Electron magnetic chiral dichroism in CrO2 thin films using monochromatic probe illumination in a transmission electron microscope

Electron magnetic chiral dichroism (EMCD) has been studied in CrO₂ thin films (with (100) and (110) growth orientations on TiO₂ substrates) using a gun monochromator in an aberration corrected transmission electron microscope operating at 300 kV. Excellent signal-to-noise ratio is obtained at spatial resolution ∼10 nm using a monochromatic probe as compared to conventional parallel illumination, large area convergent beam electron diffraction and scanning transmission electron microscopy techniques of EMCD. Relatively rapid exposure using mono probe illumination enables collection of EMCD spectra in total of 8–9 min in energy filtered imaging mode for a given Cr L_2,3 energy scan (energy range ∼35 eV). We compared the EMCD signal obtained by extracting the Cr L_2,3 spectra under three beam diffraction geometry of two different reciprocal vectors (namely g=110 and 200) and found that the g=200 vector enables acquisition of excellent EMCD signal from relatively thicker specimen area due to the associated larger extinction distance. Orbital to spin moment ratio has been calculated using EMCD sum rules for 3d elements and dichroic spectral features associated with CrO₂ are compared and discussed with XMCD theoretical spectra.     

Local trimer orbital ordering in LiNiO2 studied by quantitative convergent beam electron diffraction technique

A local trimer orbital ordering model of LiNiO₂ was studied by means of theoretical calculation and experimental measurement of electron structure factors. Based on the trimer model, the electron structure factors were calculated by using the scattering factor of non-spherical Ni³⁺ ion. From these results, it is found that the effect of local orbital ordering on the electron structure factors of several subtle reflections, such as (202) and (107), is very large. The electron structure factors of these subtle reflections were measured by quantitative convergent beam electron diffraction method. The experimentally measured electron structure factor values of these reflections indicate that the trimer orbital ordering model is more close to the true structure of LiNiO₂.     

The formation and stability of quasicrystal in Al80Mn14Si6 under high static pressure

Abstract

The method of quenching in fusing state under high static pressure (MQFSHP) was applied for the first time to prepare the quasicrystal icosahedral phase of Al₈₀Mn₁₄Si₆ alloy. The pressure was from 2.8GPa to 3.1GPa and the cooling rate during quenching was of about 100°C/s. Some sharp electron diffraction spots showing an arrangement with a five-fold symmetry axis and noncrystalline ring have been observed in electron diffraction experiment.

The crystallization temperature of I phase obtained from high pressure(HP) is close to that of rapid cooling ribbon, but the cooling rate of the sample obtained is lower than that of rapid cooling ribbon.     

Structures and magnetic anisotropy of β-Mn2V2O7 crystals synthesized by the molten salt method

β-Mn2V2O7 crystals with strip shape are successfully prepared by the molten salt method in a closed crucible,and are characterized by x-ray diffraction (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM),selected area of electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM).The results indicate that the sample is of the β-Mn2V2O7 crystal with monoclinic symmetry,level natural cleavage facets and directional growth.Magnetic properties are measured by vibration sample magnetometry (VSM) at room temperature,and the magnetic hysteresis loop indicates that the β-Mn2V2O7 has anti-ferromagnetic properties with low coercive force and remnant magnetization.The magnetic measurement results in different directions exhibit that the β-Mn2V2O7 has magnetic anisotropy,which is due to the fact that the magnetic interaction energy of the β-Mn2V2O7 is lowest only when the electron configuration is in a certain direction.     

Investigation of the phase transitions of ferroelectric KIO3 and KNbO3 crystals by optical diffraction

Optical diffraction is reviewed as a technique for investigation of the phase transitions in crystals with a multidomain structure. It has been used to study the phase transitions in KIO₃ and KNbO₃ single crystals. Strong optical diffraction bands resulted from electric domains in KNbO₃ crystals and their change with temperature were observed when a laser beam passed through the crystals. The diffraction patterns observed changed abruptly at 427°C, 223°C, and -50°C respectively, at which KNbO₃ crystals undergo structural phase transitions. It is considered that the change of the diffraction patterns with temperature is due to change of the electric domains in the crystals.     

Study of electrical conductivity changes and phase transitions in Co3O4 doped ZrO2

The electrical conductivity of ZrO₂ doped with Co₃O₄ has been measured at various temperatures for different molar ratios. The conductivity increases due to the migration of vacancies created by doping. The conductivity is also found to increase with rise in temperature up to 120°C, and after attaining a maximum the conductivity decreases due to a collapse of the lattice framework. A second rise in conductivity around 460°C in all the compositions confirms the phase transition in ZrO₂ from monoclinic to tetragonal symmetry. X-ray powder diffraction and DTA studies were carried out for confirming the doping effects and the transition in ZrO₂.     

A neutron powder diffraction study of the helimagnetic structure of TlCo2Se2−xSx

The magnetic layer structure of TlCo₂Se_2−xS_x has been thoroughly re-investigated with neutron powder diffraction. The cobalt magnetic moments are ferromagnetically arranged within the layers, but the interlayer coupling differs profoundly with varying composition (x): the spins in TlCo₂Se₂ form a helix along the c-axis with a turning-angle of ∼119° at 1.4 K. This kind of helical structure prevails for 0≤x≤1.5 with a gradual decrease of the angle with increasing sulphur content, down to 34°, showing an almost linear relationship with the interlayer distance of Co-Co. For x≥1.75 the interlayer coupling changes to ferromagnetic. Unexpectedly, two helices were found to coexist at x=0.5 and x=1.0. The interaction between adjacent cobalt layers is there characterized by an incommensurate angle (106°, resp., 73°) together with a commensurate angle of 90°. The magnetic structures have been refined as two magnetic phases, each having a characteristic wave vector. A tentative model where the symmetry of the structure and the interlayer distance compete is considered for explaining the simultaneous occurrence of the two kinds of diffraction profile satellites.     

Symmetry of the charge-ordered phases in Pr0.5Ca0.5MnO3

The crystallographic symmetry of the charge-ordered Pr_0.5Ca_0.5MnO₃ manganite is studied at ～98?K using convergent beam electron diffraction technique. These studies have revealed appearance of two different type of charge-ordered phases in different domains of the same grain. These correspond to be monoclinic and triclinic phases. These studies reveal that the symmetry of the charge-ordered phase is highly sensitive to the local strain conditions.     

Lattice site dependent cathodoluminescence behavior and surface chemical changes in a Sr5(PO4)3F host

Eu activated Sr₅(PO₄)₃F phosphor powders have been subjected to the electron bombardment at 2 keV (10 μA) at an oxygen pressure of 1×10⁻⁶ Torr. The synthesized Sr₅(PO₄)₃F phosphor was identical to the hexagonal apatite structure, with the Sr present at two different sites C_s (S1) and C₃ (S2) in the Sr₅(PO₄)₃F host, as inferred from the crystallographic study. Cathodoluminescence (CL) and Auger electron spectroscopy of the phosphor excited by the same electron beam were used to monitor changes in the surface state during prolonged electron bombardment. A direct correlation between the surface reactions and the degradation of the CL brightness was observed. Both C and F were depleted from the surface during electron bombardment. The postulated mechanism for the electron stimulated chemical reactions on the phosphor surface is electron beam dissociation of molecular species to atomic species, which subsequently react with C to form volatile compounds CO₂, CH₄, etc. and with Sr₅(PO₄)₃F to form a non luminescence layer of metal oxides of Sr and P.     

Tb3Sc2Al3O12-TbScO3 eutectic self-organized microstructure for metamaterials and photonic crystals application

Eutectics are the materials with foreseen application in the field of photonic crystals and metamaterials. In this paper, the dependence on chemical composition of the microstructures of terbium-scandium-aluminium gamet and terbium-scandium perovskite (Tb₃Sc₂Al₃O₁₂-TbScO₃) eutectics has been studied. The growth of the eutectic rods by the micro-pulling down method is presented, using compositions with several different volume fractions of the garnet and the perovskite phases, V_TSAG:V_TSP = 4, 3, 2, 1, 1/2. The phases have been characterized by powder X-ray diffraction and energy dispersive spectrometry. The relationship between the lattice constant of individual phases and the chemical composition is presented. The unidirectional growth of microrods has been also investigated by electron backscattering diffraction.     

The change in symmetry at the i-ii phase transition in dicalcium barium propionate

The symmetry change occurring at the first-order I-II transition at 267 K in dicalcium barium propionate, DBP, has been determined using X-ray diffraction: phase II is orthorhombic, with probable space group Pnma or Pn2₁a. The twinning in phase II is explained and lattice parameters calculated in the temperature range 125 K to 300 K. The behaviour of the spontaneous strain in phase II is compared with that in the similar compound dicalcium barium acrylate.     

Fabrication and characterization of Bi2Te3 nanoplates via a simple solvothermal process

Bi₂Te₃ nanoplates have been successfully obtained by a novel solvothermal method in the presence of hexadecyltrimethylammonium bromide (CTAB). Various techniques such as X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), transmission electron microscope (TEM), selected area electron diffraction (SAED), and Fourier transform infrared spectrometry (FT-IR) have been used to characterize the obtained products. The results show that the as-synthesized samples are rhombohedral-structured Bi₂Te₃ single-crystal nanoplates about 70–200 nm in diagonal and 30 nm in thickness, and the growth direction is perpendicular to c-axis. The existence of CTAB is vital to the formation of the plate-like morphology. In addition, the reaction solvents also have important influence on the shape-control of final products.     

Fabrication of flower-shaped Bi2O3 superstructure by a facile template-free process

A novel flower-shaped Bi₂O₃ superstructure has been successfully synthesized by calcination of the precursor, which was prepared via a citric acid assisted hydrothermal process. The precursor and Bi₂O₃ were characterized with respect to morphology, crystal structure and elemental chemical state by field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was shown that both the precursor and Bi₂O₃ flower-shaped superstructure were constructed of numerous nanosheets while the nanosheets consisted of a great deal of nanoparticles. Furthermore, key factors for the formation of the superstructures have been proposed; a mechanism for the growth of the superstructure has been presented based on the FESEM investigation of different growth stages.     

Modified laser ablation process for nanostructured thermoelectric nanomaterial fabrication

A modified pulsed laser deposition process was used to enhance the nanostructure generation inside Bi₂Te₃ nanocrystals. In this process, an additional femotosecond laser beam was used to add an energy shock on the ablated flume, which can result in rich nanostructures embedded inside Bi₂Te₃ nanocrystals. A large Si wafer was used to ‘freeze’ such nanostructures and to effectively collect such nanostructured nanocrystals for further processing. The generated nanocrystals were studied by X-ray diffraction and scanning transmission electron microscopy, and the results prove the existence of such embedded nanostructures. Such nanocrystals were also characterized electrically and thermally for the conductivity measurements.     

Growth of cubic MgxZn1−xO alloy films by electron beam evaporation

We report the growth of cubic Mg_xZn_1−xO alloy thin films on quartz by electron beam evaporation. It can be found that all the samples have sharp absorption edges by the absorption measurements. X-ray diffraction measurements indicate the Mg_xZn_1−xO films are cubic phase with preferred orientation along the (1 1 1) direction. Energy dispersive spectrometry (EDS) demonstrates that the Mg concentration in Mg_xZn_1−xO films is much higher than the ceramic target used, and the composition can be tuned in a small scope by varying the substrate temperature and the beam electric current. The reasons of this phenomenon are also discussed.     

Volume dependence of electronic structure and magnetic properties of Fe16N2

Using first-principles calculations based on density functional theory, we investigated systematically the electronic structures and magnetic properties of Fe₁₆N₂ system and their unit cell volume dependence. It has been found that total magnetic moment increases as increasing unit cell volume of Fe₁₆N₂. In addition, it also has been found that the d electron number on Fe I, Fe II and Fe III atoms decreases as increasing unit cell volume and the local magnetic moment on Fe atoms increases with the decrease of d electron number. The present study provides a clear insight into the numerous conflicting experimental results on the magnetic properties of Fe₁₆N₂ system.     

Investigation of the characteristics and corrosion resistance of Al2O3/TiN coatings

Al₂O₃ /TiN double and Al₂O₃/Cr/TiN triple coatings were produced on stainless steel substrates using plasma-detonation techniques. Investigation of the microstructure and characteristics of the coatings after the preparation was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Auger electron spectroscopy (AES). The corrosion resistance of the coatings was studied in several electrolytic solutions (0.5 M H₂SO₄, 1 M HCl, 0.75 M NaCl) using electrochemical techniques (open circuit potential, cyclovoltammetry and potentiodynamic polarization). The obtained results showed, in most of the cases, an improvement of the corrosion resistance, except in NaCl solutions. The effect of the controlled thickness of TiN and Cr layers as well as the additional treatment with a high-current electron beam was also investigated. Nuclear reaction analysis (NRA), Rutherford backscattering spectroscopy (RBS) and scanning electron microscopy (SEM) were applied for the characterization of the samples before and after the corrosion experiments.     

Structural characteristics and morphology of SmxCe1−xO2−x/2 thin films

Effect of the deposition temperature (200 and 500 °C) and composition of Sm_xCe_1−xO_2−x/2 (x = 0, 10.9–15.9 mol%) thin films prepared by electron beam physical vapor deposition (EB-PVD) and Ar⁺ ion beam assisted deposition (IBAD) combined with EB-PVD on structural characteristics and morphology/microstructure was investigated. The X-ray photoelectron spectroscopy (XPS) of the surface and electron probe microanalysis (EPMA) of the bulk of the film revealed the dominant occurrence of Ce⁴⁺ oxidation state, suggesting the presence of CeO₂ phase, which was confirmed by X-ray diffraction (XRD). The Ce³⁺ oxidation states corresponding to Ce₂O₃ phase were in minority. The XRD and scanning electron microscopy (SEM) showed the polycrystalline columnar structure and a rooftop morphology of the surface. Effects of the preparation conditions (temperature, composition, IBAD) on the lattice parameter, grain size, perfection of the columnar growth and its impact on the surface morphology are analyzed and discussed.     

Controlled synthesis of BaWO4 hierarchical nanostructures by exploiting oriented attachment in the solution of H2O and C2H5OH

Shape-controlled synthesis of BaWO₄ hierarchical nanostructures has been successfully achieved by exploiting oriented attachment in a mixture of water and ethanol. A controlled change in the volume ratio of C₂H₅OH and H₂O or the concentration of initial reagents has resulted in the synthesis of products of various morphologies, such as shuttle-like, ellipsoid-like, and flower-like ones. The obtained products are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy. The altered nucleation and growth rates of primary particles that assembled to the final hierarchical nanostructures through oriented attachment are the main cause of the evolution of their morphologies. The room-temperature photoluminescent intensities of the products strongly depend on their morphology.