Understanding crystallization in undoped and nitrogen doped GeTe thin films using substrate curvature measurements

Herein, we study the crystallization of undoped and nitrogen doped amorphous GeTe thin films (slightly rich in Ge) obtained by sputtering using substrate curvature measurements to understand the underlying mechanisms controlling stress evolution in the film throughout the phase transformation. At temperatures below crystallization temperature, amorphous films showed stress relaxation and the stress gradually became tensile with annealing time. The GeTe samples show a two-step crystallization wherein amorphous GeTe crystallized first (at the crystallization temperature Tx) followed by crystallization of excess Ge (Ge precipitation) at -Tx+50 °C. Upon GeTe crystallization, a sharp increase in the tensile stress is explained using a coalescence mechanism. This interpretation resolves the issue of the discrepancy between the measured stress buildup reported by several authors and the predicted stress jump from elastic accommodation of density change. The precipitation of excess Ge (from amorphous to crystalline) along grain boundaries in GeTe leads to compressive stress build-up. Nitrogen doping affects both the GeTe and Ge crystallization events leading to lesser tensile and compressive stress. The models for stress relaxation in the amorphous phase, stress build-up due to GeTe, and excess Ge crystallization are discussed