Photochemistry of dimethylcadmium on compound semiconductor surfaces

Abstract

We present dynamical studies of the surface photochemistry of dimethylcadmium (DMCd) adsorbed on GaAs(110) and CdTe(110) surfaces. This important precursor for chemical vapor deposition is studied using time-of-flight (TOF) spectroscopy in conjunction with temperature programmed desorption (TPD). For the case of greater than one monolayer coverages, on these surfaces, both photofragmentation and photodesorption are observed following irradiation. The relative probabilities of these two processes are found to be strongly dependent on adsorbate coverage and incident photon energy. Direct photoabsorption by the adsorbed molecule is found to dominate the photofragmentation process, with the substrate strongly reducing the probability of photofragmentation at low coverages due to the operation of substrate mediated channels for excited state relaxation. The CH3 fragments observed following photodissociation are found to have kinetic energies that are invariant with the energy of the exciting photon (193 and 248 nm), an effect attributed to an efficient curve crossing between excited states in this molecule. The molecular desorption process is found to exhibit an unusual coverage dependence which is linked to the probability of deposition of a significant amount of vibrational excitation in the overlayer via substrate mediated de-excitation processes. Following the adsorption of one monolayer on the GaAs substrate, the photochemistry observed is significantly different due to the thermal dissociation of DMCd to form adsorbed methylgallium moieties. In this case, multiple features are observed in the TOF spectrum with kinetic energies significantly different to those observed for the gas phase or physisorbed molecule. Correlation of the TOF spectral features with thermal desorption data allows these TOF features to be assigned to specific adsorbed intermediates.