Non-self-limiting nature of silicon reduction of WF6 in cold wall systems
Abstract
This paper addresses the kinetics and related mechanisms of non-self-limiting nature of Si reduction of WF6 in cold wall systems for the first time. The growth of such films in low-pressure chemical-vapor deposition (LPCVD) and ultrahigh vacuum (UHV) systems is compared. Both systems produce non-self-limiting, uniform, controllable, nonporous films. The growth is controlled by process parameters such as the wafer temperature and WF 6 concentration at the wafer surface. The order of the Si reduction reaction is 0.5 in the concentration of WF6. The tungsten films deposited in the LPCVD system contaminated with water vapor are thicker than the films grown in the UHV system even when the temperature is below 450°C. Such thicker films are produced as a result of the formation of an amorphous W-O layer. From the thermodynamic considerations, the origin of W-O layer is attributed to a parallel reaction between water vapor, WF6, and substrate Si. The beneficial role played by the W-O layer is that it prevents any volume shrinkage of the converted layer and restricts lateral encroachment. In the absence of such a layer as in the case of the UHV system, severe volume shrinkage and encroachment are observed. A theoretical model together with physical mechanisms explaining the non-self-limiting phenomenon are proposed. The mechanism suggests that a fine-grained W structure surrounded by a W-O layer, formed in the LPCVD system, assists faster out-diffusion of Si through the tungsten films compared to the UHV system. The higher values of the diffusion coefficient for Si out-diffusion through films grown in the LPCVD system as compared with the UHV system support this mechanism. The out-diffused Si is substituted to W by reduction reaction to complete the film growth.