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Distinguishing between Deep Trapping Transients of Electrons and Holes in TiO2 Nanotube Arrays Using Planar Microwave Resonator Sensor.

A large signal direct current (DC) bias and a small signal microwave bias were simultaneously applied to TiO2 nanotube membranes mounted on a planar microwave resonator. The DC bias modulated the electron concentration in the TiO2 nanotubes and was varied between 0 and 120 V in this study. Transients immediately following the application and removal of DC bias were measured by monitoring the S-parameters of the resonator as a function of time. The DC bias stimulated Poole-Frenkel-type trap-mediated electrical injection of excess carriers into TiO2 nanotubes, which resulted in a near-constant resonant frequency but a pronounced decrease in the microwave amplitude due to free electron absorption. When ultraviolet illumination and DC bias were both present and then stepwise removed, the resonant frequency shifted due to trapping-mediated change in the dielectric constant of the nanotube membranes. Characteristic lifetimes of 60-80, 300-800, and ∼3000 s were present regardless of whether light or bias was applied and were also observed in the presence of a hole scavenger, which we attributed to oxygen adsorption and deep electron traps, whereas another characteristic lifetime >8000 s was only present when illumination was applied, and is attributed to the presence of hole traps.