Arrays of mesoporous manganese dioxide, mp-MnO(2), nanowires were electrodeposited on glass and silicon surfaces using the lithographically patterned nanowire electrodeposition (LPNE) method. The electrodeposition procedure involved the application, in a Mn(ClO(4))(2)-containing aqueous electrolyte, of a sequence of 0.60 V (vs MSE) voltage pulses delineated by 25 s rest intervals. This "multipulse" deposition program produced mp-MnO(2) nanowires with a total porosity of 43-56%. Transmission electron microscopy revealed the presence within these nanowires of a network of 3-5 nm diameter fibrils that were X-ray and electron amorphous, consistent with the measured porosity values. mp-MnO(2) nanowires were rectangular in cross-section with adjustable height, ranging from 21 to 63 nm, and adjustable width ranging from 200 to 600 nm. Arrays of 20 nm × 400 nm mp-MnO(2) nanowires were characterized by a specific capacitance, C(sp), of 923 ± 24 F/g at 5 mV/s and 484 ± 15 F/g at 100 mV/s. These C(sp) values reflected true hybrid electrical energy storage with significant contributions from double-layer capacitance and noninsertion pseudocapacitance (38% for 20 nm × 400 nm nanowires at 5 mV/s) coupled with a Faradaic insertion capacity (62%). These two contributions to the total C(sp) were deconvoluted as a function of the potential scan rate.

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.

We describe the fabrication of arrays of nanowires on glass in which a gold core nanowire is encapsulated within a hemicylindrical shell of manganese dioxide. Arrays of linear gold (Au) nanowires are first prepared on glass using the lithographically patterned nanowire electrodeposition (LPNE) method. These Au nanowires have a rectangular cross-section with a width and height of ≈200 and 40 nm, respectively, and lengths in the 1 mm to 1 cm range. Au nanowires are then used to deposit MnO2 by potentiostatic electrooxidation from Mn2+ solution, forming a conformal, hemicylindrical shell with a controllable diameter ranging from 50 to 300 nm surrounding each Au nanowire. This MnO2 shell is δ-phase and mesoporous, as revealed by X-ray diffraction and Raman spectroscopy. Transmission electron microscopy (TEM) analysis reveals that the MnO2 shell is mesoporous (mp-MnO2), consisting of a network of ≈2 nm fibrils. The specific capacitance, C sp , of arrays of gold:mp-MnO2 nanowires is measured using cyclic voltammetry. For a mp-MnO2 shell thickness of 68 ± 3 nm, core:shell nanowires produce a C sp of 1020 ± 100 F/g at 5 mV/s and 450 ± 70 F/g at 100 mV/s. The cycle stability of this C sp , however, is extremely limited in aqueous electrolyte, decaying by >90% in 100 scans, but after oven drying and immersion in dry 1.0 M LiClO4, acetonitrile, dramatically improved cycle stability is achieved characterized by the absence of C sp fade for 1000 cycles at 100 mV/s. Core:shell nanowires exhibit true hybrid energy storage, as revealed by deconvolution of C sp into insertion and noninsertion components.

The performance of a single platinum (Pt) nanowire for detecting H(2) in air is reported. A Pt nanowire shows no resistance change upon exposure to H(2) in N(2), but H(2) exposure in air causes a reversible resistance decrease for H(2) concentrations above 10 ppm. The amplitude of the resistance change induced by H(2) exposure and the time rate of change of the nanowire resistance both increased with increasing temperature from 298 to 550 K. This resistance decrease of the Pt nanowire in the presence of H(2) results from reduced electron diffuse scattering at hydrogen-covered Pt surfaces as compared with oxygen-covered platinum surfaces, we hypothesize. The properties for the detection of H(2) in air of single Pt and Pd nanowires of similar size are compared in this study. Pt nanowires have a limit-of-detection for H(2) (LOD(H(2))) of 10 ppm; 3 orders of magnitude lower than for Pd nanowires of the same size, as well as a response time that is 1/100th of Pd for [H(2)] ≈ 1%.

Nanocrystalline cadmium selenide (nc-CdSe) nanowires were prepared using the lithographically patterned nanowire electrodeposition method. Arrays of 350 linear nc-CdSe nanowires with lateral dimensions of 60 nm (h) × 200 nm (w) were patterned at 5 μm pitch on glass. nc-CdSe nanowires electrodeposited from aqueous solutions at 25 °C had a mean grain diameter, d(ave), of 5 nm. A combination of three methods was used to increase d(ave) to 10, 20, and 100 nm: (1) The deposition bath was heated to 75 °C, (2) nanowires were thermally annealed at 300 °C, and (3) nanowires were exposed to methanolic CdCl(2) followed by thermal annealing at 300 °C. The morphology, chemical composition, grain diameter, and photoconductivity of the resulting nanowires were studied as a function of d(ave). As d(ave) was increased from 10 to 100 nm, the photoconductivity response of the nanowires was modified in two ways: First, the measured photoconductive gain, G, was elevated from G = 0.017 (d(ave) = 5 nm) to ∼4.9 (100 nm), a factor of 290. Second, the photocurrent rise time was increased from 8 μs for d(ave) = 10 nm to 8 s for 100 nm, corresponding to a decrease by a factor of 1 million of the photoconduction bandwidth from 44 kHz to 44 mHz.