Thermodynamics and kinetic behaviors of thickness-dependent crystallization in high-k thin films deposited by atomic layer deposition

Abstract

Atomic layer deposition is adopted to prepare HfO2 and Al2O3 high-k thin films. The HfO2 thin films are amorphous at the initial growth stage, but become crystallized when the film thickness (h) exceeds a critical value (hcritical*). This phase transition from amorphous to crystalline is enhanced at higher temperatures and is discussed, taking into account the effect of kinetic energy. At lower temperatures, the amorphous state can be maintained even when h>hcritical* owing to the small number of activated atoms. However, the number of activated atoms increases with the temperature, allowing crystallization to occur even in films with smaller thickness. The Al2O3 thin films, on the other hand, maintain their amorphous state independent of the film thickness and temperature owing to the limited number of activated atoms. A thermodynamic model is proposed to describe the thickness-dependent phase transition.