Initial applications of the molecular model to compute defect vibrations of oxygen in silicon

Abstract

We have employed the molecular model introduced first by Jaswal to compute the vibrational spectra of oxygen bearing defects in a silicon crystal. This was done in the context of a silicon molecular cluster with outer valencies terminated by hydrogen. We employ the MINDO/3 semi-empirical electronic structure method to compute the total energy of the molecular cluster. We examine the conditions in applications of the molecular model required for accurate predictions of oxygen local-mode vibrational frequencies. We find that the oxygen atom and its nearest neighbor silicon atoms must be allowed to vibrate. The nearest-neighbor and next nearest-neighbor shells of silicon atoms must be allowed to relax from their lattice positions. The outermost relaxed shell of silicon atoms should be bonded to silicon atoms in their lattice positions. We apply the molecular model to three defects of crystalline silicon; interstitial oxygen, oxygen in a vacancy (the A-center), and two oxygen atoms in a vacancy. Comparison of our computed local-mode oxygen vibration frequencies with experiment shows the computed oxygen local-mode frequencies to be almost uniformly 10% greater than those observed. Isotope shifts fit experiment equally well. We conclude that the molecular model represents an accurate and efficient approach for the computation of defect local mode vibrational frequencies for oxygen and other defects in crystalline silicon.