Morphology dependent electrical conduction and breakdown in single TiO2 nanotubes

Nanoscale Adv. 2020 Nov 27;3(2):432-445. doi: 10.1039/d0na00713g. eCollection 2021 Jan 26.

Abstract

Understanding the electrical conduction properties of a single nanostructure is essential for gaining insight into the fundamental charge transport through 1D materials and also for exploring the collective behavior of an array of such nanostructures. TiO2 nanostructures, such as electrochemically grown nanotubes, have been widely studied in recent times for several applications. The electrolyte plays a vital role in deciding the morphology, which, in turn, governs the charge transport behavior. Here we present a comparative study of the charge transport through a single TiO2 nanotube grown by electrochemical anodization using ethylene glycol and dimethyl sulphoxide electrolytes. The individual nanotubes are assembled into nanodevices using photolithography without relying on complex and sophisticated process like electron beam lithography or focused ion beam deposition. The electric field dependent charge transport properties show Schottky emission at a lower field regime and Poole-Frenkel emission in the higher region. The temperature-dependent electrical conduction (110 K-410 K) is mediated by two thermal activation processes, attributed to shallow impurities in the low-temperature range (T < 230 K) and to the donors at deep intermediate levels at higher temperatures (T > 230 K). The activation energies for EG based nanotubes are found to be higher than those for DMSO nanotubes owing to the double wall morphology of the formed tubes. Also, the study of the electrical breakdown phenomena of these nanotubes reveals three distinct categories of collapse. 'Model A' type breakdown is characterized by a stepwise rise of the current up to the breakdown point and a fall to zero following a non-uniform step by step decrease, which is driven by crack formation near the electrode interface and its propagation. 'Model B' shows a transient rise and fall in current, leading to breakdown due to electromigration, whereas 'Model C' type breakdown observed in a bundle of nanotubes shows a mixed trend of 'Model A' and 'Model B'. The data and analysis provide insight into the current limit through an individual nanotube or bundle of nanotubes and will be useful for designing prototype nanodevices from titania nanostructures.