BSTRACTExtreme cooling rates during physical vapor deposition (PVD) allow growth of metastable phases. However

we propose that reactive PVD processes can be described by a gas–solid paraequilibrium defining chemical composition and thus point defect concentration. We show that this notion allows for point defect engineering by controlling deposition conditions. As example we demonstrate that thermal stability of metastable (Ti

Al)N

x

the industrial benchmark coating for wear protection

can be increased from 800°C to unprecedented 1200°C by minimizing the vacancy concentration. The thermodynamic approach formulated here opens a pathway for thermal stability engineering by point defects in reactively deposited thin films.