Structural,electrical and magnetic properties of (Fe,Co) co-doped SnO2 diluted magnetic semiconductor nanostructures

Nanostructures (NSs) of basic composition Sn_1−xFe_x/2Co_x/2O₂ with x=0.00, 0.04, 0.06, 0.08 and 0.1 were synthesized by citrate-gel route and characterized to understand their structural, electrical and magnetic properties. X-ray diffraction and Raman spectroscopy were used to confirm the formation of single phase rutile type tetragonal structure. The crystallite sizes calculated by using Williamson Hall were found to decrease with increasing doping level. In addition to the fundamental Raman peaks of rutile SnO₂, the other three weak Raman peaks at about 505, 537 and 688 cm⁻¹ were also observed. Field emission scanning electron microscopy studies showed the emergence of structural transformation. Electric properties such as dc electrical resistivity as a function of temperature and ac conductivity as a function of frequency were also studied. The variation of dielectric properties with frequency reveals that the dispersion is due to Maxwell–Wagner type of interfacial polarization in general. Hysteresis loops were clearly observed in M–H curves of Fe and Co co-doped SnO₂ NSs. However, pure SnO₂ nanoparticles (NPs) showed paramagnetic behaviour which vanished at higher values of magnetic field. The grain and grain boundary contribution in the conduction process is estimated through complex impedance plot fitted with non-linear least square (NLLS) approach which shows that the role of grain boundaries increases rapidly as compared to the grain volume with the increase of Fe and Co ions in to system.     

Conductivity behaviour of a cubic/tetragonal phase stabilized nanocrystalline La2O3-ZrO2

La₂O₃ doped nanocrystalline zirconia (ZrO₂) was prepared by chemical co-precipitation method for the 3, 5, 8, 10, 15, 20 and 30 mol.% concentrations of La₂O₃. Structural studies were performed using X-ray diffraction (XRD). All the as-synthesized samples were found to be in monoclinic phase. As-synthesized samples were given heat treatment at higher temperatures for tetragonal/cubic structural phase stabilization. Sintering the samples at temperature 1173 K stabilized the tetragonal and cubic phases. A slight shift in the 100% peak of the cubic phase was observed towards the low diffraction angle indicating the substitution of the bigger La³⁺ ion into the ZrO₂ lattice. Grain sizes were found to lie between 10 and 13 nm. Electrical conductivity studies were performed on the cubic phase stabilized La₂O₃-ZrO₂ by complex impedance spectroscopy. The conductivity increases up to the dopant concentration 10 mol.% and then decreases with further increase in La₂O₃ concentration. Initial increase in conductivity is correlated to the stabilization of the cubic phase and the subsequent decrease in the conductivity with the dopant content is interpreted on the basis of the oxygen-ion movement model. Electrical conductivity has contributions from grain and grain boundary regions. But the grain boundary conductivity is slightly higher than the corresponding grain conductivity. Higher grain boundary conductivity shows higher diffusion coefficient for the atoms on the surface of the ZrO₂ grains. The possible mechanism of the oxygen ion conduction in the La₂O₃ stabilized zirconia (LSZ) is reported. The Barton, Nakajima and Namikawa (BNN) relation has been applied to the conductivity data and found that the d.c. and a.c. conductions have been correlated to each other by the same mechanism.     

Pressure-induced polymorphism in enstatite (MgSiO3) at room temperature: clinoenstatite and orthoenstatite

The phase transition of a synthetic clinoenstatite in a diamond-anvil cell has been studied by using Raman spectroscopy at various pressures and room temperature. The phenomena observed in clinoenstatite have been compared with that observed in orthoenstatite. It is found that the pressure-induced phase transitions in the two enstatites are reversible, but with different transition pressures and transition behavior. An analysis of Raman spectra has revealed that the two enstatites have different high-pressure polymorphs. This result suggests that the space group of the high-pressure polymorph of orthoenstatite is not of C2/c, and that orthoenstatite and orthoferrosilite have different transition routes at room temperature and high pressure. The compressional behavior of the high-PC2/c enstatite is also discussed according to the pressure dependences of Raman frequencies.     

A first principles lattice dynamics and Raman spectra of the ferroelastic rutile to CaCl2 phase transition in SnO2 at high pressure

A first principles calculation of the lattice dynamical properties of rutile SnO₂ has been performed using density functional perturbation theory at ambient and high‐pressure conditions to understand the pressure‐induced phase transition. The calculated zone centre phonon modes at ambient and high pressures have been compared with Raman scattering and infrared measurements. Full phonon dispersion curves and phonon densities of states and Raman intensities at high pressures are calculated and given for the first time in literature. The ferroelastic transition from the rutile to the CaCl₂‐type structure was confirmed. It is clearly illustrated that the first transition is associated with macroscopic shear instability which arises from the strong coupling between elastic constants and softening of Raman active B_1g mode. The observed pressure of phase transition in experimental measurements was reproduced more accurately than in previous calculations, and the difference between observed and calculated transition pressure is only of the order of 2%. The mode Grüneisen parameter is quantitatively as well as qualitatively different from the earlier reported values. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface characterization of TiO2 thin films obtained by high-energy reactive magnetron sputtering

This paper presents the results of surface characterization of TiO₂ thin films deposited on different substrates by the use of high-energy reactive magnetron sputtering. Structural investigations carried out by X-ray diffraction (XRD) and atomic force microscopy (AFM) have shown a strong influence of both the substrate type, and its placement in the deposition chamber (relative to the sputtering target), on the structural properties of the films. In all cases, there is evidence for pseudoepitaxial growth. XRD examination showed existence of TiO₂-rutile phase with preferred (1 1 0) orientation and AFM measurements revealed nanocrystalline structure directly after deposition. X-ray photoelectron spectroscopy analysis showed that the TiO₂ films have stoichiometric composition.     

Phonon confinement effect on nanocrystalline LiCoO2 studied with Raman spectroscopy

A systematic investigation on nanocrystalline LiCoO₂ has been carried out using Raman spectroscopy. We synthesized nanocrystalline LiCoO₂ (ca. 20-50 nm) through a combination of rapid thermal annealing at various annealing temperatures and a sol-gel method assisted with a triblock copolymer surfactant. Powder X-ray diffraction measurements revealed the formation of LiCoO₂. The crystallite size of LiCoO₂ from the Scherrer equation strongly depended on the annealing temperature. The crystallite size was confirmed by SEM and TEM measurements. Raman shifts of the A_1g and E_g modes for nanocrystalline LiCoO₂ exhibited a broadening and a frequency shift according to the crystallite size. While the frequency shift could be ascribed to a structural strain at the surface, the broadening was due to the phonon confinement effect produced by narrow crystal boundaries.     

Study of phase transition on nanocrystalline (La, Sr)(Mn, Fe)O system using high-pressure Mössbauer spectroscopy and high-pressure X-ray diffraction

Pressure-induced structural changes on nano-crystalline La_0.8Sr_0.2Mn_0.8Fe_0.2O₃ were studied using high-pressure Mössbauer spectroscopy and high-pressure X-ray diffraction. Mössbauer measurements up to 10 GPa showed first order transition at 0.52 GPa indicating transformation of Fe^4?+? to high spin Fe^3?+?, followed by another subtle transition at 3.7 GPa due to the convergence of two different configurations of Fe into one. High-pressure X-ray diffraction measurements carried up to 4.3 GPa showed similar results at 0.6 GPa as well as 3.6 GPa. Attempts were made to explain the changes at 0.6 GPa by reorientation of grain/grain boundaries due to uniaxial stress generated on the application of pressure. Similarly variation at 3.6 GPa can be explained by orthorhombic to monoclinic transition.     

High pressure phase transition in metallic LaB6: Raman and X-ray diffraction studies

High pressure Raman and angle dispersive X-ray diffraction (ADXRD) measurements on the metallic hexaboride LaB₆ have been carried out upto the pressures of about 20 GPa. The subtle phase transition around 10 GPa indicated in Raman measurements is confirmed by ADXRD experiments to be a structural change from cubic to orthorhombic phase. Ab-initio electronic band structure calculations using full potential linear augmented plane wave method carried out as a function of pressure show that this transition is driven by the interception of Fermi level by electronic band minimum around the transition pressure.     

Phase transitions in KIO(3)

The high-pressure behavior of KIO(3) was studied up to 30?GPa using single crystal and powder x-ray diffraction, Raman spectroscopy, second harmonic generation (SHG) experiments and density functional theory (DFT)-based calculations. Triclinic KIO(3) shows two pressure-induced structural phase transitions at 7?GPa and at 14?GPa. Single crystal x-ray diffraction at 8.7(1)?GPa was employed to solve the structure of the first high-pressure phase (space group R3, a?=?5.89(1) ?, α?=?62.4(1)°). The bulk modulus, B, of this phase was obtained by fitting a second order Birch-Murnaghan equation of state (eos) to synchrotron x-ray powder diffraction data resulting in B(exp,second)?=?67(3)?GPa. The DFT model gave B(DFT,second)?=?70.9?GPa, and, for a third order Birch-Murnaghan eos, B(DFT,third)?=?67.9?GPa with a pressure derivative of [Formula: see text]. Both high-pressure transformations were detectable by Raman spectroscopy and the observation of second harmonic signals. The presence of strong SHG signals shows that all high-pressure phases are acentric. By using different pressure media, we showed that the transition pressures are very strongly influenced by shear stresses. Earlier work on low- and high-temperature transitions was complemented by low-temperature heat capacity measurements. We found no evidence for the presence of an orientational glass, in contrast to earlier dielectric studies, but consistent with earlier low-temperature diffraction studies.     

Micro‐Raman investigation of tin dioxide nanostructured material based on annealing effect

Rutile‐structured nanocrystalline tin dioxide (SnO₂) powder was synthesized by the chemical precipitation method using the precursor SnCl₂• 5H₂O. The SnO₂ powder was annealed at different temperatures, namely, 600, 800 and 1000 °C. Micro‐Raman spectra were recorded for both the as‐grown and annealed SnO₂ nanocrystalline samples. Micro‐Raman spectral measurements on the SnO₂ nanoparticle show the first‐order Raman modes A_1g (633 cm⁻¹), E_1g (475 cm⁻¹) and B_2g (775 cm⁻¹), indicating that the grown SnO₂ belongs to the rutile structure. The first‐order A_1g mode is observed as an intense band, whereas the other two modes show low intensity. The full width at half‐maximum and band area of the Raman lines of SnO₂ nanoparticle annealed at various temperatures were calculated. The effect of high‐temperature annealing on the vibrational modes of SnO₂ was studied. The optical image of SnO₂ nanocrystalline material was used to understand the surface morphology effect. Copyright © 2011 John Wiley & Sons, Ltd.     

High-Temperature Dielectric Response and Multiscale Mechanism of SiO2/Si3N4 Nanocomposites

The high-temperature dielectric properties of SiO₂/Si₃N₄ nanocomposites are investigated theoretically and experimentally. Its permittivities and loss tangents at the temperature ranging from room temperature to 1300°C at 9.0GHz are measured by the resonant cavity method. The SiO_2/Si₃N₄ nanocomposites show complex dielectric behaviour at elevated temperature, and a multi-scale model is proposed to describe the dependence of the dielectric properties in the SiO₂/Si₃N₄ on its compositional variations. Such a theory is needed so that the available property measurements could be extrapolated to other operating frequencies and temperatures.     

Direct conversion of a metal organic compound to epitaxial Sb-doped SnO2 film on a (0 0 1) TiO2 substrate using a KrF laser, and its resulting electrical properties

Epitaxial Sb-doped SnO₂ (0 0 1) thin film on a TiO₂ (0 0 1) substrate was successfully prepared by laser-assisted metal organic deposition at room temperature. The effects of the precursor thin film and laser fluence on the resistivity, carrier concentration, and mobility of the Sb-doped SnO₂ film were investigated. The resistivity of the Sb-doped SnO₂ film prepared by direct irradiation to metal organic film is one order of magnitude lower than that of film prepared by irradiation to amorphous Sb-doped SnO₂ film. From an analysis of Hall measurements, the difference between the resistivity of the Sb-doped SnO₂ film prepared using the metal organic precursor film and that of amorphous precursor film appears to be caused by the mobility. Direct conversion of the metal organic compound by excimer laser irradiation was found to be effective for preparing epitaxial Sb-doped SnO₂ film with low resistivity.     

Fe3O4/β-CD的高压电学性质研究

 高压下的电学性质测量是获得材料物理性质的有效手段。利用集成在金刚石对顶砧上的薄膜微电路,测量了高压下Fe₃O₄/β-CD（β-糊精）的电导率,并分析了电导率随压力的变化关系。在0～39.9 GPa范围内,Fe₃O₄/β-CD的电导率随压力的增加而逐渐增大,并呈半导体的特征;而在17.0 GPa处其电导率发生突变,表明样品发生了高压相变。在卸压过程中,电导率随压力的变化呈线性关系,并且卸压后样品的电导率不能回到最初的状态,推测这是一个不可逆的高压结构相变。     

Influence of bases on hydrothermal synthesis of titanate nanostructures

A hydrothermal treatment of titanium dioxide (TiO₂) with various bases (i.e., LiOH, NaOH, KOH, and NH₄OH) was used to prepare materials with unique morphologies, relatively small crystallite sizes, and large specific surface areas. The experimental results show that the formation of TiO₂ is largely dependent on the type, strength and concentration of a base. The effect of the nature of the base used and the concentration of the base on the formation of nanostructures were investigated using X-ray diffraction, Raman spectroscopy, transmission and scanning electron microscopy, as well as surface area measurements. Sodium hydroxide (NaOH) and potassium hydroxide (KOH) were both used to transform the morphology of starting TiO₂ material.     

Large-scale synthesis of rutile SnO2 nanorods

A high yield of tin oxide (SnO₂) nanorods was obtained via annealing a nanoscale precursor in the molten salt flux and surfactant. X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction and infrared spectroscopy showed that the nanorods are composed of SnO₂ with rutile structure. The surfactant and temperature have a profound influence on the production of SnO₂ nanorods.     

Grain size effect on the universality of AC conductivity in SnO2

Nanocrystalline tin oxide (SnO₂) material with different grain sizes was synthesized by using a chemical precipitation method. This material was characterized by using the X-ray diffraction and transmission electron microscopy. The electrical properties of compressed nanocrystalline SnO₂ were studied by using impedance spectroscopy. AC conductivity data for SnO₂ material having grain sizes between 9 and 34 nm were analyzed using a power law. The exponent n is found to be 0.5 for bulk (34 nm) and unity for material with grain size below 18 nm. The results show a universal behavior for very low average grain sizes and the non-universal behavior for larger grain sizes even at room temperature.     

Unexpected behaviour of YbCu4.5 at very high pressures

We report resistivity measurements of the heavy fermion compound YbCu_4.5 for pressures up to 23.5 GPa. Although the temperature dependence of the resistivity in general does not change compared to previous results at lower pressures, surprisingly the temperature of the Kondo resistivity maximum increases with pressure at pressures exceeding 12.5 GPa. At the highest pressure of 23.5 GPa the resistivity was measured down to 50 mK. No trace of magnetic order, i.e. any anomaly in the resistivity behaviour has been found at this highest pressure reached.     

Structural, thermal and optical studies of mechanical alloyed Ga40Se60 mixture

A mixture of elemental Ga and Se with the nominal composition Ga₄₀Se₆₀ was submitted to the Mechanical alloying technique and their structural, thermal and optical properties were followed by X-ray diffraction, differential thermal analysis, photoacoustic spectroscopy, UV-VIS‐NIR absorbance spectroscopy and Raman spectroscopy techniques. After 10 h of milling the X-ray pattern showed monoclinic Ga₂Se₃ phase nucleation, which is in the nanometric form, and also a minority amorphous phase. The DSC results showed exothermic reactions between 430 and 720 K attributed to amorphous-crystalline phase transition and structural relaxation of Ga₂Se₃ phase. Based on this a small amount of the as-milled sample was annealed at 723 K. Its XRD pattern showed evidences of grain growth, reduction of the interfacial component, as well as, disappearance of the amorphous phase. The annealing process induced thermal diffusivity increasing, while the optical band gap energy and Raman profile remained practically unchanged.     

Studies on the structural and electrical properties of F-doped SnO2 film prepared by APCVD

Fluorine-doped tin oxide films (SnO₂:F, FTO) were deposited by atmosphere pressure chemical vapor deposition (APCVD) on Na-Ca-Si glass coated with a diffusion barrier layer of SiO_xC_y. The effects of post-heating time at 700 °C on the structural and electrical properties of SnO₂:F films were investigated. The results showed that SnO₂:F films were polycrystalline with tetragonal SnO₂ structure, SnO phase was present in SnO₂ film, and abnormal grain growth was observed. The element distribution in the film depth was measured with X-ray photoelectron spectroscopy (XPS) and revealed that when the heating time increased from 202 s to 262 s, the oxygen content in the surface increased from 78.63% to 83.38%. The resistivity increased from 3.13 × 10⁻⁴ for as-deposited films to 4.73 × 10⁻⁴ Ω cm when post-heated for 262 s. Hall mobility is limited by the ionized impurity scattering rather than the grain boundary scattering.     

Effect of Sn concentration on structural and optical properties of zinc oxide nanobelts

We investigated structural and optical properties of Sn-doped ZnO nanobelts with different Sn concentrations. X-ray diffraction and Raman spectra showed that the Sn-doped ZnO nanobelts have wurtzite structure at low Sn concentration (<2.1 at%) and over 2.1 at% a part of them starts to have the inverse spinel Zn₂SnO₄ structure phase. In addition, for Sn-doped ZnO nanobelts, the photoluminescence spectra indicate that ultraviolet emission peak appears first a blue shift with the increase of Sn concentration due to Burstein-Moss effect and then exhibits a red shift due to band gap renormalization effect.