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Fast Energy Relaxation by Trap States Decreases Electron Mobility in TiO2 Nanotubes: Time-Domain Ab Initio Analysis

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Institute of Functional Nano & Soft Materials (FUNSOM), Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou, Jiangsu 215123, China
Department of Chemistry, University of Rochester, Rochester, New York 14642, United States
Cite this: J. Phys. Chem. Lett. 2014, 5, 10, 1642–1647
Publication Date (Web):April 21, 2014
Copyright © 2014 American Chemical Society
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Highly ordered TiO2 nanotube arrays can be grown by simple electrochemical anodization of a titanium metal sheet, stimulating intense research and applications to solar cells and fuels. TiO2 nanotubes were expected to exhibit better electron transport than nanocrystal films. However, experiments showed that nanotubes provided little advantage over nanoparticles. Using nonadiabatic molecular dynamics, we demonstrate that oxygen vacancies, which are common in TiO2, accelerate nonradiative energy losses by an order of magnitude. Oxygen vacancies produce localized Ti3+ states hundreds of millielectronvolts below the TiO2 conduction band. The states lower the nanotube band gap, trap excited electrons, induce stronger electron–phonon couplings, and facilitate the relaxation. Our results rationalize the unforeseen experimental observations and provide the atomistic basis for improving the structure and charge transport by TiO2 nanotubes.

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