In situ investigation of the formation of Cu(In,Ga)Se2 from selenised metallic precursors by X-ray diffraction—The impact of Gallium, Sodium and Selenium excess Original Research Article

The chemical reactions during rapid thermal processing of stacked elemental layers were investigated by angle-dispersive in situ X-ray diffraction. With a time resolution of 5 diffractograms per minute four different solid state reactions resulting in ternary chalcopyrites were identified: (A) CuSe+InSe→CuInSe2, (B) Cu2Se+2InSe+Se→2CuInSe2, (C) Cu2Se+In2Se3→2CuInSe2, (D) Cu2Se+Ga2Se3→2CuGaSe2. All these reactions form pure tenary chalcopyrites. The reaction resulting in the mixed crystal Cu(In,Ga)Se2 starts not before (B) has begun. The reaction speed of (A) and the fraction of CuInSe2 formed by (B) depend on Na-doping and Se-pressure, (C) takes place only, if the reaction paths (A) and (B) are suppressed. Reaction (D) is observed only, if 25% In is replaced by Ga in the precursor. The diffractograms were evaluated by Rietveld refinement to give the phase contents of the samples as a function of reaction time.