Studies on electrophoretically deposited nanostructured barium titanate systems and carrier transport phenomena

We report on the development of nanostructured barium titanate (BaTiO₃, BT) films on ~200-μm-thick Ag substrates by employing a cathodic electrophoretic deposition (EPD) technique, where solid-state-derived BT nanoparticles are used as the starting material. Structural, morphological and compositional analyses of the as-synthesized BT nanoparticles and films were performed by X-ray diffraction, electron microscopy and energy-dispersive spectroscopy studies. The synthesized nano-BT system has an average crystallite size of ~8.1 nm and a tetragonality (c/a) value ~1.003. To reveal current transport mechanism, the BT films possessing microporous structures and surrounded by homogeneously grown islands were assessed in a metal–insulator–metal (MIM) conformation. The forward current conduction was observed to be purely thermionic up to respective voltages of ~1.4 and 2.2 V as for the fresh and 3-day aged samples. On the other hand, direct tunneling (DT)-mediated Ohmic feature was witnessed at a comparatively higher voltage, beyond which Fowler–Nordheim tunneling (FN) dominates in the respective MIM junctions. The magnitude of current accompanied by FN process was observed to be stronger in reverse biasing than that of forward biasing case. The use of microporous BT films can offer new insights as regards regulated tunneling events meant for miniaturized nanoelectronic elements/components.     

Photochromism and magneto-optic response of ZnO:Mn semiconductor quantum dots fabricated by microemulsion route

ZnO:Mn semiconductor quantum dots were prepared by solution casting led microemulsion route. Quantum dots of average size ∼2 nm were noticed in transmission electron micrographs. The present work highlights colour change phenomena (photochromic effect) of quantum dots while subjected to photon illumination. The magneto-optic measurements e.g. magnetic field (H) vs angle of rotation (θ) show step like behavior and is ascribed to the quantum confinement effect of diluted magnetic ZnO:Mn nanostructures. Further, underlying mechanism responsible for exhibiting photochromism and magneto-optic effects are also discussed.      

Significant Fowler–Nordheim tunneling across ZnO – Nanorod based nanojunctions for nanoelectronic device applications

We demonstrate significant Fowler–Nordheim (FN) tunneling across Al/Al₂O₃/ZnO metal–insulator–semiconductor (MIS) and Ag/ZnO metal–semiconductor (MS) nanojunctions. The transport properties of ZnO nanostructures in the form of urchins and randomly distributed nanorods were investigated in terms of various conduction mechanism. The minimum voltage necessary for triggering Fowler–Nordheim (FN) tunneling, under forward biasing, was ～1.2 V and ～3.4 V; respectively, below which only direct tunneling and thermionic emission events were evident. Mediated through Al₂O₃ layer, the FN tunneling was more prominent across MIS junction than MS one. The weak FN tunneling across MS junction was owing to interfacial charge transfer process through the atomic scale gapping between adjacent nanostructures. The extent of such type of tunneling is found to be nanostructure morphology dependent and largely rely on the free electrons donated by the native donor defects in the crystal structure of ZnO. The significant FN tunneling across the MIS and MS junctions has a direct relevance in designing nanoscale field emission devices/components working at low voltage with high throughputs.     

Functionalization of Cotton by In-Situ Reaction of Styrene in Atmospheric Pressure Plasma Zone

Cotton fabric was treated using styrene/helium glow plasma at the atmospheric pressure. After the treatment, the substrate was found to turn into a highly hydrophobic material showing water drop disappearance time of 60?min and water contact angle of 133°. The treatment was found to be durable even after vigorous washing. The effect of various parameters, such as discharge voltage and frequency, on fragmentation of styrene inside plasma zone was investigated using optical emission spectroscopy and GC?CMS. The types of fragments formed in the plasma zone were correlated with the hydrophobicity of the substrate. The chemical nature of surface of the substrate was analyzed using SEM and Raman spectroscopy to elucidate the possible mechanism of plasma modification.     

Effect of Gd3+ doping on structural,optical and frequency-dependent dielectric response properties of pseudo-cubic BaTiO3 nanostructures

We report on the structural, optical and dielectric characterization of solid state derived, pseudo-cubic nanoscale barium titanates (BTs) with gadolinium (Gd³⁺) as substitutional dopant. Referring to X-ray diffractograms, apart from the BT peaks related to perovskite structure, the non-existence of any additional peaks due to byproducts has revealed that Gd³⁺ has undergone substitutional doping into the BT host lattice. The well-separated BT nanoparticles of typical size ～10–15 nm were observed through electron microscopy studies. Following a direct, allowed type carrier transition (n=1/2), a reduction in the optical band gap value (from 3.28 to 3.255 eV) was observed when the Gd-doping level was varied within 0–7 %. Conversely, the Urbach energy followed an increasing trend, from a value of 0.741 to 1.879 eV. Furthermore, the dielectric constant showed a decreasing tendency with doping content and with increasing frequency. However, in the low-frequency region, the loss tangent (tanδ), which is the combined result of orientational polarization and electrical conduction, was found to be quite high in the doped samples as compared to their un-doped counterpart. The frequency-dependent electrical data were also analyzed in the framework of conductivity and impedance formalisms. In particular, the ac conductivity which varies as ～ω ^s approaches ideal Debye behavior (s→1) for a low Gd level and a higher doping concentration did not show improved dielectric feature of the host. The incorporation of rare-earth (Gd³⁺) ions into the BT host system could greatly manifest dielectric relaxation and carrier conduction mechanisms, in a given frequency range, and thus can find immense scope in miniaturized nanoelectronic elements including ceramic capacitors and transducers.     

Enhanced magneto-optic activity of magnetite-based ferrofluids subjected to gamma irradiation

We report here the effect of γ-irradiation on the particle size and size distribution dependent spectroscopic and magneto-optic properties of ferrofluids, synthesized by a co-precipitation method. The X-ray diffraction (XRD) study exhibits magnetite (Fe₃O₄) phase of the particles while electron microscopic and dynamic light scattering (DLS) studies have predicted particle growth upon γ-irradiation. Further, Fourier transform infrared (FT-IR) spectroscopy studies ensured that no dissociation has occurred due to irradiation effect. As a consequence of magneto-optic behavior reflected in the Faraday rotation (FR) measurement, the Verdet constant increased from a value of 0.64×10⁻² for the pristine sample to 5.6×10⁻² deg/Gauss-cm for the sample irradiated with the highest dose (2.635 kGy). The substantial enhancement in the FR is assigned to the improvement in associated chaining effect owing to adequate particle growth where an increased stoichiometry variation of Fe²⁺/Fe³⁺ is assured.     

Enhanced vacuum-photoconductivity of chemically synthesized ZnO nanostructures

We report on the enhanced ultraviolet (UV) photoconductivity of zinc oxide (ZnO) nanostructures in vacuum. Nanoparticles and nanorods of ZnO were fabricated using a simple cost-effective solid state grinding method. Morphology of the nanostructures was studied using transmission electron microscopy, while the optical properties were investigated using UV–visible absorption and photoluminescence spectroscopy. The emission spectra of the nanostructures revealed the existence of various native defect states of ZnO and also indicated the presence of surface adsorbed water molecules. In the photoconductivity measurements, although the ZnO nanoparticles exhibited lower photoconductivity in comparison to the nanorods, a similar trend of photoresponse was observed for both the cases. An initial decrease in the photoconductivity followed by a large enhancement was observed in vacuum compared to that in ambient condition. Such unusually increased photoconductivity has been correlated to the desorption of physisorbed water molecules from nanostructure surfaces under vacuum. This desorption is responsible for the rise in dark current and an initial decrease in photoconductivity. Continual UV irradiation in vacuum leads to the desorption of chemisorbed water molecules from the defect sites of the nanostructures, resulting in the occurrence of high photoconductivity.     

Influence of ion bombardment on the photoluminescence response of embedded CdS nanoparticles

Semiconductor nanoparticles (CdS) were fabricated by an inexpensive chemical route using polyvinyl alcohol (PVA) as the dielectric host matrix. Nano-CdS in PVA were subjected to ion irradiation (using oxygen, chlorine and gold) in the medium energy range (80–100 MeV) and under fluence variation of 10¹¹–10¹³ ions/cm². The nature of light emission was found to be drastically different in each of the three cases. Photoluminescence spectra of oxygen irradiated samples exhibit band edge emission (2.8 eV) as well as trap related emission (1.76 eV) whereas band edge emission is found to be bleached out for chlorine ion irradiated nano-CdS. The intense broad PL peaks, noticeable in the case of gold ion irradiated samples suggest superposition of the two peaks — namely, band edge emission and trap related emission. Furthermore, in the case of gold ion irradiated nano-CdS, energy shift in the PL spectra reveals variation in size distribution caused by the extra pressure effect of heavy gold ion beams. The mechanism of such a difference as a result of ion irradiation-type and ion-fluence is discussed in detail.