Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy.

Penfold, Thomas J; Szlachetko, Jakub; Santomauro, Fabio G; Britz, Alexander; Gawelda, Wojciech; Doumy, Gilles; March, Anne Marie; Southworth, Stephen H et al. · Nat Commun · 2018

basic_science · Level V

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Abstract

Nanostructures of transition metal oxides, such as zinc oxide, have attracted considerable interest for solar-energy conversion and photocatalysis. Both applications are sensitive to the transport and trapping of photoexcited charge carriers. The probing of electron trapping has recently become possible using time-resolved element-sensitive methods, such as X-ray spectroscopy. However, valence-band-trapped holes have so far escaped observation. Herein we use X-ray absorption spectroscopy combined with a dispersive X-ray emission spectrometer to probe the charge carrier relaxation and trapping processes in zinc oxide nanoparticles after above band-gap photoexcitation. Our results, supported by simulations, demonstrate that within 80 ps, photoexcited holes are trapped at singly charged oxygen vacancies, which causes an outward displacement by ~15% of the four surrounding zinc atoms away from the doubly charged vacancy. This identification of the hole traps provides insight for future developments of transition metal oxide-based nanodevices.