Structural and electronic properties of Cu4O3 (paramelaconite): the role of native impurities
Zivkovic, A.; Sheehama,, Jacobina; Warwick, Michael E.A.; Jones, Daniel R.; Mitchel, Claire; Likius, Daniel; Uahengo, Veikko; Dzade, Nelson Y.; Meenakshisundaram,, Sankar; Dunnill, Charles W.; de Leeuw, Nora H.
(2021) Pure and Applied Chemistry, volume 93, issue 10, pp. 1229 - 1244
(Article)
Abstract
Hybrid density functional theory has been used to study the phase stability and formation of native point defects in Cu4O3. This intermediate copper oxide compound, also known as paramelaconite, was observed to be difficult to synthesize due to stabilization issues between mixed-valence Cu1+ and Cu2+ ions. The stability range of
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Cu4O3 was investigated and shown to be realized in an extremely narrow region of phase space, with Cu2O and CuO forming readily as competing impurity phases. The origin of p-type conductivity is confirmed to arise from specific intrinsic copper vacancies occurring on the 1+ site. Away from the outlined stability region, the dominant charge carriers become oxygen interstitials, impairing the conductivity by creating deep acceptor states in the electronic band gap region and driving the formation of alternative phases. This study further demonstrates the inadequacy of native defects as a source of n-type conductivity and complements existing experimental findings.
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Keywords: Chemistry and its applications, Cu4O3, VCCA-2020, density functional theory (DFT), instrinsic defects, p-type conductivity, paramelaconite, General Chemistry, General Chemical Engineering
ISSN: 0033-4545
Publisher: IUPAC Secretariat
Note: Funding Information: Research funding: This work was funded by Cardiff University, Royal Society, and Engineering and Physical Sciences Research Council (EP/S001395/1, EP/L000202). Funding Information: We acknowledge the Cardiff University School of Chemistry for a PhD studentship for AŽ and the Royal Society DfID Africa programme for funding. NYD acknowledges the UK Engineering and Physical Sciences Research Council (EPSRC) for funding (Grant No. EP/S001395/1). This work was performed using the computational facilities of the Advanced Research Computing @ Cardiff (ARCCA) Division, Cardiff University. Via our membership of the UK’s HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work made use of the ARCHER facility, the UK’s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC’s High End Computing Programme. Publisher Copyright: © 2021 IUPAC & De Gruyter.
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