Magnetic ordering in manganites substituted by chromium ions

NdMn_1?x Cr _x O₃ and Nd_0.6Ca_0.4Mn_1?x Cr _x O₃ solid solutions have been studied by neutron diffraction and magnetic measurements. NdMn_0.5Cr_0.5O₃ is found to have a magnetic structure consisting of an antiferromagnetic G-type component and a ferromagnetic component, which are caused by 3d ions. The magnetic moments of the neodymium ions are parallel to the ferromagnetic component. Nd_0.6Ca_0.4Mn_0.5Cr_0.5O₃ mainly has a G-type magnetic structure, and the magnetic moments of the neodymium ions are normal to the antiferromagnetism vector. Magnetic phase diagrams are plotted for both systems. They are interpreted on the assumption that the Mn³⁺-O-Cr³⁺ superexchange interactions are positive and the Mn⁴⁺-O-Cr³⁺ interactions are negative; the fact that manganese and chromium ions are not ordered in a crystal lattice is taken into account. Concentration magnetic phase transformations proceed through a two-phase state because of the internal chemical inhomogeneity of the solid solutions.     

High resolution diffraction and small angle scattering neutron investigations of LaCo<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>3+</Subscript><Subscript>δ</Subscript>: effect of oxygen content

We have investigated LaCo_0.5Mn_0.5O_{3+ δ} compounds with different oxygen content by means of magnetization, high resolution and small-angle neutron diffraction measurements. Oxygen content decrease down to stoichiometric composition leads to an essential increase of T_C and magnetic moment while Co/Mn ionic ordering degree is kept almost constant. It is assumed that upon oxygen reduction Co³⁺ ions change their valence state down to 2+ one that leads to dominating of Co²⁺-Mn⁴⁺ ferromagnetic interactions as well as T_C increase. Magnetic properties can be explained in terms of coexistence of long-range ferromagnetic order and short-range clusters with antiferromagnetic interactions prevailing. Size distribution of the mentioned short-range magnetic inhomogeneities is rather mild within the samples but it is strongly temperature dependent.     

Magnetic properties and Griffiths singularity in La0.45Sr0.55 Mn1−xCoxO3

The magnetic properties and the Griffiths singularity were investigated in Mn-site doped manganites of La_0.45Sr_0.55Mn_1−xCo_xO₃ (x=0, 0.05, 0.10 and 0.15) in this work. The parent sample La_0.45Sr_0.55MnO₃ undergoes a paramagnetic-ferromagnetic transition at T_C=290 K and a ferromagnetic-antiferromagnetic transition at T_N=191 K. The doping of Co ions enhances the ferromagnetism and suppresses the antiferromagnetism. The enhanced ferromagnetism results from the fact that the Co doping enhances the Mn³⁺-Mn⁴⁺ double-exchange interaction and induces the Co²⁺-Mn⁴⁺ ferromagnetic superexchange interaction. Detailed investigation on the magnetic behavior above T_C exhibits that the Griffiths singularity takes place in this series of Mn-site doped compounds. The correlated disorder induced by the Co ionic doping, together with the phase competition from the ferromagnetic and the antiferromagnetic interactions among Mn ions, is responsible for the Griffiths singularity.     

Phase separation in a manganite La<Subscript>0.95</Subscript>Ba<Subscript>0.05</Subscript>MnO<Subscript>3</Subscript> crystal

The structure and magnetic states of a crystal of lightly doped manganite La_0.95Ba_0.05MnO₃ were studied using thermal-neutron diffraction, magnetic measurements, and electrical resistance data in a wide temperature range. It is shown that, in terms of its magnetic properties, the orthorhombic crystal is characterized by two order parameters, namely, antiferromagnetic (T _N = 123.6 K) and ferromagnetic (T _C = 136.7 K). The results obtained differ in detail from known information on the manganites La_0.95Ca_0.05MnO₃ and La_0.94Sr_0.06MnO₃. Two models of the magnetic state of the La_0.95Ba_0.05MnO₃ crystal are discussed, one of which is a model of a canted antiferromagnetic spin system and another is associated with the phase separation of the manganite. Arguments are advanced in favor of the coexistence in this crystal of the antiferromagnetic phase (about 87%) with a Mn⁴⁺ ion concentration of 0.048 and the 1/16-type charge-ordered ferromagnetic phase (about 13%) with a Mn⁴⁺ ion concentration of 0.0625. The specific features of the manganite studied are due to self-organization of the La_0.95Ba_0.05MnO₃ crystal lattice caused by the relatively large barium ion size.     

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.     

Phase transitions in La1−x CaxMnO3−x/2 manganites

The crystal structure parameters and magnetic and electrical properties of La_1?x Ca_xMnO_3?x/2 reduced manganites with 0≤x≤0.5 are established. These investigations contribute to the understanding of magnetic interactions in manganites without Mn⁴⁺ ions. It is found that these manganites show a long-range antiferromagnetic order up to x=0.09 and transform into spin glasses at 0.09<x≤0.35. The compositions in the range 0.35<x≤0.5 show a strong increase in the spontaneous magnetization and critical point associated with the appearance of spontaneous magnetization and can therefore be viewed as inhomogenious ferromagnets. The magnetic and crystal structure peculiarities of La_0.5Ca_0.5MnO_2.75 are established by the neutron diffraction method. The strongly reduced samples show a large magnetoresistance below the point where the spontaneous magnetization develops. The magnetic phase diagram of La_1?x Ca_xMnO_3?x/2 is established by magnetization measurements. The magnetic behavior is interpreted assuming that the Mn³⁺-O-Mn³⁺ magnetic interaction is anisotropic (positive-negative) in the orbitally ordered phase and isotropic (positive) in the orbitally disordered phase. Introduction of the oxygen vacancies changes the magnetic interaction sign from positive to negative, thereby leading to a spin glass state in strongly reduced compounds. The results obtained reveal unusual features of strongly reduced manganites such as a large ferromagnetic component, a high magnetic ordering temperature, and a large magnetoresistance despite the absence of Mn³⁺-Mn⁴⁺ pairs. In order to explain these results, the oxygen vacancies are supposed to be ordered.     

Antiferromagnet-ferromagnet transition in α-MnxS manganese sulfides

Off-stoichiometric manganese monosulfides α-Mn_xS (1≤x≤1.25) are synthesized, and their crystal structure and magnetic properties are studied in the 4.2-to 300-K range. The compounds have a NaCl fcc lattice. Increasing the manganese ion concentration x in the antiferromagnetic semiconductors α-Mn_xS is found to result in concentration-(x _c ～ 1.05) and temperature-driven (T _c ～ 50 K) magnetic transitions from the antiferromagnetic to ferromagnetic state, with the cubic structure remaining unchanged.     

Synthesis and magnetic properties of hexagonal Y(Mn,Cu)O3 multiferroic materials

Single-phase hexagonal-type solid solutions based on the multiferroic YMnO₃ material were synthesized by a modified Pechini process. Copper doping at the B-site (YMn_1−xCu_xO₃; x<0.15) and self-doping at the A-site (Y_1+yMnO₃; y<0.10) successfully maintained the hexagonal structure. Self-doping was limited to y(Y)=2 at% and confirmed that excess yttrium avoids formation of ferromagnetic manganese oxide impurities but creates vacancies at the Mn site. Chemical substitution at the B-site inhibits the geometrical frustration of the Mn³⁺ two-dimensional lattice. The magnetic transition at T_N decreases from 70 K down to 49 K, when x(Cu) goes from 0 to 15 at%. Weak ferromagnetic Mn³⁺-Mn⁴⁺ interactions created by the substitution of Mn³⁺ by Cu²⁺, are visible through the coercive field and spontaneous magnetization but do not modify the overall magnetic frustration. Presence of Mn³⁺-Mn⁴⁺ pairs leads to an increase of the electrical conductivity due to thermally-activated small-polaron hopping mechanisms. Results show that local ferromagnetic interactions can coexist within the frustrated state in the hexagonal polar structure.     

Ferromagnetic superstructure of an La0.85Sr0.15MnO3 manganite single crystal

The elastic thermal-neutron scattering patterns of a La_0.85Sr_0.15MnO₃ manganite orthorhombic single crystal are investigated in the temperature range 4.2–300 K. It is found that, in addition to the known ferromagnetic ordering (T _C=240 K), this compound exhibits a ferromagnetic superstructure with the (010)2π/b wave vector (in the Pnma setting of the space group D _2h ¹⁶ ). The ferromagnetic superstructure is observed in the studied crystal at temperatures ranging from 4.2 to 200 K. It is shown that the formation of the ferromagnetic superstructure in this compound is directly associated with a 1/8-type charge ordering of Mn³⁺ and Mn⁴⁺ ions.     

Structural and magnetic inhomogeneities,phase transitions, 55Mn nuclear magnetic resonance,and magnetoresistive properties of La0.6 − x Nd x Sr0.3Mn1.1O3-δ ceramics

The structure, lattice imperfection, and properties of ceramic samples La_{0.6 ? x} Nd _x Sr_0.3Mn_1.1O_3-δ (x = 0–0.4) have been investigated using the X-ray diffraction, resistive, magnetic (χ_ac, ⁵⁵Mn NMR), magnetoresistive and microscopic methods. It has been shown that there is a satisfactory agreement between the concentration decrease in the lattice parameters a of the rhombohedral (x = 0, 0.1, 0.2) and cubic (x = 0.3, 0.4) perovskite structures and the average ionic radii $\bar R$ for the lattice containing anion vacancies, cation vacancies, and nanostructured clusters with Mn²⁺ ions in A-positions. With an increase in the neodymium concentration x, the vacancy-type imperfection increases, the cluster-type imperfection decreases, the temperatures of metal-semiconductor phase transition T _ms and ferromagnetic-paramagnetic phase transition T _C decrease, and the content of the ferromagnetic phase decreases. The anomalous hysteresis is associated with the appearance of unidirectional exchange anisotropy induced in a clustered perovskite structure consisting of a ferromagnetic matrix and a planar antiferromagnetic cluster coherently coupled with it. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra has revealed a high-frequency electronic double exchange (Mn³⁺-O^2?-Mn⁴⁺) ? (Mn⁴⁺-O^2?-Mn³⁺) and an inhomogeneity of the magnetic and charge states of manganese due to the heterogeneous environment of the manganese ions by other ions and defects. The observed changes in the resonant frequency and width of the resonance curve are caused by changes in the ratio Mn³⁺/Mn⁴⁺ and magnetic inhomogeneity. An increase in the neodymium concentration x leads to a decrease in the ferromagnetic phase content determined from the dependences 4πNχ_ac(T) and the ⁵⁵Mn NMR curves. The phase diagram characterizes an interrelation between the composition, the imperfection of the structure, and the transport, magnetic, and magnetoresistive properties of lanthanum neodymium manganite perovskites. It has been found that there is a correlation between the imperfection, magnetic inhomogeneity, coercive force, and magnetoresistance effect exhibited by the perovskite structure.     

Charge ordering and structural transitions in Pr0.5Sr0.41Ca0.09MnO3

The structural and magnetic transitions in Pr_0.5Sr_0.41Ca_0.09MnO₃ have been investigated by neutron diffraction and electron microscopy. Two structural transitions, Imma to I4/mcm and I4/mcm to Pmmn, are observed by decreasing the temperature. Two magnetic transitions, from a paramagnetic insulating to a ferromagnetic metallic and from a ferromagnetic metallic to an antiferromagnetic insulating states at T_C=250 K and T_N=180 K, respectively, are also observed. The structures of these three forms have been determined from neutron powder diffraction data. The first important result concerns the low temperature antiferromagnetic CE type and charge ordered structure, which has been refined in the Pmmn space group, without any constraint. This structure is completely long range ordered, with two Mn-sites, Mn³⁺ in tetragonally elongated octahedra, and Mn⁴⁺, off-centered in nearly regular octahedra. The second important point concerns the abrupt character of the structural transition from the I4/mcm to the Pmmn structure, without any appearance of incommensurability. The magnetic and transport properties of this compound are compared with those of Pr_0.5Sr_0.5MnO₃.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.     

Effect of Ca doping on the magnetic properties of Nd0.5Sr0.5MnO3 studied by electron spin resonance

The magnetic properties of Ca-doped Nd_0.5Sr_0.5MnO₃ have been studied by electron spin resonance (ESR) and dc magnetization measurements. The antiferromagnetic order and charge order are found to occur separately at T_N=200 K and T_co=150 K, respectively. Compared to the undoped Nd_0.5Sr_0.5MnO₃, the ferromagnetic correlations are suppressed by doping of the small Ca²⁺ ion. In addition, the antiferromagnetic transition temperature is enhanced to 200 K, which can be explained by an increase of superexchange interaction between Mn³⁺ and Mn⁴⁺ ions as their distance decreases.     

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.     

Magnetic, electrical, and optical properties of electron-doped Ca1 − x LaxMnO3 − δ(x ≤ 0.12) single crystals

The magnetic, electrical, and optical properties of Ca_{1 ? x} La_xMnO_{3 ? δ}(x ≤ 0.12) manganite single crystals have been studied. The state with a spatially inhomogeneous electron distribution has been found. Interrelations between the electric and magnetic subsystems are analyzed. The obtained magnetic data show evidence for the formation of a G-type antiferromagnetic (G-AFM) phase with a spin-canted structure in the crystal with x = 0.05, for which the Curie and Néel temperatures are T _C = T _N(G) = 115 K. On cooling from the paramagnetic state, the crystals with x = 0.10 and 0.12 exhibit transitions from the paramagnetic to a C-type antiferromagnetic (C-AFM) phase in a part of the volume at T _N(C) = 150 and 200 K, and from the paramagnetic to the G-type antiferromagnetic (G-AFM) phase in the remaining volume at T _N(G) = 110 and 108 K, respectively. The onset of the C-type magnetic phase nucleation in crystals is observed at lower dopant (La) concentrations than in polycrystalline samples, which is explained by the deviation of single crystals from the stoichiometry with respect to oxygen. The magnetic phase transitions are manifested by anomalies in the electric resistance and magnetoresistance of doped crystals. An analysis of the electrical and optical properties of the samples shows evidence of (i) the formation of a charge energy gap in the C-AFM phase with retained paramagnetic metallic regions and (ii) the presence of ferromagnetic “metallic” droplets in the insulating G-AFM phase. The multiphase state of Ca_{1 ? x} La_xMnO_{3 ? δ} manganite single crystals featuring the coexistence of two magnetic phases, the regions with orbital/charge ordering, and the FM “metallic” droplets is related to a competition of exchange interactions by the superexchange and double exchange mechanisms.     

Understanding the magnetic ground state of rare-earth intermetallic compound Ce4Sb3: Magnetization and neutron diffraction studies

Magnetization and neutron diffraction studies have been performed on Ce₄Sb₃ compound (cubic Th₃P₄-type, space group I4¯3d, no. 220). Magnetization of Ce₄Sb₃ reveals a ferromagnetic transition at ∼5 K, the temperature below which the zero-field-cooled and field-cooled magnetization bifurcate in low applied fields. However, a saturation magnetization (M_S) value of only ∼0.93μ_B/Ce³⁺ is observed at 1.8 K, suggesting possible presence of crystal field effects and a paramagnetic/antiferromagnetic Ce³⁺ moment. Magnetocaloric effect in this compound has been computed using the magnetization vs. field data obtained in the vicinity of the magnetic transition, and a maximum magnetic entropy change, −ΔS_M, of ∼8.9 J/kg/K is obtained at 5 K for a field change of 5 T. Inverse magnetocaloric effect occurs at ∼2 K in 5 T indicating the presence of antiferromagnetic component. This has been further confirmed by the neutron diffraction study that evidences commensurate antiferromagnetic ordering at 2 K in zero magnetic field. A magnetic moment of ∼1.24μ_B/Ce³⁺ is obtained at 2 K and the magnetic moments are directed along Z-axis.     

Structure and magnetism of the manganite LaMnO3 with defects

The structural and magnetic states of LaMnO₃ samples containing various concentrations of antisite defects created by fast-neutron irradiation were studied by neutron diffraction, x-ray diffraction, and magnetic measurements. It is found that the static uncorrelated displacements of oxygen ions induced by the formation of antisite defects break the Jahn-Teller Q ₂ mode and the initial orthorhombic O′-type structure transforms into the pseudocubic O ^* modification. As a result, the indirect ferromagnetic exchange caused by the overlap of the e _g orbitals of manganese ions and the p _σ orbitals of oxygen ions becomes three-dimensional and the initial A-type antiferromagnetic phase transforms into a canted ferromagnetic phase. The magnetic phase diagram of LaMnO₃ is plotted for various defect concentrations.     

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 and properties of the Nd0.6Ca0.4Mn0.5Cr0.5O3 manganite

The effect of high chromium concentrations on the charge and orbital ordering in manganites is studied using neutron diffraction and magnetic measurements. It is found that the Nd_0.6Ca_0.4Mn_0.5Cr_0.5O₃ manganite exhibits a CE-type antiferromagnetic ordering with a weak ferromagnetic component below 160 K. In the Nd_0.6Ca_0.4Mn_0.5Cr_0.5O₃ manganite, the Mn and Cr ions form antiferromagnetic zigzag chains that are likewise antiferromagnetically coupled with one another in the basal plane and are arranged along the b axis of the orthorhombic structure with oppositely directed spins. An applied magnetic field of 5 T does not change the magnetic structure.     

Investigation of the GdMn2O5 multiferroic by the μSR method

The GdMn₂O₅ multiferroic (a ceramic sample and a sample consisting of a large array of randomly oriented single crystals with linear dimensions 2–3 mm) has been studied by the μSR method within the temperature range 10–300 K. Three anomalies in the temperature behavior of the parameters of the muon polarization relaxation function, namely, close to the phase transition driven by the onset of long-range magnetic order in the manganese ion subsystem (T _N1 = 40–41 K), near the lock-in transition initiated by an abrupt change of the wave vector of magnetic order (T _L = 35 K), and close to the Gd³⁺ ion ordering temperature (T _N2 = 15 K), have been found. An analysis of the time spectra of muon spin precession in the internal magnetic field of the samples has revealed two positions of preferable muon localization sites in samples, which differ in precession frequencies and the character of their behavior with temperature. The lower-frequency precession driven by Mn⁴⁺ ions, ferromagnetic Mn4⁺-Mn⁴⁺ + muonium complexes, and Gd³⁺ions is observed throughout the temperature region T < T _N1 and is practically independent of temperature. At temperatures T < T _L = 35 K, a higher-frequency precession associated with Mn³⁺ ions appears also. It is characterized by a temperature dependence ～(T/T _N1)^β with the index β = 0.39, which is typical of Heisenberg-type 3D magnets. For T < T _N1, a deficiency of the rest total asymmetry is observed. This phenomenon can probably be assigned to formation of muonium, which suggests that charge transfer processes play an important role in formation of long-range magnetic order.