Structure and magnetic order in Fe2+xV1-xAl

We present a detailed structural investigation via neutron diffraction of differently heat treated samples Fe2VAl and Fe2+xV1-xAl. Moreover, the magnetic behaviour of these materials is studied by means of mSR and Mossbauer-experiments. Our structural investigation indicates that quenched Fe2VAl, exhibiting the previously reported "Kondo insulating like" behaviour, is off-stoichiometric (6%) in its Al content. Slowly cooled Fe2VAl is structurally better ordered and stoichiometric, and the microscopic magnetic probes establish long range ferromagnetic order below TC = 13K, consistent with results from bulk experiments. The magnetic state can be modelled as being generated by diluted magnetic ions in a non-magnetic matrix. Quantitatively, the required number of magnetic ions is too large as to be explained by a model of Fe/V site exchange. We discuss the implications of our findings for the ground state properties of Fe2VAl, in particular with respect to the role of crystallographic disorder.Comment: accepted for publication in J. Phys.: Condens. Matte

Determination of the miscibility gap in the solid solutions series of methylammonium lead iodide chloride

Perovskites are widely known for their enormous possibility of elemental substitution, which leads to a large variety of physical properties. Hybrid perovskites such as CH3NH3PbI3 MAPbI3 and CH3NH3PbCl3 MAPbCl3 are perovskites with an A[XII]B[VI]X[II] 3 stoichiometry, where A is an organic molecule, B is a lead II cation and X is a halide anion of iodine or chlorine. Whereas MAPbCl3 crystallizes in the cubic space group Pm3m, MAPbI3 is in the tetragonal space group I4 mcm. The substitution of I by Cl leads to an increased tolerance against humidity but is challenging or even impossible due to their large difference in ionic radii. Here, the influence of an increasing Cl content in the reaction solution on the miscibility of the solid solution members is examined systematically. Powders were synthesized by two different routes depending on the I Cl ratio. High resolution synchrotron X ray data are used to establish values for the limits of the miscibility gap which are 3.1 1.1 mol MAPbCl3 in MAPI and 1.0 1 mol MAPbI3 in MAPCl. The establishment of relations between average pseudo cubic lattice parameters for both phases allows a determination of the degree of substitution from the observed lattice parameter

Lattice Instability and Competing Spin Structures in the Double Perovskite Insulator Sr2FeOsO6

The semiconductor Sr2FeOsO6, depending on temperature, adopts two types of spin structures that differ in the spin sequence of ferrimagnetic iron - osmium layers along the tetragonal c-axis. Neutron powder diffraction experiments, 57Fe M\"ossbauer spectra, and density-functional theory calculations suggest that this behavior arises because a lattice instability resulting in alternating iron-osmium distances fine-tunes the balance of competing exchange interactions. Thus, Sr2FeOsO6 is an example for a double perovskite, in which the electronic phases are controlled by the interplay of spin, orbital, and lattice degrees of freedom.Comment: 8 Pages, 3 Figure

Two stage cracking of metallic bi layers on polymer substrates under tension

Cu Nb nanoscale metallic multilayers have been extensively investigated to understand how their mechanical behavior is influenced by the individual layer thickness. The general observed trend is that the yield stress of the multilayer increases with decreasing layer thickness. Important mechanical behaviors that have not been studied in depth are the fracture of these multilayers and adhesion energy between the multilayer films and their substrate. Here, the influences of the layer thickness, layer order, and initial residual stresses of Cu Nb multilayers on polyimide were examined using in situ x ray diffraction and confocal laser scanning microscopy under tensile loading. With these techniques, it was possible to calculate the stresses developing in the individual materials and measure buckles that could be used to evaluate the interfacial adhesion. Layer thickness, deposition order, and the initial residual stresses were not shown to influence the initial fracture strains of the Cu Nb multilayer systems under tensile loading conditions. However, the adhesion energy between the multilayer and substrate was affected by the layer deposition order and by the initial residual stresse

Effect of annealing on the size dependent deformation behavior of thin cobalt films on flexible substrates

The effect of film thickness as well as the influence of heat treatment on the deformation behavior of thin cobalt films 50 2000 nm on polyimide substrates was investigated using various tensile tests. Straining under an optical light microscope provides information about the fracture strain and cracking behavior. The annealed films exhibit enhanced crack onset strains between 4 and 7 compared to the as deposited films with fracture strains of 1 2 . This is partly achieved by a mechanically induced martensitic phase transformation of cobalt from the face centered cubic FCC to the hexagonal closed packed HCP phase. Thereby, it was shown that the heat treatment can be used to increase the amount ofmetastable FCC phase. Complementary synchrotron diffraction experiments were used to determine the lattice strains which initially increase during straining. After reaching a maximum, the lattice strains decrease in the case of the as deposited films due to crack formation and in the case of the annealed films due the strain induced phase transformation and localized plastic deformation in the form of necks. At higher engineering strains, the formation of cracks is also observed in the heat treated samples. Additionally, a decrease of the maximum lattice strain could be found for the HCP phase below a film thickness of 200 nm and grain size of 50 nm in the as deposited films which is caused by crackin

Crystal and magnetic structure of the La1−x_{1-x}Cax_{x}MnO3_{3} compound (x=0.8,0.85)(x=0.8,0.85)

We studied the crystal and magnetic structure of the La$_{1-x}$Ca$_{x}$MnO$_{3}$ compound for $x=0.8$ and $x=0.85$. At T=300 K both samples are paramagnetic with crystallographic symmetry $Pnma$. At low temperatures they undergo a monoclinic distortion from orthorhombic $Pnma$-type structure with $a_p\sqrt{2}\times 2a_p\times a_p\sqrt{2}$ to a monoclinic structure with ($a_p\sqrt{2}\times 2a_p\times a_p\sqrt{2}$, $\beta=90+\epsilon\sim 91.4^{\rm o}$) and $P2_1/m$ space group below $T_N$. The onset of the structural transformation coincides with the development of the $C$-type long range antiferromagnetic order with propagation vector ${\bf k}=({1/2},0,{1/2})$. The monoclinic unit cell allowed us to determine the direction of the Mn magnetic moment with respect to the crystallographic axes: it is perpendicular to the propagation vector, ${\bf m}\perp {\bf k}=({1/2},0,{1/2})$. The amplitude of the ordered magnetic moment at $T=1.6$ K is found to be $2.53(2)$ and $2.47(2)\mu_{B}$ for $x=0.8$ and 0.85, respectively.Comment: In press (Phys. Rev B 01 Feb 2002

In Situ Monitoring of Unique Switching Transitions in the Pressure Amplifying Flexible Framework Material DUT 49 by High Pressure 129Xe NMR Spectroscopy

The pronounced flexibility of special metal amp; 8722;organic frameworks MOFs , so called soft porous crystals, is attracting increasing research interest. Studies of host amp; 8722;guest interactions in such materials are especially powerful if the measurements are performed in situ. 129Xe NMR spectroscopy is favorable because it provides characteristic, structure sensitive parameters such as chemical shifts. The combination of highpressure xenon adsorption with 129Xe NMR spectroscopy was used to elucidate the adsorption induced phase transitions in the recently discovered pressure amplifying framework material DUT 49, showing a unique negative gas adsorption NGA transition. In the open pore state, DUT 49op exhibits a hierarchical pore system involving both micro and mesopores. After reaching a critical relative pressure of ca. 0.15, adsorbed xenon induces mesopore contraction, resulting in a purely microporous contracted pore phase. This contraction is accompanied by release of xenon from the mesopores. Further increase of the pressure initiates the recovery of the mesopores without any indication of a structural intermediate in the NMR spectra. According to the NMR data, the structural transition induced by xenon is a collective, stepwise phenomenon rather than a continuous process. This is the first time that NGA has been studied by directly monitoring the guest and its interaction with the host framewor

Cooperative light-induced breathing of soft porous crystals via azobenzene buckling

Although light is a prominent stimulus for smart materials, the application of photoswitches as light-responsive triggers for phase transitions of porous materials remains poorly explored. Here we incorporate an azobenzene photoswitch in the backbone of a metal-organic framework producing light-induced structural contraction of the porous network in parallel to gas adsorption. Light-stimulation enables non-invasive spatiotemporal control over the mechanical properties of the framework, which ultimately leads to pore contraction and subsequent guest release via negative gas adsorption. The complex mechanism of light-gated breathing is established by a series of in situ diffraction and spectroscopic experiments, supported by quantum mechanical and molecular dynamic simulations. Unexpectedly, this study identifies a novel light-induced deformation mechanism of constrained azobenzene photoswitches relevant to the future design of light-responsive materials

Crystal and magnetic structure transitions in BiMnO3 d ceramics driven by cation vacancies and temperature

The crystal structure of BiMnO3 d ceramics has been studied as a function of nominal oxygen excess and temperature using synchrotron and neutron powder diffraction, magnetometry and differential scanning calorimetry. Increase in oxygen excess leads to the structural transformations from the monoclinic structure C2 c to another monoclinic P21 c , and then to the orthorhombic Pnma structure through the two phase regions. The sequence of the structural transformations is accompanied by a modification of the orbital ordering followed by its disruption. Modification of the orbital order leads to a rearrangement of the magnetic structure of the compounds from the long range ferromagnetic to a mixed magnetic state with antiferromagnetic clusters coexistent in a ferromagnetic matrix followed by a frustration of the long range magnetic order. Temperature increase causes the structural transition to the nonpolar orthorhombic phase regardless of the structural state at room temperature; the orbital order is destroyed in compounds BiMnO3 d d lt; 0.14 at temperatures above 470