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arXiv · 1710.09925

Polaron formation, native defects, and electronic conduction in metal tungstates

Khang Hoang
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Abstract

Iron tungstate (FeWO$_4$) and manganese tungstate (MnWO$_4$) belong to a family of wolframite-type materials that has applications in various areas, including supercapacitors, batteries, and multiferroics. A detailed understanding of bulk properties and defect physics in these transition-metal tungstates has been lacking, however, impeding possible improvement of their functional properties. Here, we report a first-principles study of FeWO$_4$ and MnWO$_4$ using screened hybrid density-functional calculations. We find that in both compounds the electronic structure near the band edges are predominantly the highly localized transition-metal $d$ states, which allows for the formation of both hole polarons at the Fe (Mn) sites and electron polarons at the W sites. The dominant native point defects in FeWO$_4$ (MnWO$_4$) under realistic synthesis conditions are, however, the hole polarons at the Fe (Mn) sites and negatively charged Fe (Mn) vacancies. The presence of low-energy and highly mobile polarons provides explanation for the good p-type conductivity observed in experiments and the ability of the materials to store energy via a pseudocapacitive mechanism.

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Khang Hoang. 2017-10-26. Polaron formation, native defects, and electronic conduction in metal tungstates. https://doi.org/10.1103/physrevmaterials.1.024603

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