Fine structure and magnetism of the cubic oxide compound Ni<Subscript>0.3</Subscript>Zn<Subscript>0.7</Subscript>O

The fine structure and spin system of the cubic oxide Ni_0.3Zn_0.7O compound prepared from the initial hexagonal phase by quenching a sample with a high temperature and applying an external hydrostatic pressure to it have been studied using magnetic measurements, synchrotron and X-ray diffraction. It has been revealed that the diffraction patterns of this compound contain a system of weak diffuse maxima with the wave vectors q = (1/6 1/6 1/6)2π/a and (1/3 1/3 1/3)2π/a, along with strong Bragg peaks of the cubic phase. It has been shown that the origin of the diffuse peaks is due to longitudinal and transverse displacements of ions with respect to symmetric crystallographic directions of the {111} type. The reasons for the ion displacement and specific features of the structure of the spin system of the strongly correlated oxide Ni_0.3Zn_0.7O compound have been briefly discussed.     

Neutron diffraction study of the plastic phases of polycrystalline SF6 and CBr4

An investigation of the plastic phases of polycrystalline specimens of sulphur hexafluoride (SF₆) and carbon tetrabromide (CBr₄) by neutron elastic scattering and neutron diffraction experiments is reported. A theory of neutron diffraction in plastic crystals, which treats the Bragg scattering and the diffuse scattering from a unified point of view, is developed and applied in the interpretation of the neutron results. The Debye-Scherrer peaks are analysed, both by a cumulant expansion technique and a cubic harmonic analysis, to determine the crystal structures of the plastic phase which are found to be body-centred cubic (space group Im3_m) for SF₆ and face-centred cubic (space group Fm3m) for CBr₄. The bond-orientation distribution function, f(Ω), has maxima in the <100> directions for SF₆ and in the <110> directions for CBr₄. Since, in both cases, f(Ω) is appreciably different from zero for all orientations, it is apparent that significant thermal reorientation takes place in both these crystals. The translational and librational displacements in CBr₄ are exceptionally large and give rise to extensive diffuse scattering which is analysed on the basis of a simple Einstein model. The model predicts that the centre-of-mass thermal vibration and the orientational disorder give approximately equal contributions to the total diffuse scattering. The calculated scattering is in good agreement with experiment for all wave vector transfers outside the range 2 to 3 Å^-1. Inside this range discrepancies occur which are interpreted as evidence for the existence of orientational short-range order in CBr₄.     

Superstructure of atomic displacements in cubic compounds Zn0.9Ni0.1S and Zn0.7Ni0.3O

The fine structure of cubic compounds Zn_0.9Ni_0.1S and Zn_0.7Ni_0.3O has been discussed. At room temperature, their diffraction patterns contain, along with intense Bragg reflections of the face-centered cubic phase, superstructure diffuse maxima demonstrating the ordering of short-wavelength deformations due to Jahn-Teller nickel ions.     

The structure of the glass phase of Rb1−x(ND4)xD2PO4

X-ray scattering techniques have been used to study the diffuse scattering from a single crystal of Rb_1–x(ND₄)_xD₂PO₄ withx=0.65. This system has a structural glass phase at low temperatures resulting from the competing ferroelectric interactions of RbD₂PO₄ and antiferroelectric interactions of (ND₄)D₂PO₄. The diffuse scattering shows a broad peak with a maximum occurring at a wavevector of about 0.3a ^*, and the intensity of these peaks is surprisingly different for wavevectorsq on opposite sides of the Bragg reflections. A model of the D bonding is developed which suggests that the diffuse scattering arises from the interaction between ferroelectric displacements alongc, ferroelectric displacements alongb, and transverse acoustic modes polarized alongb andc. The model accounts for the incommensurate wavevector and, qualitatively, for the intensity of the diffuse scattering around different Bragg reflections. The temperature dependence of the scattering is also measured.     

Edge of disorder

Polyanilines belong to a family of electronic polymers. Due to a wide range of variable parameters in the synthesis of polyanalines, a variety of samples with different physical properties can be achieved. Different investigators have identified the degree of crystallinity for different varieties of polyanilines. They have classified them into two classes of emeraldine forms. In these structural investigations, the traditional “concept of the two phase system” was used for differentiating the crystalline phase. Recently, it has been shown that washing the emeraldine base (EB) by NMP or THF will establish two different X-ray patterns. The X-ray pattern of the sample washed with THF shows a limited number of Bragg lines superimposed on the broad diffuse halos. Other patterns only indicated broad diffuse halos. These experimental facts do not advocate the “two phase system model”, especially with scarce Bragg reflections. We have set-up an elegant prototype for X-ray diffractometry which allows us to obtain a high resolution X-ray pattern from polymers with coherent intrinsic backgrounds. Formally, this coherent background was excluded for polymer structural identification. Nevertheless, we have introduced a new method of separating the reflected lines from a coherent background. The interference functions F(K) of the coherent background were obtained applying this novel technique. The advantage of our method of separation is verified by comparing the background of F(K) with the F(K) of the sample washed with NMP. Fourier inversion is used to identify the short range order of the atoms responsible for the diffuse scattering. This result enabled us to choose a standard state of disorder in polymers. This standard state of randomness can be considered as the edge of disorder. By defining this reference state of randomness, it can be seen that the atomic arrangements of long and fast changing structural chains correspond best to the random array model rather than the two phase system model. The novel experiment and analysis technique presented here offer a possibility of application of structural studies to many common polymers, all of which have the characteristic of the diffuse halo underlying the diffraction lines. Received: 7 May 1997 / Revised: 2 July 1998 / Accepted: 25 September 1998     

Validity of the Darwin and Ewald reflectivity functions in the range of the far wings: Neutron diffraction study

Using the neutron time-of-flight (TOF) technique, we have examined the reason for the dramatic departure of experimental results from the Darwin and Ewald reflectivity functions in the far wings. The scattering from Si(111) single- and triple-bounce crystals set up at the Bragg angle θB=24.4° was dispersed in time-of-flight in the wavelength range 0.3<λ<3.0 Å. The experiment reveals admixture of the single-scattered Bragg peaks and thermal diffuse scattering (TDS) originating at λ<0.6 Å in the spectrum registered from a triple-bounce crystal. Our study explains the discrepancy between the theory and the experimental results reported in many neutron studies and proves the validity of the Darwin and Ewald theories in the far wings.     

Diffuse scattering and phason fluctuations in the Zn-Mg-Sc icosahedral quasicrystal and its Zn-Sc periodic approximant

We report on the absolute scale measurement of the x-ray diffuse scattering in the ZnMgSc icosahedral quasicrystal and its periodic approximant. Whereas the diffuse scattering in the approximant is purely accounted for by thermal diffuse scattering, an additional signal is observed in the quasicrystal. It is related to phason fluctuations as indicated by its Q(2)(per) dependence. Moreover, when compared to previous measurements carried out on the i-AlPdMn phase, we find that the amount of diffuse scattering is smaller in the i-ZnMgSc phase, in agreement with larger phason elastic constants in this phase. This is confirmed by the observation of a large number of weak Bragg peaks having a high Q(per) reciprocal space component.     

Fine structure of the cubic semiconductor compound Zn0.9Ni0.1S

The fine structure of a single crystal of the Zn_0.9Ni_0.1S cubic compound synthesized by the chemical transport method has been investigated at room temperature using thermal neutron diffraction. It has been found that the diffraction patterns of this compound, along with strong Bragg reflections of the facecentered cubic phase, include a system of diffuse maxima, which indicate the occurrence of a local deformation of the cubic structure by the Jahn-Teller nickel ions. Results of this experiment have been compared with the previously obtained data for the lightly doped Zn_{1 ? x} Ni _x Se single crystal (x = 0.002).     

Spatial topology of local nano scale inhomogeneity of crystal structure Zn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se (<Emphasis Type="Italic">x</Emphasis> = 0.001)

The method of thermal neutron diffraction is used to study a structural state of crystal Zn_{1 − x} Fe _x Se (x = 0.001) obtained in the sphalerite modification. It was found that the diffractive pictures of a cubic crystal contain the regions of diffuse scattering in the vicinity of Bragg reflections of an initial crystal lattice. It was shown that the diffuse scattering effects were caused by the local transverse displacements of atoms in a crystal lattice induced by Fe²⁺ ions. It is concluded that a static tetragonal-type Jahn-Teller effect exists in a ZnSe alloy doped by magnetoactive iron ions.     

In situ Raman and photoluminescence study on pressure‐induced phase transition in C60 nanotubes

Single crystalline C₆₀ nanotubes having face‐centered‐cubic structure with diameters in the nanometer range were synthesized by a solution method. In situ Raman and photoluminescence spectroscopy under high pressure were employed to study the structural stabilities and transitions of the pristine C₆₀ nanotubes. A phase transition, probably because of the orientational ordering of C₆₀ molecules, from face‐centered‐cubic structure to simple cubic structure occurred at the pressure between 1.46 and 2.26 GPa. At above 20.41 GPa, the Raman spectrum became very diffuse and lost its fine structure in all wavenumber regions, and only two broad and asymmetry peaks initially centered at 1469 and 1570 cm^–1 were observed, indicating an occurrence of amorphization. This amorphous phase remained to be reversible until 31.1 GPa, and it became irreversible to the ambient pressure after the pressure cycle of 34.3 GPa was applied. Copyright © 2012 John Wiley & Sons, Ltd.     

Time-domain interferometry using synchrotron radiation applied to diffusion in ordered alloys

Time-domain interferometry of synchrotron radiation (TDI) has recently been used as a tool for investigating diffusion in glasses. This work deals with an extension of this technique to ordered structures. In a TDI experiment performed on the B2 alloy CoGa at the APS the intensity scattered into Bragg directions showed no detectable quasielastic signal. Experimental lower limits of the elastic contribution are given. They are in accordance with the coherent scattering function derived in this paper. This result indicates that TDI can be applied to diffusion in crystalline solids, e.g. intermetallic alloys, by using diffuse scattering. Requirements and limitations of diffuse scattering experiments are discussed. Received 21 September 2000 and Received in final form 13 December 2000     

Pressure‐induced anomalous phase transformation in nano‐crystalline dysprosium sesquioxide

The phase transformation in nano‐crystalline dysprosium sesquioxide (Dy₂O₃) under high pressures is investigated using in situ Raman spectroscopy. The material at ambient was found to be cubic in structure using X‐ray diffraction (XRD) and Raman spectroscopy, while atomic force microscope (AFM) showed the nano‐crystalline nature of the material which was further confirmed using XRD. Under ambient conditions the Raman spectrum showed a predominant cubic phase peak at 374 cm⁻¹, identified as F_g mode. With increase in the applied pressure this band steadily shifts to higher wavenumbers. However, around a pressure of about 14.6 GPa, another broad band is seen to be developing around 530 cm⁻¹ which splits into two distinct peaks as the pressure is further increased. In addition, the cubic phase peak also starts losing intensity significantly, and above a pressure of 17.81 GPa this peak almost completely disappears and is replaced by two strong peaks at about 517 and 553 cm⁻¹. These peaks have been identified as occurring due to the development of hexagonal phase at the expense of cubic phase. Further increase in pressure up to about 25.5 GPa does not lead to any new peaks apart from slight shifting of the hexagonal phase peaks to higher wavenumbers. With release of the applied pressure, these peaks shift to lower wavenumbers and lose their doublet nature. However, the starting cubic phase is not recovered at total release but rather ends up in monoclinic structure. The factors contributing to this anomalous phase evolution would be discussed in detail. Copyright © 2010 John Wiley & Sons, Ltd.     

Dynamic Deformations of the Crystal Lattice of Sphalerite in the Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se(<Emphasis Type="Italic">x</Emphasis>=0.01) Compound

Local distortions of the crystal lattice of the semiconductor compound Zn_{1 − x} Co _x Se (x = 0.01) have been investigated using thermal neutron diffraction. It has been found that the diffraction patterns of the crystal contain regions of diffuse scattering in the vicinity of strong Bragg peaks at 300 K. As the temperature decreases, the intensity of diffuse scattering effects substantially decreases. Arguments in favor of the assumption that the origin of the diffuse scattering is caused by the Jahn-Teller vibronic effect are presented.     

An inhomogeneously distorted state of the crystal structure of a Zn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>Se cubic crystal

The structural state of a bulk Zn_0.95Fe_0.05Se cubic crystal grown by the chemical transport method from the gas phase has been investigated using thermal neutron diffraction at room temperature. It has been found that the measured neutron diffraction patterns of the crystal, in addition to structural Bragg peaks, contain a clearly identified system of superstructure reflections with the wave vector k = (1/3 1/3 1/3)2π/a (where a is the parameter of the cubic unit cell), which is interpreted as a clear evidence of the incipient transition state preceding the concentration phase transformation fcc ? hcp. It has been shown that the resulting structural state includes an inhomogeneous microstrain field with the possible appearance of long-wavelength modulations based on the initial sphalerite structure.     

Selective properties of volume phase holograms in photorefractive crystals

The paper deals with the selective properties (both angular and spectral) of volume phase holograms in birefringent and cubic optically active photorefractive crystals. It is shown that in birefringent crystals of LiNbO₃ type, the spectral selectivity of the grating depends remarkably on the type of diffraction (isotropic or anisotropic) and the polarization of the reconstructing plane light wave. In cubic optically active crystals the peculiarities of diffraction reveal themselves in a fine structure of differently polarized peaks in the Bragg maximum that can be easily observed, in particular in Bi₁₂SiO₂₀ samples with a thickness d ≈ 8 mm.     

High pressure behavior of nano-crystalline CeO2 up to 35 GPa: a Raman investigation

The present paper reports the results of in situ Raman studies carried out on nano-crystalline CeO₂ up to a pressure of 35 GPa at room temperature. The material was characterized at ambient conditions using X-ray diffraction and Raman spectroscopy and was found to have a cubic structure. We observed the Raman peak at ambient at 465 cm^?1, which is characteristic of the cubic structure of the material. The sample was pressurized using a diamond anvil cell using ruby fluorescence as the pressure monitor, and the phase evolution was tracked by Raman spectroscopy. With an increase in the applied pressure, the cubic band was seen to steadily shift to higher wavenumbers. However, we observed the appearance of a number of new peaks around a pressure of about 34.7 GPa. CeO₂ was found to undergo a phase transition to an orthorhombic α -PbCl₂-type structure at this pressure. With the release of the applied pressure, the observed peaks steadily shift to lower wavenumbers. On decompression, the high pressure phase existed down to a total release of pressure.     

Signal distortion noise in volume phase holograms

Signal distortion noise in volume phase holograms is analysed for the case in which the object beam consists of two plane waves. It is shown that, for a given (on-Bragg) signal diffraction efficiency, the magnitude of the signal distortion noise is inversely proportional to the square of crystal thickness. Furthermore, as a function of the angular position of the reconstruction beam, the signal distortion noise has two peaks: one at the Bragg angle and the other at a deviation ₀ from the Bragg angle, where ₀ is a function of relative angles between the components of the object beam and the reference beam. The on-Bragg peak of the signal distortion noise is experimentally located for volume phase holograms recorded in Fe-doped LiNbO₃. The measured angular position is found to be in accord with the calculated value.     

Effects of annealing in nitrogen atmosphere and HCl-etching on the photoluminescence spectra of spray-deposited CdS:In thin films

The aim of this work is to find the effect of processing on the photoluminescence (PL) of spray-deposited CdS:In thin films. So the PL spectra of the as-deposited, annealed and HCl-etched CdS:In thin films prepared by the spray pyrolysis (SP) technique were recorded at T = 23 K. The yellow and red bands were observed in the spectrum of the as-deposited film beside bands with weaker intensity in the infrared region. The PL signal was weakened by annealing in nitrogen atmosphere at T = 400 °C and HCl-etching. A deconvolution peak fit was established to find the effects of these treatments on the different bands. The spectrum of the as-deposited film was deconvoluted to 12 peaks, which were reduced to 6 peaks after both treatments. It was found that both treatments have approximately the same effects on the PL spectra; that is they removed most of the peaks and shoulders in the red and infrared regions and attenuated most of the peaks in the yellow region. Some peaks were blue-shifted after annealing which was explained by the growth of nanocrystallites due to the thermal stress that results from the different expansion coefficients of the film and the substrate. These changes were accompanied by a phase change from the mixed (cubic and hexagonal) phase to the hexagonal phase as shown in the X-ray diffractograms.     

Phase transitions at high pressure in tetracyanoethylene

We report in situ x-ray diffraction studies in tetracyanoethylene (TCNE) at high pressure using diamond anvil cell (DAC) at Elettra synchrotron source, Trieste, Italy. Experiments were performed with both the polymorphic phases (monoclinic and cubic) of TCNE as the starting phase. While starting with monoclinic (the high temperature stable) TCNE, it was found that the Bragg peaks get broadened with increase of pressure and above 5 GPa only few broad peaks remained to be observed. On release of pressure from 6.4 GPa, when the sample started turning black, the diffraction pattern at ambient pressure corresponds to cubic, the other crystalline phase of TCNE. Results reconfirm the monoclinic to cubic transition at high pressure but via an intermediate ‘disordered’ phase. This settles a number of conflicting issues. TCNE represents only system, which undergoes transition from one crystalline to another crystalline phase via a ‘disordered’ metastable phase at high pressure. When the starting phase was cubic (the low temperature stable) no apparent phase transition was observed up to 10.8 GPa.     

Application of a pnCCD in X‐ray diffraction: a three‐dimensional X‐ray detector

The first application of a pnCCD detector for X‐ray scattering experiments using white synchrotron radiation at BESSY II is presented. A Cd arachidate multilayer was investigated in reflection geometry within the energy range 7 keV < E < 35 keV. At fixed angle of incidence the two‐dimensional diffraction pattern containing several multilayer Bragg peaks and respective diffuse‐resonant Bragg sheets were observed. Since every pixel of the detector is able to determine the energy of every incoming photon with a resolution ΔE/E? 10^?2, a three‐dimensional dataset is finally obtained. In order to achieve this energy resolution the detector was operated in the so‐called single‐photon‐counting mode. A full dataset was evaluated taking into account all photons recorded within 10⁵ detector frames at a readout rate of 200 Hz. By representing the data in reciprocal‐space coordinates, it becomes obvious that this experiment with the pnCCD detector provides the same information as that obtained by combining a large number of monochromatic scattering experiments using conventional area detectors.