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Role of Vacancy Condensation in the Formation of Voids in Rutile TiO2 Nanowires

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Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Straße 1, 40237 Düsseldorf, Germany
Department of Materials Science and Engineering, NTNU, Norwegian University of Science and Technology, 7491 Trondheim, Norway
§ Materials Analytics, RWTH Aachen University, Kopernikusstr. 10, 52074 Aachen, Germany
Cite this: ACS Appl. Mater. Interfaces 2017, 9, 15, 13471–13479
Publication Date (Web):March 30, 2017
https://doi.org/10.1021/acsami.7b01160
Copyright © 2017 American Chemical Society
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Abstract

Titanium dioxide nanowire (NW) arrays are incorporated in many devices for energy conversion, energy storage, and catalysis. A common approach to fabricate these NWs is based on hydrothermal synthesis strategies. A drawback of this low-temperature method is that the NWs have a high density of defects, such as stacking faults, dislocations, and oxygen vacancies. These defects compromise the performance of devices. Here, we report a postgrowth thermal annealing procedure to remove these lattice defects and propose a mechanism to explain the underlying changes in the structure of the NWs. A detailed transmission electron microscopy study including in situ observation at elevated temperatures reveals a two-stage process. Additional spectroscopic analyses and X-ray diffraction experiments clarify the underlying mechanisms. In an early, low-temperature stage, the as-grown mesocrystalline NW converts to a single crystal by the dehydration of surface-bound OH groups. At temperatures above 500 °C, condensation of oxygen vacancies takes place, which leads to the fabrication of NWs with internal voids. These voids are faceted and covered with Ti3+-rich amorphous TiOx.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b01160.

  • In situ TEM heating experiment (AVI)

  • Three-dimensional reconstruction of the annealed NW (AVI)

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