Magnetic phase transitions in Nd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

The magnetic properties of manganites of the Nd_1?xCa_xMnO₃ system with x≤0.15 have been studied. It is shown that, in the 0.06≤x≤0.1 interval, the results can be interpreted using a model according to which the concentrational transition from a weakly ferromagnetic (WFM) state (x=0) to a ferromagnetic (FM) state (x>0.15) proceeds via a mixture of the exchange-coupled FM and WFM phases. In the vicinity of T=9 K, samples with 0.06≤x≤0.1 exhibit a spontaneous magnetic phase transition involving reorientation of the magnetization vectors of the WFM and the exchange-coupled FM phases. In the temperature interval between 5 and 20 K, a sample with the composition Nd^0.92Ca^0.08MnO^2.98 exhibits metamagnetic behavior. Magnetic phase diagrams in the H?T and T?x coordinates are presented. The appearance of the spin-reorientation transitions is explained in terms of the magnetic analog of the Jahn-Teller effect with allowance for the fact that, according to the neutron diffraction data, the magnetic moments of neodymium ions in the FM phase are parallel to the magnetic moments of manganese ions.     

Magnetocaloric effect in Pr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites

The magnetocaloric effect in alternating magnetic fields has been investigated in Pr_{1 − x} Ag _x MnO₃ manganites with x = 0.05−0.25. The stepwise reversal of the sign of the magnetocaloric effect has been revealed in a weakly doped sample (x = 0.05) at low temperatures (∼80 K). This reversal is attributed to the coexistence of the ferromagnetic and canted antiferromagnetic phases with different critical temperatures.     

Seebeck coefficient of Ln<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> perovskites in paramagnetic state

The Seebeck coefficient is a function of carrier concentration and configurational entropy. In this report, we semi-theoretically investigate the Seebeck coefficient of Ln _x Ca_1−x MnO₃ (Ln=Rare-earth) perovskites based on the electronic structure of the 3d orbitals of Mn ions, using the developed Heikes model, Boltzmann transport model, and diffusion model. The results show that the Seebeck coefficient of such a strongly correlated electron system in paramagnetic state is remarkably affected by site degeneracy. As temperature decreases, the evolution of the spin and orbital degrees of freedom together with the change in phonon scattering mode describes the Seebeck coefficient behavior satisfactorily. The phonon drag effect at low temperature is also discussed.     

Phase states in the Y<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> solid solution system

The room-temperature stability region of the tetragonal phase in the Y_{1 − x} Ca _x MnO₃ solid solution system has been found for the first time. The concentration boundaries between this phase and the orthorhombic (x > 0.5) and hexagonal (x < 0.25) phases are sensitive to the sample preparation conditions. The coexistence of the hexagonal and tetragonal phases in the range 0.15 < x < 0.25 indicates that these phases undergo a first-order reconstructive phase transition. Preliminary measurements of magnetic ordering effects for compositions with x = 0.3, 0.5, and 0.7 have been performed.     

Magnetic ordering in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3−<Emphasis Type="Italic">x</Emphasis>/2</Subscript> anion-deficient manganites

The structural, magnetic, and electrotransport properties of La_1?xSr_xMnO_{3? x/2}(0≤x≤0.30) manganites with perovskite structure are investigated experimentally as a function of oxygen deficiency. In the solid solutions La_1?xSr_xMnO₃, a change in the type of symmetry of the unit cell is observed at x=0.125. Samples with x≤0.125 are characterized by an O′-orthorhombic unit cell, whereas samples with x>0.125 are characterized by a rhombohedral unit cell. The structural properties of the anion-deficient solid solutions La_1?xSr_xMnO_3?x/2 are analogous to those of the stoichiometric system. It is assumed that, as the oxygen content decreases, La_{1? x}Sr_xMnO_3?x/2 anion-deficient solid solutions experience a series of successive magnetic phase transformations in the ground state: from an A-type (x=0) antiferromagnet to a cluster spin-glass-type inhomogeneous magnetic state (0.175>x≤0.30) through a two-phase (antiferromagnetic and ferromagnetic) state (0>x≤0.175). The anion-deficient solid solution with x=0.175 has the maximal value of the ferromagnetic component. As the oxygen deficiency increases, the resistivity of La_{1? x}Sr_xMnO_3?x/2 samples first decreases (up to a value of x=0.175), acquiring an activation character, and then increases (up to a value of x=0.30). In this case, none of the anion-deficient solid solutions exhibits a metal-semiconductor transition in the whole range of concentrations considered. A peak of magnetoresistance at a temperature below the point of magnetic ordering is observed only in the sample with x=0.175. The results of experiments carried out with a series of La_1?xSr_xMnO_3?x/2 anion-deficient solid solutions are summarized in the concentration diagrams of the spontaneous magnetic moment and the critical temperature of magnetic phase transitions. Hypothetical magnetic phase states are pointed out. The experimental results obtained can be interpreted in terms of the phase-separation model and the competition between ferromagnetic and antiferromagnetic indirect superex-change interactions. It is assumed that Mn³⁺-O-Mn³⁺ indirect superexchange interactions in the orbitally disordered phase are positive in the case of octahedral coordination of manganese ions and are negative when the coordination of at least one Mn³⁺ ion is pentahedral.     

Theory of the giant magnetoresistance in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>A<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

To clarify the origin of the giant magnetoresistance (GMR) observed in La_1?x A _x MnO₃ (A²⁺=Sr²⁺, Pb²⁺, Ba²⁺ and Ca²⁺), we have investigated theoretically the electrical resistivity ρ of carriers in the background of Mn spins which interact with each other through the double exchange interaction. It has been found that extraordinarily large pin fluctuations caused by the instability of the ferromagnetic state are responsible for the transport anomalies including the GMR.     

Metal-insulator transition in Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S crystals

Results of an experimental study of MnS, FeS, and Fe _x Mn_1?x S single crystals are presented. The phase composition, the lattice parameters, and the state of paramagnetic ions in Fe _x Mn_1?x S have been determined by x-ray diffraction analysis and Mössbauer spectroscopy. A sequence of transitions have been found in iron manganese sulfide with x = 0.29 at temperatures T ₁ ≈ 25–50 K, T ₂ ≈ 125 K, and T ₃ ≈ 190 K with a change in kinetic properties and the formation of a metallic state at low temperatures T ≈ 2 K. The possibility of a Mott-Hubbard transition in Fe _x Mn_1?x S sulfides with variation of the composition and the temperature is discussed.     

Magnetocaloric properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>K<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

A technology for obtaining single-phase ceramic samples of La_{1 − x} K _x MnO₃ manganites, as well as the dependence of their structure parameters on the potassium content, is described. The magnetocaloric effect in the samples has been measured by two direct methods, the classical method and the magnetic field modulation method, and has been calculated from the specific heat data. The values of the magnetocaloric effect obtained by these methods are significantly different. The observed discrepancies have been explained. Correlation between the doping level and the value of the effect has been found. It has been shown that the magnetic-field dependence of variation of the magnetic entropy near T _C in weak fields corresponds to theoretical calculations and that the value of the magnetocaloric effect in high magnetic fields can be predicted using this dependence.     

Spin-glass like behaviors in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Tb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> perovskite

A series of samples of La_1−x Tb _x MnO₃ (0⩽x⩽0.15) are prepared. The static and dynamic magnetizations of La_1−x Tb _x MnO₃ have been investigated. The results indicate that the spins with the short-range order are frozen into random direction at low enough temperatures which leads to the samples exhibiting the spin-glass like behavior. It is considered that the spin-glass like behavior originates from the competition between ferromagnetic double exchange among Mn³⁺ and Mn²⁺ and antiferromagnetic superexchange among Mn³⁺ and Mn³⁺, as well as Tb³⁺ and Tb³⁺.     

The magnetic properties of nanosized La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> (0.5 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.8)

Magnetic properties of La_1−x Ca _x MnO₃ (0.5 ≤ x ≤ 0.8) samples with an equivalent average particle size ~50 nm prepared by a sol–gel method were investigated. The charge ordering (CO) transition that is observed in the bulks disappears and the ferromagnetic (FM) transition occurs in all the prepared samples. For all the samples, the spontaneous magnetization (M _S) value is much lower than the corresponding theoretic value, which shows that the majority of the sample is antiferromagnetic (AFM). However, the M _S value is much larger than the corresponding value reported by some other groups. The invisible of CO transition and the large M _S value can be attributed to the good connection among the adjacent particles. Moreover, the exchange bias (EB) phenomenon is observed except the x = 0.5 sample. With x increasing, the M _S value decreases and the EB field increases, which can be understood by considering the coexistence of FM phase with Mn³⁺–Mn⁴⁺ spin clusters in the shell and the AFM phase in the core of the nanoparticles.     

High-temperature study of SrFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3−<Emphasis Type="Italic">z</Emphasis></Subscript> perovskites

The structure of high-temperature SrFe_{1 − x} Mo _x O_{3 − z} (0 ≤ x ≤ 0.5) phases was studied. Such studies are necessary to understand the mechanism of oxygen transport in membrane materials used for high-temperature oxygen separation.     

Thermal and magnetic properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The thermodynamic and magnetic properties of the La_{1 − x} Pb _x MnO₃ (0.24 ≤ x ≤ 0.40) solid solution system were investigated in the temperature range of 4.2–340 K. All objects were ferromagnetics with Curie temperature T _C ≈ 320–340 K, which slowly increased with x. The M(T) behavior in the magnetic ordering region indicated a nonuniform ground state, due possibly to the competition of ferromagnetic and antiferromagnetic interactions. The increase in the saturation magnetic moment with x can be described by a simple model of the binary bonds in La_{1 − x} Pb _x MnO₃.     

The theory of morphotropic phase transition in PbZr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ti<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript>

The concept of the mechanism of formation of morphotropic boundaries in T?x phase diagrams of solid solutions of complex oxides with the perovskite structure has been formulated. This concept is illustrated by calculation of the conditions for existence of morphotropic phase transition in a quasy-binary solid solution of the PbZr_{1 ? x} Ti _x O₃ and (1 ? x)PbMg_1/3Nb_2/3O₃ + xPbTiO₃ compositions.     

Intercluster conduction in lightly doped La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites in the paramagnetic temperature range

The magnetotransport and magnetic properties of La _{1 ? x} Ca _x MnO₃ polycrystalline samples (x = 0–0.3) annealed under vacuum and in the oxygen environment are investigated in the temperature range from 77 to 400 K. The magnetic studies of lightly doped manganites reveal persistence of short-range magnetic order up to a temperature T* ≈ 300 K, which is about 2–3 times higher than their Curie temperature T _C. The temperature dependence of the electrical resistivity measured from T* down to nearly T ≈ T _C is fitted by the relation logρ ～ T ^?1/2, which is characteristic of granular metals with electrons tunneling among nanoclusters of magnetic metals embedded in a dielectric host. The magnetoresistance of polycrystalline samples annealed in the oxygen environment has been observed to increase. The electrical, magnetic, and magnetotransport properties of the manganites can be accounted for by the formation of magnetic nanoclusters below T*, tunneling (or hopping) of carriers among the nanoclusters, variation in the magnetic cluster size, and tunneling barrier thickness with variations in temperature and magnetic field strength, as well as by the effect of annealing in different media on the cluster properties.     

Photoluminescence measurements in the phase transition region of Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S films

Thin films of Zn_1−x Cd _x S (0.1 ≤ x ≤ 0.5) were prepared by using pulsed laser ablation technique on corning glass substrates. Phase transition from cubic to hexagonal in Zn_1−x Cd _x S films is determined by X-ray diffraction analysis. We observed a lowering in the phase transition temperature with increase in the cadmium concentration. Transmission electron microscopy suggests the crystalline nature of thin films with average particle size of 15 nm. The grown Zn_1−x Cd _x S samples show the high peak intensity ratio of the near band edge emission to the defect center luminescence even at room temperature, which indicates the small concentration of complex defects in the samples. Photoluminescence measurement show stoichiometric dependence of the energy band gap and is found to have quadratic dependence on x.     

Abrupt changes in the temperature dependence of the ESR linewidth of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript> Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> MnO<Subscript>3</Subscript> single crystals

The temperature dependence of the ESR linewidth in La_{1 ? x} Ca _x MnO₃ single crystals with various dopant concentrations (x = 0.18, 0.2, 0.22, 0.25, and 0.3) has been studied. An abrupt decrease in the ESR linewidth has been observed in the samples with a dopant concentration of x = 0.18 and 0.2 near the respective temperatures T _OO′ ≈ 260 and 240 K of the orthorhombic to pseudocubic structural phase transition. The abrupt decrease in the ESR linewidth by approximately 180 Oe has been also observed in the whole temperature range when the concentration is increased from x = 0.2 to x = 0.22. The formula for the fourth moment of the ESR line has been derived including both crystal fields and isotropic exchange interactions and taking into account the difference between the exchange coupling of a spin to its nearest in-plane and out-of-plane neighbors. The formula has been used to estimate the parameter D of the crystalline field on Mn³⁺ ions.     

Relationship between the magnetoresistance and the magnetocaloric effect in La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites

A generalized expression relating the magnetoresistance of manganites La_{1 − x} Ag _x MnO₃ with the change in the magnetic entropy has been proposed. The correct inclusion of the acting mechanisms of appearance of the magnetoresistance is shown to lead to adequate agreement between the experimental and calculated values of ΔS _M .     

Electron spin resonance study of the local properties of the microscopic phase separation in La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> single-crystal films

Electron spin resonance is studied in films of La_1?x Ca _x MnO₃ manganites with compositions in the vicinity of the calcium content x = 0.5, in which the phase separation is most clearly pronounced. It is found that the La_0.5Ca_0.5MnO₃ manganite undergoes different types of phase separation: (i) at temperatures above the Curie point, ferromagnetic regions exist in the paramagnetic phase; and (ii) at temperatures below the Néel point, antiferromagnetic microregions coexist with ferromagnetic microregions. Two types of ferromagnetic domains with different magnetization orientations are revealed In the temperature range between the Curie and Néel points.     

Short-range order in Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>(<Emphasis Type="Italic">x</Emphasis>=0.05−0.08) alloys with induced magnetic anisotropy

Previously, iron—silicon alloys were investigated using X-ray diffraction and Mössbauer spectroscopy. It was demonstrated that, at low silicon concentrations, the alloys undergo a local separation into regions of the α iron phase depleted in silicon and silicon-rich clusters with a B2 ordering. The structure of locally ordered regions of the B2 phase is characterized by a pair ordering of silicon atoms: the Si—Si pairs are formed by next-nearest neighbors, and the axes of pairs are oriented along the 〈100〉 directions, which are the easy-magnetization axes. The thermomagnetic treatment in a constant magnetic field applied along the 〈100〉 axis induces an axial magnetic anisotropy, results in the formation of an anisotropic distribution of the B2 phase, and leads to a slight decrease in the volume fraction of the coordination 6: 2 with two silicon atoms in the first coordination shell of the iron atom. Therefore, the formation of an anisotropic local order of pairs of silicon atoms occurs as a result of their reorientation.     

Magnetostriction of Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S (<Emphasis Type="Italic">x</Emphasis> = 0.27) crystals

The magnetostriction of Fe _x Mn_{1 − x} S (x = 0.27) single crystals in strong magnetic fields up to 120 kOe has been investigated. It has been found that the magnetostriction reaches colossal values (±3 × 10⁻⁴) atypical of compounds of 3d elements. It has been found that the magnetostriction changes sign when varying temperature and magnetic field; this behavior indicates an important role of the spin-phonon interactions in the formation of the magnetic order in solid solutions of iron-manganese sulfides.