Magnetic dilution and electronic nature in La0.7Pb0.3Mn1−xZnxO3

We have studied the magnetic dilution and electronic nature of Zn doping on the Mn site in the colossal magnetoresistant material La_0.7Pb_0.3MnO₃ (x≤0.3). Small non-magnetic Zn²⁺ doping tends to separate the system into ferromagnetic clusters to weaken the long-range ferromagnetic order and to reduce the Curie temperature. The spin polarizability of the x=0–0.3 samples is estimated to be 0.97–1.00, indicating that the x=0–0.3 samples are the spin polarized materials in which the conductivity is dominated by single-spin charge carriers. Small doping (x≥0.1) induces the metal–insulator transition and destroys the metallic state with long-range ferromagnetic order.     

Magnetic phase transitions and magnetoresistance in the La0.7Ba0.3(Mn1−xMex)O3 (Me=Fe,Al) single crystals and La0.7Sr0.3(Mn1−xMex)O3 (Me=Fe,Cr, Al) ceramics

The single crystals of La_0.7Ba_0.3(Mn_1−xFe_x)O₃ (x⩽0.28) and La_0.7Ba_0.3(Mn_1−xAl_x)O₃ (x⩽0.15) compositions were grown using flux method and characterized by X-ray, electrical and magnetization measurements. The Fe-doping above x=0.2 destroys a long range ferromagnetic order thus leading to a spin glass state. It is found that insulating spin glasses exhibit a large magnetoresistance in the paramagnetic region which is comparable to that for ferromagnetic crystals showing metal–insulator transition close to T_C. The magnetic behavior of La_0.7Ba_0.3(Mn_1−xMe_x)O₃ (Me=Fe, Cr, Al) ceramics is in agreement with superexchange magnetic interactions via oxygen.     

Critical behavior near the paramagnetic to ferromagnetic phase transition temperature in La0.7Pb0.05Na0.25MnO3

Critical behavior in La_0.7Pb_0.05Na_0.25MnO₃ has been investigated by dc magnetization measurements. Magnetic data indicate that the compound exhibits a continuous (second-order) paramagnetic (PM) to ferromagnetic (FM) phase transition. Estimates of critical exponents yield δ=4.80±0.01, γ=1.296±0.002 and β=0.344±0.007 (consistent with both the predictions for the three-dimensional-Heisenberg model and with those reported for materials when the FM transition is ascribed to the double exchange (DE) mechanism as a major origin) with T_C=334.54±0.08. The critical exponent γ is slightly inferior than predicted from the 3D Heisenberg model. Such a difference may be due, within the context of the quenched disorder, to the presence of some alterations of short-range magnetic order of FM clusters in the PM phase. The temperature variation in the effective exponent (γ_eff) is similar to those for disordered ferromagnets.     

Effect of Al doping on the magnetic and electrical properties of layered perovskite La1.3Sr1.7Mn2−xAlxO7

The effect of Al substitution for Mn site in layered manganese oxides La_1.3Sr_1.7Mn_2−xAl_xO₇ on the magnetic and electrical properties has been investigated. It is interesting that all the samples undergo a similar and complex transition with lowing temperature; they transform from the two-dimensional short-range ferromagnetic order at T*, then enter the three-dimensional long-range ferromagnetic state at T_C, at last they display the canted antiferromagnetic state below T_N. T*, T_C and T_N are all reduced with Al content. Resistivity increases sharply with increasing Al concentration, and the metal-insulator transition disappears when x reaches 10%. Additionally, magnetoresistance (MR) effect is weakened. Al substitution dilutes the magnetic active Mn-O-Mn network and weakens the double exchange interaction, and further suppresses FM ordering and metallic conduction. Owing to the anisotropic interaction in the layered perovskite, the magnetic and electrical properties are more sensitive to Al doping level than those in ABO₃-type perovskite.     

Effects of divalent alkaline earth ions on the magnetic and transport features of La0.65A0.35Mn0.95Fe0.05O3 (A = Ca, Sr, Pb, Ba) compounds

We have studied the magnetic and transport properties of Fe doped La_0.65A_0.35Mn_0.95Fe_0.05O₃ (A = Ca, Sr, Pb, Ba) manganites. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition (T_C) except the Pb doped sample which is insulating and ferromagnetic (FM) in the entire temperature range. The magnetization and T_C are decreased by decreasing the cation size on La site. The transition temperature and magnetic moment at 77 K is a maximum for Sr doped sample and is decreasing if we increase or decrease the cation size from Sr size. The maximum value of T_C and magnetic moment for Sr based sample is most likely due to the closer ionic sizes of La and Sr as compared to the other dopants (Ca, Pb, and Ba). We observed a spin freezing type effect in the Pb doped sample below 120 K in resistivity, ac susceptibility and in magnetization. This suggests that the AFM interactions introduced by the Fe are most effective in the Pb doped composition leading to increased competition between the FM and AFM interactions. This FM and AFM interaction generates some degree of frustration leading to the appearance of spin glass like phase whose typical magnetic behavior is studied for small ion when the metallic like behavior is lost.     

Evidence of ferromagnetic domains in the perovskite La0.7Sr0.3Co0.9Mn0.1O3

The magnetic and electronic ground states of the polycrystalline perovskite compound La_0.7Sr_0.3Co_0.9Mn_0.1O₃ have been studied using AC susceptibility, resistivity and neutron depolarization techniques. Results of neutron depolarization study establish the existence of ferromagnetic domains of ∼3 μm size below 180 K. The substitution of 10 at% Mn ions at the Co site in the compound La_0.7Sr_0.3CoO₃ reduces the effective e_g electron transfer and suppresses the double exchange interaction. The competition between the reduced ferromagnetic double exchange interaction and the coexisting antiferromagnetic interaction along with the random nature of substitution leads to a randomly canted ferromagnetic ground state for the substituted compound. Resistivity study confirms that the randomly canted ferromagnetic ground state is insulating.     

Room temperature ferromagnetism and magnetotransport properties of the layered manganite system La1.2Ba1.8Mn2−xRuxO7 (0≤x≤1.0)

The dc magnetization and ac susceptibility measurements on two dimensional layered manganite La_1.2Ba_1.8Mn₂O₇ samples reveal the occurrence of ferromagnetism above room temperature with ferromagnetic (FM) to paramagnetic (PM) transitions at 338 K. The bifurcation temperatures shown by the zero-field cooled (ZFC) and field cooled (FC) dc magnetization curves at high temperatures shift towards lower temperatures as the applied field is increased from 100 to 2500 Oe. The data are suggestive of a large magnetic anisotropy due to the strong competing ferromagnetic and antiferromagnetic interactions resulting in a spin-glass-like state. Ru doping is found to enhance the ferromagnetism and metallicity of the system in a remarkable way. The magnetoresistance (MR) values obtained are very high and about 40% even at 260 K for the undoped sample.     

Fine structure of the field-induced magnetic transition in Nd0.1La0.9Fe11.5Al1.5

For the Nd_0.1La_0.9Fe_11.5Al_1.5 compound, the fine structure of the magnetic transition from the ferromagnetic (FM) to the antiferromagnetic (AFM) states has been studied carefully by means of magnetization (M) and heat capacity (C_p) measurements. Although a single phase with the cubic NaZn₁₃-type structure (Fm3c) has been proved by the room temperature X-ray diffraction pattern, the phase transition has been clearly found to be a stepwise process in M(T) and C_p(T) curves under proper fields. Due to the strong competition between the FM order and AFM order, the characteristic is especially evident under low fields, weakens gradually with the increasing applied field and finally vanishes when the field is higher than 2 T. This multi-step magnetic transition results from the inhomogeneity of the sample, probably due to the inhomogeneous distribution of Nd atoms.     

Critical behavior studies in Ti-substituted lanthanum bismuth perovskite manganites

Perovskite manganite La_0.4Bi_0.6Mn_1−xTi_xO₃ (x = 0.05 and 0.1) synthesized using conventional solid state route method give rise to critical phenomenon in their magnetic interactions due to the substitution of non magnetic Ti ions. The critical behavior is observed near paramagnetic–ferromagnetic transition and is studied by magnetization measurements. Various techniques like Modified Arrott plot, Kouvel–Fisher method, scaling equation of state analysis and the critical magnetization isotherm were used to analyze the magnetization data on magnetic phase transition. The values of critical exponents β and γ obtained using different techniques are in good agreement. The obtained critical exponents are found to follow scaling equation with the magnetization data scaled into two different curves below and above the transition temperature, T_C. This confirms that the critical exponents and T_C are reasonably accurate. The obtained critical exponents for both the samples deviates from mean-field model and do not completely follow the static long range ferromagnetic ordering. This behavior is consistent with non magnetic nature of Ti substituted at Mn site and can be associated with Griffiths phase like phenomenon.     

Critical behavior and magnetic entropy change in the La0.6Sr0.4Mn0.8Fe0.1Cr0.1O3 perovskite

Critical behavior in the La_0.6Sr_0.4Mn_0.8Fe_0.1Cr_0.1O₃ ceramics was studied using magnetization methods. Results show that the paramagnetic–ferromagnetic transition is of second order. Based on the critical behavior analysis using the Banerjee criterion and the Kouvel–Fisher method, we find the critical exponents: β=0.395±0.010, γ=1.402±0.010, and δ=5.208±0.007, for which the magnetic interaction is satisfied within the three-dimensional Heisenberg model. Results indicate the presence of short-range interactions. The magnetic entropy change (−ΔS_M) reached maximum values of 1.75, 1.45, 1.15, 0.8 and 0.43 J Kg⁻¹ K⁻¹ under a magnetic field variation of 5, 4, 3, 2 and 1 T, respectively. Nevertheless, these (−ΔS_M) values are much low for any potential application at this moment. The nature of this phenomenon is discussed in relation to the characteristics of the magnetic phase transition and critical exponents.     

Study on the phase separation of La0.7Sr0.3MnO3 nanoparticles by electron magnetic resonance

In this work, the technique of electron magnetic resonance (EMR) is used to measure the magnetic resonant spectra of La_0.7Sr_0.3MnO₃ nanoparticles synthesized by sol–gel routes with three different gelation agents (S1: Urea+citric acid; S2: citric acid, and S3: Urea+tri-sodium citrate). The purpose of this study is to investigate the influence of synthesis conditions on the magnetic properties of nanoparticles. Our ESR results show that Curie temperatures of La_0.7Sr_0.3MnO₃ nanoparticles with different gelation agents are slightly different (T_c∼340 to 360 K) and possess both paramagnetic (PM) and ferromagnetic (FM) phases in the temperature below T_c. Besides, a sharp FM–PM transition indicates that the combined agent of Urea+tri-sodium citrate creates a better quality in CMR nanomagnets.     

The large anisotropy of the magnetic and transport properties in the Ba5Co5ClO13 single crystal

In this Letter, the single crystals of Ba₅Co₅ClO₁₃ were grown by the flux method successfully. Their structure, magnetic and transport properties were studied. A large anisotropy of the magnetic and transport properties has been detected in this compound. Below the TN∼108 K, the magnetic susceptibility exhibits an antiferromagnetic peak in χc and an upturn transition in χab. We suggest that this behavior is consistent with the competition of the ferromagnetic (FM) intra-blocks coupling and antiferromagnetic (AFM) inter-blocks coupling in this compound. The temperature dependence of the resistivity displays a hump in ρab and a kink in ρc around TN, suggesting the strong coupling between the transport and magnetic properties. Above and below the transition, the transport properties in ab plane follow the three-dimensional (3D) variable range hopping (VRH) mechanism.     

Cation disorder and size effects on the magnetic transition in Ba-containing ferromagnetic manganites

The results of ⁵⁵Mn NMR, dc magnetization, and ac susceptibility studies are presented for La_0.7Ca_0.15Ba_0.15MnO₃, La_0.7Sr_0.15Ba_0.15MnO₃, and La_0.7Ba_0.3MnO₃ ferromagnetic manganites. While is a function of the mean radius of the La and alkaline-earth ions and the cation disorder, the form of the temperature dependence of the magnetic moment may be expressed as function of only. The phase transition is continuous for all three compounds. Received 5 March 1999     

Critical behavior in Co-doped manganites La0.67Pb0.33Mn1−xCoxO3 (0≤x≤0.08)

The critical properties of perovskite manganite La_0.67Pb_0.33Mn_1−xCo_xO₃ (0≤x≤0.08) around the paramagnetic-ferromagnetic phase transition are investigated through various techniques such as the modified Arrott plot, Kouvel-Fisher method and critical isotherm analysis. Though the nature of this transition was found to be in second order, the estimated critical exponents β (0.233≤β≤0.368), γ (1.03≤γ≤1.40) and δ (4.32≤δ≤5.54) are in between the theoretically predicted values for three-dimensional Heisenberg and tricritical mean-field model. This model suggests the coexistence of the short-range and long-range ferromagnetic orders around the critical temperature. The values of the critical exponents obtained from different methods and the well-obeyed scaling behavior confirm that the calculated exponents are unambiguous and purely intrinsic to the system.     

Electron magnetic resonance (EMR) in sonochemically prepared doped nano-manganites

X-band electron magnetic resonance method was explored for study of sonochemically prepared nano-powders of La-based doped manganites: La_0.7Sr_0.3MnO₃ and La_0.9Ca_0.1MnO₃ at 115 ⩽ T ⩽ 600 K temperature interval, including main characteristic points of its magnetic transitions. The data obtained were compared with those for crushed bulk single crystals of the same compositions. It is shown that nano-powder of La_0.7Sr_0.3MnO₃ has the same ferromagnetic ordering as its bulk counterpart, being more homogeneous and less anisotropic. While, nano-powder of La_0.9Ca_0.1MnO₃ shows two distinct ferromagnetic phases in a marked contrast to the bulk sample, where complex magnetic structure comprising canted antiferromagnetic matrix and ferromagnetic clusters is observed. To explain the observed phenomena, the crucial role of nano-scale grain size and its interplay with spin and charge degrees of freedom in considered systems are discussed.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.     

Magnetic properties of transition metal substituted La0.85Ag0.15Mn1−yMyO3 compounds (M=Co, Cr and Al)

In this paper we report a systematic study of Mn-site substitution by M=Co, Cr and Al in La_0.85Ag_0.15MnO₃ series to understand the magnetic interactions between Mn and other transition metals. The long-range ferromagnetic (FM) ordering of the parent compound was significantly affected by Mn-site substitution. The measured magnetic properties of Co-doped samples have been explained on the basis of FM interactions in Mn³⁺-O-Mn⁴⁺, Co²⁺-O-Mn⁴⁺, Co³⁺-O-Mn⁴⁺ networks and simultaneous antiferromagnetic (AFM) interactions in Mn⁴⁺-O-Mn⁴⁺, Co²⁺-O-Mn³⁺ networks. The magnetic properties of Cr-doped compounds could be understood on the basis of double exchange FM interactions in Mn³⁺-O²⁻-Mn⁴⁺ networks and competing AFM in Cr³⁺-O-Mn⁴⁺, Mn⁴⁺-O-Mn⁴⁺, Cr³⁺-O-Mn³⁺ networks. However, it is found that the doping of Al ions play a role of magnetic dilution, without contributing any other competing magnetic interaction. The field variations of magnetization of all the above three series could be analysed by fitting to Brillouin function model and the effective spin contribution for FM has been determined. The measured saturation magnetization has been explained quantitatively.     

Critical behaviour of Ho 2 Fe 17 − x Mn x —magnetisation and Mössbauer spectroscopy

The magnetic properties of Ho₂Fe_17???xMn_x compounds (x = 0–2) of ferromagnetic ordering temperatures up to T_C ~344 K have been investigated by DC magnetization and Mössbauer effect measurements. The nature of the magnetic phase transitions and the critical behaviour around T_C has been investigated by analysis of the magnetisation data and the critical exponents β, γ and δ determined. The critical exponents are found to be similar to the theoretical values of the mean-field model for which β?=?0.5 and γ?=?1.0, indicating the existence of a long-range ferromagnetic interactions. The isothermal entropy changes ΔS around T_C have been determined as a function of temperature in different magnetic fields.     

The influence of oxygen deficiency on the magnetic and electric properties of La<Subscript>0.70</Subscript>Ba<Subscript>0.30</Subscript>MnO<Subscript>3 −γ</Subscript> (0≤γ≤0.30) manganite with a perovskite structure

The crystal structure and the magnetic and electric properties of La_0.70Ba_0.30MnO_{3 ? γ} manganite (0≤γ≤0.30) with a perovskite structure were studied experimentally depending on the concentration of oxygen vacancies. The stoichiometric La_0.70Ba_0.30MnO₃ compound (γ = 0) had cubic unit cell symmetry, which did not change as oxygen deficiency increased up to γ=0.30. A decrease in the content of oxygen in the compound under study caused the occurrence of several sequential magnetic phase transitions in the ground state, from the ferromagnetic state at γ=0 through the cluster spin glass state (γ=0.15) to the antiferromagnetic state (γ=0.30) with the presence of a small ferromagnetic component. The specific electric resistance grew to become activation in character at γ=0.11, and the metal-semiconductor transition disappeared as oxygen deficiency increased. The magnetoresistance of anion-deficient compositions included (1) magnetoresistance close to the temperature of the transition to the magnetically ordered state and (2) low-temperature magnetoresistance. The magnetoresistance peak at T_C disappeared as γ increased (γ=0.11), whereas the low-temperature magnetoresistance component first increased to attain a maximum of about 34% at γ=0.15 and then decreased. The results of experimental studies were used to construct a magnetic phase diagram. These results could be interpreted within the framework of superexchange magnetic ordering theory. The suggestion was made that Mn³⁺-O-Mn³⁺ indirect exchange interactions were positive in the orbitally disordered phase only when manganese was in octahedral coordination, whereas these interactions became negative if at least one of the Mn³⁺ ions was five-coordinate or had a smaller coordination number.     

Neutron-diffraction studies of the antiferromagnetic–ferromagnetic transition in anion-deficient cobaltites

Anion-deficient La_0.5Ba_0.5CoO_2.8 and Y_0.25Ca_0.25Sr_0.5CoO_2.62 cobaltites are studied under pressures up to 6.5 GPa in the temperature range of 5?300 K by neutron powder diffraction. Under ambient pressure both compounds are antiferromagnetic with T _N = 250 K. The applied pressure induces in the first compound a gradual transition from the antiferromagnetic to ferromagnetic state through a mixed magnetic state, whereas the second compound remains antiferromagnetic in the whole pressure range. We suggest that the magnetic ground state depends on the unit-cell volume and the magnetic transition is associated with the transition of cobalt ions from the mixed high-spin/low-spin state to the intermediate-spin/low-spin state.