Identifying Crystallization- and Incorporation-Limited Regimes during Vapor–Liquid–Solid Growth of Si Nanowires

The vapor-liquid-solid (VLS) mechanism is widely used for the synthesis of semiconductor nanowires (NWs), yet several aspects of the mechanism are not fully understood. Here, we present comprehensive experimental measurements on the growth rate of Au-catalyzed Si NWs over a range of temperatures (365-480 °C), diameters (30-200 nm), and pressures (0.1-1.6 Torr SiH4). We develop a kinetic model of VLS growth that includes (1) Si incorporation into the liquid Au-Si catalyst, (2) Si evaporation from the catalyst surface, and (3) Si crystallization at the catalyst-NW interface. This simple model quantitatively explains growth rate data collected over more than 65 distinct synthetic conditions. Surprisingly, upon increasing the temperature and/or pressure, the analysis reveals an abrupt transition from a diameter-independent growth rate that is limited by incorporation to a diameter-dependent growth rate that is limited by crystallization. The identification of two distinct growth regimes provides insight into the synthetic conditions needed for specific NW-based technologies, and our kinetic model provides a straightforward framework for understanding VLS growth with a range of metal catalysts and semiconductor materials.