S. T. Picraux

Adaptable Silicon-Carbon Nanocables Sandwiched between Reduced Graphene Oxide Sheets as Lithium Ion Battery Anodes

Silicon has been touted as one of the most promising anode materials for next generation lithium ion batteries. Yet, how to build energetic silicon-based electrode architectures by addressing the structural and interfacial stability issues facing silicon anodes still remains a big challenge. Here, we develop a novel kind of self-supporting binder-free silicon-based anodes via the encapsulation of silicon nanowires (SiNWs) with dual adaptable apparels (overlapped graphene (G) sheaths and reduced graphene oxide (RGO) overcoats). In the resulted architecture (namely, SiNW@G@RGO), the overlapped graphene sheets, as adaptable but sealed sheaths, prevent the direct exposure of encapsulated silicon to the electrolyte and enable the structural and interfacial stabilization of silicon nanowires. Meanwhile, the flexible and conductive RGO overcoats accommodate the volume change of embedded SiNW@G nanocables and thus maintain the structural and electrical integrity of the SiNW@G@RGO. As a result, the SiNW@G@RGO electrodes exhibit high reversible specific capacity of 1600 mAh g⁻¹ at 2.1 A g⁻¹, 80% capacity retention after 100 cycles, and superior rate capability (500 mAh g⁻¹ at 8.4 A g⁻¹) on the basis of the total electrode weight.

Are nanoporous materials radiation resistant

The key to perfect radiation endurance is perfect recovery. Since surfaces are perfect sinks for defects, a porous material with a high surface to volume ratio has the potential to be extremely radiation tolerant, provided it is morphologically stable in a radiation environment. Experiments and computer simulations on nanoscale gold foams reported here show the existence of a window in the parameter space where foams are radiation tolerant. We analyze these results in terms of a model for the irradiation response that quantitatively locates such window that appears to be the consequence of the combined effect of two length scales dependent on the irradiation conditions: (i) foams with ligament diameters below a minimum value display ligament melting and breaking, together with compaction increasing with dose (this value is typically ∼5 nm for primary knock on atoms (PKA) of ∼15 keV in Au), while (ii) foams with ligament diameters above a maximum value show bulk behavior, that is, damage accumulation (few hundred nanometers for the PKAs energy and dose rate used in this study). In between these dimensions, (i.e., ∼100 nm in Au), defect migration to the ligament surface happens faster than the time between cascades, ensuring radiation resistance for a given dose-rate. We conclude that foams can be tailored to become radiation tolerant.

Direct observation of nanoscale size effects in Ge semiconductor nanowire growth.

Progress in the synthesis of semiconductor nanowires (NWs) has prompted intensive inquiry into understanding the science of their growth mechanisms and ultimately the technological applications they promise. We present new results for the size-dependent growth kinetics of Ge NWs and correlate the results with a direct experimental measurement of the Gibbs-Thomson effect, a measured increase in the Ge solute concentration in liquid Au-Ge droplets with decreasing diameter. This nanoscale-dependent effect emerges in vapor-liquid-solid Ge NW growth and leads to a decrease in the NW growth rate for smaller diameter NWs under a wide range of growth conditions with a cutoff in growth at sufficiently small sizes. These effects are described quantitatively by an analytical model based on the Gibbs-Thomson effect. A comprehensive treatment is provided and shown to be consistent with experiment for the effect of NW growth time, temperature, pressure, and doping on the supersaturation of Ge in Au, which determines the growth rate and critical cutoff diameter for NW growth. These results support the universal applicability of the Gibbs-Thomson effect to sub-100 nm diameter semiconductor NW growth.

Controlling heterojunction abruptness in VLS-grown semiconductor nanowires via in situ catalyst alloying.

For advanced device applications, increasing the compositional abruptness of axial heterostructured and modulation doped nanowires is critical for optimizing performance. For nanowires grown from metal catalysts, the transition region width is dictated by the solute solubility within the catalyst. For example, as a result of the relatively high solubility of Si and Ge in liquid Au for vapor-liquid-solid (VLS) grown nanowires, the transition region width between an axial Si-Ge heterojunction is typically on the order of the nanowire diameter. When the solute solubility in the catalyst is lowered, the heterojunction width can be made sharper. Here we show for the first time the systematic increase in interface sharpness between axial Ge-Si heterojunction nanowires grown by the VLS growth method using a Au-Ga alloy catalyst. Through in situ tailoring of the catalyst composition using trimethylgallium, the Ge-Si heterojunction width is systematically controlled by tuning the semiconductor solubility within a metal Au-Ga alloy catalyst. The present approach of alloying to control solute solubilities in the liquid catalyst may be extended to increasing the sharpness of axial dopant profiles, for example, in Si-Ge pn-heterojunction nanowires which is important for such applications as nanowire tunnel field effect transistors or in Si pn-junction nanowires.

Enhanced thermoelectric figure of merit in SiGe alloy nanowires by boundary and hole-phonon scattering

We report the thermoelectric characteristics of individual p-type SiGe alloy nanowires for diameters of 100 to 300 nm and temperatures between 40 to 300 K. A technique that allows for electrical and thermal characterization on the same nanowire was developed in this work. Experimental data provide evidence of the scattering of low-frequency phonons by the boundary of the nanowires. The thermal conductivities for SiGe alloy nanowires with different free carrier concentrations reveal that the long free path phonons are also scattered by hole-phonon interactions. Combined boundary and hole-phonon scattering mechanisms with alloy scattering resulted in thermal conductivities as low as 1.1 W/m-K at 300 K, which is one of the lowest measured for SiGe alloys and is comparable to that of bulk silica. The enhanced thermal properties observed in this work yielded ZT close to 0.18 at 300 K—more than a factor of 2 higher than the bulk SiGe alloy.

Advanced core/multishell germanium/silicon nanowire heterostructures: Morphology and transport

A precise level of control over morphology and transport in germanium/silicon core/multishell semiconductor nanowires is attained by interface engineering. Epitaxial in situ growth of such advanced heterostructures is achieved, enabling smooth and crystalline shell quality without ex situ thermal or chemical treatment. Transport simulation predicts such heterostructures with engineered energy band-edges will exhibit enhanced on-currents and transconductances over traditional device designs. Based on this synthesis approach, a 2× improvement in experimental hole mobility, transconductance, and on-currents is demonstrated for heterostructures with smooth surface morphologies compared to those with rough surface morphologies and record normalized on-currents for p-type field effect transistors are achieved.

Mapping carrier diffusion in single silicon core-shell nanowires with ultrafast optical microscopy.

Recent success in the fabrication of axial and radial core-shell heterostructures, composed of one or more layers with different properties, on semiconductor nanowires (NWs) has enabled greater control of NW-based device operation for various applications. (1-3) However, further progress toward significant performance enhancements in a given application is hindered by the limited knowledge of carrier dynamics in these structures. In particular, the strong influence of interfaces between different layers in NWs on transport makes it especially important to understand carrier dynamics in these quasi-one-dimensional systems. Here, we use ultrafast optical microscopy (4) to directly examine carrier relaxation and diffusion in single silicon core-only and Si/SiO(2) core-shell NWs with high temporal and spatial resolution in a noncontact manner. This enables us to reveal strong coherent phonon oscillations and experimentally map electron and hole diffusion currents in individual semiconductor NWs for the first time.

Highly efficient charge separation and collection across in situ doped axial VLS-grown Si nanowire p-n junctions.

VLS-grown semiconductor nanowires have emerged as a viable prospect for future solar-based energy applications. In this paper, we report highly efficient charge separation and collection across in situ doped Si p-n junction nanowires with a diameter <100 nm grown in a cold wall CVD reactor. Our photoexcitation measurements indicate an internal quantum efficiency of ~50%, whereas scanning photocurrent microscopy measurements reveal effective minority carrier diffusion lengths of ~1.0 μm for electrons and 0.66 μm for holes for as-grown Si nanowires (d(NW) ≈ 65-80 nm), which are an order of magnitude larger than those previously reported for nanowires of similar diameter. Further analysis reveals that the strong suppression of surface recombination is mainly responsible for these relatively long diffusion lengths, with surface recombination velocities (S) calculated to be 2 orders of magnitude lower than found previously for as-grown nanowires, all of which used hot wall reactors. The degree of surface passivation achieved in our as-grown nanowires is comparable to or better than that achieved for nanowires in prior studies at significantly larger diameters. We suggest that the dramatically improved surface recombination velocities may result from the reduced sidewall reactions and deposition in our cold wall CVD reactor.

Transport characterization in nanowires using an electrical nanoprobe

Electrical transport in semiconductor nanowires is commonly measured in a field effect transistor configuration, with lithographically defined source, drain and in some cases, top gate electrodes. This approach is labor intensive, requires high-end fabrication equipment, exposes the nanowires to extensive processing chemistry and places practical limitations on minimum nanowire length. Here we describe an alternative, simple method for characterizing electrical transport in nanowires directly on the growth substrate, without any need for post growth processing. Our technique is based on contacting nanowires using a nano-manipulator probe retrofitted inside of a scanning electron microscope. Using this approach, we characterize electrical transport in GaN nanowires grown by catalyst-free selective epitaxy, as well as InAs and Ge nanowires grown by a Au-catalyzed vapor solid liquid technique. We find that in situations where contacts are not limiting carrier injection (GaN and InAs nanowires), electrical transport transitions from Ohmic conduction at low bias to space-charge-limited conduction at higher bias. Using this transition and a theory of space-charge-limited transport which accounts for the high aspect ratio nanowires, we extract the mobility and the free carrier concentration. For Ge nanowires, we find that the Au catalyst forms a Schottky contact resulting in rectifying current‐voltage characteristics, which are strongly dependent on the nanowire diameter. This dependence arises due to an increase in depletion width at decreased nanowire diameter and carrier recombination at the nanowire surface. (Some figures in this article are in colour only in the electronic version)

Nanoscale manipulation of Ge nanowires by ion irradiation

Nanowires have generated considerable interest as nanoscale interconnects and as active components of both electronic and electromechanical devices. However, in many cases, manipulation and modification of nanowires are required to fully realize their potential. It is essential, for instance, to control the orientation and positioning of nanowires in some specific applications. This work demonstrates a simple method to reversibly control the shape and the orientation of Ge nanowires using ion beams. Crystalline nanowires were amorphized by 30 keV Ga+ implantation. Subsequently, viscous flow and plastic deformation occurred causing the nanowires to bend toward the beam direction. The bending was reversed multiple times by ion implanting the opposite side of the nanowires, resulting in straightening and subsequent bending into that opposite direction. This effect demonstrates the detailed manipulation of nanoscale structures is possible through the use of ion irradiation.