The competitive growth of cubic domains in Ti1–xAlxN films studied by diffraction anomalous near‐edge structure spectroscopy

Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K‐edge X‐ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X‐ray diffraction anomalous fine structure, which is sensitive to short‐ and long‐range order within a given crystallized domain, are carried out on a set of Ti_1–xAl_xN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre‐edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face‐centred‐cubic Ti‐rich (TiN, Ti_0.54Al_0.46N) samples or tetrahedral in hexagonal‐close‐packed Al‐rich (Ti_0.32Al_0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy‐dependent structure factor for the Bragg reflections is applied to the pre‐edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre‐edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre‐edge spectra associated with face‐centred‐cubic 200 and 111 Bragg reflections of Ti_0.54Al_0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti_0.32Al_0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal‐close‐packed nitride.     

Development of magnetic anisotropies in ultrathin epitaxial films of Fe(001) and Ni(001)

Ultrathin films, bcc Fe(001) on Ag(001), fcc Fe(001) on Cu(001) and Fe/Ni(001) bilayers on Ag, were grown by molecular beam epitaxy. A wide range of surface science tools were employed to establish the quality of epitaxial growth. Ferromagnetic resonance and Brillouin light scattering were used to extract the magnetic properties. Emphasis was placed on the study of magnetic anisotropies. Large uniaxial anisotropies with easy axis perpendicular to the film surface were observed in all ultrathin structures studied. These anisotropies were particularly strong in fcc Fe and bcc Fe films. In sufficiently thin samples the saturation magnetization was oriented perpendicularly to the film surface in the absence of an applied field. It has been demonstrated that in bcc Fe films the uniaxial perpendicular anisotropy originates at the film interfaces. In situ measurements indentified the strength of the uniaxial perpendicular anisotropy constant at the Fe/vacuum, Fe/Ag and Fe/Au interfaces asK _us = 0.96, 0.63, and 0.3 ergs/cm² respectively. The surface anisotropies deduced for [bulk Fe/noble metal] interfaces are in good agreement with the values obtained from ultrathin films. Hence the perpendicular surface ansiotropies originate in the broken symmetry at abrupt interfaces. An observed decrease in the cubic anisotropy in bcc Fe ultrathin films has been explained by the presence of a weak 4th order in-plane surface anisotropy,K _1S=0.012 ergs/cm². Fe/Ni bilayers were also investigated. Ni grew in the pure bcc structure for the first 3–6 ML and then transformed to a new structure which exhibited unique magnetic properties. Transformed ultrathin bilayers possessed large inplane 4th order anisotropies far surpassing those observed in bulk Fe and Ni. The large 4th order anisotropies originate in crystallographic defects formed during the Ni lattice transformation.     

Solid-phase synthesis of L1<Subscript>0</Subscript>-FePd(001) epitaxial thin films: Structural transformations and magnetic anisotropy

The solid-phase synthesis of the L1₀-FePd magnetically hard phase in Fe(001)/Pd(001) epitaxial films has been experimentally investigated. The formation of three types of L1₀-FePd ordered crystallites whose c axes coincide with the 〈100〉 directions of the MgO(001) substrate begins at the Fe/Pd interface at a temperature of 450°C. After an increase in the annealing temperature to 500°C, structural rearrangement occurs and gives rise to the predominant growth of L1₀-FePd crystallites with the c axis perpendicular to the film plane. After 10-h annealing, the fraction of such crystallites becomes dominant, leading to large perpendicular anisotropy. The first magnetocrystalline-anisotropy constant of the L1₀-FePd phase has been determined and the second constant has been estimated. It has been shown that magnetic anisotropy in the L1₀-FePd(001) basal plane cannot be described by the biaxial anisotropy of the tetragonal crystal. The annealing above 500°C results in the evolution of L1₀-FePd to a disordered cubic phase.     

Cubic symmetry around iron in CoSi2

The Mössbauer spectra of ⁵⁷Fe in CoSi₂ have been measured in 3.5 and 4.0 T external magnetic fields. The measured spectra showed only magnetic splitting thereby proving the cubic symmetry around ⁵⁷Fe atoms in CoSi₂ (fluorite‐type lattice). Two iron positions were found: in one the iron atoms substitute Co atoms, in the other one the iron populates the empty cubic site in the lattice. It is considered that the results may well contribute to clarifying the atomic positions and local symmetries in metastable Co‐ and Fe‐silicides forming after implantation of Co and Fe in Si at elevated temperatures.     

Magnetism of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> manganite in structurally ordered and disordered states

The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn₂]O₄ and disordered Li_{1 − δ}Mn_δ[Mn_{2 − δ}Li_δ]O₄ (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E _eff ≥ 1 MeV) with a fluence of 2 × 10²⁰ cm⁻² at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn₂O₄ manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.     

Magnetite, a model system for mixed-valence oxides, does not show charge ordering

We have investigated the charge ordering (CO) in magnetite below the Verwey transition. A new set of half-integer and mixed-integer superlattice reflections of the low-temperature phase have been studied by x-ray resonant scattering. None of these reflections show features characteristic of CO. We demonstrate the absence of CO along the c axis with the periodicity of either the cubic lattice q=(001) or the doubled cubic lattice q=(001/2). This result suggests that the Verwey transition is caused by strong electron-phonon interaction instead of an electronic ordering on the octahedral Fe atoms.     

Charge redistribution and a shortening of the Fe—As bond at the quantum critical point of SmO1–xFxFeAs

Many researchers have pointed out that there is a quantum critical point (QCP) in the F‐doped SmOFeAs system. In this paper, the electronic structure and local structure of the superconductive FeAs layer in SmO_1–xF_xFeAs as a function of the F‐doping concentration have been investigated using Fe and As K‐edge X‐ray absorption spectroscopy. Experiments performed on the X‐ray absorption near‐edge structure showed that in the vicinity of the QCP the intensity of the pre‐edge feature at the Fe‐edge decreases continuously, while there is a striking rise of the shoulder‐peak at the As edge, suggesting the occurrence of charge redistribution near the QCP. Further analysis on the As K‐edge extended X‐ray absorption fine structure demonstrated that the charge redistribution originates mostly from a shortening of the Fe—As bond at the QCP. An evident relationship between the mysterious QCP and the fundamental Fe—As bond was established, providing new insights on the interplay between QCP, charge dynamics and the local structural Fe—As bond in Fe‐based superconductors.     

In-plane magnetic surface anisotropies in Fe(110)

In-plane magnetic surface anisotropies have been detected for Fe(110) on W(110) using in situ Conversion Electron Mössbauer Spectroscopy (CEMS). The phenomenon used for the determination of this anisotropy was a switching of the spontaneous magnetizationJ _s from [001] to [1¯10] with decreasing thickness. Analysis of the data is performed using a homogeneous magnetization approximation for competing surface and bulk anisotropies, which is justified by a micromagnetic analysis and established experimentally by CEMS. In-plane surface anisotropy constants for the clean Fe(110) surface, the Fe metal-interface and the FeGaAs interface are determined toK _s,p ^FeUHV =0.065 erg·cm^–2,K _s,p ^FeMetal =0.040 erg ·cm^–2, andK _s,p ^FeGaAs =0.047 erg ·cm^–2, all with an estimated accuracy of the order of 10%.     

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.     

Synthesis,crystal structure and characterization of chiral,three-dimensional anhydrous potassium tris(oxalato)ferrate(III)

The synthesis, crystal structure and physical properties of chiral, three-dimensional anhydrous potassium tris(oxalato)ferrate(III) [K₃F_e(C₂O₄)₃] are described. X-ray analysis reveals that the compound crystallized in the chiral space group P4₁32 of cubic system with a=b=c=13.5970(2), Z=4. The structure of the complex consists of infinite anionic [Fe(C₂O₄)₃]³⁻ units with distorted octahedral environment of iron surrounded by six oxygen atoms of three oxalato groups. The anionic units are interlinked through K⁺ ions of three different coordination environments of distorted octahedral, bicapped trigonal prismatic and trigonal prismatic yielding a three-dimensional motif. The two broad absorption bands at 644 and 924 nm from UV–vis–NIR transmittance spectra were ascribed to a ligand-to-metal charge transfer. The room temperature crystalline EPR spectra indicate the high-spin (S=5/2) of Fe(III) ion. The vibrating sample magnetometer measurement shows the paramagnetic nature at room temperature. Thermal studies of the compound confirm the absence of water molecule.     

Mössbauer studies and magnetic properties of spinel lead ferrite

In the present communication, we have reported the synthesis of nanocrystalline lead ferrite (PbFe₂O₄) by citrate mediated autocombustion method. X-ray diffraction pattern reveals the single phase formation in cubic (spinel) structure. The particle size and the surface morphology of the samples are characterized by TEM and SEM analysis. Magnetic studies are carried out using vibrating sample magnetometer (VSM) shows a very high coercive field for the material. Mössbauer studies were performed to investigate the local symmetry i.e. Fe is in octahedral/tetrahedral site and the charge states of Fe ions.     

Spin-engineering in the Co75Fe25/Cu(1 1 0) system

We present results on the growth and magnetic anisotropies of Co₇₅Fe₂₅ films grown on a Cu(1 1 0) single crystal. Angular dependent MOKE measurements show a thickness dependent, in-plane rotation of the easy axis of magnetisation of up to 60° from the [0 0 1] direction (towards [−1 1 0]). For a film thickness of 5 ML, just greater than that required for the onset of ferromagnetism, uniaxial anisotropy is observed with the easy axis along the [0 0 1] direction. As the film thickness increases this is seen to rotate in-plane towards the [−1 1 0] direction as the contribution from the cubic anisotropy constant grows. At a film thickness of 9 ML there is predominantly cubic anisotropy and at 10 ML the easy axis is rotated to 150° with respect to the [1 −1 0] axis, where it is stabilised.     

A method for determination of higher-order magnetic anisotropy constants — Importance of the cubic K3 and K4 for certain energy levels models

A method for determination of magnetocrystalline anisotropy constants of arbitrary order is proposed. The method is based on a least squares fitting of a phenomenological anisotropy energy for a given symmetry truncated at an arbitrary order term to a theoretical anisotropy energy computed exactly for a given energy level model. Several applications of the method to cubic systems are considered. The study reveals that the widely used expressions in the literature for the cubic constants K₁ and K₂ in terms of free energy for the three symmetry direction are of rather limitedvalidity only. The higher-order cubic constants K₃, K₄ and K₅ are determined besides the usual K₁ and K₂ in temperature range 0 to 300 K. The importance of the higher- order terms with respect to the first term in the cubic anisotropy energy is discussed. The results show that the cubic constants K₃ and K₄ cannot be neglected for most of the energy level models studied at certain temperatures.     

The anisotropy of the basic characteristics of Lamb waves in a (001)-Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> piezoelectric crystal

The orientation dependences of the phase velocity, the effective electromechanical coupling coefficient, and the angle between the wave normal and the energy flux vector are numerically calculated for zeroand first-order Lamb waves propagating in the (001) basal plane of a Bi₁₂SiO₂₀ cubic piezoelectric crystal. It is shown that the anisotropies of these modes are different and depend on the plate thickness h and the wavelength λ. For h/λ < 1, the mode anisotropy can exceed the anisotropy of the corresponding characteristics of surface acoustic waves propagating in the same plane; for h/λ > 1, it approximately coincides with the SAW anisotropy for all the characteristics.     

Rietveld and pair distribution function study of Hägg carbide using synchrotron X‐ray diffraction

Fischer–Tropsch (FT) synthesis is an important process in the manufacturing of hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The reduced iron catalyst reacts with carbon monoxide and hydrogen to form bulk Fe₅C₂ Hägg carbide (χ‐HC) during FT synthesis. Arguably, χ‐HC is the predominant catalyst phase present in the working iron catalyst. Deactivation of the working catalyst can be due to oxidation of χ‐HC to iron oxide, a step‐wise decarburization to cementite (θ‐Fe₃C), carbon formation or sintering with accompanying loss of catalytic performance. It is therefore critical to determine the precise crystal structure of χ‐HC for the understanding of the synthesis process and for comparison with the first‐principles ab initio modelling. Here the results of high‐resolution synchrotron X‐ray powder diffraction data are reported. The atomic arrangement of χ‐HC was confirmed by Rietveld refinement and subsequent real‐space modelling of the pair distribution function (PDF) obtained from direct Fourier transformation. The Rietveld and PDF results of χ‐HC correspond well with that of a pseudo‐monoclinic phase of space group Pī [a = 11.5661 (6) Å, b = 4.5709 (1) Å, c = 5.0611 (2) Å, α = 89.990 (5)°, β = 97.753 (4)°, γ = 90.195 (4)°], where the Fe atoms are located in three distorted prismatic trigonal and one octahedral arrangement around the central C atoms. The Fe atoms are distorted from the prismatic trigonal arrangement in the monoclinic structure by the change in C atom location in the structure.     

Magnetic properties of stable structures of small binary clusters

We have studied the optimum geometries and the magnetic behavior of small binary Fe_nGe_m (n+m≤4) clusters usingab initio spin-polarized density functional calculations. Our results reveal that the optimized clusters present high values in the HOMO–LUMO gap and generally prefer structures with high geometries, the local magnetic moments at Fe atoms present an enhancement with respect to Fe bulk magnetization, whereas the Ge atoms present local magnetic moments whose modulus take significative values. The magnetic coupling between Fe and Ge atoms is mainly antiferromagnetic-like. All the clusters studied here present a charge transference from Fe atoms to Ge atoms.     

First principles study on the magnetocrystalline anisotropy of Fe--Ga magnetostrictive alloys

This paper investigates the electronic structure and magnetocrystalline anisotropy of Fe--Ga magnetostrictive material by means of the full potential-linearized augmented plane-wave method within the generalized gradient approximation. The 3d-orbit splitting of Fe atoms in D0₃, B2-like and L1₂ crystalline structures of Fe--Ga is calculated with consideration of the crystal field as well as the spin--orbit coupling effect. Because of the frozen orbital angular momenta of the 3d-orbit for Fe atoms in Fe--Ga magnetostrictive alloys and the spin--orbit coupling, the distribution of the electron cloud is not isotropic, which leads to the anisotropy of exchange interaction between the different atoms. A method on estimating the magnetocrystalline anisotropy of Fe--Ga alloys by means of calculating orbit-projected density of states for Fe atoms is performed. The anisotropic distribution of the electron cloud of Fe atoms in these three crystalline structures of Fe--Ga is studied based on the above method showing the highest magnetic anisotropy for B2-like structure. This qualitative method comes closer to physical reality with a vivid physical view, which can evaluate the anisotropy of electron cloud for 3d transition atoms directly. The calculated results are in good agreement with both the previous theoretical computation and the tested value on the magnetic anisotropy constant, which confirms that the electron cloud anisotropy of Fe atoms could well characterize the magnetocrystalline anisotropy of Fe--Ga magnetostrictive material.     

Interaction and arrangement of nitrogen and carbon atoms in fcc γ-iron

A Mössbauer effect measurement has been done for Fe?N, Fe?Al?C and Fe?Ni?C austenite in order to study the interaction between the interstitial atoms and their distribution among the octahedral sites of the fcc lattice, together with the influence of Al and Ni atoms. The spectra for Fe?N and Fe?Al?C austenite are decomposed into three components; one singlet γ₀, and two sets of doublet γ₁ and γ₂, with different quadrupole splittings, while no γ₂ component is found in the spectrum for Fe?Ni?C. By analyzing the component ratio in each spectrum, it is concluded that, in Fe?N and Fe?Al?C, the interaction between 2nd nearest neighboring nitrogen or carbon atoms is attractive, and is repulsive between 1st nearest for Fe?N, and that the interaction between 2nd nearest atoms is repulsive for Fe?Ni?C. By measuring the spectra of Fe?Ni?C in magnetic field, the sign of EFG for most of the γ₁ component is determined to be negative.     

FMR Studies of Ultra-Thin Epitaxial Pd<Subscript>0.92</Subscript>Fe<Subscript>0.08</Subscript> Film

Magnetic anisotropies of 20 nm epitaxial film of palladium–iron alloy Pd_0.92Fe_0.08 grown on the (001) MgO substrate were studied. Ferromagnetic resonance (FMR) spectroscopy and vibrating sample magnetometry (VSM) were exploited to determine magnetic parameters of the film. It was found that the synthesized film reveals cubic anisotropy with tetragonal distortion. The simulated magnetic hysteresis loops, obtained utilizing the magnetic anisotropy constants taken from the FMR spectra analysis, agree well with those measured by VSM.     

NMR study of local magnetic properties of beryllium substituted copper ferrite

The spin echo NMR spectra of⁵⁷Fe have been taken at 77 K to describe the local magnetic properties of beryllum substituted copper ferrite Cu_1−xBe_xFe₂O₄ for 0≤x≤0.2. From the spectra the concentration dependence of hyperfine magnetic fields for tetrahedral and octahedral sites have been derived. The results show that statistical distribution of beryllium atoms over magnetic sublattices takes place and suggest that only below x=0.2 solid solutions of beryllium copper ferrites can exist.