TW201349254A - 用於太陽能電池接點的導電厚膜膏 - Google Patents
用於太陽能電池接點的導電厚膜膏 Download PDFInfo
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- TW201349254A TW201349254A TW102113671A TW102113671A TW201349254A TW 201349254 A TW201349254 A TW 201349254A TW 102113671 A TW102113671 A TW 102113671A TW 102113671 A TW102113671 A TW 102113671A TW 201349254 A TW201349254 A TW 201349254A
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- Prior art keywords
- reaction system
- lead
- inorganic reaction
- cerium oxide
- conductive paste
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
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- 239000005350 fused silica glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
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- 238000009413 insulation Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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Abstract
本發明係關於一種用於製造導電膏之無機反應系統。該無機反應系統包含含鉛基質形成組成物及氧化碲添加劑。較佳地,該含鉛基質形成組成物佔該無機反應系統之5wt.%至95wt.%,且該氧化碲添加劑佔該無機反應系統之5wt.%至95wt.%。該含鉛基質形成組成物可為玻璃粉且可包含氧化鉛。本發明之另一態樣係關於一種導電膏組成物,其包含金屬粒子、如先前所揭示之無機反應系統以及有機媒劑。本發明之另一態樣係關於一種有機媒劑,其包含黏合劑、界面活性劑、溶劑及觸變劑中之一或多者。本發明之另一態樣係關於一種印刷有如所揭示之導電膏組成物的太陽能電池以及一種組裝之太陽能電池模組。本發明之另一態樣係關於一種製備太陽能電池之方法。
Description
本發明係關於如太陽電池板技術中所用之導電膏。特定而言,在一個態樣中,本發明係關於一種用於導電膏中之無機反應系統。本發明之另一態樣係關於一種導電膏組成物,其包含導電金屬組分、無機反應系統以及有機媒劑。本發明之另一態樣係關於一種太陽能電池,其係藉由將導電膏塗覆於矽晶圓上而製得,該導電膏包含導電金屬、無機反應系統以及有機媒劑。本發明之另一態樣係關於一種太陽能電池模組,其係使用太陽能電池組裝而成,該等太陽能電池係藉由將導電膏塗覆至矽晶圓上而製得,其中該導電膏包含導電金屬、無機反應系統以及有機媒劑。
太陽能電池為使用光電效應將光能轉換成電的裝置。太陽能為一種吸引人之綠色能源,因為其可持續且僅產生無污染之副產物。因此,許多研究當前致力於研發效率有所提高的太陽能電池,同時持續降低材料及製造成本。當光射中太陽能電池時,一部分入射光由表面反射而其餘部分透射至太陽能電池中。透射之光/光子由太陽能電池所吸收,該太陽能電池通常由半導體材料(諸如矽)製成。所吸收之光子能量會激發來自半導體材料之原子的電子,產生電子電洞對。此等電子電洞對接著由p-n接面分離且由塗覆於太陽能電池表面上之導電
電極收集。
最常見之太陽能電池為基於矽,更特定而言由矽製成之p-n接面的太陽能電池,該p-n接面係藉由將摻雜劑擴散層塗覆於矽基板上而製成且與兩個電接觸層或電極耦接。在p型半導體中,將摻雜劑原子添加至半導體中以增加自由電荷載流子(正電洞)之數目。基本上,摻雜材料自半導體原子帶走結合較弱之外層電子。p型摻雜之目的在於產生大量電洞。在矽之狀況下,三價原子經取代至晶格中。p型半導體之一個實例為具有硼或鋁摻雜劑之矽。太陽能電池亦可由n型半導體製成。在n型半導體中,摻雜劑原子為主體基板提供額外之電子,從而產生過量之負電子電荷載流子。摻雜原子(即供體)的價電子通常比一種類型之主體原子多一個。最常見之實例為含有四個價電子之第IV族固體(矽、鍺、錫)中經含有五個鬆散結合之價電子的第V族元素(磷、砷、銻)進行原子取代。n型半導體之一個實例為具有磷摻雜劑之矽。
為了最小化太陽能電池對陽光之反射,將抗反射塗層(ARC),諸如氮化矽(SiNx)、氧化矽(SiO2)、氧化鋁(Al2O3)或氧化鈦(TiO2)塗覆於n型或p型擴散層上以增加吸收至太陽能電池中之光量。ARC通常為非導電性的,且亦可使矽基板表面鈍化。
對於矽太陽能電池金屬化製程,通常首先向矽基板塗覆後接點。典型製程涉及塗覆背側銀膏或銀/鋁膏形成焊接墊,繼而將鋁膏塗覆於整個基板背側。其次,使用導電膏,可將金屬接點網版印刷於前側抗反射層上(在背側膏乾燥之後)以用作前電極。在光進入之電池前面或前側上之此電接觸層通常以由「指狀物線」及「匯流排」製成之網格圖案而非完整層形式存在,因為金屬網格材料通常不透光。接著在約700℃至975℃之溫度下對印刷有前側及背側膏之矽基板進行燒製。燒製之後,前側膏蝕穿ARC層,在網格接點與半導體之間形成電
接觸,且在太陽能電池之光接收表面上使金屬膏轉化成金屬電極。通常將背側膏與前側膏同時燒製,且與矽基板之背側形成電接觸。所得金屬電極允許電往返於連接成太陽電池板之太陽能電池流動。
為了組裝太陽能模組,將多個太陽能電池串聯及/或並聯且第一個電池及最後一個電池之電極末端較佳連接至輸出導線。通常將太陽能電池囊封於透明熱塑性樹脂,諸如矽橡膠或乙烯乙酸乙烯酯中。將透明玻璃薄片置於囊封用透明熱塑性樹脂之前表面上。將具有良好機械特性及良好耐候性之背面保護材料,例如塗有聚氟乙烯膜之聚對苯二甲酸伸乙酯薄片置放於囊封用熱塑性樹脂下。可在適當真空爐中加熱此等層狀材料以移除空氣,接著藉由加熱及壓製整合成一個主體。此外,由於通常將太陽能電池長時間置於露天,所以需要用由鋁或其類似物組成之框架材料覆蓋太陽能電池之周圍。
典型導電膏含有金屬粒子、玻璃粉及有機媒劑。此等組分通常經選擇以充分利用所產生之太陽能電池的理論電位。舉例而言,需要使金屬膏與矽表面之間以及金屬粒子本身的接觸達到最大,使得電荷載流子可流過界面及指狀物線至匯流排。組成物中之玻璃粒子在燒製後蝕穿抗反射塗層,從而有助於在金屬與n+型矽之間建立接觸。另一方面,玻璃須不具過高之侵襲性以使其在燒製之後避開p-n接面。因此,目的在於最小化接觸電阻,同時保持p-n接面完整以便達成效率改良。已知之組成物因金屬層與矽晶圓之界面中玻璃之絕緣作用而具有高接觸電阻以及其他缺點,諸如接觸區中之再結合作用較高。此外,已知玻璃粉具有寬熔融溫度範圍,使得其性能很大程度地取決於加工參數。因此,需要電學特性得到改良之導電膏組成物。
美國專利申請公開案第2011/0308595 A1號揭示一種用於印刷於具有一或多個絕緣層之太陽能電池裝置之前側上的厚膜膏。該厚膜膏包含分散於有機介質中之導電金屬以及鉛-碲氧化物。鉛-碲氧化物以
佔膏固體之0.5 wt.%至15 wr.%之量存在且鉛與碲之莫耳比為5/95至95/5。鉛-碲氧化物(Pb-Te-O)係藉由混合TeO2及氧化鉛粉末,在空氣或含氧氛圍中加熱粉末混合物形成熔體,使熔體驟冷,研磨且球磨驟冷之材料,且篩選研磨之材料以提供具有所需粒度之粉末來製備。
美國專利第5,066,621號揭示一種密封玻璃組成物,其包含(以wt.%計)13%至50%氧化鉛、20%至50%氧化釩、2%至40%氧化碲、至多40%氧化硒、至多10%氧化磷、至多5%氧化鈮、至多20%氧化鉍、至多5%氧化銅及至多10%氧化硼;及一種導電調配物,其包含(以wt.%計)50%至77%銀、8%至34%之如先前所述之密封玻璃組成物、0.2%至1.5%樹脂及觸變劑以及10%至20%有機溶劑。'621專利揭示較佳範圍為9 wt.%至30 wt.%之氧化碲。
美國專利申請公開案第2011/0192457號揭示一種導電膏,其含有導電粒子、有機黏合劑、溶劑、玻璃粉及包括鹼土金屬、具有低熔點之金屬或與具有低熔點之金屬相關之化合物的有機化合物。'457公開案教示無鉛玻璃粉,例如含鉍(Bi)玻璃粉及含鋇(Ba)玻璃粉之用途。
美國專利第7,736,546號及第7,935,279號揭示不含有意添加之鉛且包含TeO2及Bi2O3、SiO2及其組合中之一或多者的無鉛玻璃粉。該等專利亦揭示包含玻璃粉之導電墨水及塗覆有該等導電墨水之物品。將TeO2與Bi2O3、SiO2中之一或多者一起併入無鉛玻璃基質中。
本發明提供一種用於導電膏之無機反應系統,其包含含鉛基質形成組成物及氧化碲添加劑,其中該含鉛組成物佔無機反應系統之5 wt.%至95 wt.%,且氧化碲添加劑佔無機反應系統之5 wt.%至95 wt.%。
根據本發明之另一態樣,無機反應系統包含佔無機反應系統10 wt.%至90 wt.%之含鉛基質形成組成物以及佔無機反應系統10 wt.%至
60 wt.%之氧化碲添加劑。
根據本發明之另一態樣,氧化碲添加劑可為一或多種二氧化碲、三氧化碲及/或在溫度200℃至1000℃下將轉化為氧化碲之任何碲化合物。
根據本發明之另一態樣,氧化碲添加劑之平均粒度小於10 μm。更佳,氧化碲添加劑之平均粒度小於1 μm。
根據本發明之另一態樣,含鉛基質形成組成物為具有非晶形結構之玻璃粉,且亦可併有結晶相或化合物。根據本發明之另一態樣,含鉛基質形成組成物包含氧化鉛。根據本發明之另一態樣,含鉛基質形成組成物包含約10 wt.%至90 wt.%,較佳約25 wt.%至85 wt.%之氧化鉛。在另一實施例中,含鉛組成物為包含約5 wt.%至45 wt.%,較佳約10 wt.%至15 wt.%氧化鉛之低鉛組成物。
根據本發明之另一個態樣,無機反應系統具有95:5至5:95之PbO:氧化碲添加劑重量百分比比率。較佳地,無機反應系統具有10:1至1:10之PbO:氧化碲添加劑重量百分比比率,且更佳地,PbO:氧化碲添加劑重量百分比比率為5:1至1:5。
本發明亦提供一種導電膏組成物,其包含金屬粒子、無機反應系統以及有機媒劑。
根據本發明之一個態樣,導電膏中之金屬粒子為銀、金、銅以及鎳中之至少一者。根據本發明之另一態樣,導電膏中之金屬粒子為銀。根據本發明之另一態樣,導電膏中之金屬粒子構成膏之約50 wt.%至95 wt.%。
根據本發明之另一態樣,有機媒劑包含黏合劑、界面活性劑、有機溶劑及觸變劑中之一或多者。根據本發明之另一態樣,黏合劑可以佔有機媒劑約1 wt.%至10 wt.%存在且包含乙基纖維素或酚系樹脂、丙烯酸系物、聚乙烯醇縮丁醛或聚酯樹脂、聚碳酸酯、聚乙烯或
聚胺基甲酸酯樹脂或松香衍生物中之至少一者。界面活性劑可以佔有機媒劑約1 wt.%至10 wt.%存在且包含聚氧化乙烯、聚乙二醇、苯并***、聚(乙二醇)乙酸、月桂酸、油酸、癸酸、肉豆蔻酸、亞油酸、硬脂酸、棕櫚酸、硬脂酸鹽、棕櫚酸鹽及其混合物中之至少一者。有機溶劑可以佔有機媒劑約50 wt.%至90 wt.%存在且包含卡必醇、萜品醇、己基卡必醇、醇酯十二(texanol)、丁基卡必醇、丁基卡必醇乙酸酯、己二酸二甲酯或二醇醚中之至少一者。觸變劑可以佔有機媒劑約0.1 wt.%至5 wt.%存在且包含此項技術已知之觸變劑。
本發明進一步提供一種太陽能電池,其係藉由將本發明之導電膏塗覆至矽晶圓上,且對矽晶圓進行燒製而產生。根據本發明之一個態樣,矽晶圓之薄層電阻高於60 Ω/□。根據本發明之另一態樣,矽晶圓之薄層電阻高於65 Ω/□。根據本發明之另一態樣,矽晶圓之薄層電阻高於70 Ω/□。根據本發明之另一態樣,矽晶圓之薄層電阻高於90 Ω/□。根據本發明之另一態樣,矽晶圓之薄層電阻高於95 Ω/□。
本發明進一步提供一種太陽能電池模組,其包含電互連之太陽能電池,該等太陽能電池係使用本發明之導電膏製成。
本發明進一步提供一種製備太陽能電池的方法,其包含以下步驟:提供矽晶圓,將本發明之導電膏塗覆至矽晶圓上,及根據適當型態對矽晶圓進行燒製。
根據本發明之一態樣,矽晶圓進一步包含抗反射塗層。根據本發明之另一態樣,將本發明之導電膏塗覆於矽晶圓之光接收表面。
本發明係關於用於製造太陽能電池之導電膏組成物。導電膏通常包含金屬粒子、玻璃粉(非晶形或部分結晶物質)及有機媒劑。雖然
不限於該種應用,但該等膏可用於形成太陽能電池上之電接觸層或電極。特定而言,該等膏可塗覆於太陽能電池之前側或太陽能電池之背側且提供用以使電池之間進行電導的路徑。
本發明之一個態樣提供一種無機反應系統(IRS)。本發明之IRS為金屬粒子提供傳遞介質,允許該等金屬粒子自膏遷移至金屬導體與半導體基板之界面中。本發明之IRS亦為膏組分在界面處發生物理及化學反應提供反應介質。物理反應包括(但不限於)熔融、溶解、擴散、燒結、沈澱及結晶。化學反應包括(但不限於)合成(形成新化學鍵)及分解、還原及氧化,及相轉變。最後,本發明之IRS用作黏著介質,在金屬導體與半導體基板之間提供黏結,從而確保在太陽能裝置壽命期間的電接觸效能可靠。雖然意欲達成相同作用,但現有之玻璃粉組成物會因金屬層與矽晶圓之界面中玻璃之絕緣作用而產生高接觸電阻。雖然本發明之IRS用作傳遞、反應及黏著介質,但其提供低得多之接觸電阻及較高之總體電池效率。
更特定而言,本發明之IRS使得太陽能電池中金屬導體(例如銀)與半導體發射極(例如矽基板)之間的歐姆(Ohmic)及肖特基(Schottky)接觸得到改良。本發明之IRS為對於矽具反應性之介質且在矽發射極上形成諸如經由直接接觸或穿隧改良總體接觸機制的作用區域。改良之接觸特性使得歐姆接觸及肖特基接觸較佳,且因此使得總體太陽能電池效能較佳。
本發明之IRS可包含結晶或部分結晶物質。其可包含各種化合物,包括(但不限於)氧化物、鹽、氟化物及硫化物以及合金及元素物質。
本發明之較佳實施例係關於一種用於導電膏中之IRS,其包含含鉛基質形成組成物及氧化碲添加劑。基質形成組成物在本發明IRS及/或包含本發明IRS之導電膏的燒製溫度下會發生熔融或燒結。基質形
成組成物可為玻璃、陶瓷或為熟習此項技術者所知可在高溫下形成基質的任何化合物。含鉛基質形成組成物之一較佳實施例為含鉛玻璃粉。更佳,玻璃粉包含氧化鉛作為起始物質。含鉛基質形成組成物佔IRS之5 wt.%至95 wt.%,更佳佔IRS之25 wt.%至60 wt.%。此外,含鉛基質形成組成物包含約5 wt.%至95 wt.%,較佳約10 wt.%至90 wt.%,更佳25 wt.%至85 wt.%,及甚至更佳約45 wt.%至75 wt.%之氧化鉛。在另一實施例中,鉛基質形成組成物可含有相對低之鉛含量,例如約5 wt.%至45 wt.%,較佳約10 wt.%至40 wt.%,且更佳約10 wt.%至15 wt.%氧化鉛。
本發明上下文中所用之術語添加劑係指IRS中離散的,特定而言不為基質形成組成物之一部分的組分。直接將添加劑提供於IRS中。在較佳實施例中,在含鉛基質形成組成物為含鉛玻璃粉時,氧化碲添加劑不為含鉛玻璃粉之一部分。
氧化碲添加劑之納入會極大地改良與半導體發射極之接觸且降低串聯電阻。氧化碲作為添加劑在矽晶圓上進行與含鉛黃碲礦玻璃、化合物或組成物相比完全不同的熱動態反應。氧化碲與矽具有高反應性。TeO2與Si之間的反應在1000 K下之吉布斯自由能變化(Gibbs free energy change)△G=-140.949 Kcal/mol。PbO與Si之間的反應之△G=-59.249 Kcal/mol。對於Pb-Te-O玻璃,△G應甚至更小。PbO及Pb-Te-O固體的△G小於氧化碲,表示其與矽之反應性較低。(Thermodynamic stability of binary oxides in contact with silicon,K.J.Hubbard及D.G.Schlom,J.Mater.Res.,第11卷,第11期,(1996))。咸信與矽晶圓之反應性較高會使得在矽晶圓上形成反應性接觸點。氧化碲之高反應性亦有助於在具有低表面摻雜濃度之某些高效率晶圓上形成接點。此外,含有氧化碲作為添加劑,IRS系統可易於經調適以用於針對多種導電膏應用之不同玻璃粉及玻璃化學物質中。
將氧化碲作為添加劑併入IRS中亦會在工業應用中賦予金屬化膏調配物以較大之可撓性。替代將Pb-Te-O固體製成玻璃粉且在膏調配物中使用該材料,使用氧化碲作為添加劑允許容易地對膏反應性進行調節以滿足不同Si晶圓(諸如不同摻雜濃度)及發射極結構。
太陽能電池製造在工業上趨向於快速燒製製程,具有極快之帶速及「峰值」燒製型態。根據本發明具有氧化碲添加劑之金屬化膏之可控制的高反應性極適用於該製程。
氧化碲添加劑佔IRS之5 wt.%至95 wt.%,更佳佔IRS之10 wt.%至60 wt.%。在一些實施例中,氧化碲添加劑可包含D50小於1 μm之次微米粒子。在其他實施例中,氧化碲添加劑之平均粒度(D50)可小於10 μm。
氧化碲添加劑較佳為二氧化碲(TeO2),而亦可使用三氧化碲(TeO3)。除氧化碲之外,可使用其他碲-氧化合物,包括(但不限於)亞碲酸化合物、碲酸、有機碲化合物及在燒製製程期間將產生氧化碲的任何碲化合物。
在一較佳實施例中,含鉛組成物為具有含鉛化合物作為起始物質之類型的玻璃粉(具有非晶形結構,且亦可併有結晶相或化合物)。玻璃粉中鉛之量愈高,則玻璃之玻璃轉移溫度愈低。然而,較高之鉛量亦可引起半導體基板中之分流,從而降低所得太陽能電池之效率。在一較佳實施例中,使用氧化鉛。更佳,玻璃粉含有約35 wt.%至95 wt.%氧化鉛,較佳約40 wt.%至85 wt.%氧化鉛。
本發明IRS可具有95:5至5:95之PbO:氧化碲添加劑重量百分比比率。較佳,PbO:氧化碲添加劑重量百分比比率為10:1至1:10。更佳,PbO:氧化碲添加劑重量百分比比率為5:1至1:5。
本發明之玻璃粉亦可包括為熟習此項技術者所知用於製備玻璃粉之其他氧化物或化合物。舉例而言,矽、硼、鋁、鉍、鋰、鈉、
鎂、鋅、鈦、鋯氧化物及化合物。其他玻璃基質形成劑或玻璃改質劑,諸如氧化鍺、氧化釩、氧化鎢、鉬氧化物、鈮氧化物、錫氧化物、銦氧化物、其他鹼金屬及鹼土金屬(諸如K、Rb、Cs及Be、Ca、Sr、Ba)化合物、稀土金屬氧化物(諸如La2O3、鈰氧化物)、磷氧化物或金屬磷酸鹽、過渡金屬氧化物(諸如銅氧化物及鉻氧化物)、金屬鹵化物(諸如鉛氟化物及鋅氟化物)亦可為玻璃組成物之一部分。
含鉛玻璃粉可藉由為熟習此項技術者所知之任何方法製備。舉例而言,可在V型梳式摻合器中將呈粉末形式之玻璃粉組分混合在一起。接著將混合物加熱至極高溫度(約1200℃)持續約30至40分鐘。接著將玻璃驟冷,從而呈現砂樣稠度。接著諸如在球磨機或噴射研磨機中研磨此粗玻璃粉直至得到細粉為止。含鉛玻璃粉或者可包含鉛氧化物;鹽,如鹵化鉛、鉛硫族化物、碳酸鉛、硫酸鉛、磷酸鉛、硝酸鉛及有機金屬鉛化合物或可在熱分解期間形成鉛氧化物或鹽的化合物。在另一實施例中,可直接將氧化鉛與本發明IRS之其他組分混合,而無需先將氧化鉛加工成玻璃粉之形式。
本發明IRS可經由熟習此項技術者所知之許多方法產生。舉例而言,自不同IRS原料混合平均粒度為約0.1至10 μm(D50)之IRS粒子。平均粒度係視IRS原料之粒度及混合製程而定。良好之混合製程應產生IRS組分之良好分散混合物。
在另一實例中,可使用習知固態合成來製備IRS。在此狀況下,在真空下將原料密封於熔融石英管或鉭或鉑管中,接著加熱至700℃至1200℃。使該等材料在此高溫下靜置12小時至48小時,接著將其緩慢冷卻(0.1℃/分鐘)至室溫。在一些狀況下,可在氧化鋁坩堝中在空氣中進行固態反應。
在另一實例中,可使用共同沈澱來形成IRS。在此方法中,藉由調節pH值或藉由併入還原劑將金屬元素還原且與其他金屬氧化物或
氫氧化物自含有金屬陽離子之溶液中共同沈澱。接著乾燥此等金屬、金屬氧化物或氫氧化物之沈澱物且在真空下在400℃至600℃下燒製且形成化合物之細粉。
本發明之IRS亦可包含其他添加劑,其可為熟習此項技術者所知適用作添加劑之任何氧化物及化合物。舉例而言,硼、鋁、鉍、鋰、鈉、鎂、鋅、磷酸鹽。其他玻璃基質形成劑或玻璃改質劑,諸如氧化鍺、氧化釩、氧化鎢、鉬氧化物、鈮氧化物、錫氧化物、銦氧化物、其他鹼金屬及鹼土金屬(諸如K、Rb、Cs及Be、Ca、Sr、Ba)化合物、稀土金屬氧化物(諸如La2O3、鈰氧化物)、磷氧化物或金屬磷酸鹽、過渡金屬氧化物(諸如銅氧化物及鉻氧化物)、金屬鹵化物(諸如鉛氟化物及鋅氟化物),亦可用作添加劑來調節玻璃特性,諸如玻璃轉移溫度。
本發明之另一態樣係關於一種導電膏組成物,其包含金屬粒子、本發明IRS及有機媒劑。較佳之金屬粒子為銀,但可為任何已知導電金屬或其混合物,包括(但不限於)金、銅或鎳。金屬粒子佔膏之固體含量的約50 wt.%至95 wt.%,較佳佔膏之固體含量的約75 wt.%至95 wt.%。IRS佔膏之固體含量的約1 wt.%至10 wt.%,較佳佔膏之固體含量的約2 wt.%至8 wt.%,更佳約5%。氧化碲添加劑之量亦可以佔膏之重量百分比計來量測。通常,氧化碲添加劑可佔膏之0.1 wt.%至5 wt.%。更佳,佔膏之0.3 wt.%至5 wt.%。
有機媒劑可包含黏合劑及溶劑以及界面活性劑及觸變劑。有機媒劑之典型組成物為熟習此項技術者所知。舉例而言,常用於該等應用之黏合劑為纖維素或酚系樹脂,且常用溶劑可為卡必醇、萜品醇、己基卡必醇、醇酯十二、丁基卡必醇、丁基卡必醇乙酸酯或己二酸二甲酯或二醇醚中之任一者。有機媒劑亦包括為熟習此項技術者所知之界面活性劑及觸變劑。界面活性劑可包括(但不限於)聚氧化乙烯、聚
乙二醇、苯并***、聚(乙二醇)乙酸、月桂酸、油酸、癸酸、肉豆蔻酸、亞油酸、硬脂酸、棕櫚酸、硬脂酸鹽、棕櫚酸鹽及其混合物。有機媒劑佔膏約1 wt.%至20 wt.%,較佳佔膏約5 wt.%至15 wt.%。觸變劑佔膏約0.1 wt.%至5 wt.%。
為了形成導電膏,可使用此項技術中已知用於製備膏組成物之任何方法將IRS材料與導電粒子(例如銀)及有機媒劑組合。製備方法並非關鍵,只要其產生均質分散之膏即可。可諸如用混合器混合組分,接著使其通過三輥研磨機,例如以製成分散之均一膏。除同時將所有組分混合在一起之外,亦可在球磨機中將IRS原料與銀粒子一起共同研磨2至24小時以達成IRS與銀粒子之均質混合物,接著可在混合器中將其與有機溶劑組合。
該種膏可接著用於諸如藉由網版印刷將該膏塗覆至矽基板上之抗反射層,接著乾燥及燒製以在矽基板上形成電極來形成太陽能電池。
具有含鉛基質形成組成物及氧化碲添加劑的本發明IRS系統以及由其製成之導電膏之如上文所述之較佳實施例通常塗覆於矽晶圓之光接收表面上。通常,將本發明導電膏網版印刷於矽晶圓之ARC上。亦可使用其他塗覆方法,諸如模版印刷來塗覆導電膏。然而,上述舉措並不妨礙將本發明IRS系統併入於意欲用於矽晶圓背側之導電膏中。
如表1中所示,用包含含約43% PbO(佔IRS)之玻璃粉及多種金屬氧化物添加劑的IRS製備例示性導電膏T1-T4。特定而言,例示性導電膏T1包含佔膏1.5 wt.%之氧化鉍(Bi2O3),T2包含佔膏1.5 wt.%之氧化碲(TeO2),T3包含佔膏1.5 wt.%之氧化錫(SnO),且T4包含佔膏1.5 wt.%之三氧化銻(Sb2O3)。添加約85 wt.%(佔膏)之量的銀粒子及約1 wt.%至10 wt.%(佔膏)之量的有機媒劑以形成例示性膏。使用薄層電
阻為80 Ω/□之輕微摻雜之p型矽晶圓製備例示性太陽能電池。
以150 mm/s之速度,使用325(篩目)×0.9(密耳,導線直徑)×0.6(密耳,乳液厚度)×70 μm(指狀物線開口)壓光網幕將膏網版印刷於矽晶圓之前側上。亦將鋁背側膏塗覆於矽晶圓之背側。在150℃下乾燥印刷之晶圓,接著在線性多區紅外線鍋爐中在峰值溫度為約750℃至900℃之型態下燒製幾秒。使用市售膏作為參照。
接著使用I-V測試儀測試所有太陽能電池。使用I-V測試儀中之Xe弧光燈模擬具有已知強度的陽光且照射太陽能電池之前表面以產生I-V曲線。使用此曲線,確定提供電學效能比較的此量測方法共同的各種參數,包括太陽能電池效率(Eta,%)、在三種標準光強下的串聯電阻(Rs3,mΩ)、填充因數(FF,%)。研究人員總是使用藉由四探針技術對接觸電阻進行直接量測,但量測精度極大程度地取決於樣品製備。因此,在指狀物線電阻率(通常相同之銀材料及燒製條件)及指狀物線幾何形狀(與印刷相關)相同的情況下,可使用由H.A.L.M IV測試儀給出之串聯電阻Rs3評估導電膏與矽基板之電接觸性能。一般而言,Rs3愈小,銀膏之接觸性能愈佳。參照膏之數據校正為1。實驗膏之有關數據係藉由將適當量測結果除以經校正之參照電池數據來計算。例示性膏T1-T4之所選電學效能數據彙編於表2中。
自表2中呈現之數據顯而易見的是,具有氧化碲添加劑之例示性膏T2出人意料地改良串聯電阻,如經由Rs3量測結果顯著降低所示,
其亦使得太陽能電池效率及填充因數增益有所增加。其他所測試金屬氧化物未能展示出相似之有益作用,儘管此等金屬氧化物亦已知可改變玻璃軟化溫度及調節玻璃流動性。
用四種玻璃粉A(43% PbO)、B(60% PbO)、C(67% PbO)、D(73% PbO)及各種量之氧化碲添加劑製備多種其他例示性膏E1-E22。例示性膏調配物及各例示性膏之PBO及TeO2含量以及重量比的細節呈現於表3中。使用具有不同薄層電阻之單晶或多晶矽晶圓藉由上述實例1中所述之方法製備例示性太陽能電池。更特定而言,用多晶矽晶圓類型1A(薄層電阻為70 Ω/□)製備之太陽能電池的所選電學效能數據呈現於表4中,用多晶矽晶圓1B(薄層電阻為95 Ω/□)製備之太陽能電池的電學效能數據呈現於表5中,用單晶矽晶圓類型2(薄層電阻為65 Ω/□)製備之太陽能電池的電學效能數據呈現於表6中,用單晶矽晶圓類型3(薄層電阻為90 Ω/□)製備之太陽能電池的電學效能數據呈現於表7中,用多晶矽晶圓類型4(薄層電阻為60 Ω/□)製備之太陽能電池的電學效能數據呈現於表8中,用單晶矽晶圓類型5(薄層電阻為60 Ω/□1)製備之太陽能電池的電學效能數據呈現於表9中,用多晶矽晶圓類型6(薄層電阻為70 Ω/□)製備之太陽能電池的電學效能數據呈現於表10中,用單晶矽晶圓類型7(薄層電阻為70 Ω/□)製備之太陽能電池的電學效能數據呈現於表11中,且用多晶矽晶圓類型8(薄層電阻為65 Ω/□)製備之太陽能電池的電學效能數據呈現於表12中。所有數據皆針對矽
晶圓類型1A上之參照膏進行校正。特定而言,在所有其他矽晶圓類型上所有例示性膏E1-E22之相對效率、相對填充因數以及相對Rs3量測結果皆分別針對在矽晶圓類型1A上參照膏之效率、填充因數及Rs3量測結果進行校正。
如表4至12中所示,例示性膏E1-E22經展示可製造串聯電阻總體改良之太陽能電池,如由Rs3量測結果所證明。串聯電阻之改良亦有助於總體太陽能電池效能得到改良。對於所測試之所有類型之矽晶圓,例示性膏依據相對效率及/或填充因數優於參照膏。相較於市售參照膏最顯著之改良由本發明之包含氧化碲添加劑之例示性膏在高薄層電阻矽晶圓(例如類型3晶圓(薄層電阻為90 Ω/□之單晶晶圓))情況下展示。參照膏在此類型之矽晶圓情況下的效能不良,提供不良之串聯電阻及總體低於正常之太陽能電池效能。與參照膏包含相同類型之含PbO玻璃粉的例示性膏E1及E2相較於參照膏展示出顯著改良之效能,提供極佳之串聯電阻量測結果及優良之太陽能電池總體效能。
展示於表4至12中之參照膏之電學效能數據亦清楚地展現出金屬化膏技術中持續存在的一個困難。使用完全相同之網版印刷及燒製程序在具有不同薄層電阻之多種矽晶圓上塗覆之相同參照膏產生效能特
徵各不相同之太陽能電池。舉例而言,在表4至12中參照膏之電池相關效率為0.8040至1.0915,差異超過28%。作為工業製程,該種大變化為不可接受的。膏組成物因此須針對各類型之矽晶圓進行改質以達成所得太陽能電池之最佳效能。改質製程通常為耗時的,因為導電膏包含多種可能需要最佳化之組分。
本發明併有氧化碲添加劑。作為添加劑而非基質形成組成物之一部分,氧化碲添加劑之量可容易地進行調節以用於不同類型之矽晶圓。咸信IRS系統之反應性可藉由調節氧化碲添加劑來進行微調。表4至12中呈現之數據展示藉由調節含鉛基質形成組成物及氧化碲添加劑,可預期由所有所測試矽晶圓達成最佳效能。對於例示性膏E1至E22,調節含鉛玻璃粉之類型及量及氧化碲之量。如上所示,所得太陽能電池依據相對效率及/或填充因數優於參照膏(表4至12)。此對於參照膏未能發揮作用之矽晶圓尤其如此(表7)。
本發明之此等及其他優勢對於熟習此項技術者而言將因上述說明書而顯而易見。因此,熟習此項技術者將瞭解可對上述實施例進行變化或修改而不背離本發明之廣泛之發明概念。僅出於說明目的描述任何特定實施例之特定尺寸。因此應瞭解,本發明不限於本文所述之特定實施例,而意欲包括處於本發明範疇及精神內之所有變化及修改。
Claims (20)
- 一種用於導電膏之無機反應系統,其包含含鉛基質形成組成物及氧化碲添加劑,其中該含鉛組成物佔該無機反應系統之5 wt.%至95 wt.%,且該氧化碲添加劑佔該無機反應系統之5 wt.%至95 wt.%。
- 如請求項1之無機反應系統,其中該含鉛基質形成組成物佔該無機反應系統之10 wt.%至90 wt.%,且該氧化碲添加劑佔該無機反應系統之10 wt.%至60 wt.%。
- 如請求項1至2中任一項之無機反應系統,其中該氧化碲添加劑包含二氧化碲、三氧化碲及在溫度200℃至1000℃下將轉化為氧化碲之任何碲化合物中之一或多者。
- 如請求項1至3中任一項之無機反應系統,其中該氧化碲添加劑之平均粒度小於10 μm,或小於1 μm。
- 如請求項1至4中任一項之無機反應系統,其中該含鉛基質形成組成物為較佳具有非晶形結構之玻璃粉,且亦可併有結晶相或化合物。
- 如請求項1至5中任一項之無機反應系統,其中該含鉛基質形成組成物包含氧化鉛。
- 如請求項1至6中任一項之無機反應系統,其中該含鉛基質形成組成物包含約10 wt.%至90 wt.%,較佳約25 wt.%至85 wt.%之氧化鉛。
- 如請求項1至6中任一項之無機反應系統,其中該含鉛基質形成組成物包含約5 wt.%至45 wt.%,較佳約10 wt.%至15 wt.%之氧化鉛。
- 如請求項1至8中任一項之無機反應系統,其中該無機反應系統 具有95:5至5:95之PbO:氧化碲添加劑重量百分比比率,較佳地,該無機反應系統具有10:1至1:10之PbO:氧化碲添加劑重量百分比比率,且更佳地,該PbO:氧化碲添加劑重量百分比比率為5:1至1:5。
- 一種導電膏組成物,其包含:金屬粒子;如請求項1至9中任一項之無機反應系統;及有機媒劑。
- 如請求項10之導電膏,其中該等金屬粒子為銀、金、銅及鎳中之至少一者。
- 如請求項10至11中任一項之導電膏,其中該等金屬粒子為銀。
- 如請求項10至12中任一項之導電膏,其中該等金屬粒子佔該膏之固體含量的約50 wt.%至95 wt.%。
- 如請求項10至13中任一項之導電膏,其中該有機媒劑包含黏合劑、界面活性劑、有機溶劑及觸變劑。
- 如請求項14之導電膏,其中該有機媒劑包含黏合劑,該黏合劑包含乙基纖維素或酚系樹脂、丙烯酸系物、聚乙烯醇縮丁醛或聚酯樹脂、聚碳酸酯、聚乙烯或聚胺基甲酸酯樹脂或松香衍生物中之至少一者。
- 如請求項14至15中任一項之導電膏,其中該有機媒劑包含界面活性劑,該界面活性劑包含聚氧化乙烯、聚乙二醇、苯并***、聚(乙二醇)乙酸、月桂酸、油酸、癸酸、肉豆蔻酸、亞油酸、硬脂酸、棕櫚酸、硬脂酸鹽、棕櫚酸鹽及其混合物中之至少一者。
- 如請求項14至16中任一項之導電膏,其中該有機媒劑包含溶劑,該溶劑包含卡必醇、萜品醇、己基卡必醇、醇酯十二 (texanol)、丁基卡必醇、丁基卡必醇乙酸酯或己二酸二甲酯或二醇醚中之至少一者。
- 如請求項14至16中任一項之導電膏,其中該黏合劑佔該有機媒劑之約1 wt.%至10 wt.%,該界面活性劑佔該有機媒劑之約1 wt.%至10 wt.%,該有機溶劑佔該有機媒劑之約50 wt.%至90 wt.%,且該觸變劑佔該有機媒劑之約0.1 wt.%至5 wt.%。
- 一種太陽能電池,其係藉由將如請求項10至18中任一項之導電膏塗覆至矽晶圓且對該矽晶圓進行燒製來製得。
- 如請求項19之太陽能電池,其中該矽晶圓之薄層電阻高於60 Ω/□,或高於65 Ω/□,或高於70 Ω/□,或高於90 Ω/□,或高於95 Ω/□。
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EP (1) | EP2654086B1 (zh) |
JP (1) | JP6356389B2 (zh) |
KR (1) | KR101908738B1 (zh) |
CN (1) | CN103377751B (zh) |
BR (1) | BR102013009357A2 (zh) |
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-
2013
- 2013-04-17 EP EP13002029.0A patent/EP2654086B1/en not_active Not-in-force
- 2013-04-17 JP JP2013086686A patent/JP6356389B2/ja not_active Expired - Fee Related
- 2013-04-17 SG SG2013029186A patent/SG194311A1/en unknown
- 2013-04-17 CN CN201310221918.4A patent/CN103377751B/zh not_active Expired - Fee Related
- 2013-04-17 TW TW102113671A patent/TW201349254A/zh unknown
- 2013-04-17 ES ES13002029T patent/ES2703905T3/es active Active
- 2013-04-17 KR KR1020130042528A patent/KR101908738B1/ko active IP Right Grant
- 2013-04-17 US US13/864,331 patent/US20130269772A1/en not_active Abandoned
- 2013-04-17 BR BRBR102013009357-2A patent/BR102013009357A2/pt not_active Application Discontinuation
-
2016
- 2016-09-07 US US15/258,248 patent/US10014418B2/en not_active Expired - Fee Related
Cited By (2)
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TWI756180B (zh) * | 2015-08-26 | 2022-03-01 | 日商昭和電工材料股份有限公司 | 用於矽太陽能電池的銀-鉍非接觸金屬化膏劑 |
TWI746503B (zh) * | 2016-01-20 | 2021-11-21 | 英商強生麥特公司 | 導電膠、方法、電極及太陽能電池 |
Also Published As
Publication number | Publication date |
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US20170301803A9 (en) | 2017-10-19 |
SG194311A1 (en) | 2013-11-29 |
JP2014038829A (ja) | 2014-02-27 |
KR101908738B1 (ko) | 2018-10-16 |
US10014418B2 (en) | 2018-07-03 |
CN103377751B (zh) | 2018-01-02 |
US20160380129A1 (en) | 2016-12-29 |
US20130269772A1 (en) | 2013-10-17 |
CN103377751A (zh) | 2013-10-30 |
EP2654086A1 (en) | 2013-10-23 |
EP2654086B1 (en) | 2018-10-03 |
BR102013009357A2 (pt) | 2015-06-23 |
ES2703905T3 (es) | 2019-03-13 |
KR20130117344A (ko) | 2013-10-25 |
JP6356389B2 (ja) | 2018-07-11 |
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