Synthesis and X‐ray powder diffraction studies of semiconducting alloys in the system AgCd2‐xZnxGaS4

X‐ray powder technique was used in the investigation of AgCd₂GaS_4–'AgZn₂GaS₄' section to determine the region of AgCd₂GaS₄‐based solubility. It was established that the solid solution forms up to 75 mol.% 'AgZn₂GaS₄'. The refinement of AgCd_0.5Zn_1.5GaS₄ structure was performed. This alloy crystallizes in orthorhombic structure (space group Pmn2₁ ) with unit cell parameters a =0.78772(2), b =0.67221(2), c =0.64019(2) nm, V =0.33899(3) nm³. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Automatic detection and high resolution fine structure analysis of conic X‐ray diffraction lines

The presented method demonstrates a first step in the development of a high resolution “Residual stress microscope” and facilitates through the implementation of largely automated procedures a fast detection of diffraction lines in the form of conic sections. It has been implemented for, but is not exclusively used for the Kossel technique and the “X‐ray Rotation‐Tilt Method” (XRT). The resulting multifaceted evaluable data base of many X‐ray diffraction radiographies can be used not only for the systematic analysis of anomalies in diffraction lines (reflection fine structure), but also for direct calculation and output of precision residual stress tensors. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X‐ray,synchrotron, and neutron diffraction analysis of Roman cavalry parade helmet fragment

A partially corroded fragment of the neck guard of a Roman cavalry helmet excavated in the former military camp of Gerulata, a part of the Limes Romanus on the River Danube, was analysed by laboratory X‐ray, synchrotron and neutron powder diffraction. The approximate phase composition determined by the neutron diffraction of the bulk, 82% (wt) of the copper alloy phase, 12 % (wt) of cuprite and 6% of nantokite indicate a significant degree of corrosion of the artefact. Elemental EDX analysis of cleaned surface showed that the chemical composition of the original alloy is 78 to 82 % (wt) of Cu and 21.4 to 16.5 % of Zn with minute amounts of Sn, Si and S. High contents of Cu and Zn with the negligible amount of Sn showed that the body of the helmet was made of brass and not of bronze as expected before. The amount of zinc in the copper alloy calculated from the refined lattice parameter agrees fairly well with the value determined by EDX. The most abundant phase in the synchrotron powder diffraction pattern of the corrosion products scrapped from the artefact is cuprite, but presence of atacamite, malachite, brochantite, nantokite, mixed Cu‐Zn hydroxyl carbonates and probably also of simonkolleite (Zn₅(OH)₈Cl₂·H₂O) have been detected. In contrast, the X‐ray pattern taken directly from the surface of the artefact is dominated by atacamite with some traces of malachite and quartz. Because the penetration depth of laboratory X‐rays is in order of tens of microns, the phase analysis based only on a diffraction pattern taken from a surface can lead to erroneous conclusions concerning the phase composition of the patina. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Observation of the δ to ε Zr‐hydride transition by in‐situ synchrotron X‐ray diffraction

We investigate the formation and dissolution of hydrides in commercially pure zirconium powder in‐situ using high‐energy synchrotron X‐ray radiation. Experimental results showed a continuous phase transition between the δ and ε zirconium hydride phases with indication of a second order phase transformation.     

X‐ray diffraction refinement of the crystal structure of anosovite prepared from leucoxene

The crystal structure of anosovite, (Ti_1.69Al_0.26Fe_0.05)³⁺(Ti_0.97Zr_0.03)⁴⁺O₅, prepared by carbothermal reduction of leucoxene under vacuum at 1450°C has been refined by Rietveld method using powder X‐ray diffraction data. It was found that it represents slightly monoclinically deformed pseudobrookite type structure with lattice parameters a = 9.8111 Å, b = 3.7509 Å, c = 9.9468 Å, β = 90.628°. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X‐ray diffraction and magnetization studies of BiFeO3 multiferroic compounds substituted by Sm3+, Gd3+, Ca2+

The multiferroic compounds Bi_0.9Sm_0.1FeO₃, Bi_0.9Gd_0.1FeO₃, Bi_0.9Ca_0.1FeO₃, Bi_0.9Sm_0.05Ca_0.05FeO₃, and Bi_0.9Gd_0.05Ca_0.05FeO₃ were prepared by the conventional ceramic method and were characterized by X‐ray diffraction, vibrating sample magnetometry, and differential scanning calorimetry. The compounds were found to have the rhombohedral perovskite‐like structure, accompanied by a small residual Bi₂Fe₄O₉ impurity phase. Magnetic hysteresis loops with enhanced remnant magnetization and coercive field were obtained for the Gd‐containing compounds. The improvement of magnetic behavior of the Gd‐containing compounds is thought to arise mainly from the partial suppression of the spiral spin structure and the stronger interaction between magnetic ions. The magnetic transition temperatures of the compounds were found to be in the range 300‐310 °C. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spatially resolved X‐ray diffraction as a tool for strain analysis in laterally modulated epitaxial structures

Spatially resolved X‐ray diffraction (SRXRD) is applied for micro‐imaging of strain in laterally modulated epitaxial structures. In GaAs layers grown by liquid phase epitaxial lateral overgrowth (ELO) on SiO₂‐masked GaAs substrates a downward tilt of ELO wings caused by their interaction with the mask is observed. The distribution of the tilt magnitude across the wings width is determined with μm‐scale spatial resolution. This allows measuring of the shape of the lattice planes in individual ELO stripes. If a large area of the sample is studied the X‐ray imaging provides precise information on the tilt of an individual wing and its distribution. In heteroepitaxial GaSb/GaAs ELO layers local mosaicity in the wing area is found. By the SRXRD the size of microblocks and their relative misorientation were analyzed. Finally, the SRXRD technique was applied to study distribution of localized strain in AlGaN epilayers grown by MOVPE on bulk GaN substrates with AlN mask. X‐ray mapping proves that by mask patterning strain in AlGaN layer can be easily engineered, which opens a way to produce thicker, crack‐free AlGaN layers with a higher Al content needed in GaN‐based laser diodes. All these examples show that high spatial and angular resolutions offered by SRXRD makes the technique a powerful tool to study local lattice distortions in semiconductor microstructures. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Divergent beam hard X‐ray diffraction used for the simultaneous imaging of radiographic and crystallographic information

A transmission method and experimental set‐up were developed for the nondestructive characterisation of the quality of bulk single crystals/ large coarsely crystalline polycrystals or components. The method works by combination of X‐ray projection microscopy (X‐ray shadow microscopy) with bremsstrahlung interferences from divergent beam hard X‐rays, in order to form simultaneously enlarged radiographic images and crystallographic information in one measurement. The method and equipment are patent registered. In the paper some of the first results are presented. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure refinement of the ternary compound Cu2SnTe3 by X‐ray powder diffraction

The ternary compound Cu₂SnTe₃ crystallizes in the Imm2 (Nº 44) space group, Z = 2, with a = 12.833(4) Å, b = 4.274(1) Å, c = 6.043(1) Å, V = 331.5(1) ų. Its structure was refined from X‐ray powder diffraction data using the Rietveld method. The refinement of 25 instrumental and structural variables led to R_p = 10.2%, R_wp = 11.8%, R_exp = 7.7%, R_B = 10.6%, S = 1.6 and χ² = 2.6, for 5501 step intensities and 163 independent reflections. This compound is isostructural with Cu₂GeSe₃, and consists of a three‐dimensional arrangement of slightly distorted CuTe₄ and SnTe₄ tetrahedra connected by common corners. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X‐ray powder diffraction study of the semiconducting alloy Cu2Cd0.5Mn0.5GeSe4

The structure of the semiconducting alloy Cu₂Cd_0.5Mn_0.5GeSe₄ was refined from an X‐ray powder diffraction pattern using the Rietveld method. The present alloy crystallizes in the wurtz‐stannite structure, space group Pmn2₁ (N^o 31), and unit cell parameters values of a = 8.0253(2) Å, b = 6.8591(2) Å, c = 6.5734(2) Å and V = 361.84(2) ų. The structure exhibits a three‐dimensional arrangement of slightly distorted CuSe₄, Cd(Mn)Se₄ and GeSe₄ tetrahedras connected by corners. © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

An X‐ray powder diffraction study of the microstructural evolution on heating 3:2 and 2:1 mullite single‐phase gels

Single‐phase gels with compositions 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂ were prepared by gelling mixtures of aluminium nitrate and tetraethylorthosilicate. Gels were fast heated at different temperatures between 900°C and 1600°C. The phase transformation and microstructural changes of both mullite precursor gels over the temperature range were followed by X‐ray powder diffraction (XRD), lattice parameter determination (LP), and scanning and transmission electron microscopies (SEM and TEM). The distribution of crystallite sizes and strains were determined by linewidth refinements of X‐ray diffraction patterns using the integral breadth method of Langford and the Warren‐Averbach analysis. XRD of both heated gels showed the formation of crystalline mullite single phase. Some amount of glassy phase coexisted with mullites at low temperatures, i. e. below 900°C. The compositional range of mullites formed on heating gels at temperatures between 900°C and 1600°C was dependent on the starting nominal composition of gels. SEM and TEM micrographs of both heated gels below 1200°C showed the formation of small, discrete, prismatic, well‐shaped nanocrystals in a very ordered arrangement. The size of these nanocrystals was dependant on the nominal composition of gels and increased on rising the heating temperature of gel precursors. The microstructural features obtained from linewidth refinement results of X‐ray diffraction patterns also allowed to suggest the formation of prismatic a little elongated nanocrystals at temperatures below 1200°C. Microstrain values were small and only displayed a relatively significant value for mullites processed at 900°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,spectroscopic studies and ab‐initio structure determination from X‐ray powder diffraction of bis‐(N‐3‐acetophenylsalicylaldiminato)copper(II)

The synthesis, spectroscopic studies and crystal structure determination from X‐ray powder diffraction have been carried out for bis‐(N‐3‐acetophenylsalicylaldiminato)copper(II). The structure is triclinic, space group P1 with unit cell dimensions a = 11.817(1) Å, b = 12.087(1) Å, c = 9.210(1) Å, α = 102.62(1)°, β = 111.16(1)°, γ = 86.15(1)°, V = 1197.0(2)ų, Z = 2. The structure has been solved by Monte Carlo simulated annealing approach and refined by GSAS package. The final Rp value was 8.68%. The coordination geometry around the copper atom in the complex is intermediate between square‐planar and tetrahedral with two salicylaldimine ligands in trans arrangement. Intermolecular C–H…O hydrogen bonds between molecules related by translation generate infinite chains along [010] direction. The molecular chains are linked via additional C–H…O hydrogen bonds to form a three‐dimensional supramolecular network. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure refinement of CuxAg1‐xInTe2 bulk material determined from X‐ray powder diffraction data using the Rietveld method

The influence of the Cu‐content in the quaternary compounds Cu_xAg_1‐xInTe₂ (0 ≤ x ≤1) on the structural properties of the bulk material was discussed. Bulk ingot materials of Cu_xAg_1‐xInTe₂ solid solutions (x = 0.0, 0.25, 0.50, 0.75 and 1.0) have been synthesized by fusion of the constituent elements in the stoichiometric ratios in vacuum‐sealed silica tubes. The materials compositions were confirmed by using energy dispersive analysis of X‐rays (EDAX). X‐ray powder diffraction measurements were performed for all the prepared samples at 300 K in step scanning mode. The analysis of X‐ray data has indicated that the crystal structure of the prepared materials with different compositions is single‐phase polycrystalline materials corresponding to the tetragonal chalcopyrite structure with space group I 2d. The crystal structural parameters were refined by Rietveld method using the Full Prof program. The refined lattice constants (a and c), anion positional parameter, u, and the determined bond distances and angles were found to vary with composition, x, attaining zero tetragonal distortion at x ≈ 0.75, which corresponds to an ideal tetragonal unit cell. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Control of the phase composition and morphology of a Cu‐Sb eutectic alloy via liquid‐liquid structure transition

The current paper focuses on the solidification characteristics of a Cu‐Sb eutectic alloy in its different liquid states. Liquid alloy resistivity‐temperature patterns suggest an irreversible temperature‐induced liquid‐liquid structure transition (TI‐LLST), and a reversible TI‐LLST occurred during the heating‐cooling runs. A set of solidification experiments was conducted based on the results. The irreversible TI‐LLST caused an enhanced solidification undercooling, increased solidification rate, refined regular eutectic morphologies, and absence of a pre‐eutectic Cu₂Sb phase. The reversible TI‐LLST resulted in different phase compositions and eutectic structures. The mechanisms behind these transitions are also briefly discussed.     

High temperature x‐ray diffraction studies of zirconia thin films prepared by reactive pulsed laser deposition

Zirconium oxide thin films have been deposited on Si (100) substrates at room temperature at an optimized oxygen partial pressure of 3x10^‐2 mbar by reactive pulsed laser deposition. High temperature x‐ray diffraction (HTXRD) studies of the film in the temperature range room temperature‐1473 K revealed that the film contained only monoclinic phase at temperatures ≤ 673 K and both monoclinic and tetragonal phases were present at temperatures ≥ 773 K. The tetragonal phase content was significantly dominating over monoclinic phase with the increase of temperature. The phase evolution was accompanied with the increase in the crystallite size from 20 to 40 nm for the tetragonal phase. The mean thermal expansion coefficients for the tetragonal phase have been found to be 10.58x10^‐6 K^‐1 and 20.92x10^‐6K^‐1 along a and c‐axes, respectively. The mean volume thermal expansion coefficient is 42.34x10^‐6 K^‐1 in the temperature range 773‐1473 K. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A neutron diffraction study of the phase transition of fully deuterated triglycine sulphate (ND2CD2COOD)3.D2SO4

Using neutron single crystal and powder diffraction, the first thorough investigation of the structure of fully deuterated triglycine sulphate, (ND₂CD₂COOD)₃.D₂SO₄ is presented, including its evolution with T, through its structural phase transition. This includes new precise structural parameters determined at several key temperatures above and below T_C using single crystal diffraction, and for the first time a parametric study has been undertaken over a wide temperature range — from 4 to 500 K in 2 K steps. It was found that fully deuterated TGS shows a structure consistent with hydrogenous TGS and partially deuterated TGS. The evolution of several key hydrogen bond lengths suggests that weakening of the H‐bond network with T is crucial in decoupling the polarising glycine molecules from the other glycines and allowing the long‐range ferroelectric order to break down. A new parameterisation of the phase transition is demonstrated. Contrary to results of physical properties measurements, there is no evidence of a second low temperature phase transition in TGS – no low temperature anomalies were observed in the crystal structure.     

A comparison of the KOSSEL and the X‐ray Rotation‐Tilt Technique

There are world‐wide efforts to analyse micron regions of compact samples by means of X‐ray diffraction (“X‐ray Microdiffraction”). Two micro diffraction procedures, the KOSSEL technique excited by electron or synchrotron radiation beams and the new X‐ray Rotation‐Tilt Method (XRT), are compared to show their possibilities and limitations. Some selected examples of new applications are presented.     

Crystal structures of X‐phase in the Sb–Te binary alloy system

It is well known that the Sb–Te binary system has a large number of incommensurately or commensurately modulated structures between Sb and Sb₂Te₃ compounds. These structures, which are long‐period trigonal stacking structures, possess their own modulation period γ, according to their composition in the thermal equilibrium. However, the structure of sputtered Sb–Te films with various compositions between the two compounds at both ends formed in a non‐thermal equilibrium showed smaller γ values, than those expected from their compositions without exception. A smaller γ value implies that its structure is closer to that of Sb with the shortest period in all Sb–Te modulated structures. With increase in temperature, all these transient structures with smaller γ, however, became stable, accompanying an increase of γ to acquire their original modulated structures.     

Determination of lateral block size and mosaicity of crystals using X‐ray diffraction from the edge of the sample

In this paper a novel lateral block size characterization method based on X‐ray diffractometry (XRD) is presented. The developed method based on scans of plans perpendicular to the surface visible from the edge of the sample and subconsequent numerical analysis based on Scherrer equation. In presented investigations as a reference sample bulk GaN substrate fabricated by AMMONO Ltd. was used. The GaN layers deposited on sapphire substrate were investigated as a case of study. Moreover, a method of analyzing the magnitude of the tilt and twist mosaicity based on the scans of rocking curves and reciprocal lattice maps (RLM) from the edge of sample is presented. As an example for this methodology highly mosaicited SiC crystal was used. Presented approach allows to directly determine the value of the angular deviation of mosaicity in a direction perpendicular and parallel to the sample surface.     

In‐situ investigation of the temperature dependent structural phase transition in CuInSe2 by synchrotron radiation

The temperature dependent structural phase transition from the tetragonal chalcopyrite like structure to the cubic sphalerite like structure in CuInSe₂ was investigated by in‐situ high temperature synchrotron radiation X‐ray diffraction. The data were collected in 1K steps during heating and cooling cycles (rate 38 K/h). The Rietveld analysis of the diffractograms led us to determine the temperature dependence of the lattice parameters, including the tetragonal deformation, |1‐η|, and distortion |u‐¼| (η=c/2a, a and c are the tetragonal lattice constant; u is the anion x‐coordinate). The thermal expansion coefficients α_a and α_c of the tetragonal lattice constant which are related to the linear thermal expansion coefficient α_L were obtained, as were α_a of the cubic lattice constant, also α_u and α_η. The transition temperature is clearly identified via a strong anomaly in α_L. The temperature dependence of the anion position parameter was found to be rather weak, nearly α_u∼0, whereas α_η increases slightly. However, both increase strongly when approaching to within 10 K of the transition temperature (the critical region) and |1‐η| as well as |u‐¼| go to zero with |T‐T_trans|^0.2 approaching the phase transition. The cation occupancy values, derived from the Rietveld analysis, remain constant below the critical region. Close to the transition temperature, the number of electrons at the Cu site increases with a dercrease in the number of electrons at the In site with increasing temperature, indicating a Cu‐In anti site occupancy, which is assumed to be the driving force of the phase transition. At the transition temperature 67% of Cu⁺ were found to occupy the Me1 site with a corresponding 67% of In³⁺ at the Me2 site. Although full disorder is reached with 50%, this level seems to be high enough that the phase transition takes place. The order parameter of the phase transition, goes with |T‐T_trans|^β to zero with the critical exponent β=0.35(7) which is in good agreement to the critical exponent β=0.332 calculated for order‐disorder transitions according to the Ising model. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)