Neutron studies of the iron-based family of high TC magnetic superconductors

We review neutron scattering investigations of the crystal structures, magnetic structures, and spin dynamics of the iron-based RFe(As, P)(O, F) (R = La, Ce, Pr, Nd), (Ba,Sr,Ca)Fe₂As₂, and Fe_1+x(Te–Se) systems. On cooling from room temperature all the undoped materials exhibit universal behavior, where a tetragonal-to-orthorhombic/monoclinic structural transition occurs, below which the systems become antiferromagnets. For the first two classes of materials the magnetic structure within the a–b plane consists of chains of parallel Fe spins that are coupled antiferromagnetically in the orthogonal direction, with an ordered moment typically less than one Bohr magneton. Hence these are itinerant electron magnets, with a spin structure that is consistent with Fermi-surface nesting and a very energetic spin wave bandwidth ～0.2 eV. With doping, the structural and magnetic transitions are suppressed in favor of superconductivity, with superconducting transition temperatures up to ≈55 K. Magnetic correlations are observed in the superconducting regime, with a magnetic resonance that follows the superconducting order parameter just like the cuprates. The rare earth moments order antiferromagnetically at low T like ‘conventional’ magnetic superconductors, while the Ce crystal field linewidths are affected when superconductivity sets in. The application of pressure in CaFe₂As₂ transforms the system from a magnetically ordered orthorhombic material to a ‘collapsed’ non-magnetic tetragonal system. Tetragonal Fe_1+xTe transforms to a low T monoclinic structure at small x that changes to orthorhombic at larger x, which is accompanied by a crossover from commensurate to incommensurate magnetic order. Se doping suppresses the magnetic order, while incommensurate magnetic correlations are observed in the superconducting regime.     

Magnetic ordering in Fe<Subscript>1.087</Subscript>Te under pressure

The crystal and magnetic structures of Fe_1.087Te have been studied by neutron powder diffraction in the temperature range from 1.7 to 80 K at pressures of  ≈0.4 and ≈1.2 GPa. No symmetry change of the tetragonal paramagnetic ambient pressure phase (space group P4/nmm) was observed for temperatures above 60 K and pressures up to  ≈1.2 GPa. A novel pressure-induced phase of Fe_1.087Te having orthorhombic symmetry (space group Pmmn) and incommensurate antiferromagneticbicollinear order was observed in the temperature range from 50 to 60 K at  ≈1.2 GPa. The known monoclinic ambient pressure phase of Fe_1.087Te (space group P2 ₁/n) with commensurate antiferromagnetic order was found to be stable up to at least  ≈1.2 GPa at low temperature.     

Physical properties,crystal and magnetic structure of layered Fe<Subscript>1.11</Subscript>Te<Subscript>1-</Subscript><Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> superconductors

The physical and structural properties of Fe_1.11Te and Fe_1.11Te_0.5Se_0.5 have been investigated by means of X-ray and neutron diffraction as well as physical property measurements. For the Fe_1.11Te compound, the structure distortion from a tetragonal to monoclinic phase takes place at 64 K accompanied with the onset of antiferromagnetic order upon cooling. The magnetic structure of the monoclinic phase was confirmed to be of antiferromagnetic configuration with a propagation vector k = (1/2, 0, 1/2) based on Rietveld refinement of neutron powder diffraction data. The structural/magnetic transitions are also clearly visible in magnetic, electronic and thermodynamic measurements. For superconducting Fe_1.11Te_0.5Se_0.5 compound, the superconducting transition with T _c = 13.4 K is observed in the resistivity and ac susceptibility measurements. The upper critical field H _c2 is obtained by measuring the resistivity under different magnetic fields. The Kim’s critical state model is adopted to analyze the temperature dependence of the ac susceptibility and the intergranular critical current density is calculated as a function of both field amplitude and temperature. Neutron diffraction results show that Fe_1.11Te_0.5Se_0.5 crystalizes in tetragonal structure at 300 K as in the parent compound Fe_1.11Te and no structural distortion is detected upon cooling to 2 K. However an anisotropic thermal expansion anomaly is observed around 100 K.     

Specific heat studies on pristine and oxygenated iron tellurides

Specific heat studies carried out on Fe_1.1Te and oxygenated Fe_1.1Te and FeTe₂ in the range 77-300 K exhibit interesting behavior. The specific heat of the pristine sample reveals a well known structural transition associated with antiferromagnetic ordering near 67 K with a small thermal hysteresis of ∼1 K. Contrastingly, the oxygenated samples exhibit a phase transition with a very large thermal hysteresis of ∼100 K. The specific heat transition observed at the 150 and 260 K regions in the oxygenated Fe_1.1Te sample could not be captured by the magnetization measurements indicating that specific heat transitions seen in oxygenated samples may not be of magnetic origin.     

Pressure induced phase transformations and band structure of different high pressure phases in tellurium

We report here high-pressure x-ray diffraction (XRD) studies on tellurium (Te) at room temperature up to 40 GPa in the diamond anvil cell (DAC). The XRD measurements clearly indicate a sequence of pressure-induced phase transitions with increasing pressure. The data obtained in the pressure range 1 bar to 40 GPa fit five different crystalline phases out of Te: hexagonal Te (I) → monoclinic Te(II) → orthorhombic Te (III) → Β-Po-type Te(IV) → body-centered-cubic Te(V) at 4, 6.2, 11 and 27 GPa, respectively. The volume changes across these transitions are 10%, 1.5%, 0.3% and 0.5%, respectively. Self consistent electronic band structure calculations both for ambient and high pressure phases have been carried out using the tight binding linear muffin tin orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Reported here apart from the energy band calculations are the density of states (DOS), Fermi energy (E _f) at various high-pressure phases. Our calculations show that the ambient pressure hexagonal phase has a band gap of 0.42 eV whereas high-pressure phases are found to be metallic. We also found that the pressure induced semiconducting to metallic transition occurs at about 4 GPa which corresponds to the hexagonal phase to monoclinic phase transition. Equation of state and bulk modulus of different high-pressure phases have also been discussed.     

Study of phase transition on nanocrystalline (La, Sr)(Mn, Fe)O system using high-pressure Mössbauer spectroscopy and high-pressure X-ray diffraction

Pressure-induced structural changes on nano-crystalline La_0.8Sr_0.2Mn_0.8Fe_0.2O₃ were studied using high-pressure Mössbauer spectroscopy and high-pressure X-ray diffraction. Mössbauer measurements up to 10 GPa showed first order transition at 0.52 GPa indicating transformation of Fe^4?+? to high spin Fe^3?+?, followed by another subtle transition at 3.7 GPa due to the convergence of two different configurations of Fe into one. High-pressure X-ray diffraction measurements carried up to 4.3 GPa showed similar results at 0.6 GPa as well as 3.6 GPa. Attempts were made to explain the changes at 0.6 GPa by reorientation of grain/grain boundaries due to uniaxial stress generated on the application of pressure. Similarly variation at 3.6 GPa can be explained by orthorhombic to monoclinic transition.     

Etude par diffraction des neutrons de la structure magnetique de l'antiferromagnetique La2Fe2S5

The magnetic structure of orthorhombic La₂Fe₂S₅ is found to be monoclinic with space group P₂. It points out that each kind of magnetic ions (octahedral or tetrahedral) which are separetely found on chains parallel to [001] are antiferromagnetically coupled on each chain through super- exchange interactions. Nearest neighbour antiferromagnetic chains are uncoupled; coupling between next-nearest neighbour chains is realized through super-superexchange interactions of the type Fe-S-S-Fe or possible more complex paths including La³⁺.     

Effect of Si/Ge ratio on resistivity and thermopower in Gd5SixGe4−x magnetocaloric compounds

The effect of Si/Ge ratio on resistivity and thermopower behavior has been investigated in the magnetocaloric ferromagnetic Gd₅Si_xGe_4−x compounds with x=1.7-2.3. Microstructural studies reveal the presence of Gd₅(Si,Ge)₄-matrix phase (5:4-type) along with traces of secondary phases (5:5 or 5:3-type). The x=1.7 and 2.0 samples display the presence of a first order structural transition from orthorhombic to monoclinic phase followed by a magnetic transition of the monoclinic phase. The alloys with x=2.2 and 2.3 display only magnetic transitions of the orthorhombic phase. A low temperature feature apparent in the AC susceptibility and resistivity data below 100 K reflects an antiferromagnetic transition of secondary phase(s) present in these compounds. The resistivity behavior study correlates with microstructural studies. A large change in thermopower of −8 μV/K was obtained at the magneto-structural transition for the x=2 compound.     

Optical and magneto-optical studies of a multiferroic GaFeO<Subscript>3</Subscript> with a high Curie temperature

Single crystals of a noncentrosymmetric orthorhombic pyroelectric ferrimagnet Ga_2?xFe_xO₃ with a Curie temperature within 260–345 K have been grown by the flux method. It has been found that the electrical properties of the single crystals varied over a broad range from 10⁵ to 10¹³ Ω cm depending on the presence of transitionmetal oxide impurities. The dispersion relations for all three principal dielectric functions of orthorhombic GaFeO₃ have been determined in the range 0.7–5.4 eV by spectroscopic ellipsometry. The spectra of the dielectric functions of the orthorhombic Ga_2?xFe_xO₃ crystals are compared with the spectra of the trigonal crystals. The Faraday effect and second-harmonic generation are studied, and the law of the transition to the paramagnetic state has been determined. The crystallographic and magnetic contributions to the second-harmonic generation are analyzed.     

Crystal and magnetic structure of KFeO2

The crystal and magnetic structures of KFeO₂ have been determined by neutron and X-ray powder-diffraction and Mössbauer-effect techniques. The crystal structure at 4.2 K and 300 K is orthorhombic and the magnetic space group is Pbca'. The Fe³⁺-ions in this structure are tetrahedrally coordinated by oxygen ions, and each Fe³⁺-ion has a magnetic moment which is antiferromagnetically coupled to the moments of four Fe³⁺-neighbours. The direction of the moments is parallel to the a-axis. A crystal phase transition has been observed near the Néel temperature?960 K.     

A case of magnetic field-induced change in final product

An interesting case of magnetic field-induced change in the final product of chemical reaction was observed. XRD patterns indicate that both of the products prepared at room temperature are amorphous regardless of the external magnetic field applied or not. However, after vacuum-annealed at 873 K, the product prepared at room temperature with 0.25 T magnetic field applied was orthorhombic Fe₃BO₅, but the product prepared without magnetic field applied changed to orthorhombic Fe₃O₄ or tetragonal Fe₂B. It indicates that the magnetic field induction is a dominating factor to the final product of chemical reaction. It suggests us an important method to fabricate new materials under mild magnetic field induction.     

Mössbauer studies of selected synthetic silicates

Mössbauer spectra of fayalite-, 7#x03B1;-Fe₂SiO₄, powder and single crystals were taken in the antiferromagnetic temperature region below T _N?65 K. The orientation of the efg and H(0) with respect to the crystallographic axes was determined as function of the temperature and compared to neutron diffraction and magnetic susceptibility data. A similar study was performed with Li‐acmite LiFeSi₂O₆, whose magnetic structure can be regarded as a model compound for quasi one‐dimensional systems. Synthetic annite KFe₃[AlSi₃O₁₀(OH)₂] has to contain at least about 10% Fe³⁺ in order to be stable. A comparison of the evaluation of the spectra assuming either Lorentzian line shape of the doublets or quadrupole splitting distributions QSDs shows that Fe³⁺/Fe²⁺‐ratios can be determined precisely by both methods. However, M2/M1-site distributions cannot be evaluated with great accuracy. In ilvaite CaFe₃[Si₂O₇/O/(OH)], there is a thermally activated intersite electron hopping between Fe²⁺ and Fe³⁺ at temperatures around 300 K in a double octahedron chain. At temperatures above 395 K there is extended electron delocalization in a narrow d‐ or polaron‐band. The substitution of Fe by Mn favours both effects and lowers the temperature of the crystallographic phase transition monoclinic to orthorhombic distinctly. In the solid solution series member acmite(50%)‐hedenbergite(50%) Na_0.5Ca_0.5Fe₂[Si₂O₆] just intersite electron hopping between Fe²⁺ and Fe³⁺ in the M1 octahedron chain and no formation of polaron bands is observed. This is explained by the larger Fe–Fe‐intrachain distances compared to those in ilvaite or magnetite.     

Modulated magnetic structure in quasi-one-dimensional clinopyroxene NaFeGe<Subscript>2</Subscript>O<Subscript>6</Subscript>

The magnetic structure of the NaFeGe₂O₆ monoclinic compound has been experimentally investigated using the elastic scattering of neutrons. At a temperature of 1.6 K, an incommensurate magnetic structure has been observed in the form of an antiferromagnetic helix formed by a pairs of the spins of the Fe³⁺ ions with helical modulation in the ac plane of the crystal lattice. The wave vector of the magnetic structure has been determined and its temperature behavior has been studied. The analysis of the temperature dependences of the specific heat and susceptibility, as well as the isotherms of the field dependence of the magnetization, has revealed the existence of not only the order-disorder magnetic phase transition at the point T _N = 13 K, but also an additional magnetic phase transition at the point T _c = 11.5 K, which is assumingly an orientation phase transition.     

Preparation of Bi2Fe4O9 particles by hydrothermal synthesis and functional properties

In the present study, particles with different Bi₂Fe₄O₉ micro/nanostructures with a few particular morphologies (flower-like nanoplatelets, hierarchical microstructures, perfectly square platelets single crystals, etc.) obtained under specific hydrothermal synthesis conditions were investigated. The role of the processing parameters (such as NaOH concentration, reaction temperature, and reaction duration time) on the phase formation mechanism and on the microstructural characteristics was investigated. All the Bi₂Fe₄O₉ morphologies showed orthorhombic symmetry with space group Pbam. The photocatalytic properties and magnetic behavior as a function of the micro/nanostructural characteristics of various Bi₂Fe₄O₉ powders were determined. In the presence of Bi₂Fe₄O₉, a degradation rate of Rose Bengal in the range of 52–61% was determined after 180?min under UV light irradiation (λ?=?254?nm). Magnetic activity with antiferromagnetic behavior and a transition at ～240?K slightly dependent on the microstructures was found. The role of Bi₂Fe₄O₉ microstructures in the photocatalytic activity and magnetic properties was discussed.     

Multiple magnetic transitions in single crystals of Ce<Subscript>12</Subscript>Fe<Subscript>57.5</Subscript>As<Subscript>41</Subscript> and La<Subscript>12</Subscript>Fe<Subscript>57.5</Subscript>As<Subscript>41</Subscript>

Measurements of magnetic and transport properties were performed on needle-shaped single crystals of Ce₁₂Fe_57.5As₄₁ and La₁₂Fe_57.5As₄₁. The availability of a complete set of data enabled a side-by-side comparison between these two rare earth compounds. Both compounds exhibited multiple magnetic orders within 2–300 K and metamagnetic transitions at various fields. Ferromagnetic transitions with Curie temperatures of 100 and 125 K were found for Ce₁₂Fe_57.5As₄₁ and La₁₂Fe_57.5As₄₁, respectively, followed by antiferromagnetic type spin reorientations near Curie temperatures. The magnetic properties underwent complex evolution in the magnetic field for both compounds. An antiferromagnetic phase transition at about 60 K and 0.2 T was observed merely for Ce₁₂Fe_57.5As₄₁. The field-induced magnetic phase transition occurred from antiferromagnetic to ferromagnetic structure. A strong magnetocrystalline anisotropy was evident from magnetization measurements of Ce₁₂Fe_57.5As₄₁. A temperature-field phase diagram was present for these two rare earth systems. In addition, a logarithmic temperature dependence of electrical resistivity was observed in the two compounds within a large temperature range of 150–300 K, which is rarely found in 3D-based compounds. It may be related to Kondo scattering described by independent localized Fe 3d moments interacting with conduction electrons.     

High-pressure in situ investigation of cubanite (CuFe2S3): Electronic structure

An in situ study of cubanite (CuFe₂S₃) was performed using energy dispersive X-ray diffraction and Mössbauer spectroscopy in a diamond anvil cell at room temperature and pressures up to 5 GPa. Mössbauer spectra of orthorhombic cubanite show a single iron site with a hyperfine magnetic field that is relatively insentive to pressure, and a centre shift which decreases with pressure at a rate consistent with no significant changes in bonding. Above 3 GPa, however, a nonmagnetic component appears that can be fitted to a single asymmetric quadrupole doublet with a centre shift corresponding to valence between Fe²⁺ and Fe³⁺. This is consistent with X-ray diffraction data that show an accompanying transition from the orthorhombic structure to the NiAs structure, where localised electron transfer could occur across pairs of face-shared octahedra or extended electron delocalisation could occur along sheets of face- and edge-shared octahedra.     

Magnetic properties of the uranium sesquichalcogenides

Magnetic measurements on the orthorhombic uranium sesquichalcogenides and orthorhombic U₃Te₄ were performed in the temperature range 4.2–1000 K and in magnetic fields up to 140 kOe. The temperature dependence of the reciprocal susceptibility was found to be curvilinear for all the investigated compounds. At low temperatures U₂Te₃ and U₃Te appeared to be antiferromagnetic below 106 K. U₂Se₃ and U₂S₃ seem to have a more considerable ferromagnetic contribution below 60 and 80 K, respectively. The magnetic properties are discussed in terms of crystal structure and related properties of the investigated compounds.     

Experimental and theoretical studies of Si/P substituted orthorhombic Fe2P

A Mössbauer spectroscopic study of orthorhombic Fe₂P_1–x Si _x withx 0.35 was performed. A large spread in magnetic hyperfine fields was found at the six Fe positions ranging from 10–26 T at 4.2 K. Small rearrangements in the crystal positions as compared to the hexagonal phase cause large changes in the magnetic field. Large changes in Fe magnetic moments have also been obtained in a spin-polarized LMTO band calculation performed on orthorhombic Fe₂P as compared to a similar calculation of hexagonal Fe₂P.     

A study of the magnetic and dielectric properties of Y Fe0.5Cr0.5O3

Y Fe_0.5Cr_0.5O₃ ceramics have been synthesized by a conventional solid-state reaction. Powder X-ray diffraction shows that this compound possesses an orthorhombic structure with Pnma space group. It exhibits a high magnetic transition temperature at around 250 K with weak ferromagnetic behavior below this temperature. A dielectric relaxation following the Arrhenius law found in the Y Fe_0.5Cr_0.5O₃ compound can be attributed to the charge carrier hopping conduction.     

Crystal structure and the magnetic state of Pr0.5Sr0.5Co0.5Fe0.5O3

The magnetic properties and crystal structure of the Pr_0.5Sr_0.5Co_0.5Fe_0.5O₃ compound are studied by neutron and x-ray diffractions using synchrotron radiation. These measurements show that this compound is a dielectric spin glass with a magnetic moment freezing temperature of about 70 K. As temperature decreases in the range 30–95 K, a structure phase transition of the first order occurs with an increase in the symmetry from orthorhombic (space group Imma) to tetragonal (space group I4/mcm). It is assumed that the transition is caused by a change in the 4f electron configuration of the Pr³⁺ ions.