Reginald M. Penner

Photoluminescence and polarized photodetection of single ZnO nanowires

Single crystal ZnOnanowires are synthesized and configured as field-effect transistors.Photoluminescence and photoconductivity measurements show defect-related deep electronic states giving rise to green-red emission and absorption. Photocurrent temporal response shows that current decay time is significantly prolonged in vacuum due to a slower oxygen chemisorption process. The photoconductivity of ZnOnanowires is strongly polarization dependent. Collectively, these results demonstrate that ZnOnanowire is a remarkable optoelectronic material for nanoscale device applications.

Fabrication and Use of Nanometer-Sized Electrodes in Electrochemistry

Electrodes with electrochemical dimensions as small as 10 angstroms have been fabricated and used for electrochemical studies. These nanometer-scale electrodes have enabled the measurement of electron-transfer rate constants, khet, that are two orders of magnitude faster than khet values accessible with any other electrochemical method.

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.

Smaller is faster and more sensitive: the effect of wire size on the detection of hydrogen by single palladium nanowires.

Palladium nanowires prepared using the lithographically patterned nanowire electrodeposition (LPNE) method are used to detect hydrogen gas (H2). These palladium nanowires are prepared by electrodepositing palladium from EDTA-containing solutions under conditions favoring the formation of β-phase PdHx. The Pd nanowires produced by this procedure are characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. These nanowires have a mean grain diameter of 15 nm and are composed of pure Pd with no XPS-detectable bulk carbon. The four-point resistance of 50-100 μm segments of individual nanowires is used to detect H2 in N2 and air at concentrations ranging from 2 ppm to 10%. For low [H2] < 1%, the response amplitude increases by a factor of 2-3 with a reduction in the lateral dimensions of the nanowire. Smaller nanowires show accelerated response and recovery rates at all H2 concentrations from, 5 ppm to 10%. For 12 devices, response and recovery times are correlated with the surface area/volume ratio of the palladium detection element. We conclude that the kinetics of hydrogen adsorption limits the observed response rate seen for the nanowire, and that hydrogen desorption from the nanowire limits the observed recovery rate; proton diffusion within PdHx does not limit the rates of either of these processes.

Controlling the Morphology of Electronically Conductive Polymers

Methode pour forcer les polymeres conducteurs a adopter une morphologie fibrillaire, macroporeuse

The nature of water on surfaces of laboratory systems and implications for heterogeneous chemistry in the troposphere

A number of heterogeneous reactions of atmospheric importance occur in thin water films on surfaces in the earths boundary layer. It is therefore important to understand the interaction of water with various materials, both those used to study heterogeneous chemistry in laboratory systems, as well as those found in the atmosphere. We report here studies at 22 °C to characterize the interaction of water with such materials as a function of relative humidity from 0–100%. The surfaces studied include borosilicate glass, both untreated and after cleaning by three different methods (water, hydrogen peroxide and an argon plasma discharge), quartz, FEP Teflon film, a self assembled monolayer of n-octyltrichlorosilane (C8 SAM) on glass, halocarbon wax coatings prepared by two different methods, and several different types of Teflon coatings on solid substrates. Four types of measurements covering the range from the macroscopic level to the molecular scale were made: (1) contact angle measurements of water droplets on these surfaces to obtain macroscopic scale data on the water-surface interaction, (2) atomic force microscopy measurements to provide micron to sub-micron level data on the surface topography, (3) transmission FTIR of the surfaces in the presence of increasing water vapor concentrations to probe the interaction with the surface at a molecular level, and (4) X-ray photoelectron spectroscopy measurements of the elemental surface composition of the glass and quartz samples. Both borosilicate glass and the halocarbon wax coatings adsorbed significantly more water than the FEP Teflon film, which can be explained by a combination of the chemical nature of the surfaces and their physical topography. The C8 SAM, which is both hydrophobic and has a low surface roughness, takes up little water. The implications for the formation of thin water films on various surfaces in contact with the atmosphere, including building materials, soil, and vegetation, are discussed.

20 μs Photocurrent Response from Lithographically Patterned Nanocrystalline Cadmium Selenide Nanowires

Lithographically patterned nanowire electrodeposition (LPNE) provides a method for patterning nanowires composed of nanocrystalline cadmium selenide (nc-CdSe) over wafer-scale areas. We assess the properties of (nc-CdSe) nanowires for detecting light as photoconductors. Structural characterization of these nanowires by X-ray diffraction and transmission electron microscopy reveals they are composed of stoichiometric, single phase, cubic CdSe with a mean grain diameter of 10 nm. For nc-CdSe nanowires with lengths of many millimeters, the width and height dimensions could be varied over the range from 60 to 350 nm (w) and 20 to 80 nm (h). Optical absorption and photoluminescence spectra for nc-CdSe nanowires were both dominated by band-edge transitions. The photoconductivity properties of nc-CdSe nanowire arrays containing approximately 350 nanowires were evaluated by electrically isolating 5 microm nanowire lengths using evaporated gold electrodes. Photocurrents, i(photo), of 10-100 x (i(dark)) were observed with a spectral response characterized by an onset at 1.75 eV. i(photo) response and recovery times were virtually identical and in the range from 20 to 40 micros for 60 x 200 nm nanowires.

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.