TW201408755A - 光伏元件 - Google Patents
光伏元件 Download PDFInfo
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- TW201408755A TW201408755A TW102122353A TW102122353A TW201408755A TW 201408755 A TW201408755 A TW 201408755A TW 102122353 A TW102122353 A TW 102122353A TW 102122353 A TW102122353 A TW 102122353A TW 201408755 A TW201408755 A TW 201408755A
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- photoelectric conversion
- electron
- layer
- photovoltaic element
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 238000000605 extraction Methods 0.000 claims abstract description 41
- 150000001875 compounds Chemical group 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 description 35
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
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Abstract
本發明係提供一種具有高光電轉換效率之光伏元件,其係至少依序具有陽極、光電轉換層、電子提取層及陰極之光伏元件,其特徵為該電子提取層包含特定通式所表示之化合物群當中的至少一種。
Description
本發明係有關於光伏元件。
太陽能電池係屬環境友善的電能來源,目前作為針對嚴重度日增之能源問題的有力解決手段備受矚目。現今,作為太陽能電池之光伏元件的半導體材料,係使用單晶矽、多晶矽、非晶矽、化合物半導體等無機物。然而,由於使用無機半導體所製造之太陽能電池相較於火力發電或核能發電等的發電方式,其成本較高,尚未達到廣泛普及至一般家庭的地步。高成本的原因主要在於在真空且高溫下形成半導體薄膜的製程。因此,作為可達製程簡化之半導體材料,使用共軛系聚合物或有機結晶等有機半導體或有機色素之有機太陽能電池在被研究當中。於此類有機太陽能電池中,由於可依塗布法製作半導體材料,製程得以簡化。
惟,使用共軛系聚合物等之傳統有機太陽能電池相較於傳統上使用無機半導體之太陽能電池,其光電轉換效率較低,因此尚未達到實用化的地步。為達有機太陽能電池的實用化,則必須開拓可實現更高光電轉換效率之手法。
作為提升有機太陽能電池的光電轉換效率之方法,可舉出例如在包含銅酞青素與富勒體之積層膜的光電轉換層與銀陰極之間設置電子提取層的方法。藉此方法,藉由蒸鍍銀陰極來抑制光電轉換層的劣化等,可使轉換效率提升。而且,有機太陽能電池的電子提取層也在研究使用導入有離子性基的材料。
例如,已有揭露藉由將導入有乙酸銨鹽作為離子性基之經取代茀系聚合物(非專利文獻1)等作為有機太陽能電池的電子提取層使用,可提升轉換效率。
此外,已有揭示包含具有屬離子性基之配位性官能基的芳香族化合物的有機裝置用電荷注入材料,並指出其適用於有機太陽能電池之電子提取層(茲參照專利文獻1、非專利文獻2)。
專利文獻1 日本特開2005-353401號公報(請求項1、8)
非專利文獻1 Advanced Materials, 2011年,23卷,4636-4643頁
非專利文獻2 Advanced Functional Materials, 2011年,21卷,4338-4341頁
然而,根據本發明人等之見解,藉由插入傳統的電子提取層所產生的光電轉換效率的提升效果在以實用化為目標方面尚不充分。其原因在於,例如,若為如非專利文獻1之茀系聚合物時,由於其具有共軛長度較長之特徵,予以積層時會因吸收可見光區域的光而成為元件特性下降的原因,適應膜厚有其限制。欲均勻塗布較薄的電子提取層實屬困難,其表面粗糙度容易增大,且未能充分發揮作為電子提取層之功能。
再者,若為如專利文獻1或非專利文獻2之芳香族化合物時,本發明人等認為,於單分子中其共軛長度雖不長,惟予以積層時可能會因堆疊(stacking)等而具有分子間相互作用所產生的新的光吸收區域。
因此,本發明係以提供一種藉由將在可見光區域不具光吸收之有機材料用於電子提取層,而具有更高的光電轉換效率之光伏元件為目的。
本發明人等根據上述課題,著眼於不含芳香環或共軛雙鍵的烷基化合物。而且,盡心重複多次努力,終得以發現:藉由將導入有特定之離子性基的烷基化合物用於電子提取層,可獲得光電轉換效率優良的光伏元件。
即,本發明為一種光伏元件,其係至少依序具有陽極、光電轉換層、電子提取層及陰極之光伏元件,
其特徵為該電子提取層包含下述通式(1)所表示之化合物:R-X- M+ (1)
(R係由氫、可具取代基之烷基中選擇;X-係由-COO-、-SO3 -、-PO4H-、-PO4 2-、-O-SO3 -中選擇;M則由鹼金屬、鹼土金屬中選擇)。
根據本發明,可提供一種光電轉換效率高的光伏元件。
1‧‧‧基板
2‧‧‧陽極
3‧‧‧光電轉換層
4‧‧‧電子提取層
5‧‧‧陰極
第1圖為表示本發明之光伏元件之一形態的剖面圖。
本發明之光伏元件為至少依序具有陽極、光電轉換層、電子提取層及陰極之光伏元件,其中該電子提取層包含以下述通式(1)所表示之化合物:R-X- M+ (1)
(R係由氫、可具取代基之烷基中選擇;X-係由-COO-、-SO3 -、-PO4H-、-PO4 2-、-O-SO3 -中選擇;M則由鹼金屬、鹼土金屬、銨離子中選擇)。
可具取代基之烷基係表示例如甲基、乙基、丙基、丁基等飽和脂肪烴基。可具取代基之烷基亦可為聚乙烯或聚丙烯等飽和脂肪烴聚合物。
作為經取代時之取代基的實例,可列舉上述烷基或烷氧基、鹵素原子、羥基、氰基、胺基、羧基、羰基、乙醯基、磺醯基、矽烷基、氧硼基(boryl)、腈基、及彼等組合而成之基等。經取代時之取代基中不含芳基或共軛雙鍵系有機基。上述烷氧基係表示例如甲氧基、乙氧基、丙氧基、丁氧基等經由醚鍵之脂肪烴基。
茲例示上述R所表示之具體的取代基。惟,所例示之取代基係本發明所包含之一部分,不特別限定於此。再者,在以下所例示之取代基中,朝左側水平延伸的單線係表示取代基之鍵結位置。又,對於末端之甲基偶有省略其記載。
X-係由-COO-、-SO3 -、-PO4H-、-PP4 2-、-O-SO3 -中選擇。在實現更高的電子提取效率方面,較佳為-SO3 -、-COO-。更佳為-COO-。
M係由鹼金屬、鹼土金屬、銨離子中選擇。鹼金屬係指Li、Na、K、Rb、Cs、Fr之任一者。鹼土金屬則指Be、Mg、Ca、Sr、Ba、Ra之任一者。更佳為Na。
其次,例示上述通式(1)所表示之具體的化合物。惟,所例示之取代基係本發明所包含之一部分,不特別限定於此。作為上述通式(1)所表示之化合物,可列舉例如如下述之結構。
其次,就本發明之光伏元件加以說明。第1圖為表示本發明之光伏元件之一形態的剖面圖。於基板1上依序具有陽極2、光電轉換層3、包含上述通式(1)所表示之化合物群的電子提取層4、及陰極5。
基板1可以選擇使用可積層電極或光電轉換層者。例如可使用由無鹼玻璃、石英玻璃等無機材料、聚酯、聚碳酸酯、聚烯烴、聚醯胺、聚醯亞胺、聚苯硫、聚對二甲苯、環氧樹脂或氟系樹脂等有機材料採用任意方法所製作的薄膜或板。此外,使光由基板1側入射時,基板的透光率較佳為60-100%。於此,透光率係指依[穿透光強度(W/m2)/入射光強度(W/m2)]×100(%)所得之值。
本發明之光伏元件的陽極或陰極係具有透光性。只要至少任一者具有透光性即可,亦可兩者均具有透光性。於此,具有透光性意指入射光到達光電轉換層而產生電動勢之程度。亦即,當透光率具有超過0%之值時,即所謂具有透光性。具此透光性之電極較佳在400nm以上900nm以下的整個波長區域具有60-100%的透光率。此外,具有透光性之電極的厚度只要可獲得充分的導電性即可,係因材料而異,較佳為20nm~300nm。再者,不具透光性之電極只要具有導電性即可,就其厚度亦不特別限定。
作為電極材料,陽極較佳使用功函數較大的導電性材料,另一者之陰極則較佳使用功函數較小的導電性材料。
作為功函數較大的導電性材料,較佳採用金、鉑、鉻、鎳等金屬、具透明性之銦、錫等的金屬氧化物或複合金屬氧化物(銦錫氧化物(ITO)、銦鋅氧化物(IZO)等)之導電性高分子。尚且,陽極更佳為具有電洞
提取層。藉由電洞提取層,得以形成適於提取載子的界面狀態。甚而,尚有防止電極間的短路之效果。作為形成電洞提取層之材料,較佳採用含摻雜物之聚噻吩系聚合物、聚對苯撐乙烯系聚合物、聚茀系聚合物等導電性高分子、或氧化鉬等金屬氧化物。此外,聚噻吩系聚合物、聚對苯撐乙烯系聚合物、聚茀系聚合物分別指於主鏈具有噻吩骨架、對苯撐乙烯骨架、茀骨架之聚合物。此等當中,更佳為氧化鉬、或者含摻雜物之聚乙烯二氧噻吩(PEDOT)等聚噻吩系聚合物,尤佳為PEDOT與聚苯乙烯磺酸酯(PSS)之混合物。又,就電洞提取層而言,可將此等材料以複數層積層,亦可使積層材料相異。
作為功函數較小的導電性材料,較佳採用鋰等鹼金屬、鎂或鈣等鹼土金屬、錫、銀、鋁等。甚而,亦較佳採用包含上述金屬之合金或包含上述金屬積層體之電極。此外,陰極還可含有氟化鋰、氟化銫等金屬氟化物。
其次,就本發明之光伏元件中的光電轉換層加以說明。光電轉換層係由該陽極及陰極夾持,至少包含後述之(A)電子供給性有機半導體及(B)電子接收性有機半導體。可列舉例如包含電子供給性有機半導體與電子接收性有機半導體的混合物之層、積層包含電子供給性有機半導體之層與包含電子接收性有機半導體之層的構造、於包含電子供給性有機半導體之層與包含電子接收性有機半導體之層之間積層包含此等混合物之層的構造等。可含有2種以上之電子供給性有機半導體或電子
接收性有機半導體。本發明中之電子供給性有機半導體與電子接收性有機半導體,較佳為以混合層形成。光電轉換層中的電子供給性有機半導體與電子接收性有機半導體的含有比例不特別限定,惟電子供給性有機半導體:電子接收性有機半導體的重量分率較佳處於1~99:99~1之範圍,更佳處於10~90:90~10之範圍,再佳處於20~60:80~40之範圍。光電轉換層只要具有使(A)電子供給性有機半導體及(B)電子接收性有機半導體藉由光吸收產生光電動勢所需之足夠的厚度即可。其係因材料而異,惟較佳為10nm~1000nm之厚度,更佳為50nm~500nm。本發明中的光電轉換層在不妨害本發明目的之範圍內,可含有界面活性劑或黏著劑樹脂、填料等其他的成分。
電子供給性有機半導體只要是顯示p型半導體特性的有機物則未特別限定。可列舉例如聚噻吩系聚合物、2,1,3-苯并噻二唑-噻吩系共聚物、喹啉-噻吩系共聚物、噻吩-苯并二噻吩系共聚物、聚對苯撐乙烯系聚合物、聚對苯烯系(poly(p-phenylene))聚合物、聚茀系聚合物、聚吡咯系聚合物、聚苯胺系聚合物、聚乙炔系聚合物、聚噻吩乙烯系聚合物等共軛系聚合物、H2酞青素(H2Pc)、銅酞青素(CuPc)、鋅酞青素(ZnPc)等酞青素衍生物、紫質衍生物、N,N’-二苯基-N,N’-二(3-甲基苯基)-4,4’-二苯基-1,1’-二胺(TPD)、N,N’-二萘基-N,N’-二苯基-4,4’-二苯基-1,1’-二胺(NPD)等三芳基胺衍生物、4,4’-二(咔唑-9-基)聯苯(CBP)等咔唑衍生物、寡噻吩衍生
物(聯三噻吩、聯四噻吩、聯六噻吩、聯八噻吩等)等低分子有機化合物等。此等能以2種以上使用。
聚噻吩系聚合物係指於主鏈具有噻吩骨架之共軛系聚合物,於側鏈具有者亦包含在內。具體而言,可列舉聚-3-甲基噻吩、聚-3-丁基噻吩、聚-3-己基噻吩、聚-3-辛基噻吩、聚-3-癸基噻吩等聚-3-烷基噻吩、聚-3-甲氧基噻吩、聚-3-乙氧基噻吩、聚-3-十二氧基噻吩等聚-3-烷氧基噻吩、聚-3-甲氧基-4-甲基噻吩、聚-3-十二氧基-4-甲基噻吩等聚-3-烷氧基-4-烷基噻吩等。
2,1,3-苯并噻二唑-噻吩系共聚物係指於主鏈具有噻吩骨架與2,1,3-苯并噻二唑骨架之共軛系共聚物。作為2,1,3-苯并噻二唑-噻吩系共聚物,具體而言可舉出如下述之結構。於下式中,n表示1~1000之範圍。
喹啉-噻吩系共聚物係指於主鏈具有噻吩骨架與喹啉骨架之共軛系共聚物。作為喹啉-噻吩系共聚物,具體而言可舉出如下述之結構。於下式中,n表示1~1000之範圍。
噻吩-苯并二噻吩系聚合物係指於主鏈具有噻吩骨架與苯并二噻吩骨架之共軛系共聚物。作為噻吩-苯并二噻吩系共聚物,具體而言可舉出如下述之結構。於下式中,n表示1~1000之範圍。
聚對苯撐乙烯系聚合物係指於主鏈具有對苯撐乙烯骨架之共軛系聚合物,於側鏈具有者亦包含在內。具體而言,可列舉聚[2-甲氧基-5-(2-乙基己基氧基)-1,4-苯撐乙烯]、聚[2-甲氧基-5-(3’,7’-二甲基辛基氧基)-1,4-苯撐乙烯]等。
(B)電子接收性有機半導體只要是顯示n型半導體特性的有機物則未特別限定。可列舉例如1,4,5,8-萘四羧酸二酐、3,4,9,10-苝四羧酸二酐、N,N'-二辛基-3,4,9,10-萘基四羧基二醯亞胺、唑衍生物(2-(4-聯苯基)-5-(4-三級丁基苯基)-1,3,4-二唑、2,5-二(1-萘基)-1,3,4-二唑等)、三唑衍生物(3-(4-聯苯基)-4-苯基-5-(4-三級丁基苯基)-1,2,4-三唑等)、啡啉衍生物、富勒體衍生物、奈米碳管、於聚對苯撐乙烯系聚合物導入氰基之衍生物(CN-PPV)等。此等能以2種以上使用。由屬於穩定且載子移動率高的n型半導體言之,較佳使用富勒體衍生物。
作為上述富勒體衍生物的具體例,可列舉以C60、C70、C76、C78、C82、C84、C90、C94為首之未經取代者、與以[6,6]-苯基-C61-丁酸甲酯([6,6]-C61-PCBM、或[60]PCBM)、[5,6]-苯基-C61-丁酸甲酯、[6,6]-苯基-C61-丁酸己酯、[6,6]-苯基-C61-丁酸十二酯、苯基-C71-丁酸甲酯([70]PCBM)為首之經取代衍生物等。其中更佳為[70]PCBM。
本發明之光伏元件係具有包含上述通式(1)所表示之化合物群的電子提取層。上述電子提取層係以
「不僅可實現較習知者為高之電子提取效率,且在可見光區域不具吸收,因而可適應之膜厚範圍較廣」為特徵。該電子提取層在不妨礙本發明效果之範圍內,亦可含有上述通式(1)所表示之化合物群以外的物質。例如為傳統上電荷輸送層等用之啡啉單體化合物(BCP)等的電子輸送性有機物、或TiO2、ZnO、SiO2、SnO2、WO3、Ta2O3、BaTiO3、BaZrO3、ZrO2、HfO2、Al2O3、Y2O3、ZrSiO4之類的氧化物、Si3N4之類的氮化物、CdS、ZnSe及ZnS之類的半導體等的電子輸送性無機物。
此外,在不明顯妨礙本發明之光伏元件中的電子自光電轉換層向陰極提取之範圍內,亦可含有不具電子輸送性之物質。此等上述通式(1)所表示之化合物群以外的物質可與上述通式(1)所表示之化合物群形成混合層,亦可為積層構造。若為混合層時,該電子提取層中的上述通式(1)所表示之化合物群的含有比例不特別限定,以重量比例計較佳為1~99%之範圍,更佳為10~99%之範圍。
電子提取層只要依據所欲之光伏元件的光電轉換效率適當設定成最佳膜厚即可,較佳為0.1nm~50nm之厚度,更佳為0.5nm~10nm。
又,本發明之光伏元件亦可隔著1層以上之電荷再結合層積層(堆疊化)2層以上之光電轉換層而形成串聯接合。舉例言,可例舉「基板/陽極/第1光電轉換層/第1電子提取層/電荷再結合層/第2光電轉換層/第2電子提取層/陰極」之積層構造。藉由如此積層,即
可提高開路電壓。再者,可於陽極與第1光電轉換層之間、及電荷再結合層與第2光電轉換層之間設置上述電洞提取層,亦可於第1光電轉換層與電荷再結合層之間、及第2光電轉換層與陰極之間設置上述電洞提取層。對於此處所使用之電荷再結合層,為使複數光電轉換層可吸收光,則必需具有透光性。
且,電荷再結合層只要設計成使電洞與電子充分再結合即可,故不必然為膜,例如可為在光電轉換層上同樣地形成之金屬團簇。從而,電荷再結合層係採用包含上述金、鉑、鉻、鎳、鋰、鎂、鈣、錫、銀、鋁等之數埃至數十埃左右之具透光性的極薄金屬膜或金屬團簇(含合金)、ITO、IZO、AZO、GZO、FTO、氧化鈦或氧化鉬等透光性高之金屬氧化物膜及團簇、添加有PSS之PEDOT等之導電性有機材料膜、或此等之複合體等。
例如,只要採用真空蒸鍍法將銀在晶體共振器膜厚計上蒸鍍成數埃~1nm,可形成同樣的銀團簇。除此之外,如欲形成氧化鈦膜,只要採用Advanced Materials,2006年,18卷,572-576頁所記載之溶膠凝膠法即可。如為ITO、IZO等複合金屬氧化物,則採用濺鍍法進行製膜即可。此等電荷再結合層形成法或種類,只要考量電荷再結合層形成時對光電轉換層的非破壞性、或次一積層之光電轉換層之形成法等來適當選擇即可。
其次,就本發明之光伏元件之製造方法加以說明。於基板上採用濺鍍法等形成ITO等的透明電極(此
時相當於陽極)。接著,使包含電子供給性有機半導體材料、及電子接收性有機材料之光伏元件用材料溶解於溶媒來製作溶液,並予以塗布於透明電極上而形成光電轉換層。此時所使用之溶媒較佳為有機溶媒,可列舉例如甲醇、乙醇、丁醇、甲苯、二甲苯、鄰氯酚、丙酮、乙酸乙酯、乙二醇、四氫映喃、二氯甲烷、氯仿、二氯乙烷、氯苯、二氯苯、三氯苯、氯萘、二甲基甲醯胺、二甲基亞碸、N-甲基吡咯烷酮、γ-丁內酯等。此等能以2種以上使用。更且,透過將適當的添加劑添加至溶媒,可改變光電轉換層中的電子供給性有機半導體材料、及電子接收性有機材料的相分離構造。作為添加劑,可列舉例如1,8-辛烷二硫醇等硫醇化合物、1,8-二碘辛烷等碘化合物。
當混合本發明之電子供給性有機材料及電子接收性有機材料而形成光電轉換層時,係將本發明之電子供給性有機材料與電子接收性有機材料以所欲之比例添加至溶媒,並利用加熱、攪拌、超音波照射等方法使其溶解來製作溶液,再予以塗布於透明電極上。又,當積層本發明之電子供給性有機材料及電子接收性有機材料而形成光電轉換層時,係例如塗布本發明電子供給性有機材料的溶液而形成具電子供給性有機材料之層後,塗布電子接收性有機材料的溶液而形成層。於此,若本發明之電子供給性有機材料及電子接收性有機材料為分子量為1000以下左右之低分子量體時,亦可採用蒸鍍法來形成層。
為了形成光電轉換層,可採用旋轉塗布、刮刀塗布、縫模塗布、網版印刷塗布、棒式塗布、鑄型塗布、印刷轉印法、浸漬提起法、噴墨法、噴霧法、真空蒸鍍法等任一種方法,只要根據膜厚控制或配向控制等、所欲獲得之光電轉換層特性來選擇形成方法即可。例如在進行旋轉塗布時,本發明之電子供給性有機材料、及電子接收性有機材料較佳為1~20g/L之濃度(相對於含有本發明之電子供給性有機材料、電子接收性有機材料與溶媒之溶液體積、本發明之電子供給性有機材料與電子接收性有機材料的重量),予以調成此濃度,可得到厚度5~200nm之均質的光電轉換層。為了對形成之光電轉換層去除溶媒,亦可在減壓下或惰性氣體環境下(氮氣或氬氣環境下)等進行退火處理。退火處理之較佳溫度係為40℃~300℃,更佳為50℃~200℃。此退火處理亦可於陰極形成後進行。
其次,使包含上述通式(1)所表示之化合物的電子提取層用材料溶解於溶媒來製作溶液,於光電轉換層上形成電子提取層。此時所使用之溶媒較佳為有機溶媒,可列舉例如甲醇、乙醇、丁醇、甲苯、二甲苯、鄰氯酚、丙酮、乙酸乙酯、乙二醇、四氫映喃、二氯甲烷、氯仿、二氯乙烷、氯苯、二氯苯、三氯苯、氯萘、二甲基甲醯胺、二甲基亞碸、N-甲基吡咯烷酮、γ-丁內酯等。此等能以2種以上使用。
為了形成電子提取層,可採用與光電轉換層製作同樣的塗布法來製膜,只要根據膜厚控制或配向控
制等、所欲獲得之電子提取層來選擇形成方法即可。例如在進行旋轉塗布時,本發明之上述通式(1)所表示之化合物較佳為0.01~5g/l之濃度,予以調成此濃度,可得到厚度約0.1~40nm之電子提取層。為了對形成之電子提取層去除溶媒,亦可在減壓下或惰性氣體環境下(氮氣或氬氣環境下)等進行退火處理。退火處理之較佳溫度係為40℃~300℃,更佳為50℃~200℃。此退火處理亦可於陰極形成後進行。
於電子提取層上利用真空蒸鍍法或濺鍍法形成Ag等的金屬電極(此時相當於陰極)。就金屬電極而言,當真空蒸鍍電子提取層時,係以連續保持真空狀態持續形成為佳。
於陽極與光電轉換層之間設置電洞提取層時,係將所欲之p型有機半導體材料(PEDOT等)以旋轉塗布法、棒式塗布法、使用刮刀之成形法等塗布於陽極上後,利用真空恆溫槽或加熱板等去除溶媒,而形成電洞提取層。若使用氧化鉬等的無機材料時,亦可適用使用真空蒸鍍機之真空蒸鍍法。
本發明之光伏元件可應用於利用光電轉換機能、光整流機能等的各種光電轉換裝置。例如可用於光電池(太陽能電池等)、電子元件(光感測器、光開關、光電晶體等)、光記錄材料(光記憶體等)等。
以下,根據實施例對本發明更具體地加以說明。此外,本發明不限定於下述實施例。又,以下示出實施例等中所使用之化合物當中使用簡稱者。
Isc:短路電流密度
Voc:開路電壓
η:光電轉換效率
ITO:銦錫氧化物
PEDOT:聚乙烯二氧噻吩
PSS:聚苯乙烯磺酸酯
A-1:下式所表示之化合物(1-Material公司製)
[70]PCBM:苯基-C71-丁酸甲酯
CF:氯仿
IPA:2-丙醇
BCP:2,9-二甲基-4,7-二苯基-1,10-啡啉(浴銅靈)
各實施例.比較例中的光電轉換效率η(%)係依下式求取。
η(%)=Isc(mA/cm2)×Voc(V)×FF/照射光強度(mW/cm2)×100
FF=JVmax/(Isc(mA/cm2)×Voc(V))
JVmax(mW/cm2)為施加電壓在0V至開路電壓之間電流密度與施加電壓的積達最大之點處的電流密度與施加電壓的積之值。
各實施例.比較例中的光電轉換效率的劣化率係依下式求取。
劣化率(%)=連續照光後之光電轉換效率(%)/照光開始後隨即之光電轉換效率(%)×100
將0.10mL之CF溶媒添加至裝有0.4mg之A-1、0.6mg之[70]PCBM(Sorenu公司製)的樣品瓶中,於超音波清洗機(井內盛榮堂(股)製US-2、輸出功率120W)中進行超音波照射30分鐘而得到溶液A。
將利用濺鍍法堆積作為陽極之ITO透明導電層達125nm的玻璃基板切成38mm×46mm後,將ITO利用光微影法圖案化成38mm×13mm之長方形。以日立分光光度計U-3010測定所得基板的透光率的結果,在400nm~900nm的整個波長區域為85%以上。對該基板以鹼清洗液(Furuuchi Chemical(股)製、Semicoclean EL56)進行超音波清洗10分鐘後,以超純水加以清洗。對該基板實施UV/臭氧處理30分鐘後,於基板上利用旋轉塗布法塗布PEDOT:PSS水溶液(PEDOT0.8重量%、PSS0.5重量%),並使用加熱板於200℃加熱乾燥5分鐘而成膜為約60nm之厚度。將上述溶液A滴落至PEDOT:PSS層上,利用旋轉塗布法形成膜厚100nm之光電轉換層。其後,將肉豆蔻酸鈉(十四酸鈉)(東京化成工業(股)製)的0.5g/l乙醇溶液滴落至光電轉換層上,利用旋轉塗布法予以成膜(膜厚約5nm)。其後,將基板與陰極用遮罩設置於真空蒸鍍裝置內,抽氣至裝置內之真空度達
1×10-3Pa以下,再利用電阻加熱法,蒸鍍作為陰極的鋁層至100nm厚。由製作之元件的上下電極取出引出電極,即製成帶狀之ITO層與銀層重合之部分的面積為5mm×5mm的光伏元件。
將如此製作之光伏元件的上下電極連接至Keithley公司製2400系列Sourcemeter,於大氣下自ITO層側照射白光(AM1.5;100mW/cm2),並測定施加電壓由-1V變化至+2V時的電流值。測定係於開始照光後隨即進行。由所得電流值算出光電轉換效率(η)的結果為4.90%。
除使用1-十六烷磺酸鈉(東京化成工業(股)製)來替代肉豆蔻酸鈉以外係與實施例1完全同樣地製作光伏元件,算出光電轉換效率(η)的結果為4.60%。
除使用十二基硫酸鈉(東京化成工業(股)製)的0.2g/l IPA溶液來替代肉豆蔻酸鈉的0.5g/l乙醇溶液以外係與實施例1完全同樣地製作光伏元件,算出光電轉換效率(η)的結果為4.06%。
除使用單十二基磷酸鈉(東京化成工業(股)製)的0.2g/l甲醇溶液來替代肉豆蔻酸鈉的0.5g/l乙醇溶液以外係與實施例1完全同樣地製作光伏元件,算出光電轉換效率(η)的結果為4.39%。
除使用膽酸鈉(東京化成工業(股)製)的0.1g/l乙醇溶液來替代肉豆蔻酸鈉的0.5g/l乙醇溶液以外係與實施例1完全同樣地製作光伏元件,算出光電轉換效率(η)的結果為4.82%。
除未設置電子提取層以外係與實施例1完全同樣地製作光伏元件,算出光電轉換效率(η)的結果為3.59%。
除使用苯甲酸鈉(東京化成工業(股)製)的0.1g/l甲醇溶液來替代肉豆蔻酸鈉的0.5g/l乙醇溶液以外係與實施例1完全同樣地製作光伏元件,算出光電轉換效率(η)的結果為4.07%。
將實施例與比較例的結果彙整於表1。由實施例1~5與比較例1的比較、及實施例1、5與比較例2的比較可知,依本發明可提升光伏元件的光電轉換效率。
1‧‧‧基板
2‧‧‧陽極
3‧‧‧光電轉換層
4‧‧‧電子提取層
5‧‧‧陰極
Claims (3)
- 一種光伏元件,其係至少依序具有陽極、光電轉換層、電子提取層及陰極之光伏元件,其特徵為該電子提取層包含下述通式(1)所表示之化合物:R-X- M+ (1)(R係由氫、可具取代基之烷基中選擇;X-係由-COO-、-SO3 -、-PO4H-、-PO4 2-、-O-SO3 -中選擇;M則由鹼金屬、鹼土金屬、銨離子中選擇)。
- 如請求項1之光伏元件,其中X-為-COO-。
- 如請求項1或2之光伏元件,其中M為Na。
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