Abstract
Perovskite tantalates have become potential candidates for water splitting photocatalysts. Therefore, it is of importance to understand the behavior of the photoinduced excess charges in these materials. Herein, we investigate the formation of electron and hole polarons in ${\mathrm{NaTaO}}_{3}$ and ${\mathrm{KTaO}}_{3}$. We perform Perdew-Burke-Ernzerhof hybrid density functional $\mathrm{PBE}0(\ensuremath{\alpha})$ calculations, in which we define the fraction $\ensuremath{\alpha}$ of the Fock exchange by enforcing the Koopmans' condition, to properly account for self-interaction corrections in these calculations. We find that the hole polaron mainly localizes on one oxygen site in both materials, leading to a structural distortion where two Ta--O bonds are elongated. The electron polaron, on the other hand, localizes within one atomic plane and exhibits a two-dimensional electron gas nature. Finally, we find that the strong localization of holes leads to a low hole mobility at room temperature $\ensuremath{\sim}2.94\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}6}\phantom{\rule{0.28em}{0ex}}{\mathrm{cm}}^{2}$/Vs and $\ensuremath{\sim}1.87\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}4}\phantom{\rule{0.28em}{0ex}}{\mathrm{cm}}^{2}$/Vs for ${\mathrm{KTaO}}_{3}$ and ${\mathrm{NaTaO}}_{3}$, respectively.
Highlights
Green hydrogen production by photocatalytic water splitting is a promising technology
The structures are distorted in such a way that two Ta–O bonds increase by about 0.15 Å for KTaO3 and 0.13 Å for NaTaO3
We have investigated the properties of the excess holes and electrons in NaTaO3 and KTaO3
Summary
Green hydrogen production by photocatalytic water splitting is a promising technology. 1(a) and 1(b)], have been extensively studied and have shown high chemical stability under (photo)electrochemical conditions, but their light absorption is limited to UV radiation due to their wide band gaps (NaTaO3 = 4.1 eV, KTaO3 = 3.6 eV) [1,2,3,4] Despite this limitation, tantalates are still considered to be promising materials for water splitting, for instance owing to the development of strategies to reduce their band gaps and increase efficiencies [5,6]. The photogenerated electrons and holes need to diffuse efficiently through the material and reach the surface where the reactions are taking place This process can be disrupted when photogenerated excess charges self-trap and form localized polarons accompanied by lattice distortion [7,8]. By employing the nudged elastic band (NEB) calculation [21], we evaluate the activation energy of hole hopping and the hole mobility in both materials
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