TW201440288A - 紫質光敏染料化合物以及染料敏化太陽能電池 - Google Patents
紫質光敏染料化合物以及染料敏化太陽能電池 Download PDFInfo
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Abstract
一種紫質光敏染料化合物，適用於如染料敏化太陽能電池的光電轉換裝置中，該紫質光敏染料化合物為以下任一具有乙炔基取代之四吡咯基結構：□□□□□□其中同一結構式下的兩個電子予體單元D可為相同或不同；同一結構式下的兩個電子受體單元A可為相同或不同；同一結構式下的兩個阻隔單元P，如存在，可為相同或不同。
Description
本案關於一種光敏染料化合物，尤指一種適用於光電轉換裝置中的紫質光敏染料化合物。本案亦關於一種染料敏化太陽能電池。
太陽能電池可將自然存在、取之不盡、用之不竭的太陽光轉換成電能，且在產生能量時不會造成汙染，是一種具高價值，值得開發的替代能源。
傳統太陽能電池係以半導體太陽能電池為主，尤其以矽基材太陽能電池為主流，並隨著光電轉換效能與成本上的諸多考量加以逐步改良。即使如此，傳統太陽能電池在光電轉換效率與成本上仍有很大的改善空間，因此學界與業界一方面致力於對原有太陽能架構進行改良，同時也在找尋新的架構以提升效能並降低成本。其中，染料光敏化太陽能電池即為一種可行的選項，其成本甚至可低至傳統矽基材太陽能電池的1/5~1/10，而且不需要如矽基材太陽能電池般須在
高溫、真空的環境中製作，其製作條件相對容易。
染料敏化太陽能電池(Dye-Sensitized Solar Cell；DSSC)，是一種光化學電池，利用染料系列光敏化劑的光激發效應產生化學反應，進而產生光電流的一種電池。一般而言，染料敏化太陽能電池係由基板、透明導電膜、半導體膜、染料、電解質、以及相對電極等所構成，其發電原理是將特殊的染料吸附在二氧化鈦或氧化鋅等半導體膜上，染料照光後電子會躍遷到激發態，並有機會遷移到半導體上變成自由電子，這些自由電子會經由連接到半導體的導電玻璃或導電塑膠流出，形成電流。染料的另一側是電解質，失去電子的染料分子會從電解質接受電子，恢復至原有的狀態。而一開始從染料流出的電子，則在經過負載後，流到和電解質連接的鉑電極，補充電解質失去的電子，成為完整的迴路。在染料敏化太陽能電池中，光敏染料連接到半導體膜表面的方式，以及光敏染料的結構，都會影響光電轉換效率與電池的穩定性。光敏染料的選擇亦與成本息息相關，甚至攸關太陽能電池的發展潛力。
有機光敏染料因其高吸收係數(high absorption coefficient)、分子結構修飾(facile modification)及容易調整的光物理特性而在太陽能電池技術的研究發展中佔有一席之地。例如本案發明人與其他共同發明人先前所申請並已核准公告的台灣專利申請案公開第201020254號中提出一種紫質
光敏染料，紫質分子可視為一種人工葉綠素(chlorophyll)，葉綠素是一種眾所周知使植物呈現綠色的色素，它在植物中吸收太陽光進行光合作用而使二氧化碳與水轉換成醣類。紫質分子在DSSC中所扮演的角色類似於葉綠素分子在光合作用中所扮演的角色，它可以有效的吸收太陽光的可見光以及近紅外光部分再將之轉換為電能。紫質分子應用於太陽能電池上的優點在於其分子能階接近二氧化鈦，具有寬的吸收光譜，且電子停留在激發態的時間長。然而，過去以紫質分子作為光敏染料的元件效能不彰，部分原因是一般紫質分子易於堆疊所造成，而在台灣專利申請案公開第201020254號中利用一系列具推-拉電子基的高效能紫質染料可有效克服分子堆疊問題，提升光電轉換效率。
因此，本案在現有的紫質光敏染料的研發基礎上進一步就光敏染料的各項特性進行改善。例如當光敏染料應用於太陽能電池中時，在光電轉換效率、電池的穩定性、製成便利性、以及成本考量之間取得平衡，以提昇太陽能電池商業化發展的潛力。
本發明提供一種紫質光敏染料化合物，適用於如染料敏化太陽能電池的光電轉換裝置中，該紫質光敏染料化合物為以下任一具有乙炔基取代之四吡咯基結構：
本發明另外提供一種紫質光敏染料化合物，適用於如染料敏化太陽能電池的光電轉換裝置中，該紫質光敏染料化合物為以下任一具有乙炔基取代之四吡咯基結構：
本發明更提供一種紫質光敏染料化合物，適用於如染料敏化太陽能電池的光電轉換裝置中，該紫質光敏染料化合物為具有下式結構式的5-(4-羧基苯基乙炔基)-15-(4-(N,N-二辛基胺基)苯基乙炔基)-10,20-參(3,5-二-三級丁基-4-甲氧基苯基)鋅(II)紫質)
(5-(4-Carboxyphenylethynyl)-15-(4-(N,N-dioctylamino)phenylethynyl)-10,20-tri(3,5-di-tert-butyl-4-methoxyphenyl)porphyrinato Zinc(II))：
本發明亦關於一種染料敏化太陽能電池，包括如前述任一種之紫質光敏染料化合物。
本發明的紫質光敏染料化合物可用於各種應用染料光敏特性進行光電反應的光電轉換裝置，例如染料敏化太陽能電池中。在染料敏化太陽能電池中所使用的光敏染料，需要的條件不只電子會受光激發，還必須照光後電子躍遷的能階可以與半導體膜材料(如二氧化鈦)的能階匹配，如此激發態的電子才會轉移到半導體膜上，形成電流。此外，染料吸光的頻譜範圍也要越寬越好，如此才能吸收較多光能，而提高光電轉換效率。
為達上述要求，本案發明人致力研發出新穎的紫質光敏染料化合物，因此提出一系列紫質光敏染料化合物，具有如下式中的任一具有乙炔基取代之四吡咯基結構：
以下針對上述染料化合物中所包含的各單元的具體實例加以說明。
D為一電子予體單元(donor)，包括一推電子基，其係由下式組合中選取：
在一較佳實施例中，該電子予體單元D的推電子基係由下式組合中選取：
其中R=CnH2n+1或OCnH2n+1，n=0-12，m=0-5。
A為一電子受體單元(acceptor)，包括一拉電子基，該電子受體單元A的拉電子基與該電子予體單元D的推電子基形成推拉(push-pull)特性，有助於光敏染料性質的提升。其中該電子受體單元A的拉電子基係由下式組合中選取：
在一較佳實施例中，該電子受體單元A的拉電子基，其係由下式組合中選取：
P為一視情況存在的阻隔單元(blocker)，用以加大紫質分子間的距離，避免紫質分子間的堆疊，阻止電解質靠近二氧化鈦，避免電荷再結合，因而提升所製得太陽能電池的效能。該阻隔單元P較佳但不限於芳基，尤其是長碳鏈芳基，但事實上，隨著本發明紫質主結構下各單元取代基的不同，紫質分子間的堆疊若不嚴重則不需特別引入此阻隔單元(亦即P=H)，或者只需要具取代或不具取代的苯基、烷基等。如果阻隔單元的存在有其必要，可由下式組合中選取：
其中R=CnH2n+1或CnH2F2n-1或OCnH2n+1或OCnH2F2n-1，n=0-12，m=0-5。
在一較佳實施例中，該阻隔單元P，如存在，可為選自下式結構之一：
該電子受體單元A的拉電子基與該電子予體單元D的推電子基形成推拉(push-pull)特性，有助於光敏染料性質的提升。另外，該電子受體單元A與該電子予體單元D若選用大分子基團，具有加寬吸收光譜的優點。不過，當光敏染料應用於太陽能電池中時，除了光電轉換效率、電池的穩定性之外，製程便利性、以及成本考量之間也應取得平衡，方可提昇太陽能電池商業化發展的潛力。
在以上各種不同乙炔基四吡咯基中心結構、電子予體單元推電子基、電子受體單元拉電子基、以及視情況存在的阻隔單元分別與碳碳三鍵所構成不同組合的化合物中，會因所要求性質的不同而有所取捨。例如選擇分子較大的電
子予體D與電子受體A有助於加寬染料的吸收光譜；在電子受體A中採用二羥基、二羧基、二酮等雙官能基結構有助於與如二氧化鈦等半導體膜的結合穩定性；簡單的中心單元結構有助於成本的降低與製程的簡易化等等。例如，下式的5-(4-羧基苯基乙炔基)-15-(4-(N,N-二辛基胺基)苯基乙炔基)-10,20-參(3,5-二-三級丁基-4-甲氧基苯基)鋅(II)紫質)(5-(4-Carboxyphenylethynl)-15-(4-(N,N-dioctylamino)phenylethynyl)-10,20-tri(3,5-di-tert-butyl-4-methoxyphenyl)porphyrinato Zinc(II))即在兼顧光電轉換效率、製程容易度、以及成本的諸多考量之下為本發明較佳實施例之一：
為使熟習此技藝之人士可藉由合成方法而得知本發明製程簡易的優勢，以下舉例說明該5-(4-羧基苯基乙炔基)-15-(4-(N,N-二辛基胺基)苯基乙炔基)-10,20-參(3,5-二-三級丁基-4-甲氧基苯基)鋅(II)紫質)化合物的合成方法。請注意以
下合成方法僅為例舉，本發明染料分子亦可以其他方法加以合成。
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，故本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (9)
- 一種紫質光敏染料化合物，適用於一光電轉換裝置中，該光敏染料化合物具有如下式中的任一具有乙炔基取代之四吡咯基結構：
- 如申請專利範圍第1項所述之紫質光敏染料化合物，為具有下式結構式的5-(4-羧基苯基乙炔基)-15-(4-(N,N-二辛基胺基)苯基乙炔基)-10,20-參(3,5-二-三級丁基-4-甲氧基苯基)鋅(II)紫質)(5-(4-Carboxyphenylethynl)-15-(4-(N,N-dioctylamino)phenylethynyl)-10,20-tri(3,5-di-tert-butyl-4-methoxyphenyl)porphyrinato Zinc(II))：
- 一種紫質光敏染料化合物，適用於一光電轉換裝置中，該紫質光敏染料化合物具有如下式中的任一具有乙炔基取代之四吡咯基結構：
- 如申請專利範圍第1項所述之紫質光敏染料化合物，其中其中該電子予體單元D係由下式組合中選取：
- 如申請專利範圍第1項所述之紫質光敏染料化合物，其中該電子受體單元A係由下式組合中選取：
- 如申請專利範圍第1項所述之紫質光敏染料化合物，其中該阻隔單元P具有選自下式之一的結構：
- 一種紫質光敏染料化合物，適用於一染料敏化太陽能電池中，為具有下式結構式的5-(4-羧基苯基乙炔基)-15-(4-(N,N-二辛基胺基)苯基乙炔基)-10,20-參(3,5-二-三級丁基-4-甲氧基苯基)鋅(II)紫質)(5-(4-Carboxyphenylethynl)-15-(4-(N,N-dioctylamino)phenylethynyl)-10,20-tri(3,5-di-tert-butyl-4-methoxyphenyl)porphyrinato Zinc(II))：
- 一種染料敏化太陽能電池，包括一種如申請專利範圍第1-2項中任一項所述之紫質光敏染料化合物，塗佈於一半導體膜上作為光敏化劑。
- 一種染料敏化太陽能電池，包括一種如申請專利範圍第3-6項中任一項所述之紫質光敏染料化合物，塗佈於一半導體膜上作為光敏化劑。
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| US14/551,867 US9691555B2 (en) | 2014-07-01 | 2014-11-24 | Photosensitive porphyrin dyes for dye-sensitized solar cells |
| EP15173501.6A EP2977412A3 (en) | 2014-07-01 | 2015-06-24 | Photosensitive porphyrin-based dye and dye-sensitized solar cell |
| KR1020150092060A KR20160003566A (ko) | 2014-07-01 | 2015-06-29 | 감광성 포르피린계 염료 및 염료-감응형 태양 전지 |
| JP2015130977A JP6106217B2 (ja) | 2014-07-01 | 2015-06-30 | 感光性のポルフィリン系染料、及び色素増感太陽電池 |
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| US9688858B1 (en) | 2016-04-13 | 2017-06-27 | National Chi Nan University | Bacteriochlorin-based organic dye |
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| CN111187271B (zh) * | 2020-01-08 | 2021-05-14 | 华南理工大学 | 一种卟啉有机小分子受体材料及其制备方法和在有机太阳电池中的应用 |
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| US6943054B2 (en) | 2003-07-25 | 2005-09-13 | The Regents Of The University Of California | Attachment of organic molecules to group III, IV or V substrates |
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| US7582751B2 (en) | 2005-07-29 | 2009-09-01 | North Carolina State University | Methods and intermediates for the synthesis of porphyrins |
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| CN103044952A (zh) | 2013-01-04 | 2013-04-17 | 北京科技大学 | 一类不对称卟啉太阳能电池染料及其制备方法 |
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| US9688858B1 (en) | 2016-04-13 | 2017-06-27 | National Chi Nan University | Bacteriochlorin-based organic dye |
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| EP2977412A3 (en) | 2016-05-11 |
| JP2016015488A (ja) | 2016-01-28 |
| US20160005546A1 (en) | 2016-01-07 |
| US9691555B2 (en) | 2017-06-27 |
| KR20160003566A (ko) | 2016-01-11 |
| TWI474536B (zh) | 2015-02-21 |
| EP2977412A2 (en) | 2016-01-27 |
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