Structural transformation from amorphous to hexagonal tungsten bronze FeF3, studied by Mössabauer spectroscopy

By annealing vapor-deposited amorphous FeF₃ at 180°C for 2 days, a crystalline phase has been obtained; it was identified by Mössbauer spectroscopy as hexagonal tungsten bronze FeF₃. the structural quality of this phase was good enough to provide the hyperfine parameters and notably the electric field gradient tensor. The role of Fe²⁺ impurities in this new synthesis method is discussed.     

Photo-electronic phenomena in narrow gap Hg1−xCdxTe

The photo-electronic properties of Hg_1−xCd_xTe grown by molecular beam epitaxy (MBE) or by liquid phase epitaxy (LPE) were investigated using Fourier transform transmission spectroscopy, Fourier transform photoluminescence measurements, spectroscopic ellipsometry (SE), as well as magneto-optics and magnetic-field-dependent Hall studies. The investigation was carried out from liquid helium to room temperatures in the infrared band up to 10 μm. Some important impurities and defects states, including As, Sb, Ag, Fe impurities and Hg vacancy as well as their complexes in Hg_1−xCd_xTe, were carefully studied. We obtained the energy levels of the impurity states and their optical, electric and magnetic behaviors. By SE measurement, a number of very useful parameters, such as the real and the imaginary part of dielectric constant, gap energies corresponding to important critical points, were extracted. Mobility spectra and multi-carrier fitting procedure were used to separate the contributions to the measured mobility from the light holes, heavy holes, and electrons. As a result, the sign change of transverse conductivity component with applied magnetic-field is explained according to multi-carrier process.Hg_1−xCd_xTe (MCT) is one of the most important infrared materials, which is subjected to intensive studies. Its optical and electrical properties are widely used for the fabrication of high performance photoconductive and photovoltaic detectors. Some of characteristics that directly affect device performance, such as impurities, defects, as well as the lifetime of the minority carriers, remain as the major concern. Recently, the quality of the MCT material grown by MBE and LPE has been improved and accurate control over the doping levels for several dopants have been realized [1], [2], [3]. Following the progresses made in material preparation and doping, we are able to study the material systematically.In this paper, we report the recent progress made on the investigation of the electrical and optical properties of both doped and undoped MCT in our laboratory using Fourier transform spectroscopy (FTIR), photoluminescence, magneto-photoconductivity, transport measurement, as well as SE.     

Amorphous to crystalline transformation in Ta2O5 studied by Raman spectroscopy

Many of the interesting properties that make Ta₂O₅ a strategic material for current and future applications in chemistry, microelectronics and optics, depend on its structural characteristics. In this work, we use Raman spectroscopy to probe structural modifications in amorphous Ta₂O₅ coatings submitted to thermal annealing. On the basis of previous knowledge on the crystalline material, we perform Raman spectrum simulations in disordered and partially ordered Ta₂O₅ from a phonon density of states. Calculated spectra are in good agreement with complex experimental spectra. Our original approach allows assignment of the vibrational features of the amorphous material, and quantitative interpretation of observed structural modifications in terms of ordering scales. In addition, it provides numerical indicators to analyse amorphous to crystalline phase transformation. Copyright © 2012 John Wiley & Sons, Ltd.     

A microstructural study of the structure of plasma electrolytically oxidized titanium foils

The structure and distribution of TiO₂ rutile and anatase phases of anodized titanium foil, subjected to a special high-voltage electrochemical preparation technique, are reported. We applied X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy on samples that were oxidized for various times. Combining data from the different techniques led to a model in which the initially formed porous, micrometer-thick TiO₂ layer, consisting in a large part of anatase, is transformed into rutile. The result is a porous rutile layer on top of anatase, which is in direct contact with the Ti metal. The first structural model is derived from the evaluated data and the phenomena that occurred during preparation are clarified.     

Infrared spectroscopy characterization of thin films used in solid state micro-batteries

In the perspective to use thin solid films of both Li borate glasses and layered insertion compounds in Li microbatteries, we have investigated their structural characterization as function of the growth conditions by IR spectroscopy.Taking into consideration the ratio of absorption peaks in the mid-IR spectrum of the binary glass system, the composition of the film is determined with good accuracy, and measurements on films doped with different Li salts are comparable to those obtained for bulk material.The far-IR reflectivity spectra of the semiconductors of the In-Se family are found to be those of InSe and In₂Se₃ for given ratio of fluxes during the film preparation by the MBD technique.     

Characterization of the NiNa6□Cl8 ordered phase by crystal field spectroscopy

We show that the formation of an ordered phase of transition metal impurities in ionic crystals can be monitored by means of crystal field spectroscopy of the d-d vibronic excitons. We present an optical absorption study of the Suzuki phase NiNa₆□Cl₈ in doped NaCl:Ni, in combination with ionic thermocurrent measurements and Raman spectroscopy. We find that the complex crystal field spectra are due to the coexistence of the Suzuki phase with free impurity-vacancy dipoles. The comparison with the frequencies and the absolute absorption intensities of crystal field transitions in NiCl₂ yield detailed structural information (long range order, point symmetry and anion relaxation) on the Suzuki phase, and an accurate determination of the phase concentrations.     

Revelation of the microstructure of oxide FeAl/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite

The structural transformations at different stages of the preparation of oxide FeAl/Al₂O₃ nanocomposite by mechanosynthesis with the use of a preliminarily activated FeAl precursor are studied by means of transmission electron microscopy, X-ray diffraction and Mössbauer spectroscopy.     

Application of high-resolution IR and microwave spectroscopies for investigation of the impurity composition of silicon tetrafluoride

The possibility of combined application of gas chromatography, high-resolution IR spectroscopy, and transient microwave gas spectroscopy (TMGS) for investigation of the impurity composition of silicon tetrafluoride is studied. Using high-resolution IR Fourier spectroscopy, the lines of a number of impurities are observed in the region from 4500 to 550 cm^?1. The absorption lines of some of the main well-known impurities in silicon tetrafluoride in the 2-mm wavelength range are analyzed. The advantages of the TMGS method for investigating the multicomponent SiF₄-impurities system are demonstrated. Using the TMGS method, the freons CHF₃, CH₂F₂, and CH₃F are experimentally detected in silicon tetrafluoride.     

Improvement in the photocatalytic activity of TiO2 by the partial oxidation of the C impurities

TiO₂ was treated by water in an ultrasonic bath, resulting in the enhancement of the photocatalytic activity for the decomposition of methylene blue under UV and visible light irradiation. No change in the crystallinity and optical properties of TiO₂ by the H₂O-treatment was observed. The X-ray photoelectron spectroscopy (XPS) and FT-IR data revealed that the C impurities were oxidized by this treatment, indicating that the change in the structure of the C impurities plays a pivotal role in the photocatalytic activity of TiO₂.     

Preparation and characterization of a novel luminescent nanoparticles

In this paper, a new kind of fluorescent nanomaterial with morin modified alumina core and silica shell was prepared. Samples were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), photoluminescent (PL) spectroscopy and fluorescence microscope. TEM results indicated that this material could be synthesized in nanometer range. PL spectra suggested that this new synthesized material was photostable and it showed nearly no dye leakage. This was because the dye molecules could form stable complex with the reactive aluminum cations on the surfaces of the alumina particles. The excitation and emission maxima of this new luminescent material were located at 420 and 493 nm, respectively. This new kind of luminescent nanomaterial was prepared by morin, AlCl₃ and tetraethyl orthosilicate, which was very important for the large-scale and economic preparation luminescent nanoparticles because these precursors were inexpensive and the preparation process was convenient.     

Mössbauer effect studies of magnetism in superconducting systems

The applications of Mössbauer spectroscopy to studies of superconductivity are reviewed. with an emphasis on magnetic properties. Important contributions utilizing this technique have included studies of spin-lattice relaxation rates for magnetic impurities as a measure of magnetic pair-breaking effects, studies of magnetic ordering and its relationship to superconductivity in ternary superconductors such as the Chevrel phase, Re-Rh₄B₄ and oxide superconducting compounds, evaluation of crystal field ground states for magnetic ions, and studies of substitutional sites and the role of impurities on superconductivity in the high temperature superconductors.     

Surface termination of BaTiO3 (001) single crystals: A combined electron spectroscopic and theoretical study

The surface termination of oxide surfaces is of crucial importance for the growth of a second material like metals or other oxides. In this study we have investigated the surface of a BaTiO₃ (001) single crystal during sample preparation by various electron spectroscopic methods. It is shown by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable induced electron spectroscopy (MIES) that during sputtering a Ba rich overlayer is formed, in which the Ba²⁺ ions are under coordinated. Below this layer, an oxygen deficient BaTiO₃ layer is found. During annealing, we observe the reformation of the crystalline structure. UP and MIE spectra provide clear evidence of a BaO terminated surface. X-ray photoelectron diffraction studies support this result, comparing recorded polar angle scans with calculated intensity modulations using multiple scattering cluster models.     

Microstructure of LaCoO3 prepared by freeze-drying of metal-citrate precursors revealed by EPR

Two methods for the preparation of LaCoO₃ samples were used: thermal decomposition of La-Co citrate precursors obtained by freeze-drying of the corresponding solutions and by a solid state reaction. Microstructural characterization was made by electron paramagnetic resonance spectroscopy (EPR). For assignment of the EPR signals, La_1−xSr_xCoO₃ samples were used as EPR references. The LaCoO₃ oxides prepared from citrates and by a solid state reaction were shown to differ in respect of the mean oxidation state of the cobalt ions, the specific surface area and the particle morphology. EPR spectroscopy reveals for ex-citrate LaCoO₃ ferromagnetic Co³⁺ and Co⁴⁺ coupled ions. For LaCoO₃ samples obtained by a solid state reaction, EPR permits detecting Co₃O₄ impurities only.     

Ab initio study of Fe-doped SnO: Local structure and hyperfine interactions at the Fe nucleus

In this work we perform an ab initio study of the electric field gradient (EFG) at the nucleus of Fe impurities in crystalline SnO. The Augmented Plane Waves plus Local Orbitals method is used to obtain the electronic structure of the doped system and the atomic relaxations introduced by the impurities in the SnO host in a fully self-consistent way. Most calculations are performed assuming that Fe ions replace the Sn atoms of the structure, in some cases including oxygen vacancies in order to discuss their role in the hyperfine interactions and in determining the local structure around Fe impurities. The case of interstitial Fe sites is also considered. Our predictions are compared with available Müssbauer spectroscopy results and also with theoretical and experimental results obtained for rutile SnO₂ and TiO₂.     

Effect of mechanical activation on the phase composition,structure, and polymorphism of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O6 + δ oxide

The mechanical activation of YBa₂Cu₃O_6+δ powders is studied comprehensively using thermal analysis, scanning electron microscopy, high-temperature x-ray diffraction, and x-ray photoelectron spectroscopy. It is shown that the size of the coherent scattering regions is substantially reduced by intensive grinding (from 83 to 17 nm) and the material transforms to a nanostructured state. An increase in the reactivity of the material is found, which shows up as an enhanced accumulation of intercalated water in its structure. At the same time, no significant increase in the volume of impurity phases in the powder or in the influence of impurities on the crystal lattice parameters was observed. High-temperature x-ray studies of the lattice parameters of the YBa₂Cu₃O_6+δ phase reveal a jump (at temperatures of 430–630°C) and a decrease (above 630°C) in the parameter c when the powder is mechanically activated. A significant reduction in the temperature of the transition from the orthorhombic to the tetragonal structural modification is observed. These effects are explained by a change in the charge states of oxygen ions belonging to the base plane of the YBa₂Cu₃O_6+δ oxide during mechanical activation.     

Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH₃ as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about −80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH₃ is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp² sites dispersed in sp³ skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films.     

Effect of element substitution on nanostructure and hard magnetism of rapidly quenched Nd2Fe14B

The structural and magnetic properties of Nd₁₂Fe₈₂B₆ and Nd₁₀M₂Fe₈₂B₆ (M = Nb, Ti, Zr, Cr) alloys prepared using arc melting and melt spinning have been investigated. All the samples are found to crystallise with a tetragonal Nd₂Fe₁₄B phase without any alloy or elemental impurities. There is a small decrease in the unit cell volume of Nd₂Fe₁₄B due to transition metal (M) addition. The substitution of Nb and Ti refines and homogenises the nanostructure of the alloys, promoting intergrain exchange coupling leading to an increase in the remanence and energy product. For example, the remanence and energy product of Nd₁₂Fe₈₂B₆ and Nd₁₀Nb₂Fe₈₂B₆ are 8.4 kG and 15 MGOe, and 9.9 kG and 20 MGOe, respectively. The J(T) curves are similar to those of a single phase ferromagnetic material suggesting no segregation of ferromagnetic impurities. The observed structural and magnetic properties are consistent with the fact that the substitutional transition metal atoms occupy the Nd site of the tetragonal Nd₂Fe₁₄B crystal lattice. The improvement of magnetic properties of nanocrystalline Nd₂Fe₁₄B alloys with the decrease in Nd concentration may be beneficial for the application of this material in bonded magnets.     

Some problems concerning theT c depression of non-transition element superconductors doped with 3d-transition element impurities

A critical discussion of the measurements of theT _c depression of superconductors doped with 3d-element impurities is given under metallurgical aspects. Particularly, the formation of binary solid solutions in these systems is investigated. The contradictions between thin film and bulk material work are removed by showing that metallurgical difficulties connected with the sample preparation have led to incorrect interpretation of the results. Furtheron it is shown that an exact proof of the Abrikosov-Gorkov theoretical dependence of the critical temperature versus concentration has so far not been given.     

Synthesis and performance study of cobalt-substituted lithium iron phosphate

LiCo_0.2Fe_0.8PO₄ cathode material was prepared by succinic assisted soft combustion technique. This method of synthesis ensures homogeneity of the precursor material, improved activity and crystal grain size. Calcinations at high temperature confirm the purity of the cathode material. The aim of this work is to investigate the effects of cobalt substitution in LiFePO₄. The structural characterization of the products was analysed by the X-ray powder diffraction. Conductivity measurements were made to characterize the transport property of the cathode material. Fourier transform infrared spectroscopy and differential scanning calorimeter and thermogravimetry analysis have been studied to investigate the functional group present and the phase transition involved in the sample, respectively.     

Elimination of metal catalyst and carbon-like impurities from single-wall carbon nanotube raw material

The purification of as-produced single-wall carbon nanotube (SWCNT) material is one important step in order to make the material optimally suited for a number of potential applications. We present a purification procedure based upon oxidation of the raw material in oxygen atmosphere at elevated temperatures and a subsequent treatment in HCl. It is shown that this procedure results in the removal of the majority of the impurities comprising carbonaceous species and metal catalyst particles. The purification and the evolution of SWCNT material using this procedure are monitored using optical absorption spectroscopy, transmission electron microscopy including electron energy-loss spectroscopy as well as electron diffraction. Furthermore, the method has a sufficiently high yield of about 50% to be applicable for a large-scale purification. PACS 81.05.-t; 81.20.-n; 81.07.-b