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Hydrothermally grown rutile TiO2 nanowires are intrinsically full of lattice defects, especially oxygen vacancies. These vacancies have a significant influence on the structural and electronic properties of the nanowires. In this study, we report a post-growth heat treatment in different environments that allows control of the distribution of these defects inside the nanowire, and thus gives direct access to tuning of the properties of rutile TiO2 nanowires. A detailed transmission electron microscopy study is used to analyze the structural changes inside the nanowires which are correlated to the measured optical and electrical properties. The highly defective as-grown nanowire arrays have a white appearance and show typical semiconducting properties with n-type conductivity, which is related to the high density of oxygen vacancies. Heat treatment in air atmosphere leads to a vacancy condensation and results in nanowires which possess insulating properties, whereas heat treatment in N2 atmosphere leads to nanowire arrays that appear black and show almost metal-like conductivity. We link this high conductivity to a TiO2-x shell which forms during the annealing process due to the slightly reducing N2 environment. [ABSTRACT FROM AUTHOR]

Three dimensional hierarchical metal oxide nanostructures, like TiO2 nanowire arrays, have attracted great attention for electrochemical energy conversion and storage applications. The functionality of such devices can be further enhanced by adding a nanowire shell with a different stoichiometry or composition compared to the core. Here, we report an approach with a facile heat treatment at 1050 °C, which allows the fabrication of rutile TiO2-SiOx core-shell nanowire arrays on silicon substrates. Our detailed electron microscopic investigation shows that this method is able to cover hydrothermally grown rutile TiO2 nanowires with a uniform shell of several nanometers in thickness. Moreover, the treatment improves the quality of the rutile TiO2 core by removing lattice defects, introduced from the hydrothermal growth. Electron energy loss spectroscopy reveals that the homogeneous shell around the TiO2 core consists of amorphous SiOx and does not form any intermediate phase with TiO2 at the interface. Thus, the properties of the TiO2 core are not affected by the shell, while the shell suppresses undesired electron back transfer. Latter leads to performance losses in many applications, e.g., dye sensitized solar cells, and is the main reason for a fast degradation of devices incorporating organic materials and TiO2. [ABSTRACT FROM AUTHOR]

Hydrothermally grown rutile TiO₂ nanowires are intrinsically full of lattice defects, especially oxygen vacancies. These vacancies have a significant influence on the structural and electronic properties of the nanowires. In this study, we report a post-growth heat treatment in different environments that allows control of the distribution of these defects inside the nanowire, and thus gives direct access to tuning of the properties of rutile TiO₂ nanowires. A detailed transmission electron microscopy study is used to analyze the structural changes inside the nanowires which are correlated to the measured optical and electrical properties. The highly defective as-grown nanowire arrays have a white appearance and show typical semiconducting properties with n-type conductivity, which is related to the high density of oxygen vacancies. Heat treatment in air atmosphere leads to a vacancy condensation and results in nanowires which possess insulating properties, whereas heat treatment in N₂ atmosphere leads to nanowire arrays that appear black and show almost metal-like conductivity. We link this high conductivity to a TiO 2- x shell which forms during the annealing process due to the slightly reducing N₂ environment., Competing Interests: The authors declare no conflict of interest.

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 Ti 3+ -rich amorphous TiO x .