Magnetic properties and charge ordering in Pr0.75Na0.25MnO3 manganite

The structural and magnetic properties of Pr_0.75Na_0.25MnO₃ have been investigated experimentally. At room temperature, the compound shows paramagnetic characteristic. Along with decreasing temperature, a peak appears in the magnetization versus temperature curve around 220 K. To clarify whether this peak is associated with the ordering arrangement of Mn³⁺ and Mn⁴⁺ ions, electron diffraction experiments were carried out below and above 220 K respectively. Only basic Brag diffraction spots can be observed at high temperatures, however, superlattice diffraction appears below 220 K. This provides direct evidence for the existence of charge ordering in Pr_0.75Na_0.25MnO₃. We find the Mn³⁺ and Mn⁴⁺ cations form zigzag chains in a-c plane by analyzing the diffraction patterns. Combining with the magnetization measurements and the results of electron spin resonance, we confirm the antiferromagnetic phase and ferromagnetic component coexist in Pr_0.75Na_0.25MnO₃ below 120 K.     

Giant electroresistance and nonlinear conduction in electron-doped Ca0.9Ce0.1MnO3

We report a large resistance drop induced by Dc electrical currents in charge-ordered Ca_0.9Ce_0.1MnO₃. A giant electroresistance (ER) of ∼90% at 100 mA current below charge ordering (CO) transition temperature (T_CO) is found. Nonlinear conduction, which starts above a threshold current, gives rise to a region of negative differential resistance (NDR). The nonlinear conduction cannot be explained by homogeneous Joule heating of the sample. The origin of these phenomena is discussed in view of current induced collapse of CO state associated with phase-separation mechanism. This work can be useful for the potential applications of ER such as nonvolatile memory elements.     

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.     

Intrinsic inhomogeneity in the electron-doped manganite Sr0.95Ce0.05MnO3

Systematic studies of structural, magnetic, electronic, and elastic properties have been performed for the electron-doped manganite Sr_0.95Ce_0.05MnO₃. The results show that light doping with Ce in place of Sr in SrMnO₃ could stabilize the perovskite-type structure. The electronic transport and magnetism measurements show that the sample exhibits a charge ordering (CO) state below , accompanied by softening of Young’s modulus due to a strong electron-phonon coupling. Cluster-glass behavior and the magnetoresistance (MR) effect are observed at low temperatures, resulting from the induced double-exchange (DE) ferromagnetic (FM) clusters embedded in the CO antiferromagnetic (AFM) matrix. Above , the high temperature range appears to be dominated by local FM fluctuations, which is further supported by internal friction measurements. Our results indicate the existence of intrinsic magnetic inhomogeneity in electron-doped Sr_0.95Ce_0.05MnO₃.     

The effect of grain size on electrical transport and magnetic properties of La0.9Te0.1MnO3

The effect of grain size on structural, magnetic and transport properties in electron-doped manganites La_0.9Te_0.1MnO₃ has been investigated. All samples show a rhombohedral structure with the space group at room temperature. The Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase of grain size. All samples undergo paramagnetic (PM)-ferromagnetic (FM) phase transitions and the interesting phenomenon that both magnetization and the Curie temperature T_C decrease with increasing grain size is observed, which is suggested to mainly originate from the increase of the Mn-O bond length d_Mn-O. Additionally, ρ obviously increases with decreasing grain size due to the increase of both the height and width of tunneling barriers with decreasing grain size. The results indicate that both the intrinsic colossal magnetoresistance and the extrinsic interfacial magnetoresistance can be effectively tuned in La_0.9Te_0.1MnO₃ by changing grain size.     

Enhanced ferromagnetic transition temperature in nanocrystalline lanthanum calcium manganese oxide (La0.67Ca0.33MnO3)

We report a novel, low temperature (450-600 °C) route for the synthesis of highly crystalline and homogeneous nanoparticles of lanthanum calcium manganese oxide La_0.67Ca_0.33MnO₃ (LCMO). The nanocrystallites, with average particle size of 30 nm, possess a ferromagnetic-paramagnetic transition temperature (T_c) of 300 K, which is about 50 K higher than that of a bulk single crystal. The transition temperature was found to be inversely proportional to the particle size. The Rietveld analysis of the powder X-ray diffraction data of the phase-pure nanopowders reveals that the particle size reduction leads to a significant contraction of the unit cell volume and a reduction of the unit cell anisotropy. We propose that these two lattice effects are responsible for the observed enhancement in T_c.     

Effect of Cr doping on the magnetic and electrical transport properties of charge-ordered Bi0.5Ca0.5MnO3

An experimental study on the magnetic and electrical transport properties of the manganites Bi_0.5Ca_0.5Mn_1−xCr_xO₃ (BCMCO) (0≤x≤0.12) is carried out. The results show that Cr doping can suppress the charge-ordering transition, favoring the ferromagnetic clusters. For x=0.12, the charge-ordering transition disappears but a very broad paramagnetic-ferromagnetic-like transition is detected at the Curie temperature T_C=72.6 K. It is caused by phase separation or coexistence of the charge-ordering and ferromagnetic phase. Moreover, the critical Cr content to destroy charge ordering phase in BCMCO does not match the general monotonous tendencies shown by Cr-doped Re_0.5Ca_0.5MnO₃ (Re-rare-earth). These differences are ascribed to the fact that the ground state in BCMCO differs markedly from the ferromagnetic metallic phase in Cr-doped Re_0.5Ca_0.5MnO₃ compounds.     

Magnetic properties of the charge ordered Nd0.75Na0.25MnO3

Nd_0.75Na_0.25MnO₃ polycrystalline ceramic is prepared via sol-gel process and its magnetic properties and electron spin resonance (ESR) spectra have been investigated experimentally. As the compound is cooled from room temperature, a charge-ordered state first develops below 170 K. A high magnetic field melts the charge ordered state and stabilizes a ferromagnetic (FM) state below 170 K. A field induced transition, analogous to a spin flip transition, is observed between 40 and 170 K. The critical temperature for spin flip increases with increasing temperature. Below 130 K, the compound tends to be intrinsically inhomogeneous, i.e. FM clusters and paramagnetic domains coexist in this system at least, which is confirmed by ESR measurements. When the external magnetic field is zero, long range FM interaction is not developed in this system; however, a tendency of re-entrant FM transition is observed in this compound.     

Electrical conduction through bond percolation in Nd0.67Sr0.33MnO3

We report our analysis of resistivity data on Nd_0.67Sr_0.33MnO₃ polycrystalline samples as a function of preparative conditions using a bond percolation model for a random mixture of metallic and insulating regions, assuming polaronic transport above and below the metal-insulator (M-I) transition temperature. Our analysis suggests that for oxygen deficient compounds the M-I transition that occurs at a lower temperature than the ferromagnetic transition arises from a percolation of the metallic regions. The temperature dependence of resistivity and thermopower suggests the existence of a bimodal distribution of conductivities.     

Low-field transport properties of (1−x)La0.7Ca0.2 Sr0.1MnO3+x(ZnO) composites

Composite samples (1−x)La_0.7Ca_0.2Sr_0.1MnO₃(LCSMO)+x(ZnO) with different ZnO doping levels x have been investigated systematically. The structure and morphology of the composites have been studied by the X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The XRD and SEM results indicate that no reaction occurs between LCSMO and ZnO grains, and that ZnO segregates mostly at the grain boundaries of LCSMO. The magnetic properties reveal that the ferromagnetic order of LCSMO is weakened by addition of ZnO. The results also show that ZnO has a direct effect on the resistance of LCSMO/ZnO composites, especially on the low-temperature resistance. With increase of the ZnO doping level, T_P shifts to a lower temperature and the resistance increases. It is interesting to note that an enhanced magnetoresisitance (MR) effect for the composites is found over a wide temperature range from low temperature to room temperature in an applied magnetic field of 3 kOe. The maximum MR appears at x=0.1. The low field magnetoresistance (LFMR) results from spin-polarized tunneling. However, around room temperature, the enhanced MR of the composites is caused by magnetic disorder.     

Superparamagnetic behavior of La0.67Sr0.33MnO3 nanoparticles prepared via sol-gel method

Magnetic nanoparticles of La_0.67Sr_0.33MnO₃ (LSMO) manganite were prepared by sol-gel method. Phase formation and crystal structure of the synthesized powder were examined by the X-ray diffraction (XRD) using the Rietveld analysis. The mean particle size was determined by the transmission electron microscopy (TEM). Infrared transmission spectroscopy revealed that stretching and bending modes are influenced by calcinations temperature. The temperature dependence of the ac magnetic susceptibility was measured at different frequencies and ac magnetic fields in the selected ranges of 40-1000 Hz and 80-800 A/m, respectively. The temperature dependence of ac susceptibility shows a characteristic maxima corresponding to the blocking temperature near room temperature. The frequency dependence of the blocking temperature is well described by the Vogel-Fulcher law. By fitting the experimental data with this law, the relaxation time τ₀=1.7×10⁻¹² s, characteristic temperature T₀=262±3 K, anisotropy energy E_a/k=684±15 K and effective magnetic anisotropy constant k_eff=2.25×10⁴ erg/cm³ have been obtained. dc Magnetization measurement versus magnetic field shows that some of LSMO nanoparticles are blocked at 293 K. The role of magnetic interparticle interactions on the magnetic behavior is also investigated.     

Synthesis of magnetoresistive La0.7Sr0.3MnO3 nanoparticles by an improved chemical coprecipitation method

La_0.7Sr_0.3MnO₃ nanoparticles were prepared by a simple chemical coprecipitation route. Structural, magnetoresistance (MR), and magnetic properties were investigated. Rietveld refinement of X-ray powder diffraction result shows that the sample is single-phase with the space group of R3¯C. The result of field-emission scanning electronic microscopy shows that most of the grain sizes are distributed from 50 to 200 nm. The composition determined by energy-dispersive spectroscopy is the stoichiometry of La_0.7Sr_0.3MnO₃. The ferromagnetic to paramagnetic transition is sharp with Curie temperature T_C=367 K, which further confirms that the sample is single-phase. The steep change in MR at low fields is attributed to the alignment of the magnetization, while the high-field MR is due to the grain boundary effect.     

Growth of single-phase c-axis aligned La1.2Ca1.8Mn2O7 films on SrTiO3 (001)

We report the growth of single phase, c-axis aligned thin films of La_1.2Ca_1.8Mn₂O₇ on SrTiO₃ (001) substrates using a controlled pulsed laser deposition method. In this method, constraint of epitaxy is utilized to stabilize the Ruddlesdon-Popper (RP) phase of La_1.2Ca_1.8Mn₂O₇. Oxygen ambient pressure and the rate of deposition play a very important role in influencing the epitaxial growth as well as maintaining phase purity of the material. The oxygen pressure inside the deposition chamber was very precisely controlled and varied during the layer-by-layer growth of the film. Films, prepared by our method, show excellent electrical and magnetic characteristics with a sharp metal-insulator transition at T_M-I=90 K, closely followed by a magnetic transition at T_C=91 K.     

Intrinsic inhomogeneity and non-linear conduction in charge-ordered Bi0.5Ca0.4Sr0.1MnO3

Systematic studies of X-ray, magnetic, electronic transport, and elastic properties have been performed on polycrystalline Bi_0.5Ca_0.4Sr_0.1MnO₃ sample. The sample exhibits charge ordering (CO) state below T_CO (=304 K), accompanied by a distinct maximum in magnetization. The softening of Young's modulus in the vicinity of T_CO indicates that there is a strong coupling of electron-phonon due to Jahn-Teller (JT) effect. The dynamic ferromagnetic spin correlations are observed at high temperatures above T_CO, which are replaced by antiferromagnetic (AFM) spin fluctuations at a concomitant CO transition. Below 32 K, a spin-glass (SG) state dominates at low temperatures. The voltage-current (V-I) characteristics measurement results indicate that the non-linear conduction starts above a threshold current, giving rise to a region of negative differential resistance (NDR). The origin of the non-linear conduction is discussed in view of current induced collapse of CO state associated with phase-separation mechanism.     

Investigation of the electrical and magnetic properties of electron-doped Ruddlesden-Popper phases, CaO(Pr0.08Ca0.92MnO3)n (n=1, 2, 3 and ∞)

The electrical and magnetic properties of Pr^3±-doped Ruddlesden-Popper manganates with the formula, CaO(Pr_0.08Ca_0.92MnO₃)_n (n=1,2,3 and ∞) have been investigated. The electrical conductivity of the samples increases with the number of perovksite slabs sandwiched between the rock-salt-like CaO layers. Magnetic susceptibility measurements show an anomalous behavior for the n=1 composition which is attributed to the near absence of ferromagnetic correlations in a two-dimensional system. The magnetic behavior of other members can, however, be understood on the basis of a ‘ferromagnetic-droplet’ model. Since the number of electrons per perovskite slab is invariant across the series, the electronic properties are readily correlated to the phase space available for exchange interactions.     

Effect of trivalent cation substitution for manganese upon ferromagnetism in Ln0.57Ca0.43MnO3 (Ln=Pr, Nd)

The substitution of small contents of trivalent cations for manganese in the oxides Ln_0.57Ca_0.43Mn_1−xM_xO₃ (Ln=Pr, Na) has been explored for M=Al, Ga, Fe, Cr, Sc, In. It is shown that similarly to Ba-doping, the M-doped Pr-manganites exhibit a great predisposition to ferromagnetism in a low magnetic field of 0.25 T, reaching ferromagnetic (FM) fractions of 85% for M=Ga and 100% for m=Cr, whereas in contrast only small FM fractions (∼8%) can be reached for the M-doped Nd-manganites. The great ability of both Pr and Nd manganites to exhibit ultrasharp steps at 2.5 K, at increasing magnetic field is also demonstrated. The different behaviors of the so-doped manganites are interpreted in terms of geometric effects (size of the A-sites cations and of the doping elements) and of electronic configurations and magnetic properties of the dopants.     

Emission Mössbauer studies of the magnetoresistive compound, La0.7Sr0.3MnO3

The magnetic behavior of the Sr_0.3 manganite is studied using a local microprobe, ⁵⁷Co. In contrast with Ca substituted manganites, a much larger fraction of the material exhibits short-range order with superparamagnetic-like behavior even at 80 K. The differences in behavior are attributed to the large mismatch between the ionic radii of La⁺³ and the divalent substituent Sr⁺², which introduces anharmonicity in local vibrations. In common with all other compounds exhibiting negative bulk magnetoresistivity, the Sr_0.3 compound also exhibits very marked softening of lattice as one approaches T_c from below. Application of an external magnetic field results in coalescing of nanosized magnetic clusters to form larger ones with better alignment of spins.     

On the coexistence of spin and lattice polarons in the La0.67−xEuxCa0.33MnO3 CMR system

The electrical and magnetic transport properties of the La_0.67−xEu_xCa_0.33MnO₃ system exhibit lowering of insulator to metal and paramagnetic to ferromagnetic transition temperature (T_C) with the increase of Eu concentration in addition to possessing CMR property. The temperature variation of electrical resistivity and magnetic susceptibility for x=0.21 is found to have two distinct regions in the paramagnetic state for T>T_P; one with the localization of lattice polaron in the high-temperature region (T>1.5T_P) satisfying the dynamics of variable range hopping (VRH) model and the other being the combination of the spin and lattice polarons in the region T_P<T<1.5T_P. The resistivity variation with temperature and magnetic field, the cusp in the resistivity peak and CMR phenomenon are interpreted in terms of coexistence of spin and lattice small polarons in the intermediate region (T_P<T<1.5T_P). The spin polaron energy in the La_0.46Eu_0.21Ca_0.33MnO₃ system is estimated to be 106.73±0.90 meV and this energy decreases with the increase of external magnetic field. The MR ratio is maximal with a value of 99.99% around the transition temperature and this maximum persists till T→0 K, at the field of 8 T.     

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.