Electron density distribution in Si and Ge using multipole, maximum entropy method and pair distribution function analysis

The local, average and electronic structure of the semiconducting materials Si and Ge has been studied using multipole, maximum entropy method (MEM) and pair distribution function (PDF) analyses, using X-ray powder data. The covalent nature of bonding and the interaction between the atoms are clearly revealed by the two-dimensional MEM maps plotted on (100) and (110) planes and one-dimensional density along [100], [110] and [111] directions. The mid-bond electron densities between the atoms are 0.554 e/?³ and 0.187 e/?³ for Si and Ge respectively. In this work, the local structural information has also been obtained by analyzing the atomic pair distribution function. An attempt has been made in the present work to utilize the X-ray powder data sets to refine the structure and electron density distribution using the currently available versatile methods, MEM, multipole analysis and determination of pair distribution function for these two systems.      

Structural properties of diamond fine particles and clusters prepared by detonation and decomposition of TNT

The thermal parameter B for three different particle sizes of diamond samples (bulk powder 1–4 μm, fine particle 144–195 Å and cluster 55–61 Å) was determined by the grazing incidence X-ray diffraction method. The values of B were found to be in the range 0.50–0.70 Å² for particles in the size range 195–55 Å and 0.27 Å² for 1–4 μm. All of them are larger than that of diamond bulk. A clear size dependence of B, increasing with decreasing particle size, was found. By analysing X-ray diffraction data at several temperatures the magnitude of B was found to be due to B_S (static part) instead of B_T (dynamic part). The average B_S values obtained were 0.04 Å², 0.19 Å² and 0.27 Å² for bulk powder, fine particle and cluster samples respectively. Ultrahigh resolution transmission electron microscope (TEM) observation confirmed the presence of strain, distortion, roughness and dislocation lines in many particles. TEM images of particles indicate that the clusters were not spherical in shape; they were mostly cubiform and some were truncated prism-like polyhedral. The present study reveals that the B_S component is responsible for the large B value in diamond fine particles and clusters. No clear surface local atomic distortion was found in the particles.     

Application of maximum entropy method for the study of electron density distribution in SrS, BaS and PuS using powder X-ray data

A study of the electronic structure of the three sulphides, SrS, BaS and PuS has been carried out in this work, using the powder X-ray intensity data from JCPDS powder diffraction data base. The statistical approach, MEM (maximum entropy method) is used for the analysis of the data for the electron density distribution in these materials and an attempt has been made to understand the bonding between the metal atom and the sulphur atom. The mid-bond electron density is found to be maximum for PuS among these three sulphides, being 0.584 e/Å3 at 2.397 Å. SrS is found to have the lowest electron density at the mid-bond (0.003 e/ų) at 2.118 Å from the origin leaving it more ionic than the other two sulphides studied in this work. The two-dimensional electron density maps on (100) and (110) planes and the one-dimensional profiles along the bonding direction [111] are used for these analyses. The overall and individual Debye-Waller factors of atoms in these systems have also been studied and analyzed. The refinements of the observed X-ray data were carried out using standard softwares and also a routine written by the author     

Local adsorption sites and bondlength changes in Ni(1 0 0)/H/CO and Ni(1 0 0)/CO

The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding.     

Structure analysis of the KBr(100) surface An investigation with a new method for surface analysis of insulators

The surface structure of highly insulating KBr(100) was investigated by a new technique, impact collision atom scattering spectroscopy with detection of neutrals (NICASS). By using neutral atoms in the scattering experiment as projectiles [different from conventional ion scattering (ISS)], uncertainties in the experimental data due to surface charging effects are avoided. As a result, a surface structure model for KBr(100) is presented. By comparing the experimental scattering information with computer simulated data, an inward relaxation in the first layer has been deduced. The relaxation is different for the two components K and Br: K is shifted by 0.5 Å and Br by 0.3 Å, resulting in a surface rumpling of 0.2 Å.     

The structure of oxygen on Cu(1 0 0) at low and high coverages

The local adsorption structure of oxygen on Cu(1 0 0) has been studied using O 1s scanned-energy mode photoelectron diffraction. A detailed quantitative determination of the structure of the 0.5 ML (√2×2√2)R45°-O ordered phase confirms the missing-row character of this reconstruction and agrees well with earlier structural determinations of this phase by other methods, the adsorbed O atoms lying only approximately 0.1 Å above the outermost Cu layer. At much lower coverages, the results indicate that the O atoms adopt unreconstructed hollow sites at a significantly larger O–Cu layer spacing, but with some form of local disorder. The best fit to these data is achieved with a two-site model involving O atoms at Cu–O layer spacings of 0.41 and 0.70 Å in hollow sites; these two sites (also implied by an earlier electron-energy-loss study) are proposed to be associated with edge and centre positions in very small c(2×2) domains as seen in a recent scanning tunnelling microscopy investigation.     

Inhibition of the reduction of Cr(VI) at the magnetite–water interface by calcium carbonate coatings

The effect of calcium carbonate coatings on the reduction of aqueous chromate on the magnetite(1 1 1) surface has been investigated using a combination of synchrotron based X-ray photoemission spectroscopy (PES) and X-ray absorption near edge structure (XANES) spectroscopy, along with laboratory-based powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). CaCO₃ coatings (dominantly calcite with minor quantities of aragonite and vaterite) of thicknesses ranging from 10 Å to 20 m were grown on magnetite(1 1 1) surfaces by exposure to supersaturated aqueous solutions followed by evaporation of the solution—a process that mimics pore-water evaporation in vadose zones leading to the formation of caliche and calcium carbonate coatings on mineral grains. Coating thicknesses were determined from attenuation of the Fe 2p photoemission signal by the carbonate coating. For coatings less than 15 Å thick, Cr 2p photoemission and Cr L_II, L_III-edge XANES spectra show that chromate is reduced by the underlying magnetite surface; however, as the minimum coating thickness increases beyond 15 Å, the magnetite surface becomes passivated and further chromate reduction ceases. Our findings suggest that carbonate coatings on natural magnetite grains can significantly reduce or eliminate their ability to reduce Cr(VI), which is a toxic and highly mobile environmental contaminant.     

Four-fold hollow site for S in a Ni(100) raft on NiO(100)

The reaction of H₂S with NiO(100) has been studied by polarization-dependent surface EXAFS. The results evidence reduction of the selvedge to form a Ni raft having S in four-fold sites with a S–Ni bond length of 2.21±0.02 Å. The Ni–Ni in-plane distance is 2.77±0.09 Å, representing a 6±4% contraction compared to that in NiO(100).     

Neutron diffraction and electrical conductivity studies of Li2UI6 ionic conductor

The room and high temperature structures of Li₂UI₆ have been determined using the neutron powder diffraction. It has been shown that at 300 K, the compound crystallizes in trigonal unit cell with a = B = 7.3927(8), c = 13.826(2) Å with space group P-31c. Above the phase transition occuring at 775 K, the structure transforms into monoclinic C2/m space group with unit cell constants: a = 7.733(5), B = 13.234(7), C = 7.645(4) Å, β = 110.59(3) deg. The measurement of electrical conductivity as a function of temperature has been performed. Based on the crystallographic data, a discussion of the shape of observed conductivity curve has been carried out.     

Surface and subsurface distortions of the Au{110}-(1×2) structure

The reconstruction of the Au{110}-(1×2) missing-row surface has been studied by means of the new scattering and recoiling imaging spectrometry (SARIS) technique. The three-dimensional focusing patterns observed for scattering of 4 keV He⁺, Ne⁺ and Ar⁺ ions are highly sensitive to the structure of both the surface and subsurface layers. Classical ion trajectory simulations using the scattering and recoiling imaging code (SARIC) were used to simulate the scattering patterns. Using an R-factor comparison of the experimental and simulated images, it is demonstrated that SARIS is sensitive to changes of the order of 0.02 Å in the structural parameters of this Au surface. These parameters involve interlayer spacings, row pairing and row buckling in the first-through fifth atomic layers. Results for the shallow surface layers are in general agreement with the those of previous studies. The new results include structural parameters for the deeper subsurface layers and the observation of an oscillatory behavior of the layer spacings which is damped towards deeper layers.     

Transparent conductive oxide thin films of CdTe-doped indium oxide prepared by pulsed-laser deposition

Transparent conducting oxide thin film CdTe-doped indium oxide (In₂O₃) has been grown by pulsed-laser deposition from a target of CdTe powder embedded in metallic indium. The electro-optical and structural properties were investigated as a function of oxygen partial pressure (PO₂) and substrate temperature (T_s). A film deposited at T_s=420 °C and PO₂=4 Pa shows the minimum resistivity 7.5×10⁻⁴ Ω cm, its optical transmission is 83% and the carrier concentration was 8.9×10²⁰ cm³. The optical band gap and the average roughness of that sample were 3.6 eV and 6.45 Å, respectively. X-ray diffraction studies indicated that the films were polycrystalline. This material is a good candidate for being used as transparent conductor in the CdTe–CdS solar cell.     

Rietveld refinement and electronic structure studies for the Sm2FeMnO6 new complex perovskite

We report synthesis and crystalline structure study of the Sm₂FeMnO₆ new complex perovskite, by X-ray diffraction experiments and through the application of Rietveld refinement. Results revealed the crystallization of system in a structure given by Pmn21 (#31) space group and lattice parameters a=7.621(1) Å, b=5.675(3) Å and c=5.378(3) Å. Ab initio calculations of density of states (DOS) and electronic structure were carried out for this perovskite-like system by the density functional theory (DFT) and using the full-potential linearized augmented plane waves (FP-LAPW) method. All calculations were carried out using spin polarization. Material evidences a conductor-like character, predominantly due to d–xy Fe orbital of the spin down channel. Magnetic response of system has contributions of Fe and Mn spin up orientation. The calculated magnetic moment in cell was 34.48 μ_B and the magnetic moment in interstitial was 1.54 μ_B.     

Relationship between electronic and crystal structure in Cu–Ni–Co–Mn–O spinels: Part A: Temperature-induced structural transformation

Local atomic and crystal structures around Cu and Mn atoms in Mn_1.68Cu_0.6Ni_0.48Co_0.24O₄ spinel samples fabricated by metal–organic decomposition synthesis at different annealing temperatures were investigated by X-ray absorption fine structure analysis. There are two distinct copper cations, Cu¹⁺ and Cu²⁺, both of which maintain tetrahedral coordination. The bond-length distances are Cu¹⁺–O = 2.00 Å and Cu²⁺–O = 1.80 Å. The manganese cations are for the most part octahedral. The spinels prepared at low temperature (600 °C) contain smaller (Mn⁴⁺–O = 1.88 Å) undistorted MnO₆ octahedrons corresponding to Mn⁴⁺ valence, whereas the manganese octahedrons in high-temperature materials (800 °C and higher) were larger and had a pronounced tetragonal distortion pertaining to Mn³⁺ oxidation state (Mn³⁺–O = 1.93 Å and 2.11 Å). By rising the fabrication temperatures, relative concentration of the species of Mn⁴⁺ and Mn³⁺ varies as a result of the reaction represented by Cu¹⁺ + Mn⁴⁺  Cu²⁺ + Mn³⁺, implying irreversible temperature-induced structural transformation. Atomic coordinates in the low-temperature phase are similar to those found in the ideal cubic spinel with oxygen parameter u = 0.27, whereas local environments of the Cu and Mn atom correspond to the tetragonal CuMn₂O₄ phase (space group I4₁/amd). Unlike in CuMn₂O₄, orientation of the lattice distortions is random, however, the long-range cubic spinel structure is retained at all time.     

Preparation and structural study of LaMnO3 magnetic material

We report the crystallographic parameters of LaMnO₃ obtained from X-ray diffraction data and electronic properties predictions using the density functional theory (DFT). LaMnO₃ was prepared by the citrate precursor method (CPM). The initial solution was 0.1 M of each cation and the citrate nitrate relation was one. The solution was dried at 373 K; the yielded foam was annealed at 873 K and then was characterized by X-ray diffraction. Diffraction peaks show that the space group is R-3c (#167) with a=b =5.523 Å and c=13.324 Å (rhombohedrally distorted perovskite). Structural results of the Rietveld method have a matching of 97% with that obtained from the Structure Prediction Diagnostic Software. DFT calculation reveals a half-metallic character and its magnetic moment is about 2.0 μ_B.     

Magnetization temperature dependence in Fe/Cr superlattices

We report the temperature dependence of the saturation magnetization, M_s(T), of Fe(t)/Cr(40 Å) superlattices grown on MgO(1 0 0) and MgO(1 1 0) and its variation with Fe-layer thickness (5 Å<t<80 Å). The structure was characterized by X-ray diffraction. M_s(t) vs. T, as measured by DC magnetization and ferromagnetic resonance, show a large interface effect. The origins of this effect are discussed.     

Study of the magnetism and the magnetic anisotropy of Fe layers in Ni/Fe/Ni(1 1 1) by Mössbauer spectroscopy

The hyperfine field and the magnetic anisotropy of a Fe layer as a function of thickness have been investigated in several Ni/⁵⁷Fe_x/Ni(1 1 1) trilayers with relatively thick Ni layers by Mössbauer spectroscopy. For Fe layers with thickness below 16 Å, the Mössbauer spectra show always the presence of two ferromagnetic phases with high-spin state. In the range between 6 and 8 Å, also a ferromagnetic phase with low-spin state and a paramagnetic phase have been found. The evolution of the mean hyperfine field of the ⁵⁷Fe nuclei is used to study the Fe growth. A structural FCCBCC phase transition is found to begin with an iron thickness of 8 Å. The easy direction of the magnetization is found out-of-plane for Fe interlayer with FCC structure, and perfectly in plane for Fe interlayer with BCC structure.     

Properties of solvent-free perylene iodine

The perylene iodine system was prepared by a vapour-phase reaction without the use of solvents. Compositions between peryleneI₂ and peryleneI₆ were synthesized and studied by gravimetric analysis, infrared spectroscopy, X-ray diffraction and temperature-dependent resistivity measurements. Infrared spectra in the region 400–4000 cm⁻¹ taken after different amounts of iodine were removed from the sample are distinct from perylene with new absorption lines at 1551 and 1302 cm⁻¹ and shifts of some perylene frequencies. Powder X-ray diffraction measurements indicate that the lattice is monoclinic with parameters a=11.65 Å, b=10.85 Å, c=10.1 Å, β=100.5°. The (1 0 0) reflection, which is forbidden in the space group of perylene, is observed from the compound. The material is electrically conductive and obeys Ohm's law at high temperatures. At low temperatures and high currents, nonlinear effects are observed. The conductivity of the material increases to 1.0 (Ω cm)⁻¹ at room temperature as the iodine content increases to a composition of peryleneI₆. The resistivity obeys an exponential temperature dependence.     

Interband Stark effects in InxGa1−xAs/InyAl1−yAs coupled step quantum wells

The effects of an electric field on the interband transitions in In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum wells have been investigated both experimentally and theoretically. A In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum well sample consisted of the two sets of a 50 Å In_0.53Ga_0.47As shallow quantum well and a 50 Å In_0.65Ga_0.35As deep step quantum well bounded by two thick In_0.52Al_0.48As barriers separated by a 30 Å In_0.52Al_0.48As embedded potential barrier. The Stark shift of the interband transition energy in the In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum well is larger than that of the single quantum well, and the oscillator strength in the In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum well is larger than that in a coupled rectangular quantum well. These results indicate that In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum wells hold promise for potential applications in optoelectron devices, such as tunable lasers.     

Antiferromagnetically coupled multilayers of (Co90Fe10 tF/Ru tRu)×N and (Ni81Fe19 tF/Ru tRu)×N prepared by ion beam deposition

This work describes multilayers of Co₉₀Fe₁₀ t_F/Ru t_Ru/Co₉₀Fe₁₀ t_F and Ni₈₁Fe₁₉ t_F/Ru t_Ru/Ni₈₁Fe₁₉ t_F (20 Åt_F200 Å) prepared at ambient temperature by ion beam deposition on Si/SiO₂ 3 kÅ substrates. The samples exhibited a maximum antiferromagnetic coupling with t_Ru=3.2 Å and M–H curves characterized by zero remanent magnetic moment and enhanced saturation field. Antiferromagnetic peaks were present with t_Ru17 and 30 Å.     

In-situ observation of an ordered sulfate adlayer on Au(100) electrodes

An ordered adlayer of sulfate or bisulfate has been found on the unreconstructed Au(100) surface in 0.1 M H₂SO₄ by in-situ STM. The ordered adlayer is formed concomitantly with lifting of the (hex)-reconstruction. The new structure consists of sulfate/bisulfate rows that run parallel to the edges of the islands that were created during the (hex)→(1×1) transition. The distance between the adions within the rows is 4.0±0.3 Å, and that between rows 10.4±0.7 Å, corresponding to a superstructure with a surface coverage of about 0.2.