Influence of epitaxial growth on phase competition in Pr0.5Sr0.5MnO3 films

A series of Pr_0.5Sr_0.5MnO₃ (PSMO) films with various thickness were epitaxially grown on substrates of (0 0 1)-oriented (LaAlO₃)_0.3(SrAl_0.5Ta_0.5O₃)_0.7 (LSAT), LaAlO₃ (LAO) and SrTiO₃ (STO), and (0 1 1)-oriented STO using pulse laser deposition. Influence of epitaxial growth on phase competition was investigated. A ferromagnetic metal to antiferromagnetic insulator (FMM-AFI) transition upon cooling is present in both largely compressed situations deposited on LAO (0 0 1) and tensile cases deposited on STO (0 0 1) but absent in little strained films grown on LSAT (0 0 1), indicating that the antiferromagnetic insulating state is favored by strains. On the other hand, the 400 nm films deposited on (0 1 1)-oriented STO as well as LAO substrates show FMM-AFI transition. These results reveal that both the orientation of epitaxial growth and substrate-induced strain affect the FMM-AFI transition.     

Research on charge-ordering state in La0.5Sr0.5MnO2.88 and La0.5Sr0.5Mn0.5Ti0.5O3 systems

The structural, magnetic and transport properties of La_0.5Sr_0.5MnO_2.88 and La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ samples have been investigated systematically. Indeed, this series has been considered to understand the influence of physical parameters such as oxygen deficiency and titanium doping effect in undoped La_0.5Sr_0.5MnO₃ sample. Ceramic material based on La_0.5Sr_0.5MnO_2.88 exhibits interesting behaviours of charge-ordering (CO), ferromagnetic (FM) states and a good conductivity down to the lowest temperatures. The substitution of Ti for Mn destroyed drastically the CO, damaged the motion of itinerant e_g electrons and changed the local parameters of perovskite cell. A change of the structure from tetragonal to rhombohedral symmetry is observed causing a weakening of double-exchange interaction. The experiment results show that the suppression of the CO is sensitive to the variety of Mn³⁺/Mn⁴⁺ ratio. In a field of 8 T at 10 K, FM and CO phase can be evaluated to be ∼20:80 according to the μ_exp/μ_cal ratio for La_0.5Sr_0.5MnO_2.88, whereas the CO state is suppressed for La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ sample, FM and anti-ferromagnetic (AFM) phase are coexisted and evaluated to be ∼54:46, respectively.     

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.     

Ultra-sharp metamagnetic transition in manganite Pr0.6Na0.4MnO3

We report the magnetic and electrical transport properties of manganite Pr_0.6Na_0.4MnO₃. At the temperature of 2 K, a field-induced steplike magnetization and resistivity transition are observed. The step transitions of magnetization and resistivity are shifted to higher fields as a result of field cooling, and transformed to a smooth broad one when the cooling field is higher than 20 kOe. Moreover, in a magnetic field slightly below the critical field, the magnetic and resistive relaxation exhibits a spontaneous step after a long incubation time when both the temperature and magnetic field are constant. Such steplike transitions are discussed in terms of a martensiticlike transformation associated with phase separation.     

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.     

Magnetocaloric effect in La0.67Sr0.33MnO3 manganite above room temperature

The La_0.67Sr_0.33MnO₃ composition prepared by sol-gel synthesis was studied by dc magnetization measurements. A large magnetocaloric effect was inferred over a wide range of temperature around the second-order paramagnetic-ferromagnetic transition. The change of magnetic entropy increases monotonically with increasing magnetic field and reaches the value of 5.15 J/kg K at 370 K for Δμ0H=5 T. The corresponding adiabatic temperature change is 3.3 K. The changes in magnetic entropy and the adiabatic temperature are also significant at moderate magnetic fields. The magnetic field induced change of the specific heat varies with temperature and has maximum variation near the paramagnetic-ferromagnetic transition. The obtained results show that La_0.67Sr_0.33MnO₃ could be considered as a potential candidate for magnetic refrigeration applications above room temperature.     

Unusual magnetization suppression induced by higher magnetic field in (La0.83Bi0.17)0.67Ca0.33MnO3

Magnetization behavior of (La_0.83Bi_0.17)_0.67Ca_0.33MnO₃ has been investigated in the temperature range from 100 to 180 K. A metamagnetic transition was observed in the temperature region, where the magnetization was measured after a zero-field-cooling from room temperature to a selected temperature. Experimental results show that, after a higher magnetization route, the field-increasing branches of the magnetization curves shows an unusual training effect: below a magnetic field H₀, the applied magnetic field enhances the value of magnetization; however, above H₀ the magnetic field suppresses the value, and the behavior cannot be totally attributed to the enhancement effect of the applied magnetic field on ferromagnetic phase fraction. It is proposed that, in the two-phase coexistence region, the higher magnetic field promotes the phase separation and leads to both the fraction of ferromagnetic domain and the stabilization of antiferromagnetic domain increase.     

Hydrothermal synthesis and Magnetocaloric effect of La0.5Ca0.3Sr0.2MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.5Ca_0.3Sr_0.2MnO₃ have been studied. The La_0.5Ca_0.3Sr_0.2MnO₃ can be produced as phase-pure, crystalline powders in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 513 K in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped particles in typical dimension of 4.0×2.5×1.6 μm. Heat treatment can improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change ΔS_M for the as-prepared sample is 0.88 J kg⁻¹ K⁻¹ at 315 K for a magnetic field change of 2.0 T. It increases to 1.52 J kg⁻¹ K⁻¹, near its Curie temperature (317 K) by annealing the sample at 1473 K for 6 h. The hydrothermal synthesis method is a feasible route to prepare high-quality perovskite material for magnetic refrigeration application.     

Low temperature magnetotransport properties of La0.55Ho0.15Sr0.3MnO3

Magnetotransport data measured in thin films of La_0.55Ho_0.15Sr_0.3MnO₃ down to very low temperatures (0.25 K) are reported. The samples presented colossal magnetoresistance with a T_C close to 200 K. A minimum in the resistance vs. T curve and a drop in the ZFC magnetization were also observed. It was also found a T-dependent relaxation effect after the magnetic field was either applied or removed. These results can be understood within the framework where electronic scattering occurs across magnetic domain walls in a reentrant spin-glassy-like phase.     

Strain induced phase separation on La0.5Ca0.5MnO3 thin films

The effect of epitaxial strain on La_0.5Ca_0.5MnO₃ films of various thicknesses grown on SrTiO₃, SrLaAlO₄, and SrLaGaO₄ substrates is studied by Raman spectroscopy, magnetic, and resistivity measurements. The transport and magnetic properties as well as Raman spectra of the films are affected by epitaxial strains. The energy of the A_g(2) mode and the tilting angle of the MnO₆ octahedra is affected by the strain imposed by the substrate. In the spectra of the films deposited on the (1 0 0) SrTiO₃ substrate strong Jahn-Teller (JT) modes appear, which couple with charge-ordering. In all other films these modes are suppressed and no additional Raman lines are present at low temperatures contrary to the bulk compound. The low frequency continuum scattering decreases at low temperatures indicating a coupling with both the charge and orbital transitions. Comparison of the Raman spectra with the magneto-transport properties suggests an interpretation in terms of a strain induced phase separation between ferromagnetic metallic and antiferromagnetic insulating states.     

Structural first-order transformation in La2/3Ba1/3MnO3: ESR study

We have studied by the electron-spin resonance (ESR) and static magnetic field techniques, the La_2/3Ba_1/3MnO₃ perovskite, which was previously shown to exhibit a martensitic phase transformation in the vicinity of T_s∼200 K [Physical Review B 68, 054109 (2003)], leading to its structural phase-segregated state. Resonant absorptions reveal that in the temperature interval from 100 K to 340 K the compound represents a mixture of two ferromagnetic phases possessing different magnetizations, in varying proportions depending on the temperature, and a small amount of a paramagnetic phase. The results agree well with the previous neutron diffraction study. Applied in the ESR experiments, magnetic fields (2–6 kOe) strongly affect the magnetization curves: even magnetic field as high as 700 Oe modifies the anomaly in the phase transformation region and removes the difference between the zero-field cooled and field-cooled magnetization curves, which implies that the difference in the magnetic susceptibility of the coexisting phases is small and the magnetic domain configuration can be easily changed.     

Dynamic phase separation as revealed by the strong resistance relaxation in epitaxially shear-strained La0.67Ca0.33MnO3/NdGaO3(0 0 1) thin-films

Strong phase competitions between the ferromagnetic metal and the charge-ordered-insulator have been induced in a wide temperature range of 10-256 K for the shear-strained La_0.67Ca_0.33MnO₃/NdGaO₃(0 0 1) films. Based on various magnetotransport measurements, the mobility of phase boundaries was inferred to change dramatically with temperature. In the high temperature range where the phase boundaries are movable, strong relaxation in resistivity was observed, while at the frozen temperatures lower than 40 K it is weakened. The resistivities tend to relax in accordance with the phase transitions driven by the temperature or magnetic field in the phase separation (PS) background. Moreover, to our surprise, while the melting fields of the insulating phase varied with film thicknesses, for a given film however, they stay unchanged when started with different phase fractions produced by the field or thermal cycling. The results show a crucial role of the inherent strain state in determining PS and phase competitions in these epitaxial thin films.     

Current density and intrinsic electroresistance of the Sm1−xSrxMnO3 manganite

We experimentally investigate the role of geometry on the current and current density dependencies of the intrinsic electroresistance of Sm_1−xSr_xMnO₃ of two compositions (x=0.40 and x=0.45). It is found that for each composition, the plot of the intrinsic electroresistance versus current density for samples with different dimensions and resistances coincide whereas this does not happen in the case of the electroresistance versus the magnitude of the current. These results confirm that the current density is indeed the relevant “universal” parameter for controlling the intrinsic electroresistance of these manganites.     

Electronic, structural and magnetic phase diagram of Sm1-xSrxMnO3 manganites

The electronic, structural and magnetic phase diagram of the colossal magnetoresistive Sm_1−xSr_xMnO₃ (0.16≤х≤0.67) manganites is constructed on the basis of their systematic studies by high-resolution neutron powder diffraction. It is shown the tendency of researched system to formation of the phase-separated states on crystallographic as well as, in the even greater extent, on magnetic level. A clear correlation between fine specific features and temperature evolution of crystal structures, spin ordering of the manganese ions, and the physical properties of the samarium-strontium series of manganites obtained from temperature magnetic and transport measurements is demonstrated. It was found that ground state of Sm-Sr manganites shows very various physical properties depending first of all on the doping level х and, for given х, determined by two distortion parameters, namely, the average A-cation size <r_A> and the local A-cation size mismatch σ².     

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.     

Correlation between magnetic and transport properties of phase-separated La0.5Ca0.5MnO3

The effect of low-magnetic fields on the magnetic and electrical transport properties of polycrystalline samples of the phase-separated compound La_0.5Ca_0.5MnO₃ is studied. The results are interpreted in the framework of the field-induced ferromagnetic fraction enlargement mechanism. A fraction expansion coefficient _f, which relates the ferromagnetic fraction f with the applied field H, was obtained. A phenomenological model to understand the enlargement mechanism is worked out.     

Comparative study of heterogeneous magnetic state above TC in La0.82Sr0.18CoO3 cobaltite and La0.83Sr0.17MnO3 manganite

The magnetic, transport and structural properties are studied for La_0.83Sr_0.17MnO₃ and La_0.82Sr_0.18CoO₃ single crystals with nearly the same doping and the metallic ground state. Their comparisons have shown that ferromagnetic clusters originate in the paramagnetic matrix below Т^?>T_C in both samples and exhibit similar properties. This suggests the possible universality of such phenomena in doped mixed-valence oxides of transition metals with the perovskite-type structure. The cluster density increases on cooling and plays an important role on the physical properties of these systems. The differences in cluster evolutions and scenarios of their insulator–metal transitions are related to different magnetic behaviors of the matrixes in these crystals that is mainly due to distinct spin states of the Mn³⁺ and Co³⁺ ions.     

Effect of calcium deficiency on the critical behavior near the paramagnetic to ferromagnetic phase transition temperature in La0.8Ca0.2MnO3 oxides

The critical behavior associated with the magnetic phase transition has been investigated by magnetization isotherms in La_0.8Ca_0.2MnO₃ and La_0.8Ca_0.1□_0.1MnO₃ (□ is the calcium deficiency). The critical exponents are estimated by various techniques such as the Modified Arrott plot, Kouvel–Fisher plot and critical isotherm technique. The critical exponents values for La_0.8Ca_0.2MnO₃ are very close to those found out by the 3D-Ising model (β=0.328, γ=1.180, and δ=4.826 at an average T_C=181.676 K). Moreover, the estimated critical exponents of La_0.8Ca_0.1□_0.1MnO₃ are consistent with the prediction of the 3D-Heisenberg model (β=0.357, γ=1.167, and δ=4.802 at an average T_C=178.182 K). We noted that the critical exponents γ are almost similar to the value of the mean-field theory which can be explained by the existence of a long-range dipole–dipole interaction. Following the Harris criterion, we deduced that the disorder in our case is relevant, which can be the cause of the change in the universality class.     

Anomalous aging and strain induced time dependent phenomena in ultra-thin La0.65Ca0.35MnO3 films

We have shown that ultra-thin La_0.65Ca_0.35MnO₃ films exhibit strong metastable behavior. The resistance can vary with time significantly, suggesting that a state of dynamic phase separation exists whereby one phase grows at the expense of another. Physical properties associated with the metastable behavior have been investigated on the films grown on different substrates. We have found that ultra-thin films age much faster than the thicker counterparts and more interestingly the metastability in the resistance of these films enhanced when aged.     

Evidence for instability in charge ordering Nd0.5Sr0.5MnO3

The transport properties and magnetic phase transitions of charge ordering manganites Nd_0.5Sr_0.5MnO₃ have been investigated. From resistivity measurements, a continuous increase of resistivity upon the thermal cycling occurs at , and shows an instable behavior in the system. The experimental results of magnetization and electron-spin-resonance spectra indicate that the ferromagnetic phase and antiferromagnetic phase coexist in a broad temperature region. We think that the origin of the instability stems from an inhomogeneous strain yielded in the ferromagnetic interface, due to the competition among different phases.