Size dependence of the bulk modulus of semiconductor nanocrystals from first-principles calculations

The variation in the bulk modulus of semiconductor nanoparticles has been studied within first-principles electronic-structure calculations using the local density approximation (LDA) for the exchange correlation. Quantum Monte Carlo calculations carried out for a silicon nanocrystal Si87H76 provided reasonable agreement with the LDA results. An enhancement was observed in the bulk modulus as the size of the nanoparticle was decreased, with modest enhancements being predicted for the largest nanoparticles studied here, a size just accessible in experiments. To access larger sizes, we fit our calculated bulk moduli to the same empirical law for all materials, the asymptote of which is the bulk value of the modulus. This was found to be within 2-10% of the independently calculated value. The origin of the enhancement has been discussed in terms of Cohen's empirical law M.L. Cohen, Phys. Rev. B 32, 7988 (1985)] as well as other possible scenarios.

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge18Te82-xBix glasses (1 <= x <= 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V-th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further. V-th of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V-th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi2Te3 phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching. (C) 2010 Elsevier B.V. All rights reserved.

Self-assembled composite nano-materials exploiting a thermo reversible n-acene fibrillar scaffold and organic-capped ZnO nanoparticles

An organic-inorganic composite material is obtained by self-assembly of 2,3-didecyloxy-anthracene (DDOA), an organogelator of butanol, and organic-capped ZnO nanoparticles (NPs). The ligand 3, 2,3-di(6-oxy-n-hexanoic acid)-anthracene, designed to cap ZnO and interact with the DDOA nanofibers by structural similarity, improves the dispersion of the NPs into the organogel. The composite material displays mechanical properties similar to those of the pristine DDOA organogel, but gelates at a lower critical concentration and emits significantly less, even in the presence of very small amounts of ZnO NPs. The ligand 3 could also act as a relay to promote the photo-induced quenching process.

Preparation and Characterization of MWCNT/ZnO nanoparticles Hybrid

ZnO nanoparticles (ZnO NPs) were grown on the surface of multiwall carbon nanotubes (MWCNTs) by a wet chemical synthesis route. The anchoring of ZnO NPs on acid-treated MWCNTs was achieved under remarkably mild reaction conditions (low temperature, atmospheric pressure, without any capping agents and no need for subsequent thermal annealing). MWCNT/ZnO NPs hybrid samples with varying loading of ZnO NPs are prepared. A very high degree of dispersion of ZnO NPs over the surface of MWCNT was achieved by suitably controlling the ratio of ZnO NPs and MWCNTs in the solution. The hybrid sample was characterized by electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). Transmission electron microscope images of the as-prepared MWCNT/ZnO NPs hybrid reveal that mono-dispersed ZnO NPs are anchored stably on functionalized MWCNTs. The interaction of ZnO NPs with MWCNT surface was interpreted through XPS analysis.

Nanoscale ZnO/CdS heterostructures with engineered interfaces for high photocatalytic activity under solar radiation

Semiconductor based nanoscale heterostructures are promising candidates for photocatalytic and photovoltaic applications with the sensitization of a wide bandgap semiconductor with a narrow bandgap material being the most viable strategy to maximize the utilization of the solar spectrum. Here, we present a simple wet chemical route to obtain nanoscale heterostructures of ZnO/CdS without using any molecular linker. Our method involves the nucleation of a Cd-precursor on ZnO nanorods with a subsequent sulfidation step leading to the formation of the ZnO/CdS nanoscale heterostructures. Excellent control over the loading of CdS and the microstructure is realized by merely changing the initial concentration of the sulfiding agent. We show that the heterostructures with the lowest CdS loading exhibit an exceptionally high activity for the degradation of methylene blue (MB) under solar irradiation conditions; microstructural and surface analysis reveals that the higher activity in this case is related to the dispersion of the CdS nanoparticles on the ZnO nanorod surface and to the higher concentration of surface hydroxyl species. Detailed analysis of the mechanism of formation of the nanoscale heterostructures reveals that it is possible to obtain deterministic control over the nature of the interfaces. Our synthesis method is general and applicable for other heterostructures where the interfaces need to be engineered for optimal properties. In particular, the absence of any molecular linker at the interface makes our method appealing for photovoltaic applications where faster rates of electron transfer at the heterojunctions are highly desirable.

Pulsed laser deposited ZnO:In as transparent conducting oxide

Zinc oxide (ZnO) and indium doped ZnO (IZO) thin films with different indium compositions were grown by pulsed laser deposition technique on corning glass substrate. The effect of indium concentration on the structural, morphological, optical and electrical properties of the film was studied. The films were oriented along c-direction with wurtzite structure and highly transparent with an average transmittance of more than 80% in the visible wavelength region. The energy band gap was found to decrease with increasing indium concentration. High transparency makes the films useful as optical windows while the high band gap values support the idea that the film could be a good candidate for optoelectronic devices. The value of resistivity observed to decrease initially with doping concentration and subsequently increases. IZO with 1% of indium showed the lowest resistivity of 2.41 x 10(-2) Omega cm and large transmittance in the visible wavelength region. Especially 1% IZO thin film was observed to be a suitable transparent conducting oxide material to potentially replace indium tin oxide. (C) 2011 Elsevier B.V. All rights reserved.

Structural, optical and EPR studies on ZnO:Cu nanopowders prepared via low temperature solution combustion synthesis

Cu (0.1 mol%) doped ZnO nanopowders have been successfully synthesized by a wet chemical method at a relatively low temperature (300 degrees C). Powder X-ray diffraction (PXRD) analysis, scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) spectroscopy, UV-Visible spectroscopy, Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) measurements were used for characterization. PXRD results confirm that the nanopowders exhibit hexagonal wurtzite structure of ZnO without any secondary phase. The particle size of as-formed product has been calculated by Williamson-Hall (W-H) plots and Scherrer's formula is found to be in the range of similar to 40 nm. TEM image confirms the nano size crystalline nature of Cu doped ZnO. SEM micrographs of undoped and Cu doped ZnO show highly porous with large voids. UV-Vis spectrum showed a red shift in the absorption edge in Cu doped ZnO. PL spectra show prominent peaks corresponding to near band edge UV emission and defect related green emission in the visible region at room temperature and their possible mechanisms have been discussed. The EPR spectrum exhibits a broad resonance signal at g similar to 2.049, and two narrow resonances one at g similar to 1.990 and other at g similar to 1.950. The broad resonance signal at g similar to 2.049 is a characteristic of Cu2+ ion whereas the signal at g similar to 1.990 and g similar to 1.950 can be attributed to ionized oxygen vacancies and shallow donors respectively. The spin concentration (N) and paramagnetic susceptibility (X) have been evaluated and discussed. (C) 2011 Elsevier B. V. All rights reserved.

Passivation of surface and bulk defects in p-GaSb by hydrogenated amorphous silicon treatment

Passivation of point and extended defects in GaSb has been observed as a result of hydrogenated amorphous silicon (a-Si:H) treatment by the glow discharge technique. Cathodoluminescence (CL) images recorded at various depths in the samples clearly show passivation of defects on the surface as well as in the bulk region. The passivation of various recombination centers in the bulk is attributed to the formation of hydrogen-impurity complexes by diffusion of hydrogen ions from the plasma a-Si:H acts as a protective cap layer and prevents surface degradation which is usually encountered by bare exposure to hydrogen plasma. An enhancement in luminescence intensity up to 20 times is seen due to the passivation of nonradiative recombination centers. The passivation efficiency is found to improve with an increase in a-Si:H deposition temperature. The relative passivation efficiency of donors and acceptors by hydrogen in undoped and Te-compensated p-GaSb has been evaluated by CL and by the temperature dependence of photoluminescence intensities. Most notably, effective passivation of minority dopants in tellurium compensated p-GaSb is evidenced for the first time. (C) 1996 American Institute of Physics.

Relationship between nonlinear resistivity and the varistor forming mechanism in ZnO ceramics

The use of a number of perovskite phases M� M�O3-x, as the only forming additive in ZnO ceramics, produces a high nonlinearity index, ?(up to 45), where M� is a multivalent transition?metal ion and M� is an alkaline earth or a rare?earth ion. From this study, the formation parameters crucial to high nonlinearity, such as nonstoichiometry in the as?received ZnO powder, low x values of the additives and fast cooling rate after the sintering, are explainable on the basis of a depletion layer formation at the presintering stage. This is because of the surface states arising out of the chemisorbed oxygen. The depletion layer is retained during sintering as a result of the higher valence state of M� ions, preferentially present at the grain?boundary regions. The fast cooling freezes in the high?temperature concentration of donor?type defects, thereby decreasing the depletion layer width.

Seebeck Coefficient in Bulk and Quantum Wells of Non-Parabolic Kane-Type Materials

We present a simplified and quantitative analysis of the Seebeck coefficient in degenerate bulk and quantum well materials whose conduction band electrons obey Kane's non-parabolic energy dispersion relation. We use k.p formalism to include the effect of the overlap function due to the band non-parabolicity in the Seebeck coefficient. We also address the key issues and the conditions in which the Seebeck coefficient in quantum wells should exhibit oscillatory dependency with the film thickness under the acoustic phonon and ionized impurity scattering. The effect of screening length in degenerate bulk and quantum wells has also been generalized for the determination of ionization scattering. The well-known expressions of the Seebeck coefficient in non-degenerate wide band gap materials for both bulk and quantum wells has been obtained as a special case and this provides an indirect proof of our generalized theoretical analysis.

Giant magnetoresistance in bulk samples of LaMnO3 with varying Mn4+ content

Magnetoresistance (MR) in bulk samples of LaMnO3 has been investigated by varying the Mn4+ content from 10 to 33 per cent by chemical means, without aliovalent doping. With the increase in Mn4+ content, the structure of LaMnO3 changes first from orthorhombic to rhombohedral and then to cubic and the material becomes increasingly ferromagnetic, exhibiting a resistivity maximum akin to an insulator-metal transition at T-Peak, just below the ferromagnetic T-c. The magnitude of MR is highest in the cubic sample (with 33% Mn4+) around the T-Peak, and negligible in the non-magnetic orthorhombic sample (12% Mn4+).

Oxidation of methanol on the surfaces of model Cu/ZnO catalysts containing Cu1+ and Cu-0 species

Interaction of CH3OH with Cu clusters deposited on ZnO films grown on a Zn foil as well as on a ZnO(0001)Zn crystal, has been examined by X-ray photoelectron spectroscopy. On clean Cu clusters, reversible molecular adsorption or formation of CH3O is observed. However if the Cu clusters are pretreated with oxygen, both CH3O and HCOO- species are produced. Model Cu/ZnO catalyst surfaces, containing both Cu1+ and Cu-0 species, show interesting oxidation properties. On a Cu-0-rich catalyst surface, only CH3O species is formed on interaction with CH3OH. On a Cu1+-rich surface, however, HCOO- ion is the predominant species.

EPR and photoluminescence studies of ZnO:Mn nanophosphors prepared by solution combustion route

Nanocrystalline ZnO:Mn (0.1 mol%) phosphors have been successfully prepared by self propagating, gas producing solution combustion method. The powder X-ray diffraction of as-formed ZnO:Mn sample shows, hexagonal wurtzite phase with particle size of similar to 40 nm. For Mn doped ZnO, the lattice parameters and volume of unit cell (a=3.23065 angstrom, c=5.27563 angstrom and V=47.684 (angstrom)(3)) are found to be greater than that of undoped ZnO (a=3.19993 angstrom, c=5.22546 angstrom and V=46.336 (angstrom)(3)). The SEM micrographs reveal that besides the spherical crystals, the powders also contained several voids and pores. The TEM photograph also shows the particles are approximately spherical in nature. The FTIR spectrum shows two peaks at similar to 3428 and 1598 cm(-1) which are attributed to O-H stretching and H-O-H bending vibration. The PL spectra of ZnO:Mn indicate a strong green emission peak at 526 nm and a weak red emission at 636 nm corresponding to T-4(1) -> (6)A(1) transition of Mn2+ ions. The EPR spectrum exhibits fine structure transition which will be split into six hyperfine components due to Mn-55 hyperfine coupling giving rise to all 30 allowed transitions. From EPR spectra the spin-Hamiltonian parameters have been evaluated and discussed. The magnitude of the hyperfine splitting (A) constant indicates that there exists a moderately covalent bonding between the Mn2+ ions and the surrounding ligands. The number of spins participating in resonance (N), its paramagnetic susceptibility (chi) have been evaluated. (C) 2011 Elsevier B.V. All rights reserved.

Pulsed laser deposited ZnO/ZnO:Li multilayer for blue light emitting diodes

Thin films of ZnO, Li doped ZnO (ZLO) and multilayer of ZnO and ZLO (ZnO/ZLO) were grown on silicon and corning glass substrates by pulsed laser deposition technique. Single phase formation and the crystalline qualities of the films were analyzed by X-ray diffraction and Li composition in the film was investigated to be 15 wt% by X-ray photoelectron spectroscopy. Raman spectrum reveals the hexagonal wurtzite structure of ZnO, ZLO and ZnO/ZLO multilayer and confirms the single phase formation. Films grown on corning glass shows more than 80% transmittance in the visible region and the optical band gaps were calculated to be 3.245, 3.26 and 3.22 eV for ZnO, ZLO and ZnO/ZLO, respectively. An efficient blue emission was observed in all films which were grown on silicon (1 0 0) substrate by photoluminescence (PL). PL measurements at different temperatures reveal that the PL emission intensity of ZnO/ZLO multilayer was weakly dependent on temperature as compared to the single layers of ZnO and ZLO and the wavelength of emission was independent of temperature. Our results indicate that ZnO/ZLO multilayer can be used for the fabrication of blue light emitting diodes. (C) 2011 Elsevier B.V. All rights reserved.

Embrittlement of a bulk metallic glass due to low-temperature annealing

Embrittlement of a bulk La-based metallic glass due to isothermal and isochronal annealing below the T-g was investigated. Results show that the impact toughness decreases with increasing annealing time or temperature, accompanied by a change in fracture morphology. Reasons for this are discussed in terms of structural relaxation. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.