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.     

Magnetic phase coexistence in Tb- and Sr-doped La0.7Ca0.3MnO3 manganite:A temperature-dependent neutron diffraction study

We report the results of the temperature-dependent neutron diffraction measurements on the nearly half-doped (La_0.325Tb_0.125)(Ca_0.3Sr_0.25)MnO₃ manganite sample. The simultaneous doping of magnetic Tb³⁺ and divalent Sr²⁺ in the La_0.7Ca_0.3MnO₃ system results into a large A-site size disorder. Rietveld refinement of neutron diffraction data reveal that the single phase sample crystallizes in a distorted orthorhombic structure. Increased 〈r_A〉 value affects the transport behavior that results into an insulating-like behavior of the sample. Under application of 1 T field sample exhibit insulating-like behavior while insulator-metal transition (T_IM) is exhibited under 5 and 8 T fields. Variable range hoping (VRH) mechanism of charge carriers is exhibited in the insulating region. Field cooled and zero field cooled magnetization measurement shows the Curie temperature (T_C)~47 K. The refinement of the ND data collected at various temperatures below 300 K shows that there is no structural phase transition in the compound. Around 100 K, a magnetic peak appears at lower angle that can be ascribed to the presence of the A-type antiferromagnetic (AFM) phase. Two more peaks are observed around 50 K at lower angles that can be fitted in CE-type antiferromagnetic phase. Splitting of the peaks at lower temperatures is the signature of orbital ordering in the presently studied nearly half-doped manganite system. Results of the detailed structural analysis of the temperature-dependent ND measurements on (LaTb)_0.45(CaSr)_0.55MnO₃ sample has been discussed in the light of coexisting A-type and CE-type antiferromagnetic phases present in the sample at low temperature.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Interplay between charge and antiferromagnetic ordering in Bi0.6−xPrxCa0.4MnO3 (0≤x≤0.6) perovskite manganite

Structure, magnetic and transport properties of polycrystalline Bi_0.6−xPr_xCa_0.4MnO₃ (x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) have been studied. Systematic substitution of Pr at Bi site induces an interesting interplay between the charge ordering and antiferromagnetism. The charge ordering temperature (T_CO) decreases with increasing x. The antiferromagnetic (AFM) ordering temperature (T_N) increases sharply at both the extremes but remains nearly constant from x=0.2 to 0.4. At temperatures lower than T_N a transition to the glassy state is observed. The nature of this glass like state appears to be controlled by the Pr content, and at lower values of x this is akin to a spin glass, while at higher x it has a characteristic of cluster glass. The Pr doping also leads to enhancement in the magnetic moment. In the present work it has been proposed that the local lattice distortion induced due to size mismatch between the A-site cations and 6s² character of Bi³⁺ lone pair electron is responsible for the observed magnetic and electrical properties.     

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.     

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 disorder induced enhanced magneto-resistance in La0.5Sr0.5Co1−xRuxO3

We observe a sharp increase in negative magneto-resistance ratio up to 40% for x=0.1, in La_0.5Sr_0.5Co_1−xRu_xO₃ which is due to the magnetic disorder induced by an anti-ferromagnetic interaction between Co and Ru ions. We also observe a metal to insulator and a ferromagnetic to anti-ferromagnetic transition for 0≤x≤0.3. Ruthenium (IV) ion disrupts an intermediate spin state of cobalt (Co³⁺:t_2g⁵e_g¹), forcing a double exchange mediated ferromagnetic state to an anti-ferromagnetic spin state for x≥0.2.     

High-pressure effects on the crystal and magnetic structure of managanites

Nuetron diffraction studies of high-pressure effects on the crystal and magnetic structure of A_1-x A _x ^′ MnO₃ manganites (A = Pr, La; A′ = Sr, Ca, Na) are reviewed. High pressure leads to various changes in the magnetic structure of manganites: the appearance of a new A-type antiferromagnetic (AFM) state in compounds with the initial ferromagnetic (FM) or pseudo-CE type AFM state, such as La_{1 ? x} Ca _x MnO₃ (x = 0.25, 0.33), Pr_{1 ? x} Sr _x MnO₃ (x = 0.48), Pr_0.7Ca_0.3Mn_{1 ? y} Fe _y O₃ (y = 0, 0.1), Pr_{1 ? x} Na _x MnO₃ (x = 0.2, 0.25); and the appearance of a new C-type AFM state in the Pr_0.44Sr_0.56MnO₃ compound with the initial A-type AFM state. The observed changes in the magnetic structure and the behavior of the transition temperature to the FM state under high pressure are discussed in the framework of the current theoretical concepts.     

Charge order melting and magnetic transition in Nd0.5(1+x)Ca0.5(1−x)Mn(1−x)CrxO3 system

The magnetic property of double doped manganite Nd_0.5(1+x)Ca_0.5(1−x)Mn_(1−x)Cr_xO₃ with a fixed ratio of Mn³⁺:Mn⁴⁺=1:1 has been investigated. For the undoped sample, it undergoes one transition from charge disordering to charge ordering (CO) associated with paramagnetic (PM)-antiferromagnetic (AFM) phase transition at T<250 K. The long range AFM ordering seems to form at 35 K, rather than previously reported 150 K. At low temperature, an asymmetrical M-H hysteresis loop occurs due to weak AFM coupling. For the doped samples, the substitution of Cr³⁺ for Mn³⁺ ions causes the increase of magnetization and the rise of T_c. As the Cr³⁺ concentration increases, the CO domain gradually becomes smaller and the CO melting process emerges. At low temperature, the FM superexchange interaction between Mn³⁺ and Cr³⁺ ions causes a magnetic upturn, namely, the second FM phase transition.     

Structure and magnetic order in La0.7Ca0.3Mn0.5Co0.5O3 and La0.8Sr0.2Mn0.5Co0.5O3 perovskites

In this paper we report the study of the perovskites La_0.7Ca_0.3Mn_0.5Co_0.5O₃ and La_0.8Sr_0.2Mn_0.5Co_0.5O₃ by neutron powder diffraction at various temperatures and magnetization measurements in zero applied field and at low cooling regimes. The replacement of half Mn by Co in La_0.7Ca_0.3MnO₃ and La_0.8Sr_0.2MnO₃ destroys their long-range ferromagnetism exhibiting a cluster glass ferromagnetic order similar to the one observed in many cobaltites.     

Electronic excitations in hole-doped La1−xSrxMnO3 studied by resonant inelastic X-ray scattering

We report a resonant inelastic X-ray scattering (RIXS) study on perovskite manganese oxides La_1−xSr_xMnO₃ (x=0, 0.2, and 0.4) at Mn K-absorption edge. Hole-doping effect on the electronic excitations in the strongly correlated electron systems is elucidated by comparing with undoped LaMnO₃. The scattering spectra of metallic La_0.6Sr_0.4MnO₃ show that a salient peak appears in low energies indicating the persistence of the Mott gap. At the same time, the energy gap is partly filled by doping holes and the spectral weight shifts toward lower energies. Though the peak position of the excitations shows weak dispersion in momentum dependence, RIXS intensity changes as a function of the scattering angle (2θ), which is related to the anisotropy. Furthermore, anisotropic temperature dependence is observed in La_0.8Sr_0.2MnO₃ which shows a metal-insulator transition associated with a ferromagnetic transition. We consider that the anisotropy in the RIXS spectra is possibly attributed to the correlation of the orbital degrees of freedom. The anisotropy is large in LaMnO₃ with long-range orbital order, while it is small but finite in hole-doped La_1−xSr_xMnO₃ which indicates persistence of short-range orbital correlation.     

Observation of mixed-phase behavior in the Mn-doped cobaltite La0.7Sr0.3Co1−xMnxO3 (x=0-0.5)

Studies on La_0.7Sr_0.3Co_1−xMn_xO₃ (x=0-0.5) compounds evidence that the interaction between Mn and Co ions in this system is antiferromagnetic super-exchange and not ferromagnetic (FM) double-exchange (DE). As a result, antiferromagnetism and magnetic glassiness develop steadily with increasing Mn content and the system becomes a spin glass at x∼0.1. Analyses of high-field magnetization data indicate that the system consists of two major phases: a metallic FM phase which magnetically saturates in rather low field, and an insulating non-FM phase which has a linear dependence of magnetization on magnetic field. In the low doping regime, the fraction of the non-FM component expands with temperature at the expense of the FM phase and becomes maximal at T_C. Ferromagnetism reappears in highly doped (x≥0.2) compounds due to the presence of DE interaction between the Mn ions. The small volume fraction of the FM phase derived from the M(H) data in high-field region supports the coexistence of insulating and FM behaviors in the highly doped samples.     

Nd1-xSrxMnO3中掺杂浓度对电脉冲诱导电阻转变效应的影响

采用两线测量模式对固相烧结方法制备的Nd_1-xA_xMnO₃ (A= Ba, Ca, Sr,x= 0-0.9) 陶瓷样品电脉冲诱导电阻转变(EPIR)效应和I-V特性进行了测量. 结果表明, 与Nd_0.7Sr_0.3MnO₃一样, 相同浓度掺杂的Nd_0.7Ba_0.3MnO₃和Nd_0.7Ca_0.3MnO₃ 样品也能诱发稳定的室温EPIR效应. 进一步对Nd_1-xSr_xMnO₃系列样品的EPIR研究表明, 这种界面相关的EPIR效应与样品中电子或空穴掺杂浓度密切相关, 在半掺杂 (x= 0.5)附近, 样品与电极接触界面能诱发稳定的EPIR效应. 然而, 随掺杂浓度的进一步增大或降低, EPIR效应逐渐出现减弱、不明显到完全消失的过程. 产生这种现象的原因可能与锰氧化物中由于掺杂浓度差异所导致的界面缺陷在不同极性脉冲激励下重新分布而产生的内电场强弱有关.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Hole delocalization by isovalent Sr substitution in Nd0.7Pr0.3Ba2−kSrkCu3O7

Thermopower measurements on the system Nd_0.7Pr_0.3Ba_2−kSr_kCu₃O₇ show that the insulator-superconductor transition for k≥0.2 is accompanied by hole delocalization. Arguments are presented to show that Sr substitution reduces the hybridization between Pr 4f and O_2pπ-orbitals and increases the hole density to sustain superconductivity.     

Effect of monovalent metal substitution on the magnetocaloric effect of perovskite manganites Pr0.5Sr0.3M0.2MnO3 (M=Na,Li, K and Ag)

The influence of monovalent doping on the magnetocaloric effect (MCE) and refrigerant capacity or relative cooling power (RCP) of Pr_0.5Sr_0.3M_0.2MnO₃ (M=Na, Li, K and Ag) materials has been investigated. A large magnetocaloric effect was inferred over a wide range of temperature around the second order paramagnetic–ferromagnetic transition. The maximum magnetic entropy changes (ΔS_M) reached 1.8, 2.2, 1.6 and 2.1 J/kg K and the relative cooling power (RCP) approached 58.9, 59.3, 69.6 and 54.6 J/kg for Na, Li, K and Ag doped materials in the magnetic change of 15 kOe, respectively. According to the results determined by the Maxwell relation, the magnetic entropy change fits well with the Landau theory of phase transition above T_C for Pr_0.5Sr_0.3Li_0.2MnO₃. The large magnetic entropy change induced by low magnetic field suggested that these materials are beneficial for practical applications.     

Size-induced ferromagnetism and metallicity in Nd0.5Sr0.5MnO3 nanoparticles: A neutron diffraction study

The phenomenon of destabilization of antiferromagnetic insulating state into a ferromagnetic metallic one in Nd_0.5Sr_0.5MnO₃ with the variation of particle/grain size is critically investigated. Based on our neutron diffraction study, magnetic and transport experiments, we observe ferromagnetism and metallic behavior in Nd_0.5Sr_0.5MnO₃ (∼40 nm grain size) as against A-type antiferromagnetic order in the sample with the largest grain size (∼800 nm). The latter shows a systematic change in the lattice parameters with temperature, and an antiferromagnetic ground state similar to that of a bulk system. Interestingly, the sample with the smallest grain sizes exhibits insignificant structural changes (compared to the largest grain size sample) but a complete change in the magnetic state (ferromagnetic behavior) as revealed from the neutron diffraction study. Magnetic measurements also confirm a ferromagnetic state in the small-grained sample. Electronic transport measurements exhibit a metal-insulator transition in this sample. The effects are primarily attributed to enhanced surface disorder.     

Magnetic and charge ordering properties of Bi0.6−xEuxCa0.4MnO3 (0.0≤x≤0.6)

We have studied structure, magnetic and transport properties of polycrystalline Bi_0.6−xEu_xCa_0.4MnO₃ (x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) perovskite manganites. Magnetic measurements show that the charge-ordering temperature (T_CO) decreases with increasing x up to x=0.4 and then slightly increases with further increasing x up to x=0.6. Further, the antiferromagnetic (AFM) ordering temperature (T_N) decreases with increasing x. At T<T_N a transition to metamagnetic glass like state is also seen. Eu doping also leads to enhancement in the magnetic moment and a concomitant decrease in resistivity up to x=0.2 and then an increase in resistivity up to x=0.5. We propose that the local lattice distortion induced by the size mismatch between the A-site cations and 6s² character of Bi³⁺ lone pair electron are responsible for the observed variation in physical properties.     

Large magnetoresistance in low temperature metallic region of manganite compounds (La0.7−2xEux)(Ca0.3Srx)MnO3 (0.05≤x≤0.15)

Magnetoresistance (MR) and magnetization (dc and ac) measurements have been carried out on the manganites, (La_0.7−2xEu_x)(Ca_0.3Sr_x)MnO₃ (0.05≤x≤0.15), in the temperature range of 5-320 K. At 5 K, an unusually large MR of almost 98% is observed in the x=0.15 sample, nearly up to fields of 4-5 T. This large high-field MR occurs in the metallic region, far below the insulator-metal transition temperature, and does not vary linearly with applied field. The unusual magnetoresistance is explained in the light of various possibilities such as phase segregation, cluster spin-glass behavior, etc.     

Analysis of low temperature specific heat in Nd0.5Sr0.5MnO3 and R0.5Ca0.5MnO3 (R=Nd,Sm, Dy and Ho) compounds

We report on the specific heat C(T) of doped manganites Nd_0.5Sr_0.5MnO₃, Nd_0.5Ca_0.5MnO₃, Sm_0.5Ca_0.5MnO₃, Dy_0.5Ca_0.5MnO₃ and Ho_0.5Ca_0.5MnO₃ in the temperature range 2?T?300 K using modified rigid ion model (MRIM). The present specific heat results are in general satisfactory agreement with experimental data except at very low temperatures (i.e. T?12 K). Also a sharp peak observed in the experimental results for these compounds around 5 K could not be revealed by our computed results as they arise due to Schottky-like anomaly. Besides, we have reported the cohesive and the thermal properties of these compounds. The results obtained by us are discussed in detail.