Controlling polaron formation at hematite surfaces by molecular functionalization probed by XUV reflection-absorption spectroscopy.

Small polaron formation is known to limit the photocatalytic charge transport efficiency of hematite via ultrafast carrier self-trapping. While small polaron formation is known to occur in bulk hematite, a complete description of surface polaron formation in this material is not fully understood. Theoretical predictions indicate that the kinetics and thermodynamics of surface polaron formation are different than those in bulk. However, to test these predictions requires the ability to experimentally differentiate polaron formation dynamics at the surface. Near grazing angle extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy is surface sensitive and provides element and oxidation state specific information on a femtosecond time scale. Using XUV-RA, we provide a systematic comparison between surface and bulk polaron formation kinetics and energetics in photoexcited hematite. We find that the rate of surface polaron formation (250 ± 40 fs) is about three times slower than bulk polaron formation (90 ± 5 fs) in photoexcited hematite. Additionally, we show that the surface polaron formation rate can be systematically tuned by surface molecular functionalization. Within the framework of a Marcus type model, the kinetics and energetics of polaron formation are discussed. The slower polaron formation rate observed at the surface is found to result from a greater lattice reorganization relative to bulk hematite, while surface functionalization is shown to tune both the lattice reorganization as well as the polaron stabilization energies. The ability to tune the kinetics and energetics of polaron formation and hopping by molecular functionalization provides the opportunity to synthetically control electron transport in hematite.