Age hardening in superhard ZrB2-rich Zr1-xTaxBy thin films

We recently showed that sputter-deposited Zr1-xTaxBy thin films have hexagonal AlB2-type columnar nanostructure in which column boundaries are B-rich for x < 0.2, while Ta-rich for x ≥ 0.2. As-deposited layers with x ≥ 0.2 exhibit higher hardness and, simultaneously, enhanced toughness. Here, we study the mechanical properties of ZrB2.4, Zr0.8Ta0.2B1.8, and Zr0.7Ta0.3B1.5 films annealed in Ar atmosphere as a function of annealing temperature Ta up to 1200 °C. In-situ and ex-situ nanoindentation analyses reveal that all films undergo age hardening up to Ta = 800 °C, with the highest hardness achieved for Zr0.8Ta0.2B1.8 (45.5±1.0 GPa). The age hardening, which occurs without any phase separation or decomposition, can be explained by point-defect recovery that enhances chemical bond density. Although hardness decreases at Ta > 800 °C due mainly to recrystallization, column coarsening, and planar defect annihilation, all layers show hardness values above 34 GPa over the entire Ta range