Encoding Highly Nonequilibrium Boron Concentrations and Abrupt Morphology in p-Type/n-Type Silicon Nanowire Superlattices.

Although silicon (Si) nanowires (NWs) grown by a vapor-liquid-solid (VLS) mechanism have been demonstrated for a range of photonic, electronic, and solar-energy applications, continued progress with these NW-based technologies requires increasingly precise compositional and morphological control of the growth process. However, VLS growth typically encounters problems such as nonselective deposition on sidewalls, inadvertent kinking, unintentional or inhomogeneous doping, and catalyst-induced compositional gradients. Here, we overcome several of these difficulties and report the synthesis of uniform, linear, and degenerately doped Si NW superlattices with abrupt transitions between p-type, intrinsic, and n-type segments. The synthesis of these structures is enabled by in situ chlorination of the NW surface with hydrochloric acid (HCl) at temperatures ranging from 500 to 700 °C, yielding uniform NWs with minimal nonselective growth. Surprisingly, we find the boron (B) doping level in p-type segments to be at least 1 order of magnitude above the solid solubility limit, an effect that we attribute to a high incorporation of B in the liquid catalyst and kinetic trapping of B during crystallization at the liquid-solid interface to yield a highly nonequilibrium concentration. For growth at 510 °C, four-point-probe measurements yield active doping levels of at least 4.5 × 10 cm, which is comparable to the phosphorus (P) doping level of n-type segments. Because the B and P dopants are in sufficiently high concentrations for the Si to be degenerately doped, both segments inhibit the etching of Si in aqueous potassium hydroxide (KOH) solution. Moreover, we find that the dopant transitions are abrupt, facilitating nanoscale morphological control in both B- and P-doped segments through selective KOH etching of the NW with a spatial resolution of ∼10 nm. The results presented herein enable the growth of complex, degenerately doped p-n junction nanostructures that can be explored for a variety of advanced applications, such as Esaki diodes, multijunction solar cells, and tunneling field-effect transistors.