The nanowire geometry is favorable for the growth of ternary semiconductor materials, because the composition and properties can be tuned freely without substrate lattice matching. To achieve precise control of the composition in ternary semiconductor nanowires, a deeper understanding of the growth is required. One unknown aspect of seeded nanowire growth is how the composition of the catalyst nanoparticle affects the resulting composition of the growing nanowire. We report the first in situ measurements of the nanoparticle and In x Ga 1– x As nanowire compositional relationship using an environmental transmission electron microscopy setup. The compositions were measured and correlated during growth, via X-ray energy dispersive spectroscopy. Contrary to predictions from thermodynamic models, the experimental results do not show a miscibility gap. Therefore, we construct a kinetic model that better predicts the compositional trends by suppressing the miscibility gap. The findings imply that compositional control of In x Ga 1– x As nanowires is possible across the entire compositional range.

With the increased demand for controlled deterministic growth of III−V semiconductors at the nanoscale, the impact and interest of understanding defect formation and crystal structure switching becomes increasingly important. Vapor−liquid−solid (VLS) growth of semiconductor nanocrystals is an important mechanism for controlling and studying the formation of individual crystal layers and stacking defects. Using in situ studies, combining atomic resolution of transmission electron microscopy and controlled VLS crystal growth using metal organic chemical vapor deposition, we investigate the simplest achievable change in atomic layer stacking−single twinned layers formed in GaAs. Using Au-assisted GaAs nanowires of various diameters, we study the formation of individual layers with atomic resolution to reveal the growth difference in forming a twin defect. We determine that the formation of a twinned layer occurs significantly more slowly than that of a normal crystal layer. To understand this, we conduct thermodynamic modeling and determine that the propagation of a twin is limited by the energy cost of forming the twin interface. Finally, we determine that the slower propagation of twinned layers increases the probability of additional layers nucleating, such that multiple layers grow simultaneously. This observation challenges the current understanding that continuous uniform epitaxial growth, especially in the case of liquid-metal assisted nanowires, proceeds one single layer at a time and that its progression is limited by the nucleation rate.

Au-seeded semiconductor nanowires have classically been considered to only grow in a layer-by-layer growth mode, where individual layers nucleate and grow one at a time with an incubation step in between. Recent in situ investigations have shown that there are circumstances where binary semiconductor nanowires grow in a multilayer fashion, creating a stack of incomplete layers at the interface between a nanoparticle and a nanowire. In the current investigation, the growth behavior in ternary InGaAs nanowires has been analyzed in situ, using environmental transmission electron microscopy. The investigation has revealed that multilayer growth also occurs for ternary nanowires and appears to be more common than in the binary case. In addition, the size of the multilayer stacks observed is much larger than what has been reported previously. The investigation details the implications of multilayers for the overall growth of the nanowires, as well as the surrounding conditions under which it has manifested. We show that multilayer growth is highly dynamic, where the stack of layers regularly changes size by transporting material between the growing layers. Another observation is that multilayer growth can be initiated in conjunction with the formation of crystallographic defects and compositional changes. In addition, the role that multilayers can have in behaviors such as growth failure and kinking, sometimes observed when creating heterostructures between GaAs and InAs ex situ, is discussed. The prevalence of multilayer growth in this ternary material system implies that, in order to fully understand and accurately predict the growth of nanowires of complex composition and structure, multilayer growth has to be considered.

No abstract

No abstract