The molecular processes during the growth of GaAs nanowires in molecular beam epitaxy (MBE) are studied from first principles. For the wurtzite crystal structure of GaAs, which is formed exclusively in nanowire growth, potential energy surfaces for sidewall diffusion of Ga, As, and GaAs surface species are calculated using density functional theory. We compare materials transport on type-I and -II nanowires (with $\left\{10\overline{1}0\right\}$ and $\left\{11\overline{2}0\right\}$ facets of wurtzite GaAs, respectively) and discuss its role for materials supply to the growth zone at the nanowire tip. On the sidewalls of type-II nanowires, the diffusion barrier for Ga along the growth direction is particularly low, only 0.30 eV compared to 0.60 eV on type-I nanowires. For As adatoms, the corresponding diffusion barriers are 0.64 eV and 1.20 eV, respectively, and hence higher than for Ga adatoms. The GaAs molecule formed by the chemical surface reaction of Ga and As finds very stable binding sites on type-II sidewalls where it inserts itself into a chemical bond between surface atoms, triggering radial growth. In contrast, on type-I nanowires the GaAs molecule adsorbed with the As end towards the surface has a low diffusion barrier of 0.50 eV. Together with our previous finding that the gold particle at the nanowire tip is efficient in promoting dissociative adsorption of As${}_2$ molecules, we conclude that the influx of Ga adatoms from sidewall diffusion is very important to maintain stoichiometric growth of GaAs nanowires, in particular when a large V-III ratio is used in MBE.

• Received 2 July 2012

DOI:https://doi.org/10.1103/PhysRevB.86.085425