A review of growth mechanism, structure and crystallinity of anodized TiO2 nanotubes

This paper reviews the state of the art of anodized titanium dioxide nanotubes (TiO2 NTs), with an emphasis on the growth mechanism leading to their formation and the effect of heat treatment on their structure and properties. The discussion is primarily focused on TiO2 NTs grown in fluoride containing electrolytes, although the mechanism of formation of NTs in fluoride free solutions via Rapid Breakdown Anodization (RBA) is briefly covered. After an initial overview of progress made on the synthesis of anodized TiO2 NTs the review provides an analysis of the factors affecting the anodizing process (fluoride concentration, electrolyte type, applied potential and anodizing time). Details of the current-time transient, the chemistry of the process and the chemical composition of the anodic films are described which provide key information to unveil the nanotube growth mechanism. The main debate is whether NTs growth in fluoride containing solutions occurs via field-assisted plastic flow (i.e. a constant upward displacement of the oxide to form the NTs) combined with field-assisted ejection of the Ti4+ ions (i.e. ions are ejected into the electrolyte without oxide formation) or via field-assisted dissolution (i.e. preferential dissolution at the pore base where the field is stronger) or whether both processes play a role. Whenever anodization takes place in organic solutions the experimental evidence supports the plastic flow model, whereas in aqueous media field-assisted (and chemical) dissolution occur. The mechanism of rib formation on the walls of the NTs is also reviewed, and it clearly emerges that the applied potential and water content in the electrolyte are key factors in determining whether the NTs are ribbed or smooth. There also appears to be a relationship between the presence of ribs and the evolution of oxygen bubbles at the anode. The impact of thermal treatment on the properties of the NTs is also described. A variety of crystalline structures are present in the NTs (i.e. anatase or rutile), depending on the heat treatment temperature and atmosphere and the resulting electrical properties can be varied from dielectric to semi-metallic. A heat treatment temperature limit ranging from 500 to 800 degrees C exists, depending on preparation history, above which sintering of nanoscale titania particles occurs leading to collapse of the NTs structure. Future work should aim at using annealing not just to influence the resulting crystalline phase, but also for generating defects to be exploited in specific applications (i.e. photocatalysis, water splitting and photovoltaics). (C) 2013 Elsevier B.V. All rights reserved.