Determining role of W+ ions in the densification of TiAlWN thin films grown by hybrid HiPIMS/DCMS technique with no external heating

Hybrid high-power impulse and dc magnetron co-sputtering (HiPIMS/DCMS) with substrate bias synchronized to the high mass metal-ion fluxes was previously proposed as a solution to reduce energy consumption during physical vapor deposition processing and enable coatings on temperature-sensitive substrates. In this approach, no substrate heating is used (substrate temperature is lower than 150 oC) and the thermally activated adatom mobility, necessary to grow dense films, is substituted by overlapping collision cascades induced by heavy ion bombardment and consisting predominantly of low-energy recoils. Here, we present direct evidence for the crucial role of W+ ion irradiation in the densification of Ti0.31Al0.60W0.09N films grown by the hybrid W-HiPIMS/TiAl-DCMS co-sputtering. The peak target current density Jmax on the W target is varied from 0.06 to 0.78 A/cm2 resulting in more than fivefold increase in the number of W+ ions per deposited metal atom, η = W+/(W + Al + Ti) determined by time-resolved ion mass spectrometry analyses performed at the substrate plane under conditions identical to those during film growth. The DCMS is adjusted appropriately to maintain the W content in the films constant at Ti0.31Al0.60W0.09N. The degree of porosity, assessed qualitatively from cross-sectional SEM images and quantitatively from oxygen concentration profiles as well as nanoindentation hardness, is a strong function of η(Jmax). Layers grown with low η values are porous and soft, while those deposited under conditions of high η are dense and hard. Nanoindentation hardness of Ti0.31Al0.60W0.09N films with the highest density is ∼33 GPa, which is very similar to values reported for layers deposited at much higher temperatures (420–500 oC) by conventional metal-ion-based techniques. These results prove that the hybrid HiPIMS/DCMS co-sputtering with bias pulses synchronized to high mass metal ion irradiation can be successfully used to replace conventional solutions. The large energy losses associated with heating of the entire vacuum chamber are avoided, by focusing the energy input to where it is in fact needed, i.e., the workpiece to be coated.