Charge Dynamics of a CuO Thin Film on Picosecond to Microsecond Timescales Revealed by Transient Absorption Spectroscopy.

Abstract

Understanding the mechanism of charge dynamics in photocatalysts is the key to design and optimize more efficient materials for renewable energy applications. In this study, the charge dynamics of a CuO thin film are unraveled via transient absorption spectroscopy (TAS) on the picosecond to microsecond timescale for three different excitation energies, i.e., above, near, and below the band gap, to explore the role of incoherent broadband light sources. The shape of the ps-TAS spectra changes with the delay time, while that of the ns-TAS spectra is invariant for all the excitation energies. Regardless of the excitations, three time constants, τ1 ∼ 0.34-0.59 ps, τ2 ∼ 162-175 ns, and τ3 ∼ 2.5-3.3 μs, are resolved, indicating the dominating charge dynamics at very different timescales. Based on these observations, the UV-vis absorption spectrum, and previous findings in the literature, a compelling transition energy diagram is proposed. Two conduction bands and two defect (deep and shallow) states dominate the initial photo-induced electron transitions, and a sub-valence band energy state is involved in the subsequent transient absorption. By solving the rate equations for the pump-induced population dynamics and implementing the assumed Lorentzian absorption spectral shape between two energy states, the TAS spectra are modeled which capture the main spectral and time-dependent features for t > 1 ps. By further considering the contributions from free-electron absorption during very early delay times, the modeled spectra reproduce the experimental spectra very well over the entire time range and under different excitation conditions.