Magnetic properties of La0.70Sr0.30MnO2.85 anion-deficient manganite under hydrostatic pressure

The magnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite are studied experimentally under hydrostatic pressure. The results show that, in the whole pressure range under investigation (0–1 GPa), the sample is a spin glass with a smeared phase transition to the paramagnetic state. It is found that the spin glass state arises from the frustration of the exchange coupling of the ferromagnetic clusters embedded in the antiferromagnetic matrix. The fraction of the sample volume occupied by the ferromagnetic phase is found to be V _fer ～ 13%. Under hydrostatic pressure, the freezing temperature T _f of the magnetic moments of the ferromagnetic clusters increases at a rate of 4.30 K/GPa and the magnetic ordering temperature T _MO increases at a rate of 12.90 K/GPa. In addition, the ferromagnetic part of the sample increases by ΔV _fer ～ 5%. The enhancement of the ferromagnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite under hydrostatic pressure is explained by the redistribution of oxygen vacancies and a decrease in the unit-cell parameters.     

Non-collinear magnetisation of V clusters supported on a Cu (1 1 1) surface: Theory

Magnetic properties and electronic structure of V clusters supported on a Cu (1 1 1) substrate, have been calculated from a first principles method. We observe in general non-collinear magnetic structures that are the result of antiferromagnetic interactions on a frustrated lattice. The values of the magnetic moments range from ∼0 to 2.7 μ_B/atom, depending on cluster geometry.     

Magnetic structure of the manganites heavily doped by Fe and Cr ions

Powder neutron diffraction and magnetic studies have been performed for NdMn_0.5Fe_0.5O₃ and NdMn_0.5Cr_0.5O₃ manganites. In NdMn_0.5Cr_0.5O₃, magnetic structure has been revealed consisting of ferromagnetic and G-type antiferromagnetic components as result of a 3d-ions magnetic moments ordering. Magnetic moments of Nd-ions are parallel to the ferromagnetic component. In NdMn_0.5Fe_0.5O₃ only the antiferromagnetic G-type structure has been found whereas Nd-sublattice was not ordered. In the both compounds, magnetic moments of 3d-ions are significantly less than one can expect, what is interpreted in terms of intrinsic chemical inhomogeneity. Magnetic phase diagrams have been constructed for the Nd(Mn_1−xM_x)O₃ (M=Fe, Cr) systems, interpreted assuming superexchange interactions Mn³⁺–O–Cr³⁺ to be positive, Mn³⁺–O–Fe³⁺ negative and taking into account a disordered arrangement of Mn and Cr ions in the crystal structure sublattice as well as interplay between Jahn–Teller effect and superexchange interactions.     

Magnetic structure of a CaMnO2.75 crystal with ordered oxygen vacancies

The magnetic state of a CaMnO_{3 ? δ} crystal with ordered oxygen vacancies (for δ = 0.25, when the numbers of Mn⁴⁺ and Mn³⁺ ions in the manganite are equal to each other) is studied using neutron diffraction. Magnetic scattering in the CaMnO_2.75 crystal in the ground state is determined by the wave vector (1/2, 1/2, 1/2)2π/a _c (G-type antiferromagnetic order). In the crystal, long-range magnetic order disappears at the temperature T _N = 116 K, whereas short-range magnetic order is retained up to 240 K. It is shown that the instability of the G-type structure in the temperature range 60 K < T < T _N is associated, in many respects, with the formation of the C′ antiferromagnetic phase in the bulk of the crystal. The structure of the C′ antiferromagnetic phase involves chains with Mn³⁺-Mn⁴⁺ ferromagnetic interaction. A comparison of the results of the neutron diffraction investigations with the experimental data on the magnetic characteristics and electrical resistivity demonstrates that the specific features revealed in the spin system of the CaMnO_2.75 crystal are governed directly by the competition of the Mn³⁺-Mn⁴⁺ ferromagnetic double exchange with the antiferromagnetic superexchange between manganese ions.     

Magnetic and crystal structures of iron-ion-doped TbBaCo<Subscript>2</Subscript>O<Subscript>5 + γ</Subscript>

Neutron diffraction and magnetic studies of a TbBaCo₂O_{5 + γ} polycrystalline sample with a perovskite-like layered structure have revealed that spontaneous magnetization appears at 305 K and decreases sharply below 200 K. It has been shown that the crystal structure is described by space group Pmmm with a 2a _p · a _tp · 2a _p unit cell. The magnetic structure in the high-temperature magnetic phase consists of the G-type antiferromagnetic and ferromagnetic components, whereas the magnetic structure in the low-temperature phase is a G-type antiferromagnetic. The ferromagnetic component appears due to the noncollinearity of the magnetic moments of Co³⁺ ions, which are in the high-spin state in pyramids and in the low-spin state in octahedrons. The antiferromagnetic component is present in the octahedral sublattice, because oxygen vacancies are partially ordered.     

A Mössbauer study of Pb4Fe3O8Cl,a three-layer magnet

The study of Mössbauer spectra from Pb₄Fe₃O₈Cl allows the observation of crystallographic sites associated with two kinds of magnetic layers present in the structure. Magnetic order appears simultaneously in the two sites below T_N at 602 K. The following features are observed (i) magnetic moments in a plane of easy magnetization perpendicular to the fourfold axis, (ii) antiferromagnetic behavior, as evidenced by the rotation of the magnetic moments under the effect of an external field, (iii) slightly different critical exponents β (0.311 ± 0.003 and 0.295 ± 0.003) for the two magnetic layers.     

Magnetic and luminescent properties of manganese-doped ZnSe crystals

Magnetic and photoluminescent properties of manganese-doped ZnSe crystals with different impurity concentrations were investigated. The concentration of Mn²⁺ ions in ZnSe crystals has been varied from 0.01 to 0.3 at%. Magnetic and photoluminescent studies have confirmed the introduction of Mn in ZnSe crystals. It was established that Mn²⁺ ions are responsible for the emission bands with maximum at 616 nm and 633 nm, which correspond to ⁴T₂→⁶A₁ and ⁴T₁→⁶A₁ intracentre transitions of Mn²⁺ ions respectively. It was found that the concentration quenching of the photoluminescent bands is associated with Mn²⁺ ions, which are due to the formation of Mn–Mn clusters. Magnetic properties studies have shown that at high doping levels the manganese atoms form Mn–Mn clusters in ZnSe. From the temperature dependence of magnetic susceptibility of ZnSe:Mn crystals that follows the Curie–Weiss law, it was possible to estimate the Curie–Weiss temperature Θ(x) and the effective Mn–Mn antiferromagnetic exchange constant (J₁).     

Structure and physical properties of layered double perovskite NdBaCo2O5.50 + δ (δ ≈ 0.25)

Magnetic, electric, and elastic properties of the crystal and magnetic structure of double layered perovskite NdBaCo₂O_{5.50 + δ} are studied by the neutron diffraction method at various temperatures. The data are analyzed using two models of crystal structure. In the first model, the sample consists of two crystal-structure phases with ordered and disordered arrangements of oxygen vacancies. In the second model, a new crystal-structure phase is formed in this compound, which is characterized by ordering of oxygen vacancies in the plane of the rare-earth ion in the 1c crystallographic position (0, 0, 1/2) of space group Pmmm. Two crystal-structure models correspond to different types of magnetic ordering (a mixture of a ferromagnetic phase and a G-type antiferromagnetic phase is presumed in the two-phase crystal-structure model, while a canted antiferromagnetic structure is presumed in the one-phase crystal structure model). The behavior of electric and elastic parameters is better described in the first model, while neutron diffraction studies are in better agreement with the second model.     

Ferromagnetism induced by intrinsic defects and nitrogen substitution in SnO2 nanotube

The possibilities of magnetism induced by intrinsic defects and nitrogen substitution in (5,5) single-wall SnO₂ nanotube are investigated by ab initio calculations. The calculated results indicate that a stoichiometric SnO₂ nanotube is nonmagnetic. The tin (Sn) vacancy can induce the magnetic moments rather than oxygen vacancy, which is originated from the polarization of O 2p electrons. A couple of tin vacancies can lead to the ferromagnetic coupling. A nitrogen substitution for oxygen also produces magnetic moments. When substituting two nitrogen atoms, the characteristics of exchange coupling depend upon the distance of two nitrogen atoms. The longer distance of two nitrogen atoms prefers the ferromagnetic coupling, whereas the short distance leads to the antiferromagnetic coupling.     

Magnetic properties of CuInSe2-(FeSe)2 solid solutions

Measurements of the magnetic characteristics of Cu_{1 ? x} In_{1 ? x} Fe_2x Se₂ solid solutions and their approximation by Langevin and Curie equations show that the properties observed in samples are the result of antiferromagnetic clusters in which magnetic moments fall to ～0.8 μ_B/atom as x rises, confirming that the antiferromagnetic interaction in the samples grows stronger.     

Imperfection of the clustered perovskite structure, phase transitions, and magnetoresistive properties of ceramic La0.6Sr0.2Mn1.2 ? x Ni x O3 ± δ (x = 0–0.3)

Ceramic samples of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 ? x} Ni _x O_{3 ± ??} (0 ?? x ?? 0.3) have been investigated using the X-ray diffraction, magnetic (??_ac), ⁵⁵Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn²⁺ ions in the A-positions. The substitution of Ni³⁺ ions (r = 0.74 ?) for Mn³⁺ ions (r = 0.785 ?) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature T _C, and the metal-semiconductor phase transition temperature T _ms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn³⁺ and Mn⁴⁺. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn²⁺ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn³⁺ ? O^2? ? Mn⁴⁺; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn⁴⁺ ions. The local hyperfine interaction fields on ⁵⁵Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn³⁺ ? O^2? ? Mn⁴⁺. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T _C and T _ms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.     

Magnetic properties of electron-doped La0.23Ca0.77MnO3 nanoparticles

Magnetic properties of electron-doped La_0.23Ca_0.77MnO₃ manganite nanoparticles, with average size of 12 and 60?nm, prepared by the glycine?Cnitrate method, have been investigated in the temperature range 5?C300?K and magnetic fields up to 90?kOe. It is suggested that weak ferromagnetic moment results from ferromagnetic shells of the basically antiferromagnetic nanoparticles and from domains of frustrated disordered phase in the core. Assumption of two distinct sources of ferromagnetism is supported by the appearance of two independent ferromagnetic contributions in the fit of the T ^3/2 Bloch law to spontaneous magnetization. The ferromagnetic components, which are more pronounced in smaller particles, occupy only a small fraction of the nanoparticle volume and the antiferromagnetic ground state remains stable. It is found that the magnetic hysteresis loops following field cooled processes, display size-dependent horizontal and vertical shifts, namely, exhibiting exchange bias effect. Time-dependent magnetization dynamics demonstrating two relaxation rates were observed at constant magnetic fields upon cooling to T?<?100?K.     

Ab initio study on magnetism at GaN (100) and (101) surfaces

The magnetism of GaN (100) and (101) surfaces containing neutral intrinsic defects has been investigated using ab inito calculations. Ideal Ga-ended GaN (100) surfaces and (101) surfaces are nonmagnetic. After surface relaxation, an N-ended GaN (100) surface transforms to a Ga-end, which presents local magnetic moments being ferromagnetically coupled. Neutral gallium vacancies at the (100) surface bring about large magnetic moments, which are ferromagnetically coupled. The spin-polarization of 2p electrons of nitrogen atoms is responsible for the induced magnetic moments. Neutral nitrogen vacancies at the (101) surface induce a zero magnetic moment. Neutral gallium vacancies at the (101) surface might lead to an antiferromagnetic state.     

Electronic structures and local magnetic moments in ferromagnetic and antiferromagnetic FexRh1−x alloys

Ground-state magnetic properties of ordered FeRh alloys are discussed by using the realistic canonical d-band model within the Hartree-Fock and coherent potential approximations. Local magnetic moments of Fe and Rh atoms in ferromagnetic and antiferromagnetic Fe_xRh_1-x alloys are computed as a function of x, the Fe concentration. Calculated results are in good agreement with the neutron-diffraction data. The band-energy calculation indicates that in Fe-rich alloys excess Fe atoms substituted on Rh sites having larger magnetic moments than Rh atoms, play an important role in the antiferromagnetic to ferromagnetic transition observed at low temperatures.     

Ferromagnetic-to-antiferromagnetic transition in (Hf1−xTix)Fe2 intermetallic compounds induced by geometrical frustration of the Fe(2a) sites

The ferromagnetic-to-antiferromagnetic transition in the hexagonal (Hf_1−xTi_x)Fe₂ (0?x?1) intermetallic compounds has been investigated by ⁵⁷Fe Mössbauer spectroscopy. At 10 K, the transition occurs within rather narrow concentration limits, around x=0.55–0.65. We found that the key factor governing the unexpected quick change of the magnetic structure is the magnetic frustration of the Fe(2a) sites. The magnetic frustration is caused by the noncollinearity of the Fe(6h) magnetic sublattice. The noncollinearity arises from the rotation of the magnetic moments due to the competition between the ferromagnetic exchange interactions and the antiferromagnetic Fe(6h)–Ti–Fe(6h) interaction. In the compounds with x=0.4–0.6, the temperature transitions to the antiferromagnetic state are observed. As an example, the Hf_0.4Ti_0.6Fe₂ compound is completely antiferromagnetic above 200 K.     

Spin reorientation effects in GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> induced by applied field and temperature

Magnetic properties of GdFe₃(BO₃)₄ single crystals were investigated by ⁵⁷Fe-Mössbauer spectroscopy and static magnetic measurements. In the ground state, the GdFe₃(BO₃)₄ crystal is an easy-axis compensated antiferromagnet, but the easy axis of iron moments does not coincide with the crystal C₃ axis, deviating from it by about 20°. The spontaneous and field-induced spin reorientation effects were observed and studied in detail. The specific directions of iron magnetic moments were determined for different temperatures and applied fields. Large values of the angle between the Fe³⁺ magnetic moments and the C₃ axis in the easy-axis phase and between Fe³⁺ moments and the a₂ axis in the easy-plane phase reveal the tilted antiferromagnetic structure.     

Ferro-and antiferromagnetic ordering in LaMnO3+δ

A neutron diffraction study of the crystalline structure and magnetic state of LaMnO_3+δ samples with different deviations from oxygen stoichiometry has been made at 4.2 K. It is shown that annealing at reduced oxygen pressure is accompanied by transformation of the magnetic structure from ferromagnetic, with magnetic moments parallel to the b axis, to antiferromagnetic, with the wave vector k=0 and the moments along the a axis (space group Pnma). A comparison of experimental with expected Mn ion moments suggests that magnetic order does not extend throughout the sample volume. Part of the Mn ions form magnetic clusters ～20 Å in size.     

Ferrimagnetic transition in Fe0.9S: Magnetic,thermodynamic and kinetic aspects

Antiferromagnetic Fe_0.9S forms a ferrimagnetic superlattice in a narrow temperature range centred at 475 K (γ-transition). We have made a study in single crystals by specific heat, Mössbauer spectroscopy and magnetic susceptibility of the magnetic structure and kinetics and thermodynamics of formation of the ferrimagnetic component.The antiferromagnetic alignment and the spontaneous moment lie in the c-plane. The magnetic anisotropy energy is of the order of 0.4 K per Fe ion. Above 475 K and below T_N ≈ 598 K there is a change in ordering of the vacancies and a new antiferromagnetic structure is formed. At lower temperatures our value (100 kJ mol^?1) of the activation energy of diffusion of iron vacancies, determined from magnetic susceptibility, is in quite good agreement with the value (88 kJ mol^?1) obtained from radiotracer measurements by Condit et al.     

Structural and magnetic inhomogeneities, phase transitions, 55Mn NMR, and magnetoresistive properties of La0.6Sr0.2Mn1.2 − x Nb x O3 ceramics

Ceramic samples of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 ? x} Nb _x O₃ (x = 0–0.3) annealed at temperatures of 1260 and 1500°C have been investigated using the X-ray diffraction, electron microscopic, resistive, magnetoresistive, and magnetic (χ_ac, ⁵⁵Mn NMR) methods. It has been found that there is a correlation between the increasing unit cell parameter a of the rhombohedral R $\bar 3$ c structure and the average ionic radius with increasing niobium concentration x and annealing temperature for the case where the lattice contains anion vacancies, cation vacancies, and nanostructured clusters. The observed increase in the electrical resistivity and decrease in the temperatures of metal-semiconductor phase transition T _ms and ferromagnetic-paramagnetic phase transition T _C with an increase in the niobium concentration x and the annealing temperature have been explained by the decrease in the content of the ferromagnetic phase, as well as by changes in the ratio Mn³⁺/Mn⁴⁺, the oxygen nonstoichiometry, and the concentration of defects weakening the high-frequency electronic exchange of the ions Mn³⁺ ? Mn⁴⁺. The presence of nanostructured clusters in the lattice has been confirmed by an anomalous hysteresis associated with the unidirectional exchange anisotropy of the interaction between the ferromagnetic matrix and antiferromagnetic clusters with Mn²⁺ and Nb³⁺ in distorted A-positions. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra and their computer decomposition have revealed a high-frequency electronic exchange and an inhomogeneity of the magnetic and valence states of manganese due to the nonuniform distribution of all ions and defects. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T _C and T _ms, is caused by scattering at intracrystalline nanostructured heterogeneities of the imperfect perovskite structure, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between the composition, structure, resistive and magnetic properties of rare-earth manganites.     

Oxygen vacancies effects on phase diagram of epitaxial La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> thin films

We investigated the effects of oxygen vacancies on the structural, magnetic, and transport properties of La_1–x Sr _x MnO₃ (x=0.1, 0.2, 0.33, 0.4, and 0.5) grown around a critical point (without/with oxygen vacancies) under low oxygen pressure (10 Pa) and high oxygen pressure (40 Pa). We found that all films exhibit ferromagnetic behavior below the magnetic critical temperature, and that the films grown under low oxygen pressures have degraded magnetic properties with lower Curie temperatures and smaller magnetic moments. These results show that in epitaxial La_1–x Sr _x MnO₃ thin films, the magnetic and transport properties are very sensitive to doping concentration and oxygen vacancies. Phase diagrams of the films based on the doping concentration and oxygen vacancies were plotted and discussed.