Tuning Patterning Conditions By Co-Adsorption Of Gases: Br-2 And H-2 On Si(001)

We have studied the co-adsorption of Br-2 and H-2 on Si(001), and obtained co-adsorption energies and the surface phase diagram as a function of the chemical potential and pressure of the two gases. To do this, we have used density functional theory calculations in combination with ab initio atomistic thermodynamics. Over large ranges of bromine and hydrogen chemical potentials, the favored configuration is found to be either one with only Br atoms adsorbed on the surface, at full coverage, in a (3 x 2) pattern, or a fully H-covered surface in a (2 x 1) structure. However, we also find regions of the phase diagram where there are configurations with either only Br atoms, or Br and H atoms, arranged in a two-atom-wide checkerboard pattern with a (4 x 2) surface unit cell. Most interestingly, we find that by co-adsorbing with H-2, we bring this pattern into a region of the phase diagram corresponding to pressures that are significantly higher than those where it is observed with Br-2 alone. We also find small regions of the phase diagram with several other interesting patterns. (C) 2013 AIP Publishing LLC.