A thermodynamic study on phase formation and thermal stability of AlSiTaTiZr high-entropy alloy thin films

The vast, unexplored chemical realm of multi-principal element alloys (MPEAs) has encouraged researchers to design and synthetize advanced materials based on refractory metals, metalloids, and deoxidizer elements, that are expected to follow single-phase, solid solution high-entropy alloys (HEAs)’ footsteps. In this paper, we have theoretically and experimentally studied the AlSiTaTiZr alloy in the thin film form, due to potential applications as a high-temperature oxidation-resistant coating. The MPEA film, synthetized by radio-frequency magnetron sputtering (RFMS), shows a considerable glass-forming ability. However, the metallic glass structure transits to several intermetallic compound phases by post-thermal annealing at ∼873 K, confirming that both thermodynamics and kinetics determine the formation of phases in sputtered MPEAs. Moreover, a strong tendency of Si and Al to form compounds with transition metals was revealed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and thermodynamic investigations. Special focus is given to the role played by both entropy and enthalpy on the phase evolution, demonstrated by thermodynamic calculations using the regular solution model and the CALculation of PHAse Diagrams (CALPHAD) method. This methodology is presented as a useful approach for starting deeper thermodynamic investigations in the thin film literature of MPEAs and HEAs, currently focused on the ultimate properties of such alloys. [Display omitted] •Phase formation in AlSiTaTiZr films is theoretically and experimentally studied.•Solid solution is destabilized due to the tendency of Si and Al to form compounds.•The as-deposited glassy metal transits to intermetallics after thermalannealing.•The role of entropy and enthalpy is demonstrated by thermodynamic calculations.•Design strategies are drawn in the large chemical realm of multicomponent alloys.