Theoretical investigations for zinc blende–wurtzite polytypism in GaAs layers at Au/GaAs(1 1 1) interfaces

The zinc blende (ZB)–wurtzite (W) polytypism of GaAs layers at the Au/GaAs(1 1 1)B interfaces is investigated based on total-energy electronic-structure calculations within density functional theory. The calculations for the abrupt interfaces including a GaAs top layer with ZB and W stacking sequences reveal that the ZB sequence is energetically favorable, but the energy of W sequence with an interstitial Au atom at the top GaAs layer of the interface is lower than that of ZB sequence. This is because electrons accumulate around the interstitial region due to the hybridization between Au-6s and As-4p orbitals, resulting in the reduction of Ga–As bond charges. As a result, the relative stability at the top GaAs layer is determined by the electrostatic energy due to ionic charges. The results imply that the stabilization of W sequence at the Au catalyst–semiconductor interfaces as well as that on the nanowire faces are the origins for the appearance of W segments in NWs, qualitatively consistent with experiments.