Thermodynamic route for self-forming 1.5 nm V-Nb-Mo-Ta-W high-entropy alloy barrier layer: Roles of enthalpy and mixing entropy

Abstract This study reports a thermodynamic route for self-forming an ultrathin V-Nb-Mo-Ta-W high-entropy alloy layer for potential use as a promising diffusion barrier. In Cu alloy films minor-doped with 1.2 at.% of one-to-five metallic elements (V, Nb, Mo, Ta and W), the alloying elements spontaneously segregated. Under the competition of enthalpy and mixing entropy that determines the delta Gibbs free energy, one and, in particular, five alloying element(s) formed an alloy solution layer at the Cu/Si interface, whereas three alloying elements differently formed intermetallic compound clusters at the grain boundaries of Cu. Dominant factors for the final states of the alloying elements include the large positive enthalpy between Cu and the alloying elements, the negative enthalpy among the alloying elements, and the low-to-high mixing entropy among the alloying elements. The self-forming quinary alloy layer of only 1.5 nm thick provided excellent resistance to the interdiffusion of Cu and Si up to 700°C, better than practical and other newly developed barrier materials.