New insights into thermomechanical behavior of GeTe thin films during crystallization

In this work, we reexamine Ge rejection in Ge-rich GeTe thin films with a slight deviation from stoichiometry using a unique combination of in situ measurements: curvature and x-ray diffraction as well as electrical resistance and x-ray diffraction and reflectivity during annealing. This unique combination of several experiments performed simultaneously on a synchrotron beamline allows to monitor in situ, during the crystallization and phase transformation, the microstructure, the strain and the stress changes, as well as electrical properties of GeTe films. Structural, electrical and thermomechanical evolutions of the GeTe thin films upon annealing are shown to follow three different steps. Stage I, before crystallization, is characterized by a tensile stress variation and a small decrease of the mass density. Stage II corresponds to the rhombohedral αGeTe phase crystallization leading to an abrupt tensile stress jump (+72 MPa), a mass density increase, and followed by a slight compressive stress evolution. During stage III, Ge crystallization is observed leading to a compressive stress jump (−54 MPa), an abrupt increase in αGeTe lattice spacing and diffracted intensity, whereas αGeTe diffraction peak widths decrease. During cooling a thermoelastic behavior is observed. A detailed analysis of stage III (Ge precipitation and crystallization) is performed and discussed regarding structural, stress, microstrain, electrical and thermomechanical properties. In particular, this study reveals that crystalline Ge precipitation results in important changes (volume of the unit cell, homogeneity of lattice spacing, average stress …) in the surrounding GeTe matrix. Different scenarios are proposed to understand these results.