Reaction pathways for ArF excimer laser assisted tungsten chemical vapor deposition from a WF6–H2 gas mixture

Abstract

Photolytic tungsten chemical vapor deposition by an ArF excimer laser from a WF6/H2/Ar gas mixture is a very complicated process with reactions occurring both in series and in parallel. In this article different reaction pathways were modeled and compared with experimental deposition rate data. The absorption cross section for WF6 was measured to 1.7×10−18 cm2 at the ArF excimer laser wavelength of 193 nm. From a rate equation model, it was concluded that the direct photolytic contribution to the deposition rate was negligible. Moreover, reduction of tungsten subfluorides by hydrogen atoms, formed in reactions between photolytically released fluorine atoms and molecular hydrogen, was also found to be negligible. However, photolysis in combination with various radical reactions generate a relatively high concentration of tungsten subfluorides (WF3, WF4, and WF5). Thermochemical calculations indicate that H2 reduction of tungsten subfluorides to solid tungsten, forming clusters in the vapor, is highly probable. Among the different cluster nucleation mechanisms polymerization of tungsten subfluorides seems to be an important step. This also explains the influence of WF6 partial pressure on the deposition rate.