Phase-Controlled Synthesis and Quasi-Static Dielectric Resonances in Silver Iron Sulfide (AgFeS2 ) Nanocrystals.

Ternary metal-chalcogenide semiconductor nanocrystals are an attractive class of materials due to their tunable optoelectronic properties that result from a wide range of compositional flexibility and structural diversity. Here, the phase-controlled synthesis of colloidal silver iron sulfide (AgFeS2 ) nanocrystals is reported and their resonant light-matter interactions are investigated. The product composition can be shifted selectively from tetragonal to orthorhombic by simply adjusting the coordinating ligand concentration, while keeping the other reaction parameters unchanged. The results show that excess ligands impact precursor reactivity, and consequently the nanocrystal growth rate, thus deterministically dictating the resulting crystal structure. Moreover, it is demonstrated that the strong ultraviolet-visible extinction peak exhibited by AgFeS2 nanocrystals is a consequence of a quasi-static dielectric resonance (DR), analogous to the optical response observed in CuFeS2 nanocrystals. Spectroscopic studies and computational calculations confirm that a negative permittivity at ultraviolet/visible frequencies arises due to the electronic structure of these intermediate-band (IB) semiconductor nanocrystals, resulting in a DR consisting of resonant valence-band-to-intermediate-band excitations, as opposed to the well-known localized surface plasmon resonance response typically observed in metallic nanostructures. Overall, these results expand the current library of an underexplored class of IB semiconductors with unique optical properties, and also enrich the understanding of DRs in ternary metal-iron-sulfide nanomaterials.

On-Demand Sonochemical Synthesis of Ultrasmall and Magic-Size CdSe Quantum Dots in Single-Phase and Emulsion Systems.

The sonochemical synthesis of CdSe quantum dots (QDs) in a single-liquid bulk phase and in an emulsion-based system is presented. Reactions utilized cadmium oleate and trioctylphosphine selenide precursors and were monitored as a function of sonication time under controlled temperature conditions to isolate the effects of cavitation from those of bulk temperature changes. QD synthesis was found to be slow in the single-phase liquid system (i.e., 1-octadecene) but greatly accelerated in the dispersed system (i.e., emulsions of 1-octadecene in ethylene glycol). It is hypothesized that the emulsion system increases the cavitation efficiency while also delivering acoustic energy in closer proximity to the precursor molecules. The capacity of CdSe production in the emulsion system was found to be 3.8 g/(L h), which is comparable to the typical hot-injection synthesis of CdSe QDs and can likely be further optimized. While the single-phase solvent system was found to produce ultrasmall QDs that exhibit broadband white-light emission, the emulsion system was found to produce well-defined magic-size clusters (MSCs) with photoluminescence quantum yield as high as 34%. Differences in synthesis rate and product properties from the emulsion and single-phase systems were probed by X-ray diffraction, electron microscopy, UV-visible (vis) and photoluminescence spectroscopy, and small-angle X-ray scattering (SAXS). Finally, precise temporal control of the QD synthesis was demonstrated via on-off cycling of the ultrasound waves.

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.

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.

Laser-Driven Growth of Semiconductor Nanowires from Colloidal Nanocrystals.

Semiconductor nanowire production through vapor- and solution-based processes has propelled nanowire systems toward a wide range of technological applications. Although vapor-based nanowire syntheses enable precise control over nanowire composition and phase, they typically employ batch processes with specialized pressure management systems, limiting throughput. Solution-based nanowire growth processes have improved scalability but can require even more extensive pressure and temperature management systems. Here, we demonstrate a solution-based nanowire growth process that utilizes the large Young-Laplace interfacial surface pressures and collective heating effects of colloidal metal nanocrystals under irradiation to drive nanowire growth photothermally. Laser irradiation of a solution containing metal nanocrystals and semiconductor precursors facilitates rapid heating, precursor decomposition, and nanowire growth on a benchtop in simple glassware under standard conditions, potentially enabling a range of solution-based experiments including in-line combinatorial identification of optimized reaction parameters, in situ measurements, and the production of nanowires with complex compositions.

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.

Optically oriented attachment of nanoscale metal-semiconductor heterostructures in organic solvents via photonic nanosoldering.

As devices approach the single-nanoparticle scale, the rational assembly of nanomaterial heterojunctions remains a persistent challenge. While optical traps can manipulate objects in three dimensions, to date, nanoscale materials have been trapped primarily in aqueous solvents or vacuum. Here, we demonstrate the use of optical traps to manipulate, align, and assemble metal-seeded nanowire building blocks in a range of organic solvents. Anisotropic radiation pressure generates an optical torque that orients each nanowire, and subsequent trapping of aligned nanowires enables deterministic fabrication of arbitrarily long heterostructures of periodically repeating bismuth-nanocrystal/germanium-nanowire junctions. Heat transport calculations, back-focal-plane interferometry, and optical images reveal that the bismuth nanocrystal melts during trapping, facilitating tip-to-tail "nanosoldering" of the germanium nanowires. These bismuth-semiconductor interfaces may be useful for quantum computing or thermoelectric applications. In addition, the ability to trap nanostructures in oxygen- and water-free organic media broadly expands the library of materials available for optical manipulation and single-particle spectroscopy.

Quantum Dot Cellular Uptake and Toxicity in the Developing Brain: Implications for Use as Imaging Probes.

Nanometer-sized luminescent semiconductor quantum dots (QDs) have been utilized as imaging and therapeutic agents in a variety of disease settings, including diseases of the central nervous system. QDs have several advantages over traditional fluorescent probes including their small size (5-10 nm), tunable excitation and emission spectra, tailorable surface functionality, efficient photoluminescence, and robust photostability, which are ideal characteristics for in vivo imaging. Although QDs are promising imaging agents in brain-related applications, no systematic evaluation of QD behavior in brain-relevant conditions has yet been done. Therefore, we sought to investigate QD colloidal stability, cellular uptake, and toxicity in vitro, ex vivo, and in vivo in the brain environment. We found that QD behavior is highly dependent on surface functionality and that treatment of cultured organotypic whole hemisphere (OWH) slices with QDs results in dose-dependent toxicity and metallothionein increase, but no subsequent mRNA expression level changes in inflammatory cytokines or other oxidative stress. QDs coated with poly(ethylene glycol) (PEG) were protected from aggregation in neurophysiologically relevant fluids and in tissue, allowing for greater penetration. Importantly, QD behavior differed in cultured slices as compared to monolayer cell cultures, and behavior in cultured slices aligned more closely with that seen in vivo. Irrespective of surface chemistry and brain-relevant platform, non-aggregated QDs were primarily internalized by microglia in a region-dependent manner both in slices and in vivo upon systemic administration. This knowledge will help guide further engineering of candidate QD-based imaging probes for neurological application.

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 film's 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.

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.

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 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 degrees 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 degrees 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 degrees C; Au diffusion was several orders of magnitude slower than in a bulk Ge crystal.