Andrew L. Schmitt

Dislocation-Driven Nanowire Growth and Eshelby Twist

Hierarchical nanostructures of lead sulfide nanowires resembling pine trees were synthesized by chemical vapor deposition. Structural characterization revealed a screwlike dislocation in the nanowire trunks with helically rotating epitaxial branch nanowires. It is suggested that the screw component of an axial dislocation provides the self-perpetuating steps to enable one-dimensional crystal growth, in contrast to mechanisms that require metal catalysts. The rotating trunks and branches are the consequence of the Eshelby twist of screw dislocations with a dislocation Burgers vector along the 〈110〉 directions having an estimated magnitude of 6 ± 2 angstroms for the screw component. The results confirm the Eshelby theory of dislocations, and the proposed nanowire growth mechanism could be general to many materials.

Synthesis and applications of metal silicide nanowires

Transition metal silicides represent an extremely broad set of refractory materials that are currently employed for many applications including CMOS devices, thin film coatings, bulk structural components, electrical heating elements, photovoltaics, and thermoelectrics. Many of these applications may be improved by making 1-dimensional nanomaterials. Chemical synthesis of silicide nanowires is more complicated compared to other classes of nanomaterials due to the complex phase behaviour between metals and silicon and the complex stoichiometries and structures of their resulting compounds. Recently, several synthetic strategies have been developed to overcome this challenge resulting in increasing reports of silicide nanowires in the literature. These strategies are highlighted in this feature article, along with future synthetic challenges and a review of the applications emerging from current silicide nanowires.

Higher Manganese Silicide Nanowires of Nowotny Chimney Ladder Phase

We report the synthesis, structural identification, and electrical properties of the first one-dimensional (1-D) nanomaterials of a semiconducting higher manganese silicide (MnSi(2-x)) with widths down to 10 nm via chemical vapor deposition of the single-source precursor Mn(CO)(5)SiCl(3). The complex Nowotny chimney ladder structure of these homologous higher manganese silicides, also referred to as Mn(n)Si(2n-m), MnSi(1.75), or MnSi(1.8), contributes to the excellent thermoelectric performance of the bulk materials, which would be enhanced by phonon scattering due to 1-D nanoscale geometry. The morphology, structure, and composition of MnSi(2-x) nanowires and nanoribbons are examined using electron microscopy and X-ray spectroscopy. Elaborate select area electron diffraction analysis on single-crystal nanowires reveals the phase to be Mn(19)Si(33), one of a series of crystallographically distinct higher manganese silicides that have a Nowotny chimney ladder structure. Electrical transport study of single nanowires shows that they are degenerately doped with a low resistivity (17 mohms x cm) similar to the bulk.

Chemical synthesis and magnetotransport of magnetic semiconducting Fe1-xCoxSi alloy nanowires.

We report single-crystal nanowires of magnetic semiconducting Fe1-xCoxSi alloys synthesized using a two-component single source precursor approach. Extending our previous syntheses of FeSi and CoSi nanowires from Fe(SiCl3)2(CO)4 and Co(SiCl3)(CO)4 precursors, we found that a homogeneous solution formed upon mixing these two precursors due to melting point suppression. This liquid constitutes the single-source precursor suitable for delivery through chemical vapor deposition, which enables the chemical synthesis of Fe1-xCoxSi alloy nanowires on silicon substrates covered with a thin (1-2 nm) SiO2 layer. Using scanning and transmission electron microscopy and energy dispersive X-ray spectroscopy and mapping, we demonstrate two homogenously mixed alloy nanowire samples with very different Co substitution concentrations (x): 6+/-5%, the ferromagnetic semiconductor regime, and 44+/-5%, the helical magnetic regime. The magnetotransport properties of these alloy nanowires are pronouncedly different from that of the host structures FeSi and CoSi, as well as from one another, and consistent with the physical properties as expected for their corresponding compositions. These novel magnetic semiconducting silicide nanowires will be important building blocks for silicon-based spintronic nanodevices.

Spin Polarization Measurement of Homogeneously Doped Fe1–xCoxSi Nanowires by Andreev Reflection Spectroscopy

We report a general method for determining the spin polarization from nanowire materials using Andreev reflection spectroscopy implemented with a Nb superconducting contact and common electron-beam lithography device fabrication techniques. This method was applied to magnetic semiconducting Fe(1-x)Co(x)Si alloy nanowires with x̅ = 0.23, and the average spin polarization extracted from 6 nanowire devices is 28 ± 7% with a highest observed value of 35%. Local-electrode atom probe tomography (APT) confirms the homogeneous distribution of Co atoms in the FeSi host lattice, and X-ray magnetic circular dichroism (XMCD) establishes that the elemental origin of magnetism in this strongly correlated electron system is due to Co atoms.

Mechanistic Investigation of the Growth of Fe1−xCoxSi (0 ≤ x ≤ 1) and Fe5(Si1−yGey)3 (0 ≤ y ≤ 0.33) Ternary Alloy Nanowires

We present the chemical vapor deposition (CVD) reactions of the single source precursor Fe(SiCl(3))(2)(CO)(4) over Si, Ge, CoSi(2)/Si, and CoSi/Si substrates to explore the growth and doping processes of silicide nanowires (NWs). Careful investigation of the composition and morphology of the NW products and the intruded silicide films from which they nucleate revealed that the group IV elements (Si, Ge) in the NW products originate from both the precursor and the substrate, while the metal elements incorporated into the NWs (Fe, Co) originate from vapor phase precursor delivery. The use of a Ge growth substrate enabled the successful synthesis of Fe(5)Si(2)Ge NWs, the first report of a metal silicide-germanide alloy NW. Further, investigation of the pyrolysis of the CoSiCl(3)(CO)(4) precursor revealed independent delivery of Co and Si species during CVD reactions. This understanding enabled a new, more robust two-precursor synthetic route to Fe(1-x)Co(x)Si alloy NWs using Fe(SiCl(3))(2)(CO)(4) and CoCl(2).

Polydispersity-driven shift in the lamellar mesophase composition window of PEO-PB-PEO triblock copolymers

The influence of broad and continuous center block polydispersity on the melt-phase self-assembly of OBO triblock copolymers (O = poly(ethylene oxide) and B = poly(1,4-butadiene)) is reported for a series of samples derived from tandem chain transfer ring-opening metathesis polymerization (ROMP-CT) and anionic ring-opening polymerization (AROP). By virtue of the polymerization techniques employed in these syntheses, the midblocks exhibit polydispersity indices Mw/Mn = 1.75, whereas the end blocks have relatively narrow dispersities Mw/Mn ≤ 1.25. Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) to characterize these materials and their narrow dispersity homologues derived from anionic polymerization, we demonstrate that the combination of both chain length and composition polydispersity inherent in these polydisperse triblocks shifts the composition window of stability for the lamellar mesophase. Furthermore, these studies reveal that polydispersity in the center B segments of these OBO triblocks results in large lamellar domain spacing increases, enables stable coexistence of two morphologies in a single sample, and frustrates lattice ordering in a composition-dependent manner.

Spin-dependent tunneling transport into CrO2 nanorod devices with nonmagnetic contacts.

Single-crystal nanorods of half-metallic chromium dioxide (CrO2) were synthesized and structurally characterized. Spin-dependent electrical transport was investigated in individual CrO2 nanorod devices contacted with nonmagnetic metallic electrodes. Negative magnetoresistance (MR) was observed at low temperatures due to the spin-dependent direct tunneling through the contact barrier and the high spin polarization in the half-metallic nanorods. The magnitude of this negative magnetoresistance decreases with increasing bias voltage and temperature due to spin-independent inelastic hopping through the barrier, and a small positive magnetoresistance was found at room temperature. It is believed that the contact barrier and the surface state of the nanorods have great influence on the spin-dependent transport limiting the magnitude of MR effect in this first attempt at spin filter devices of CrO2 nanorods with nonmagnetic contacts.

Mesoporous Carbon–Vanadium Oxide Films by Resol-Assisted, Triblock Copolymer-Templated Cooperative Self-Assembly

Unlike other crystalline metal oxides amenable to templating by the combined assemblies of soft and hard chemistries (CASH) method, vanadium oxide nanostructures templated by poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) triblock copolymers are not preserved upon high temperature calcination in argon. Triconstituent cooperative assembly of a phenolic resin oligomer (resol) and an OBO triblock in a VOCl3 precursor solution enhances the carbon yield and can prevent breakout crystallization of the vanadia during calcination. However, the calcination environment significantly influences the observed mesoporous morphology in these composite thin films. Use of an argon atmosphere in this processing protocol leads to nearly complete loss of carbon-vanadium oxide thin film mesostructure, due to carbothermal reduction of vanadium oxide. This reduction mechanism also explains why the CASH method is not more generally successful for the fabrication of ordered mesoporous vanadia. Carbonization under a nitrogen atmosphere at temperatures up to 800 °C instead enables formation of a block copolymer-templated mesoporous structure, which apparently stems from the formation of a minor fraction of a stabilizing vanadium oxynitride. Thus, judicious selection of the inert gas for template removal is critical for the synthesis of well-defined, mesoporous vanadia-carbon composite films. This resol-assisted assembly method may generally apply to the fabrication of other mesoporous materials, wherein inorganic framework crystallization is problematic due to kinetically competitive carbothermal reduction processes.

Synthesis, characterization, and physical properties of transition metal silicide nanowires

We develop rational chemical strategies to synthesize novel one-dimensional nanowire materials of transition metal silicides, investigate their physical properties, and use them as nanoscale building blocks for the bottom-up assembly of integrated photonic, electronic, and spintronic nanosystems. Transition metal silicides are extremely important to microelectronics because of the ohmic contact and interconnect many silicides (NiSi, CoSi2, and TiSi2) provide. Furthermore, many silicides are direct bandgap semiconductors (CrSi2, β-FeSi2) and are promising for silicon-based photonics. The recent discovery of FexCo1-xSi alloys as ferromagnetic semiconductors make them promising for spintronic applications as well. Herein, we describe the chemical synthesis of free standing single-crystal nanowires (NWs) of FeSi, the only transition metal Kondo insulator and isostructural CoSi, an important metallic silicide for CMOS electronics. Straight and smooth FeSi and CoSi nanowires are produced on silicon substrates covered with a thin layer of silicon oxide through the decomposition of the single source organometallic precursors trans-Fe(SiCl3)2(CO)4 and Co(SiCl3)(CO)4, respectively, in a simple chemical vapor deposition (CVD) process. Unlike typical vapor-liquid-solid (VLS) NW growth, silicide NWs form without the addition of metal catalysts, have no catalyst tips, and depend strongly on the surface employed. The physical properties of these new FeSi and CoSi nanowires, including electrical transport and X-ray spectroscopy, are reported. This general approach to silicide nanowire growth is likely to yield other functional silicide nanosystems with significant applications in nanoelectronics and nanophotonics, and for FexCo1-xSi, silicon based spintronics.