Extreme Ultraviolet Reflection-Absorption Spectroscopy: Probing Dynamics at Surfaces from a Molecular Perspective.

Extreme ultraviolet light sources based on high harmonic generation are enabling the development of novel spectroscopic methods to help advance the frontiers of ultrafast science and technology. In this Account, we discuss the development of extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy at near grazing incident reflection geometry and highlight recent applications of this method to study ultrafast electron dynamics at surfaces. Measuring core-to-valence transitions with broadband, femtosecond pulses of XUV light extends the benefits of X-ray absorption spectroscopy to a laboratory tabletop by providing a chemical fingerprint of materials, including the ability to resolve individual elements with sensitivity to oxidation state, spin state, carrier polarity, and coordination geometry. Combining this chemical state sensitivity with femtosecond time resolution provides new insight into the material properties that govern charge carrier dynamics in complex materials. It is well-known that surface dynamics differ significantly from equivalent processes in bulk materials and that charge separation, trapping, transport, and recombination occurring uniquely at surfaces govern the efficiency of numerous technologically relevant processes spanning photocatalysis, photovoltaics, and information storage and processing. Importantly, XUV-RA spectroscopy at near grazing angle is also surface sensitive with a probe depth of ∼3 nm, providing a new window into electronic and structural dynamics at surfaces and interfaces. Here we highlight the unique capabilities and recent applications of XUV-RA spectroscopy to study photoinduced surface dynamics in metal oxide semiconductors, including photocatalytic oxides (FeO, CoO NiO, and CuFeO) as well as photoswitchable magnetic oxide (CoFeO). We first compare the ultrafast electron self-trapping rates via small polaron formation at the surface and bulk of FeO where we note that the energetics and kinetics of this process differ significantly at the surface. Additionally, we demonstrate the ability to systematically tune this kinetics by molecular functionalization, thereby providing a route to control carrier transport at surfaces. We also measure the spectral signatures of charge transfer excitons with site specific localization of both electrons and holes in a series of transition metal oxide semiconductors (FeO, NiO, CoO). The presence of valence band holes probed at the oxygen L-edge confirms a direct relationship between the metal-oxygen bond covalency and water oxidation efficiency. For a mixed metal oxide CuFeO in the layered delafossite structure, XUV-RA reveals that the sub-picosecond hole thermalization from O 2p to Cu 3d states of CuFeO leads to the spatial separation of electrons and holes, resulting in exceptional photocatalytic performance for H evolution and CO reduction of this material. Finally, we provide an example to show the ability of XUV-RA to probe spin state specific dynamics in a photoswitchable ferrimagnet, cobalt ferrite (CoFeO). This study provides a detailed understating of ultrafast spin switching in a complex magnetic material with site-specific resolution. In summary, the applications of XUV-RA spectroscopy demonstrated here illustrate the current abilities and future promise of this method to extend molecule-level understanding from well-defined photochemical complexes to complex materials so that charge and spin dynamics at surfaces can be tuned with the precision of molecular photochemistry.