Efficient MOF-Sensitized Solar Cells Featuring Solvothermally Grown [100]-Oriented Pillared Porphyrin Framework-11 Films on ZnO/FTO Surfaces
Efficient MOF-Sensitized Solar Cells Featuring Solvothermally Grown [100]-Oriented Pillared Porphyrin Framework-11 Films on ZnO/FTO Surfaces
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DOI：
10.1021/acsami.8b17807
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发表时间：
2019-01-23
影响因子：
9.5
通讯作者：
Saha, Sourav
中科院分区：
文献类型：
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作者：
Gordillo, Monica A.;Panda, Dillip K.;Saha, Sourav
由于能够以高度有序的周期性方式组装和组织大量氧化还原和光活性成分，结晶多孔金属有机框架（MOF）有潜力执行无数复杂的功能，包括在满足所需条件时的电荷传输和光能转换。在此，我们展示了精确[100]取向的柱状卟啉骨架11（PPF-11）薄膜的前所未有的自发溶剂热生长，该薄膜具有垂直排列的四（4-羧基苯基）卟啉（ZnTCPP）壁和水平排列的2,2'-二甲基-4,4'-联吡啶梁，附着在退火的ZnO-氟掺杂氧化锡（FTO）表面上，及其在光伏发电中的卓越光伏性能。液体结太阳能电池。 [100]取向的PPF-11/ZnO-FTO光阳极表现出优异的光伏响应（短路电流（J（SC））：4.65 mA/cm（2），开路电压（V-OC）：470 mV，功率转换效率：0.86％），轻松超越所有控制装置以及先前报道的卟啉和Ru（bpy）（3）（2+）基可见光光捕获 MOF 的光电流密度提高 10-1000 倍，效率提高 2-375 倍。与绝缘自组装单层上外延生长的 MOF 薄膜和不同取向的滴铸 PPF 薄膜相比，[100] 取向的 PPF-11/ZnO 薄膜的优异光伏行为可归因于几个因素，包括前者更好的电荷分离、传输和注入能力。非串联的 PPF-11 能够容纳缺电子的 C-60 客体，填充其近一半的空腔，并使它们参与 ZnTCPP/C-60 电荷转移相互作用。然而，C-60掺杂的PPF-11/ZnO薄膜表现出比未掺杂的[100]取向PPF-11/ZnO薄膜弱得多的光伏响应，这可能是由于C-60占据的空腔中排除了I-/I-3(-)电解质以及孤立的C-60客体无法支持长距离电荷移动。
Owing to their abilities to assemble and organize a large number of redox and photoactive components in highly ordered periodic fashion, crystalline porous metal-organic frameworks (MOFs) have the potential to execute myriad complex functions, including charge transport and light to electrical energy conversion when the required conditions are fulfilled. Herein, we demonstrate an unprecedented spontaneous solvothermal growth of precisely [100]-oriented pillared porphyrin framework-11 (PPF-11) films featuring vertically aligned Zn-tetrakis(4-carboxyphenyl)porphyrin (ZnTCPP) walls and horizontally aligned 2,2'-dimethyl-4,4'-bipyridine beams attached to annealed ZnO-fluorine-doped tin oxide (FTO) surfaces and their remarkable photovoltaic performance in liquid-junction solar cells. The [100]-oriented PPF-11/ZnO-FTO photoanodes displayed excellent photovoltaic response (short-circuit current (J(SC)): 4.65 mA/cm(2), open-circuit voltage (V-OC): 470 mV, power conversion efficiency: 0.86%) that easily outperformed all control devices as well as previously reported porphyrin and Ru(bpy)(3)(2+)-based visible light-harvesting MOFs with 10-1000 times greater photocurrent density and 2-375 times higher efficiency. The superior photovoltaic behavior of [100]-oriented PPF-11/ZnO films compared to epitaxially grown MOF thin films on insulating self-assembled monolayers and drop-cast PPF films with different orientations can be attributed to several factors, including better charge separation, transport, and injection capabilities of the former. The noncatenated PPF-11 was able to host electron-deficient C-60 guests, filling in nearly half of its cavities and engage them in ZnTCPP/C-60 charge-transfer interaction. However, the C-60-doped PPF-11/ZnO films displayed much weaker photovoltaic response than undoped [100]-oriented PPF-11/ZnO films presumably due to exclusion of I-/I-3(-) electrolyte from the C-60 occupied cavities and the inability of isolated C-60 guests to support long-range charge movement.