Abstract: The formation of CH⋯S and CH⋯P hydrogen bonded complexes of halothane, CHBrClCF3, with dimethyl sulfide(-d6) and trimethylphosphine(-d9) have been studied in solutions of liquid krypton using infrared and Raman spectroscopy. In the 1:1 complexes, the halothane CH stretching mode is found to be red-shifted by 43 cm−1 in the dimethyl sulfide complex, and by 63 cm−1 in the trimethylphosphine complex. The complexation enthalpies were derived and amount to −10.7(2) and −11.2(2) kJ mol−1 for the respective complexes. The experiments were supported by ab initio calculations and Monte Carlo simulations. The obtained data for the CH⋯S and CH⋯P hydrogen bonds is compared to that of corresponding CH⋯O and CH⋯N hydrogen bonds.

Abstract: Scheelite-type compounds with the general formula (A1,A2)n[(B1,B2)O4]m (2/3 ≤ n/m ≤ 3/2) are the subject of large interest owing to their stability, relatively simple preparation, and optical properties. The creation of cation vacancies (□) in the scheelite-type framework and the ordering of A cations and vacancies can be a new factor in controlling the scheelite-type structure and properties. For a long time, cation-deficient Nd3+:M2/7Gd4/7□1/7MoO4 (M = Li, Na) compounds were considered as potential lasers with diode pumping. They have a defect scheelite-type 3D structure (space group I41/a) with a random distribution of Li+(Na+), Gd3+, and vacancies in the crystal. A Na2/7Gd4/7MoO4 single crystal with scheelite-type structure has been grown by the Czochralski method. Transmission electron microscopy revealed that Na2/7Gd4/7MoO4 has a (3 + 2)D incommensurately modulated structure. The (3 + 2)D incommensurately modulated scheelite-type cation-deficient structure of Na2/7Gd4/7MoO4 [super space group I4̅ (αβ0,βα0)00] has been solved from single-crystal diffraction data. The solution of the (3 + 2)D incommensurately modulated structure revealed the partially disordered distribution of vacancies and Na and Gd cations. High-temperature conductivity measurements performed along the [100] and [001] orientation of the single crystal revealed that the conductivity of Na2/7Gd4/7MoO4 at T = 973 K equals σ = 1.13 × 105 Ω1 cm1.

Abstract: Nanocrystalline Pd films were produced by electron-beam evaporation and sputter deposition. The electron-beam-evaporated films reveal randomly oriented nanograins with a relatively high density of growth twins, unexpected in view of the high stacking fault energy of Pd. In contrast, sputter-deposited films show a clear 〈1 1 1〉 crystallographic textured nanostructure without twins. These results provide insightful information to guide the generation of microstructures with enhanced strength/ductility balance in high stacking fault energy nanocrystalline metallic thin films.

Abstract: A focused electron beam in a scanning transmission electron microscope (STEM) is used to create arrays of core-shell structures in a specimen of amorphous SiO2 doped with Ge. The same electron microscope is then used to measure the changes that occurred in the specimen in three dimensions using electron tomography. The results show that transformations in insulators that have been subjected to intense irradiation using charged particles can be studied directly in three dimensions. The fabricated structures include core-shell nano-columns, sputtered regions, voids, and clusters. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4731765]

Abstract: The size and lattice constant evolution of Pb nanoparticles (NPs) synthesized by high fluence implantation in crystalline Si have been studied with a variety of experimental techniques. Results obtained from small-angle x-ray scattering showed that the Pb NPs grow with increasing implantation fluence and annealing duration. The theory of NP growth kinetics can be applied to qualitatively explain the size evolution of the Pb NPs during the implantation and annealing processes. Moreover, the lattice constant of the Pb NPs was evaluated by conventional x-ray diffraction. The lattice dilatation was observed to decrease with increasing size of the Pb NPs. Such lattice constant tuning can be attributed to the pseudomorphism caused by the lattice mismatch between the Pb NPs and the Si matrix.

Abstract: The aim of this paper is to provide a thorough study on the occurrence and importance of deformation twinning in simple shear deformed pure α-Ti. A statistically relevant inspection of the morphology of the deformation twins in relation to the applied strain/deformation is performed. The investigated microstructural aspects are the twin volume fraction, the twin thickness distribution and the resolved shear stress distribution on the twin plane. All these aspects are examined as a function of the twin types and two initial textures. Monotonic simple shear experiments are carried out for three different loading directions with respect to a direction linked to the initial crystallographic texture. EBSD and TEM observations reveal the presence of View the MathML source and View the MathML source twins. The statistical analysis reveals that View the MathML source and View the MathML source twins have a similar average thickness around 1.9 nm, but the View the MathML source twins show a far larger spread on their thickness and can grow to almost the size of the original parent grain. Correlation of the twin fractions with the RSS analysis shows that RSS is an acceptable method explaining the difference in twin fractions for different textures and orientations. A detailed analysis shows that View the MathML source twins occur in average with a smaller volume fraction but with a higher RSS, indicating they are more difficult to nucleate or grow compared to View the MathML source twinning. In general a higher RSS value on the twin plane is not connected to a higher twin thickness; only in the case of View the MathML source twins the highest RSS values show clearly thicker twins.

Abstract: The local and average crystal structures and magnetic properties of the oxygen-deficient perovskite Sr2Fe1.5Cr0.5O5+y were studied using powder X-ray and neutron diffraction, neutron-pair distribution function analysis, and electron energy-loss spectroscopy. This material crystallizes in the cubic Pm3̅m space group, with a = 3.94491(14) Å. The oxygen vacancies are distributed randomly throughout the perovskite-type structure, and the average coordination number of the Fe(Cr) sites is 5. Refinement of the neutron diffraction data indicates y 0.05. This is in discordance with an earlier report on a material with the same nominal composition and cell constant. Electron energy-loss Cr L2,3-edge spectroscopy shows that Cr3+ is present, which is also contrary to previous speculation. Neutron-pair distribution function studies show that a brownmillerite-like model involving ordered vacancies and alternating octahedral and tetrahedral coordination at the metal sites, gives a better description of the local structure out to 5 Å. A remarkable phenomenon determined by neutron diffraction in Sr2Fe1.5Cr0.5O5 is the occurrence of a long-range G-type antiferromagnetic ordering with Tc ≈ 565 K because cubic oxygen-deficient perovskites with B-site disorder usually do not undergo transitions to magnetically ordered states. The observation of long-range antiferromagnetic order and the Tc value are in accordance with previous Mössbauer spectroscopic studies.

Abstract: We demonstrate that near-edge X-ray-absorption fine-structure spectra combined with full-field transmission X-ray microscopy can be used to study the electronic structure of graphite flakes consisting of a few graphene layers. The flake was produced by exfoliation using sodium cholate and then isolated by means of density-gradient ultracentrifugation. An image sequence around the carbon K-edge, analyzed by using reference spectra for the in-plane and out-of-plane regions of the sample, is used to map and spectrally characterize the flat and folded regions of the flake. Additional spectral features in both π and σ regions are observed, which may be related to the presence of topological defects. Doping by metal impurities that were present in the original exfoliated graphite is indicated by the presence of a pre-edge signal at 284.2 eV.

Abstract: The depth strain profile in silicon from the Si (001) substrate to the surface of a 2 nm thick Si/12 nm thick SiGe/bulk Si heterostructure has been determined by medium energy ion scattering (MEIS). It shows with sub-nanometer resolution and high strain sensitivity that the thin Si cap presents residual compressive strain caused by Ge diffusion coming from the fully strained SiGe layer underneath. The strain state of the SiGe buffer have been checked by X-ray diffraction (XRD) and nano-beam electron diffraction (NBED) measurements.

Abstract: Strain engineering in the conduction channel is a cost effective method of boosting the performance in state-of-the-art semiconductor devices. However, given the small dimensions of these devices, it is difficult to quantitatively measure the strain with the required spatial resolution. Three different transmission electron microscopy techniques, high-angle annular dark field scanning transmission electron microscopy, dark field electron holography, and nanobeam electron diffraction have been applied to measure the strain in simple bulk and SOI calibration specimens. These techniques are then applied to different gate length SiGe SOI pFET devices in order to measure the strain in the conduction channel. For these devices, improved spatial resolution is required, and strain maps with spatial resolutions as good as 1 nm have been achieved. Finally, we discuss the relative advantages and disadvantages of using these three different techniques when used for strain measurement.

Abstract: We present the GW band structure of ZnO in its wurtzite (WZ), zincblende (ZB) and rocksalt (RS) phases at the Γ point, calculated within the GW approximation. We have used a Zn20+ pseudopotential which is essential for the adequate treatment of the exchange interaction in the self-energy. The accuracy of the pseudopotential used is also discussed. The effect of the pd hybridization on the GW corrections to the band gap is correlated by comparing the ZB and RS phase.

Abstract: We demonstrate for the first time a possibility to vary the anion content in perovskites over a wide range through a long-range-ordered arrangement of crystallographic shear (CS) planes. Anion-deficient perovskites (Pb,Bi)1−xFe1+xO3−y with incommensurately modulated structures were prepared as single phases in the compositional range from Pb0.857Bi0.094Fe1.049O2.572 to Pb0.409Bi0.567Fe1.025O2.796. Using a combination of electron diffraction and high-resolution scanning transmission electron microscopy, we constructed a superspace model describing a periodic arrangement of the CS planes. The model was verified by refinement of the Pb0.64Bi0.32Fe1.04O2.675 crystal structure from neutron powder diffraction data ((3 + 1)D S.G. X2/m(α0γ), X = [1/2,1/2,1/2,1/2], a = 3.9082(1) Å, b = 3.90333(8) Å, c = 4.0900(1) Å, β = 91.936(2)°, q = 0.05013(4)a* + 0.09170(3)c* at T = 700 K, RP = 0.036, RwP = 0.048). The (Pb,Bi)1−xFe1+xO3−y structures consist of perovskite blocks separated by CS planes confined to nearly the (509)p perovskite plane. Along the CS planes, the perovskite blocks are shifted with respect to each other over the 1/2[110]p vector that transforms the corner-sharing connectivity of the FeO6 octahedra in the perovskite framework to an edge-sharing connectivity of the FeO5 pyramids at the CS plane, thus reducing the oxygen content. Variation of the chemical composition in the (Pb,Bi)1−xFe1+xO3−y series occurs mainly because of a changing thickness of the perovskite block between the interfaces, that can be expressed through the components of the q vector as Pb6γ+2αBi1−7γ−αFe1+γ−αO3−3γ−α. The Pb, Bi, and Fe atoms are subjected to strong displacements occurring in antiparallel directions on both sides of the perovskite blocks, resulting in an antiferroelectric-type structure. This is corroborated by the temperature-, frequency-, and field-dependent complex permittivity measurements. Pb0.64Bi0.32Fe1.04O2.675 demonstrates a remarkably high resistivity >0.1 T Ω cm at room temperature and orders antiferromagnetically below TN = 608(10) K.

Abstract: Solid solutions of BiFe1xMnxO3 (0.0 ≤ x ≤ 0.4) were prepared at ambient pressure and at 6 GPa. The ambient-pressure (AP) phases crystallize in space group R3c similarly to BiFeO3. The high-pressure (HP) phases crystallize in space group R3c for x = 0.05 and in space group Pnma for 0.15 ≤ x ≤ 0.4. The structure of HP-BiFe0.75Mn0.25O3 was investigated using synchrotron X-ray powder diffraction, electron diffraction, and transmission electron microscopy. HP-BiFe0.75Mn0.25O3 has a PbZrO3-related √2ap × 4ap × 2√2ap (ap is the parameter of the cubic perovskite subcell) superstructure with a = 5.60125(9) Å, b = 15.6610(2) Å, and c = 11.2515(2) Å similar to that of Bi0.82La0.18FeO3. A remarkable feature of this structure is the unconventional octahedral tilt system, with the primary ab0a tilt superimposed on pairwise clockwise and counterclockwise rotations around the b-axis according to the oioi sequence (o stands for out-of-phase tilt, and i stands for in-phase tilt). The (FeMn)O6 octahedra are distorted, with one longer metaloxygen bond (2.222.23 Å) that can be attributed to a compensation for covalent BiO bonding. Such bonding results in the localization of the lone electron pair on Bi3+ cations, as confirmed by electron localization function analysis. The relationship between HP-BiFe0.75Mn0.25O3 and antiferroelectric structures of PbZrO3 and NaNbO3 is discussed. On heating in air, HP-BiFe0.75Mn0.25O3 irreversibly transforms to AP-BiFe0.75Mn0.25O3 starting from about 600 K. Both AP and HP phases undergo an antiferromagnetic ordering at TN ≈ 485 and 520 K, respectively, and develop a weak net magnetic moment at low temperatures. Additionally, ceramic samples of AP-BiFe0.75Mn0.25O3 show a peculiar phenomenon of magnetization reversal.

Abstract: Electron vortex beams were only recently discovered and their potential as a probe for magnetism in materials was shown. Here we demonstrate a method to produce electron vortex beams with a diameter of less than 1.2 Å. This unique way to prepare free electrons to a state resembling atomic orbitals is fascinating from a fundamental physics point of view and opens the road for magnetic mapping with atomic resolution in an electron microscope.