Evolution of target condition in reactive HiPIMS as a function of duty cycle: An opportunity for refractive index grading

Competition between target erosion and compound layer formation during pulse cycles in reactive HiPIMS opens up the possibility of tuning discharge conditions and the properties of deposited films by varying the duty cycle in situ without altering the reactive gas mixture. Three different reactive systems, hafnium in oxygen, tungsten in oxygen, and tungsten in oxygen/nitrogen, are studied in which amorphous films of hafnium oxide (HfO₂), tungsten oxide (WO₃), and tungsten oxynitride (WO_xN_y) are deposited. We show that the cyclic evolution of the target surface composition depends on the properties of the target including its affinity for the reactive gas mix and the compound layer melting point and volatility. We find that pulse length variations modulate the target compound layer and hence the discharge chemistry and properties of the films deposited. The refractive indices of HfO₂ and WO₃ were progressively reduced with the duty cycle, whereas that of WO_xN_y increased. These variations were found to be due to changes in the chemical composition and/or densification. We present and validate a phenomenological model that explains these findings in terms of a compound layer on the target surface that undergoes evolution during each pulse resulting in a cyclic equilibrium. The end points of the composition of the target surface depend on the duty cycle. Tuning the pulse characteristics holds great promise for the fabrication of multilayer films with through thickness graded properties.