TiO(2) is one of the most studied compounds in materials science. Owing to some outstanding properties it is used for instance in photocatalysis, dye-sensitized solar cells, and biomedical devices. In 1999, first reports showed the feasibility to grow highly ordered arrays of TiO(2) nanotubes by a simple but optimized electrochemical anodization of a titanium metal sheet. This finding stimulated intense research activities that focused on growth, modification, properties, and applications of these one-dimensional nanostructures. This review attempts to cover all these aspects, including underlying principles and key functional features of TiO(2), in a comprehensive way and also indicates potential future directions of the field.

TiO2 nanotubes: synthesis and applications.

The conditions for the self-organized formation of ordered hexagonal structures in anodic alumina were investigated for both oxalic and sulfuric acid as an electrolyte. Highly ordered pore arrays were obtained for oxidation in both acids. The size of the ordered domains depends strongly on the anodizing voltage. This effect is correlated with a voltage dependence of the volume expansion of the aluminum during oxidation and the current efficiency for oxide formation. The resulting mechanical stress at the metal/oxide interface is proposed to cause repulsive forces between the neighboring pores which promote the formation of ordered hexagonal pore arrays.

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Self-organized formation of hexagonal pore arrays in anodic alumina

Nanoporous anodic aluminium oxide has been widely used for the development of various functional nanostructures. So far these self-organized pore structures could only be prepared within narrow processing conditions. Here we report a new oxalic-acid-based anodization process for long-range ordered alumina membranes. This process is a new generation of the so-called "hard anodization" approach that has been widely used in industry for high-speed fabrication of mechanically robust, very thick (>100 microm) and low-porosity alumina films since the 1960s. This hard anodization approach establishes a new self-ordering regime with interpore distances, (D(int))=200-300 nm, which have not been achieved by mild anodization processes so far. It offers substantial advantages over conventional anodization processes in terms of processing time, allowing 2,500-3,500% faster oxide growth with improved ordering of the nanopores. Perfectly ordered alumina membranes with high aspect ratios (>1,000) of uniform nanopores with periodically modulated diameters have been realized.

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Fast fabrication of long-range ordered porous alumina membranes by hard anodization

The present paper gives an overview and review on self-organized TiO2 nanotube layers and other transition metal oxide tubular structures grown by controlled anodic oxidation of a metal substrate We describe mechanistic aspects of the tube growth and discuss the electrochemical conditions that need to be fulfilled in order to synthesize these layers Key properties of these highly ordered, high aspect ratio tubular layers are discussed In the past few years, a wide range of functional applications of the layers have been explored ranging from photocatalysis, solar energy conversion, electrochromic effects over using the material as a template or catalyst support to applications in the biomedical field A comprehensive view on state of the art is provided

TiO2 nanotubes: Self-organized electrochemical formation, properties and applications

The development of the ordered channel array in the anodic porous alumina was initiated by the textured pattern of the surface made by the molding process, and growth of an almost defect-free channel array can be achieved throughout the textured area. The long-range-ordered channel array with dimensions on the order of millimeters with a channel density of 1010 cm−2 was obtained, and the aspect ratio was over 150. The master for molding could be used many times, which makes it possible to overcome problems in the conventional nanolithographic technique, such as low through-put and high cost.

Highly ordered nanochannel-array architecture in anodic alumina

The morphology of porous anodic oxide films formed on aluminium in phosphoric acid electrolytes at constant current density or voltage, and under changing electrical or electrolytic conditions, has been studied quantitatively by electron microscopy. Replicas from film sections and from both film interfaces have been prepared, as well as transmission micrographs of thin films, produced under accurately defined conditions. During formation at constant current density, pore initiation occurs by the merging of locally thickening oxide regions, which seem related to the substructure of the substrate, and the consequent concentration of current into the residual thin areas. The pores grow in diameter and change in number until the steady-state morphology is established. The film barrier layer thickness has been measured directly for the first time. The steady-state barrier-layer thickness, cell diameter and pore diameter are all observed to be directly proportional to the formation voltage. It becomes evident that the barrier-layer thickness, decided largely by an equilibrium established between oxide formation in the barrier-layer and field-assisted dissolution (probably thermally enhanced) at the pore bases, determines the cell and pore sizes by a simple geometrical mechanism. Anion incorporation into the film and its hydrogen-bonded structure play secondary roles to these factors in determining the actual film morphology, although not its subsequent properties. A consequence of the mechanism is that, at constant current density, relatively non-aggressive electrolytes give thicker barrier layers, larger cells and larger pores next to the barrier layer than aggressive media, although subsequent pore widening at the outer surface of the film by simple chemical dissolution is more severe in aggressive electrolytes.

J. P. O'Sullivan

Papers

The morphology and mechanism of formation of porous anodic films on aluminium