25 16.1 529 8$ 樣本5 54 10 30 7 570 63 樣本(J 25 24 29 5 5 a 6 54$ 70 樣木7 28 21.3 3 26.5 5 7 6 3 568 7〇 樣本8 30 fi 6 38 3 12 445 77 然後，製作分別包含在表1中顯示之各玻料(樣本i〜8) 的共計8種鋁糊（試驗例1〜試驗例8)。 各試驗例之玻料係只有上述玻料之性狀不同，而其他 成分(鋁粉末、有機載體)及混合比等是相同的。即，各試驗 例之鋁糊之内容如下。 (1) 鋁粉末： 將平均粒徑6μηι之鋁粉末混合成為只有糊全體之66質 量％的量來使用》 (2) 有機載體： 將松香醇混合成為只有糊全體之26質量％的量來作為 有機溶劑使用。 又，將乙基纖維素混合成為只有糊全體之大約2質量％ 的量來作為有機黏結劑使用。 (3) 玻料：將上述樣本1〜8之任一性狀夂玻料混合成為 只有糊全體之6質量％的量來使用。 <接著強度試驗（1)> 接著’就使用如上述般製造之試驗例1〜8之各鋁糊在 24 201250716 矽半導體基板上製作的紹電極進行接著強度試驗。在此， 使用試驗例1〜8之各銘糊在石夕半導體基板i i之—面（背面） 上形成銘電極的步驟如下。 即，準備市售125mm四周尺寸之太陽電池用p型單晶石夕 基板(板厚度20_)，且使用氫氧化财溶祕料^其 表面。接著，在以上述蝕刻處理形成紋理構造之矽基板的 受光面上塗布含磷溶液，且藉由進行熱處理在該矽基板之 受光面上形成厚度大約〇.5μηι之n_Si層（n+層）。 接著，在n-Si層上藉由電漿CVD(PECVD)法形成厚度為 大約50mn以上且100nmw下之抗反射膜（氧化鈦膜）。又使 用預疋表面電極(Ag電極）形成用銀糊，在抗反射膜上藉由 . 網版印刷法形成成為表面電極(Ag電極）之塗膜（厚度2〇μιη 以上且50μηι以下）。 另一方面’在石夕半導體基板之背面側，藉由網版印刷 (使用鋼製篩網SUS#165)，印刷（塗布）上述試驗例1〜8中任 一糊組成物’且呈線狀地形成大約5mm寬度之膜厚約3〇μιη 的塗布膜。接著，燒成該基板，且形成試驗評價用之線狀 紹電極28 °具體而言，在大氣環境中使用近紅外線高速燒 成爐’以燒成溫度大約700eC以上且800°C以下燒成。 使用如此得到之試驗例評價用電池（太陽電池）實行接 著強度之評價試驗，藉此測量由各試驗例之鋁電極形成用 糊組成物形成之鋁電極的接著強度。 上述形成之鋁電極之接著強度（剝離強度）的評價（即剝 離強度評價）係使用如第5圖所示之強度測量裝置300進行。 25 201250716 具體而言，第5圖顯示之強度測量裝置300係透過固定 螺絲43及卡止板44將玻璃基板41固定在固定夹具4〇上，且 在該玻璃基板41藉由環氧接著材42將上述得到之試驗用矽 半導體基板11之受光面側固定在該玻璃基板41上。 藉由加熱加壓附著將市售品之導電性接著薄膜30黏貼 在位於如此固定在玻璃基板41上之矽半導體基板u之露出 表面側的上述形成之鋁電極28上，再將片狀線35黏貼在該 導電性接著薄膜30上。 又，如第5圖所示，使強度測量裝置3〇〇傾斜成固定夾 具40之底面成為135°，且朝垂直方向上方拉伸預先形成於 片狀線35之延長部35e’藉此測量片狀線35/導電性接著薄膜 30/鋁電極28之接著強度。 . 結果顯示在表2之對賴巾。接著強度謂價試驗(剝 離強度試驗)係以由各試驗例之_形成之多數⑽）銘電 極實行’評側於㈣個㈣極之％結果(測纽）的平均 值（即’儀器測量數n=2)，作為接著強户。 又，第6圖之圖表顯示藉由本試驗得到之接著強度與链 糊中之玻料軟化點的關係。 、 26 201250716 【表2】 AI糊 玻璃 軟化點（°C) 熱膨脹率 (xl〇-7/°C) 接著強度(Ν) 數據 平均 試驗例1 樣本1 644 45 0.3386 0.6147 0.48 試驗例2 樣本2 690 67 0.6873 0.6921 0.69 試驗例3 樣本3 716 66 0.3822 0.4156 0.40 試驗例4 樣本4 530 86 0.01 0.01 0.01 試驗例5 樣本5 570 63 0.8 0.7 0.75 試驗例6 樣本6 548 70 1.6822 1.2724 1.48 試驗例7 樣本7 568 70 0.9712 0.9297 0.95 試驗例8 樣本8 445 77 0.977 1.0775 1.03 如表2及第6圖所示，看到鋁糊中之玻璃軟化點在400°C 以上且600°C以下（特別是500°C以上且600°C以下）之範圍内 顯示高接著強度。特別在使用玻璃軟化點為550°C附近之試 驗例6的銘糊時，看到極高之接著強度。 又，看到玻料之熱膨脹係數為6〇xicr7/°c以上且 80xl〇-7/°C以下（特別是65xl〇-7/°C以上且75xl〇-7/°C以下）者 顯示高接著強度。 <接著強度試驗(2)> 依照與上述之接著強度試驗（1)同樣之步驟，使用試驗 例6之鋁糊在上述矽半導體基板11上形成膜厚大約30μιη之 大約2mm寬度之線狀鋁電極且進行同樣之剝離強度評價試 驗，結果如表3之實施例之欄所示，看到平均值 (n=2)3.25N/2mm之接著強度。 27 201250716 作為比較對照，使用通常之銀糊取代試驗例6之鋁糊在 上述石夕半導體基板11上形成膜厚大约30μηι之大約2mm寬 度之線狀Ag電極，且透過黏結劑將上述片狀線35黏貼在其 表面上’並進行同樣之剝離強度評價試驗，結果如表3之比 較例八之攔所示，看到平均值(n=2)3.5N/2mm之接著強度。 又’表3中之比較例b係使用試驗例1之鋁糊取代試驗例 6之紹糊時的結果。 【表3】 比較例A 比較例B 實施例 接著強度 (N/2mm) 3.50 0.50 3.25 由表3可了解，確認由試驗例6之紹糊形成之紹電極可 知到與比較例A中之焊接Ag電極同等之接著強度。又，與 比較例B中之鋁電極之接著強度比較時，確認由試驗例6之 鋁糊形成之鋁電極之接著強度顯著地提高。 由以上說明之實施形態及試驗例的記載可了解，在由 本發明所提供之太陽電池中，可採用銘電極作為背面側外 部連接用f極。絲，可實行使財財之料極係接著 強度低而無法使狀導電性接著薄膜的接合。因此，盘使 用Ag電極作為背面側外部連接用電極之習知構成比較可 在石夕半導體基板（晶圓）之背面的全面上均_地形成膽 層。又，可達成相當於銀與紹之材料價格差之成本下降。 又，藉由提高銘膜之接著強度（剝離強度)之外部連接用 紹電極，可洲使科紐接㈣狀接合，因此可構築 不包含用以焊接之電極部份的心結果如細晶圓） 28 201250716 之背面全面之铭化’可由於BSF層之均—形成而提高太陽電 池之發電效率’並且由於省略匯電條電極之圖案而提高太 1%電池之發電效率。 以上，雖然已詳細說明了本發明，但是這些只不過是 舉例說明，且本發明亦可以其他態樣實施，並且可在不脫 離本發明主旨之範圍内增加種種變更。例如，亦可使用在 此揭示之紹電極形成用糊組成物，形成受光面電極(例如構 成受光面電極之匯電條電極或格線)之至少一部份。 I：圖式簡單説明3 第1圖是模式地顯示本發明一實施形態之太陽電池100 之構造一例的載面圖。 第2(a)及(b)圖分別是模式地顯示太陽電池丨〇〇中之基 板11之背面側之構成的俯視圖及截面圖。 第3圖是模式地顯示在太陽電池1〇〇之背面側外部連接 用銘電極22上，配置有導電性接著賴Μ之構成的立體圖。 第4(a)及(b)圖係顯示在外部連接用鋁電極22上 ，透過 導電性接著薄膜30配置有導線（片狀線)35之構造的截面圖。 第5圖是模式地顯示實行接著強度評價之強度測量裝 置300之構成的截面圖。 第6圖是顯示接著強度與坡料軟化點之關係的圖表。 第7圖是模式地顯示習知太陽電池1〇〇〇構造之〆例的 截面圖。 29 201250716 【主要元件符號說明】 11.. .矽半導體基板(石夕晶圓） 12.. .受光面電極；表面電極 14.. .抗反射膜 16…n-Si層 18.. .p-Si 層 20.. .背面大範圍铭電極 22.. .外部連接用鋁電極 23.. .開口部 24.. .P+層；BSF層 28.. .鋁電極 30.. .導電性接著薄膜 31.. .導電粒子 32.. .接著材成分 35.. .片狀線；導線(導電帶狀線） 35e...延長部 40.. .固定失具 41.. .玻璃基板 42.. .環氧接著材 43.. .固定螺絲 44.. .卡止板 45，50，55…箭號 100，1000…太陽電池 111.. .砍半導體基板(Si晶圓） 112.. .表面電極(受光面電極) 114…抗反射膜 116.. .n-Si 層 118".p-Si 層 120.. .鋁電極 122.··電極 124.. .p+層；BSF層 300.. .強度測量裝置 30At least one of CaO, SrO and BaO 2~l〇m〇i〇/0, and the total amount of these components is 95m〇1% or more (typically lOOmol%) of the total glass (glass composition) . The bonding strength (peeling strength) of the formed aluminum electrode can be further improved by containing the glass frit as described above. For example, SiCb, which is a constituent component, constitutes the main component of the glass skeleton. When the content of Si〇2 is too high, the glass softening point becomes too high, which is not preferable. On the other hand, when the content of Si〇2 is too low, it is not preferable because of chemical resistance or water resistance. Further, the effect of the B2〇3 system to lower the softening point and the melting temperature of the glass material is still a component. When the content of B2〇3 is too low, the effect of lowering the softening point and the melting temperature of the glass cannot be obtained. On the other hand, when the content of B2〇3 is too high, it is not desirable because of the reduction in the water content. Also, 'ZnO or PbO system can reduce the softening point of the glass material (glass composition) or the composition which can be adjusted to the thermal expansion coefficient, and it is preferable to contain either or both of ZnO and PbO in the above content range. Kind. When the content ratio of these components is too low, the glass softening point is too low, which is not preferable. Also, no pb is ideal. Further, Al2〇3 is a component b Αία which controls the fluidity at the time of melting and is related to the adhesion stability at the time of formation of the electrode; when the content is too low, the adhesion stability is lowered, which is not desirable, and the gossip 2 When the content of 〇3 is too high, the chemical resistance of the glass is lowered and it is not preferable. Further, an alkali metal oxide component such as Li2〇, Na2〇 or K2〇 is a component which increases the coefficient of thermal expansion. The content of the metal oxide component in the shai test is too low. 15 201250716 The coefficient of thermal expansion becomes too low. On the other hand, when the content ratio is too high, the coefficient of thermal expansion is excessively high, which is not preferable. The glass material may contain any component in addition to the above-mentioned essential components. For example, it is preferable to contain an oxide component of an alkaline earth metal such as CaO, SrO or BaO at a content of 10 mol% or less. By containing at least one alkaline earth metal oxide, the thermal expansion coefficient can be more easily adjusted and borrowed. It is preferable that the composition of the glass is varied (constituting a plurality of types of metal elements) to improve chemical resistance and the like, and to improve the stability of the glass. For example, it is preferably 1 mol% or more and 1 mol mol /. The content ratio of the following (e.g., 2 to 10 mol%, particularly 5 to 10 m%) is an oxide component of a soil of a soil of a group such as CaO, SrO or BaO. Further, in order to achieve the purpose of improving the stability of the glass after firing (and the aluminum electrode after firing), an appropriate amount may be contained in a ratio of, for example, 10% or less (preferably 5,111% or less). Bi2〇3. Further, an oxide component such as zr, Ti, V, Nb, La, Ce, Sn, or P may be appropriately contained in a ratio of 5 m 〇 1% or less (for example, 〇 to 5 mol%) of the entire glass composition. In order to safely and uniformly adhere (sinter) the paste composition (coating film) on the semiconductor substrate, the glass composition contained in the paste composition is preferably about Q 5 m 2 /g or more according to the BET specific surface area. If it is more than %, the average grain is 0) It is suitable to ride the secret _ is _ or _ or less. Further, the content of the above-mentioned paste-formed product of the glass powder is not particularly limited, but the content of the product is about 9% by mass and is about 16% by weight, and 2 to 10% by mass. The left and right are ideal. By using a paste composition containing a glass frit having an elemental composition as described above, it is possible to suitably form an aluminum electrode having a high bonding strength (for example, an aluminum electrode for external connection on the back side). The paste composition disclosed herein contains aluminum powder, glass frit (glass powder) as a solid as described above, and contains a liquid medium (organic vehicle) for dispersing the solid. The organic solvent constituting the carrier may be any one which can disperse aluminum powder or glass material well, and can be used without any particular limitation. For example, the organic solvent constituting the carrier may be ethylene glycol or a diethylene glycol derivative (solvent), toluene, diphenylbenzene, butyl carbitol (BC), diethylene glycol butyl ether acetate (BDGA), One type or a combination of high boiling point organic solvents such as rosin alcohol is used in combination. Further, the organic binder constituting the carrier may contain various resin components. The resin component is not particularly limited as long as it can impart good adhesion to the paste composition and adhesion to the substrate (adhesion to the substrate), and can be used without any particular limitation. For example, an acrylic resin, an epoxy resin, a resin, an alkyd resin, a cellulose polymer, a polyvinyl alcohol, a rosin resin, or the like may be used. Among them, a cellulose-based polymer such as ethyl cellulose is particularly preferred. Although it is not particularly limited, the organic carrier content is suitably from 10 to 30% by mass based on the entire paste, and is preferably from 15 to 25% by mass. The paste composition disclosed herein can be easily prepared by mixing aluminum powder, glass (glass powder), and a suitable organic vehicle, similarly to the conventional aluminum paste for solar cells. For example, three rolling mills and other mixing machines can be used, and the aluminum powder and the glass material of the predetermined mixing ratio are mixed and mixed with the organic vehicle at a predetermined mixing ratio. The paste composition disclosed herein can be processed in the same manner as the conventionally used aluminum paste in order to form an aluminum electrode (further a P+ layer, that is, a BSF layer) as a back surface electrode on the substrate, and can be used without any particular limitation. method. Typically, the composition of the Shishi semiconductor substrate paste is applied (coated) by a screen printing method, a dispensing method, a dip coating method or the like to have a desired film thickness or a coating film pattern. The thickness of the substrate can be set in consideration of the desired solar cell size, the thickness of the aluminum electrode film formed on the substrate, the strength of the substrate (e.g., the breaking strength), and the like. Although it is not particularly limited, it is suitable for about 5 μm to 300 μm, and is preferably about 5 μm to 200 μm (especially i〇ym to i〇〇gm). Next, the paste coating is dried at an appropriate temperature (for example, at room temperature or higher and typically about 1). After drying, in a suitable baking furnace (for example, a high-speed firing furnace), appropriate heating conditions (for example, 6 ° C or more and 9 ° C or less, and preferably 700 C or more and 800 ° C or less). The heating is performed for a predetermined time, whereby the drying of the dried coating is performed. Therefore, the paste coating material is sintered on the substrate, and the external connection aluminum electrode 22 as shown in Fig. 1 which will be described later can be formed. Fig. 1 is a cross-sectional view showing the configuration of a solar cell 1 according to an embodiment of the present invention. The solar cell 1 of the present embodiment is a light-receiving surface electrode U' formed on one surface side (surface side) of the substrate 11 by a germanium semiconductor substrate (Si B circle) U' and the other surface side (back surface) of the substrate 11 The side is formed by electrodes (2〇, 22). The Shixia semiconductor substrate (10) of the present embodiment is composed of, for example, a crystalline stone and an amorphous sand. In the solid state, the n-Si layer 16 is formed on the light-receiving side of the p-Si layer (p-type crystallized stone) 18 of the substrate 11 by the pn junction. Further, an anti-reflection film 14 formed of titanium oxide or tantalum nitride formed by a general chemical vapor deposition (CVD) method or the like is located on the surface of the ?-Si layer 16. Further, on the surface of the anti-reflection film 14, a surface electrode (light-receiving surface electrode) 12 made of Ag which is typically formed by firing a silver paste by screen printing is provided. In the configuration of the present embodiment, a paste composition for forming an aluminum electrode (hereinafter, referred to as "first aluminum paste" for convenience) is provided on the back side of the P-Si layer 18. The aluminum electrode 22 is formed of a material. The aluminum electrode 22 corresponds to the external connection electrode 22 on the back side which is electrically connected to other external connection members such as a lead wire (conductive strip line). The external connection aluminum electrode 22 of the present embodiment is similar to the conventional case of forming such an electrode (for example, when a silver paste is used as a material for forming an external connection Ag electrode), by screen printing and firing. Formed as the jth aluminum paste. On the back side of the p-Si layer 18, an aluminum electrode 20 formed of another aluminum paste (hereinafter, referred to as "second aluminum paste" for convenience) is formed together with the aluminum electrode 22 for external connection. The aluminum electrode 20 is formed on the entire back surface of the p-Si layer 18, and has an effect of a back surface field (BSF) effect (hereinafter referred to as "back surface wide-range aluminum electrode"). In the configuration of the present embodiment, the external connection aluminum electrode 22 is formed linearly on the back side of the p-Si layer 18, and the back surface wide-range aluminum electrode 20 is provided on the back side of the p-Si layer 18, and is formed substantially uniformly. It is outside the region where the external connection aluminum electrode 22 is formed. Further, in the configuration of the present embodiment, the large-surface aluminum electrode 20 on the back surface covers the portion of the back surface of the cover of the 2012 20121616, which is a part of the front surface (specifically, the two edge portions of the linear structure), and has an exposed external connection. The state of the opening portion 23 of the secret electrode 22 is formed. Further, in addition to the state in which the both sides of the external connection electrode 22 are covered, the back surface of the large-surface-filled electrode 20 may be formed in a state in which the side surface of the back-side electrode 20 is connected to the side of the externally-cooked core (4). . Further, in the present embodiment, the back surface wide-range electrode 2 〇 includes the formation of the powder, the glass material, and the organic Wei, and may be used for forming the S-electrode of the conventional solar cell. There are no special restrictions on the content. Therefore, the detailed description is omitted since there is no feature of the present invention. In the present embodiment, the first paste is applied to a germanium semiconductor substrate (on a wafer to be a desired film thickness or a coating film by a screen printing, a dispensing method, a dip coating method, or the like). Then, the coating material is dried at an appropriate temperature (room temperature to about 100 ° C), and the second aluminum paste is applied onto the ruthenium semiconductor substrate u to form an opening portion 23 through which the external connection electrode 22 is exposed. Dry the coating at an appropriate temperature (from room temperature to about 100 ° C), and then heat it in a suitable firing furnace (for example, a speed-fired furnace) under appropriate heating conditions (for example, 7 ° C to 8 ° C). The heating is performed for a predetermined period of time. Therefore, the dried coating film is fired. Therefore, the coating material is sintered on the substrate, and the external connection electrode 22 and the large-scale electrode 20 are formed as shown in Fig. i. The aluminum electrode 22 for external connection and the large-sized aluminum electrode for the back surface are fired, and the P+ layer (BSF layer) 24 is formed by 玎. The second (a) and (b) diagrams schematically show the embodiment. A top view of the structure of the back side of the substrate 11 of the solar cell 100 In the 20th 201250716 2(a) and (b), 'for the sake of convenience, the back side of the display substrate u is located above. The external connection aluminum electrode 22 is formed in the configuration shown in Fig. 7 for external connection. The position where the electrode (Ag electrode) is located. In the example shown in Figs. 2(a) and (b), the external connection aluminum electrode 22 can have a function as an electrode having a width of, for example, 2 to 6 mm. In general, aluminum and In the configuration of the present embodiment, the conductive adhesive film 3 is adhered to the external connection aluminum electrode 22 in a state of being pressed (see FIG. 3 to be described later). The film 30 (Fig. 3) is typically an anisotropic conductive adhesive film. For example, the adhesive composition may be an epoxy resin, a phenoxy resin, an acrylic resin, a polyimide resin, or a polyamide resin. a carbonated resin and another thermosetting resin or a thermoplastic resin. Then, a plurality of conductive particles (typically, metal particles such as copper or precious metal) are dispersed in the tree=(substrate) component, and Conductive connection by heating and pressurization The film 30 can be adhered to a predetermined portion by the conductive adhesive film 3, and the conductive particles can be ensured to be electrically connected. Further, the conductive connection is not particularly limited, and the commercially available one can be used without any limitation. The conductive adhesive film for the purpose of use. Fig. 3 is a perspective view schematically showing the external connection of the back side of the conductive electrode 14 as shown in Fig. 3, as shown in Fig. 3. 22 or more _3G configuration in the external connection configuration in the conductive purchase strip line - Figure 4 (a) and (b) shows on the post, through the conductivity followed by the thin blue set; electricity 21 201250716 First, such as As shown in Fig. 4(a), the external connection electrode 42 formed on the substrate 11 is provided with a thin film, and a sheet line 35 is laminated on the electropositive film 3A. The thinner is then uniformly dispersed in the adhesive component 32 formed of, for example, an epoxy-based thermosetting resin in the conductive particles 3U, for example, the particles of the bond gold. Next, as shown in FIG. 4(b), the conductive adhesive film is used as a sheet-like wire bonding material', and by externally connecting (four) electric ribs by pressurization and heating, the conductive film 3G and the sheet line 35 (please Referring to the arrow %), the conductive particle material in the film 30 is connected to the (10) electric rib and the sheet line 35 (refer to arrow 55). At the same time, it is possible to achieve the same degree of electrical conduction as the solder joint by the electrical conductivity followed by the binder component (here, the heat-curing adhesive) 32. Further, when the sheet-like wire 35 is welded, it is necessary to apply a high temperature of 2 以上 or more, but the bonding of the conductive film 3G can be performed for 18 generations of low-temperature bonding. Therefore, the influence of the heating on the solar cell (battery) 100 (e.g., strain due to heat) can be reduced or prevented in advance. In the embodiment described above, a configuration in which the rib electrode 22 is connected to the outside by the third aluminum paste and the back surface electrode 20 composed of the second paste is used as the back surface aluminum electrode is shown. However, the present invention is not limited thereto. For example, all of the back aluminum electrodes can be formed by the first paste, including the portion of the large-sized aluminum electrode on the back side. Several experimental examples of the present invention are described below, but the present invention is not intended to be limited to the test examples shown. In the following test, the difference in the bonding strength when the glass properties of the solid content of the paste composition for aluminum electrode formation (aluminum paste) were different from each other was evaluated. 22 201250716 In this test, a total of 8 glass samples (sample 1 to sample 8) of the glass composition (mol%), the glass softening point (°C), and the thermal expansion coefficient (thermal expansion coefficient) shown in Table 1 below were used. 23 201250716 [Table 1] Composition (moiS) Soft im hate account itch Si02 B2〇j bi2o3 2nO PbO AI2〇a CaO SrO BoO ϋ,Ο Na20 K2〇(°C) Sample 1 15 24.9 60.1 644 45 Sample 2 29 36 β 4 to 13 690 67 Sample 3 33.6 33.6 7.5 3.7 9.3 12.1 716 66 Sample 4 14.5 29.2 15.3 25 16.1 529 8$ Sample 5 54 10 30 7 570 63 Sample (J 25 24 29 5 5 a 6 54$ 70 7 28 21.3 3 26.5 5 7 6 3 568 7〇sample 8 30 fi 6 38 3 12 445 77 Then, a total of 8 kinds of aluminum pastes were prepared for each glass material (samples i to 8) shown in Table 1 (test Example 1 to Test Example 8) The glass materials of the respective test examples differ only in the properties of the glass materials described above, and the other components (aluminum powder, organic vehicle) and the mixing ratio were the same, that is, the aluminum paste of each test example. (1) Aluminum powder: The aluminum powder having an average particle diameter of 6 μm is mixed and used in an amount of only 66% by mass of the entire paste. (2) Organic carrier: The rosin alcohol is mixed to have only 26% by mass of the entire paste. The amount is used as an organic solvent. The cellulose was mixed and used as an organic binder in an amount of only about 2% by mass of the whole paste. (3) Glass material: The glaze of any of the above samples 1 to 8 was mixed to have only 6 mass% of the entire paste. The amount was used. <Bottom strength test (1)> Next, the bonding strength of each of the aluminum pastes of Test Examples 1 to 8 manufactured as described above on 24 201250716 矽 semiconductor substrate was subjected to a bonding strength test. The steps of forming the electrode on the surface (back surface) of the Shishi semiconductor substrate ii using the respective test examples 1 to 8 are as follows. That is, a commercially available p-type single crystal substrate for a solar cell of a size of 125 mm is prepared. (the thickness of the plate is 20_), and the surface of the substrate is coated with a hydroxide solution. Then, a phosphorus-containing solution is applied to the light-receiving surface of the substrate having the texture structure formed by the above etching treatment, and heat-treated on the substrate An n-Si layer (n+ layer) having a thickness of about 0.5 μm is formed on the light-receiving surface. Next, an anti-reflection film (titanium oxide) having a thickness of about 50 nm or more and 100 nmw is formed on the n-Si layer by a plasma CVD (PECVD) method. Membrane) A silver paste was formed by using a pre-tanned surface electrode (Ag electrode), and a coating film (having a thickness of 2 μm or more and 50 μm or less) which was a surface electrode (Ag electrode) was formed on the anti-reflection film by a screen printing method. On the other hand, on the back side of the Shishi semiconductor substrate, the paste composition of any of the above Test Examples 1 to 8 was printed (coated) by screen printing (using a steel mesh SUS #165) and was linear. A coating film having a film thickness of about 3 mm μm of about 5 mm width was formed. Then, the substrate is fired, and a linear electrode for test evaluation is formed. Specifically, the near-infrared high-speed firing furnace is used in the atmosphere to be fired at a firing temperature of about 700 eC or more and 800 ° C or less. The adhesion strength test was carried out by using the battery (solar cell) for evaluation of the test example thus obtained, and the adhesion strength of the aluminum electrode formed of the paste composition for forming an aluminum electrode of each test example was measured. The evaluation of the adhesion strength (peel strength) of the aluminum electrode formed as described above (i.e., the peel strength evaluation) was carried out using the strength measuring device 300 as shown in Fig. 5. 25 201250716 Specifically, the intensity measuring device 300 shown in FIG. 5 fixes the glass substrate 41 to the fixing jig 4 through the fixing screw 43 and the locking plate 44, and the epoxy substrate 42 is bonded to the glass substrate 41. The light-receiving surface side of the semiconductor substrate 11 for the test obtained as described above was fixed to the glass substrate 41. The conductive adhesive film 30 of the commercial product is adhered to the formed aluminum electrode 28 on the exposed surface side of the tantalum semiconductor substrate u thus fixed on the glass substrate 41 by heat and pressure adhesion, and the sheet line 35 is further attached. Adhered to the conductive adhesive film 30. Further, as shown in Fig. 5, the strength measuring device 3 is tilted so that the bottom surface of the fixing jig 40 becomes 135°, and the extension portion 35e' previously formed on the sheet line 35 is stretched upward in the vertical direction. The line 35/conductivity follows the bonding strength of the film 30/aluminum electrode 28. The results are shown in Table 2 of the pair of towels. Then, the strength predation test (peel strength test) is performed by the majority (10) of the test examples, and the average value of the (four) (four) poles of the results (measured) is calculated. n=2), as a strong customer. Further, the graph of Fig. 6 shows the relationship between the adhesion strength obtained by this test and the softening point of the glass frit in the chain paste. 26 201250716 [Table 2] Softening point of AI paste glass (°C) Thermal expansion rate (xl〇-7/°C) Then strength (Ν) Data average test example 1 Sample 1 644 45 0.3386 0.6147 0.48 Test example 2 Sample 2 690 67 0.6873 0.6921 0.69 Test Example 3 Sample 3 716 66 0.3822 0.4156 0.40 Test Example 4 Sample 4 530 86 0.01 0.01 0.01 Test Example 5 Sample 5 570 63 0.8 0.7 0.75 Test Example 6 Sample 6 548 70 1.6822 1.2724 1.48 Test Example 7 Sample 7 568 70 0.9712 0.9297 0.95 Test Example 8 Sample 8 445 77 0.977 1.0775 1.03 As shown in Table 2 and Figure 6, it is seen that the glass softening point in the aluminum paste is above 400 ° C and below 600 ° C (especially above 500 ° C) A high adhesion strength is shown in the range of 600 ° C or less. In particular, when the paste of Test Example 6 in which the glass softening point was around 550 ° C was used, an extremely high bonding strength was observed. Moreover, it is seen that the thermal expansion coefficient of the glass material is 6〇xicr7/°c or more and 80xl〇-7/°C or less (especially 65xl〇-7/°C or more and 75xl〇-7/°C or less). Then the intensity. <Bottom strength test (2)> The aluminum paste of Test Example 6 was used to form a line having a thickness of about 30 μm and a width of about 2 mm on the above-mentioned tantalum semiconductor substrate 11 in the same manner as in the above-described adhesive strength test (1). The aluminum electrode was subjected to the same peel strength evaluation test, and as a result, as shown in the column of the Example of Table 3, the average value (n = 2) of the adhesion strength of 3.25 N / 2 mm was observed. 27 201250716 As a comparative control, a linear Ag electrode having a width of about 30 μm and a width of about 2 mm was formed on the above-mentioned Shi Xi semiconductor substrate 11 by using a usual silver paste instead of the aluminum paste of Test Example 6, and the above-mentioned sheet line was passed through a binder. 35 was pasted on the surface thereof and subjected to the same peel strength evaluation test, and the results were as shown in Comparative Example 8 of Table 3, and the average strength (n = 2) of 3.5 N / 2 mm was observed. Further, Comparative Example b in Table 3 was obtained by substituting the aluminum paste of Test Example 1 for the paste of Test Example 6. [Table 3] Comparative Example A Comparative Example B Example Next Strength (N/2 mm) 3.50 0.50 3.25 It can be understood from Table 3 that it was confirmed that the electrode formed in Test Example 6 was welded to Ag in Comparative Example A. The equivalent strength of the electrode. Further, when compared with the adhesion strength of the aluminum electrode in Comparative Example B, it was confirmed that the adhesion strength of the aluminum electrode formed of the aluminum paste of Test Example 6 was remarkably improved. As is apparent from the description of the above-described embodiments and test examples, in the solar battery provided by the present invention, the electrode can be used as the f-pole for the back side external connection. In the case of silk, it is possible to carry out the bonding of the film by the fact that the material of the wealth is extremely low and the strength cannot be made. Therefore, the conventional configuration of the disk using the Ag electrode as the electrode for the back side external connection can form a cholester on the entire surface of the back surface of the Shihua semiconductor substrate (wafer). In addition, a cost reduction equivalent to the price difference between the materials of silver and Shao can be achieved. In addition, by using the external electrode for improving the bonding strength (peeling strength) of the film, the keel can be joined by a four-joint joint, so that a core result that does not include the electrode portion for soldering, such as a fine wafer, can be constructed. 28 201250716 The back of the full-fledged 'can increase the power generation efficiency of the solar cell due to the formation of the BSF layer' and improve the power generation efficiency of the 1% battery by omitting the pattern of the bus bar electrode. The present invention has been described in detail above, but these are merely illustrative, and the invention may be embodied in other forms and various modifications may be made without departing from the spirit and scope of the invention. For example, the electrode composition for electrode formation disclosed herein may be used to form at least a portion of a light-receiving surface electrode (e.g., a bus bar electrode or a grid line constituting a light-receiving surface electrode). I. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view schematically showing an example of a structure of a solar cell 100 according to an embodiment of the present invention. Figs. 2(a) and 2(b) are a plan view and a cross-sectional view, respectively, schematically showing a configuration of the back side of the substrate 11 in the solar cell stack. Fig. 3 is a perspective view schematically showing the configuration in which the conductive electrode is placed on the front side of the solar cell 1 外部. 4(a) and 4(b) are cross-sectional views showing a structure in which a wire (sheet line) 35 is disposed on the external connection aluminum electrode 22 through the conductive adhesive film 30. Fig. 5 is a cross-sectional view schematically showing the configuration of the intensity measuring device 300 for performing the subsequent strength evaluation. Figure 6 is a graph showing the relationship between the strength of the bond and the softening point of the slope. Fig. 7 is a cross-sectional view schematically showing an example of a conventional solar cell 1 〇〇〇 structure. 29 201250716 [Description of main component symbols] 11.. 矽 Semiconductor substrate (Shi Xi wafer) 12.. Light-receiving surface electrode; Surface electrode 14: Anti-reflection film 16...n-Si layer 18.. .p- Si layer 20.. Back side wide range of electrode 22.. External connection with aluminum electrode 23.. Opening 24: P+ layer; BSF layer 28.. Aluminum electrode 30.. Conductive film 31 .. . Conductive particles 32.. .substrate composition 35.. sheet-like line; wire (conductive strip line) 35e...extension 40.. fixed fixture 41...glass substrate 42.. Epoxy adhesive material 43.. fixing screw 44.. locking plate 45, 50, 55... arrow 100, 1000... solar battery 111.. cutting semiconductor substrate (Si wafer) 112.. surface electrode ( Light-receiving electrode) 114...anti-reflection film 116..n-Si layer 118".p-Si layer 120.. aluminum electrode 122.·electrode 124..p+ layer; BSF layer 300.. Device 30
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| JP (1) | JPWO2012165167A1 (en) |
| KR (1) | KR20140027372A (en) |
| CN (1) | CN103597548B (en) |
| DE (1) | DE112012002354T5 (en) |
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| WO (1) | WO2012165167A1 (en) |
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| JP2014220293A (en) * | 2013-05-02 | 2014-11-20 | 株式会社ノリタケカンパニーリミテド | Solar cell and paste composition for forming aluminum electrode for solar cell |
| JP6107394B2 (en) * | 2013-05-08 | 2017-04-05 | 株式会社村田製作所 | Conductive paste, method for producing the same, and ceramic electronic component using the same |
| JP6268759B2 (en) * | 2013-06-11 | 2018-01-31 | 日立化成株式会社 | Solar cell and solar cell module |
| JP2015115400A (en) * | 2013-12-10 | 2015-06-22 | 東洋アルミニウム株式会社 | Conductive aluminum paste |
| JP2016213284A (en) | 2015-05-01 | 2016-12-15 | 東洋アルミニウム株式会社 | Aluminum paste composition for PERC type solar cell |
| JP6074483B1 (en) * | 2015-11-10 | 2017-02-01 | 株式会社ノリタケカンパニーリミテド | Conductive composition |
| CN114409249B (en) * | 2022-01-06 | 2023-11-24 | 江苏日御光伏新材料科技有限公司 | Silicon-lithium-lead system, conductive paste thereof and preparation method |
| CN114725224A (en) * | 2022-04-12 | 2022-07-08 | 安徽华晟新能源科技有限公司 | Grid line prefabricated structure and preparation method thereof, and preparation method of heterojunction battery |
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| JP4464708B2 (en) * | 2004-02-26 | 2010-05-19 | 信越半導体株式会社 | Solar cell module and method for manufacturing solar cell module |
| JP4907331B2 (en) * | 2006-12-25 | 2012-03-28 | 京セラ株式会社 | Conductive paste for photoelectric conversion element, photoelectric conversion element, and method for producing photoelectric conversion element |
| JP4970026B2 (en) * | 2006-12-26 | 2012-07-04 | 京セラ株式会社 | Conductive paste for photoelectric conversion element, photoelectric conversion element, and method for producing photoelectric conversion element |
| US7485245B1 (en) * | 2007-10-18 | 2009-02-03 | E.I. Du Pont De Nemours And Company | Electrode paste for solar cell and solar cell electrode using the paste |
| KR101139197B1 (en) * | 2007-11-15 | 2012-04-26 | 히다치 가세고교 가부시끼가이샤 | Solar battery cell and method of producing the same |
| JP5113710B2 (en) * | 2008-10-08 | 2013-01-09 | 京都エレックス株式会社 | Conductive paste for forming electrode of solar cell element, solar cell element, and method for manufacturing the solar cell element |
| JP2010192480A (en) * | 2009-02-16 | 2010-09-02 | Nippon Electric Glass Co Ltd | Glass composition for electrode formation, and electrode forming material |
| JP5796270B2 (en) * | 2009-04-16 | 2015-10-21 | 日本電気硝子株式会社 | Electrode forming material |
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| DE112012002354T5 (en) | 2014-02-20 |
| CN103597548B (en) | 2016-05-11 |
| JPWO2012165167A1 (en) | 2015-02-23 |
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