Ultrafast Solvation Dynamics Of An Ion In A Restricted Environment

The solvation dynamics of an excited coumarin dye molecule (C-480) enclosed within a restricted space have been studied using molecular hydrodynamic theory (MHT) and compared with the recent experimental findings. The solvation dynamics of the dye molecule within the cavity of a toroidal gamma-cyclodextrin molecule have been shown to be explained only in terms of the freezing of the solvent translational modes using MHT. The results of the theoretical calculation are in good agreement with the experimental results. The inertial components of the solvation time correlation function remain the same in both the restricted environment and in the free space. These results are interesting in the light of the simulation studies of Maroncelli and Fleming [J chem Phys, 89 (1988) 5044] which concludes that the participation of the different solvation shells in controlling the dynamics are much different. The earlier studies have been reviewed and the recent findings are discussed.

Structural and transport properties of high energy ion irradiated YBCO

The effects of 100 MeV Oxygen and 200 MeV Silver ions on the structural and transport properties of YBCO thin films are reported. Both normal state and superconducting properties were studied on Laser ablated and high pressure oxygen sputtered films. Precise electrical resistance and critical current measurements near T-c were made and the data obtained were analysed in the light of existing models of para-coherence near T-c and the other aspects of radiation damage arising from microstructural studies such as atomic force microscopy (AFM). There was evidence of sputtering by high energy ions from AFM measurement. (C) 1998 Elsevier Science Ltd. All rights reserved.

X-ray reflectivity study of semiconductor interfaces

The results of an X-ray reflectivity study of thick AlAs-AlGaAs and thin GeSi-Ge multilayers grown using metal-organic vapour-phase epitaxy and ion-beam sputtering deposition techniques, respectively, are presented. Asymmetry in interfaces is observed in both of these semiconductor multilayers. It is also observed that although the Si-on-Ge interface is sharp, an Si0.4Ge0.6 alloy is formed at the Ge-on-Si interface. In the case of the III-V semiconductor, the AlAs-on-AlGaAs interface shows much greater roughness than that observed in the AlGaAs-on-AlAs interface. For thin multilayers it is demonstrated that the compositional profile as a function of depth can be obtained directly from the X-ray reflectivity data.

Optical and Electronic Properties of Conjugated Polymer -Nanocluster Semiconductor Hybrid Systems

Conjugated polymers are intensively pursued as candidate materials for emission and detection devices with the optical range of interest determined by the chemical structure. On the other hand the optical range for emission and detection can also be tuned by size selection in semiconductor nanoclusters. The mechanisms for charge generation and separation upon optical excitation, and light emission are different for these systems. Hybrid systems based on these different class of materials reveal interesting electronic and optical properties and add further insight into the individual characteristics of the different components. Multilayer structures and blends of these materials on different substrates were prepared for absorption, photocurrent (Iph), photoluminescence (PL) and electroluminscence (EL) studies. Polymers chosen were derivatives of polythiophene (PT) and polyparaphenylenevinylene (PPV) along with nanoclusters of cadmium sulphide of average size 4.4 nm (CdS-44). The photocurrent spectral response in these systems followed the absorption response around the band edges for each of the components and revealed additional features, which depended on bias voltage, thickness of the layers and interfacial effects. The current-voltage curves showed multi-component features with emission varying for different regimes of voltage. The emission spectral response revealed additive features and is discussed in terms of excitonic mechanisms.

Suppressed rf dissipation in 107Ag17+ ion irradiated Bi2Sr2CaCu2O8 single crystals by enhanced flux line tilt modulus

We have studied the isothermal, magnetic field (H‖c) dependent rf power P(H) dissipation (Hrf‖a) in the superconducting state of Bi2Sr2CaCu2O8 single crystals prior to and after irradiation with 250 MeV 107Ag17+ ions. In the pristine state, P(H) shows an initial decrease with increase in field, reaches a minimum at HM(T) and increases monotonically for H>HM(T). This behavior arises when the electromagnetic coupling between the pancake vortices in adjacent CuO layers becomes dominant on increasing the field and minimizes the distortions of the flux lines by confining the 2D vortices. In the post irradiated state, such an initial decrease and the minimum in P(H) is not observed but only a much reduced rf dissipation that monotonically increases with field from H = 0 onwards is seen. We attribute this difference to the strong enhancement of the tilt modulus C44 of the flux lines on irradiation when the pancake vortices in adjacent CuO bilayers are pinned along the track forming a well-stacked flux line in the field direction (‖c). We have also observed that the rf dissipation disappears at a certain temperature Tsf, at which the normal core of the flux line becomes commensurate with the columnar track diameter.

Enhanced photoluminescence of Gd2O3:Eu3+ nanophosphors with alkali (M = Li+, Na+, K+) metal ion co-doping

Gd1.95Eu0.4M0.01O3 (M = Li+ Na+ K+) nanophosphors have been synthesized by a low temperature solution combustion (LSC) method. Powder X-ray diffraction pattern (PXRD), scanning electron microscopy (SEM), UV-vis and photoluminescence (PL) measurements were carried out to characterize their structural and luminescent properties. The excitation and emission spectra indicated that the phosphor could be well excited by UV light (243 nm) and emit red light about 612 nm. The effect of alkali co-dopant on PL properties has been examined. The results showed that incorporation of Li+, Na+ and K+ in to Gd2O3:Eu3+ phosphor would lead to a remarkable increase of photoluminescence. The PL intensity of Gd2O3:Eu3+ phosphor was improved evidently by co-doping with Li+ ions whose radius is less than that of Gd3+ and hardly with Na+, K+ whose radius is larger than that of Gd3+. The effect of co-dopants on enhanced luminescence was mainly regarded as the result of a suitable local distortion of crystal field surrounding the Eu3+ activator. These results will play an important role in seeking some more effective co-dopants. (C) 2011 Published by Elsevier B.V.

Nanoindentation response of an ion irradiated Zr-based bulk metallic glass

Nanoindentation experiments were conducted on a Ni+ ion-irradiated Zr-based bulk metallic glass (BMG). The irradiation was carried out using 2.5, 5, 10 and 15 MeV ions and a flux of similar to 10(16) ions/cm(2). Post mortem imaging of the indents reveals a transition in the deformation mechanism of the irradiated regions from heterogeneous shear banding to homogeneous flow. Additionally, the load-displacement curves exhibit a transition from serrated to continuous flow with increasing severity of irradiation damage. The stress-strain response obtained from micro-pillar compression experiments complements the indentation response exhibiting a decrease in the flow stress and an `apparent' strain hardening at the lowest irradiation damage investigated, which is not observed in the as-cast alloy. (C) 2011 Elsevier B.V. All rights reserved.

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Effect of Metal Ions (Ag, Co, Ni, and Pd) on the Visible Light Degradation of Rhodamine B by Carbon-Covered Alumina-Supported TiO2 in Aqueous Solutions

Metal-ion (Ag, Co, Ni, and Pd) doped TiO2 nanocatalysts were successfully embedded on carbon-covered alumina supports. The CCA-embedded catalysts were crystalline and had a high surface area compared to the free metal-ion doped titania nanocatalysts while they still retained the anatase phase of the core TiO2. These catalysts were photocatalytically active under solar light irradiation. Rhodamine B was used as a model pollutant and the reactivity followed a pseudo-first-order reaction kinetics. The reaction rate of the CCA-supported catalysts was Pd > Ag > Co > Ni. Among the ratios of the CCA:catalyst used, it was found that the 1:1 ratio had the fastest reaction rate, followed by the 1:2 ratio, while the 2:1 ratio exhibited the lowest reaction rate. The CCA/metal-ion doped titania were found to have photocatalytic activities comparable with those of CCA-supported titania.

Dependence of electron recombination time and light to electricity conversion efficiency on shape of the nanocrystal light sensitizer

Tunability of electron recombination time and light to electricity conversion efficiency to superior values in semiconductor sensitized solar cells via optimized design of nanocrystal light sensitizer shape is discussed here.

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sal gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

Effect of post-deposition annealing on composition and electrical properties of dc reactive magnetron sputtered Al2O3 thin films

We have investigated the effect of post- deposition annealing on the composition and electrical properties of alumina (Al2O3) thin films. Al2O3 were deposited on n-type Si < 100 >. substrates by dc reactive magnetron sputtering. The films were subjected to post- deposition annealing at 623, 823 and 1023 K in vacuum. X-ray photoelectron spectroscopy results revealed that the composition improved with post- deposition annealing, and the film annealed at 1023 K became stoichiometric with an O/Al atomic ratio of 1.49. Al/Al2O3/Si metal-oxide-semiconductor (MOS) structures were then fabricated, and a correlation between the dielectric constant epsilon(r) and interface charge density Q(i) with annealing conditions were studied. The dielectric constant of the Al2O3 thin films increased to 9.8 with post- deposition annealing matching the bulk value, whereas the oxide charge density decreased to 3.11 x 10(11) cm(-2.) Studies on current-voltage IV characteristics indicated ohmic and Schottky type of conduction at lower electric fields (<0.16 MV cm(-1)) and space charge limited conduction at higher electric fields.

Metal-metal charge transfer and interfacial charge transfer mechanism for the visible light photocatalytic activity of cerium and nitrogen co-doped TiO2

Nanosized cerium and nitrogen co-doped TiO2 (Ce-TiO2-xNx) was synthesized by sol gel method and characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), FESEM, Fourier transform infrared, N-2 adsorption and desorption methods, photoluminescence and ultraviolet-visible (UV-vis) DRS techniques. PXRD analysis shows the dopant decreases the crystallite sizes and slows the crystallization of the titania matrix. XPS confirm the existence of cerium ion in +3 or +4 state, and nitrogen in -3 state in Ce-TiO2-xNx. The modified surface of TiO2 provides highly active sites for the dyes at the periphery of the Ce-O-Ti interface and also inhibits Ce particles from sintering. UV-visible DRS studies show that the metal-metal charge transfer (MMCT) of Ti/Ce assembly (Ti4+/Ce3+ -> Ti3+/Ce4+) is responsible for the visible light photocatalytic activity. Photoluminescence was used to determine the effect of cerium ion on the electron-hole pair separation between the two interfaces Ce-TiO2-xNx and Ce2O3. This separation increases with the increase of cerium and nitrogen ion concentrations of doped samples. The degradation kinetics of methylene blue and methyl violet dyes in the presence of sol gel TiO2, Ce-TiO2-xNx and commercial Degussa P25 was determined. The higher visible light activity of Ce-TiO2-xNx was due to the participation of MMCT and interfacial charge transfer mechanism.

Efficient Solid-State Light-Emitting CuCdS Nanocrystals Synthesized in Air

Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long-range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25eV. Overcoating the NCs leads to a high solid-state PL quantum yield (QY) of ca. 55% measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X-ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu-rich surface and Cd-rich interior with 46% Cu-I being randomly distributed within 84% of the NC volume creating additional transition states for PL. Color-tunable solid-state luminescence remains stable in air enabling fabrication of light-emitting diodes (LEDs).

Fabrication of novel Ag3PO4/BiOBr heterojunction with high stability and enhanced visible-light-driven photocatalytic activity

Herein, we report a facile and effective method to enhance the photocatalytic activity of bismuth oxybromide (BiOBr) semiconductor through the fabrication of heterojunction with Ag3PO4. The as synthesized Ag3PO4/BiOBr microspheres were characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and UV-vis diffuse reflectance spectroscopy (DRS). The new Ag3PO4/BiOBr heterojunctions exhibited wide absorption in the visible-light region and compared to pure BiOBr and Ag3PO4 samples displayed exceptionally high photocatalytic activity for the degradation of typical organic pollutants such as Rhodamine B (RhB) and phenol. The optimal Ag/Bi weight ratio in Ag3PO4/BiOBr microsphere (AB7) was found to be 0.7. The enhanced photocatalytic activity was related to the efficient separation of electron-hole pairs derived from matching band potentials between BiOBr and Ag3PO4 which results into the generation of natural energy bias at heterojunction and subsequent transfer of photoinduced charge carriers. Moreover, the synthesized samples exhibited almost no loss of activity even after 6 recycling runs indicating their high photocatalytic stability. Considering the facile and environment friendly route for the synthesis of Ag3PO4/BiOBr hybrids with enhanced visible-light induced photocatalytic activity, it is possible to widely apply these hybrids in various fields such as waste water treatment. (C) 2015 Elsevier B.V. All rights reserved.