J. Mitra

One-step synthesis of ZnO nanosheets: a blue-white fluorophore.

Zinc oxide is synthesised at low temperature (80°C) in nanosheet geometry using a substrate-free, single-step, wet-chemical method and is found to act as a blue-white fluorophore. Investigation by atomic force microscopy, electron microscopy, and X-ray diffraction confirms zinc oxide material of nanosheet morphology where the individual nanosheets are polycrystalline in nature with the crystalline structure being of wurtzite character. Raman spectroscopy indicates the presence of various defects, while photoluminescence measurements show intense green (centre wavelength approximately 515 nm) blue (approximately 450 nm), and less dominant red (approximately 640 nm) emissions due to a variety of vacancy and interstitial defects, mostly associated with surfaces or grain boundaries. The resulting colour coordinate on the CIE-1931 standard is (0.23, 0.33), demonstrating potential for use as a blue-white fluorescent coating in conjunction with ultraviolet emitting LEDs. Although the defects are often treated as draw-backs of ZnO, here we demonstrate useful broadband visible fluorescence properties in as-prepared ZnO.

Unusual photoresponse of indium doped ZnO/organic thin film heterojunction

Photoresponse of n-type indium-doped ZnO and a p-type polymer (PEDOT:PSS) heterojunction devices are studied, juxtaposed with the photoluminescence of the In-ZnO samples. In addition to the expected photoresponse in the ultraviolet, the heterojunctions exhibit significant photoresponse to the visible (532 nm). However, neither the doped ZnO nor PEDOT:PSS individually show any photoresponse to visible light. The sub-bandgap photoresponse of the heterojunction originates from visible photon mediated e-h generation between the In-ZnO valence band and localized states lying within the band gap. Though increased doping of In-ZnO has limited effect on the photoluminescence, it significantly diminishes the photoresponse. The study indicates that optimally doped devices are promising for the detection of wavelengths in selected windows in the visible.

Growth of oriented films of La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 on SrTiO3 using chemical solution deposition

Oriented thin films of La 0.67 Sr 0.33 MnO 3 and La 0.67 Ca 0.33 MnO 3 were fabricated on a SrTiO 3 (002) single crystal substrate by the chemical solution deposition (CSD) process. The CSD grown films have electronic and magnetotransport properties which are comparable to those of films prepared by the pulsed laser technique and to those of the bulk single crystal samples. The magnetoresistance of the films was found to be very similar to those of pulsed laser deposition grown films and they show no contribution of grain boundaries unlike polycrystalline films. The atomic force microscopy study of the roughness and its scaling with length shows that the surfaces of the films are self affine.

Non-linear electronic transport in Pt nanowires deposited by focused ion beam

Electrical transport and structural properties of platinum nanowires, deposited using the focused ion beam method, have been investigated. Energy dispersive x-ray spectroscopy reveals metal-rich grains (atomic composition 31% Pt and 50% Ga) in a largely non-metallic matrix of C, O and Si. Resistivity measurements (15–300 K) reveal a negative temperature coefficient with the room-temperature resistivity 80–300 times higher than that of bulk Pt. Temperature-dependent current–voltage characteristics exhibit non-linear behaviour in the entire range investigated. The conductance spectra indicate increasing non-linearity with decreasing temperature, reaching 4% at 15 K. The observed electrical behaviour is explained in terms of a model for inter-grain tunnelling in disordered media, a mechanism that is consistent with the strongly disordered nature of the nanowires observed in the structure and composition analysis.

The tip-sample water bridge and light emission from scanning tunnelling microscopy.

The light emission spectrum from a scanning tunnelling microscope (LESTM) is investigated as a function of relative humidity and shown to provide a novel and sensitive means for probing the growth and properties of a water meniscus on the nanometre scale. An empirical model of the light emission process is formulated and applied successfully to replicate the decay in light intensity and spectral changes observed with increasing relative humidity. The modelling indicates a progressive water filling of the tip-sample junction with increasing humidity or, more pertinently, of the volume of the localized surface plasmons responsible for light emission; it also accounts for the effect of asymmetry in structuring of the water molecules with respect to the polarity of the applied bias. This is juxtaposed with the case of a non-polar liquid in the tip-sample nanocavity where no polarity dependence of the light emission is observed. In contrast to the discrete detection of the presence/absence of a water bridge in other scanning probe experiments through measurement of the feedback parameter for instrument control, LESTM offers a means of continuously monitoring the development of the water bridge with sub-nanometre sensitivity. The results are relevant to applications such as dip-pen nanolithography and electrochemical scanning probe microscopy.

Electromagnetic interaction between a metallic nanoparticle and surface in tunnelling proximity—modelling and experiment

We simulate the localized surface plasmon resonances of an Au nanoparticle within tunnelling proximity of an Au substrate. The results demonstrate that the calculated resonance energies can be identified with those experimentally detected for light emission from the tip–sample junction of a scanning tunnelling microscope. Relative to the modes of an isolated nanoparticle these modes show significant red-shifting, extending further into the infrared with increasing radius, primarily due to a proximity-induced lowering of the effective bulk plasmon frequency. Spatial mapping of the field enhancement factor shows an oscillatory variation of the field, absent in the case of a dielectric substrate; also the degree of localization of the modes, and thus the resolution achievable electromagnetically, is shown to depend primarily on the nanoparticle radius, which is only weakly dependent on wavelength.

Spatially resolved photoresponse on individual ZnO nanorods: correlating morphology, defects and conductivity.

Electrically active native point defects have a significant impact on the optical and electrical properties of ZnO nanostructures. Control of defect distribution and a detailed understanding of their physical properties are central to designing ZnO in novel functional forms and architecture, which ultimately decides device performance. Defect control is primarily achieved by either engineering nanostructure morphology by tailoring growth techniques or doping. Here, we report conducting atomic force microscopy studies of spatially resolved photoresponse properties on ZnO nanorod surfaces. The photoresponse for super-band gap, ultraviolet excitations show a direct correlation between surface morphology and photoactivity localization. Additionally, the system exhibits significant photoresponse with sub-bandgap, green illumination; the signature energy associated with the deep level oxygen vacancy states. While the local current-voltage characteristics provide evidence of multiple transport processes and quantifies the photoresponse, the local time-resolved photoresponse data evidences large variations in response times (90 ms–50 s), across the surface of a nanorod. The spatially varied photoconductance and the range in temporal response display a complex interplay of morphology, defects and connectivity that brings about the true colour of these ZnO nanostructures.

The electrical characterization and response to hydrogen of Schottky diodes with a resistive metal electrode?rectifying an oversight in Schottky diode investigation

Schottky-barrier structures with a resistive metal electrode are examined using the 4-point probe method where the probes are connected to the metal electrode only. The observation of a significant decrease in resistance with increasing temperature (over a range of ~100 K) in the diode resistance–temperature (RD–T) characteristic is considered due to charge carrier confinement to the metal electrode at low temperature (high resistance), with the semiconductor progressively opening up as a parallel current carrying channel (low resistance) with increasing temperature due to increasing thermionic emission across the barrier. A simple model is constructed, based on thermionic emission at quasi-zero bias, that generates good fits to the experimental data. The negative differential resistance (NDR) region in the RD–T characteristic is a general effect and is demonstrated across a broad temperature range for a variety of Schottky structures grown on Si-, GaAs- and InP-substrates. In addition the NDR effect is harnessed in micro-scaled Pd/n-InP devices for the detection of low levels of hydrogen in an ambient atmosphere of nitrogen.

High sensitivity (1 ppm) hydrogen detection using an unconventional Pd/n-InP Schottky device

Hydrogen is detected using a Pd/n-InP Schottky diode in which the elongated, very thin Pd electrode is of greater resistance than the underlying semiconductor substrate. Four-probe measurements of the device resistance, as a function of hydrogen concentration, are made by contacting only the Pd electrode, with a sensitivity of 1 ppm being achieved. On hydrogen exposure the device resistance drops from an initial high value, characteristic of the Pd electrode alone, to a lower value due to a hydrogen-induced lowering of the Schottky barrier that opens up the InP substrate as a parallel current carrying channel.

Photon Emission at Step Edges of Single Crystalline Gold Surfaces Investigated by Scanning Tunnelling Microscopy

Light emission in scanning tunnelling microscopy arising from Au tips scanning Au(111) surfaces with multiple defects is mapped simultaneously with topography. The remarkably good correspondence between features in the topography and the photon maps masks marked differences in the details of the correlation between the topographic and photonic signal profiles across different types of features. The variation of photon signal with topography is qualitatively explained in terms of the influence of changes in the geometry of the tip–sample nanocavity on the support and scattering of localised surface plasmon modes that are responsible for the light emission. In particular, evidence from optical spectroscopy shows the existence of a higher energy mode when a sharp step edge profiles the tip; this mode is not present in planar facet areas of the same sample.