Kristie J. Koski

Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers

Layered materials consist of molecular layers stacked together by weak interlayer interactions. They often crystallize to form atomically smooth thin films, nanotubes, and platelet or fullerene-like nanoparticles due to the anisotropic bonding. Structures that predominately expose edges of the layers exhibit high surface energy and are often considered unstable. In this communication, we present a synthesis process to grow MoS2 and MoSe2 thin films with vertically aligned layers, thereby maximally exposing the edges on the film surface. Such edge-terminated films are metastable structures of MoS2 and MoSe2, which may find applications in diverse catalytic reactions. We have confirmed their catalytic activity in a hydrogen evolution reaction (HER), in which the exchange current density correlates directly with the density of the exposed edge sites.

The New Skinny in Two-Dimensional Nanomaterials

While the advent of graphene has focused attention on the extraordinary properties of two-dimensional (2D) materials, graphenes lack of an intrinsic band gap and limited amenability to chemical modification has sparked increasing interest in its close relatives and in other 2D layered nanomaterials. In this issue of ACS Nano, Bianco et al. report on the production and characterization of one of these related materials: germanane, a one-atom-thick sheet of hydrogenated puckered germanium atoms structurally similar to graphane. It is a 2D nanomaterial generated via mechanical exfoliation from GeH. Germanane has been predicted to have technologically relevant properties such as a direct band gap and high electron mobility. Monolayer 2D materials like germanane, in general, have attracted enormous interest for their potential technological applications. We offer a perspective on the field of 2D layered nanomaterials and the exciting growth areas and discuss where the new development of germanane fits in, now and in the foreseeable future.

Ambipolar field effect in the ternary topological insulator (BixSb1-x)2Te3 by composition tuning

Topological insulators exhibit a bulk energy gap and spin-polarized surface states that lead to unique electronic properties, with potential applications in spintronics and quantum information processing. However, transport measurements have typically been dominated by residual bulk charge carriers originating from crystal defects or environmental doping, and these mask the contribution of surface carriers to charge transport in these materials. Controlling bulk carriers in current topological insulator materials, such as the binary sesquichalcogenides Bi2Te3, Sb2Te3 and Bi2Se3, has been explored extensively by means of material doping and electrical gating, but limited progress has been made to achieve nanostructures with low bulk conductivity for electronic device applications. Here we demonstrate that the ternary sesquichalcogenide (Bi(x)Sb(1-x))2Te3 is a tunable topological insulator system. By tuning the ratio of bismuth to antimony, we are able to reduce the bulk carrier density by over two orders of magnitude, while maintaining the topological insulator properties. As a result, we observe a clear ambipolar gating effect in (Bi(x)Sb(1-x))2Te3 nanoplate field-effect transistor devices, similar to that observed in graphene field-effect transistor devices. The manipulation of carrier type and density in topological insulator nanostructures demonstrated here paves the way for the implementation of topological insulators in nanoelectronics and spintronics.

Strain-Dependent Photoluminescence Behavior of CdSe/CdS Nanocrystals with Spherical, Linear, and Branched Topologies

The photoluminescence of CdSe/CdS core/shell quantum dots, nanorods, and tetrapods is investigated as a function of applied hydrostatic and non-hydrostatic pressure. The optoelectronic properties of all three nanocrystal morphologies are affected by strain. Furthermore, it is demonstrated that the unique morphology of seeded tetrapods is highly sensitive to non-isotropic stress environments. Seeded tetrapods can thereby serve as an optical strain gauge, capable of measuring forces on the order of nanonewtons. We anticipate that a nanocrystal strain gauge with optical readout will be useful for applications including sensitive optomechanical devices and biological force investigations.

High-Density Chemical Intercalation of Zero-Valent Copper into Bi2Se3 Nanoribbons

A major goal of intercalation chemistry is to intercalate high densities of guest species without disrupting the host lattice. Many intercalant concentrations, however, are limited by the charge of the guest species. Here we have developed a general solution-based chemical method for intercalating extraordinarily high densities of zero-valent copper metal into layered Bi(2)Se(3) nanoribbons. Up to 60 atom % copper (Cu(7.5)Bi(2)Se(3)) can be intercalated with no disruption to the host lattice using a solution disproportionation redox reaction.

Non-invasive determination of the complete elastic moduli of spider silks

Spider silks possess natures most exceptional mechanical properties, with unrivalled extensibility and high tensile strength. Unfortunately, our understanding of silks is limited because the complete elastic response has never been measured-leaving a stark lack of essential fundamental information. Using non-invasive, non-destructive Brillouin light scattering, we obtain the entire stiffness tensors (revealing negative Poissons ratios), refractive indices, and longitudinal and transverse sound velocities for major and minor ampullate spider silks: Argiope aurantia, Latrodectus hesperus, Nephila clavipes, Peucetia viridans. These results completely quantify the linear elastic response for all possible deformation modes, information unobtainable with traditional stress-strain tests. For completeness, we apply the principles of Brillouin imaging to spatially map the elastic stiffnesses on a spider web without deforming or disrupting the web in a non-invasive, non-contact measurement, finding variation among discrete fibres, junctions and glue spots. Finally, we provide the stiffness changes that occur with supercontraction.

Chemical Intercalation of Zerovalent Metals into 2D Layered Bi2Se3 Nanoribbons

We have developed a chemical method to intercalate a variety of zerovalent metal atoms into two-dimensional (2D) layered Bi(2)Se(3) chalcogenide nanoribbons. We use a chemical reaction, such as a disproportionation redox reaction, to generate dilute zerovalent metal atoms in a refluxing solution, which intercalate into the layered Bi(2)Se(3) structure. The zerovalent nature of the intercalant allows superstoichiometric intercalation of metal atoms such as Ag, Au, Co, Cu, Fe, In, Ni, and Sn. We foresee the impact of this methodology in establishing novel fundamental physical behaviors and in possible energy applications.

Luminescent nanocrystal stress gauge

Microscale mechanical forces can determine important outcomes ranging from the site of material fracture to stem cell fate. However, local stresses in a vast majority of systems cannot be measured due to the limitations of current techniques. In this work, we present the design and implementation of the CdSe-CdS core-shell tetrapod nanocrystal, a local stress sensor with bright luminescence readout. We calibrate the tetrapod luminescence response to stress and use the luminescence signal to report the spatial distribution of local stresses in single polyester fibers under uniaxial strain. The bright stress-dependent emission of the tetrapod, its nanoscale size, and its colloidal nature provide a unique tool that may be incorporated into a variety of micromechanical systems including materials and biological samples to quantify local stresses with high spatial resolution.

In situ observation of divergent phase transformations in individual sulfide nanocrystals.

Inorganic nanocrystals have attracted widespread attention both for their size-dependent properties and for their potential use as building blocks in an array of applications. A complete understanding of chemical transformations in nanocrystals is important for controlling structure, composition, and electronic properties. Here, we utilize in situ high-resolution transmission electron microscopy to study structural and morphological transformations in individual sulfide nanocrystals (copper sulfide, iron sulfide, and cobalt sulfide) as they react with lithium. The experiments reveal the influence of structure and composition on the transformation pathway (conversion versus displacement reactions), and they provide a high-resolution view of the unique displacement reaction mechanism in copper sulfide in which copper metal is extruded from the crystal. The structural similarity between the initial and final phases, as well as the mobility of ions within the crystal, are seen to exert a controlling influence on the reaction pathway.

Effects of Magnetic Doping on Weak Antilocalization in Narrow Bi2Se3 Nanoribbons

We report low-temperature, magnetotransport measurements of ferrocene-doped Bi(2)Se(3) nanoribbons grown by vapor-liquid-solid method. The Kondo effect, a saturating resistance upturn at low temperatures, is observed in these ribbons to indicate presence of localized impurity spins. Magnetoconductances of the ferrocene-doped ribbons display both weak localization and weak antilocalization, which is in contrast with those of undoped ribbons that show only weak antilocalization. We show that the observed magnetoconductances are governed by a one-dimensional localization theory that includes spin orbit coupling and magnetic impurity scattering, yielding various scattering and dephasing lengths for Bi(2)Se(3). The power law decay of the dephasing length on temperature also reflects one-dimensional localization regime in these narrow Bi(2)Se(3) nanoribbons. The emergence of weak localization in ferrocene-doped Bi(2)Se(3) nanoribbons presents ferrocene as an effective magnetic dopant source.