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.

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.

Nanocrystalline cadmium selenide (nc-CdSe) was electrodeposited within a sub-50 nm gold nanogap, prepared by feedback-controlled electromigration, to form a photoconductive metal-semiconductor-metal nanojunction. Both gap formation and electrodeposition were rapid and automated. The electrodeposited nc-CdSe was stoichiometric, single cubic phase with a mean grain diameter of ∼7 nm. Optical absorption, photoluminescence, and the spectral photoconductivity response of the nc-CdSe were all dominated by band-edge transitions. The photoconductivity of these nc-CdSe-filled gold nanogaps was characterized by a detectivity of 6.9 × 10(10) Jones and a photosensitivity of 500. These devices also demonstrated a maximum photoconductive gain of ∼45 and response and recovery times below 2 μs, corresponding to a 3 dB bandwidth of at least 175 kHz.

Electroluminescent (EL) metal-semiconductor-metal nanojunctions are prepared by electrodepositing nanocrystalline cadmium selenide (nc-CdSe) within ∼250 nm gold (Au) nanogaps prepared by focused ion beam milling. The electrodeposition of nc-CdSe is carried out at two temperatures: 20 °C (“cold”) and 75 °C (“hot”), producing mean grain diameters of 6 ± 1 nm and 11 ± 2 nm, respectively, for the nc-CdSe. Light-emitting nanojunctions (LEnJs) prepared at both temperatures show a low threshold voltage for light emission of <2 V; just above the 1.74 eV bandgap of CdSe. The EL intensity increases with the injection current and hot-deposited LEnJs produced a maximum EL intensity that is an order of magnitude higher than the cold-deposited LEnJs. Emitted photons are bimodal in energy with emission near the band gap of CdSe, and also at energies 200 meV below it; consistent with a mechanism of light emission involving the radiative recombination of injected holes with electrons at both band-edge and defect states. The quantum yield for “hot” electrodeposited nc-CdSe LEnJs is comparable to devices constructed from single crystalline nanowires of CdSe, and the threshold voltage of 1.9 (±0.1) V (cold) and 1.5 (±0.2) V (hot) is at the low end of the range reported for CdSe nanowire based devices.

Field-effect transistors (NWFETs) have been prepared from arrays of polycrystalline cadmium selenide (pc-CdSe) nanowires using a back gate configuration. pc-CdSe nanowires were fabricated using the lithographically patterned nanowire electrodeposition (LPNE) process on SiO(2)/Si substrates. After electrodeposition, pc-CdSe nanowires were thermally annealed at 300 °C × 4 h either with or without exposure to CdCl(2) in methanol-a grain growth promoter. The influence of CdCl(2) treatment was to increase the mean grain diameter from 10 to 80 nm as determined by grazing incidence X-ray diffraction and to convert the crystal structure from cubic to wurtzite. Measured transfer characteristics showed an increase of the field effect mobility (μ(eff)) by an order of magnitude from 1.94 × 10(-4) cm(2)/(V s) to 23.4 × 10(-4) cm(2)/(V s) for pc-CdSe nanowires subjected to the CdCl(2) treatment. The CdCl(2) treatment also reduced the threshold voltage (from 20 to 5 V) and the subthreshold slope (by ~35%). Transfer characteristics for pc-CdSe NWFETs were also influenced by the channel length, L. For CdCl(2)-treated nanowires, μ(eff) was reduced by a factor of eight as L increased from 5 to 25 μm. These channel length effects are attributed to the presence of defects including breaks and constrictions within individual pc-CdSe nanowires.

Electroluminescence (EL) from nanocrystalline CdSe (nc-CdSe) nanowire arrays is reported. The n-type, nc-CdSe nanowires, 400-450 nm in width and 60 nm in thickness, were synthesized using lithographically patterned nanowire electrodeposition, and metal-semiconductor-metal (M-S-M) devices were prepared by the evaporation of two gold contacts spaced by either 0.6 or 5 μm. These M-S-M devices showed symmetrical current voltage curves characterized by currents that increased exponentially with applied voltage bias. As the applied biased was increased, an increasing number of nanowires within the array "turned on", culminating in EL emission from 30 to 50% of these nanowires at applied voltages of 25-30 V. The spectrum of the emitted light was broad and centered at 770 nm, close to the 1.74 eV (712 nm) band gap of CdSe. EL light emission occurred with an external quantum efficiency of 4 × 10(-6) for devices with a 0.60 μm gap between the gold contacts and 0.5 × 10(-6) for a 5 μm gap-values similar to those reported for M-S-M devices constructed from single-crystalline CdSe nanowires. Kelvin probe force microscopy of 5 μm nc-CdSe nanowire arrays showed pronounced electric fields at the gold electrical contacts, coinciding with the location of strongest EL light emission in these devices. This electric field is implicated in the Poole-Frenkel minority carrier emission and recombination mechanism proposed to account for EL light emission in most of the devices that were investigated.

We report electronic transport mapping in a single dielectric layer of a polycrystalline BaTiO3 multilayer ceramic capacitor (MLCC) by electron beam induced current (EBIC) measurements using a scanning transmission electron microscope. Ga+ focused ion beam-lift out techniques with organometallic Pt-deposition are used to extract and electrically connect to these devices while maintaining high (&gt;gigaohm) resistance between electrodes. Different modes of EBIC are observed depending on device resistivity. We demonstrate the use of EBIC resulting from secondary electron emission as a method for performing resistance contrast imaging (RCI), with resistive grain boundaries appearing as steps in EBIC contrast. These RCI maps are also used to calculate the potential and electric field of the device under an arbitrary bias. A mix of high- and low-resistance ohmic as well as rectifying grain boundaries is observed. These results help to better establish the distribution of resistivities critical to the prevention of performance-limiting current leakage in MLCCs.

The microstructural features determining the leakage current through polycrystalline BaTiO3 films are investigated using Conductive Atomic Force Microscopy. Grain boundaries are found to be the dominant conductive paths compared to the conduction through the grains. Grain boundary currents are observed to reversibly rise with the increase of the applied DC voltages, indicating that the current is controlled by a field-activated charge transport process.