Tapering control of Si nanowires grown from SiCl₄ at reduced pressure

Device applications of tapered Si nanowire (SiNW) arrays require reliable technological approaches for fabricating nanowires with controlled shape and orientation. In this study, we systematically explore effects of growth conditions on tapering of Si nanowires grown by chemical vapor deposition (CVD) at reduced pressure from SiCl(4) precursor. Tapering of SiNWs is governed by the interplay between the catalyzed vapor-liquid-solid (VLS) and uncatalyzed vapor-solid (VS) growth mechanisms. We found that the uncatalyzed Si deposition on NW sidewalls, defined by a radial growth rate, can be enhanced by lowering SiCl(4)/H(2) molar ratio, applying higher gas flow rate, or reducing growth pressure. Distinct dependences of the axial and radial growth rates on the process conditions were employed to produce SiNWs with a tapering degree (i.e., a ratio of the radial/axial growth rates) varying by almost 2 orders of magnitude. The results are explained by an interplay between the thermodynamic and kinetic effects on the axial (VLS) and radial (VS) growth rates. Established correlation between the SiCl(4)/H(2) molar ratio and vertical alignment of nanowires was used to develop a two-stage growth procedure for producing tapered SiNW arrays with a predominantly vertical orientation.