Influence of HiPIMS pulse widths on the deposition behaviour and properties of CuAgZr compositionally graded films

In this work, the influence of different pulse widths (25, 50 and 100 μs) during high power impulse magnetron sputtering (HiPIMS) of copper, silver and zirconium was investigated in terms of plasma properties and properties of combinatorial composition gradient CuAgZr film libraries. In situ plasma diagnostics via optical emission spectroscopy (OES), time-of-flight mass spectrometry (TOFMS), and modified quartz crystal microbalance (m-QCM), followed by film ex situ X-ray diffraction (XRD) and scanning electron microscopy (SEM) investigations allowed to determine the effect of deposition parameters on the thin films' microstructural changes. Changing the pulse width, while keeping the duty cycle constant, modified the discharge composition in the target region and the ionised fraction of the sputtered species in the substrate region. The maximum Cu ionised fraction (19 %) was found for 50 μs, resulting in compact and smooth morphology for Cu-rich films, whereas short 25 μs pulses provided porous columnar films with rough surfaces, as the result from Ar+ bombardment. For Ag-rich films, Ag segregation allowed the deposition of dense layers, regardless of the used pulse width.
Furthermore, low Ag (<10 at.%) CuAgZr films produced via HiPIMS and direct-current magnetron sputtering (DCMS) were compared in terms of structural and mechanical property changes as a function of Zr contents. For the studied chemical composition range, a linear relationship between Zr content, XRD phase shift and mechanical properties was observed for HiPIMS films, in contrast to DCMS's more abrupt transitions. An increase in hardness and elastic modulus (up to 44 % and 22 %, respectively) was found for the HiPIMS films compared to DCMS ones. The obtained results highlight HiPIMS's flexibility in providing a wide range of tailoring possibilities to meet specific application requirements, such as crystalline microstructure, density and associated mechanical properties.