Phonon anharmonicity in binary chalcogenides for efficient energy harvesting.

Thermoelectric (TE) materials have received much attention due to their ability to harvest waste heat energy. TE materials must exhibit a low thermal conductivity (κ) and a high power factor (PF) for efficient conversion. Both factors define the figure of merit (ZT) of the TE material, which can be increased by suppressing κ without degrading the PF. Recently, binary chalcogenides such as SnSe, GeTe, and PbTe have emerged as attractive candidates for thermoelectric energy generation at moderately high temperatures. These materials possess simple crystal structures with low κ in their pristine forms, which can be further lowered through doping and other approaches. Here, we review the recent advances in the temperature-dependent behavior of phonons and their influence on the thermal transport properties of chalcogenide-based TE materials. Because phonon anharmonicity is one of the fundamental contributing factors for low thermal conductivity in SnSe, Sb-doped GeTe, and related chalcogenides, we discuss complementary experimental approaches such as temperature-dependent Raman spectroscopy, inelastic neutron scattering, and calorimetry to measure anharmonicity. We further show how data gathered using multiple techniques helps us understand and engineer better TE materials. Finally, we discuss the rise of machine learning-aided efforts to discover, design, and synthesize TE materials of the future.

Increase in the reduction potential of uranyl upon interaction with graphene oxide surfaces.

Coordination of uranyl (U(vi)) with carboxylate groups on functionalized graphene oxide (GO) surfaces has been shown to alter the reduction potential of the sorbed uranium ion. A quantitative measure of the reduction potential and qualitative estimation of sorption/desorption processes were conducted using cyclic voltammetry, and the proposed coordination environment was determined using the surface sensitive attenuated total reflection mode of infrared spectroscopy (ATR-FTIR). GO is a nanostructured material possessing a large amount of oxygen-containing functional groups both on basal planes and at the edges, which can form strong surface complexes with radionuclides. The presence of these functional groups on the surface of GO allows efficient immobilization of uranium due to sorption of uranyl (UO22+) to carboxylate, hydroxide, or sulfonate functional groups and the potential for enhanced reduction of U(vi) to more strongly sorbing and insoluble U(iv). Herein, binding of U(vi) to carboxylate groups on the GO surface is proposed as the primary sorption mechanism based on the FTIR study. Furthermore, the coordination of uranium with the surface increases the reduction potential of the U(vi)/U(iv) redox couple as compared to the case of the aqueous U(vi)/U(iv) species. This is consistent with the alteration of the electronic structure of the sorbed ion, which can be determined in our case due to the use of a GO-coated working electrode. Thus, GO-coated glassy carbon electrodes and other semi-conducting electrodes with high ion sorption capacities may provide a means of examining the oxidation/reduction potentials of sorbed ions.

Influence of dopants on the impermeability of graphene.

Graphene has attracted much attention as an impermeable membrane and a protective coating against oxidation. While many theoretical studies have shown that defect-free graphene is impermeable, in reality graphene inevitably has defects in the form of grain boundaries and vacancies. Here, we study the effects of N-dopants on the impermeability of few-layered graphene (FLG) grown on copper using chemical vapor deposition. The grain boundaries in FLG have minimal impact on their permeability to oxygen as they do not provide a continuous channel for gas transport due to high tortuosity. However, we experimentally show that the N-dopants in FLG display multiple configurations that create structural imperfections to selectively allow gas molecules to permeate. We used a comprehensive array of tools including Raman spectroscopy, X-ray photoelectron spectroscopy, optically stimulated electron emission measurements, and density functional theory of N-doped graphene on copper to elucidate the effects of dopant configuration on the impermeability of graphene. Our results clearly show that oxygen can permeate through graphene with non-graphitic nitrogen dopants that create pores in graphene and oxidize the underlying Cu substrate while graphitic nitrogen dopants do not show any changes compared to the pristine form. Furthermore, we observed that the work function of graphene can be tuned effectively by changing the dopant configuration.

Modulation of the Electrostatic and Quantum Capacitances of Few Layered Graphenes through Plasma Processing.

It is shown that charged defect generation, through argon ion-based plasma processing, in few layer graphene, could substantially enhance the electrical capacitance for electrochemical energy storage. Detailed consideration of the constituent space charge and quantum capacitances were used to delineate a new length scale, correlated to electrically active defects contributing to the capacitance, and was found to be smaller than a structural correlation length determined through Raman spectroscopy. The study offers insights into an industrially viable method (i.e., plasma processing) for modifying and enhancing the energy density of graphene-based electrochemical capacitors.

Direct measurement of shear properties of microfibers.

As novel fibers with enhanced mechanical properties continue to be synthesized and developed, the ability to easily and accurately characterize these materials becomes increasingly important. Here we present a design for an inexpensive tabletop instrument to measure shear modulus (G) and other longitudinal shear properties of a micrometer-sized monofilament fiber sample, such as nonlinearities and hysteresis. This automated system applies twist to the sample and measures the resulting torque using a sensitive optical detector that tracks a torsion reference. The accuracy of the instrument was verified by measuring G for high purity copper and tungsten fibers, for which G is well known. Two industrially important fibers, IM7 carbon fiber and Kevlar(®) 119, were also characterized with this system and were found to have G = 16.5 ± 2.1 and 2.42 ± 0.32 GPa, respectively.

Mechanical resonances of helically coiled carbon nanowires.

Despite their wide spread applications, the mechanical behavior of helically coiled structures has evaded an accurate understanding at any length scale (nano to macro) mainly due to their geometrical complexity. The advent of helically coiled micro/nanoscale structures in nano-robotics, nano-inductors, and impact protection coatings has necessitated the development of new methodologies for determining their shear and tensile properties. Accordingly, we developed a synergistic protocol which (i) integrates analytical, numerical (i.e., finite element using COMSOL) and experimental (harmonic detection of resonance; HDR) methods to obtain an empirically validated closed form expression for the shear modulus and resonance frequency of a singly clamped helically coiled carbon nanowire (HCNW), and (ii) circumvents the need for solving 12th order differential equations. From the experimental standpoint, a visual detection of resonances (using in situ scanning electron microscopy) combined with HDR revealed intriguing non-planar resonance modes at much lower driving forces relative to those needed for linear carbon nanotube cantilevers. Interestingly, despite the presence of mechanical and geometrical nonlinearities in the HCNW resonance behavior the ratio of the first two transverse modes f2/f1 was found to be similar to the ratio predicted by the Euler-Bernoulli theorem for linear cantilevers.

Synthesis and characterization of gold graphene composite with dyes as model substrates for decolorization: a surfactant free laser ablation approach.

A facile surfactant free laser ablation mediated synthesis (LAMS) of gold-graphene composite is reported here. The material was characterized using transmission electron microscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, powdered X-ray diffraction, Raman spectroscopy, Zeta potential measurements and UV-Visible spectroscopic techniques. The as-synthesized gold-graphene composite was effectively utilized as catalyst for decolorization of 4 important textile and laser dyes. The integration of gold nanoparticles (AuNPs) with high surface area graphene has enhanced the catalytic activity of AuNPs. This enhanced activity is attributed to the synergistic interplay of pristine gold's electronic relay and π-π stacking of graphene with the dyes. This is evident when the Rhodamine B (RB) reduction rate of the composite is nearly twice faster than that of commercial citrate capped AuNPs of similar size. In case of Methylene blue (MB) the rate of reduction is 17,000 times faster than uncatalyzed reaction. This synthetic method opens door to laser ablation based fabrication of metal catalysts on graphene for improved performance without the aid of linkers and surfactants.

Evidences For Charge Transfer-Induced Conformational Changes In Carbon Nanostructure-Protein Corona.

The binding of proteins to a nanostructure often alters protein secondary and tertiary structures. However, the main physical mechanisms that elicit protein conformational changes in the presence of the nanostructure have not yet been fully established. Here we performed a comprehensive spectroscopic study to probe the interactions between bovine serum albumin (BSA) and carbon-based nanostructures of graphene and single-walled carbon nanotubes (SWNTs). Our results showed that the BSA "corona" acted as a weak acceptor to facilitate charge transfer from the carbon nanostructures. Notably, we observed that charge transfer occurred only in the case of SWNTs but not in graphene, resulting from the sharp and discrete electronic density of states of the former. Furthermore, the relaxation of external α-helices in BSA secondary structure increased concomitantly with the charge transfer. These results may help guide controlled nanostructure-biomolecular interactions and prove beneficial for developing novel drug delivery systems, biomedical devices and engineering of safe nanomaterials.

Effects of surface functional groups on the formation of nanoparticle-protein corona.

Herein, we examined the dependence of protein adsorption on the nanoparticle surface in the presence of functional groups. Our UV-visible spectrophotometry, transmission electron microscopy, infrared spectroscopy, and dynamic light scattering measurements evidently suggested that the functional groups play an important role in the formation of nanoparticle-protein corona. We found that uncoated and surfactant-free silver nanoparticles derived from a laser ablation process promoted a maximum protein (bovine serum albumin) coating due to increased changes in entropy. On the other hand, bovine serum albumin displayed a relatively lower affinity for electrostatically stabilized nanoparticles due to the constrained entropy changes.

Binary III-V semiconductor core optical fiber.

For the first time to the best of our knowledge a glass-clad optical fiber comprising a crystalline binary III-V semiconductor core has been fabricated. More specifically, a phosphate glass-clad fiber containing an indium antimonide (InSb) core was drawn using a molten core approach. The core was found to be highly crystalline with some oxygen and phosphorus diffusing in from the cladding glass. While optical transmission measurements were unable to be made, most likely due to free carrier absorption associated with the conductivity of the core, this work constitutes a proof-of-concept that optical fibers comprising semiconductor cores of higher crystallographic complexity than previously realized can be drawn using conventional fiber fabrication techniques. Such binary semiconductors may open the door to future fiber-based nonlinear devices.

Superconductivity in thin films of boron-doped carbon nanotubes.

Superconductivity in carbon nanotubes (CNTs) is attracting considerable attention. However, its correlation with carrier doping has not been reported. We report on the Meissner effect found in thin films consisting of assembled boron (B)-doped single-walled CNTs (B-SWNTs). We find that only B-SWNT films consisting of low boron concentration leads to evident Meissner effect with Tc=12 K and also that a highly homogeneous ensemble of the B-SWNTs is crucial. The first-principles electronic-structure study of the B-SWNTs strongly supports these results.

Silicon optical fiber.

Described herein are initial experimental details and properties of a silicon core, silica glass-clad optical fiber fabricated using conventional optical fiber draw methods. Such semiconductor core fibers have potential to greatly influence the fields of nonlinear fiber optics, infrared and THz power delivery. More specifically, x-ray diffraction and Raman spectroscopy showed the core to be highly crystalline silicon. The measured propagation losses were 4.3 dB/m at 2.936 microm, which likely are caused by either microcracks in the core arising from the large thermal expansion mismatch with the cladding or to SiO(2) precipitates formed from oxygen dissolved in the silicon melt. Suggestions for enhancing the performance of these semiconductor core fibers are provided. Here we show that lengths of an optical fiber containing a highly crystalline semiconducting core can be produced using scalable fiber fabrication techniques.

Electrochemical organization of monolayer protected gold nanoclusters on single-walled carbon nanotubes: significantly enhanced double layer capacitance.

This paper reports a novel electrochemical route for anchoring monolayer protected gold nanoclusters (size 8 +/- 0.2 nm) on single-walled carbon nanotube bundles, resulting in the formation of hybrid materials. Monolayer protected gold nanoclusters prepared by modified Brust synthesis route were organized on SWNT bundles by cycling the potential in dichloromethane between -1 to +1 V at a scan rate of 50 mV/s. Monolayer protected nanoclusters in electrolyte solutions possess ionic space charge around them (double layer charging), making them suitable for organization on nanotube bundles, by tuning the electrostatic interactions. More significantly, analysis of the double layer capacitance of these hybrid materials shows almost ten times increase in capacitance compared to that of bare SWNT bundles. We believe that these hybrid materials are potentially useful in nanoelectronics.

A GH receptor antisense oligonucleotide inhibits hepatic GH receptor expression, IGF-I production and body weight gain in normal mice.

Diabetic retinopathy and acromegaly are diseases associated with excess action of GH and its effector IGF-I, and there is a need for improved therapies. We have designed an optimised 2'-O-(2-methoxyethyl)-modified phosphorothioate oligodeoxynucleotide, ATL 227446, and demonstrated its ability to suppress GH receptor mRNA in vitro. Subcutaneous injections of ATL 227446 reduced GH receptor mRNA levels, GH binding activity and serum IGF-I levels in mice after seven days of dosing. The reduction in serum IGF-I could be sustained for over ten weeks of dosing at therapeutically relevant levels, during which there was also a significant decrease in body weight gain in antisense-treated mice relative to saline and mismatch control-treated mice. The findings indicate that administration of an antisense oligonucleotide to the GH receptor may be applicable to human diseases in which suppression of GH action provides therapeutic benefit.

Determination of the bending modulus of an individual multiwall carbon nanotube using an electric harmonic detection of resonance technique.

We report a new method of measuring the amplitude and phase of oscillations of individual multiwall carbon nanotubes (MWNTs). As in many other experiments, we excite the oscillations electrostatically, but we show that we can detect the amplitude and phase of the resulting oscillation electrically. As an example, we present measurements of the fundamental and first two overtones of the diving board resonance of a MWNT at 0.339, 2.42, and 5.31 MHz in ambient conditions. The corresponding quality factors were 67, 36, and 25.

ZnO nanowires by pulsed laser vaporization: synthesis and properties.

We report a new pulsed-laser vaporization (PLV) technique to synthesize nanowires of single-crystal ZnO having a wurtzite structure by using colloidal gold nanoparticles as seeding catalysts. The average diameter of the nanowires is approximately 13 nm, with a very narrow range of 7 to 25 nm. The nanowires are straight for the most part, with the axes parallel to the [0001] growth direction. Raman and photoluminescence spectra from the nanowires and bulk ZnO are similar except for a approximately 510 nm band in the nanowires due to oxygen vacancies. The bulk-like vibrational and electronic properties of the nanowires is due to the diameter being larger than the threshold below which quantum confinement-induced effects are expected.

Novel electrical switching behaviour and logic in carbon nanotube Y-junctions.

Carbon-nanotube-based electronics offers significant potential as a nanoscale alternative to silicon-based devices for molecular electronics technologies. Here, we show evidence for a dramatic electrical switching behaviour in a Y-junction carbon-nanotube morphology. We observe an abrupt modulation of the current from an on- to an off-state, presumably mediated by defects and the topology of the junction. The mutual interaction of the electron currents in the three branches of the Y-junction is shown to be the basis for a potentially new logic device. This is the first time that such switching and logic functionalities have been experimentally demonstrated in Y-junction nanotubes without the need for an external gate. A class of nanoelectronic architecture and functionality, which extends well beyond conventional field-effect transistor technologies, is now possible.

Synthesis and thermoelectric power of nitrogen-doped carbon nanotubes.

We have previously shown that high-purity multiwalled carbon nanotubes (pristine MWNTs) can be prepared from a mixture of xylene-ferrocene (99 at% C:1 at% Fe) inside a quartz tube reactor operating at approximately 700 degrees C. In a similar process, approximately 3 g of melamine (C3H6N6) was introduced during the growth of MWNTs to prepare nitrogen-doped nanotubes. The structural and electronic properties of nitrogen-doped MWNTs were determined by scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and thermopower measurements. The individual nitrogen-doped nanotube exhibits a bamboo-like structure and comprises 6-16 tube walls, as evidenced by HRTEM studies. The EELS measurements yielded an average nitrogen content of approximately 5 at% in the doped tubes. The thermoelectric power data of nitrogen-doped MWNTs remained negative even after exposure to oxygen for an extended period of time, suggesting that nitrogen doping of MWNTs renders them n-type, consistent with scanning tunneling spectroscopic studies on similar nanotubes.

High-pressure Raman study of debundled single-walled carbon nanotubes.

We report the pressure dependence for the radial (omega R) and tangential (omega T) band frequencies in debundled single-walled carbon nanotubes (SWNTs) derived from laser-synthesized SWNT bundles. As previously described, a chemical procedure was used to prepare debundled SWNTs from as-prepared, large SWNT bundles. The normalized pressure coefficient for omega R in the debundled sample was compared with the corresponding value in the bundled sample to quantify the strength of van der Waals interactions between tubes in these nanotube materials. Furthermore, the pressure dependences for the radial (omega R) and tangential (omega T) band frequencies in debundled tubes were also compared with corresponding dependences predicted for isolated SWNTs, obtained with generalized tight binding molecular dynamic (GTBMD) simulations described in our previous work. The results presented here collectively suggest that the van der Waals interaction is still strong in the debundled sample studied here, which contained predominantly small bundles of SWNTs rather than isolated tubes.