TW201005756A - Environment-friendly paste for electrode of solar cell and solar cell using the same - Google Patents
Environment-friendly paste for electrode of solar cell and solar cell using the same Download PDFInfo
- Publication number
- TW201005756A TW201005756A TW098116657A TW98116657A TW201005756A TW 201005756 A TW201005756 A TW 201005756A TW 098116657 A TW098116657 A TW 098116657A TW 98116657 A TW98116657 A TW 98116657A TW 201005756 A TW201005756 A TW 201005756A
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- Prior art keywords
- paste
- component
- lead
- solar cell
- formula
- Prior art date
Links
- 239000011521 glass Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 35
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
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- 239000000203 mixture Substances 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 30
- 239000004332 silver Substances 0.000 claims description 30
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- 238000005245 sintering Methods 0.000 claims description 17
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- 239000004215 Carbon black (E152) Chemical group 0.000 claims description 13
- -1 alkoxide salt Chemical class 0.000 claims description 13
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
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- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 claims 1
- 239000002003 electrode paste Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000035515 penetration Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
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- 231100001261 hazardous Toxicity 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 26
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- 239000010410 layer Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000011858 nanopowder Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
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- 125000005594 diketone group Chemical group 0.000 description 6
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- 238000007650 screen-printing Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 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 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 229960004667 ethyl cellulose Drugs 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 229910000978 Pb alloy Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- GKQWCGILHSRTBZ-UHFFFAOYSA-N [B].[Bi]=O Chemical compound [B].[Bi]=O GKQWCGILHSRTBZ-UHFFFAOYSA-N 0.000 description 1
- GEUONWOWBXVPPO-UHFFFAOYSA-N acetonitrile;lead Chemical compound [Pb].CC#N GEUONWOWBXVPPO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000000675 anti-caries Effects 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- NUVIWMRYHSSRHP-UHFFFAOYSA-N bismuth;oxolead Chemical compound [Bi].[Pb]=O NUVIWMRYHSSRHP-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 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
- 238000007646 gravure printing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 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
-
- 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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
201005756 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於太陽能電池電極的膏及使用其 之太陽能電池，具體而言，係關於一種用於環保太陽能電 池電極的膏，可將有害的的鉛含量降至最低，藉此可製造 具有低串聯電阻（Rs)與高分路電阻（Rsh)的環保太陽能電池 .電極，以及關於使用該膏的太陽能電池。 【先前技術】 φ 作為將日光轉換成有用的電能的潔淨能源，一種使用 光的半導體裝置（如太陽能電池）已成為注目焦點，而太陽 能電池的商業化目前也正在進步之中。大體上，電極係形 成於使用像是太陽能電池之半導體裝置以及其類似物中。 此時，該電極在其光接受表面上應佔有一個小面積，好讓 光盡可能遠射而不被攔截。因此，太陽能電池的電極形成 如格栅（grid)型狀之格狀（lattice)圖形。 第1圖顯示一般石夕晶圓類型太陽能電池之剖面圖。參 ®照第1圖，太陽能電池通常包含上面有太陽光入射之半導 體基底10 ;形成於半導體基底10的頂部上之前電極20 ; 以及形成在半導體基底10的底部上之背電極30。該太陽 能電池復包含敷設於半導體基底10的表面之抗反射塗層 12，以防止對半導體基底10入射之曰光的反射損失。 半導體基底10係由具有η-型矽層10a和p-型矽層10b 之矽晶圓製成。此外，背電極30主要係由鋁（A1)薄膜製 成。具體而言，將包括鋁粉末作為主要材料之膏敷設到p- 3 94679 201005756 型矽層10b，然後A1離子於燒結過程中擴散進入p-型矽 層10b内，以致背電極30與p-型矽層10b成為歐姆接觸。 更進一步，抗反射塗層12包含氮化矽（Si3N4)作為有效成 分主要用來避免日光的反射損失。前電極20主要係以銀 (Ag)形成。具體而言，前電極20是在抗反射塗層12上以 含銀粉末的膏作為主要材料印上格狀圖形之後，藉由燒結 - 膏而形成。此時，透過熱處理而在燒結過程中讓前電極20 · 穿透入抗反射塗層12而與η-型矽層10a成為歐姆接觸， 藉此降低太陽能電池的串聯電阻。 ❿ 太陽能電池的電極，具體而言，太陽能電池的前、背 電極20和30以燒結膏而形成，該膏包含上述像是Ag和 A1作為主要材料之導電金屬。此外，用於電極20和30的 膏包含玻璃原料作為無機燒結劑以便讓導電金屬成分經過 燒結程序黏附在半導體基底10上，以及包含如有機溶劑之 有機材料作為分散媒介來分散這些固體成分。 曰本早期公開第2001-202822號的專利公開案（專利 文件1)和韓國早期公開第2004-0025609號的專利公開案 (專利文件2)中提出一種包含鋁粉粉末、玻璃原料、有機 材料和類似物的膏，當做與用於背電極30之膏相關的先前 技術文件。此外，一種包含銀粉末、玻璃原料、有機材料（樹 脂黏結劑）以及類似物的膏，已在韓國早期公開第2007-0066938號的專利公開案（專利文件3)、韓國早期公開第 2007-0067636號的專利公開案（專利文件4)和韓國早期公 開第2007-0084100號的專利公開案（專利文件5)中被提 4 94679 201005756 - 出，做為與以膏作為前電極20相關的先前技術文件。如這 些先前專利文件中所提出的，玻璃原料係用作為含鉛成分 且具低熔點之無機燒結劑使用。 鉛成分降低了玻璃原料的熔點以改良導電金屬（像是 銀及鋁）對半導體基底10的黏著力，藉此能夠提高電極20 和30的佈線（wiring)強度。尤其，就用於前電極20的膏 而言，内含於玻璃原料的鉛成分會穿透入氮化矽（Si3N4)薄 膜層（抗反射塗層12)，使其與氮化矽（Si3N4)薄膜層成為歐 ◎姆接觸。具體而言，該鉛成分在燒結過程中與氮化矽起反 應而腐蝕了抗反射塗層12，所以Ag電極穿透入抗反射塗 層12藉此與η-型矽層10a成為歐姆接觸。因此，含鉛成 分的玻璃原料係在膏中當作玻璃原料使用以用於電極20 和30。尤其，用於前電極20之膏含有鉛成分是必要的， 因為鉛成分係作為穿透劑的功能用於形成與η型矽層10a 的歐姆接觸。 _ 然而，由於該膏含有相當量之有害的鉛成分，根據包 括前述專利文件等先前技術之用於電極20和30的膏會引 起環境上的嚴重問題。具體而言，雖然鉛成分本質上就包 含於前電極20中，但只有當包含在玻璃原料中之鉛成分含 量相當多的時候，前電極才會因為含有鉛成分而展現出傳 統上作為一個穿透劑的角色。舉例來說，專利文件5提出 一種膏，包含佔總固體成分重量1至15個重量百分率（wt %)的玻璃原料，及玻璃原料中15至75莫耳百分率（莫耳 %)的Pb和5至50莫耳百分率（莫耳％)的Si〇2。當把鉛 5 94679 201005756 (Pb)成分轉換成重量基準時，固體成分的100重量分 (weight parts)中所含錯成分的量大約達14. 6重量百分率 (wt% )。因此，根據先前技術用於電極之膏，由於有害的 鉛之高度含量，存在著產生嚴重環境問題的缺陷。 [專利文件1]曰本專利早期公開第2001-202822號的專 利公開案 [專利文件2]韓國專利早期公開第2004-0025609號的 專利公開案 [專利文件3]韓國專利早期公開第2007-0066938號的 ❿ 專利公開案 [專利文件4]韓國專利早期公開第2007-0067636號的 專利公開案 [專利文件5]韓國專利早期公開第2007-0084100號的 專利公開案 【發明内容】 [技術問題] _ 本發明係構思用以解決上述先前技術中的問題。本發 明的一個目的在於提供一種用於太陽能電池電極之膏，其 讓最小化有害的Pb含量變得可能，藉此讓環保太陽能電池 電極得以製造，並且具有低串聯電阻（Rs)和高分路電阻 (Rsh)，以及提供一種使用用於太陽能電池電極之膏的太陽 能電池。具體而言，本發明之目的在於提供一種用於環保 太陽能電池電極之膏，其中該膏含有低量之有害鉛成分， 並在熱處理期間穿透抗反射塗層（Si3N4薄膜），讓電極與半 6 94679 201005756 •導體基底（N型矽層）有著極佳的結合強度，藉此具有低串 聯電阻及向分路電阻，以及提供一種使用用於環保太陽能 電池電極之膏作為前電極的太陽能電池。 '[技術方案] 為達成上述目的，本發明提供一種用於太陽能電池電 極之膏，其包含固體成分及分散媒介，其中該固體成分包 含選自金屬及含金屬之化合物的至少其中一種導電粉末； 不含鉛成分的玻璃原料；以及粒度為i至丨，〇〇〇奈米（nm) ❹之鉛成分顆粒。鉛成分顆粒較佳的粒度是1至2〇〇奈米。 舉例來說’至少一種選自鉛（pb)、鉛合金、以及鉛氧化物（下 列式1)可用來作為鉛成分顆粒使用。 此外，本發明提供一種用於太陽能電池電極之膏，其 包含固體成分及分散媒介’其中該固體成分包含選自金屬 及含金屬之化合物的至少其中一種導電粉末；不含鉛成分 的玻璃原料；以及選自鉛醇鹽（lead alkoxide)(下列式 ❹2)、斜聚縮合（poiycondensuion)聚合物（下列式3)、及 錄與冷一雙酿j(beta-diketones)的錯合物（下列式4)的 至少其中一種鉛成分化合物。 再者，該固體成分復包含絲（Bi)成分。此處，纽成分 疋選自叙:金屬及含祕之化合物的至少其中一者。舉例來說， 該祕成分是選自鉍、鉍合金、鉍氧化物（下列式5)、鉍醇 鹽（下列式6)、鉍聚縮合聚合物（下列式7)、及鉍與点〜 雙酮（下列式8)的錯合物的至少其中一者。如果絲成分（如 叙單一金屬’鉍合金，及鉍氧化物（下列式5)是呈顆粒形 7 94679 201005756 式，這些顆粒較隹是1至1，000奈米的尺寸，而更佳是1 至200奈米。 根據本發明的較佳實施例，固體成分較佳包含40.0 至99. 0重量分的導電粉末；0. 1至57. 0重量的不含鉛的 玻璃原料；以及0. 1至3. 0重量分的鉛或鉛化合物。該固 體成分可復包含0. 1至3. 0重量分的鉍或鉍化合物。 此外，本發明提供一種太陽能電池，其包含半導體基 底；敷設於該半導體基底之頂部的抗反射塗層；在形成於 抗反射塗層之頂部上後藉由燒結而與半導體基底接觸的前 ❿ 電極；以及形成在半導體基底之底部上的背電極，其中該 前電極是根據本發明之膏的燒結體。 [發明功效] 根據本發明，有害的鉛成分的含量可降至最低。具體 而言，根據本發明，一種用於太陽能電池電極的膏不包含 内含於玻璃原料狀態下的鉛成分，但是包含作為單獨成分 之奈米大小（最好為200奈米或更小）的錯成分，或包含以 下列式2至4表示之化合形式的鉛成分，所以雖然鉛成分 是低的使用量，但因該錯成分的表面積增加，而其活性（像 如反應性）也得到改良，故藉此在熱處理期間獲得對抗反射 塗層的優良穿透效果並改善與半導體基底的結合強度。因 此，根據本發明，其優點在於使製造環保的電極成為可能， 因為鉛成分的消耗量可降至不超過其傳統消耗量的一半， 且由於穿透抗反射塗層的強化效果以及與半導體基底改良 的結合強度，可藉由獲得低串聯電阻（Rs)及高分路電阻（Rs〇 8 94679 201005756 / 改良太陽能電池的電性質。再者，根據本發明，藉由形成 具緊密（compact)結構的電極則可展現出極佳的導電性。 【實施方式】 . 以下將針對本發明作詳細地描述。 根據本發明之一種用於太陽能電池電極的膏，包含固 -體成分、及用於分散固體成分之分散媒介。該固體成分包 •含導電粉末、作為無機燒結劑將導電粉末結合至半導體基 底之無鉛玻璃原料、以及在燒結程序中作為穿透劑而與抗 〇反射塗層成為歐姆接觸的鉛成分。 該導電粉末是選自金屬及含金屬之化合物的至少其中 一者，其中該金屬包含單一金屬及合金，而該含金屬之化 合物包含金屬氧化物及金屬鹽。舉例來說，該導電粉末為 銀（Ag)、銅（Cu)、金（An)、翻（Pt)、I呂（A1)或其中至少二 者之混合物或合金。再者，該導電粉末是一種含金屬之化 合物且其可選自於例如銀或銀的氧化物，或銀或銀的鹽類 (包括有機、無機鹽類）。此種導電粉末可以球形或片狀顆 粒的形式或以膠體的形式内含於膏中，其中該球形或片狀 顆粒係分散的。此外，顆粒可當作導電粉末使用，其選自 前述的金屬或含金屬之化合物且塗佈有機材料。 較佳地，銀、銀合金、銀化合物（銀的氧化物或銀的鹽 類）、及其類似物可當作用於太陽能電池之前電極的導電粉 末使用。舉例來說，銀化合物包含銀的氧化物，像是氧化 銀（Ag2〇)、而銀的鹽類包含像是氯化銀（AgCl)、硝酸銀 (AgNOs)及醋酸銀（AgOOCCHs)。最佳的是，銀顆粒用來當作 9 94679 201005756 太陽能電池之前電極的導電粉末使用。再者，鋁、鋁合金、 鋁化合物（鋁的氧化物或鋁的鹽類）可較佳地當作太陽能電 池之背電極之導電粉末使用。 該導電粉末具有〇. 〇1至30. 0微米（μπι)的粒度，且因 為田該導電粉末之粒度报小時其燒結特性極佳，所以該導 電叙末較佳具有100至500奈米之粒度。 〇 再者’該導電粉末佔總固體成分之重量，即固體成分 的100重量分中，較佳者為含有40.0至99. 0重量分。該 導電粉末含量低於40重量分不是較佳的’因為其導電率 了降j且導電粉末含量超過99. 〇重量分也不是較佳的，言 是因為玻壤補與錯成分的含量會相對地減少，而由人^ 匕們所引起的效果也料會明顯。更佳地是，該 佔總固體量成分重量係含有7〇. 〇至99. 〇重量成分之含量 根據本發明所使用的是沒有包含錯成分的無 夏 〇 料。在本發明巾’任何可經由減理進行燒結且不糾 成分但至少含有碎（Si)成分之玻璃原料均能使用。: 說’該玻璃原料包含基於Si〇2的玻璃祕、基於Si〇 7 的玻璃原料（基於S卜Zn_◦的玻璃原料）、基於Si(J n0 的玻璃原料（基於Sl|〇的玻璃原料）、和基於^ 2 的玻璃原料（基於s卜Bi_〇的玻璃原料），其中基於 玻璃原料意指包含Si〇2作為主要成分的玻璃原料，而基於 Si〇2 ZnO的麵原料意指包含Si㈣為主要成分並二 助成分的玻璃原料，，除了主要成分及』 73 ’該坡璃原料可包含氧化物作為其它成分。這 94679 10 201005756 。些氧化物為選自於像是Ah〇201005756 VI. Description of the Invention: [Technical Field] The present invention relates to a paste for a solar cell electrode and a solar cell using the same, and more particularly to a paste for an environmentally friendly solar cell electrode, which can Harmful lead content is minimized, thereby enabling the manufacture of environmentally friendly solar cells with low series resistance (Rs) and high shunt resistance (Rsh). Electrodes, as well as solar cells using the paste. [Prior Art] φ As a clean energy source that converts sunlight into useful electric energy, a semiconductor device using light (such as a solar cell) has become a focus of attention, and the commercialization of solar cells is currently progressing. In general, the electrodes are formed using semiconductor devices such as solar cells and the like. At this time, the electrode should occupy a small area on its light receiving surface so that the light can be projected as far as possible without being intercepted. Therefore, the electrodes of the solar cell form a lattice pattern such as a grid shape. Figure 1 shows a cross-sectional view of a typical Shixi wafer type solar cell. Referring to Fig. 1, a solar cell generally includes a semiconductor substrate 10 having solar light incident thereon; an electrode 20 formed on top of the semiconductor substrate 10; and a back electrode 30 formed on the bottom of the semiconductor substrate 10. The solar cell includes an anti-reflective coating 12 applied to the surface of the semiconductor substrate 10 to prevent reflection loss of the incident light incident on the semiconductor substrate 10. The semiconductor substrate 10 is made of a germanium wafer having an n-type germanium layer 10a and a p-type germanium layer 10b. Further, the back electrode 30 is mainly made of an aluminum (A1) film. Specifically, a paste including aluminum powder as a main material is applied to the p- 3 94679 201005756 type tantalum layer 10b, and then the A1 ions are diffused into the p-type tantalum layer 10b during the sintering process, so that the back electrode 30 and the p-type are formed. The ruthenium layer 10b becomes an ohmic contact. Further, the anti-reflective coating 12 contains tantalum nitride (Si3N4) as an effective component mainly for avoiding reflection loss of sunlight. The front electrode 20 is mainly formed of silver (Ag). Specifically, the front electrode 20 is formed by sintering a paste after the grid-like pattern is printed on the anti-reflective coating layer 12 with a paste containing silver powder as a main material. At this time, the front electrode 20 is penetrated into the anti-reflection coating 12 by the heat treatment to make an ohmic contact with the n-type tantalum layer 10a, thereby reducing the series resistance of the solar cell.电极 The electrode of the solar cell, specifically, the front and back electrodes 20 and 30 of the solar cell are formed by a frit paste containing the above-mentioned conductive metal such as Ag and A1 as main materials. Further, the paste for the electrodes 20 and 30 contains a glass raw material as an inorganic sintering agent for adhering the conductive metal component to the semiconductor substrate 10 through a sintering process, and an organic material containing an organic solvent as a dispersion medium to disperse these solid components. An aluminum powder, a glass raw material, an organic material, and a patent publication (Patent Document 2) of the Korean Patent Publication No. 2001-202822 (Patent Document 1) and Korean Patent Publication No. 2004-0025609 (Patent Document 2) A paste of the analog is used as a prior art document relating to the paste for the back electrode 30. In addition, a paste containing a silver powder, a glass raw material, an organic material (resin binder), and the like is disclosed in Korean Patent Publication No. 2007-0066938 (Patent Document 3) and Korean Early Public Publication No. 2007-0067636. Patent Publication No. 4 (Patent Document 4) and Patent Publication No. 2007-0084100 (Patent Document 5) of the Korean Patent Publication No. 2007-0084100, the entire disclosure of which is related to the prior art relating to the use of the paste as the front electrode 20. file. As suggested in these prior patent documents, the glass raw material is used as an inorganic sintering agent having a low melting point as a lead-containing component. The lead component lowers the melting point of the glass raw material to improve the adhesion of the conductive metal (such as silver and aluminum) to the semiconductor substrate 10, whereby the wiring strength of the electrodes 20 and 30 can be improved. In particular, in the case of the paste for the front electrode 20, the lead component contained in the glass raw material penetrates into the tantalum nitride (Si3N4) film layer (anti-reflective coating layer 12) to be made with tantalum nitride (Si3N4). The film layer becomes a contact. Specifically, the lead component corrodes the anti-reflective coating 12 in response to the tantalum nitride during sintering, so that the Ag electrode penetrates into the anti-reflective coating layer 12 to thereby make ohmic contact with the n-type tantalum layer 10a. Therefore, the glass raw material containing the lead component is used as a glass raw material in the paste for the electrodes 20 and 30. In particular, the paste for the front electrode 20 contains a lead component because the lead component functions as a penetrating agent for forming an ohmic contact with the n-type tantalum layer 10a. _ However, since the paste contains a considerable amount of harmful lead components, the paste for the electrodes 20 and 30 according to the prior art including the aforementioned patent documents causes serious environmental problems. Specifically, although the lead component is included in the front electrode 20 intrinsically, only when the content of the lead component contained in the glass raw material is quite large, the front electrode exhibits a tradition as a wearer because it contains a lead component. The role of the agent. For example, Patent Document 5 proposes a paste comprising a glass raw material in an amount of 1 to 15% by weight (wt%) based on the total solid content, and Pb and 5 in a glass raw material having a percentage of 15 to 75 mol% (% by mole). Up to 50 mole percent (% by mole) of Si〇2. 6重量百分比 (wt%) When the amount of the component of the weight component is about 14.6% by weight (wt%). Therefore, according to the prior art paste for electrodes, there is a drawback of causing serious environmental problems due to the high content of harmful lead. [Patent Document 1] Patent Publication No. 2001-202822 [Patent Document 2] Korean Patent Laid-Open Publication No. 2004-0025609 (Patent Document 3) Korean Patent Early Publication No. 2007-0066938 Patent Publication No. [Patent Document 4] Patent Publication No. 2007-0067636 [Patent Document 5] Patent Publication No. 2007-0084100 [Patent Document] [Technical Problem] The present invention is conceived to solve the problems in the prior art described above. It is an object of the present invention to provide a paste for a solar cell electrode that minimizes the harmful Pb content, thereby enabling environmentally friendly solar cell electrodes to be fabricated with low series resistance (Rs) and high shunt A resistor (Rsh), and a solar cell using a paste for a solar cell electrode. In particular, it is an object of the present invention to provide a paste for an environmentally friendly solar cell electrode, wherein the paste contains a low amount of harmful lead component and penetrates the antireflective coating (Si3N4 film) during heat treatment to allow the electrode to be half 6 94679 201005756 • Conductor substrate (N-type germanium layer) has excellent bonding strength, thereby having low series resistance and shunt resistance, and providing a solar cell using a paste for environmentally friendly solar cell electrodes as a front electrode. [Technical Solution] In order to achieve the above object, the present invention provides a paste for a solar cell electrode, comprising a solid component and a dispersion medium, wherein the solid component comprises at least one conductive powder selected from the group consisting of a metal and a metal-containing compound; A glass raw material containing no lead component; and a lead component particle having a particle size of i to 丨, 〇〇〇 nanometer (nm) ❹. The preferred particle size of the lead component particles is from 1 to 2 nanometers. For example, at least one selected from the group consisting of lead (pb), lead alloy, and lead oxide (Formula 1 below) can be used as the lead component particles. Furthermore, the present invention provides a paste for a solar cell electrode comprising a solid component and a dispersion medium 'wherein the solid component comprises at least one of a conductive powder selected from the group consisting of a metal and a metal-containing compound; and a glass raw material containing no lead component; And a complex selected from the group consisting of lead alkoxide (hereinafter referred to as formula 2), poiycondensuion polymer (the following formula 3), and cold-double-diketones (the following formula) 4) at least one of the lead component compounds. Further, the solid component further contains a wire (Bi) component. Here, the New Zealand component is selected from at least one of a metal and a compound containing a secret. For example, the secret ingredient is selected from the group consisting of ruthenium, osmium alloy, iridium oxide (Formula 5 below), decyl alkoxide (Formula 6 below), ruthenium polycondensation polymer (Formula 7 below), and ruthenium and dots ~ double At least one of a complex of a ketone (Formula 8 below). If the silk component (such as a single metal 'antimony alloy, and the cerium oxide (the following formula 5) is in the form of a granule 7 94679 201005756, these granules are 1 to 1,000 nm in size, and more preferably 1 The weight of the lead-free glass material; and 0.10 by weight of the lead-free glass raw material; and 0.10, the weight of the conductive material is preferably from 40.0 to 90.0 parts by weight; To a weight ratio of 0.1 to 3.0 parts by weight of a ruthenium or osmium compound. Further, the present invention provides a solar cell comprising a semiconductor substrate; An anti-reflective coating on top of the semiconductor substrate; a front germanium electrode that is in contact with the semiconductor substrate after being formed on top of the anti-reflective coating; and a back electrode formed on the bottom of the semiconductor substrate, wherein the front electrode It is a sintered body of a paste according to the present invention. [Effect of the Invention] According to the present invention, the content of a harmful lead component can be minimized. Specifically, according to the present invention, a paste for a solar cell electrode is not contained in glass a lead component in a raw material state, but contains a miscomponent of a nanometer size (preferably 200 nm or less) as a separate component, or a lead component containing a compounded form represented by the following formulas 2 to 4, so although lead The composition is low in use, but the surface area of the wrong component is increased, and its activity (such as, for example, reactivity) is also improved, thereby obtaining excellent penetration effect of the antireflection coating and improving the semiconductor substrate during the heat treatment. The strength of the bond. Therefore, according to the present invention, it is advantageous in that it is possible to manufacture an environmentally friendly electrode because the consumption of the lead component can be reduced to less than half of its conventional consumption, and the reinforcing effect by penetrating the antireflection coating And improved bonding strength with the semiconductor substrate, by obtaining low series resistance (Rs) and high shunt resistance (Rs 〇 8 94679 201005756 / improving the electrical properties of the solar cell. Furthermore, according to the present invention, by forming a tight The electrode of the (compact) structure can exhibit excellent electrical conductivity. [Embodiment] The following will be described in detail with respect to the present invention. A paste for a solar cell electrode comprising a solid body component and a dispersion medium for dispersing a solid component. The solid component comprises a conductive powder and a lead-free glass material which is an inorganic sintering agent for bonding the conductive powder to the semiconductor substrate. And a lead component that acts as an osmotic contact with the anti-caries reflective coating as a penetrating agent in the sintering process. The conductive powder is at least one selected from the group consisting of a metal and a metal-containing compound, wherein the metal comprises a single metal and an alloy. And the metal-containing compound comprises a metal oxide and a metal salt. For example, the conductive powder is silver (Ag), copper (Cu), gold (An), turn (Pt), Ilu (A1) or A mixture or alloy of at least two. Further, the conductive powder is a metal-containing compound and may be selected from, for example, an oxide of silver or silver, or a salt of silver or silver (including organic or inorganic salts). Such a conductive powder may be contained in the paste in the form of spherical or flaky particles or in the form of a colloid in which the spherical or flaky particles are dispersed. Further, the particles may be used as a conductive powder selected from the aforementioned metal or metal-containing compound and coated with an organic material. Preferably, silver, a silver alloy, a silver compound (a silver oxide or a salt of silver), and the like can be used as a conductive powder for the front electrode of a solar cell. For example, the silver compound contains an oxide of silver such as silver oxide (Ag2〇), and the salt of silver contains, for example, silver chloride (AgCl), silver nitrate (AgNOs), and silver acetate (AgOOCCHs). Most preferably, silver particles are used as the conductive powder for the electrodes of the 9 94679 201005756 solar cell. Further, aluminum, an aluminum alloy, an aluminum compound (aluminum oxide or a salt of aluminum) can be preferably used as the conductive powder of the back electrode of the solar battery. The conductive powder has a particle size of 〇1 to 30. 0 μm (μπι), and since the particle size of the conductive powder is excellent in sintering characteristics, the conductive phase preferably has a particle size of 100 to 500 nm. .重量。 The conductive powder in the total solid content of the weight, that is, 100 parts by weight of the solid component, preferably containing 40.0 to 99.0 weight points. The content of the conductive powder of less than 40 parts by weight is not preferred 'because its conductivity is decreased by j and the conductive powder content exceeds 99. The weight fraction is not preferred, because the content of the complement and the wrong component of the glassy soil is relatively The ground is reduced, and the effect caused by people ^ is also expected to be obvious. More preferably, the total solids component weight is 7 〇 to 99. 〇 Weight component content According to the present invention, no summer mash containing no wrong component is used. Any glass material which can be sintered by reduction and which does not correct the composition but contains at least the component (Si) can be used. : Say 'The glass raw material contains Si〇2-based glass secret, Si〇7-based glass raw material (SbZn_◦ based glass raw material), Si based (J n0 based glass raw material (Sl|〇 based glass raw material) And a glass raw material based on ^ 2 (a glass raw material based on sb Bi_〇), wherein the glass raw material means a glass raw material containing Si 〇 2 as a main component, and the surface raw material based on Si 〇 2 ZnO means containing Si (four) The glass raw material which is the main component and the second auxiliary component, in addition to the main component and the sapphire raw material, may contain an oxide as another component. This 94647 10 201005756. Some oxides are selected from the group consisting of Ah 〇
In2〇3、G述、Y2〇3、和 Μ/』5 Sb2〇5、ZrC)2、_、 T 1D2U3之一者或客土 •該玻璃原料較佳具有低炫 電粉末使用，則該_原料較佳言，若銀當作導 ^ 、 权1"•具有450至55(TC之軟化 點(S〇fteningP〇int)。當銀當作導電粉末使用時熱處理 (繞結）可在，約600至80(rc的溫度範圍中進行。此處，因 •為當玻璃原料的軟化點低於45代時，破璃原料會很快速 地融熔，所以對銀燒結是困難的，然而由於當玻璃原料之 〇軟化點高於45(TC時，良好的玻璃原料的融溶與流動尚未 產生，所以銀與半導體基底可能不會展現出良好的結合強 度。 此外’該玻璃原料佔總固體成分之重量，即固體成分 白勺1〇〇重量分中，較佳者為含有〇.u57.〇重量分。因 為結合強度降低使得玻璃原料難以尋求與半導體某底之^ 好結合強度，所以其含有之玻璃原料含量低於o f重 ❹並非是較佳的’而且由於過量的玻璃原料其效果不佳而導 電粉末與敍成分的含量也會相對地降低，以致包a它們所 :丨起的效果並不明顯’所以含量超過57. 〇重量分二玻璃原 枓不是較佳的。更佳地是，所包含該坡鴇原料佔總固體成 分重量的含量為1. 0至20. 0重量分。 ~ 根據本發明’該錯成分不以内含於破螭原料的形式存 在於膏中，而是作為一個單獨的成分内含。此—^成八功 能為穿透抗反射塗層（ShN4薄膜）之穿透劑，以與=導 底（N型矽層）成為歐姆接觸。 94679 11 201005756 根據本發明的第一種形式，該鉛成分係選自尺寸為1 至1,000奈米（nm)的顆粒。該鉛成分顆粒（其顆粒大小為1 至1,000奈米）為選自鉛及含鉛之化合物的至少其中一 者。該鉛成分顆粒較佳具有1至200奈米的尺寸。在這裡， 鉛包含單一鉛金屬及鉛合金，而含鉛之化合物則包含鉛的 氧化物與鉛的鹽類。此處，以下列式1表示之鉛的氧化物 可有效地用作為含有鉛之化合物使用。 [式1]In2〇3, G, Y2〇3, and Μ/』5 Sb2〇5, ZrC)2, _, T 1D2U3 or the guest soil • The glass material is preferably used with low sleek powder, then _ The raw material is better, if silver is used as the guide, the weight 1 "• has 450 to 55 (TC softening point (S〇fteningP〇int). When silver is used as a conductive powder, heat treatment (winding) can be 600 to 80 (in the temperature range of rc. Here, because when the softening point of the glass raw material is lower than 45 generations, the glass raw material will melt very quickly, so it is difficult to silver sintering, however When the softening point of the glass raw material is higher than 45 (TC, the melting and flow of good glass raw materials have not yet been produced, so the silver and the semiconductor substrate may not exhibit good bonding strength. In addition, the glass raw material accounts for the total solid content. The weight, that is, the weight fraction of the solid content of 1 ,, preferably contains 〇.u57. 〇 by weight. Because the bonding strength is lowered, it is difficult for the glass raw material to seek a good bonding strength with a semiconductor substrate, so it contains Glass raw material content is less than that of heavy weight is not preferred 'and because Excessive glass raw materials have a poor effect and the content of conductive powder and the composition of the composition is relatively lowered, so that the package a: the effect of lifting is not obvious 'so the content exceeds 57. 〇 weight is not the same as the original glass Preferably, the content of the raw material of the sorghum is from 1.0 to 20. 0 parts by weight. ~ According to the invention, the wrong component is not present in the form of the raw material. In the paste, but as a separate component. This is a penetrating agent that penetrates the anti-reflective coating (ShN4 film) to make ohmic contact with the = bottom (N-type layer). 94679 11 201005756 According to a first form of the invention, the lead component is selected from particles having a size of from 1 to 1,000 nanometers (nm). The lead component particles (having a particle size of from 1 to 1,000 nm) are selected from the group consisting of At least one of lead and a lead-containing compound. The lead component particles preferably have a size of from 1 to 200 nm. Here, lead contains a single lead metal and a lead alloy, and the lead-containing compound contains a lead oxide. Salt with lead. Here, the following formula The oxide of lead represented by 1 can be effectively used as a compound containing lead.
PbpOcHr 其中p和q是大於0的整數或質數，而r是0或大於0的 整數或質數。 再者，根據本發明的第二種形式，選自以下列式2表 示之錯醇鹽（lead alkoxide)、以下列式3表示之錯聚縮合 聚合物（lead polycondensation polymer)、以及以下列式 4表示之鉛的；5 _雙酮錯合物的至少一個鉛成分化合物係 可作為鉛成分使用。 [式2 ]PbpOcHr where p and q are integers or prime numbers greater than 0, and r is 0 or an integer or prime number greater than zero. Further, according to the second form of the present invention, a lead alkoxide represented by the following formula 2, a lead polycondensation polymer represented by the following formula 3, and the following formula 4 are selected. At least one lead component compound of the 5 _ diketone complex can be used as a lead component. [Formula 2]
Pba(0R)b 其中R是氫或烴，且a和b是大於0的整數或質數， [式3]Pba(0R)b wherein R is hydrogen or a hydrocarbon, and a and b are integers or prime numbers greater than 0, [Formula 3]
Pbx0y(0R)z 其中R是氫或烴、而x、y和z是大於0的整數或質數，及 12 94679 201005756 [式 4]Pbx0y(0R)z wherein R is hydrogen or a hydrocarbon, and x, y and z are integers or prime numbers greater than 0, and 12 94679 201005756 [Formula 4]
Q. Ο II IIQ. Ο II II
其中R和R’是氫或煙。 在式2至4中，當R和R’是烴時，它們可為具有各 種不同官能基之烴，像是直鏈之烷基、芳香基及其類似物。 然而，它們並不受限於此。 再者，本發明中，鉛成分係選自於前述之鉛成分顆粒 ❹的至少一者、選自於該鉛成分化合物（即以式2及3表示之 化合物，及錯和以式4表示之化合物的錯合物）的至少一 者、或鉛成分顆粒和鉛成分化合物的混合物（即以式2及3 表示之化合物，及錯和以式4表示之化合物的錯合物）。具 體而言，該鉛成分為鉛、鉛合金、式1表示之鉛的氧化物、 式2表示的錯醇鹽（lead alkoxide)、式3表示之船聚縮 合聚合物（lead poly condensation polymer)、式 4 表示之 鉛與β _雙酮的錯合物，或其中至少二者之混合物。舉例 〇 來說，該鉛成分係選自於式1表示之鉛的氧化物、式2表 示之敍醇鹽、式3表示之錯聚縮合聚合物、式4表示之船 與石一雙酮的錯合物、式1表示之錯的氧化物與式3表示 之鉛聚縮合聚合物的混合物、以及式1表示之鉛的氧化物 與式4表示之鉛與—雙酮的錯合物的混合物的其中一 者。 鉛成分的功能為完成本發明目的之要件。具體而言， 該錯成分已改良了表面積、反應性（react i vi ty)以及極佳 13 94679 201005756 的燒結特性，藉由讓膏以與此膏中所内含之玻璃原料分離 ' 的形式包含鉛成分來得到之優良的活性，而該鉛成分是呈 顆粒形式，尺寸不超過1，000奈米，較佳則不超過200奈 米；或是呈以各式表示的化合物形式（即以式2和3表示之 化合物、及錯與式4表示之化合物的錯合物）。更具體而 言，此膏包含與該玻璃原料分離、呈顆粒或以各式表示的 化合物形式之鉛成分，所以，即使鉛成分僅少量的使用， 藉由改良此膏的表面積及反應性，也能獲得對於抗反射塗 層（ShN4薄膜）的鉛成分極佳之穿透性；並藉由改良燒結特 © 性，獲得與半導體基底極佳的結合強度。此外，由於極佳 的穿透性與結合強度所導致之低串聯電阻（Rs)和高分路電 阻（Rsh)，電池的電性能表現也得到了改良。因此，因為有 害的鉛成分的含量降至最低，所以能夠製造環保電極並改 良電池的電性能表現。具體而言，鉛成分的消耗能降低至 不超過先前技術消耗量的一半。 雖然期望儘可能地降低所包含的鉛成分（鉛成分顆粒 _ ❹ 及鉛成分化合物），但是若鉛成分的含量太低，將很難以獲 得對於抗反射塗層（ShN4薄膜）極佳之穿透性以及經改良 之與半導體基底的結合強度。在該膏中之鉛的總含量較佳 是佔總固體成分之重量（即固體成分的100重量分）中的 0. 1至3.0重量分，更佳為0. 1至1.5重量分。因為穿透 性與結合強度可能均不好，所以鉛成分的含量低於0. 1重 量分並非是較佳的，且由於過量導致錯成分的效果不佳且 含量過量就環境而言也非所欲，所以鉛成分的含量超過 14 94679 201005756 3. 0重量分也不是較佳的。 此外，根據本發明的另一實施例，固體成分可復包含 鉍成分。鉍成分的作用如鉛成分為抗反射塗層（Si3K薄膜） 的穿透劑，藉以支持鉛成分。根據本發明，鉍成分扮演著 與鉛成分相同的角色（即抗反射塗層的穿透劑），所以鉛成 分的含量可藉由含有絲成分而進一步最小化。 該絲成分選自叙:與含银之化合物。錢包含單一银金屬 及鉍合金，而含鉍之化合物舉例來說，包含下列式代表的 ©錢的氧化物、祕醇鹽（bismuth alkoxide)，錢聚縮合聚合 物（bismuth polycondensation polymer)、及祕與；5 —雙 酮之錯合物。 具體而言，下列式5表示之鉍的氧化物可有用地作為 錢成分使用。 [式5]Wherein R and R' are hydrogen or fumes. In the formulae 2 to 4, when R and R' are hydrocarbons, they may be hydrocarbons having various different functional groups such as a linear alkyl group, an aromatic group and the like. However, they are not limited to this. Furthermore, in the present invention, the lead component is selected from at least one of the lead component particles 、, and is selected from the lead component compound (that is, the compound represented by Formulas 2 and 3, and the wrong combination is represented by Formula 4. At least one of the compound complexes or a mixture of the lead component particles and the lead component compound (that is, a compound represented by Formulas 2 and 3, and a complex of the compound represented by Formula 4). Specifically, the lead component is lead, a lead alloy, an oxide of lead represented by Formula 1, a lead alkoxide represented by Formula 2, and a lead poly condensation polymer represented by Formula 3, Formula 4 represents a complex of lead and β-dione, or a mixture of at least two of them. For example, the lead component is selected from the group consisting of an oxide of lead represented by Formula 1, a sodium alkoxide represented by Formula 2, a mispolymerized condensation polymer represented by Formula 3, and a ship and a diketone represented by Formula 4. a mixture of the complex compound, the oxide represented by Formula 1 and the lead polycondensation polymer represented by Formula 3, and the oxide of lead represented by Formula 1 and the complex of lead and diketone represented by Formula 4 One of them. The function of the lead component is to fulfill the objectives of the present invention. Specifically, the wrong component has improved surface area, reactivity, and excellent sintering characteristics of 13 94679 201005756, including by allowing the paste to be separated from the glass raw material contained in the paste. Lead component to obtain excellent activity, and the lead component is in the form of particles, the size does not exceed 1,000 nm, preferably does not exceed 200 nm; or is in the form of a compound expressed by various formulas (ie, by Formula 2) And a compound represented by 3 and a complex of a compound represented by Formula 4). More specifically, the paste contains a lead component which is separated from the glass raw material and is in the form of a granule or a compound represented by each formula. Therefore, even if the lead component is used only in a small amount, by improving the surface area and reactivity of the paste, Excellent penetration of the lead component of the anti-reflective coating (ShN4 film) can be obtained; and by improving the sintering characteristics, excellent bonding strength with the semiconductor substrate can be obtained. In addition, the electrical performance of the battery has been improved due to the excellent series resistance (Rs) and high shunt resistance (Rsh) due to excellent penetration and bonding strength. Therefore, since the content of the harmful lead component is minimized, it is possible to manufacture an environmentally friendly electrode and improve the electrical performance of the battery. Specifically, the consumption of the lead component can be reduced to less than half of the prior art consumption. Although it is desirable to reduce the lead component (lead component particles _ ❹ and lead component compounds) as much as possible, if the content of the lead component is too low, it will be difficult to obtain excellent penetration into the antireflection coating (ShN4 film). And the improved bonding strength to the semiconductor substrate. 1至1.5重量分。 The total amount of lead in the paste is preferably from 0.1 to 3.0 parts by weight, more preferably from 0.1 to 1.5 parts by weight, based on the total solid content (i.e., 100 parts by weight of the solid component). Since the penetrability and the bonding strength may not be good, the content of the lead component is less than 0.1 part by weight, and the effect of the wrong component due to the excess is not good and the content is excessive. Desire, so the content of lead components exceeds 14 94679 201005756 3. 0 weight points are not preferred. Further, according to another embodiment of the present invention, the solid component may further comprise a bismuth component. The action of the bismuth component, such as the lead component, is a penetrating agent for the anti-reflective coating (Si3K film) to support the lead component. According to the present invention, the bismuth component plays the same role as the lead component (i.e., the penetrating agent of the antireflective coating), so the content of the lead component can be further minimized by containing the silk component. The silk component is selected from the group consisting of: a compound containing silver. The money contains a single silver metal and a niobium alloy, and the niobium-containing compound includes, for example, an oxide of the formula represented by the following formula, a bismuth alkoxide, a bismuth polycondensation polymer, and a secret. And 5; diketone complex. Specifically, an oxide of cerium represented by the following formula 5 can be usefully used as a money component. [Formula 5]
Bip〇qHr ^ 其中ρ和q是大於0的整數或質數，而r是0或大於 ❹ 0的整數或質數。 再者，下列式6表示之鉍醇鹽可有用地作為鉍成分使 用。 [式6]Bip〇qHr ^ where ρ and q are integers or prime numbers greater than 0, and r is 0 or an integer or prime greater than ❹ 0. Further, the oxime salt represented by the following formula 6 can be usefully used as a quinone component. [Equation 6]
Bia(0R)b 其中R是氫或烴，而a和b是大於0的整數或質數。 再者，下列式7表示之鉍聚縮合聚合物可有用地作為 叙成分使用。 15 94679 201005756 [式7]Bia(0R)b wherein R is hydrogen or a hydrocarbon, and a and b are integers or prime numbers greater than zero. Further, the fluorene condensation polymer represented by the following formula 7 can be usefully used as a component. 15 94679 201005756 [Formula 7]
Bix0y(0R)z 其中R是氫或烴、而x、y和z是大於0的整數或質 數。 再者，下列式8之鉍與雙酮的錯合物可有用地作為鉍 成分使用。 [式8] 0 0Bix0y(0R)z wherein R is hydrogen or a hydrocarbon, and x, y and z are integers or prime numbers greater than zero. Further, a complex of hydrazine with a diketone of the following formula 8 can be usefully used as a quinone component. [Equation 8] 0 0
r )|·. II "· ' Zt ·· 其中R和R’是氫或烴。 在式6至8中，當R和R’是烴時，它們可為具有各 種不同官能基的烴，如直鏈之烷基、芳香基及類似物。然 而，它們並不受限制於此。 在本發明中，叙：、叙:合金、式5表示之叙的氧化物、 式6表示之叙醇鹽、式7表示之錢聚縮合聚合物（bismuth polycondensation polymer)、式 8 表示之祕與 /5 —雙酮 的錯合物、或其中至少兩者之混合物均可有用地作為鉍成 分使用。具體而言，錢、叙合金、式5表示之絲的氧化物， 式6表示之祕醇鹽、式7表示之絲聚縮合聚合物、叙與式 8表示之化合物與錯合物、絲與式5表示之级的氧化物的 混合物、或式5表示之叙的氧化物與式7表示之叙聚縮合 聚合物的混合物均可作為鉍成分使用。 由於顆粒般之上述鉛成分會增加活性並改良燒結特 201005756 -性，所以當絲成分是呈顆粒的形式時，需要錢成分為奈米 大小的顆粒。舉例來說，當鉍成分呈顆粒形式時，像是單 一祕金屬、叙:合金、及式5之紐的氧化物，銀成分較佳為 1至1, 000奈米尺寸的顆粒，更佳為1至200奈米。再者， 因為即使當鉍成分為化合物（像是式6之鉍醇鹽、式7之鉍 聚縮合聚合物、及祕與式8之化合物尚錯合物）時，其活性 • 仍會增加，使得鉍成分獲得對於抗反射塗層極佳的穿透性 以及與半導體基底改良的結合強度。 © 在該膏中之鉍的總含量較佳是佔總固體成分之重量 (即固體成分的100重量分）中的0.1至3.0重量分。鉍成 分的含量低於0. 1重量分並不是較佳的，因為會很難協助 鉛成分（即尋求穿透性與結合強度的改良），且由於過量會 導致叙成分的效果不佳，所以絲成分的含量超過3.0重量 分也不是較佳的。缺的總含量更佳者是佔總固體成分之重 量的0. 1至1. 5重量分。 _ 如上所述，根據本發明之一種用於電極的膏包含固體 ❹ 成分和分散固體成分的分散媒介，其中任何能夠分散固體 成分之分散媒介均可使用。雖然分散媒介不特別受限，但 是分散媒介可以固體成分對分散媒介1:0.05至60.0的重 量比内含。該分散媒介舉例來說，至少包含水、有機溶劑 如酒精、二醇類、以及其類似物。可進一步包含用於改良 該固體成分的可分散性之分散媒介。舉例來說，該分散媒 介包含烷基胺、羧酸醯胺、胺基羧酸鹽、檸檬酸鹽，及其 類似物。然而，該分散媒介並不受限於此。 17 94679 201005756 此外，除了固體成分和分散媒介之外，根據本發明之 ~ 用於電極的膏可復包含樹脂黏結劑、添加劑和通常使用之 類似物。該樹脂黏結劑可選自於有機材料。雖然不是特定 地限制’但該樹脂黏結劑舉例來說包括聚曱基丙烯酸酯 (polymethacrylate)、乙基纖維素、乙基羥乙基纖維素 (ethyl hydroxy ethyl cel lulose)、松月旨、乙二醇單丁謎 單乙酸酯（ethylene glycol monobutyl ether monoacetate)，及類似物。此外，該添加劑含有穩定劑、 黏度調節劑及類似物，而特定之該添加劑的類型可選自從 ❹ 通常用於本領域技術者。 上述根據本發明之用於電極的膏可具有10至500 Pa · s之黏度而且可作為太陽能電池的前與背電極使用。 尤其是，此膏可有用地作為太陽能電池的前電極使用。根 據本發明之用於電極的膏可於太陽能電池之半導體基底 (更明確說是在抗反射塗層上）上透過印刷技術而圖案化。 此印刷技術包含網印法（screen printing)，軋親印刷 ❹ (roll-to-roll)，凹版印刷（gravure printing)、偏版印 刷（offset printing)、喷墨印刷，及其類似技術。該前電 極較佳在格狀的格柵圖案中形成。在這圖案化之後，需要 使經圖案化的膏受到600至800°C溫度之熱處理藉以使其 燒結。 同時，根據本發明之太陽能電池的前電極包含上述根 據本發明之膏的燒結體。 具體而言，根據本發明之太陽能電池包含：半導體基 18 94679 201005756 -底；敷設於該半導體基底之頂部之抗反射塗層；前電極， 其形成於抗反射塗層之頂部上之後經過燒結而與該半導體 基底接觸；以及背電極，其形成於該半導體基底（矽晶圓） ‘的底部上，其中該前電極是上述本發明的膏之燒結體。 該半導體基底及抗反射塗層可以普通之方法形成。同 • 時’背電極可以藉由燒結普通的鋁膏或前述本發明的膏而 .形成。 以下，本發明將經過實例和比較例更進一步詳細地說 β明。然而，下面的諸實例只是提供用來幫助了解本發明， 本發明非受限於下面諸實例。 [製備例1 ]-銀粉末 製備了具200奈米之平均粒度之球狀的銀粉末（導電 金屬粉末），其購自位於Buyong工業綜合大樓之先進奈米 產品公司（Advanced Nano Products Co.，Ltd，地址 Kumho-ri ， Buyong-myeon ， Chungwon-kun ， Chung 參cheongbuk-do，韓國），其表面塗佈有機材料。該銀粉末之 照片顯示於第2圖。 [製備例2]- Pb(0H)2*散溶液 藉由執行Pb(0H)2奈米粉末之球磨（bal 1-mi 11 ing)程 序使用甲苯為溶劑配成30wt%濃度，製備一種平均分散粒 度為50奈米之Pb(0H)2分散溶液，該Pb(0H)2奈米粉末講 自位於Buyong工業綜合大樓之先進奈米產品公司 (Advanced Nano Products Co.，Ltd，地址 Kumho-ri， Buyong-myeon ， Chungwon-kun ， Chung cheongbuk-do ，韓 19 94679 201005756 國）°Pb( OH)2奈米粉末的好處在於，當以球磨程序從 .r )|·. II "· ' Zt ·· where R and R' are hydrogen or a hydrocarbon. In the formulae 6 to 8, when R and R' are hydrocarbons, they may be hydrocarbons having various different functional groups such as a linear alkyl group, an aromatic group and the like. However, they are not limited to this. In the present invention, the alloy, the oxide represented by the formula 5, the alkoxide represented by the formula 6, the bismuth polycondensation polymer represented by the formula 7, and the secret of the formula 8 /5 - a complex of a diketone, or a mixture of at least two thereof, can be usefully used as a bismuth component. Specifically, the sugar, the alloy, the oxide of the filament represented by the formula 5, the alkoxide represented by the formula 6, the silk polycondensation polymer represented by the formula 7, the compound and the complex represented by the formula 8, and the silk and A mixture of oxides of the formula represented by Formula 5 or a mixture of the oxides represented by Formula 5 and the depolymerized condensation polymer represented by Formula 7 can be used as the rhodium component. Since the above-mentioned lead component in the form of particles increases the activity and improves the sintering property, when the silk component is in the form of particles, it is required that the money component is a nanometer-sized particle. For example, when the bismuth component is in the form of particles, such as a single metal, an alloy, and an oxide of the formula 5, the silver component is preferably a particle having a size of 1 to 1,000 nm, more preferably 1 to 200 nm. Furthermore, even when the hydrazine component is a compound (such as the oxime alkoxide of the formula 6, the fluorene condensation polymer of the formula 7, and the compound of the formula 8), the activity of the compound is increased. The niobium component is made to have excellent penetration to the antireflective coating and improved bonding strength to the semiconductor substrate. The total content of ruthenium in the paste is preferably from 0.1 to 3.0 parts by weight based on the total solid content (i.e., 100 parts by weight of the solid content). The content of the bismuth component is less than 0.1% by weight, which is not preferable because it is difficult to assist the lead component (i.e., improvement in penetration and bonding strength is sought), and the excessive effect may result in poor effect of the composition. A content of the silk component of more than 3.0 parts by weight is also not preferable. 5重量分。 The total weight of the total weight of the total weight of the total weight of 0. 1 to 1. 5 weight points. As described above, a paste for an electrode according to the present invention comprises a solid ❹ component and a dispersion medium for dispersing a solid component, and any dispersion medium capable of dispersing a solid component can be used. Although the dispersion medium is not particularly limited, the dispersion medium may contain a weight ratio of the solid component to the dispersion medium of 1:0.05 to 60.0. The dispersion medium, for example, contains at least water, an organic solvent such as alcohol, glycols, and the like. A dispersion medium for improving the dispersibility of the solid component may be further included. For example, the dispersing medium comprises an alkylamine, a guanamine amide, an aminocarboxylate, a citrate, and the like. However, the dispersion medium is not limited to this. 17 94679 201005756 Further, in addition to the solid component and the dispersion medium, the paste for the electrode according to the present invention may further comprise a resin binder, an additive, and the like which are generally used. The resin binder may be selected from organic materials. Although not specifically limited 'but the resin binder includes, for example, polymethacrylate, ethyl cellulose, ethyl hydroxy ethyl cel lulose, 松月, ethylene glycol. Ethylene glycol monobutyl ether monoacetate, and the like. Further, the additive contains a stabilizer, a viscosity modifier, and the like, and the type of the additive may be selected from those generally used in the art. The above-described paste for an electrode according to the present invention may have a viscosity of 10 to 500 Pa·s and can be used as a front and back electrode of a solar cell. In particular, this paste can be usefully used as the front electrode of a solar cell. The paste for electrodes according to the present invention can be patterned by printing techniques on a semiconductor substrate of a solar cell, more specifically on an anti-reflective coating. This printing technique includes screen printing, roll-to-roll, gravure printing, offset printing, ink jet printing, and the like. The front electrode is preferably formed in a grid pattern. After this patterning, the patterned paste needs to be subjected to a heat treatment at a temperature of 600 to 800 ° C to cause it to be sintered. Meanwhile, the front electrode of the solar cell according to the present invention contains the sintered body of the above-described paste according to the present invention. Specifically, the solar cell according to the present invention comprises: a semiconductor substrate 18 94679 201005756 - a bottom; an anti-reflective coating applied to the top of the semiconductor substrate; a front electrode formed on the top of the anti-reflective coating and then sintered Contacting the semiconductor substrate; and a back electrode formed on the bottom of the semiconductor substrate (矽 wafer), wherein the front electrode is the sintered body of the paste of the present invention described above. The semiconductor substrate and the anti-reflective coating can be formed in a conventional manner. The same time can be formed by sintering a conventional aluminum paste or the aforementioned paste of the present invention. Hereinafter, the present invention will be further described in detail by way of examples and comparative examples. However, the following examples are merely provided to aid in understanding the invention, and the invention is not limited to the following examples. [Preparation Example 1] - Silver powder A spherical silver powder (conductive metal powder) having an average particle size of 200 nm was prepared, which was purchased from Advanced Nano Products Co., located in Buyong Industrial Complex. Ltd., address Kumho-ri, Buyong-myeon, Chungwon-kun, Chung ginseng cheongbuk-do, Korea), whose surface is coated with organic materials. A photograph of the silver powder is shown in Fig. 2. [Preparation Example 2] - Pb(0H)2* dispersion solution was prepared by performing a ball milling (PB1-mi 11 ing) procedure of Pb(0H)2 nano powder using a toluene solvent to prepare a concentration of 30% by weight to prepare an average dispersion. Pb(0H)2 dispersion solution having a particle size of 50 nm, which is from Advanced Nano Products Co., Ltd., located in Kumho-ri, Buyong Industrial Complex. Buyong-myeon, Chungwon-kun, Chung cheongbuk-do, Han 19 94679 201005756) The advantage of Pb(OH)2 nano powder is that when using a ball milling procedure.
Pb(OH)2奈米粉末製得該分散溶液時，可使其於膏的製備過 程中均勻地分散於該膏中。作為溶劑使用之甲笨不存於該 膏中，因為大部分於的曱苯於該膏的製備過程中使用三輥 研磨機（three-roll mi 11)時即已揮發。該包含奈米大小分 散顆粒之Pb(0H)2分散溶液的照片顯示於第3圖。 [製備例3]-鉛錯合物（乙醯丙酮鉛（II)) · 使用購自美國的Sigma Aldrich公司之乙醯丙g同鉛 (II)粉末。所購買的粉末經幾次清洗後於室溫下乾燥。粉 ❿ 末中的鉛含量經確認為51. 107%。 [製備例4]- Bi(0H)3分散溶液 以最初平均粒度（primary average particle size) 為50奈米之Bi(OH)3奈米粉末的球磨程序使用甲苯為溶劑 配成25wt%濃度，製備一種平均分散粒度為8〇奈米之 Bi(0H)3分散溶液’該Bi(〇H)3奈米粉末購自位於Buyong 工業細合大樓之先進奈米產品公司（ANP，Advanced Nano ❹When the Pb(OH)2 nanopowder is used to prepare the dispersion solution, it can be uniformly dispersed in the paste during the preparation of the paste. The use of the solvent as a solvent is not present in the paste because most of the toluene has volatilized when a three-roll mill 11 (three-roll mi 11) is used in the preparation of the paste. A photograph of the Pb(0H)2 dispersion solution containing nano-sized dispersed particles is shown in Fig. 3. [Preparation Example 3] - Lead complex (acetonitrile lead (II)) - A powder of lead (II) powder from Sigma Aldrich Co., Ltd., USA was used. The purchased powder was washed several times and then dried at room temperature. The lead content in the powder was confirmed to be 51.107%. [Preparation Example 4] - Bi(0H)3 dispersion solution was prepared by a ball milling procedure of a Bi(OH)3 nanometer powder having a primary average particle size of 50 nm using a toluene solvent to prepare a concentration of 25 wt%. A Bi(0H)3 dispersion solution having an average dispersed particle size of 8 nanometers. The Bi(〇H)3 nano powder was purchased from Advanced Nano Products Co., Ltd. (ANP, Advanced Nano ❹) located in Buyong Industrial Building.
Products Co.，Ltd ’ 地址 Kuinho_ri，Buyong_niyeon， Chungwon-kun ’ Chung cheongbuk-do，韓國）〇 Bi(0H)3奈 米粉末的好處在於，當以球磨程序從奈米粉末製 得該分散溶液時，可使其於膏的製備過程中均勻地分散於 該膏中。作為溶劑使用之曱苯不存於該紊中，因為大部分 於的甲笨於該膏的製備過程中使用三幸昆筒磨粉機時即已揮 發。該包含奈米大小分散顆粒之B i () 3分散溶液的照片 顯示於第3圖。 94679 20 201005756 [製備例5]- Bi2〇3分散溶液 以600°C下之Bi(OH)3奈米粉末之燒結程序製備淺褐 色的Βή〇3粉末’ Bi(OH)3奈米粉末係購自位於Buyong工 業综合大樓之先進奈米產品公司（ANP，Advanced NanoProducts Co.,Ltd 'Address Kuinho_ri, Buyong_niyeon, Chungwon-kun 'Chung cheongbuk-do, Korea) The advantage of 〇Bi(0H)3 nanopowder is that when the dispersion solution is prepared from nanopowder by a ball milling program, It can be uniformly dispersed in the paste during the preparation of the paste. The benzene which is used as a solvent is not present in the turbidity because most of the cockroaches have been volatilized when the Sanxun cylinder mill was used in the preparation of the paste. A photograph of the B i () 3 dispersion solution containing nanoparticles of dispersed size is shown in Fig. 3. 94679 20 201005756 [Preparation Example 5] - Bi2〇3 dispersion solution Preparation of light brown Βή〇3 powder 'Bi(OH)3 nano powder series by sintering procedure of Bi(OH)3 nano powder at 600 °C Advanced Nano Products Company (ANP, Advanced Nano) from Buyong Industrial Complex
Products Co.，Ltd ’ 地址 Kuroho-ri，Buyong-myeon， • Chungwon-kun，Chung cheongbuk-do，韓國）。在經過已經 燒結程序之Bi2〇3粉末的壓碎程序（crushing process) 後’將經壓碎Biz〇3粉末使用甲苯為溶劑配成3〇wt%濃度， ❹以球磨程序製備具50奈米平均分散粒度的Bi2〇3分散溶 液。具經分散之奈米尺寸顆粒的Bi2〇3分散溶液照片顯示於 .第5圖。 [實例1 ] 製備一混合物，其係藉由將平均粒度〇. 7至3. 0微米 之無鉛基於Si-B-0的玻璃原料，以膏總重量的3· Owt%含 量加入製備例1中所製備之銀粉末（平均粒度200奈米）之 鲁中。在將作為黏結劑的乙基纖維素使用品醇（terp i ne〇 1 ) 溶解成30 wt%的濃度之後，將已溶解的溶液加至經製備 的混合物中至均勻分散於其中。在額外加入就總固體含量 而言佔總素重量〇· 5wt%含量之製備例2的Pb(0H)2分散溶 液（平均分散粒度為50奈米）且接著以攪拌機（mixer)初步 混合該Pb(OH)2分散溶液與該混合物之後，藉由使用三報 研磨機（three-roll mi 11)反複地分散該混合物以形成該 貧。因為該膏在三軋輥的研磨過程中具有高黏度，品醇被 加至該膏中以調整膏的黏度，藉此製備適用於網印法 94679 201005756 (screen printing)之用於太陽能電池電極的膏。當使用 Brookfield 型號 LVDV-II + Pro CPE-51 旋轴機（spindle) 測量所製備的膏之黏度時，該黏度在每分鐘0.4轉的旋轉 速度下為210, 000 cps。根據本實例之膏其組成物含量及 黏度示於下面表1。在表1中，含量是佔全部膏的重量百 分比，而總量差額則為剩餘量，用於黏結劑、黏度調整用 . 之溶劑、及其類似物。 · [實例2] 使用三輥研磨機加入品醇並以實例1相同之方式調整 © 其黏度來製備膏，除了製備例2中平均分散粒度為50奈米 的P b (0 Η) 2分散溶液其加入的量為就總固體含量而言佔總 膏重量1. 0 wt%的量之外。根據本實例之膏其組成物含量 及黏度示於下面表1。 [實例3] 使用三輥研磨機加入品醇並以實例1相同之方式調整 其黏度來製備膏，除了加入的是佔總膏重量0. 5wt%含量的 製備例3中的乙醯丙酮鉛（II)而非Pb(0H)2分散溶液之 外。根據本實例之膏其組成物含量及黏度示於下面表1。 [實例4] 使用三輥研磨機加入品醇並以實例3相同之方式調整 其黏度來製備膏，除了加入的是佔總膏重量〇.8wt%含量的 製備例3中乙醯丙酮鉛（II)之外。根據本實例之膏其組成 物含量及黏度示於下面表1。 [實例5] 22 94679 201005756 使用三輥研磨機加入品醇並以實例1相同之方式調整 其黏度來製備膏，除了加入了 〇. 5wt%的Pb(0H)2分散溶 液還加入就總固體含量而言佔總膏重量0. 5 wt%含量具有 80奈米平均分散粒度之製備例4中的Bi(0H)3分散溶液之 外。根據本實例之膏其組成物含量及黏度示於下面表1。 [實例6] • 使用三輥研磨機加入品醇並以實例3相同之方式調整 其黏度來製備膏，除了加入了 〇.5wt%製備例3的乙醯丙 ©酮錯（11)還加入就總固體含量而言佔總膏重量0.5 wt%含 量具有50奈米平均分散粒度之製備例5中的Bi2〇3分散溶 液之外。根據本實例之膏其組成物含量及黏度示於下面表 1 ° [比較例1] 製備一混合物’其係藉由將平均粒度〇. 5至3. 5微来 之包含80wt%的鉛化合物的基於Si_Pb_〇的玻璃原料，以 ❹膏總重量的3· Owt%含量加入製備例！中所製備之銀粉末 (平均粒度200奈米）之中。在將作為黏結劑的乙基纖維素 使用品醇溶解成30 wt%的濃度之後，將已溶解的溶液加 至經製備的混合物中以均勻分散於其中。在以攪拌機作初 步犯合之後，使用二輕研磨機（让ree-r〇l 1 mi 1 1 )反複地分 散該混合物以形成該膏。因為該膏在三軋輥研磨程序 (three-roll milling pr〇cess)中具有高黏度，膏中加入 品醇（Terpineol)以調整膏的黏度’藉以製備適用於網印法 之用於太陽能電池電極的膏。根據此比較例的膏之組成物 94679 23 201005756 含量及黏度示於表1。 [比較例2] 使用三輥研磨機加入品醇並以與比較例1相同之方式 調整其黏度來製備膏，除了加入的平均粒度0.5至3. 5微 米之包含80wt%鉛化合物的基於Si-Pb-Ο玻璃原料被調整 成膏總重量的0. 5wt%含量，以及加入的平均粒度0. 7至 3. 0微米之無鉛基於S i - B - 0玻璃原料被調整成膏總重量的 3. Owt%含量之外。根據本實例之膏其組成物含量及黏度示 於下面表1。 [表1 ]膏的組成物含量與黏度 標示 實例1 實例2 實例3 實例4 實例5 實例6 比較例 1 比較例 2 銀粉末 81.2 81.0 80.8 80.5 80.7 80.1 81.2 80.4 乙基纖維 素 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 基於矽-硼-氧之 玻璃原料 3 3 3 3 3 3 3 基於矽-鉛-氧之 玻璃原料 3 0. 5 50奈米 Pb(0H)2 0.5 1.0 ~~ 0.5 一 ~1 乙醯丙酮 鉛（II) — 一 0.5 0.8 一 0.5 一 80奈米 Bi(0H)3 — 一 一 一 0.5 一 一 50奈米 Bl2〇3 — 一 — 一 一 0.5 — 一 黏度 cps(§0.4 轉/每分） 210,000 200, 500 198,000 192,000 201,000 195,000 199,000 204, 000 〈太陽能電池的製造及其電性質的評估〉 24 94679 201005756 - 在根據諸實例與比較例將膏網印於6吋單晶矽晶圓 (其背侧塗佈有鋁）上之後，以15(TC將該膏乾燥。金屬325 網目遮罩（Metallic 325 mesh mask)係用於此網印法，評 -估用之圖案具有寬度為120微米之手指線（finger line) 與寬度2公釐的匯流排線（bus line)。太陽能電池基底（電 • 池）以紅外線锻燒爐（firing furnace)在約780°C下對所施 •用之膏煅燒約4分鐘而製成。製成的基底（電池）的電性質 使用PASAN CT801電池試驗器測量。受測之電性質包括根 參據諸實例與比較例之膏所施用之太陽能電池的轉換效率 (Eff %)、填充因數（filling factor)(FF %)、斷路電壓 (Voc)、短路電流（Isc)、最大電壓（V即）及最大電流（Imp) 示於下列表2中。 [表2]根據膏組成物之太陽能電池的電性質 標不 Voc(V) Isc(A) Vmp(V) Imp(A) FF⑻ Eff(%) 實例1 0. 612 8. 002 0. 501 7. 100 72.635 15.315 實例2 0. 614 7. 994 0. 508 7. 089 73.370 15. 505 實例3 0. 621 8. 105 0.499 7. 068 70.073 15. 185 實例4 0. 618 8. 101 0. 506 7. 079 71.548 15. 422 實例5 0. 608 8. 095 0. 504 7. 034 71.427 15.250 實例6 0. 612 8. 104 0.512 7. 124 72.860 15.336 比較例1 0. 620 8. 154 0. 505 7. 087 70.793 15.409 比較例2 0. 607 7. 751 0.402 6.450 55.122 11. 161 如表2所示，可知以相當程度地降低鉛化合物的使用 量所製備的本發明實例1至6之膏，透過電極的有效接觸 實現了極佳的電性質。因此，可知由於鉛化合物的消耗減 低之故，此根據本發明用於太陽能電池電極的膏實現了極 25 94679 201005756 佳的電性質並而且是環保的。此外，也可知當基於S-Pb_0 的玻璃原料為了要減少鉛化合物的消耗量而以0. 5wt%少 量使用（如比較例2的膏）時，電性質，特別地是FF %及 Eff%會非常低。 另一方面，第6圖是一張顯示使用導電銀奈米顆粒與 鉛氧化物（Pb(0H)2)奈米顆粒製成電極之電極剖面的照 . 片，該電極係使用根據實例1的膏，而第7圖則是一張顯 · 示使用傳統具微米粒度銀顆粒及具微米粒度之含有鉛的玻 璃原料製成電極之電極剖面的照片。可知當與第7圖的電 Θ 極相比較時，第6圖的電極形成緊密的結構，並由於其緊 密的結構而展現出極佳的導電性。 【圖式簡單說明】 第1圖是一般矽晶圓類型的太陽能電池之剖面圖。 第2圖為顯示用於本發明之實施例之具有平均粒度 2 0 0奈米的銀奈米粉末之照片。 第3圖為顯示用於本發明之實施例之含有奈米大小之 卩1)(01〇2粉末的分散溶液照片。 第4圖為顯示用於本發明之實施例之含有奈米大小之 Bi(0H)3粉末的分散溶液之照片。 第5圖為顯示用於本發明之實施例之含有奈米大小之 Bi2〇3粉末的分散溶液之照片。 第6圖為顯示根據本發明之實施例製造之具緊密結構 的銀電極的剖面圖之照片。 第7圖是顯示使用傳統銀微顆粒所製造之多孔性 26 94679 201005756 (porous)銀電極的剖面圖之照片D 【主要元件符號說明】 10 半導體基底 10a N型矽層 10b P型矽層 12 抗反射塗層 20 如電極 30 背電極Products Co.,Ltd ’ address Kuroho-ri, Buyong-myeon, • Chungwon-kun, Chung cheongbuk-do, South Korea). After the crushing process of the Bi2〇3 powder which has been subjected to the sintering procedure, the crushed Biz〇3 powder is formulated into a concentration of 3〇wt% using toluene as a solvent, and the crucible is prepared by a ball milling procedure with an average of 50 nm. A dispersed particle size Bi2〇3 dispersion solution. A photograph of a Bi2〇3 dispersion solution with dispersed nano-sized particles is shown in Fig. 5. [Example 1] A mixture was prepared by adding a lead-free Si-B-0-based glass raw material having an average particle size of from 0.7 to 3.0 μm, and adding it to the preparation example 1 in an amount of 3.0% by weight based on the total weight of the paste. The prepared silver powder (average particle size 200 nm) was used. After the ethyl cellulose as a binder was dissolved to a concentration of 30 wt% using terpineol (terp i ne〇 1 ), the dissolved solution was added to the prepared mixture to be uniformly dispersed therein. The Pb(0H)2 dispersion solution of Preparation Example 2 (average dispersion particle size of 50 nm) was added in an amount of 〇·5 wt% based on the total solid content, and then the Pb was initially mixed with a mixer. After the (OH) 2 dispersion solution and the mixture, the mixture was repeatedly dispersed by using a three-roll mi 11 to form the lean. Since the paste has a high viscosity during the grinding process of the three rolls, the alcohol is added to the paste to adjust the viscosity of the paste, thereby preparing a paste for the solar cell electrode suitable for screen printing 94679 201005756 (screen printing). . When the viscosity of the prepared paste was measured using a Brookfield model LVDV-II + Pro CPE-51 spindle, the viscosity was 210 000 cps at a rotational speed of 0.4 revolutions per minute. The composition and viscosity of the paste according to this example are shown in Table 1 below. In Table 1, the content is the percentage by weight of the entire paste, and the total amount difference is the remaining amount, which is used for the binder, viscosity adjustment, and the like. [Example 2] A paste was prepared by adding a mercaptan using a three-roll mill and adjusting the viscosity thereof in the same manner as in Example 1, except that the P b (0 Η) 2 dispersion solution having an average dispersion size of 50 nm in Preparation Example 2 was prepared. The amount is added in an amount of 1.0% by weight based on the total solid content. The composition and viscosity of the paste according to this example are shown in Table 1 below. [Example 3] A bismuth acetone lead in Preparation Example 3 was added in the same manner as in Example 1 except that the viscosity was adjusted in the same manner as in Example 1 except that the total paste weight was 0.5% by weight. II) Not in addition to the Pb(0H)2 dispersion solution. The composition and viscosity of the paste according to this example are shown in Table 1 below. [Example 4] A paste was prepared by adding a mercaptan using a three-roll mill and adjusting its viscosity in the same manner as in Example 3, except that lead acetoacetate (II) was prepared in Preparation Example 3 in an amount of 88 wt% based on the total paste weight. Outside. The composition and viscosity of the paste according to this example are shown in Table 1 below. [Example 5] 22 94679 201005756 A tastrol was added using a three-roll mill and the viscosity was adjusted in the same manner as in Example 1 except that 〇. 5 wt% of the Pb(0H)2 dispersion solution was added to the total solid content. In the case of the total paste weight of 0.5% by weight, the Bi(0H)3 dispersion solution in Preparation Example 4 having an average dispersion particle size of 80 nm was used. The composition and viscosity of the paste according to this example are shown in Table 1 below. [Example 6] • A paste was prepared by adding a sterol using a three-roll mill and adjusting its viscosity in the same manner as in Example 3, except that 〇. 5 wt% of the acetophenone ketone (11) of Preparation Example 3 was added. The total solid content was in addition to the Bi2〇3 dispersion solution in Preparation Example 5 having a 50 nm average dispersion particle size in an amount of 0.5 wt% of the total paste weight. The composition and the viscosity of the composition according to the present example are shown in the following Table 1 ° [Comparative Example 1] A mixture was prepared by using an average particle size of 0.5 to 3.5 μm of a lead compound containing 80% by weight. The glass raw material based on Si_Pb_〇 is added to the preparation example in an amount of 3.0% by weight based on the total weight of the ointment! Among the silver powders prepared (the average particle size of 200 nm). After the ethyl cellulose as a binder was dissolved to a concentration of 30 wt% using a pin alcohol, the dissolved solution was added to the prepared mixture to be uniformly dispersed therein. After initial mixing with a blender, the mixture was repeatedly dispersed using a two light grinder (for ree-r〇l 1 mi 1 1 ) to form the paste. Because the paste has a high viscosity in the three-roll milling pr〇cess, the paste is added with Terpineol to adjust the viscosity of the paste to prepare a solar cell electrode suitable for screen printing. paste. The composition of the paste according to this comparative example 94679 23 201005756 The content and viscosity are shown in Table 1. [Comparative Example 2] A paste was prepared by adding a mercaptan using a three-roll mill and adjusting its viscosity in the same manner as in Comparative Example 1, except that an average particle size of 0.5 to 3.5 μm was added based on Si-containing 80 wt% of lead compound. The Pb-Ο glass raw material is adjusted to a total weight of the paste of 0. 5wt% content, and the average particle size added is 0. 7 to 3. 0 micron lead-free based on S i - B - 0 glass raw material is adjusted to the total weight of the paste 3 . Owt% content. The composition and viscosity of the paste according to this example are shown in Table 1 below. [Table 1] Composition content and viscosity of the paste are shown in Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Silver powder 81.2 81.0 80.8 80.5 80.7 80.1 81.2 80.4 Ethyl cellulose 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Glass material based on bismuth-boron-oxygen 3 3 3 3 3 3 3 Glass material based on bismuth-lead-oxygen 3 0. 5 50 nm Pb(0H)2 0.5 1.0 ~~ 0.5 ～1 acetonitrile Lead (II) — a 0.5 0.8 to 0.5 to 80 nm Bi(0H) 3 — one to one 0.5 to one 50 nm Bl 2 〇 3 — one — one to one 0.5 — one viscosity cps (§ 0.4 rpm) 210,000 200, 500 198,000 192,000 201,000 195,000 199,000 204, 000 <Evaluation of the manufacture of solar cells and their electrical properties> 24 94679 201005756 - In the case of the examples and comparative examples, the paste is screen printed on a 6-inch single crystal germanium wafer (the back thereof) After the side is coated with aluminum), the paste is dried at 15 (TC). A metallic 325 mesh mask is used for the screen printing method, and the pattern for evaluation has a width of 120 μm. A finger line and a bus line with a width of 2 mm. The solar cell substrate (electric cell) was prepared by firing a paste for about 4 minutes at about 780 ° C in an infrared firing furnace. The electrical properties of the resulting substrate (battery) were PASAN. CT801 battery tester measurement. The measured electrical properties include the conversion efficiency (Eff %), filling factor (FF %), and open circuit voltage (Voc) of the solar cell applied by the root and the paste of the comparative example. ), short-circuit current (Isc), maximum voltage (V), and maximum current (Imp) are shown in Table 2. [Table 2] The electrical properties of the solar cell according to the paste composition are not Voc(V) Isc(A) Vmp(V) Imp(A) FF(8) Eff(%) Example 1 0. 612 8. 002 0. 501 7. 100 72.635 15.315 Example 2 0. 614 7. 994 0. 508 7. 089 73.370 15. 505 Example 3 0 。 。 。 。 。 。 。 。 0. 612 8. 104 0.512 7. 124 72.860 15.336 Comparative Example 1 0. 620 8. 154 0. 505 7. 087 70.793 15.409 Comparative Example 2 0. 607 7. 751 0.402 6.450 55.122 11. As shown in Table 2, it is understood that the pastes of Examples 1 to 6 of the present invention prepared by considerably reducing the amount of use of the lead compound achieve excellent electrical properties through the effective contact of the electrodes. Therefore, it is understood that the paste for solar cell electrodes according to the present invention achieves excellent electrical properties and is environmentally friendly because of the reduced consumption of lead compounds. In addition, it is also known that when the glass raw material based on S-Pb_0 is used in a small amount of 0.5 wt% in order to reduce the consumption of the lead compound (such as the paste of Comparative Example 2), the electrical properties, particularly FF % and Eff% will be very low. On the other hand, Fig. 6 is a photograph showing an electrode section of an electrode made of conductive silver nanoparticles and lead oxide (Pb(0H)2) nanoparticles, which is used according to Example 1. Paste, and Figure 7 is a photograph showing an electrode profile of an electrode made using conventional micron-sized silver particles and micron-sized lead-containing glass materials. It is understood that the electrode of Fig. 6 forms a compact structure when compared with the electrode of Fig. 7, and exhibits excellent conductivity due to its tight structure. [Simple description of the drawing] Fig. 1 is a cross-sectional view of a solar cell of a general germanium wafer type. Fig. 2 is a photograph showing a silver nanoparticle having an average particle size of 200 nm for use in an embodiment of the present invention. Fig. 3 is a photograph showing a dispersion solution containing a nanometer-sized 卩1) (01〇2 powder used in an embodiment of the present invention. Fig. 4 is a view showing a nano-sized Bi for use in an embodiment of the present invention. Photograph of (0H)3 dispersion solution of powder. Fig. 5 is a photograph showing a dispersion solution of a nano-sized Bi2〇3 powder used in an embodiment of the present invention. Fig. 6 is a view showing an embodiment according to the present invention. Photograph of a cross-sectional view of a silver electrode fabricated with a compact structure. Fig. 7 is a photograph D showing a cross-sectional view of a porous 26 94679 201005756 (porous) silver electrode made using conventional silver microparticles [Explanation of main component symbols] 10 Semiconductor substrate 10a N-type germanium layer 10b P-type germanium layer 12 anti-reflective coating 20 such as electrode 30 back electrode
27 9467927 94679
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080048653A KR100961226B1 (en) | 2008-05-26 | 2008-05-26 | Environment-friendly paste for electrode of solar cell and solar cell using the same |
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| Publication Number | Publication Date |
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| TW201005756A true TW201005756A (en) | 2010-02-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW098116657A TW201005756A (en) | 2008-05-26 | 2009-05-20 | Environment-friendly paste for electrode of solar cell and solar cell using the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100961226B1 (en) |
| TW (1) | TW201005756A (en) |
| WO (1) | WO2009145386A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107438885A (en) * | 2015-03-27 | 2017-12-05 | 贺利氏德国有限责任两合公司 | Electrocondution slurry comprising organo metallic oxide |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170271535A1 (en) * | 2014-05-19 | 2017-09-21 | Sun Chemical Corporation | A silver paste containing bismuth oxide and its use in solar cells |
| JP5998178B2 (en) * | 2014-06-05 | 2016-09-28 | 株式会社ノリタケカンパニーリミテド | Photovoltaic surface electrode paste for solar cell, method for producing the same, and method for producing solar cell |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002217434A (en) * | 2001-01-19 | 2002-08-02 | Sharp Corp | Solar cell, interconnector and string for the solar cell |
| JP2004179618A (en) * | 2002-10-04 | 2004-06-24 | Sharp Corp | Solar cell, its manufacturing method, interconnector for solar cell, string, and module |
| US7494607B2 (en) | 2005-04-14 | 2009-02-24 | E.I. Du Pont De Nemours And Company | Electroconductive thick film composition(s), electrode(s), and semiconductor device(s) formed therefrom |
| US8093491B2 (en) | 2005-06-03 | 2012-01-10 | Ferro Corporation | Lead free solar cell contacts |
| US7771623B2 (en) * | 2005-06-07 | 2010-08-10 | E.I. du Pont de Nemours and Company Dupont (UK) Limited | Aluminum thick film composition(s), electrode(s), semiconductor device(s) and methods of making thereof |
| US7718092B2 (en) | 2005-10-11 | 2010-05-18 | E.I. Du Pont De Nemours And Company | Aluminum thick film composition(s), electrode(s), semiconductor device(s) and methods of making thereof |
| KR100801167B1 (en) | 2007-06-18 | 2008-02-05 | 한국다이요잉크 주식회사 | Front electrode material for fabrication of high efficient solar cell |
-
2008
- 2008-05-26 KR KR1020080048653A patent/KR100961226B1/en not_active IP Right Cessation
- 2008-07-25 WO PCT/KR2008/004365 patent/WO2009145386A1/en active Application Filing
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- 2009-05-20 TW TW098116657A patent/TW201005756A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107438885A (en) * | 2015-03-27 | 2017-12-05 | 贺利氏德国有限责任两合公司 | Electrocondution slurry comprising organo metallic oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100961226B1 (en) | 2010-06-03 |
| WO2009145386A1 (en) | 2009-12-03 |
| KR20090122709A (en) | 2009-12-01 |
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