In situ observations during vapor–liquid–solid (VLS) growth of semiconductor nanowires in the chamber of an environmental scanning electron microscope (ESEM) are reported. For nanowire growth, a powder mixture of CdS and ZnS is used as a source material and silver nanoparticles as a metal catalyst. Through tracing growth kinetics of nanowires, it is found that nanowires with a relatively bigger catalyst droplet on the tip grow faster. Intriguingly, it is also found that the growth of nanowires can involve catalyst splitting: while the majority of catalyst remains at the nanowire tip and continues facilitating the growth, a portion of it is removed from the tip due to the splitting. It remains attached to the nanowire at the position where the splitting occurred and subsequently induces the growth of a nanowire branch. As far as it is known, this is the first time that catalyst splitting is revealed experimentally in situ. It is proposed that the instability of catalyst droplet caused by the volume increase is the main reason for the splitting. It is believed that in situ growth inside the ESEM can largely enrich our understanding on the metal-catalyzed VLS growth kinetics, which may open up more opportunities for morphology-controlled synthesis of 1D semiconductor nanowires in future study. 

Advanced Functional Materials,2015