Influence of secondary phases during annealing on re-crystallization of CuInSe2 electrodeposited films

Electrodeposited CuInSe2 thin films are of potential importance, as light absorber material, in the next generation of photovoltaic cells as long as we can optimize their annealing process to obtain dense and highly crystalline films. The intent of this study was to gain a basic understanding of the key experimental parameters governing the structural-textural-composition evolution of thin films as function of the annealing temperature via X-ray diffraction, scanning/transmission electron microscopy and thermal analysis measurements. The crystallization of the electrodeposited CuInSe2 films, with the presence of Se and orthorhombic Cu2 − xSe (o-Cu2 − xSe) phases, occurs over two distinct temperature ranges, between 220 °C and 250 °C and beyond 520 °C. Such domains of temperature are consistent with the melting of elemental Se and the binary CuSe phase, respectively. The CuSe phase forming during annealing results from the reaction between the two secondary species o-Cu2 − xSe and Se (o-Cu2 − xSe + Se → 2 CuSe) but can be decomposed into the cubic β-Cu2 − xSe phase by slowing down the heating rate. Formation of liquid CuSe beyond 520°C seems to govern both the grain size of the films and the porosity of the substrate-CuInSe2 film interface. A simple model explaining the competitive interplay between the film crystallinity and the interface porosity is proposed, aiming at an improved protocol based on temperature range, which will enable to enhance the film crystalline nature while limiting the interface porosity.