Gas phase versus surface contributions to photolytic laser chemical vapor deposition rates

The rate of cwphotolytic laser chemical vapor deposition (LCVD) of platinum is measured for 350 nm as a function of the light intensity and the metalorganic vapor pressure. The growth of the metal films is studied in situ and in real time by monitoring their optical transmission. At low intensities the transmitted light decreases monotonically with time, and the LCVD process is photolytic with its rate limiting step in the surface adlayer. At higher intensities we observe two distinct time domains: Relatively slow initial photolytic deposition with its rate limiting step in the gas phase, which is followed by much faster pyrolytic LCVD. An improved method for distinguishing between adlayer and gas-phase limiting processes is demonstrated. These observations are confirmed by studying the photolytic deposition rates while varying the thickness of the adlayer.