Oriented single crystalline TiO2 nano-pillar arrays directly grown on titanium substrate in tetramethylammonium hydroxide solution

Oriented single crystalline titanium dioxide (TiO2) nano-pillar arrays were directly synthesized on the Ti plate in tetramethylammonium hydroxide (TMAOH) solution by one-pot hydrothermal method. The samples were characterized respectively by means of field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD). Results showed that the TiO2 nano-pillar with a tetrahydral bipyramidal tip grew vertically on the titanium substrate. HRTEM and Raman results confirmed that the TiO2 nano-pillar arrays were single crystalline anatase. The controls of morphology, size, and orientation of the nano-pillar could be achieved by varying the solution concentration and hydrothermal temperature. Furthermore, the special morphology of the TiO2 nano-pillar arrays was caused by the selectively absorption of the tetramethylammonium (TMA) through hydrogen bonds on the lattice planes parallel to (0 0 1) of anatase TiO2. Less grain boundaries and direct electrical pathway for electron transferring were crucial for the superior photoelectrochemical properties of the single anatase TiO2 nano-pillar arrays. This approach provides a facile in situ method to synthesize TiO2 nano-pillar arrays with a special morphology on titanium substrate.