KrF laser deposition of chromium films from Cr(CO) 6: in situ detection of film growth by laser transmission experiments

Abstract

The results of a detailed study of laser-induced chemical vapour deposition (LICVD) of thin chromium films from Cr(CO) 6 using a KrF excimer laser are presented. The following deposition parameters were varied: the laser fluence, the pulse repetition rate, the total gas pressure in the deposition cell, the flow rate of the gas mixture supply, the type of carrier or buffer gas and the substrate temperature. The influence of these parameters on the nucleation time and rate, and the main film growth rate as well as on film properties such as the optical absorption coefficient was investigated. The film growth kinetics was monitored in situ by measuring the transmission of an HeNe laser probe beam through the deposit. The experimental results are discussed in the framework of a model of pulsed LICVD based on gas phase diffusion mass transport to the substrate surface of chromium-containing precursor species as the rate-limiting step. The model describes the experimental data reasonably well, the deviations observed being indicative of processes not included in the model such as reactions at the film surface. The results indicate that in pulsed LICVD of chromium films from Cr(CO) 6 at 248 nm the main precursors of the film growth during the nucleation period are chromium atoms and other highly reactive unsaturated chromium carbonyls formed on illumination in the gas phase, while during the main growth stage the role of more stable saturated species adsorbed on the surface between the laser pulses may be dominant.