Bismuth-stabilized(2×1)and(2×4)reconstructions on GaAs(100) surfaces: Combined first-principles, photoemission, and scanning tunneling microscopy study

Abstract

Bismuth adsorbate-stabilized $(2\ifmmode\times\else\texttimes\fi{}1)$ and $(2\ifmmode\times\else\texttimes\fi{}4)$ reconstructions of the GaAs(100) surfaces have been studied by first-principles calculations, valence-band and core-level photoelectron spectroscopies, and scanning tunneling microscopy. It is demonstrated that large Bi atom size leads to the formation of the pseudogap at the Fermi energy and to the lower energy of an adsorbate-derived surface band, which contributes to the stabilization of the exceptional $\text{Bi}/\text{GaAs}(100)(2\ifmmode\times\else\texttimes\fi{}1)$ reconstruction. It is proposed that the $\text{Bi}/\text{GaAs}(100)(2\ifmmode\times\else\texttimes\fi{}4)$ reconstructions include asymmetric mixed Bi-As dimers, in addition to the Bi-Bi dimers. Based on the calculations, we solve the atomic origins of the surface core-level shifts (SCLSs) of the $\text{Bi}\text{ }5d$ photoemission spectra from the $\text{Bi}/\text{GaAs}(100)(2\ifmmode\times\else\texttimes\fi{}4)$ surfaces. This allows for resolving the puzzle related to the identification of two SCLS components often found in the measurements of the $\text{Bi}\text{ }5d$ and $\text{Sb}\text{ }4d$ core-level emissions of the Bi/III-V and $\text{Sb}/\text{III-V}(100)(2\ifmmode\times\else\texttimes\fi{}4)$ surfaces. Finally, the reason for the absence of the common $(2\ifmmode\times\else\texttimes\fi{}4)\text{\ensuremath{-}}\ensuremath{\beta}2$ structure and additional support for the stability of the $(2\ifmmode\times\else\texttimes\fi{}1)$ structure on the Bi/III-V(100) surfaces are discussed in terms of Bi atom size and subsurface stress.