Structural and Thermal Properties of Ternary Narrow-Gap Oxide Semiconductor; Wurtzite-Derived β‑CuGaO2

The crystal structure of the wurtzite-derived β-CuGaO2 was refined by Rietveld analysis of high-resolution powder diffraction data obtained from synchrotron X-ray radiation. Its structural characteristics are discussed in comparison with the other I–III–VI2 and II–VI oxide semiconductors. The cation and oxygen tetrahedral distortions of the β-CuGaO2 from an ideal wurtzite structure are small. The direct band-gap nature of the β-CuGaO2, unlike β-Ag­(Ga,Al)­O2, was explained by small cation and oxygen tetrahedral distortions. In terms of the thermal stability, the β-CuGaO2 irreversibly transforms into delafossite α-CuGaO2 at >460 °C in an Ar atmosphere. The transformation enthalpy was approximately −32 kJ mol–1, from differential scanning calorimetry. This value is close to the transformation enthalpy of CoO from the metastable zincblende form to the stable rock-salt form. The monovalent copper in β-CuGaO2 was oxidized to divalent copper in an oxygen atmosphere and transformed into a mixture of CuGa2O4 spinel and CuO at temperatures >350 °C. These thermal properties indicate that β-CuGaO2 is stable at ≤300 °C in both reducing and oxidizing atmospheres while in its metastable form. Consequently, this material could be of use in optoelectronic devices that do not exceed 300 °C.