David K. Taggart

Fast, sensitive hydrogen gas detection using single palladium nanowires that resist fracture.

Two types of pure palladium (Pd) nanowires, differentiated by microstructure, were electrodeposited: (1) nanocrystalline Pd nanowires (grain diameter approximately 5 nm, henceforth nc5-Pd) and (2) nanocrystalline Pd nanowires with a grain diameter of 15 nm (nc15-Pd). These nanowires were evaluated for the detection of hydrogen gas (H(2)). Despite their fundamental similarities, the behavior of these nanowires upon exposure to H(2) was dramatically and reproducibly different: nc5-Pd nanowires spontaneously fractured upon exposure to H(2) above 1-2%. Fractured nanowires continued to function as sensors for H(2) concentrations above 2%, actuated by the volume change associated with the alpha to beta phase transition of PdH(x). nc15-Pd nanowires, in contrast, withstood repeated exposures to H(2) up to 10% without fracturing. nc15-Pd nanowires showed a rapid (2 s at 10%) increase in resistance in the presence of H(2) and a response that scaled smoothly with [H(2)] spanning 5 orders of magnitude down to 2 ppm.

Enhanced Thermoelectric Metrics in Ultra-long Electrodeposited PEDOT Nanowires

The Seebeck coefficient, S, and the electrical conductivity, σ, of electrodeposited poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires and thin films are reported. PEDOT nanowires were prepared by electropolymerizing 3,4-ethylenedioxythiophene (EDOT) in aqueous LiClO(4) within a template prepared using the lithographically patterned nanowire electrodeposition (LPNE) process. These nanowires were 40-90 nm in thickness, 150-580 nm in width, and 200 μm in length. σ and S were measured from 190 K to 310 K by fabricating heaters and thermocouples on top of arrays of 750 PEDOT nanowires. Such PEDOT nanowire arrays consistently produced S values that were higher than those for PEDOT films: up to -122 μV/K (310 K) for nanowires and up to -57 μV/K (310 K) for films. The sample-to-sample variation in S for 14 samples of PEDOT nanowires and films, across a wide range of critical dimensions, is fully explained by variations in the carrier concentrations in accordance with the Mott equation. In spite of their higher |S| values, PEDOT nanowires also had higher σ than films, on average, because electron mobilities were greater in nanowires by a factor of 3.

Virus-PEDOT nanowires for biosensing.

The separate fields of conducting polymer-based electrochemical sensors and virus-based molecular recognition offer numerous advantages for biosensing. Grafting M13 bacteriophage into an array of poly (3,4-ethylenedioxythiophene) (PEDOT) nanowires generated hybrids of conducting polymers and viruses. The virus incorporation into the polymeric backbone of PEDOT occurs during electropolymerization via lithographically patterned nanowire electrodeposition. The resultant arrays of virus-PEDOT nanowires enable real-time, reagent-free electrochemical biosensing of analytes in physiologically relevant buffers.

Lithographically patterned nanowire electrodeposition: a method for patterning electrically continuous metal nanowires on dielectrics.

Lithographically patterned nanowire electrodeposition (LPNE) is a new method for fabricating polycrystalline metal nanowires using electrodeposition. In LPNE, a sacrificial metal (M(1)=silver or nickel) layer, 5-100 nm in thickness, is first vapor deposited onto a glass, oxidized silicon, or Kapton polymer film. A (+) photoresist (PR) layer is then deposited, photopatterned, and the exposed Ag or Ni is removed by wet etching. The etching duration is adjusted to produce an undercut approximately 300 nm in width at the edges of the exposed PR. This undercut produces a horizontal trench with a precisely defined height equal to the thickness of the M(1) layer. Within this trench, a nanowire of metal M(2) is electrodeposited (M(2)=gold, platinum, palladium, or bismuth). Finally the PR layer and M(1) layer are removed. The nanowire height and width can be independently controlled down to minimum dimensions of 5 nm (h) and 11 nm (w), for example, in the case of platinum. These nanowires can be 1 cm in total length. We measure the temperature-dependent resistance of 100 microm sections of Au and Pd wires in order to estimate an electrical grain size for comparison with measurements by X-ray diffraction and transmission electron microscopy. Nanowire arrays can be postpatterned to produce two-dimensional arrays of nanorods. Nanowire patterns can also be overlaid one on top of another by repeating the LPNE process twice in succession to produce, for example, arrays of low-impedance, nanowire-nanowire junctions.

Synthesis of PbTe Nanowire Arrays using Lithographically Patterned Nanowire Electrodeposition

We describe the preparation by electrodeposition of arrays of lead telluride (PbTe) nanowires using the lithographically patterned nanowire electrodeposition (LPNE) method. PbTe nanowires had a rectangular cross-section with adjustable width and height ranging between 60-400 nm (w) and 20-100 nm (h). The characterization of these nanowire arrays using X-ray diffraction, transmission electron microscopy and electron diffraction, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy (XPS) is reported. PbTe nanowires were electrodeposited using a cyclic electrodeposition-stripping technique that produced polycrystalline, stoichiometric, face-centered cubic PbTe with a mean grain diameter of 10-20 nm. These nanowires were more than 1 mm in length and two additional processing steps permitted their suspension across 25 microm air gaps microfabricated on these surfaces. The LPNE synthesis of lithographically patterned PbTe nanowires was carried out in unfiltered laboratory air. Nanowires with lengths of 70-100 microm showed an electrical resistivity comparable to bulk PbTe. XPS reveals that exposure of PbTe nanowires to air causes the formation on the nanowire surface of approximately one monolayer of a mixed lead oxide and tellurium oxide within a few minutes.

Spatial Control of Coherent Anti-Stokes Emission with Height-Modulated Gold Zig-Zag Nanowires

Intrinsic coherent anti-Stokes emission is observed in lithographically patterned gold nanowires. Polarization dependent measurements reveal that the nanostructures anti-Stokes response is polarized in the direction of the transverse surface plasmon resonance of the wire. We have used specially fabricated gold nanozigzag wires that are modulated in height between 20 and 80 nm to demonstrate tuning of the plasmon polarizability through control of wire height. Stronger anti-Stokes emission is shown to correlate with structures that support higher plasmon polarizability, underlining the primary role of the transverse plasmon resonance in the generation of anti-Stokes radiation from gold nanostructures. Our results also point out that a potential surface-enhanced coherent anti-Stokes Raman scattering (CARS) assay for detecting the vibrational response of surface-tethered molecules needs to include a mechanism for separating the molecular response from the strong intrinsic anti-Stokes emission of the metallic nanosubstrate.

Wafer-Scale Patterning of Lead Telluride Nanowires: Structure, Characterization, and Electrical Properties

Nanowires of lead telluride (PbTe) were patterned on glass surfaces using lithographically patterned nanowire electrodeposition (LPNE). LPNE involved the fabrication by photolithography of a contoured nickel nanoband that is recessed by approximately 300 nm into a horizontal photoresist trench. Cubic PbTe was then electrodeposited from a basic aqueous solution containing Pb(2+) and TeO(3)(2-) at the nickel nanoband using a cyclic deposition/stripping potential program in which lead-rich PbTe was first deposited in a negative-going potential scan and excess lead was then anodically stripped from the nascent nanowire by scanning in the positive direction to produce near stoichiometric PbTe. Repeating this scanning procedure permitted PbTe nanowires 60-400 nm in width to be obtained. The wire height was controlled over the range of 20-100 nm based upon the nickel film thickness. Nanowires with lengths exceeding 1 cm were prepared in this study. We report the characterization of these nanowires using X-ray diffraction, transmission electron microscopy and electron diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The surface chemical composition of PbTe nanowires was monitored by XPS as a function of time during the exposure of these nanowires to laboratory air. One to two monolayers of a mixed Pb and Te oxide are formed during a 24 h exposure. The electrical conductivity of PbTe nanowires was strongly affected by air oxidation, declining from an initial value of 2.0(+/-1.5) x 10 (4) S/m by 61% (for nanowires with a 20 nm thickness), 55% (for 40 nm), and 12% (for 60 nm).

Coherent anti-Stokes generation from single nanostructures

Dual color four-wave-mixing is used to visualize individual gold nanowires and single carbon nanotubes. The strong nonlinear signals, which are detected at the anti-Stokes frequency, originate from the electronic response of the nanostructures. In gold nanowires, the collective electron motions produce detectable coherent anti-Stokes signals that can be used to study the orientation and relative strength of the structures plasmon resonances. In single walled carbon nanotubes, coherent anti-Stokes contrast can be used to map the orientation of the electronic resonances in single tubes. Coherent anti-Stokes imaging of the materials electronic response allows the first close-ups of the coherent nonlinear properties of individual structures and molecules.

Gold nanowires: Deposition, characterization and application to the Mass Spectrometry detection of low-molecular weight analytes

Nanowire fabrication methods are usually classified either as ‘top down’, including for example photo- or electron beam-lithography, or ‘bottom up’, involving the synthesis of nanowires from smaller precursors. Lithographically patterned nanowire electrodeposition (LPNE) combines the attributes of the photolithography approach with the versatility of bottom-up electrodeposition methods. In the present study, gold nanowires (Au-NWs) have been electrodeposited using LPNE. The nanomaterials have been then subjected to a spectroscopic and morphological characterization by means of X-Ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD) and Atomic Force Microscopy (AFM). Finally, Au-NWs have been successfully used as desorption/ionization promoters for the Laser-Induced Desorption-Ionization Mass Spectrometry (LDI-MS) detection of low-molecular weight analytes, such as amino acids and peptides.