We used experiments and physically based process simulations to study the re-emission of Ti and W during sputter deposition of Ti-W films and Ti during the sputter deposition of Ti films. Ti-W thin films have previously been shown to become Ti rich in geometrically confined areas, such as in features of a microelectronic device, compared to unconfined areas. This spatial composition variation was attributed to re-emission of Ti during the deposition process. Re-emission during Ti-W sputter deposition was confirmed by depositing a Ti-W film onto test structures with large areas with no direct line-of-sight to the target. Transmission electron microscopy was used to image the film deposited on all areas of the structure and Auger electron spectroscopy was used to determine the composition of the film. EVOLVE, a physically based process simulator, was used along with the experimental data to estimate the effective sticking coefficients of Ti and W during Ti-W deposition. Simulation results indicate the effective sticking factors of Ti and W to be 0.30 and 0.74, respectively. The Ti to W effective sticking factor ratio determined in this study, 0.40, was in good agreement with that previously reported, 0.38. In comparison, sputter deposition of Ti onto these test structures showed little re-emission. Process simulation of Ti sputter deposition indicated the Ti effective sticking factor to be essentially unity.