New first order Raman-active modes in few layered transition metal dichalcogenides.

Although the main Raman features of semiconducting transition metal dichalcogenides are well known for the monolayer and bulk, there are important differences exhibited by few layered systems which have not been fully addressed. WSe2 samples were synthesized and ab-initio calculations carried out. We calculated phonon dispersions and Raman-active modes in layered systems: WSe2, MoSe2, WS2 and MoS2 ranging from monolayers to five-layers and the bulk. First, we confirmed that as the number of layers increase, the E', E″ and E2g modes shift to lower frequencies, and the A'1 and A1g modes shift to higher frequencies. Second, new high frequency first order A'1 and A1g modes appear, explaining recently reported experimental data for WSe2, MoSe2 and MoS2. Third, splitting of modes around A'1 and A1g is found which explains those observed in MoSe2. Finally, exterior and interior layers possess different vibrational frequencies. Therefore, it is now possible to precisely identify few-layered STMD.

An atomic layer deposition reactor with dose quantification for precursor adsorption and reactivity studies.

An atomic layer deposition reactor has been constructed with quantitative, precision dose control for studying precursor adsorption characteristics and to relate dose quantity and exposure dynamics to fluid flow in both the viscous and molecular flow regimes. A fixed volume of gas, held at a controlled temperature and measured pressure, is dosed into the reaction chamber by computer-controlled pneumatic valves. Dual in situ quartz crystal microbalances provide parallel mass measurement onto two differently coated substrates, which allows adsorption coverage and relative sticking coefficients to be determined. Gas composition in the reaction chamber was analyzed in situ by a quadrupole mass spectrometer. Absolute reactant exposure is unambiguously calculated from the impingement flux, and is related to dose, surface area, and growth rates. A range of control over the dose amount is demonstrated and consequences for film growth control are demonstrated and proposed.

Proximity-induced superconductivity in nanowires: minigap state and differential magnetoresistance oscillations.

We study proximity-induced superconductivity in gold nanowires as a function of the length of the nanowire, magnetic field, and excitation current. Short nanowires exhibit a sharp superconducting transition, whereas long nanowires show nonzero resistance. At intermediate lengths, however, we observe two sharp transitions; the normal and superconducting regions are separated by what we call the minigap phase. Additionally, we detect periodic oscillations in the differential magnetoresistance. We suggest that the minigap phase as well as the periodic oscillations originate from a coexistence of proximity-induced superconductivity with a normal region near the center of the wire, created either by temperature or the application of a magnetic field.

Investigation of superconductivity in electrochemically fabricated AuSn nanowires.

We have fabricated intermetallic AuSn nanowires by electrochemical deposition in porous polycarbonate membranes. By controlling the deposition parameters, nanowires of a single intermetallic phase, namely AuSn, can be fabricated. AuSn nanowires are found to be crystalline and fairly resistant to oxidation. Electrical transport measurements on arrays of nanowires showed a superconducting transition temperature, T(c)∼1.5 K. In addition, four-probe measurements were made on individual freestanding nanowires with electrodes formed by a focused ion beam (FIB). Results from the two sets of measurements are found to be in close agreement.

Autonomously moving nanorods at a viscous interface.

We study the autonomous motion of catalytic nanorods in Gibbs monolayers. The catalytic activity of the rods on a hydrogen peroxide aqueous subphase gives rise to anomalous translational and rotational diffusion. The rods perform a Levy-walk superdiffusive motion that can be decomposed into thermal orientation fluctuations and an active motion of the rods with a constant velocity along their long axis. Since interfacial dissipation increases relative to bulk phase dissipation when miniaturizing the size of objects moving in the interface, the autonomous nanorods allow for precise measurements of surface shear viscosities as low as a few nN s/m. The cross over from active motion toward passive diffusion when increasing the surfactant concentration is explained by a loss of friction asymmetry of the rods.

Combined experimental and theoretical DFT study of molecular nanowires negative differential resistance and interaction with gold clusters.

Electric-field-assisted assembly has been used to place rod-shaped metal nanowires containing 4-[[2-nitro-4-(phenylethynyl) phenyl] ethynyl] benzenthiol molecules onto lithographically defined metal pads. These junctions exhibited negative differential resistance. The quantum chemical approach was used to compare the properties of Au-bonded 4-[[2-nitro-4-(phenylethynyl) phenyl] ethynyl] benzenthiol molecule and a molecule that does not exhibit the negative differential resistance, Au-bonded 4-[[4-(phenylethynyl) phenyl] ethynyl] benzenthiol. The influence of the static electric field and charge variation were modelled for both systems.

Combinatorial discovery of alloy electrocatalysts for amperometric glucose sensors.

Combinatorial methods were used to search for active alloy electrocatalysts for use in enzyme-free amperometric glucose sensors. Electrode arrays (715-member) containing combinations of Pt, Pb, Au, Pd, and Rh were prepared and screened by converting anodic current to visible fluorescence. The most active compositions contained both Pt and Pb. Bulk quantities of catalysts with compositions corresponding to those identified in the screening experiments were prepared and characterized. The best alloy electrocatalysts catalyzed glucose oxidation at substantially more negative potentials than pure platinum in enzyme-free voltammetric measurements. They were also insensitive to potential interfering agents (ascorbic and uric acids, and 4-acetamidophenol), which are oxidized at slightly more positive potentials. Rotating disk electrode (RDE) experiments were carried out to study the catalytic mechanism. The improvement in catalytic performance was attributed to the inhibition of adsorption of oxidation products, which poison Pt electrodes.

Modular synthesis of pi-acceptor cyclophanes derived from 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene.

Three neutral cyclophanes were synthesized, and their association with indole, an aromatic pi-donor, was studied. The cyclophanes were designed to contain a rigid, hydrophobic binding cavity with 1,4,5,8-naphthalenetetracarboxylic diimide or 1,5-dinitronaphthalene as the pi-acceptor. Two of the cyclophanes also contain a (S)-(valine-leucine-alanine) tripeptide unit to provide chiral hydrogen bonding interactions with guest molecules. Despite the fact that these cyclophanes contain a hydrophobic binding cavity of appropriate dimensions, their association with indole is very weak. In the case of cyclophanes derived from 1,5-dinitronaphthalene, steric interactions force the nitro groups out of the plane of the naphthalene ring, diminishing their effectiveness as pi-acceptors. A simple UV--visible titrimetric method, using N,N,N',N'-tetramethyl-1,4-phenylenediamine (TMPD) as a pi-donor, was used to rank the pi-acceptor strength of these and other aromatic units. These titrations show that 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene derivatives are weaker pi-acceptors than viologens, which make good pi-acceptor cyclophanes. Methyl viologen is in turn a weaker pi-acceptor than anthaquinone disulfonate, suggesting that the latter may serve as a useful building block for pi-accepting cyclophane hosts.

Ordered mesoporous polymers of tunable pore size from colloidal silica templates.

Ordered mesoporous polymers have been prepared by replication of colloidal crystals made from silica spheres 35 nanometers in diameter. The pores in the colloidal crystals were filled with divinylbenzene (DVB), ethyleneglycol dimethacrylate (EDMA), or a mixture of the two. Polymerization and subsequent dissolution of the silica template leaves a polycrystalline network of interconnected pores. When mixtures of DVB and EDMA are used, the pore size of the polymer replicas can be varied continuously between 35 and 15 nanometers because the polymer shrinks when the silica template is removed.

Turning down the heat: design and mechanism in solid-state synthesis.

Solid-state compounds have historically been prepared through high-temperature solid-solid reactions. New mechanistic understanding of these reactions suggests possible routes to metastable compositions and structures as well as to thermodynamically stable, low-temperature phases that decompose at higher temperatures. Intermediate-temperature synthetic techniques, including flux and hydrothermal methods, as well as low-temperature intercalation and coordination reactions, have recently been developed and have been used to prepare unprecedented materials with interesting electronic, optical, and catalytic properties. The trend in modern solid-state synthesis resembles increasingly the approach used in small-molecule chemistry, in the sense that attention to reaction mechanism and the use of molecular building blocks result in an ability to prepare new materials of designed structure.

Structure of [Mg(HO3PCH(C6H5)2)2].8H2O, a layered phosphonate salt.

Bis(hydrogen diphenylmethylphosphonato)-magnesium octahydrate, [Mg(C13H12O3P)2].8H2O. Mr = 662.85, triclinic, P1, a = 6.1051 (15), b = 8.8308(14), c = 15.312(3) A, alpha = 78.514(13), beta = 83.993(11), gamma = 75.772(15) degrees, V = 782.8(3) A3, Z = 1, Dx = 1.41 g cm-3 (163 K), Mo K alpha, lambda = 0.71069 A, mu = 2.171 cm-1, F(000) = 350, T = 163 K, R = 0.0351 for 3749 reflections [F0 greater than or equal to 4 sigma(F0)]. The structure consists of alternating polar and nonpolar layers stacked along the crystallographic c axis. The polar layers contain Mg(H2O)26+ ions, water of hydration and the phosphonate O atoms, and the nonpolar layers contain the benzhydryl groups. Two-dimensional hydrogen-bonding networks link Mg(H2O)26+ and the water of hydration to the phosphonate O atoms. The shortest hydrogen bonds in the structure, 1.68(2) A, connect the P-OH H atom and the water of hydration. Slightly longer contacts [1.79(2), 1.85(2), 1.91(2), 1.92(2) A] connect the phosphonate O atoms (O1 and O3) to the H atoms of the Mg(H2O)26+ group. The coordination environment of the Mg atom is a very nearly regular octahedron of water O atoms.