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The structural, electronic, magnetic, optical and vibrational properties of the delafossite CuAlO2: DFT calculations and experimental study

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Abstract

Due to its electro-optical properties, the delafossite CuAlO2 is a potential candidate for energy conversion. Here, employing the Density Functional Theory (DFT), we performed the first-principles study of the electronic, dielectric, and dynamical properties of CuAlO2. The structural study shows a good agreement between the experimental and theoretical data. The electronic properties of CuAlO2 are investigated by the calculation of the band structure and the total and partial density of states. The optical gap (1.95 eV), indirectly allowed, is slightly over-estimated compared to the experiment value (1.96 eV), determined by diffuse reflectance. The diamagnetism conforms with closed-shell configurations of Cu+ (3d10) and Al3+ which obey the octet and 18 electron rules, respectively. However, a Curie constant of 0.014 uem CGS mol−1 with a slight paramagnetism is ascribed to the small amount of inserted O2− species with concomitant oxidation of Cu+ to Cu2+. The calculated Born effective charges are close to the nominal charges of the ions. Calculation of the full phonon dispersion spectrum with the atomic displacements allows a better understanding of the vibrational properties of CuAlO2: The Raman active modes (Eg and A1g) exhibit an O-site character while the infrared active modes (A2u and Eu) are featured by a combined shift of the three atoms. The photo-electrochemistry confirms the p-type behavior with a valence band edge of 5.35 eV below a vacuum, made up of Cu+: 3d orbital and far from the theoretical value of 6.9 eV. The discrepancy can be due to the fact that theoretical values are calculated at 0 Kelvin and at the point of zero charge (pzc).

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The authors confirm that the data supporting the findings of the study are available within the included “figure” and “table” files.

Notes

  1. Calculated from Al metal crystallizing in a face centered cubic structure with a lattice constant of 0.405 nm.

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Authors and Affiliations

  1. Laboratory of theoretical, computational and photonic chemistry (LCTCP), Faculté de Chimie, USTHB, B.P.32, Algiers, Algeria

    Mohamed Khedidji

  2. Scientific and Technical Research Centre in Physico-chemical Analysis (C.R.A.P.C), BP384, RP 42004, Bou-Ismail, Tipaza, Algeria

    Faouzi Saib

  3. Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, USTHB, B.P.32, Algiers, Algeria

    Oussama Mahroua & Mohamed Trari

Authors
  1. Mohamed Khedidji
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  2. Faouzi Saib
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  3. Oussama Mahroua
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  4. Mohamed Trari
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Contributions

MK, FS, OM, and MT contributed to the provided roles: Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing—original draft, Writing—review and editing.

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Correspondence to Mohamed Khedidji.

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Khedidji, M., Saib, F., Mahroua, O. et al. The structural, electronic, magnetic, optical and vibrational properties of the delafossite CuAlO2: DFT calculations and experimental study. J Mater Sci: Mater Electron 33, 26474–26483 (2022). https://doi.org/10.1007/s10854-022-09326-y

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