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Defect Density-Dependent Electron Injection From Excited-State Ru(II) Tris-Diimine Complexes Into Defect- Controlled Oxide Semiconductors

DOI:10.1021/acs.jpcc.9b09781 期刊:The Journal of Physical Chemistry C 出版年份:2019 更新时间:2025-09-11 14:15:04
摘要: Dye-sensitized solar cells and photocatalysts that consist of a light absorbing dye and a wide gap oxide semiconductor substrate have been studied extensively as a means of solar energy conversion. Although defects existing at an oxide surface have a significant impact on the electron injection efficiency from the excited state dye-molecule into the oxide, the effects of defects on the electron injection process has not been fully understood in any dye-sensitized system. In this study, we present a systematic evaluation of electron injection into defects using emissive Ru(II) complexes adsorbed on oxide substrates (HCa2Nb3O10 nanosheets and nonstoichiometric SrTiO3—"), which had different defect densities. Using these oxides, electron injection from adsorbed Ru(II) complexes was observed by time-resolved emission spectroscopy. It was shown that electron injection from the excited state Ru(II) complex into an oxide was influenced by the defect density of the oxide as well as by the excited state oxidation potential (Eox*) of the Ru(II) complex. Electron injection was clearly accelerated with increasing defect density of the oxide, and was inhibited with increasing electron density of the oxide because of a trap-filling effect. Even though the Eox* of the Ru(II) complex was more positive than the conduction band edge potential of the oxide, electron injection into defects could be identified when a defective oxide was employed. The electron injection event is discussed in detail, on the basis of the defect density and the energy levels of oxides as well as the Eox* values of Ru(II) complexes. Overall the results suggest that it is possible to estimate the potential of surface defect states in an oxide by changing Eox* of an emissive complex dye.
作者: Shunta Nishioka,Yasuomi Yamazaki,Megumi Okazaki,Keita Sekizawa,Go Sahara,Riho Murakoshi,Daiki Saito,Ryo Kuriki,Takayoshi Oshima,Junji Hyodo,Yoshihiro Yamazaki,Osamu Ishitani,Thomas E Mallouk,Kazuhiko Maeda
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Investigating the effects of defect density in oxide semiconductors on the electron injection efficiency from excited-state Ru(II) tris-diimine complexes into the semiconductors.

The study demonstrates that electron injection from excited-state Ru(II) complexes into oxide semiconductors is significantly influenced by the defect density of the oxide. Higher defect densities accelerate electron injection, but excessive electron density can inhibit injection due to trap-filling effects. The methodology provides a new way to estimate the energy levels of surface defects in oxides using emissive metal complexes.

The study is limited by the qualitative control of defect densities in the oxide substrates and the specific range of Ru(II) complexes used, which may not cover all possible variations in excited state oxidation potentials. Additionally, the wide distribution of trap states in the oxides complicates a quantitative analysis of electron transfer kinetics.

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