Formation of PbS nanowire pine trees driven by screw dislocations

The basic characteristics of nanowire growth driven by screw dislocations were investigated by synthesizing hierarchical lead sulfide (PbS) nanowire "pine trees" using chemical vapor deposition of PbCl(2) and S precursors and systematically observing the effects of various growth parameters, such as hydrogen flow, temperature, pressure, and the growth substrates employed. Statistical surveys showed that the growth rate of the dislocation-driven trunk is about 6 mum/min and that of the vapor-liquid-solid (VLS) driven branch nanowire is about 1.2 mum/min under the typical reaction conditions at 600 degrees C, 900 Torr, and a hydrogen flow rate of 1.5 sccm. The onset of hydrogen flow plus the presence of fresh silicon have been identified as the critical ingredients for generating PbS nanowire trees reproducibly. To explain the experimental findings in the context of classical crystal growth theory, the former is suggested to create a spike in supersaturation of the actual sulfur precursor H(2)S and initiate dislocations with screw components that then propagate anisotropically to form the PbS nanowire trunks. Maintaining suitable hydrogen flow provides a favorable low supersaturation that promotes dislocation-driven trunk nanowire growth and enables the simultaneous VLS nanowire growth of branches. Furthermore, thermodynamic consideration and experiments showed that silicon fortuitously controls the supersaturation by reversibly reacting with H(2)S to form SiS(2) and that SiS(2) can also be a viable precursor for PbS nanowire growth. The key requirements of screw dislocation-driven nanowire growth are summarized. This study provides some general guidelines for further nanowire growth driven by screw dislocations.