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Electrochemical and photoelectrochemical characterization of CuFeO2 single crystal

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Abstract

CuFeO2 single crystal, synthesized by the flux method, is a narrow band gap semiconductor crystallizing in the delafossite structure with a direct optical transition of 1.63 eV. The oxide exhibits a good chemical stability; the semi-logarithmic plot gave an exchange current density of 0.60 µA cm−2 in KCl (0.5 M) electrolyte. CuFeO2 shows p-type conductivity; the origin of acceptors Cu2+ results from oxygen insertion in the layered lattice where most of excess holes are trapped in surface-polaron states. The electrochemical study is confined in the (a,b) plane and reversible oxygen intercalation is evidenced from the intensity potential characteristics. The detailed photoelectrochemical studies have been reported for the first time on the single crystal. The photocurrent is ascribed to the transfer Cu+:3d→3d. The capacitance measurement (C−2–V) shows a linear behavior from which a flat band potential of +0.54 VSCE and a density N A of 1.60 × 1018 cm−3 were determined. The valence band, located at 5.33 eV below vacuum, is made up of Cu-3d orbital typical of delafossite oxides. The Nyquist plot shows a semicircle attributed to a capacitive behavior with a low density of surface states within the gap. The centre is localized below the real axis with an angle of 16.2° ascribed to a constant phase element (CPE), a single barrier of the junction CuFeO2/electrolyte and one relaxation time of the electrical equivalent circuit.

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Notes

  1. Calculated from the lattice constant (0.3885 nm) of iron crystallizing in a face centered cubic lattice.

  2. χ is the geometrical mean of EA values of the constituent atoms, \(\chi \left( {{\text{CuFeO}}_2 } \right) = \left\{ {\left( {\chi {\text{Cu}}} \right)\left( {\chi {\text{Fe}}} \right)\left( {\chi {\text{O}}} \right)^2 } \right\}^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \). For a neutral atom, χ is given by \({{\left( {A_f + I_1 } \right)} \mathord{\left/ {\vphantom {{\left( {A_f + I_1 } \right)} 2}} \right. \kern-\nulldelimiterspace} 2}\) where A f is the electron affinity and I 1 the first ionization energy, the values were taken from [23].

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Acknowledgement

The authors are grateful to M. Younsi for valuable suggestions regarding to the corrosion measurements. Financial support of this work was provided the Faculty of Chemistry (Algiers).

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Authors and Affiliations

  1. Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, USTHB, P.O. Box 32, 16111, Algiers, Algeria

    S. Omeiri, B. Bellal, A. Bouguelia, Y. Bessekhouad & M. Trari

  2. Technical and Scientific Research Center of Physical Analysis, P.O. Box 248, 16004, Algiers, Algeria

    S. Omeiri

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  1. S. Omeiri
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  2. B. Bellal
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Correspondence to M. Trari.

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Omeiri, S., Bellal, B., Bouguelia, A. et al. Electrochemical and photoelectrochemical characterization of CuFeO2 single crystal. J Solid State Electrochem 13, 1395–1401 (2009). https://doi.org/10.1007/s10008-008-0703-3

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