Transient XUV spectroscopy is growing in popularity for the measurement of solar fuel and photovoltaic materials as it can separately measure electron and hole energies for multiple elements at once. However, interpretation of transient XUV measureme
nts is complicated by changes in core-valence exciton and angular momentum effects after photoexcitation. Here, we report the photoexcited electron and hole dynamics for ZnTe, a promising material for CO2 reduction, following 400 nm excitation. We apply a newly developed, ab-initio theoretical approach based on density functional theory and the Bethe-Salpeter equation to accurately predict the excited state change in the measured transient XUV spectra. Electrons excited to the conduction band are measured with a thermalization rate of 70 $pm$ 40 fs. Holes are excited with an average excess energy of ~1 eV and thermalize in 1130 $pm$ 150 fs. The theoretical approach also allows an estimated assignment of inter- and intra-valley relaxation pathways in k-space using the relative amplitudes of the core-valence excitons.
Transient X-ray absorption techniques can measure ultrafast dynamics of the elemental edges in a material or multiple layer junction, giving them immense potential for deconvoluting concurrent processes. However, the interpretation of the photoexcite
d changes to an X-ray edge is not as simple as directly probing a transition with optical or infrared wavelengths. The core hole left by the core-level transition distorts the measured absorption and reflection spectra, both hiding and revealing different aspects of a photo-induced process. In this perspective, we describe the implementation and interpretation of transient X-ray experiments. This description includes a guide of how to choose the best wavelength and corresponding X-ray sources when designing an experiment. As an example, we focus on the rising use of extreme ultraviolet (XUV) spectroscopy for understanding performance limiting behaviors in solar energy materials, such as measurements of polaron formation, electron and hole kinetics, and charge transport in each layer of a metal-oxide-semiconductor junction. The ability of measuring photoexcited carriers in each layer of a multilayer junction could prove particularly impactful in the study of molecules, materials, and their combinations that lead to functional devices in photochemistry and photoelectrochemistry.
