Synthesis and growth mechanism of multilayer TiO2nanotube arrays

Abstract

High-aspect-ratio TiO₂ nanotube arrays formed by anodic oxidation have drawn extensive attention due to their easy fabrication and various excellent optical, electrical and biomedical properties. In contrast to conventional single-layer TiO₂ nanotubes prepared via constant-voltage anodization, we synthesize multilayer TiO₂ nanotube arrays with high surface area by using alternating-voltage anodization steps. This work presents synthesis and growth mechanisms of single-layer smooth TiO₂ nanotubes, bamboo-type nanotubes and double-layer nanotubes, by tuning various parameters such as voltage, time, and water content in the electrolyte. It is found that ion diffusion inside the nanotubes dominates growth of these three structures. A stable pH and ion-diffusion profile allows the steady growth of smooth TiO₂ tubes in NH₄F-containing ethylene glycol (EG). The addition of a low-voltage anodization step reduces the pH and ion-diffusion gradient in the nanotubes and induces formation of bamboo-type nanotubes and double-layer nanotubes when a second high-voltage anodization is conducted. Ion diffusion through a nanotube takes time; thus formation of lower-layer TO₂ nanotubes costs more time if longer nanotubes are grown in the upper layer, since ions diffuse through these longer nanotubes. This ion-diffusion controlled growth mechanism is further confirmed by tailoring the water content (0–20 vol%) in the electrolyte and the voltage gaps to control the time needed for initiation of lower-layer TiO₂ nanotube arrays. The fundamental understanding of the growth characteristics of double-layer TiO₂ nanotubes presented in this paper offers us more flexibility in engineering morphology, tuning dimensions and phase compositions of multilayer TiO₂ nanotubes. In addition, we synthesize double-layer TiO₂ nanotube arrays composed of one layer of anatase phase and another layer of amorphous phase.