Shape Effect on Electronic and Photovoltaic Properties of CdS Nanocrystals

Changes in electronic and photovoltaic properties of semiconductor nanocrystals predominantly due to changes in shape are discussed here. Cadmium sulfide (CdS) semiconductor nanocrystals of various shapes (tetrapod, tetrahedron, sphere and rod) obtained using an optimized solvothermal process exhibited a mixed cubic (zinc blende) and hexagonal (wurtzite) crystal structure. The simultaneous presence of the two crystal phases in varying amounts is observed to play a pivotal role in determining both the electronic and photovoltaic properties of the CdS nanocrystals. Light to electrical energy conversion efficiencies (measured in two-electrode configuration laboratory solar cells) remarkably decreased by one order in magnitude from tetrapod -> tetrahedron -> sphere -> rod. The tetrapod-CdS nanocrystals, which displayed the highest light to electrical energy conversion efficiency, showed a favorable shift in position of the conduction band edge leading to highest rate of electron injection (from CdS nanocrystal to the wide band gap semiconductor viz, titanium dioxide, TiO2) and lowest rate of electron-hole recombination (higher free electron lifetimes).

Random copolymers consisting of dithienylcyclopentadienone, thiophene and benzothiadiazole for bulk heterojunction solar cells

Novel random copolymers containing dithienylcyclopentadienone, thiophene and benzothiadiazole were synthesized and photovoltaic properties of these materials were evaluated. Thermal, structural, optical and electrochemical characterization of the synthesized copolymers was carried out. These thermally stable copolymers are solution processable unlike the homopolymer. The absorption spectra indicated that with the incorporation of alkyl chains in the thiophene moiety, the onset of absorption increases and hence band gap decreases (1.47 eV to 1.41 eV). Bulk heterojunction solar cells were fabricated with the blend of copolymer and phenyl-C61-butyric acid methyl ester (PCBM) as the active material and device parameters were extracted. The copolymer consists of alkyl thiophene exhibit higher open circuit voltage than the copolymer consisting of thiophene moiety. (c) 2012 Elsevier B.V. All rights reserved.

Nonlocal continuum mechanics based ultrasonic flexural wave dispersion characteristics of a monolayer graphene embedded in polymer matrix

Wave propagation in graphene sheet embedded in elastic medium (polymer matrix) has been a topic of great interest in nanomechanics of graphene sheets, where the equivalent continuum models are widely used. In this manuscript, we examined this issue by incorporating the nonlocal theory into the classical plate model. The influence of the nonlocal scale effects has been investigated in detail. The results are qualitatively different from those obtained based on the local/classical plate theory and thus, are important for the development of monolayer graphene-based nanodevices. In the present work, the graphene sheet is modeled as an isotropic plate of one-atom thick. The chemical bonds are assumed to be formed between the graphene sheet and the elastic medium. The polymer matrix is described by a Pasternak foundation model, which accounts for both normal pressure and the transverse shear deformation of the surrounding elastic medium. When the shear effects are neglected, the model reduces to Winkler foundation model. The normal pressure or Winkler elastic foundation parameter is approximated as a series of closely spaced, mutually independent, vertical linear elastic springs where the foundation modulus is assumed equivalent to stiffness of the springs. For this model, the nonlocal governing differential equations of motion are derived from the minimization of the total potential energy of the entire system. An ultrasonic type of flexural wave propagation model is also derived and the results of the wave dispersion analysis are shown for both local and nonlocal elasticity calculations. From this analysis we show that the elastic matrix highly affects the flexural wave mode and it rapidly increases the frequency band gap of flexural mode. The flexural wavenumbers obtained from nonlocal elasticity calculations are higher than the local elasticity calculations. The corresponding wave group speeds are smaller in nonlocal calculation as compared to local elasticity calculation. The effect of y-directional wavenumber (eta(q)) on the spectrum and dispersion relations of the graphene embedded in polymer matrix is also observed. We also show that the cut-off frequencies of flexural wave mode depends not only on the y-direction wavenumber but also on nonlocal scaling parameter (e(0)a). The effect of eta(q) and e(0)a on the cut-off frequency variation is also captured for the cases of with and without elastic matrix effect. For a given nanostructure, nonlocal small scale coefficient can be obtained by matching the results from molecular dynamics (MD) simulations and the nonlocal elasticity calculations. At that value of the nonlocal scale coefficient, the waves will propagate in the nanostructure at that cut-off frequency. In the present paper, different values of e(0)a are used. One can get the exact e(0)a for a given graphene sheet by matching the MD simulation results of graphene with the results presented in this article. (c) 2012 Elsevier Ltd. All rights reserved.

CdSiO3:Pr3+ nanophosphor: Synthesis, characterization and thermoluminescence studies

A series of Pr3+ (1-9 mol%) doped CdSiO3 nanophosphors have been prepared for the first time by a low temperature solution combustion method using oxalyldihydrizide (ODH) as a fuel. The final product was characterized by Powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The average crystallite size was calculated using Debye-Scherrer's formula and Williamson-Hall (W-H) plots and found to be in the range 31-37 nm. The optical energy band gap (E-g) of undoped for Pr3+ doped samples were estimated from Tauc relation which varies from 5.15-5.36 eV. Thermoluminescence (TL) properties of Pr3+ doped CdSiO3 nanophosphor has been investigated using gamma-irradiation in the dose range 1-6 kGy at a heating rate of 5 degrees C s(-1). The phosphor shows a well resolved glow peak at similar to 171 degrees C along with shouldered peak at 223 degrees C in the higher temperature side. It is observed that TL intensity increase with increase of Pr3+ concentration. Further, the TL intensity at 171 degrees C is found to be increase linearly with increase in gamma-dose which is highly useful in radiation dosimetry. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics was estimated by Luschiks method and the results are discussed. (c) 2012 Elsevier B.V. All rights reserved.

SCALE EFFECTS ON ULTRASONIC WAVE DISPERSION CHARACTERISTICS OF MONOLAYER GRAPHENE EMBEDDED IN AN ELASTIC MEDIUM

Ultrasonic wave propagation in a graphene sheet, which is embedded in an elastic medium, is studied using nonlocal elasticity theory incorporating small-scale effects. The graphene sheet is modeled as an one-atom thick isotropic plate and the elastic medium/substrate is modeled as distributed springs. For this model, the nonlocal governing differential equations of motion are derived from the minimization of the total potential energy of the entire system. After that, an ultrasonic type of wave propagation model is also derived. The explicit expressions for the cut-off frequencies are also obtained as functions of the nonlocal scaling parameter and the y-directional wavenumber. Local elasticity shows that the wave will propagate even at higher frequencies. But nonlocal elasticity predicts that the waves can propagate only up to certain frequencies (called escape frequencies), after which the wave velocity becomes zero. The results also show that the escape frequencies are purely a function of the nonlocal scaling parameter. The effect of the elastic medium is captured in the wave dispersion analysis and this analysis is explained with respect to both local and nonlocal elasticity. The simulations show that the elastic medium affects only the flexural wave mode in the graphene sheet. The presence of the elastic matrix increases the band gap of the flexural mode. The present results can provide useful guidance for the design of next-generation nanodevices in which graphene-based composites act as a major element.

Layer-dependent resonant Raman scattering of a few layer MoS2

We report resonant Raman scattering of MoS2 layers comprising of single, bi, four and seven layers, showing a strong dependence on the layer thickness. Indirect band gap MoS2 in bulk becomes a direct band gap semiconductor in the monolayer form. New Raman modes are seen in the spectra of single- and few-layer MoS2 samples which are absent in the bulk. The Raman mode at similar to 230 cm(-1) appears for two, four and seven layers. This mode has been attributed to the longitudinal acoustic phonon branch at the M point (LA(M)) of the Brillouin zone. The mode at similar to 179 cm(-1) shows asymmetric character for a few-layer sample. The asymmetry is explained by the dispersion of the LA(M) branch along the G-M direction. The most intense spectral region near 455 cm(-1) shows a layer-dependent variation of peak positions and relative intensities. The high energy region between 510 and 645 cm(-1) is marked by the appearance of prominent new Raman bands, varying in intensity with layer numbers. Resonant Raman spectroscopy thus serves as a promising non invasive technique to accurately estimate the thickness of MoS2 layers down to a few atoms thick. Copyright (C) 2012 John Wiley & Sons, Ltd.

Gap-Dependent Quasiparticle Dynamics and Coherent Acoustic Phonons in CaFe2As2 across Spin Density Wave Phase Transition

We report ultrafast quasiparticle (QP) dynamics and coherent acoustic phonons in undoped CaFe2As2 iron pnictide single crystals exhibiting spin-density wave (SDW) and concurrent structural phase transition at temperature T-SDW similar to 165K using femtosecond time-resolved pump-probe spectroscopy. The contributions in transient differential reflectivity arising from exponentially decaying QP relaxation and oscillatory coherent acoustic phonon mode show large variations in the vicinity of T-SDW. From the temperature-dependence of the QP recombination dynamics in the SDW phase, we evaluate a BCS-like temperature dependent charge gap with its zero-temperature value of similar to(1.6 perpendicular to 0.2)k(B)T(SDW), whereas, much above T-SDW, an electron-phonon coupling constant of similar to 0.13 has been estimated from the linear temperature-dependence of the QP relaxation time. The long-wavelength coherent acoustic phonons with typical time-period of similar to 100 ps have been analyzed in the light of propagating strain pulse model providing important results for the optical constants, sounds velocity and the elastic modulus of the crystal in the whole temperature range of 3 to 300 K.

Nano-size and miscibility gap

Reports on the alloys formed from immiscible atoms when they are contained in a nano-sized system have initiated several research activities in the recent years. Bridging of the miscibility gap at nanoscale is significant as it has the potential to produce novel alloy materials with useful technological applications. Although the literature contains noticeable number of reports on the formation of solid solution between bulk immiscible atoms, several issues related to phase stability and microstructure remain unaddressed. This article discusses some of these issues using examples from the work done by the author's research group on isolated nanoparticles of bulk immiscible binary systems such as Ag-Ni, Ag-Fe and Ag-Co.

Deposition and characterization of pure and Cd doped SnO2 thin films by the nebulizer spray pyrolysis (NSP) technique

Pure and cadmium doped tin oxide thin films were deposited on glass substrates from aqueous solution of cadmium acetate, tin (IV) chloride and sodium hydroxide by the nebulizer spray pyrolysis (NSP) technique. X-ray diffraction reveals that all films have tetragonal crystalline structure with preferential orientation along (200) plane. On application of the Scherrer formula, it is found that the maximum size of grains is 67 nm. Scanning electron microscopy shows that the grains are of rod and spherical in shape. Energy dispersive X-ray analysis reveals the average ratio of the atomic percentage of pure and Cd doped SnO2 films. The electrical resistivity is found to be 10(2) Omega cm at higher temperature (170 degrees C) and 10(3) Omega cm at lower temperature (30 degrees C). Optical band gap energy was determined from transmittance and absorbance data obtained from UV-vis spectra. Optical studies reveal that the band gap energy decreases from 3.90 eV to 3.52 eV due to the addition of Cd as dopant with different concentrations.

Nanostructured GdxZn1-xO thin films by nebulizer spray pyrolysis technique: Role of doping concentration on the structural and optical properties

Nanostructured GdxZn1-xO thin films with different Gd concentration from 0% to 10% deposited at 400 degrees C using the NSF technique. The films were characterized by structural, surface and optical properties, respectively. X-ray diffraction analysis shows that the Gd doped ZnO films have lattice parameters a = 3.2497 angstrom and c = 5.2018 angstrom with hexagonal structure and preferential orientation along (002) plane. The estimated values compare well with the standard values. When film thickness increases from 222 to 240 nm a high visible region transmittance (>70%) is observed. The optical band gap energy, optical constants (n and k), complex dielectric constants (epsilon(r), and epsilon(i)) and optical conductivities (sigma(r), and sigma(i)) were calculated from optical transmittance data. The optical band gap energy is 3.2 eV for pure ZnO film and 3.6 eV for Gd0.1Zn0.9-O film. The PL studies confirm the presence of a strong UV emission peak at 399 nm. Besides, the UV emission of ZnO films decreases with the increase of Gd doping concentration correspondingly the ultra-violet emission is replaced by blue and green emissions.

Channel II photocurrent quantification in narrow optical gap polymer-fullerene solar cells with complimentary acceptor absorption

Most charge generation studies on organic solar cells focus on the conventional mode of photocurrent generation derived from light absorption in the electron donor component (so called channel I). In contrast, relatively little attention has been paid to the alternate generation pathway: light absorption in the electron acceptor followed by photo-induced hole transfer (channel II). By using the narrow optical gap polymer poly(3,6-dithieno3,2-b] thiophen-2-yl)-2,5-bis(2-octyldodecyl)-pyrrolo- 3,4-c]pyrrole-1,4-dione-5',5 `'-diyl-alt-4,8-bis(dodecyloxy) benzo1,2-b:4,5-b'] dithiophene-2,6-diyl with two complimentary fullerene absorbers; phenyl-C-61-butyric acid methyl ester, and phenyl-C-71-butyric acid methyl ester (70-PCBM), we have been able to quantify the photocurrent generated each of the mechanisms and find a significant fraction (>30%), which is derived in particular from 70-PCBM light absorption.

Comparative study on optical properties of Se-Zn-In and Se-Zn-Te-In chalcogenide glasses

In contemporary world optoelectronics materials are used in daily life owing to its verity of applications. Utility of these materials makes them attractive for investigations. Specifically study regarding optical properties of recent developed materials is worth for technical uses. Therefore, this work demonstrates a comparative study of extinction coefficient (K), real dielectric (epsilon') and imaginary dielectric (epsilon `') constants, refractive index (n) and optical energy band gap (E-g) with structural unit < r > for Se98-xZn2Inx (0 <= X-In <= 10) and Se93-yZn2Te5Iny (0 <= Y-In <= 10) chalcogenide glasses. Fixed amount of Te with increasing In concentration as cost of Se is largely influence the optical parameters of the materials. Values of optical parameters are obtained higher and lower respectively at thresholds structural units values. This comparative study demonstrates that enhanced values of optical parameters have been obtained for Te containing Se-Zn-In glasses.

Characteristics of Photo Electrodes Based on TiO2 Nanoparticles, Nanotubes and Microspheres for Dye Solar Cell

We have analyzed the characteristics of electrodes made of TiO2 nanotubes, microspheres and commercially available nanoparticles for dye sensitized solar cell. The morphology of the electrodes and the formation of aggregates have been analyzed by scanning electron microscopy and surface profiling technique. The concentration of Ti3+ type impurity state on the surface of these electrodes is quantified by X-ray photoelectron spectroscopy. Micro structural properties have been characterized by Brunauer, Emmett and Teller method The optical properties of the electrodes such as band gap energy, the type of band formation and the diffuse reflectance are evaluated by UV-Visible spectroscopy. The photovoltaic characteristics of dye solar cell made of these electrodes have been evaluated and it is found that the characteristics of the TiO2 film alone can alter the overall conversion efficiency to a great extent. Additional analysis using electrochemical impedance spectroscopy has been carried out to probe the electron transport properties and charge collection efficiency of these electrodes.

Gap renormalization of molecular crystals from density-functional theory

Fundamental gap renormalization due to electronic polarization is a basic phenomenon in molecular crystals. Despite its ubiquity and importance, all conventional approaches within density-functional theory completely fail to capture it, even qualitatively. Here, we present a new screened range-separated hybrid functional, which, through judicious introduction of the scalar dielectric constant, quantitatively captures polarization-induced gap renormalization, as demonstrated on the prototypical organic molecular crystals of benzene, pentacene, and C-60. This functional is predictive, as it contains system-specific adjustable parameters that are determined from first principles, rather than from empirical considerations.

Plasmons in spatially separated rolled-up electron-hole double-layer systems

Using the two-component random phase approximation, we report the collective mode spectrum of a quasi-one-dimensional spatially separated electron-hole double-layer system characterized by rolled-up type-II band aligned quantum wells. We find two intra-subband collective excitations, which can be classified into optic and acoustic plasmon branches, and several inter-subband plasmon modes. At the long wavelength limit and up to a given wave vector, our model predicts and admits an undamped acoustic branch, which always lies in the gap between the intra-subband electron and hole continua, and an undamped optic branch residing within the gap between the inter-subband electron and hole continua, for all values of the electron-hole charge separations. This theoretical investigation suggests that the low-energy and Landau-undamped plasmon modes might exist based on quasi-one-dimensional, two-component spatially separated electron-hole plasmas, and their possibility could be experimentally examined. (C) 2013 AIP Publishing LLC.