Pure and Applied Chemistry

Abstract: The process of axial and radial Si–Ge heterostructure formation during nanowire growth by vapor–liquid–solid (VLS) mechanism was studied using Monte Carlo (MC) simulation. It was demonstrated that radial growth can be stimulated by adding chemical species that decrease the activation energy of precursor dissociation or the solubility of semiconductor material in catalyst drop. Reducing the Si adatom diffusion length also leads to Si shell formation around the Ge core. The influence of growth conditions on the composition and abruptness of axial Ge–Si heterostructures was analyzed. The composition of the Ge_xSi_1–x axial heterojunction (HJ) was found to be dependent on the flux ratio, the duration of Si and Ge deposition, and the catalyst drop diameter. Maximal Ge concentration in the HJ is dependent on Ge deposition time owing to gradual changing of catalyst drop composition after switching Ge and Si fluxes. The dependence of junction abruptness on the nanowire diameter was revealed: in the adsorption-induced growth mode, the abruptness decreased with diameter, and in the diffusion-induced mode it increased. This implies that abrupt Ge–Si HJ in nanowires with small diameter can be obtained only in the chemical vapor deposition (CVD) process with negligible diffusion component of growth.