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Excited‐State Dynamics of Ru(bpy)32+ Thin Films on Sensitized TiO2 and ZrO2

机译:敏化的TiO2和ZrO2上Ru(bpy)3 2+薄膜的激发态动力学

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摘要

The excited state dynamics of Tris(2,2′‐bipyridine)ruthenium(II) hexafluorophosphate, [Ru(bpy)3(PF6)2], was investigated on the surface of bare and sensitized TiO2 and ZrO2 films. The organic dyes LEG4 and MKA253 were selected as sensitizers. A Stern–Volmer plot of LEG4‐sensitized TiO2 substrates with a spin‐coated [Ru(bpy)3(PF6)2] layer on top shows considerable quenching of the emission of the latter. Interestingly, time‐resolved emission spectroscopy reveals the presence of a fast‐decay time component (25±5 ns), which is absent when the anatase TiO2 semiconductor is replaced by ZrO2. It should be specified that the positive redox potential of the ruthenium complex prevents electron transfer from the [Ru(bpy)3(PF6)2] ground state into the oxidized sensitizer. Therefore, we speculate that the fast‐decay time component observed stems from excited‐state electron transfer from [Ru(bpy)3(PF6)2] to the oxidized sensitizer. Solid‐state dye sensitized solar cells (ssDSSCs) employing MKA253 and LEG4 dyes, with [Ru(bpy)3(PF6)2] as a hole‐transporting material (HTM), exhibit 1.2 % and 1.1 % power conversion efficiency, respectively. This result illustrates the possibility of the hypothesized excited‐state electron transfer.
机译:研究了三(2,2'-联吡啶)六氟磷酸钌(II)[Ru(bpy)3(PF6)2]在裸露和敏化的TiO2和ZrO2薄膜表面的激发态动力学。选择有机染料LEG4和MKA253作为敏化剂。在顶部具有旋涂的[Ru(bpy)3(PF6)2]层的LEG4敏化的TiO2衬底的Stern-Volmer图显示了后者发射的相当大的淬灭。有趣的是,时间分辨发射光谱显示存在快速衰变时间分量(25±5 ns),而锐钛矿型TiO2半导体被ZrO2取代时则不存在。应当指出,钌络合物的正氧化还原电势可防止电子从[Ru(bpy)3(PF6)2]基态转移到氧化敏化剂中。因此,我们推测观察到的快速衰变时间成分是由于激发态电子从[Ru(bpy)3(PF6) 2 ]转移至氧化敏化剂。固态染料敏化太阳能电池(ssDSSC),采用MKA253和LEG4染料,[Ru(bpy) 3 (PF 6 2 ]作为一种空穴传输材料(HTM),其功率转换效率分别为1.2%和1.1%。该结果说明了假设的激发态电子转移的可能性。

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