Nanowires (NWs) offer unique opportunities for tuning the properties of III-V semiconductors by simultaneously controlling their nanoscale dimensions and switching their crystal phase between zinc-blende (ZB) and wurtzite (WZ). While much of this control has been enabled by direct, forward growth, the reverse reaction, i.e., crystal decomposition, provides very powerful means to further tailor properties towards the ultra-scaled dimensional level. Here, we use in situ transmission electron microscopy (TEM) to investigate the thermal decomposition kinetics of clean, ultrathin GaAs NWs and the role of distinctly different crystal polytypes in real-time and on the atomic scale. The whole process, from the NW growth to the decomposition, is conducted in situ without breaking vacuum to maintain pristine crystal surfaces. Radial decomposition occurs much faster for ZB- compared to WZ-phase NWs, due to the development of nano-faceted sidewall morphology and sublimation along the entire NW length. In contrast, WZ NWs form single-faceted, vertical sidewalls with decomposition proceeding only via step-flow mechanism from the NW tip. Concurrent axial decomposition is generally faster than the radial process, but is significantly faster (∼4-fold) in WZ phase, due to the absence of well-defined facets at the tip of WZ NWs. The results further show quantitatively the influence of the NW diameter on the sublimation and step-flow decomposition velocities elucidating several effects that can be exploited to fine-tune the NW dimensions.
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