Structural and electronic properties of Cu4O3 (paramelaconite): the role of native impurities

A. Zivkovic, Jacobina Sheehama,, Michael E.A. Warwick, Daniel R. Jones, Claire Mitchel, Daniel Likius, Veikko Uahengo, Nelson Y. Dzade, Sankar Meenakshisundaram,, Charles W. Dunnill, Nora H. de Leeuw

Research output: Contribution to journalArticleAcademicpeer-review


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 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.

Original languageEnglish
Pages (from-to)1229-1244
Number of pages16
JournalPure and Applied Chemistry
Issue number10
Publication statusPublished - 1 Oct 2021


  • Chemistry and its applications
  • Cu4O3
  • VCCA-2020
  • density functional theory (DFT)
  • instrinsic defects
  • p-type conductivity
  • paramelaconite


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