Cu-Zn disorder in Cu2ZnGeSe4: A complementary neutron diffraction and Raman spectroscopy study

The crystal structure of the quaternary compound semiconductor Cu₂ZnGeSe₄ (CZGSe) was investigated by the complementary use of neutron diffraction, and Raman spectroscopy. The powder sample, which resulting from wavelength dispersive X-ray spectroscopy (WDX) turned out to be single phase Cu-rich CZGSe, was synthesized by solid state reaction of the pure elements in an evacuated silica tube at 700 °C. Raman spectroscopy confirmed the homogeneity and phase purity of the sample, in addition, the kesterite type structure was suggested. Rietveld analysis of the neutron diffraction data confirmed that the compound crystallizes in the tetragonal kesterite type structure. The refined site occupancy factors were used to determine the average neutron scattering lengths of the cation sites, giving insights into cation distribution and finally point defect types. Thus it has been shown, that additional to the Cu_Zn-Zn_Cu anti-site defects in the lattice planes at z=¼ and ¾ (Cu-Zn disorder) also the off-stoichiometry type related point defects like Cu_i and Cu_Zn occur in Cu-rich CZGSe.     

The dynamics of water in nanoporous silica studied by dielectric spectroscopy

Broad-band dielectric spectroscopy is used to investigate the dynamics of hydration water on the surface of the cylindrical pores of a nanostructured silica material (MCM-41, with pore diameter of 3.2 nm) at various hydrations, in the temperature range 250-150 K. We focus our attention on orientational relaxations that shift from 0.5 MHz at 250 K to less than 1 Hz at 150 K. The measurements distinguish the relaxation of the hydroxyl groups at the surface of silica from the orientational dynamics of hydration water which strongly depends on the degree of hydration. Although it is significantly faster than the dynamics of water in ice, the orientational relaxation of non-freezing water has an activation energy comparable to that in ice when the hydration layer is complete and approximately two-molecule thick.     

Phase transitions in BaCeO3: neutron diffraction and Raman studies

Polycrystalline samples and small single crystals of the perovskite BaCeO₃ were studied by neutron diffraction and Raman spectrometry between 300 and 1200 K. The controversy about the phase transitions originally deduced from our previous Raman study and those observed since by neutron diffraction by Knight has stimulated this work. Pretransitional effects which are detected by Raman much before long-range ordering takes place can partly explain the above disagreement. A continuous monitoring of the structural changes by neutron diffraction and by Raman spectroscopy including polarization analysis has allowed discussion of the transition mechanisms: The first transition Pnma–Imma takes place at 573 K and is of second order. Although some modes soften when the temperature is raised as in many of these perovskite compounds the transition is likely partly displacive partly order–disorder. The Raman modes which disappear transform in modes at the X point of the Brillouin zone of the Imma phase. The second transition Imma–R c takes place at 673 K and is first order. The last transition R c–Pm3m occurs above 1200 K and the transition temperature which can be deduced by extrapolation to zero Raman intensity is in good agreement with neutron results. This second order transition is progressive and begins at about 400 K, the intermediate R c structure appearing as an attempt for slowing down the structural evolution toward the cubic perovskite form.     

Normalisation and assessment of neutron diffraction data from liquids

A couple of normalisation criteria have been proposed to assess liquid structure data over the past decade. In this paper, a critical examination of these and other plausible criteria is made. Neutron diffraction data from liquid krypton measured by Clayton and Heaton is used to study these criteria. It is shown that if the structure factorS (Q)=1+γ (Q) satisfies the Krogh-Moe relation, namely whereQ is the wavevector transfer andρ ₀ the mean atomic number density,S (Q) is properly normalised. Subjecting such data to the other criteria would reveal, however, the quality of data in so far as systematic errors and/or termination errors are concerned. If the data is measured with reasonable accuracy to sufficiently large values of the wavevector transfer all these criteria would assess the quality of the data to almost the same extent. This is established in this paper by improving and extending the liquid krypton data by procedures similar to that of Kaplow, Strong and Averbach and subjecting this revised data to the various criteria. It is concluded, thereby, that (i) one can study the neutron diffraction data from liquids using any of the criteria mentioned in the paper to improve the quality of the data and (ii) for normalisation purposes the simple relation {ie328-2} would suffice.     

Magnetic order in CaMn2Sb2 studied via powder neutron diffraction

This paper reports a neutron powder diffraction study of CaMn₂Sb₂ in the temperature range of 20–300 K. Collinear long-range antiferromagnetic order of manganese ions occurs below 85 K, where a transition is observed in the dc magnetic susceptibility measured with a single crystal. Short-range magnetic order, characterized by a broad diffraction peak corresponding to a d-spacing of approximately 4 Å (2θ≈22°), is also observed above 20 K. The long-range antiferromagnetic order is indexed by the chemical unit cell, indicating a propagation vector k=(0 0 0), with a refined magnetic moment of 3.38 μ_B at 20 K. Two possible magnetic models have been identified, which differ in spin orientation for the two manganese ions with respect to the ab plane. The model with spins oriented at a 25±2° angle relative to the ab plane gives an improved fit compared to the other model in which the spins are constrained to the ab plane. Representational analysis can account for a model involving a c-axis component only by the mixing of two irreducible representations.     

A Mössbauer spectroscopy and neutron diffraction study of magnetostrictive,melt-spun Fe–Ga alloy ribbons

Ribbons of Fe_100−xGa_x (x=15, 17.5, 19.5 and 22.5) were prepared by rapid solidification from the melt. ⁵⁷Fe Mössbauer spectroscopy and high resolution neutron diffraction have revealed that Fe_100−xGa_x alloys with x=15 and 17.5 have the disordered bcc (A2) structure even after annealing, but the alloy with x=19.5 developed the short-range ordered D0₃ phase when annealed. The x=22.5 alloys showed mainly D0₃ phase with a fraction of bcc phase. A fraction of the bcc phase transformed into D0₃ phase and the long-range ordering of D0₃ phase was improved after annealing. ⁵⁷Fe Mössbauer spectra showed no observable L1₂ phase in any samples even though less than 1% volume of L1₂ phases has been found in the annealed samples by neutron diffraction. The additional absorption at hyperfine field of 25 T in x=22.5 samples was regarded as a result of imperfect D0₃ structure, rather than L1₂ phase.     

Spherical neutron polarimetry applied to spin-echo and time-of-flight spectroscopy

The changes in direction of the neutron spin that take place on scattering by a magnetic interaction vector are highly dependent on their relative directions. In some circumstances, without zero-field polarimeter, it is impossible to distinguish between a simple depolarisation and a rotation of the polarisation vector.Motivated by the investigation of chiral magnetic fluctuations, we have implemented the third-generation zero-field polarimeter Cryopad on the neutron spin-echo spectrometer SPAN at the Helmholtz Centre Berlin (HCB). We present the method and the limitations of this novel technique that is now available on IN15 at the ILL.The huge progress accomplished with ³He neutron spin filters/flippers are going to facilitate the exploitation of polarised beams at spallation sources. Zero-field polarimeters like Cryopad are used routinely at several steady-state sources but their design would be inefficient at a pulse source. We have investigated the possibility to implement a zero-field polarimeter on a time-of-flight spectrometer. We propose a design that would lead to a better efficiency and present the finite element calculations.     

Developments of nano-polycrystalline diamond anvil cells for neutron diffraction experiments

ABSTRACT

A new high pressure cell for neutron diffraction experiments using nano-polycrystalline anvils is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to ～82?GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of Fe₃O₄ at ambient conditions using this cell and discuss the current limitation and future developments.     

The kiel/berlin pressure cells for neutron powder diffraction

Abstract

Two piston/cylinder type pressure cells for neutron powder diffraction are presented. They provide a large sample volume and hence allow rapid data collection at moderate flux neutron sources. Structure refinements from the diffraction data are possible. The maximum attainable pressure is above 2 GPa for Ti/Zr zero-scattering pressure cylinders. Both cells may be equipped with a micro-furnace. This allows measurement up to 700 K, simultaneously to the application of pressure. The low temperature setup for the cell-I is presented which will allow experiments down to 1·5K.     

A new high P-T cell for neutron diffraction up to 7 GPa and 2000 K with measurement of temperature by neutron radiography

Abstract

This paper reports developments to enable neutron diffraction at simultaneous high temperatures and pressures using the Paris-Edinburgh cell. These include a new design of a cell assembly with internal heating. One of the novel features of our system is the use of neutron radiographic methods for measurement of temperature. Fully refinable neutron diffraction patterns obtained by time of flight technique with our apparatus are found to be of comparable quality to previous high-pressure studies at ambient temperatures. In this paper we describe the procedures for the generation and measurement of pressure and temperature and illustrate the quality of the data which can be obtained. The present system may be used on a routine basis for experiments up to 7 GPa and temperature approaching 2000 K. Current attempts are discussed for extending these measurements to a wider domain of pressures and temperatures.     

Investigation of Nd2CuO4 crystal structure at high pressure by neutron diffraction

Abstract

The crystal structure of Nd₂CuO₄ has been studied by neutron diffraction at pressure up to 5 Gpa. The volume compressibility value was determined as 5·6·10^?3/Gpa. The decrease of positional parameter of neodymium at high pressure has been observed. This structural change is explained by pressure induced neodymium ions charge increase.     

Temperature dependent structural changes in liquid benzene studied using neutron diffraction

We present neutron diffraction data for liquid benzene measured as a function of temperature from 10°C to 70°C. Isotopic substitution and Empirical Potential Structure Refinement were used to obtain a complete spatial and orientational understanding of nearest neighbour correlations. We find an increased prevalence of nearest neighbour molecules where the angle between the aromatic planes is perpendicular, and at an angle of around 60°, when the temperature is reduced. There is no significant change in prevalence parallel stacked arrangements of nearest neighbour molecules as a function of temperature. The structure of the increased local order is consistent with structural motifs observed in benzene dimers and clusters from quantum chemistry calculations in the literature.     

Some peculiarities for grazing incidence neutron diffraction from 3D near-surface nanostructures

Neutron diffraction at grazing incidence was simulated for the regularly ordered nanostructures on the surface and in the near-surface volume of a homogeneous matrix. Silicon was used as a matrix material and nanoparticles consisting of gold or nickel. This allowed obtaining a good scattering contrast between the matrix and nanoparticles and, as a result, high contrast diffraction patterns. It is shown that the modified kinematic approximation which takes into account the refraction of a neutron wave at the interface makes it possible to obtain a reasonable agreement with the available experimental data. In addition, it was demonstrated that in contrast to the traditional diffraction on point-like scattering centers, some unusual systematic absences could be observed due to the experiment geometric conditions and the finite geometric sizes of the nanoparticles. The results demonstrate that modified kinematic approximation can be successfully used to model non-specular neutron scattering from near-surface nanostructures and thereby facilitate the interpretation of experimental results.     

A tof neutron diffraction system for high pressure and low temperature

Abstract

Time-of-flight method of neutron diffraction is applied for materials under high pressure and low temperature. Extra-scattering from the pressure cell is reduced by geometrical design and by shielding with boron-plastics. Temperature is controled by adjusting the supply of liquid nitrogen: Successive transformations with pressure are observed in heavy ice.     

Magnetization and neutron diffraction studies on FeCrP

Crystal structure and magnetic behaviour of FeCrP have been investigated using magnetization and neutron diffraction measurements. FeCrP crystallizes in orthorhombic FeZrP type structure (P_nma space group,Z = 4) in which Cr atoms occupy the pyramidal site and Fe atoms occupy the tetrahedral site with total preference. Structural parameters including positional parameters have been refined. The refined values of positional parameters for Fe and Cr are quite different from those in FeZrP. The nature of magnetization-temperature curve is suggestive of antiferromagnetic nature withT _N = 280 (±10) K. Preliminary analysis of neutron diffraction pattern at 13 K is indicative of a rather complicated magnetic structure.     

Low-temperature neutron diffraction study of the crystal and magnetic phase transitions in DyCrO4

The crystal and magnetic structures of DyCrO₄ were studied using neutron powder diffraction. Complete diffraction data at 3.6, 17, 27, and 40 K show that a crystal structural phase transition from tetragonal I4₁/amd to orthorhombic Imma symmetry is found to take place between 27 and 40 K. This transition does not involve a significant change in the unit cell volume. Strong ferromagnetic reflections are observed at 3.6 and 17 K, and can be fit well using the magnetic model of space group Im'ma', with the moments of both Dy³⁺ and Cr⁵⁺ ions aligning along the y-axis. Detailed temperature dependent magnetic intensities of 101/011 and 211/121 peaks reveal a Curie temperature of T_c=22.35(15) K.     

Challenges in neutron spin echo spectroscopy

With the new brilliant neutron sources and the developments of novel optical elements, neutron spin echo (NSE) spectroscopy evolves to tackle new problems and scientific fields. The new developments pave the way to complex experimental set-ups such as the intensity modulated variant of NSE (IMNSE), a powerful technique which was introduced some 20 years ago but found limited use up to now. With the new compact supermirror or He³ polarizers IMNSE becomes attractive for a broad range of applications in magnetism, soft matter and biology. A novel development along this line is the polarimetric NSE technique, which combines IMNSE and the zero-field polarimeter Cryopad to access components of the scattered polarization that are transverse to the incoming polarization. Polarimetric NSE is the method of choice for studying chiral fluctuations, as illustrated by new results on the reference helimagnet MnSi.     

Surface oxidation of a Melinex 800 PET polymer material modified by an atmospheric dielectric barrier discharge studied using X-ray photoelectron spectroscopy and contact angle measurement

Surface properties of a Melinex 800 PET polymer material modified by an atmospheric-pressure air dielectric barrier discharge (DBD) have been studied using X-ray photoelectron microscopy (XPS) and contact angle measurement. The results show that the material surface treated by the DBD was modified significantly in chemical composition, with the highly oxidised carbon species increasing as the surface processing proceeds. The surface hydrophilicity was dramatically improved after the treatment, with the surface contact angle reduced from 81.8° for the as-supplied sample to lower than 50° after treatment. Post-treatment recovery effect is found after the treated samples were stored in air for a long period of time, with the ultimate contact angles, as measured, being stabilised in the range 58-69° after the storage, varying with the DBD-treatment power density. A great amount of the C-O type bonding formed during the DBD treatment was found to be converted into the CO type during post-treatment storage. A possible mechanism for this bond conversion has been suggested.