Hole antidoping of oxides

Malyi, Oleksandr I.; Zunger, Alex

doi:10.1103/physrevb.101.235202

Title: Hole antidoping of oxides

Journal Article · Mon Jun 08 00:00:00 EDT 2020 · Physical Review B

DOI:https://doi.org/10.1103/physrevb.101.235202· OSTI ID:1802112

^[1]; Zunger, Alex ^[1]

Univ. of Colorado, Boulder, CO (United States)

In standard doping, adding charge carrier to a compound results in a shift of the Fermi level towards the conduction band for electron doping and towards the valence band for hole doping. In this paper, we discuss the curious case of antidoping, where the direction of band movements in response to doping is reversed. Specifically, $$\textit{p}$$-type antidoping moves the previously occupied bands to the principal conduction band resulting in an increase of band gap energy and reduction of electronic conductivity. We find that this is a generic behavior for a class of materials: early transition and rare-earth metal (e.g., Ti, Ce) oxides where the sum of composition-weighed formal oxidation states is positive; such compounds tend to form the well-known electron-trapped intermediate bands localized on the reduced cation orbitals. What is less known is that doping by a hole annihilates a single trapped electron on a cation. The latter thus becomes electronically inequivalent with respect to the normal cation in the undoped lattice, thus representing a symmetry-breaking effect. We give specific theoretical predictions for target compounds where hole antidoping might be observed experimentally: Magnéli-like phases (i.e., CeO_2–x and TiO_2–x) and ternary compounds (i.e., Ba₂Ti₆O₁₃ and Ba₄Ti₁₂O₂₇), and note that this unique behavior opens the possibility of unconventional control of materials conductivity by doping.

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Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: SC0010467; DMR-1806939

OSTI ID:: 1802112

Journal Information:: Physical Review B, Vol. 101, Issue 23; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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