Small Polarons and Surface Defects in Metal Oxide Photocatalysts Studied Using XUV Reflection–Absorption Spectroscopy
Savini Bandaranayake, Emily Hruska, Stephen Londo, Somnath Biswas, L. Robert Baker
Abstract
In photocatalytic transition metal oxides, the surface electronic structure and carrier kinetics are complicated by both charge trapping at defects and self-trapping by small polaron formation. These effects are specific to both the material and the type of defect or surface states involved. Here we review recent studies on ultrafast photoexcited charge carrier dynamics at the surfaces of α-Fe2O3 (hematite) and NiO and at the interface of a α-Fe2O3/NiO heterojunction using extreme ultraviolet (XUV) reflection–absorption spectroscopy. We study the dynamics of small polaron formation at hematite surfaces showing that the rate of carrier self-trapping is slower than in the bulk due to a greater lattice reorganization energy required for surface polaron formation. We also show that surface dynamics of hematite can be systematically tuned to control carrier transport properties through surface functionalization. To better understand the impact of defects on carrier events, we study charge carrier recombination of NiO. It is shown that O vacancies have no detrimental effect on carrier lifetime while grain boundaries cause fast recombination. Finally, we study a model heterojunction consisting of α-Fe2O3 and NiO and find that interfacial charge transfer across these two materials occurs by a two-step mechanism where the interfacial electric field drives fast exciton dissociation followed by hole injection from α-Fe2O3 to NiO. These examples illustrate future opportunities to observe surface electron dynamics in photocatalytic materials with element and chemical state resolution using ultrafast XUV spectroscopy.