Direct observations of crystallization processes of amorphous GeSn during thermal annealing: A temperature window for suppressing Sn segregation

Abstract

The solubility limit of tin (Sn) in germanium (Ge) is very small, and, therefore, it is difficult to synthesize high Sn concentration GeSn crystals by conventional methods. An amorphous phase can contain elements beyond the solubility limit of the crystal state, and, therefore, recrystallization of the amorphous alloy is one of the possible ways to realize materials far from the equilibrium state. To suppress Sn precipitation during thermal annealing, knowledge of crystallization processes is required. In the present study, amorphous GeSn thin films with different Sn concentrations were prepared by sputtering, and their crystallization processes were examined by in situ transmission electron microscopy. It was found that the crystallization temperature decreases with increasing Sn concentration, and it became lower than the eutectic temperature when the Sn concentration exceeded ∼25 at. %. Radial distribution function analyses revealed that phase decomposition occurs in the amorphous state of the specimens which crystallize below the eutectic temperature, and Sn crystallites were simultaneously precipitated with crystallization. On the other hand, no remarkable phase decomposition was detected in amorphous GeSn with <25 at. % Sn. Sn precipitation occurred at a higher temperature than the crystallization in these specimens, and the difference between the crystallization and Sn precipitation temperatures became large with decreasing Sn concentration. Because of the existence of this temperature difference, a temperature window for suppressing Sn segregation existed. We demonstrated that large GeSn grains with high Sn concentration could be realized by annealing the specimens within the temperature window.