Spatially resolved correlation of active and total doping concentrations in VLS grown nanowires.

Controlling axial and radial dopant profiles in nanowires is of utmost importance for NW-based devices, as the formation of tightly controlled electrical junctions is crucial for optimization of device performance. Recently, inhomogeneous dopant profiles have been observed in vapor­liquid­solid grown nanowires, but the underlying mechanisms that produce these inhomogeneities have not been completely characterized. In this work, P-doping profiles of axially modulation-doped Si nanowires were studied using nanoprobe scanning Auger microscopy and Kelvin probe force microscopy in order to distinguish between vapor­liquid­solid doping and the vapor­solid doping. We find that both mechanisms result in radially inhomogeneous doping, specifically, a lightly doped core surrounded by a heavily doped shell structure. Careful design of dopant modulation enables the contributions of the two mechanisms to be distinguished, revealing a surprisingly strong reservoir effect that significantly broadens the axial doping junctions.

On-surface formation of metal nanowire transparent top electrodes on CdSe nanowire array-based photoconductive devices.

A simple wet chemical approach was developed for a unique on-surface synthesis of transparent conductive films consisting of ultrathin gold/silver nanowires directly grown on top of CdSe nanowire array photoconductive devices enclosed in polycarbonate membranes. The metal nanowire film formed an ohmic contact to the semiconductor nanowires without additional treatment. The sheet resistance and transparency of the metal nanowire arrays could be controlled by the number of metal nanowire layers deposited, ranging from ∼98-99% transmission through the visible range and several kOhm/sq sheet resistance for a single layer, to 80-85% transmission and ∼100 Ohm/sq sheet resistance for 4 layers.

Diameter and polarization-dependent Raman scattering intensities of semiconductor nanowires.

Diameter-dependent Raman scattering in single tapered silicon nanowires is measured and quantitatively reproduced by modeling with finite-difference time-domain simulations. Single crystal tapered silicon nanowires were produced by homoepitaxial radial growth concurrent with vapor-liquid-solid axial growth. Multiple electromagnetic resonances along the nanowire induce broad band light absorption and scattering. Observed Raman scattering intensities for multiple polarization configurations are reproduced by a model that accounts for the internal electromagnetic mode structure of both the exciting and scattered light. Consequences for the application of Stokes to anti-Stokes intensity ratio for the estimation of lattice temperature are discussed.

Silicon nanowire polytypes: identification by Raman spectroscopy, generation mechanism, and misfit strain in homostructures.

Silicon nanowires with predominant 9R, 27T, 2H and other polytype structures with respective hexagonalities of 50, 40 and 35.3% were identified by Raman microscopy. Transmission electron microscopy indicates that intrinsic stacking faults form the basic building blocks of these polytypes. We propose a generation mechanism in which polytypes are seeded from incoherent twin boundaries and associated partial dislocations. This mechanism explains observed prevalence of polytypes and trends in stacking for longer period structures. The percentage of hexagonal planes in a polytype is extracted from its Raman spectrum after correcting the zone-folded phonon frequencies to account for changes of the in-plane lattice parameter with respect to diamond cubic (3C) Si. The correction is found to be (i) of the same order of magnitude as frequency differences between modes of low period polytypes and (ii) proportional to the hexagonality. Corrected phonon frequencies agree with experimentally found values to within 0.4 cm(-1). Homostructures in which a central polytype region is bounded by 3C regions, with the planes (111)(3C)║(0001)(polytype) parallel to the nanowire axis, are found in 112 oriented nanowires. Strain-induced shifts of the Raman modes in such structures enable a rough estimation of the lattice misfit between polytypes, which compares favorably with first-principles calculations. Considerations presented here provide a simple and quantitative framework to interpret Raman frequencies and extract crystallographic information on polytype structures.

Electrochemical synthesis of morphology-controlled segmented CdSe nanowires.

Morphology, that is, the study of form comprising shape, size, and structure, is important for materials research in general. For nanostructured materials, popularly known as nanomaterials, morphology has a special significance since form, in this case, dictates physical and chemical properties. Unlike bulk materials, properties of nanomaterials are strongly correlated to form. Here, we present a novel strategy for the synthesis of morphology-controlled segmented CdSe semiconductor nanowires based on a straightforward sweep voltammetry approach of preprogrammed characteristics. It was found here that, by simply and simultaneously modulating the basic parameters of each cyclic voltammetry cycle during the nanowire growth process, scan rate, and cycle potential range, we can achieve a precise control over the morphology of the semiconductor material segment, density, and dimensions, obtained after each voltammetric cycle. The morphology of CdSe segments was found to be controlled by the extent of co-deposition of metal cadmium together with the deposition of CdSe. Thus "dense" CdSe segments and "nondense" segments can be achieved in the absence and presence of cadmium metal co-deposition, respectively. Accompanied by the density modulation achieved by the potential range applied, it was also observed that a fine control over each segment's length, varying between few tenths to few hundred nanometers, can be achieved by simple altering the scan rate of each cycle along the wire. Also, we propose a simple mechanism that accounts for the formation of segments of controlled morphology. This is the first report on the synthesis of "segmented" CdSe nanowires of controlled morphology, density, and length of each segment, by simple single-step cycle voltammetry preprogrammed sequences from a single electrodeposition solution. In addition, this novel strategy may be applied for the synthesis of additional analogue semiconductor materials of importance (e.g., CdS, CdTe, etc.). This segmented nanowire's synthetic route is remarkably fast and simple, leading to a high encoding capacity with a large number of distinguishable signatures.

Pressure-modulated alloy composition in Si((1-x))Ge(x) nanowires.

Si((1-x))Ge(x) nanowires (NWs) constitute promising building blocks for future electronic and optoelectronic devices due to the enhanced tuneability of their physical properties, achieved mainly by controlling their chemical composition. In this study, the pressure dependence of the chemical composition, growth and tapering rates and crystalline structure of Si((1-x))Ge(x) NWs grown by the CVD-VLS technique was investigated. It is demonstrated for the first time, that the composition of single crystal Si((1-x))Ge(x) NWs can be readily modulated between ca. x = 0.75 to x = 0.25, simply by altering the total growth pressure while keeping all other growth parameters fixed. Moreover, this procedure does not cause any undesired structural or morphological side effects. Growth pressure is hence concluded to be the most significant parameter for tailoring Si((1-x))Ge(x) NWs electron and phonon mobility, band gap, and so forth. The observed alloy-composition control phenomena can be explained by the interplay between the pressure-dependent unimolecular decomposition of the individual precursor gases, SiH(4) and GeH(4), at the given experimental conditions that leads to a direct modulation of the decomposed/activated Si/Ge precursors ratio in the gas feedstock and is finally reflected in the composition of the obtained binary alloy nanowires. In addition, a silicon-germanium cooperative growth mechanism is suggested to account for the observed growth rate pressure dependence and enhanced growth rates.