Stoichiometric deviations along an ingot of CuGaSe2

The dependence of the structural parameters on compositional deviations of CuGaSe2 has been studied. These deviations have been induced along an ingot by a single fusion of the components at 1150 °C and subsequent slow cooling in a stationary ampoule in a vertical furnace. All along the sample a single chalcopyrite phase is present and a compositional gradient along the ingot was found by energy-dispersive analysis of X-rays (EDAX) measurements, the upper part being rich in Ga (series B) and the lower part in Cu (series A), with Cu/Ga ratios of 0·95 and 1·1 respectively. A hypothesis of the existence of two phases in the melt is proposed to explain these facts. The unit cell parameters, anion displacement and Cu and Ga occupation numbers in their sublattices were analysed by X-ray powder diffraction and Rietveld refinement methods. In series A the occupation numbers are near stoichiometry, while in series B a Cu defect appears. In both series, changes in unit cell parameter are related to changes in Cu content, suggesting the presence of a fraction of Cu ions either as interstitials or at Ga sites when Cu is in excess, or of Cu vacancies in its sublattice when there is a Cu deficiency. © 1998 John Wiley & Sons, Ltd.