Vincent C. Holmberg

Silicon Nanowire Fabric as a Lithium Ion Battery Electrode Material

A nonwoven fabric with paperlike qualities composed of silicon nanowires is reported. The nanowires, made by the supercritical-fluid-liquid-solid process, are crystalline, range in diameter from 10 to 50 nm with an average length of >100 μm, and are coated with a thin chemisorbed polyphenylsilane shell. About 90% of the nanowire fabric volume is void space. Thermal annealing of the nanowire fabric in a reducing environment converts the polyphenylsilane coating to a carbonaceous layer that significantly increases the electrical conductivity of the material. This makes the nanowire fabric useful as a self-supporting, mechanically flexible, high-energy-storage anode material in a lithium ion battery. Anode capacities of more than 800 mA h g(-1) were achieved without the addition of conductive carbon or binder.

Nanostructured Si(1-x)Gex for Tunable Thin Film Lithium-Ion Battery Anodes

Both silicon and germanium are leading candidates to replace the carbon anode of lithium ions batteries. Silicon is attractive because of its high lithium storage capacity while germanium, a superior electronic and ionic conductor, can support much higher charge/discharge rates. Here we investigate the electronic, electrochemical and optical properties of Si(1-x)Gex thin films with x = 0, 0.25, 0.5, 0.75, and 1. Glancing angle deposition provided amorphous films of reproducible nanostructure and porosity. The films composition and physical properties were investigated by X-ray photoelectron spectroscopy, four-point probe conductivity, Raman, and UV-vis absorption spectroscopy. The films were assembled into coin cells to test their electrochemical properties as a lithium-ion battery anode material. The cells were cycled at various C-rates to determine the upper limits for high rate performance. Adjusting the composition in the Si(1-x)Gex system demonstrates a trade-off between rate capability and specific capacity. We show that high-capacity silicon anodes and high-rate germanium anodes are merely the two extremes; the composition of Si(1-x)Gex alloys provides a new parameter to use in electrode optimization.

Flexible Germanium Nanowires: Ideal Strength, Room Temperature Plasticity, and Bendable Semiconductor Fabric

The mechanical strengths of individual germanium (Ge) nanowires with 111 growth direction and diameters ranging from 23 to 97 nm were measured by bending each with a robotic nanomanipulator in a scanning electron microscope (SEM). The nanowires tolerate diameter-dependent flexural strains of up to 17% prior to fracture, which is more than 2 orders of magnitude higher than bulk Ge. The corresponding bending strength of 18 GPa is in agreement with the ideal strength of 14-20 GPa for a perfect Ge crystal. Nanowires also exhibited plastic deformation at room temperature, becoming amorphous at the point of maximum strain. A bendable, nonwoven fabric, or paper, of Ge nanowires is demonstrated.

Phase transitions, melting dynamics, and solid-state diffusion in a nano test tube.

Confined Germanium Thermodynamics When a material is confined to nanoscale volumes, the very high proportion of surface to bulk can alter its thermodynamic properties. This has been studied using in situ electron microscopy, but in most cases the volume of the material is not constrained. Holmberg et al. (p. 405) studied the thermodynamics of a germanium nanowire attached to a gold seed and coated with a carbon shell to restrict its volume, measuring the reaction temperature, as well as the liquid composition without changes in volume throughout the heating cycle. This enabled monitoring of phase behavior while the germanium was being heated, and tracking solid-state diffusion across the confined interface. A carbon coating allows the thermodynamic behavior of a germanium nanowire to be probed under constant-volume conditions. Confined nanoscale geometry greatly influences physical transformations in materials. The electron microscope enables direct visualization of these changes. We examined the evolution of a germanium (Ge) nanowire attached to a gold (Au) nanocrystal as it was heated to 900°C. The application of a carbon shell prevented changes in volume and interfacial area during the heating cycle. Au/Ge eutectic formation was visualized, occurring 15°C below the bulk eutectic temperature. Capillary pressure pushed the melt into the cylindrical neck of the nanowire, and Ge crystallized in the spherical tip of the carbon shell. Solid-state diffusion down the length of the confined Ge nanowire was observed at temperatures above 700°C; Au diffusion was several orders of magnitude slower than in a bulk Ge crystal.

Solution−Liquid−Solid Synthesis of CuInSe2 Nanowires and Their Implementation in Photovoltaic Devices

CuInSe₂ (CIS) nanowires were synthesized by solution-liquid-solid (SLS) growth in a high boiling solvent using bismuth nanocrystals as seeds. The nanowires tended to be slightly deficient in In and exhibited either cubic or hexagonal crystal structure, depending on the synthesis conditions. The hexagonal structure, which is not observed in bulk crystals, appears to evolve from large concentrations of twin defects. The nanowires could be compressed into a free-standing fabric or paper-like material. Photovoltaic devices (PVs) were fabricated using the nanowires as the light-absorbing layer to test their viability as a solar cell material and were found to exhibit measurable PV response.

Broadband Up-Conversion at Subsolar Irradiance: Triplet−Triplet Annihilation Boosted by Fluorescent Semiconductor Nanocrystals

Conventional solar cells exhibit limited efficiencies in part due to their inability to absorb the entire solar spectrum. Sub-band-gap photons are typically lost but could be captured if a material that performs up-conversion, which shifts photon energies higher, is coupled to the device. Recently, molecular chromophores that undergo triplet-triplet annihilation (TTA) have shown promise for efficient up-conversion at low irradiance, suitable for some types of solar cells. However, the molecular systems that have shown the highest up-conversion efficiency to date are ill suited to broadband light harvesting, reducing their applicability. Here we overcome this limitation by combining an organic TTA system with highly fluorescent CdSe semiconductor nanocrystals. Because of their broadband absorption and spectrally narrow, size-tunable fluorescence, the nanocrystals absorb the radiation lost by the TTA chromophores, returning this energy to the up-converter. The resulting nanocrystal-boosted system shows a doubled light-harvesting ability, which allows a green-to-blue conversion efficiency of ∼12.5% under 0.5 suns of incoherent excitation. This record efficiency at subsolar irradiance demonstrates that boosting the TTA by light-emitting nanocrystals can potentially provide a general route for up-conversion for different photovoltaic and photocatalytic applications.

PEGylation of Carboxylic Acid-Functionalized Germanium Nanowires

Germanium (Ge) nanowires were produced in solution by supercritical fluid-liquid-solid (SFLS) growth and then functionalized with carboxylic acid groups by in situ thermal thiolation with mercaptoundecanoic acid. Polyethylene glycol (PEG) was grafted to the carboxylic acid-terminated Ge nanowires using carbodiimide coupling chemistry. The nanowires were characterized using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and transmission electron microscopy (TEM) to confirm the surface modification of the nanowires. Dispersions of PEGylated Ge nanowires in dimethylsulfoxide (DMSO) were stable for days. The PEGylated Ge nanowires were also dispersible in aqueous solution over a wide range of pH and ionic strength.

Real-Time Observation of Impurity Diffusion in Silicon Nanowires

Solid-state diffusion of the transition metal impurities, gold (Au), nickel (Ni), and copper (Cu), in silicon (Si) nanowires was studied by in situ transmission electron microscopy. Compared to diffusion in a bulk crystal, Au diffusion is extremely slow when the amount of metal is limited but significantly enhanced when an unlimited supply is available. Cu and Ni diffusion leads to rapid silicide formation but slows considerably with physical encapsulation by a volume-restricting carbon shell.