Specific heat of Sm0.55Sr0.45MnO3 manganite in magnetic fields up to 15 T: An anomalous critical behavior of the ferromagnet in magnetic field and the observation of a tricritical point

The specific heat of Sm_0.55Sr_0.45MnO₃ manganite is measured in the vicinity of the ferromagnetic phase transition in strong magnetic fields up to 15 T. An anomalous critical behavior of the Sm_0.55Sr_0.45MnO₃ ferromagnet in magnetic field is predicted and experimentally observed. The anomalous behavior manifests itself in that, in magnetic fields up to 4 T, the field favors fluctuations and the specific-heat anomaly increases with the field and sharpens, becoming λ-shaped. In fields above 4 T, the behavior becomes classical: the field suppresses the fluctuations and the specific-heat peak is smeared out. The hysteresis of the transition temperature measured in the heating and cooling runs is about 15 K in zero magnetic field. As the field increases, it narrows gradually and vanishes completely when the field reaches 4 T. The results of the experiments are explained in terms of the competition between the hysteresis and the fluctuations of the magnetic order parameter. The H-T phase diagram of Sm_0.55Sr_0.45MnO₃ certainly indicates that, at 4 T, Sm_0.55Sr_0.45MnO₃ has a tricritical point, at which the ferromagnetic and paramagnetic phases of Sm_0.55Sr_0.45MnO₃ are leveled.     

Metamagnetic phase transitions induced by static and pulsed fields in (Sm0.5Gd0.5)0.55Sr0.45MnO3 ceramics

It has been found that the magnetic susceptibility of (Sm_0.5Gd_0.5)_0.55Sr_0.45MnO₃ ceramic samples in zero external magnetic field exhibits a sharp peak near the temperature of 48.5 K with a small temperature hysteresis that does not depend on the frequency of measurements and is characteristic of the phase transition to an antiferromagnetic state with a long-range charge orbital ordering, which is accompanied by an increase in the magnetic susceptibility with a decrease in the temperature. The magnetization isotherms in static and pulsed magnetic fields at temperatures below 60 K demonstrate the occurrence of an irreversible metamagnetic transition to a homogeneous ferromagnetic state with a critical transition field independent of the measurement temperature, which, apparently, is associated with the destruction of the insulating state with a long-range charge ordering. In the temperature range 60 K ?? T ?? 150 K, the ceramic samples undergo a magnetic-field-induced reversible phase transition to the ferromagnetic state, which is similar to the metamagnetic transition in the low-temperature phase and is caused by the destruction of local charge/orbital correlations. With an increase in the temperature, the critical transition fields increase almost linearly and the field hysteresis disappears. Near the critical fields of magnetic phase transitions, small ultra-narrow magnetization steps have been revealed in pulsed fields with a high rate of change in the magnetic field of ??400 kOe/??s.     

Effect of a magnetic field on the thermal and kinetic properties of the Sm<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3.02</Subscript> manganite

The temperature and magnetic-field dependences of the heat capacity, thermal conductivity, thermopower, and electrical resistivity of the Sm_0.55Sr_0.45MnO_3.02 ceramic material are studied in the temperature range 77–300 K and in magnetic fields up to 26 kOe. It is revealed that the quantities under investigation exhibit anomalous behavior due to a magnetic phase transition at the Curie temperature T_C. An increase in the magnetic field strength H leads to an increase in the Curie temperature T_C and a jump in the heat capacity ΔC_p at T_C. The temperature dependences of the measured quantities are characterized by hystereses that are considerably suppressed in a magnetic field of 26 kOe and depend neither on the thermocycling range nor on the rate of change in the temperature. The thermal conductivity K at temperatures above T_C shows unusual behavior for crystalline solids (dK/dT>0) and, upon the transition to a ferromagnetic state, drastically increases as a result of a decrease in the phonon scattering by Jahn-Teller distortions. It is demonstrated that the hystereses of the studied properties of the Sm_0.55Sr_0.45MnO_3.02 manganite are caused by a jumpwise change in the critical temperature due to variations in the lattice parameters upon the magnetic phase transition.     

Heat capacity and resistivity of Sm0.55Sr0.45MnO3 in magnetic fields of up to 26 kOe

Heat capacity and resistivity of Sm_0.55Sr_0.45MnO₃ ceramics were measured over the temperature range 80–300 K in magnetic fields of up to 26 kOe. These quantities show anomalies caused by the magnetic and structural phase transitions. The critical temperature T _c and the heat capacity jump ΔC _p (T _c ) at T _c increase with increasing applied magnetic field H, while the resistivity decreases. The temperature dependences of the measured quantities show hysteresis, which is strongly suppressed in a field of 26 kOe but is sensitive nor to the temperature range neither to the rate of temperature change. The hysteresis of the heat capacity and resistivity of Sm_0.55Sr_0.45MnO₃ is caused by a change in T _c with changing lattice parameters upon second-order structural phase transition. The results are discussed in terms of the electron phase separation model.     

An electron paramagnetic resonance study of phase segregation in Nd0.5Sr0.5MnO3

We present results of an electron paramagnetic resonance (EPR) study of Nd_1−xSr_xMnO₃ with x=0.5 across the paramagnetic to ferromagnetic, insulator to metal transition at 260 K (T_c) and the antiferromagnetic, charge ordering transition (T_N=T_co) at 150 K. The results are compared with those on Nd_0.45Sr_0.55MnO₃ which undergoes a transition to a homogeneous A-type antiferromagnetic phase at T_N=230 K and on La_0.77Ca_0.23MnO₃ which undergoes a transition to coexisting ferromagnetic metallic and ferromagnetic insulating phases. For x=0.5, the EPR signals below T_c consist of two Lorentzian components attributable to the coexistence of two phases. From the analysis of the temperature dependence of the resonant fields and intensities, we conclude that in the mixed phase ferromagnetic and A-type antiferromagnetic (AFM) phases coexist. The x=0.55 compound shows a single Lorentzian throughout the temperature range. The signal persists for a few degrees below T_N. The behaviour of the A-type AFM phase is contrasted with that of the two ferromagnetic phases present in La_0.77Ca_0.23MnO₃. The comparison of behaviour of A-type AFM signal observed in both Nd_0.5Sr_0.5MnO₃ and Nd_0.45Sr_0.55MnO₃ with the two FM phases of La_0.77Ca_0.23MnO₃, vis-à-vis the shift of resonances with respect to the paramagnetic phases and the behaviour of EPR intensity as a function of temperature conclusively prove that the Nd_0.5Sr_0.5MnO₃ undergoes phase separation into A-type AFM and FM phases.     

Magnetocaloric effect in manganites

The magnetocaloric effect (MCE) in La_{1 ? x} Sr _x MnO₃, Sm_0.55Sr_0.45MnO₃, and PrBaMn₂O₆ compounds is studied. The maximum values of MCE (??T _max) determined by a direct method in the second and third compositions and in La_0.9Sr_0.1MnO₃ are found to be much lower than those calculated from the change of the magnetic part of entropy in the Curie temperature (T _C) and the Néel temperature (T _N) range. The negative contribution of the antiferromagnetic (AFM) part of a sample in the La_{1 ? x} Sr _x MnO₃ system at 0.1 ?? x ?? 0.3 decreases ??T _max and changes the ??T(T) curve shape, shifting its maximum 20?C40 K above T _C. Lower values of ??T _max are detected in the range T _C = 130?142 K in polycrystalline and single-crystal Sm_0.55Sr_0.45MnO₃ samples cooled in air. If such samples were cooled in an oxygen atmosphere (which restores broken Mn-O-Mn bonds and, thus, increases the volume of CE-type AFM clusters), the maximum in the temperature dependence of MCE is located at T _N (243 K) for CE-type AFM clusters. A magnetic field applied to a sample during the MCE measurements transforms these clusters into a ferromagnetic (FM) state, and both types of clusters decompose at T = T _N. The PrBaMn₂O₆ composition undergoes an AFM-FM transition at 231 K, and the temperature dependence of its MCE has a sharp minimum at T = 234 K, where MCE is negative, and a broad maximum covering T _C. The absolute values of MCE at both extrema are several times lower than those calculated from the change in the magnetic entropy. These phenomena are explained by the presence of a magnetically heterogeneous FM-AFM state in these manganites.     

Peculiarities of magnetic field-induced ferromagnetic ordering in narrow-band manganites

The temperature dependences of the residual magnetization in narrow-band manganites (Pr_0.67Ca_0.33MnO₃, Sm_0.55Sr_0.45Mn¹⁸O₃, Sm_0.55Sr_0.45Mn¹⁶O₃, and (NdEu)_0.55Sr_0.45Mn¹⁸O₃) have been studied. All compounds studied are characterized by a fairly high residual magnetization M _R (about 0.5 μ_B/Mn) at 4.2 K, which vanishes upon sample heating to the temperature T _RE ≈ 30–35 K, which is much lower than the temperature T _C of the ferromagnetic transition. However, upon magnetization of the samples at T _RE < T < T _C , the residual magnetization (smaller in magnitude) remains up to T _C . For the composition (NdEu)_0.55Sr_0.45Mn¹⁸O₃, the residual magnetization remains at T < T _C , independent of the temperature of magnetization. The disappearance of the residual magnetization found at intermediate temperatures is apparently related to the destruction of the magnetic field-induced ferromagnetic ordering (which contains an additional contribution of the rare-earth sublattice).     

Electronic and magnetic phase transitions in (Sm0.65Sr0.35)MnO3 induced by temperature and magnetic field

Temperature (4.2–260 K) and magnetic field (0–50 kOe) dependencies of the DC electrical resistance, DC magnetization, and AC magnetic susceptibility of (Sm_0.65Sr_0.35)MnO₃ prepared from high purity components have been studied. (Sm_0.65Sr_0.35)MnO₃ undergoes a temperature-induced transition between low-temperature ferromagnetic metallic and high-temperature paramagnetic insulating-like states. A magnetic field strongly affects this transition resulting in a metallic state and “colossal” magnetoresistance in the vicinity of the metal↔insulator transition. Magnetic and electric properties of (Sm_0.65Sr_0.35)MnO₃ are different compared to those reported earlier for similar composition, which is attributable to the purity of the starting materials and/or different process of synthesis. The character of phase transformations observed in (Sm_0.65Sr_0.35)MnO₃ is compared to that reported for Gd₅(Si_xGe_4−x) intermetallic alloys with a true first order phase transition.     

Anomalies in the magnetic and magnetoelastic properties of Sm<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> single crystals (<Emphasis Type="Italic">x</Emphasis> ∼ 0.5) at phase transitions

By studying the magnetic and magnetoelastic properties, it is established that, as the temperature is lowered, Sm_1?xSr_xMnO₃ single crystals (x=0.5, 0.55) undergo spontaneous phase transitions from the paramagnetic to a local charge-ordered state at T_co=220 K and to an A-type antiferromagnetic state at T_N=175 K. It is shown that strong magnetic fields (H_cr ～ 200 kOe) break up the antiferromagnetic order and charge ordering and drive a phase transition to a conducting ferromagnetic state. H-T phase diagrams are constructed for single crystals with x=0.5 and 0.55.     

Spin glass behavior in hole- and electron-doped bismuth manganite single crystals

The hole- and electron-doped bismuth manganites Bi_0.55Ca_0.45MnO₃, Bi_0.55Sr_0.45MnO₃ and Bi_0.95Ce_0.05MnO₃ single crystals were grown using the flux-growth method. Their structural, magnetic and electrical transport properties have been compared studied. All samples show spin-glass magnetic behavior at low temperatures. In the immediate temperature region, an antiferromagnetic transition at T_A and a charge-ordering state at T_CO are observed for Bi_0.55Ca_0.45MnO₃ crystal, whereas only an antiferromagnetic transition exists in Bi_0.95Ce_0.05MnO₃ and Bi_0.55Sr_0.45MnO₃ crystals. Bi_0.55Ca_0.45MnO₃ and Bi_0.55Sr_0.45MnO₃ samples show semiconducting transport behavior in the whole studied temperature range, whereas Bi_0.95Ce_0.05MnO₃ is an insulator at room temperature. In addition, near T_CO a positive magnetoresistance as large as 70.7% is observed for Bi_0.55Ca_0.45MnO₃ sample under 5 T applied magnetic field. The obtained results may originate from the rotation of the polarized Bi-6s² lone pair electrons in the magnetic field.     

Influence of the magnetic and structural heterogeneities on the thermopower,magnetothermpower, and spontaneous generation of electric voltage in the manganite Sm0.55Sr0.45MnO3

The thermopower α and magnetothermopower Δα/α have been studied on single-crystal Sm_0.55Sr_0.45MnO₃ samples consisting of three types of magnetic clusters (ferromagnetic clusters with the Curie temperature T _C = 134 K, the A-type antiferromagnetic clusters with the Néel temperature T _NA ≥ T _C, and the CE-type antiferromagnetic clusters with T _NCE = 240 K). The temperature dependences of α and Δα/α have extremes in the vicinity of T _NCE, namely, a wide maximum in curve α(T) and a sharp minimum in curve{Δα/α}(T). The negative magnetothermopower in the minimum has a giant value of 50% in the magnetic field of 13.2 kOe. The thermopower is shown to be mainly due to the existence of the CE-type antiferromagnetic clusters, in which there is a charge-orbital ordering that displaces the oxygen atoms. The changed crystal lattice inside these clusters changes the value of the thermopower inside them. This thermopower influences the voltage drop across the sample during measuring the thermopower and, thus, the effective value of α of the whole sample. The application of a magnetic field near T _NCE accelerating the destruction of the CE-type antiferromagnetic order causes the sharp decrease in the thermopower of the whole sample. This implies that the CE-type antiferromagnetic clusters with the charge-orbital ordering make main contribution to the thermopower of the whole sample.     

The giant volume magnetostriction and colossal magnetoresistance in Eu<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript> manganite

A doped manganite with the composition Eu_0.55Sr_0.45MnO₃ exhibits giant negative magnetostriction and colossal negative magnetoresistance at temperatures in the vicinity of the magnetic phase transformation (T～41 K). In the temperature interval 4.2 K≤T ≤40 K, the isotherms of magnetization, volume magnetostriction, and resistivity exhibit jumps at the critical field strength H_c1, which decreases with increasing temperature. At 70 K ≤T ≤120 K, the jumps on the isotherms are retained, but the shapes of these curves change and the H_c1 value increases with the temperature. At H<H_c1, the magnetoresistance is positive and exhibits a maximum at 41 K; at H>H_c1, the magnetoresistance becomes negative, passes through a minimum near 41 K and then reaches a colossal value. The observed behavior is explained by the existence of three phases in Eu_0.55Sr_0.45MnO₃, including a ferromagnetic (in which the charge carriers concentrate due to a gain in the s-d exchange energy) and two antiferromagnetic phases (of the A and CE types). The volumes of these phases at low temperatures are evaluated. It is shown that the colossal magnetoresistance and the giant volume magnetostriction are related to the ferromagnetic phase formed as a result of the magnetic-field-induced transition of the CE-type antiferromagnetic phase to the ferromagnetic state.     

Relation between giant volume magnetostriction and colossal magnetoresistance near the Curie temperature of Sm0.55Sr0.45MnO3

The magnetic, transport, and elastic properties of Sm_0.55Sr_0.45MnO₃ have been established to be interrelated. At the Curie point, one observes a large volume compression ΔV/V≈0.1%, a sharp minimum in the temperature dependence of negative volume magnetostriction ω(T), and a maximum in the temperature dependence of the electrical resistivity. Giant negative volume magnetostriction ω=?5×10^?4 has been found in a magnetic field H=0.9 T, which is accompanied by a colossal negative magnetoresistance of 44% in the same field. The results obtained are discussed in terms of a model of electronic phase separation.     

Evidence of glassy ferromagnetic phase and kinetic arrest of electronic phase in Sm0.35Pr0.15Sr0.5MnO3 manganites

The effect of doping of rare earth Pr³⁺ ion as a replacement of Sm³⁺ in Sm_0.5Sr_0.5MnO₃ is investigated. Temperature dependent dc and ac magnetic susceptibility, resistivity, magnetoresistance measurements on chemically synthesized (Sm_0.5−xPr_x)Sr_0.5MnO₃ show various unusual features with doping level x=0.15. The frequency independent ferromagnetic to paramagnetic transition at higher temperature (∼191 K) followed by a frequency dependent reentrant magnetic transition at lower temperature (∼31 K) has been observed. The nature of this frequency dependent reentrant magnetic transition is described by a critical slowing down model of spin glasses. From non-linear ac susceptibility measurements it has been confirmed that the finite size ferromagnetic clusters are formed as a consequence of intrinsic phase separation, and undergo spin glass-like freezing below a certain temperature. There is an unusual observation of a 2nd harmonic peak in the non-linear ac susceptibility around this reentrant magnetic transition at low temperature (∼31 K). Arrott plots at 10 and 30 K confirm the existence of glassy ferromagnetism below this low temperature reentrant transition. Electronic- and magneto-transport measurements show a strong magnetic field—temperature history dependence and strong irreversibility with respect to the sweeping of magnetic field. These results are attributed to the effect of phase separation and kinetic arrest of the electronic phase in this phase separated manganite at low temperatures.     

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.     

Electron-doped Sm1−xSrxMnO3 perovskite manganites: Crystal and magnetic structures and physical properties

We present the results of a study of electron-doped Sm_1−xSr_xMnO₃ (x>0.5) perovskite manganites by combining high-resolution neutron powder diffraction with measurements of resistivity, magnetization and magnetic susceptibility. Although investigated Sm_0.45Sr_0.55MnO₃ and Sm_0.37Sr_0.63MnO₃ compounds belonging to the same phase diagram area differ significantly in the strontium content, they are homogeneous antiferromagnetic (AF) insulators and do not exhibit CMR. They have different crystallographic symmetries (orthorhombic Pbnm and tetragonal I4/mcm, respectively) in the entire temperature range under study (1.5-288 K), differ in the type of spin ordering at low temperatures (AF-A and AF-C), are characterized by different orbital polarizations (d_x²_−y² and d_3z²_−r²), and possess two- and one-dimensional magnetic properties, respectively. The lack of magnetoresistance for these compositions is explained by the lack of coexisting magnetic phases involving double exchange ferromagnetism, in contrast to what is observed for the magnetoresistive Sm_1−xSr_xMnO₃ compounds, that is with x?0.52.     

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.     

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.     

Magnetic-field-controlled phase separation in manganites: Electron magnetic resonance study

The electron magnetic resonance spectra of Sm_1?x Sr _x MnO₃ (x = 0.30, 0.40, 0.45) manganites have been studied. At temperatures that are higher than the Curie point by several tens of kelvins, samples with x = 0.40 and 0.45 exhibit a ferromagnetic resonance (FMR) spectrum imposed on their usual EPR spectrum. The FMR spectrum appears as the applied magnetic field H exceeds a certain critical field H _c , which decreases upon cooling and becomes zero at T = T _C . These results agree with the magnetic-measurement data and indicate the magnetic-field-induced nucleation and growth of ferromagnetic domains in a paramagnetic matrix. In the initial growth stage, the volume of the ferromagnetic domains is proportional to (H ? H _c )^β, where β = 4.0 ± 0.3, and it changes in phase with magnetic field modulation up to a frequency of 100 kHz. In the same field and temperature ranges, hysteretic phenomena and narrow unstable spectral lines are detected; these lines indicate a dynamic character of the phase separation. The results obtained are interpreted in terms of the competition of different types of magnetic and charge ordering.