RESUMEN
The ability to chemically differentiate individual subsurface Al and Ga atoms, when imaging the Al0.1Ga0.9As(001)-c(2x8)(2x4) surface with scanning tunneling microscopy (STM), has been observed for the first time. In filled-state STM images first layer As atoms bonded to second layer Al atoms appear brighter than those bonded to second layer Ga atoms. This effect is only observed experimentally with p-type Al0.1Ga0.9As grown on p-type GaAs substrates and has been computationally modeled with density functional theory (DFT) calculations. It is hypothesized that chemical specificity is not observed on n-type material because the extra surface charge given to first layer As atoms by second layer Al atoms adds negligibly to the filled-state density of the surface, thus preventing the visualization of chemical specificity with filled-state STM imaging. The ability to distinguish whether first layer As atoms are bonded to second layer Ga and/or Al atoms in STM images shows that small differences in bond ionicity affect the local electronic structure of the material.
RESUMEN
The surface structures formed upon deposition of In2O and Ga2O by molecular beam epitaxy onto the arsenic-rich GaAs(001)-c(2 x 8)/(2 x 4) surface have been studied using scanning tunneling microscopy and density functional theory. In2O initially bonds, with indium atoms bonding to second layer gallium atoms within the trough, and proceeds to insert into or between first layer arsenic dimer pairs. In contrast, Ga2O only inserts into or between arsenic dimer pairs due to chemical site constraints. The calculated energy needed to bend a Ga2O molecule approximately 70 degrees, so that it can fit into an arsenic dimer pair, is 0.6 eV less than that required for In2O. The greater flexibility of the Ga2O molecule causes its insertion site to be 0.77 eV more exothermic than the In2O insertion site. This result shows that although trends in the periodic table can be used to predict some surface reactions, small changes in atomic size can play a significant role in the chemistry of gas/surface reactions through the indirect effects of bond angle flexibility and bond length stiffness.