We observe and systematically tune an intense mid-infrared absorption mode that results from phosphorus doping in silicon nanowires synthesized via the vapor-liquid-solid technique. The angle- and shape-dependence of this spectral feature, as determined via in-situ transmission infrared spectroscopy, supports its assignment as a longitudinal localized surface plasmon resonance (LSPR). Modulation of resonant frequency (740-1620 cm(-1)) is accomplished by varying nanowire length (135-1160 nm). The observed frequency shift is consistent with Mie-Gans theory, which indicates electrically active dopant concentrations between 10(19) and 10(20) cm(-3). Our findings suggest new opportunities to confine light in this ubiquitous semiconductor and engineer the optical properties of nontraditional plasmonic materials.

We report on the first in situ chemical investigation of vapor-liquid-solid semiconductor nanowire growth and reveal the important, and previously unrecognized, role of transient surface chemistry near the triple-phase line. Real-time infrared spectroscopy measurements coupled with postgrowth electron microscopy demonstrate that covalently bonded hydrogen atoms are responsible for the (left angle bracket 111 right angle bracket) to (left angle bracket 112 right angle bracket) growth orientation transition commonly observed during Si nanowire growth. Our findings provide insight into the root cause of this well-known nanowire growth phenomenon and open a new route to rationally engineer the crystal structure of these nanoscale semi-conductors.

The controlled introduction of planar defects, particularly twin boundaries and stacking faults, in group IV nanowires remains challenging despite the prevalence of these structural features in other nanowire systems (e.g., II-VI and III-V). Here we demonstrate how user-programmable changes to precursor pressure and growth temperature can rationally generate both transverse twin boundaries and angled stacking faults during the growth of <111> oriented Si nanowires. We leverage this new capability to demonstrate prototype defect superstructures. These findings yield important insight into the mechanism of defect generation in semiconductor nanowires and suggest new routes to engineer the properties of this ubiquitous semiconductor.

Surface adsorbates are well-established choreographers of material synthesis, but the presence and impact of these short-lived species on semiconductor nanowire growth are largely unknown. Here, we use infrared spectroscopy to directly observe surface adsorbates, hydrogen atoms and methyl groups, chemisorbed to the nanowire sidewall and show they are essential for the stable growth of Ge nanowires via the vapor-liquid-solid mechanism. We quantitatively determine the surface coverage of hydrogen atoms during nanowire growth by comparing ν(Ge-H) absorption bands from operando measurements (i.e., during growth) to those after saturating the nanowire sidewall with hydrogen atoms. This method provides sub-monolayer chemical information at relevant reaction conditions while accounting for the heterogeneity of sidewall surface sites and their evolution during elongation. Our findings demonstrate that changes to surface bonding are critical to understand Ge nanowire synthesis and provide new guidelines for rationally selecting catalysts, forming heterostructures, and controlling dopant profiles.

Controlled introduction of H2 during the CVD growth of MoSe2 plays a vital role in the step-edge aligned nucleation on a c-sapphire (0001) substrate.