Transition metal dichalcogenides such as WS2 are well-known for their layered structure and solid lubricant properties. The addition of another element, such as carbon, can improve the mechanical properties of the material, such as the hardness, while still maintaining the solid lubrication.1,2 Different theories regarding the friction mechanisms in W-S-C have been proposed: the low friction could be solely due to the WS2 phase2 or both the WS2 and the carbon phase could be responsible.1 Despite the hardness increase compared to pure WS2, W-S-C films still exhibit a quite low hardness. One route to increasing the hardness is to add a fourth element, which is a strong carbide-former (e. g. titanium), to form a hard carbide phase. In this work, W-S-C-Ti films have been deposited by magnetron sputtering and characterized with a variety of techniques. The mechanical and tribological properties have been studied and related to the composition.
The films were deposited by non-reactive DC magnetron sputtering using two targets: graphitic carbon and WS2, with a ring-shaped titanium component mounted on the latter. The titanium content was varied by the size of the metal component, while the carbon content was varied by the carbon target power. Four series of films were deposited at room temperature and at 300°C.
The micro- and nanostructure of the films was investigated by SEM and TEM, and XRD was used to study the presence of crystalline phases. The composition was determined by EDS, and the chemical bonding was studied by XPS and Raman spectroscopy. Nanoindentation was used to probe the mechanical properties of the different films, and ball-on-disc tests were performed in order to evaluate the tribological properties.
Results and Discussion
Previous studies on W-S-C suggest that the material consists of WS2 nanocrystallites embedded in an amorphous matrix. Also in this study, the only phase detected with XRD is WS2, with the typical WS2 peaks becoming broader with the addition of carbon indicating a decrease in crystallinity. TEM shows WS2 nanocrystallites embedded in an amorphous matrix. However, our results indicate that the composition of the matrix is more complex than what has previously been suggested. Chemical information from XPS suggests that the matrix is not based on carbon alone, but that it also includes a carbidic component. Furthermore, the S/W ratio in the samples is approximately constant but significantly lower than 2; such substochiometry in WS2 films is well known and we will discuss possible mechanisms for this behaviour.
By adding titanium to W-S-C, the chemical bonding in the material is changed. XPS indicates the presence of Ti-C bonds even when no crystalline TiC grains are observed by XRD. For high titanium and carbon contents, a crystalline phase with the sodium chloride structure is observed, which has a cell parameter significantly larger than TiC. Furthermore, the added titanium changes the mechanical properties of the films, and an increase in hardness up to 100% from 6 GPa to 12 GPa can be observed. The effect of titanium addition, however, is dependent on the film composition and the deposition temperature.
Tribological testing show friction coefficients down to approximately 0.02 in ball-on-disc tests using a steel ball in dry atmosphere for W-S-C films. The effect of titanium addition varies with the composition; high titanium contents combined with suitable carbon levels yields films that exhibit low and stable friction coefficients well under 0.02 under the aforementioned conditions. Thus, it is possible to tune the mechanical properties of W-S-C films, while still obtaining low friction, by the addition of titanium.
 A.A. Voevodin, J.S. Zabinski, Thin Solid Films 370, 223-231 (2000)
 T. Polcar, M. Evaristo, A. Cavaleiro, Plasma Process. Polym. 6, 417-424 (2009)
15th International Conference on Thin Films, Kyoto, Japan, 8-11 November 2011