Role of different factors affecting interdiffusion in Cu(Ga) and Cu(Si) solid solutions

A detailed diffusion study was carried out on Cu(Ga) and Cu(Si) solid solutions in order to assess the role of different factors in the behaviour of the diffusing components. The faster diffusing species in the two systems, interdiffusion, intrinsic and impurity diffusion coefficients, are determined to facilitate the discussion. It was found that Cu was more mobile in the Cu-Si system, whereas Ga was the faster diffusing species in the Cu-Ga system. In both systems, the interdiffusion coefficients increased with increasing amount of solute (e.g. Si or Ga) in the matrix (Cu). Impurity diffusion coefficients for Si and Ga in Cu, found out by extrapolating interdiffusion coefficient data to zero composition of the solute, were both higher than the Cu tracer diffusion coefficient. These observed trends in diffusion behaviour could be rationalized by considering: (i) formation energies and concentration of vacancies, (ii) elastic moduli (indicating bond strengths) of the elements and (iii) the interaction parameters and the related thermodynamic factors. In summary, we have shown here that all the factors introduced in this paper should be considered simultaneously to understand interdiffusion in solid solutions. Otherwise, some of the aspects may look unusual or even impossible to explain.

Effect of Substrate Temperature on the Microstructure Variation in Sputter-deposited Hydrogenated Amorphous Silicon Thinfilms

Vacancy, void incorporation and Si-H-x configuration in hydrogenated amorphous silicon (a-Si:H) thin films was studied. Films were grown by Direct Current (DC), pulsed DC and Radio Frequency (RF) magnetron sputtering. Fourier Transform Infrared (FTIR) spectroscopic analysis has been carried out on the films and found that, the a-Si: H films grown by DC magnetron sputtering are of good quality compared to pulsed DC and RF deposited films. The effect of Substrate temperature (T-S) on the total hydrogen concentration (C-H), configuration of hydrogen bonding, density (decided by the vacancy and void incorporation) and the microstructure factor (R*) was studied. T-S is found to be an active parameter in affecting the above said properties of the films. The films contain both vacancies and voids. At low hydrogen dilutions the films are vacancy dominated and at high hydrogen dilutions they are void dominated. It is found that T-S favors monohydride (Si-H) bonding at the cost of dihydride (Si-H-2) bonding. This dividing line is at C-H=14 at.% H for DC sputter deposited films. The microstructure structure factor R* is found to be zero for as deposited DC films at T-S=773K. The threshold C-H for void dominated region is found to be C-H=23 at.% H for RF, C-H=18 at.% H for PDC and C-H similar to 14 at.%H for DC sputter deposited films.

Suppression of grain boundary relaxation in Zr-doped BiFeO3 thin films

Here, we present the results of temperature dependent dielectric studies on chemical solution processed Zr-doped BiFeO3 (BFO) thin films deposited on Pt/Si substrates. We find that in contrast to the undoped BFO films, Zr doping at Fe-site suppresses the low frequency dielectric relaxation originating from the grain boundaries, attributed to the increased dipolar rigidity due to stronger Zr-O bonds. Temperature dependent dc conductivity obtained from impedance and modulus analyses shows two distinct conduction processes occurring inside the grains. At temperature below similar to 423K, conductivity is nearly temperature independent, while in the high temperature regime (above similar to 423K), conduction is governed by the long range movement of oxygen vacancies with an activation energy of similar to 1eV. (C) 2014 AIP Publishing LLC.

Correlating defect induced ferromagnetism and gas sensing properties of undoped tin oxide sensors

A correlation between gas sensing properties and defect induced Room Temperature Ferromagnetism (RTFM) is demonstrated in non-stoichiometric SnO2 prepared by solution combustion method. The presence of oxygen vacancies (V-O), confirmed by RTFM is identified as the primary factor for enhanced gas sensing effect. The as-prepared SnO2 shows high saturation magnetization of similar to 0.018 emu/g as compared to similar to 0.002 and similar to 0.0005 emu/g in annealed samples and SnO2 prepared by precipitation respectively. The SnO2 prepared by precipitation which is an equilibrium method of synthesis shows lesser defects compared to the combustion product and hence exhibits lesser sensitivity in spite of smaller crystallite size. The study utilizes RTFM as a potential tool to characterize metal oxide gas sensors and recognizes the significance of oxygen vacancies in sensing mechanism over the microstructure. (C) 2014 AIP Publishing LLC.

Influence of source concentration on structural and optical properties of SnO2 nanoparticles prepared by chemical precipitation method

In present work, a systematic study has been carried out to understand the influence of source concentration on structural and optical properties of the SnO2 nanoparticles. SnO2 nanoparticles have been prepared by using chemical precipitation method at room temperature with aqueous ammonia as a stabilizing agent. X-ray diffraction analysis reveals that SnO2 nanoparticles exhibit tetragonal structure and the particle size is in range of 4.9-7.6 nm. High resolution transmission electron microscopic image shows that all the particles are nearly spherical in nature and particle size lies in range of 4.6-7 nm. Compositional analysis indicates the presence of Sn and O in samples. Blue shift has been observed in optical absorption spectra due to quantum confinement and the bandgap is in range of 4-4.16 eV. The origin of photoluminescence in SnO2 is found to be due to recombination of electrons in singly occupied oxygen vacancies with photo-excited holes in valance band.

Two-point correlation function of an exclusion process with hole-dependent rates

We consider an exclusion process on a ring in which a particle hops to an empty neighboring site with a rate that depends on the number of vacancies n in front of it. In the steady state, using the well-known mapping of this model to the zero-range process, we write down an exact formula for the partition function and the particle-particle correlation function in the canonical ensemble. In the thermodynamic limit, we find a simple analytical expression for the generating function of the correlation function. This result is applied to the hop rate u(n) = 1 + (b/n) for which a phase transition between high-density laminar phase and low-density jammed phase occurs for b > 2. For these rates, we find that at the critical density, the correlation function decays algebraically with a continuously varying exponent b - 2. We also calculate the two-point correlation function above the critical density and find that the correlation length diverges with a critical exponent nu = 1/(b - 2) for b < 3 and 1 for b > 3. These results are compared with those obtained using an exact series expansion for finite systems.

Observation of Room Temperature Ferromagnetism in InN Nanostructures

The room temperature ferromagnetic behavior of InN nanosfructures grown by molecular beam epitaxy (MBE) is explored by means of magnetization measurements. The saturation magnetization and remanent magnetization are found to be strongly dependent on the size of the nanostructures. This suggests that the ferromagnetism is essentially confined to the surface of the nanostructures due to the possible defects. Raman spectroscopy shows the existence of indium vacancies which could be the source of ferromagnetic ordering in InN nanostructures.

On the Origin of Steep I-V Nonlinearity in Mixed-Ionic-Electronic-Conduction-Based Access Devices

Numerical modeling is used to explain the origin of the large ON/OFF ratios, ultralow leakage, and high ON-current densities exhibited by back-end-of-the-line-friendly access devices based on copper-containing mixed-ionic-electronic-conduction (MIEC) materials. Hall effect measurements confirm that the electronic current is hole dominated; a commercial semiconductor modeling tool is adapted to model MIEC. Motion of large populations of copper ions and vacancies leads to exponential increases in hole current, with a turn-ON voltage that depends on material bandgap. Device simulations match experimental observations as a function of temperature, electrode aspect ratio, thickness, and device diameter.

Effect of Pt doping on the gas sensing properties of porous chromium oxide films through a kinetic response analysis approach

The effect of doping trace amounts of noblemetals (Pt) on the gas sensing properties of chromium oxide thin films, is studied. The sensors are fabricated by depositing chromium oxide films on a glass substrate using a modified spray pyrolysis technique and characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The films are porous and nanocrystalline with an average crystallite size of similar to 30 nm. The typical p-type conductivity arises due to the presence of Cr vacancies, formed as a result of Cr non-stoichiometry, which is found to vary upon Pt doping. In order to analyze the effect of doping on the gas sensing properties, we have adopted a kinetic response analysis approach, which is based on Langmuir Adsorption isotherm (LA) theory. The sensor response is analyzed with equations obtained from LA theory and time constants as well as energies of adsorption-desorption are evaluated. It is seen that, Pt doping lowers the Schottky barrier height of the metal oxide semiconductor sensor from 222 meV to 172 meV. Subsequently the reduction in adsorption and desorption energies led to enhancement in sensor response and improvement in the kinetics of the sensor response i.e. the response time as well as recovery times of the sensor.

Self-assembled ZnO nanoparticles on ZnO microsheet: ultrafast synthesis and tunable photoluminescence properties

We report on the tunable photoluminescence characteristics of porous ZnO microsheets fabricated within 1-5 min of microwave irradiation in the presence of a capping agent such as citric acid, and mixture of citric acid with polyvinylpyrrolidone (PVP). The UV emission intensity reduces to 60% and visible emission increases tenfold when the molar concentration of citric acid is doubled. Further diminution of the intensity of UV emission (25%) is observed when PVP is mixed with citric acid. The addition of nitrogen donor ligands to the parent precursor leads to a red shift in the visible luminescence. The deep level emission covers the entire visible spectrum and gives an impression of white light emission from these ZnO samples. The detailed luminescence mechanism of our ZnO samples is described with the help of a band diagram constructed by using the theoretical models that describe the formation energy of the defect energy levels within the energy band structure. Oxygen vacancies play the key role in the variation of the green luminescence in the ZnO microsheets. Our research findings provide an insight that it is possible to retain the microstructure and simultaneously introduce defects into ZnO. The growth of the ZnO microsheets may be due to the self assembly of the fine sheets formed during the initial stage of nucleation.

Excitation- and power-dependent photoluminescence from oxidized Ge

Wafer/microcrystallites of oxidized Ge with holes/nanoholes synthesized by thermal oxidation strategy from Ge wafer/microcrystallites can convert one wavelength to another. Both oxidized Ge wafer and microcrystallites shows excitation- and power-dependent luminescence. Red-shift is observed as the excitation wavelength is increased, while blue-shift is observed as power density is increased. Over all, blue-green-yellow-orange luminescence is observed depending on the excitation wavelength and the morphology of oxidized Ge. The various defects level associated with germanium-oxygen vacancies in GeO2 and Ge/GeO2 interface are responsible for the excitation-dependent luminescence. Being a light-conversion material, oxidized Ge is expected to find potential applications in solid-state lighting, photovoltaic devices and photocatalysis. (C) 2013 Elsevier B.V. All rights reserved.

Defect induced optical bandgap narrowing in undoped SnO2 nanocrystals

Unusual optical bandgap narrowing is observed in undoped SnO2 nanoparticles synthesized by the solution combustion method. The estimated crystallite size is nearly 7 nm. Though the quantum confinement effect predicts a larger optical bandgap for materials with small crystallite size than the bulk, the optical bandgap in the as synthesized materials is found to be 2.9 eV compared to the reported value of 3.6 eV for bulk SnO2 particles. The yellow-green photoluminescence emissions and the observed narrowing of the bandgap can be attributed to the deep donor levels of oxygen vacancies, owing to the high exothermicity of the combustion reaction and the faster cooling rates involved in the process. (C) 2013 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Synthesis of Eu3+-activated ZnO superstructures: Photoluminescence, Judd-Ofelt analysis and Sunlight photocatalytic properties

Photoluminescence and photocatalytic properties of Eu-doped ZnO nanoparticles (NPs) were synthesized by facile phyto route. XPS results demonstrated the existence of Eu3+ as dopant into ZnO. Morphologies of the NPs were mainly dependent on Eu3+ and Aloe vera gel. Red shift of energy band gap was due to the creation of intermediate energy states of Eu3+ and oxygen vacancies in the band gap. PL emission of ZnO:Eu3+ (1-11 mol%, 8 ml and 7 mol%, 2-12 ml) exhibit characteristic peaks of D-5(0) -> F-7(2) transitions. From the Judd-Ofelt analysis, intensities of transitions between different.' levels dependent on the symmetry of the local environment of Eu3+ ions. CIE chromaticity co-ordinates confirm reddish emission of the phosphor. Further, NPs exhibit excellent photocatalytic activity for the degradation of Rhodamine B (94%) under Sunlight was attributed to crystallite size, band gap, morphology and oxygen vacancies. In addition, photocatalyst reusability studies were conducted and found that Eu-doped catalyst could be reused several times with negligible decrease in catalytic activity. The present work directs new possibilities to provide some new insights into the design of new phyto synthesized nanophosphors for display devices, photocatalysts with high activity for environmental clean-up and solar energy conversion. (C) 2015 Elsevier B.V. All rights reserved.

Noble metal ions in CeO2 and TiO2: synthesis, structure and catalytic properties

In the past four decades, CeO2 has been recognized as an attractive material in the area of auto exhaust catalysis because of its unique redox properties. In the presence of CeO2, the catalytic activity of noble metals supported on Al2O3 is enhanced due to higher dispersion of noble metals in their ionic form. In the last few years, we have been exploring an entirely new approach of dispersing noble metal ions on CeO2 and TiO2 matrices for redox catalysis. In this study, the dispersion of noble metal ions by solution combustion as well as other methods over CeO2 and TiO2 resulting mainly in Ce1-xMxO2-delta, Ce1-x-yTixMyO2-delta, Ce1-x-ySnxMyO2-delta, Ce1-x-yFexMyO2-delta, Ce1-x-yZrxMyO2-delta and Ti1-xMxO2-delta (M = Pd, Pt, Rh and Ru) catalysts, the structure of these materials, their catalytic properties toward different types of catalysis, structure-property relationships and mechanisms of catalytic reactions are reviewed. In these catalysts, noble metal ions are incorporated into a substrate matrix to a certain limit in a solid solution form. Lower valent noble metal-ion substitution in CeO2 and TiO2 creates noble metal ionic sites and oxide ion vacancies that act as adsorption sites for redox catalysis. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) have been found to be catalytically more active than conventional nanocrystalline noble metal catalysts dispersed on oxide supports.

Ferroelectric origin in one-dimensional undoped ZnO towards high electromechanical response

Ferroelectricity in ZnO is an unlikely physical phenomenon. Here, we show ferroelectricity in undoped 001] ZnO nanorods due to zinc vacancies. Generation of ferroelectricity in a ZnO nanorod effectively increases its piezoelectricity and turns the ZnO nanorod into an ultrahigh-piezoelectric material. Here using piezoelectric force microscopy (PFM), it is observed that increasing the frequency of the AC excitation electric field decreases the effective d(33). Subsequently, the existence of a reversible permanent electric dipole is also found from the P-E hysteresis loop of the ZnO nanorods. Under a high resolution transmission electron microscope (HRTEM), we observe a zinc blende stacking in the wurtzite stacking of a single nanorod along the growth axis. The zinc blende nature of this defect is also supported by the X-ray diffraction (XRD) and Raman spectra. The presence of zinc vacancies in this basal stacking fault modulates p-d hybridization of the ZnO nanorod and produces a magnetic moment through the adjacent oxygen ions. This in turn induces a reversible electric dipole in the non-centrosymmetric nanostructure and is responsible for the ultrahigh-piezoelectric response in these undoped ZnO nanorods. We reveal that this defect engineered ZnO can be considered to be in the competitive class of ultrahigh-piezoelectric nanomaterials for energy harvesting and electromechanical device fabrication.