The field emission (FE) properties of TiO(2) nanotube arrays (TNAs) synthesized by anodization are dramatically improved after hydrogenation at various temperatures in a range of 400-550 °C. Compared with pristine TNAs, the turn-on fields of hydrogenated TNAs (H:TNAs) are significantly decreased from 18.23 to 1.75 V μm(-1), and closely related to hydrogenation temperature. Importantly, the optimized sample of H:TNAs prepared at 550 °C shows excellent FE performances involving both a low turn-on field of 1.75 V μm(-1), a high current density of 4.0 mA cm(-2) at 4.50V μm(-1), and a remarkable FE stability over 480 min. The substantially enhanced FE properties can be attributed to the combination of a typical tubular morphology, a reduced work function and the improved conductivity of H:TNAs.

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A mass of oxygen vacancies are successfully introduced into TiO2 nanotube arrays using low-cost NaBH4 as a reductant in a liquid-phase environment. By controlling and adjusting the reduction time over the range of 0-24 h, the doping concentration of the oxygen vacancy is controllable and eventually reaches saturation. Meanwhile, the thermal stability of oxygen vacancies is also investigated, indicating that part of the oxygen vacancies remain stable up to 250 °C. In addition, this liquid-phase reduction strategy significantly lowers the requirements of instruments and cost. More interesting, reduced TiO2 nanotube arrays show drastically enhanced field emission performances including substantially decreased turn-on field from 25.01 to 2.65 V/μm, a high current density of 3.5 mA/cm(2) at 7.2 V/μm, and an excellent field emission stability and repeatability. These results are attributed to the oxygen vacancies obtained by reducing in NaBH4 solution, resulting in a reduced effective work function and an increased conductivity.