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.     

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.     

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.     

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.     

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.     

Orbital phase transition in Pr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3</Subscript>

The phenomenological theory of phase transition in Pr_0.6 Ca_0.4 MnO₃ manganite is developed. It is shown that this is the orbital phase transition and that the two electronic states of the manganese ion, which are discussed in the literature, result from two different types of condensation of the same orbital order parameter. Thus, the manganese ions in Pr_1?xCa_x MnO₃ manganites with 0.3≤_x≤0.5 may be in either of the two electronic states, depending on the thermodynamic parameters.     

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.     

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.     

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.     

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⁺.     

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 .     

Magnetic and dielectric properties of orthorhombic and hexagonal multiferroics Tb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The transition from a stable orthorhombic structure to a hexagonal structure has been revealed in Tb_1−x Y _x MnO₃ multiferroics at x = 0.2–0.4. It has been shown that almost single-phase crystals with an orthorhombic or hexagonal structure can be obtained by choosing the growth conditions. It has been found that the magnetic and dielectric properties of orthorhombic single crystals with x = 0.2–0.3 are similar to the properties of pure TbMnO₃ and are characterized by a strong anisotropy of the magnetic susceptibility at low temperatures and by the presence of a number of magnetic phase transitions, including those to the ferroelectric state. New spontaneous (T ≤ 15 K) and magnetic-field induced (H | C ₆) phase transitions accompanied by the appearance of an uncompensated rare-earth magnetic moment ∼1 μ_B/mole have been observed in hexagonal single crystals with x = 0.3–0.5.     

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.     

Spin glass effects in Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions

The magnetization, resistance, permittivity, and thermal expansion coefficient of cation-substituted sulfides Co _x Mn_{1 ? x} S have been measured. The relationship between the magnetic, electric, and elastic subsystems of Co _x Mn_{1 ? x} S solid solutions is established and the features of physical properties characteristic of multiferroics, induced by orbital-charge ordering, are found.     

Transport properties in La<Subscript>0.7−<Emphasis Type="Italic">x</Emphasis></Subscript>Gd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> system

The influence of Gd doping at La-site on the electrical transport properties and the colossal magnetoresistance of La_0.7−x Gd _x Sr_0.3MnO₃ (x=0.00, 0.10, 0.15, 0.20, 0.30, 0.40, 0.50, 0.60, and 0.70) is studied. The experimental results indicate that the transport properties exhibit abnormal behavior under high doping condition. Forx=0.50, we find that a transition from metal to insulator occurs after the occurrence of insulator-metal transition nearT _c, which seldom occurs in ABO₃ structure. For samplesx=0.60 and 0.70, it exhibits insulator behavior far aboveT _c. These abnormal behaviors are attributed to different magnetic background, i.e. the system undergoes a transition from long range ferromagnetic order to the cluster-spin glass state and further to antiferromagnetic order.     

Effect of the oxygen excess on the properties of weakly doped La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> lanthanum manganites

The effect of an oxygen excess δ on the magnetic and electrical properties of La_1−x Ca _x MnO_3+δ (x=0.10–0.15) has been studied over wide ranges of temperatures and magnetic fields. As δ increases, the magnetic ordering temperature T_cdecreases by 70–90 K, the magnetoresistance increases (the electrical resistivity decreases by a factor of up to 10⁴ in a field of 9 T), and the effective moment μ_eff of the paramagnetic susceptibility substantially exceeds the theoretical value at temperatures two to four times higher than T _c and undergoes a jump, just as the activation energy of electrical resistivity, at T∼270 K. These results are attributed to the formation of cation vacancies, the localization of electrons in their vicinity with the subsequent formation of magnetic clusters, tunneling (or hopping) of carriers among them, changes in the sizes of clusters with variations in the temperature and magnetic field strength, the onset of frustrations initiated by the competition among different types of exchange interaction, and the dependence of the cluster parameters on the annealing conditions. Annealing of the oxygen-excess samples at high temperatures in vacuum (above 1100°C) restores the samples to a nearly initial state with the magnetic and magnetotransport properties characteristic of weakly doped manganites, as a result of the removal of cation vacancies.     

Radiative transitions to localized Eu states in Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Eu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te solid solutions

Two types of radiative transitions were observed in the low-temperature photoluminescence spectra of Pb_1?x Eu _x Te (0 ≤ x ≤ 0.09) solid solutions: an intense line corresponding to the transitions from the conduction to the valence band and a series (up to 15) of narrow lines corresponding to the transitions from the hybridized conduction band to the split Eu³⁺ levels. The intensity of the discrete lines increases with x, and their energies (and intensities) weakly depend on the temperature. The absorption and emission of the discrete lines are caused by the 4f ⁷(⁸ S _7/2) ? 4f ⁶(⁷ F _J )[L ₆ ^? + 5dt _2g ] transitions.     

Low temperature features of the local structure of Sm<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S

The particular features of the local electronic and local crystal structures of the mixed-valence compound Sm_{1 ? x} Y _x S are studied by the XAFS spectroscopy methods in the temperature range 20–300 K for the yttrium concentration x = 0.17, 0.25, 0.33, and 0.45. The temperature behavior of the valence of Sm, as well as of the lengths and the Debye-Waller factors of the bonds Sm-S, Sm-Sm(Y), Y-S, and Y-Sm(Y), has been determined. The violation of the Vegard law has been observed. A model for the estimation of the energy width of the 4f level and of its position with respect to the Fermi level is proposed.