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AgNbO3 is one of the prominent lead-free antiferroelectric (AFE) oxides, which readily exhibits a field-induced AFE to ferroelectric phase transition and thus a high energy storage density. The solid-statesynthesis of AgNbO3 is considered difficult and an oxidizing atmosphere is typically employed during AgNbO3 processing,on the premise that oxygen can prevent possible decomposition of the silver oxide at high temperatures. However, details about the influence of processing parameters on the functional properties of AFE AgNbO3 are insufficiently understood. In this work, the solid-state reaction of a stoichiometric AgO and Nb2O5 mixture was investigated. We found that ball milling can convert AgO into metallic Ag, which is beneficial for lowering the reaction temperature for the formation of the perovskite phase to 500‒600℃. Moreover, the influence of the processing atmosphere (air, O2, and N2) was investigated by thermal analysis and in situ X-ray diffraction. Since the reaction between Ag and Nb2O5 to form AgNbO3 requires oxygen uptake, AgNbO3 was only found to form in air and O2, whereby the kinetics were faster in the latter case. All the sintered AgNbO3 samples exhibited a similar crystallographic structure, although the samples processed in O2 had a lower oxygen vacancy concentration. Despite this, well-defined AFE double polarization loops were obtained in all cases. Our results indicate that decomposition of sliver oxide during ball milling is beneficial for the solid-state reaction, while a pure O2 atmosphere is not essential for the synthesis of high-quality AgNbO3. These findings may simplify the processing and facilitate further research of AgNbO3-based antiferroelectrics.

The original version of this Article contained an error where Figures 3 and 4 were interchanged. The original Figures 3 and 4 and accompanying legends appear below. The original Article has been corrected. (Figure presented.). CA Gökce

We present a detailed study of solid state dewetting choosing epitaxial bismuth films on silicon as a model system. Exploiting both diffraction and imaging methods, we determine atomistic parameters like unit cell coverage, lattice spacings and gradients thereof through the analysis of x-ray diffraction crystal truncation rods. A different dewetting behavior of samples with and without strain gradient is revealed. Additionally, we discuss possible reasons for the impeding influence of a strain gradient, such as a reduced interface energy or increased step edge diffusion energy barrier, which we quantify by using a Johnson-Mehl-Avrami-Kolmogorov model. A model for the step edge self diffusion of Bismuth is presented.

Chemical ordering in NiMn-based Heusler alloys with magnetostructural phase transition is crucial for understanding the physics of the phase transition. In the new field of all-d-metal Ni(Co)MnTi Heusler alloys, the experimental determination of chemical order is challenging due to the low difference in scattering power of the different elements. Here, we report a combined approach of neutron and x-ray diffraction for an analysis of chemical order in Ni(Co)MnTi alloys and show that no Heusler-typical L 2 1 order between Ti and Mn is present. Furthermore, Co and Ni atoms do not exhibit order among them; however, the phase transition of Co containing samples can be shifted significantly by changing the degree of B 2 order with proper heat treatment. Using first-principles calculations, we reveal how the structural and magnetic sub-systems depend on the degree of B 2 disorder.

Competition between antiferromagnetic (AFM), paramagnetic (PM), and ferromagnetic (FM) states in ${\mathrm{La}}_{0.9}{\mathrm{Ce}}_{0.1}{\mathrm{Fe}}_{12}{\mathrm{B}}_{6}$ compound is investigated by means of temperature- and magnetic field-dependent x-ray diffraction, magnetization, linear thermal expansion, and magnetostriction experiments. It is shown that both AFM and PM phases get converted into the FM phase via a first-order metamagnetic transition, which is accompanied by a huge forced-volume magnetostriction $\mathrm{\ensuremath{\Delta}}V/V(25\phantom{\rule{0.16em}{0ex}}\mathrm{K},\phantom{\rule{0.16em}{0ex}}6\phantom{\rule{0.16em}{0ex}}\mathrm{T})=1.15%$. X-ray powder diffraction reveals a magnetic field-induced crystallographic phase transition from a $R\overline{3}m$ rhombohedral (AFM, PM) to a $C2/m$ monoclinic (FM) structure. A peculiarly anisotropic lattice expansion as well as giant negative thermal expansion with a volumetric thermal expansion coefficient ${\ensuremath{\alpha}}_{V}=\ensuremath{-}193\ifmmode\times\else\texttimes\fi{}{10}^{--6}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{--1}$ are observed. These findings point to the significance of magnetoelastic effects in this metamagnet and illustrate the strength of the coupling between lattice and spin degrees of freedom in the ${\mathrm{La}}_{0.9}{\mathrm{Ce}}_{0.1}{\mathrm{Fe}}_{12}{\mathrm{B}}_{6}$ intermetallic compound.

Magnetoelastic coupling, structural, magnetic, electronic transport, and magnetotransport properties of ${\mathrm{La}}_{0.85}{\mathrm{Ce}}_{0.15}{\mathrm{Fe}}_{12}{\mathrm{B}}_{6}$ have been studied by a combination of macroscopic [magnetization, electrical resistivity, and magnetoresistance (MR)] and microscopic temperature- and magnetic-field-dependent x-ray powder diffraction measurements. The itinerant-electron system ${\mathrm{La}}_{0.85}{\mathrm{Ce}}_{0.15}{\mathrm{Fe}}_{12}{\mathrm{B}}_{6}$ exhibits an antiferromagnetic (AFM) ground state and multiple magnetic transitions, AFM-ferromagnetic (FM) and FM-paramagnetic (PM), triggered by changes in both temperature and magnetic fields. At low temperatures, the field-induced first-order AFM-FM metamagnetic phase transition is discontinuous, manifesting itself by extremely sharp steps in magnetization as well as in MR and is accompanied by large magnetic hysteresis. A remarkably large negative MR of \ensuremath{-}73% was discovered. In addition, the time evolution of the electrical resistivity displays a colossal spontaneous jump when both the applied magnetic field and temperature are constant. Diffraction data reveal a magnetic-field-induced structural phase transition associated with the AFM-FM and PM-FM transformations. The lattice distortion is driven by magnetoelastic coupling and converts the crystal structure from rhombohedral ($R\overline{3}m$) to monoclinic $(C2/m)$. The AFM and PM states are related to the rhombohedral structure, whereas the FM order develops in the monoclinic symmetry. A huge volume magnetostriction of \ensuremath{\sim}0.9% accompanies this symmetry-lowering lattice distortion. Meanwhile, a highly anisotropic thermal expansion involving giant negative thermal expansion with an average volumetric thermal expansion coefficient ${\ensuremath{\alpha}}_{V}=\ensuremath{-}195\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}6}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ was observed. The consistency seen in these different experimental data constitutes direct evidence of the strong correlations between charge, magnetic, and crystallographic degrees of freedom in this material.

The development of magnetocaloric materials represents an approach to enable efficient and environmentally friendly refrigeration. It is envisioned as a key technology to reduce CO2 emissions of air conditioning and cooling systems. Fe-Rh has been shown to be one of the best-suited materials in terms of heat exchange per material volume. However, the Fe-Rh magnetocaloric response depends on its composition. Hence, the adaptation of material processing routes that preserve the Fe-Rh magnetocaloric response in the generated structures is a fundamental step towards the industrial development of this cooling technology. To address this challenge, the temperature-dependent properties of laser synthesized Fe-Rh nanoparticles and the laser printing of Fe-Rh nanoparticle inks are studied to generate 2D magnetocaloric structures that are potentially interesting for applications such as waste heat management of compact electrical appliances or thermal diodes, switches, and printable magnetocaloric media. The magnetization and temperature dependence of the ink’s γ-FeRh to B2-FeRh magnetic transition is analyzed throughout the complete process, finding a linear increase of the magnetization M (0.8 T, 300 K) up to 96 Am2/kg with ca. 90% of the γ-FeRh being transformed permanently into the B2-phase. In 2D structures, magnetization values of M (0.8 T, 300 K) ≈ 11 Am2/kg could be reached by laser sintering, yielding partial conversion to the B2-phase equivalent to long-time heating temperature of app. 600 K, via this treatment. Thus, the proposed procedure constitutes a robust route to achieve the generation of magnetocaloric structures.

Ferromagnetic Fe3Sn, Fe5Sn3 and Fe3Sn2 single crystals were synthesized using the reactive flux technique. Derived from single crystal x-ray diffraction and Transmission Electron Microscopy (TEM), a new structural model is proposed for the Fe5Sn3 crystals - the threefold twinning of an orthorhombic unit cell with (3 + 1) dimensional space group Pbcm(α00)0s0. The spontaneous magnetization (Ms) and the anisotropy constants K1 and K2 of Fe3Sn, Fe5Sn3 and Fe3Sn2 single crystals were determined in a wide temperature range using M(H) dependencies and a modified Sucksmith-Thompson technique. Ms and K1 were also evaluated in the framework of Density Functional Theory (DFT) and an overall good agreement was observed between the calculated and experimental results. Furthermore, a critical evaluation of different analytical models for the assessment of magnetocrystalline anisotropy was performed, which are restricted to the analysis of uniaxial magnetic domain patterns, and it is shown that such high-throughput techniques can lead to unrealistic results. Finally, a DFT high-throughput screening of the Fe-Sn phase diagram was used to identify Fe-Sn based phases with potential to be stabilized upon alloying, and their magnetization and magnetocrystalline anisotropy were evaluated. The results show that a similar strong anisotropy as observed in Fe3Sn may also be found in other Fe-Sn based phases, having higher potential to be used as hard magnetic material.

Materials with strongly coupled magnetic and structural transitions can display a giant magnetocaloric effect, which is of interest in the design of energy-efficient and environmentally friendly refrigerators, heat pumps, and thermomagnetic generators. There also exist, however, a class of materials with no known magnetostructural transition that nevertheless show remarkable magnetocaloric effects. MnB has been recently suggested as such a compound, displaying a large magnetocaloric effect at its Curie temperature (570 K) showing promise in recovering low-grade waste heat using thermomagnetic generation. In contrast, we show that isostructural FeB displays very similar magnetic ordering characteristics, but is not an effective magnetocaloric. Temperature- and field-dependent diffraction studies reveal dramatic magnetoelastic coupling in MnB, which exists without a magnetostructural transition. No such behavior is seen in FeB. Furthermore, the magnetic transition in MnB is shown to be subtly first-order, a...

We present a study of the impeding influence of a capping, native oxide layer on the solid state dewetting of thin bismuth films on silicon(111) in vacuum. We study the temperature dependence of the film thickness and strain of the thin films through the analysis of crystal truncation rods of clean and capped bismuth films. This analysis reveals a dewetting temperature difference of 40 ° C between capped and uncapped films. The results are supported by scanning electron microscopy and x-ray photoelectron spectroscopy experiments. Furthermore, a model for the retarding effect of the oxide layer and the final shape of the thin film is presented.

We present a detailed study of solid state dewetting choosing epitaxial bismuth films on silicon as a model system. Exploiting both diffraction and imaging methods, we determine atomistic parameters like unit cell coverage, lattice spacings and gradients thereof through the analysis of x-ray diffraction crystal truncation rods. We use a Johnson-Mehl-Avrami-Kolmogorov model to describe the kinetics of the dewetting process on an atomic scale. The role of a vertical strain gradient, that impedes solid state dewetting, is revealed and a detailed model for the atomic jump diffusion during dewetting is presented.

The aim of the acousto-elastic theory was to measure ultrasonic velocity changes which characterize the mechanical nonlinearity of a prestressed material. In this context, our purpose is to tabulate the invariant third-order elastic coefficients including the piezoelectric, electrostrictive, and dielectric corrections. The investigation is limited to trigonal and hexagonal crystalline structures, which represent the most often encountered symmetry classes for the piezoelectric materials. In fact, the enumeration includes the high-order tensors involved in the analysis of nonlinear behaviors associated with various electromechanical coupling forms. The obtained results are extensions to previous calculations in this area which bring some corrections to certain published combinations related to the invariance rules. The numerical procedure built using the software MATLAB is based on coordinate system transformations performed on the eigenbasis of their corresponding symmetry axes three- and sixfold. In this purpose, we found some contradictions between our results and a former paper published in Journal of Applied Physics. To the authors’ knowledge, rechecking of the relationships between the invariant third-order constants and comparison with this last reference has not been discussed yet. The relationships between the invariant third-order coefficients presented in this work provide a number of attractive properties for use in mechanical and physical applications.

This article reports the development and characterization of a laboratory-based high-resolution X-ray powder diffractometer equipped with a 5.5 T magnet and closed-cycle helium cryostat that is primarily designed for the investigation of magneto-structural phase transitions. Unique features of the diffractometer include the position-sensitive detector, allowing the collection of an entire diffraction pattern at once, and the high energy resolution with Mo Kα1radiation. The ability to utilize a lower energy resolution but higher photon flux by switching to an X-ray mirror monochromator makes it a versatile setup for a variety of compounds. In this contribution, details of the design and performance of the instrument are presented along with its specifications.

The influence of germanium on microstructure, crystallography, and thermal stability of the eutectic Cr-Cr3Si alloy was investigated. Fine eutectic microstructures could be preserved but slightly degenerated when up to 2 at.% Si was substituted by Ge. A transition from eutectic to peritectic microstructure composed of primary dendrites and A15 Cr3Si matrix was observed when higher amounts of Ge were added. X-ray diffraction results showed no limit for substitution of Si and Ge in the studied composition range. The lattice parameter of both Cr solid-solution and A15 silicide increased with increasing the Ge/Si ratio. A macro was developed for the ImageJ program to automate the quantitative microstructural image analysis. Results showed that Ge addition increases the A15 phase fraction of the two-phase alloys. Microstructural investigations on annealed alloys at 1350 °C demonstrated that the coarsening of both binary Cr-Cr3Si and ternary Cr-Cr3(Si, Ge) is interface-controlled. Although Ge addition to the eutectic alloy offered an isotropic microstructure, it decreased the thermal stability by degeneration of the lamellar structure.

Acoustoelastic (AE) effect of a mechanically pre-stressed layered piezoelectric structure of BST is investigated. Two samples of BST (Ba0.8Sr0.2TiO3) thin films were grown by rf-magnetron sputtering deposition techniques on a Pt(100)/MgO(100) and Pt(110)/MgO(110) substrates. The crystallographic orientation of BST thin films is analyzed by X-ray diffraction (XRD). A laser acoustic waves (LA-waves) technique is used to generate surface acoustic waves (SAW) propagating in both samples for epitaxial relationship examination. We perform an extended model to determine the residual stress and strain in BST films using the (XRD) X-ray diffraction measurement and the piezoelectric constitutive equations. Theoretical analysis of (SAW) propagation in a pre-stressed layered piezoelectric structure is achieved to discuss the effect of the measured residual stresses of BST films on the propagation behavior of Rayleigh waves and on the coupled electromechanical factor.

A series of CaTiO3: Eu3+, Eu3+/Dy3+, Eu3+/Dy3+/xGd3+, and Eu3+/Dy3+/Gd3+/M (M = Li+, Mg2+, Sr2+) perovskite micro phosphors have been prepared via solid-state reaction method. The structural, morphological, and spectral properties were systematically characterized by XRD, MEB, FT-IR, UV-V absorption, PL, and PLE. The prepared micro powders exhibited a single-phase orthorhombic structure with Pbnm space group. The MEB images revealed grain size ranging from 5 to 20 μm. The CaTiO3 band gap energy decreases by introducing the doping elements and changes from 3.581 eV for the undoped to 2.847 eV for Eu/Dy/Gd/Li doped sample. The photoluminescence properties of Eu3+, Eu3+/Dy3+, and Eu3+/Dy3+/xGd3+ doped CaTiO3 phosphors were investigated through excitation and emission spectra. Under 365 nm excitation, Eu3+/Dy3+ co-doped samples exhibit blue emission, which is turned to near white region by introducing Gd3+ ions. In order to enhance the luminescence properties, (Li+, Mg2+, Sr2+) ions are doped into CaTiO3 Eu3+/Dy3+/Gd3+ phosphors to ensure the host charge compensation. The charge compensators not only provide luminescence enhancement but also modify the local environment of the lanthanide ions and then adjust the emission to tune the ratio of each color in the spectrum. The photometric parameters such as CIE-coordinate and correlated color temperature (CCT) were calculated, which depend on the ion charge and on the ionic radii. These perovskite phosphors can be applied for solid-state lighting applications.

Pt-decorated $$\hbox {TiO}_{2}$$ nanotubes Pt@TiO2 are prepared only by applying a set of facile wet-chemical redox reactions to ion track-etched polycarbonate templates. First, a homogeneous layer of Pt nanoparticles is deposited onto the complex template surface by reducing potassium tetrachloroplatinate with absorbed dimethylaminoborane. Second, the template is coated with a conformal $$\hbox {TiO}_{2}$$ layer, using a chemical bath deposition reaction based on titanium(III) chloride. After the removal of the template, the rutile-type $$\hbox {TiO}_{2}$$ nanotubes remain decorated with Pt nanoparticles and nanoparticle-clusters on their outside. During the process, neither vacuum techniques nor external current sources or addition of heat are employed. The crystallinity, composition, and morphology of the composite nanotubes are analysed by X-ray diffraction, scanning and transmission electron microscopy as well as by energy-dispersive X-ray spectroscopy. Finally, the obtained materials are examplarily applied in the electrooxidation of ethanol and formic acid, and their performances have been evaluated. Compared to conventional carbon black-supported Pt nanoparticles, the Pt@TiO2 nanotubes show higher reaction rates. Mass activities of 2.36 $$\hbox {A}\hbox { mg}_{\rm Pt}^{-1}\hbox { cm}^{-2}$$ are reached in ethanol oxidation and 7.56 $$\hbox {A}\hbox { mg}_{\rm Pt}^{-1}\hbox { cm}^{-2}$$ in the formic acid oxidation. The present structures are able to exploit the synergy of Pt and $$\hbox {TiO}_{2}$$ with a bifunctional mechanism to result in powerful but easy-to-fabricate catalyst structures. They represent an easily producible type of composite nanostructures which can be applied in various fields such as in catalytics and sensor technology.

Fe50Co50 was subjected to incremental forming by rotary swaging with the aim of tailoring the coercivity by changing the microstructure. The challenging part of a deformation of Fe50Co50 is an ordering phase present at room temperature, leading to low formability. To increase the formability of the alloy the presence of the ordering phase was supressed by two different concepts. The first concept consists of a heat treatment above the phase transition followed by rapid cooling and deformation at room temperature. The second concept was rotary swaging at temperatures above the phase transition temperature. A comparison in terms of resulting microstructure and magnetic properties shows that both concepts have a potential for tailoring the coercivity of Fe50Co50.

Spin fluctuations are a crucial driving force for magnetic phase transitions, but their presence usually is indirectly deduced from macroscopic variables like volume, magnetization or electrical resistivity. Here we report on the direct observation of spin fluctuations in the paramagnetic regime of the magnetocaloric model system LaFe

Theoretical analysis of surface acoustic wave (SAW) propagation in a pre-stressed layered piezoelectric structure basing on the modified ordinary differential equation (ODE) is described. Numerical calculations involve a thin piezoelectric layer of ZnO bonded perfectly to an elastic substrate of Al2O3. ZnO thin films are deposited on Al2O3 substrates using plasma assisted molecular beam epitaxial (MBE). The crystallographic orientation of ZnO thin films and the surface morphology are analyzed by X-ray diffraction (XRD) and atomic force microscopy (AFM) respectively. The density and the thickness of the ZnO films are determined by X-ray reflectivity. The initial stress and strain of ZnO films are measured by X-ray diffraction method. The effect of initial stress on the propagation behavior of Rayleigh and Love waves and on the coupled electromechanical factor is discussed.

This study evaluates the change of flow stress as related to dislocation density in SrTiO3 single crystals in order to provide guidance for later electrical studies. The key parameters varied are temperature and loading rate during the deformation. It is found that in -oriented SrTiO3 single crystals, the dislocation density is enhanced by plastic deformation, more so at higher temperature as compared to room temperature. The experimental approach of quantifying the dislocation density through a determination of ex situ X-ray diffraction rocking curves was successfully applied over the upper temperatures region of the lower temperature ductility zone for strontium titanate, i.e., in the so-called “A-regime”. For 1.0% deformed samples deformed at 300°C, a fourfold increase in dislocation density to 1.4 3 1013 m – 1 was found as compared to the nondeformed state (3.7 3 1012 m – 1). Cross-section techniques confirmed that the observed dislocation densities measured at the surfaces were identical to those seen in the core of the crystals. The use of rapid changes in loading rate provided an estimate for activation volume of the dislocation core for both 25°C and 300°C.

Solid-state nuclear magnetic resonance (NMR) spectroscopy, total X-ray scattering with a pair distribution function (PDF) analysis, and transmission electron microscopy (TEM) were employed to explore the structures of microporous and non-porous ceramics synthesized by an NH3-assisted thermolysis from polymers. Polysiloxane (SPR-212a, Starfire® Systems) and polysilazane (HTT-1800, KiON Speciality Polymers) polymers form microporous silicon oxycarbonitride ceramics with accessible and tailored micropores. 29Si magic-angle-spinning NMR showed that the introduction of nitrogen leads to structures incorporating considerable amounts of SiN4 and SiO2N2 building blocks. The samples derived from a polycarbosilane (SMP-10, Starfire® Systems) remained non-porous: for such a C-rich and N-bearing phase, the NMR, TEM, and PDF results suggested a Si network exhibiting domains dominated by either SiN or SiC bonds. 13C NMR revealed primarily “carbidic” CSi4 environments in the C-rich phases, as well as the formation of an amorphous sp2-hybridized carbon phase; both are believed to be detrimental for the micropore formation.

International audience; We report on the analysis of weak localization observed in epitaxial films of LaNiO3-delta deposited coherently on SrTiO3 (001) substrates using different oxygen pressures, controlling thus the oxygen stoichiometry delta. The structural and transport properties of 10 nm thick LaNiO3-delta films were investigated. In the films deposited under the lowest oxygen pressures, we observe localization effects at low temperatures, indicating first a high structural quality of the films, and second an influence of the growth conditions on the quantum transport properties of the nickelate. We will discuss the origin as well as the dimensionality of this effect, giving insight into novel and accurate strategies for the design of ultrathin LaNiO3 electrodes for improved next generation electronics devices.

X-ray pair distribution function (PDF) analysis of Al0.57Sn0.43O1.71, a promising candidate as anode material for Li ion batteries, has been carried out using synchrotron radiation at 60 keV. The average and short-range ordering of nanocrystalline Al0.57Sn0.43O1.71was investigated both with the traditional Rietveld refinement method and with X-ray PDF analysis. The instrumental parameters of the high-resolution powder diffraction beamline P02.1, Petra III, have been characterized. Reverse Monte Carlo (RMC) refinements based on PDF data indicate that Al substitution induces local distortions around the Al/Sn atoms and that oxygen vacancies, induced by the Al substitution, are mostly located on an anion site around the Al atoms. Additionally, RMC refinements hint at a clustering of Al atoms.

The design of core–shell materials affords additional degrees of freedom to tailor functional properties as compared to solid solution counterparts. Although to date most of the work in core–shell materials has focused on dielectrics, piezoelectric core–shell ceramics may gain similar interest. Generalities of core–shell functional ceramics features are addressed in this work. A model system, Bi1/2Na1/2TiO3–SrTiO3, is introduced to discuss structure–property relationships. We demonstrate that this system features a core–shell microstructure for the composition corresponding to 25 at.% Sr. The material is studied by means of macroscopic functional properties and in situ structural characterization techniques at different length scales, such as X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The evolution of the core–shell with field and temperature determines its functional properties. The high strain of the system, ~0.3% at 4 kV/mm, is due to an electric-field-induced phase transition of the core and shell. Upon field removal the core remains in a poled state, whereas the shell is characterized by a reversible transformation. The reversibility of the phase transition of shells and associated switching are key features in the observed giant strain. Dielectric anomalies are found to be related to changes in oxygen octahedral tilting angles within the core and shell.

The local dynamics of the lead-free relaxor $0.964{\mathrm{Na}}_{1/2}{\mathrm{Bi}}_{1/2}{\mathrm{TiO}}_{3}\ensuremath{-}0.036{\mathrm{BaTiO}}_{3}$ (NBT-3.6BT) have been investigated by a combination of quasielastic neutron-scattering (QENS) and ab initio molecular dynamics simulations. In a previous paper, we were able to show that the tetragonal platelets in the microstructure are crucial for understanding the dielectric properties of NBT-3.6BT [Pforr et al., Phys. Rev. B 94, 014105 (2016)]. To investigate their dynamics, ab initio molecular dynamics simulations were carried out using ${\mathrm{Na}}_{1/2}{\mathrm{Bi}}_{1/2}{\mathrm{TiO}}_{3}$ with 001 cation order as a simple model system for the tetragonal platelets in NBT-3.6BT. Similarly, 111-ordered ${\mathrm{Na}}_{1/2}{\mathrm{Bi}}_{1/2}{\mathrm{TiO}}_{3}$ was used as a model for the rhombohedral matrix. The measured single-crystal QENS spectra could be reproduced by a linear combination of calculated spectra. We find that the relaxational dynamics of NBT-3.6BT are concentrated in the tetragonal platelets. Chaotic stages, during which the local tilt order changes incessantly on the time scale of several picoseconds, cause the most significant contribution to the quasielastic intensity. They can be regarded as an excited state of tetragonal platelets, whose relaxation back into a quasistable state might explain the frequency dependence of the dielectric properties of NBT-3.6BT in the 100 GHz to THz range. This substantiates the assumption that the relaxor properties of NBT-3.6BT originate from the tetragonal platelets.

The oxidation behavior of Cr–Cr3(Si1−XGeX) alloys with the composition range Cr85GeXSi1−X (0

Spin fluctuations are a crucial driving force for magnetic phase transitions, but their presence usually is indirectly deduced from macroscopic variables like volume, magnetization or electrical resistivity. Here we report on the direct observation of spin fluctuations in the paramagnetic regime of the magnetocaloric model system LaFe11.6Si1.4 in the form of neutron diffuse scattering. To confirm the magnetic origin of the diffuse scattering, we correlate the temperature dependence of the diffuse intensity with ac magnetic susceptibility and x-ray diffraction experiments under magnetic field. Strong spin fluctuations are already observable at 295 K and their presence alters the thermal contraction behavior of LaFe11.6Si1.4 down to the Curie temperature of the first-order magneto-structural transition at 190 K. We explain the influence of the spin fluctuation amplitude on the lattice parameter in the framework of the internal magnetic pressure model and find that the critical forced magnetostriction follows Takashi’s spin fluctuation theory for itinerant electron systems.

Single-phase c-axis oriented NaxCoO2 thin films were grown on (001) SrTiO3 single-crystal substrates, using pulsed laser deposition. X-ray diffraction analysis indicates the epitaxial growth of NaxCoO2 thin films in two domains, rotated in-plane by 15 and 45 degrees relative to [100] SrTiO3. The sodium stoichiometry x of the films can be controlled in a range of 0.38 < x < 0.84 by in-situ post-deposition annealing the NaxCoO2 films at 720 – 760 °C in oxygen for 10 – 30 min. γ - NaxCoO2 films are obtained with a full width at half maximum of the (002) NaxCoO2 rocking curve below 0.2 degrees. The post-deposition annealing can substitute commonly used chemical deintercalation of Na which is typically associated with a loss in crystallinity.

We study the temperature-dependent evolution of the octahedral tilt order in a lead-free relaxor ferroelectric and its impact on the ferroelectric properties. Using diffuse neutron scattering on a $0.964{\mathrm{Na}}_{1/2}{\mathrm{Bi}}_{1/2}{\mathrm{TiO}}_{3}\text{\ensuremath{-}}0.036{\mathrm{BaTiO}}_{3}$ single crystal, we suggest a model for the temperature-dependent nanostructure of this perovskite that features chemically pinned tetragonal platelets embedded in the rhombohedral matrix, often separated by a cubic intermediate phase. Our results show a clear correlation between the squared thickness of the tetragonal platelets and the dielectric permittivity. This is interpreted as a sign for increased polarizability of the strained and distorted lattice at the center of the tetragonal platelets.

Coupling of order parameters provides a means to tune functionality in advanced materials including multiferroics, superconductors, and ionic conductors. We demonstrate that the response of a frustrated ferroelectric state leads to coupling between order parameters under electric field depending on grain orientation. The strain of grains oriented along a specific crystallographic direction, ⟨h00⟩, is caused by converse piezoelectricity originating from a ferrodistortive tetragonal phase. For ⟨hhh⟩ oriented grains, the strain results from converse piezoelectricity and rotostriction, as indicated by an antiferrodistortive instability that promotes octahedral tilting in a rhombohedral phase. Both strain mechanisms combined lead to a colossal local strain of (2.4 ± 0.1) % and indicate coupling between oxygen octahedral tilting and polarization, here termed “rotopolarization”. These findings were confirmed with electromechanical experiments, in situ neutron diffraction, and in situ transmission electron microscopy in 0.75Bi1/2Na1/2TiO3-0.25SrTiO3. This work demonstrates that polar and non-polar instabilities can cooperate to provide colossal functional responses This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0

Indium zinc oxide thin-film transistors are fabricated via a precursor in solution route on silicon substrates with silicon dioxide gate dielectric. It is found that the extracted mobility rises, peaks, and then decreases with increasing precursor concentration instead of rising and saturating. Investigation with scanning probe techniques reveals full thickness variations within the film which are assumed to adversely affect charge transport. Additional layers are coated, and the extracted mobility is observed to increase up to 19.7 cm(2) V(-1) s(-1). The reasons for this are examined in detail by direct imaging with scanning tunneling microscopy and extracting electron density profiles from X-ray reflection measurements. It is found that the optimal concentration for single layer films is suboptimal when coating multiple layers and in fact using many layers of very low concentrations of precursor in the solution, leading to a dense, defect and void free film, affording the highest mobilities. A consistent qualitative model of layer formation is developed explaining how the morphology of the film develops as the concentration of precursor in the initial solution is varied.

The noble gas storage and separation capability of three classes of microporous frameworks (MFs) including Metal–Organic Frameworks (HKUST-1 and MFU-4 l ), Covalent-Organic Frameworks (COF-102) and Zeolite Imidazolate Frameworks (ZIF-8) were studied using thermal desorption spectroscopy (TDS). The maxima in the TDS spectra were correlated to the adsorption sites and strength of interactions. The difference in the final desorption temperature for xenon and krypton was correlated to the separation capability of the frameworks. The results show that MFU-4 l and HKUST-1 are potential candidates for separation and storage of krypton and xenon. Further sorption studies have proved the ability of both candidates in Kr/Xe separation in larger scale.

The sensitivity of spontaneous polarization to epitaxial strain for both 10 and 50 nm thick Ba0.5Sr0.5TiO3 (BSTO) ferroelectric thin films has been studied. Crystal truncation rod (CTR) profiles in the 00L directions at different wavelengths, and grazing incidence diffraction (GID) in the 0K0 direction on a single crystal have been recorded. Modeling of the CTR data gives a detailed picture of the strain and provides clear evidence of the film out-of-plane expansion at the surface, an increase of the polarization, as well as a contraction at the interface. GID data confirm the fitting of the CTR, showing an in-plane expansion of the BSTO film at the interface and a contraction at the surface. (C) 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

High-energy synchrotron x-ray scattering offers a powerful technique for investigation of single-crystal material structures. Large, mm-sized crystals can be used, allowing complex in situ sample environments to be employed. Here, we demonstrate how this technique can be applied for the collection of single-crystal diffuse scattering volumes from the electro-active material 96%Bi0.5Na0.5TiO3-4%BaTiO3 while electric fields are applied in situ. The data obtained allow correlation of the atomic and nanoscale structures with the observed macroscopic electro-active properties of interest. This article presents a recent study relating the nanoscale stacking fault structure in BNT-BT to the relaxor-ferroelectric nature of the material [Daniels et al. in Appl. Phys. Lett. 98, 252904 (2011)], and extends this study with further experimental description and analysis.

Fast ion conductors are at the foundation of a number of important technologies, ranging from fuel cells to batteries to gas separators. Recent results suggest that strained interfaces and thin films may offer new mechanisms for achieving enhanced ionic transport. In this work, we investigate strained 40-nm films of perovskite La0.5Sr0.5CoO3−δ, which is an important material for solid oxide fuel cell cathodes and oxygen separation membranes. We demonstrate that a strained thin film of La0.5Sr0.5CoO3−δ on SrTiO3 can have dramatically different anion and cation thermodynamics and kinetics than bulk La0.5Sr0.5CoO3−δ. We use synchrotron X-ray diffraction to show that La0.5Sr0.5CoO3−δ thin films form an ordered phase at 650 K. The ordered phase consists of La and Sr cations in planes parallel to the surface and is associated with coherent expansion in the c-direction of ∼5%. This chemical ordering is not observed in the bulk material and is ascribed to the interplay between the epitaxial strain imposed by the ...

International audience; Dielectrics based on amorphous sub-nanometric laminates of TiO2 and Al2O3 are subject to elevated dielectric losses and leakage currents, in large parts due to the extremely thin individual layer thickness chosen for the creation of the Maxwell-Wagner relaxation and therefore the high apparent dielectric constants. The optimization of performances of the laminate itself being strongly limited by this contradiction concerning its internal structure, we will show in this study that modifications of the dielectric stack of capacitors based on these sub-nanometric laminates can positively influence the dielectric losses and the leakage, as for example the nature of the electrodes, the introduction of thick insulating layers at the laminate/electrode interfaces and the modification of the total laminate thickness. The optimization of the dielectric stack leads to the demonstration of a capacitor with an apparent dielectric constant of 90, combined with low dielectric loss (tan delta) of 7 . 10(-2) and with leakage currents smaller than 1 x 10(-6) A cm(-2) at 10 MV m(-1).

The structure and resistive properties of buried ${\mathrm{SrVO}}_{3}$ layers between two insulating ${\mathrm{LaVO}}_{3}$ layers are investigated by varying the thickness of the ${\mathrm{SrVO}}_{3}$ layers between 3 and 35 monolayers. The thickest ${\mathrm{SrVO}}_{3}$ layer shows a bulklike metallic behavior, while in the thinnest ${\mathrm{SrVO}}_{3}$ layer, a weak localization regime is observed below 100 K manifesting a logarithmic temperature dependence. Angular-dependent magnetoresistance measurements indicate a cylindric shape of the Fermi surface, and therefore a two-dimensional transport in the thinnest buried ${\mathrm{SrVO}}_{3}$ layer. The modification of the charge carrier properties by the reduced thickness of the ${\mathrm{SrVO}}_{3}$ layer are furthermore underlined by the appearance of a relatively strong positive magnetoresistance under a magnetic field perpendicular to the sample surface. The present study therefore highlights a way to synthesize oxide electrodes with reduced dimension for future oxide electronics application.

Osmium silicide epilayers have been grown by molecular beam epitaxy on (1 0 0)-oriented Si wafers. Multiple-phase (Os2Si3 and OsSi2) and single-phase epilayers are observed, depending on the growth parameters. In this paper we report on a detailed investigation of the structure of a single-phase Os2Si3 epilayer and epilayer/silicon interface using X-ray diffraction, and reflectivity analysis. Optical absorption results will also be presented.

For this paper, we used radio-frequency (rf) sputter deposition to synthesize epitaxial La0.5Sr0.5CoO3−∂ (LSCO) films. We investigated the influence of sputter deposition parameters, in particular, oxygen partial pressure, plasma power, total sputter pressure, and post-deposition cooling atmosphere on film composition, microstructure, and electrical resistivity. We show that rf sputtering from a single target can produce LSCO films with La/Sr and (La + Sr)/Co ratios of unity and with low electrical resistivities of about 1 mΩ cm. Film microstructures were characterized by high-resolution transmission electron microscopy and x-ray diffraction. Formation of an ordered film superlattice, most likely due to oxygen vacancy ordering, was observed. In this paper, we discuss the relationship between the film microstructure and the electrical resistivity.

We report a temperature-dependent x-ray diffraction study of critical behavior of sublattice order in thin epitaxial FeCo(001) films grown on MgO(001). The quantitative analysis of the diffraction profiles reveals a crossover phenomenon between strong-field and weak-field critical adsorption which occurs at a reduced temperature t1=1.3×10−3. We demonstrate that this scenario gives a first experimental access to the universal critical exponent η⊥ which governs the spatial decay of critical fluctuations perpendicular to the surface. We find η⊥=0.86(5).

Ba0.65Sr0.35TiO3 (BST) thin films of 300 nm were deposited on Pt(111)/TiO2/SiO2/Si(001) substrates by radio frequency magnetron sputtering. Two thin films with different (111) and (001) fiber textures were prepared. X-ray diffraction was applied to measure texture. The raw pole figure data were further processed using the MTEX quantitative texture analysis software for plotting pole figures and calculating elastic constants and Young's modulus from the orientation distribution function (ODF) for each type of textured fiber. The calculated elastic constants were used in the theoretical studies of surface acoustics waves (SAW) propagating in two types of multilayered BST systems. Theoretical dispersion curves were plotted by the application of the ordinary differential equation (ODE) and the stiffness matrix methods (SMM). A laser acoustic waves (LAW) technique was applied to generate surface acoustic waves (SAW) propagating in the BST films, and from a recursive process, the effective Young's modulus are determined for the two samples. These methods are used to extract and compare elastic properties of two types of BST films, and quantify the influence of texture on the direction-dependent Young's modulus.

Self-healing induced by structural phase transformation is demonstrated using pentacene field-effect transistors. During the self-healing process, the electrical properties at the pentacene interfaces improve due to the phase transformation from monolayer phase to thin-film phase. Enhanced mobility is confirmed by first-principles calculations.

Polarized neutron reflectometry (PNR) has an important role in solving non-collinear magnetic structures in thin films. In principle PNR provides the unambiguous determination of multi-axial magnetic depth profiles in systems of scientific and technological importance. However, only a limited number of problems have been solved unimpeachably, because the magnetic depth profiles were obtained by fitting procedures yielding solutions whose main features were not evident in the raw data. A recent formulation of reflectometry, and the concurrent development of “total polarimetry” are now stimulating the design of neutron polarization and polarization analysis geometries capable of determining directly if and how a magnetic system contains a non-collinear structure in the film ( x – y ) plane. In the simplest of these geometries the neutrons are polarized and analyzed along the z -axis perpendicular to the film plane.

Properties of the free ferrofluid (colloid of fine magnetite particles suspended in heavy water) surface and interface silicon–ferrofluid is studied by means of the neutron reflectivity and off-specular scattering. The measurements were performed in zero magnetic field, as well as in the presence of the field, applied within the surface (interface) plane, either perpendicular or parallel to the incoming beam. Proposed theoretical model allows deriving quantitative information about ferrofluid structure from the data of the interface measurements while consideration of the free surface data requires some additional contemplation. The experimental results collected, mainly in maps initial angle – scattered angle, were treated by means of two-dimensional fit (the least-squares routine) and values of the ferrofluid parameters such as correlation radius, critical angle, scattering length density were obtained in dependence on value and direction of external magnetic field. The capability of polarized neutron reflection experiment for the investigation of the magnetization process in the vicinity of the ferrofluid free surface (interface) is discussed.

We report on the application of the polarized 3He gas spin filter technique for the measurement of spin-polarized diffuse neutron reflectivity with spin analysis. The spin filter together with a one-dimensional position-sensitive detector enables the simultaneous investigation of sections in reciprocal space while exploiting spin sensitivity. An example of diffuse neutron scattering from a Fe/Cr superlattice demonstrates the potential of the method. In addition we present a first step towards the interpretation of diffuse scattering from magnetic multilayers by exploiting the supermatrix formalism.