Phase transitions in La1−x CaxMnO3−x/2 manganites

The crystal structure parameters and magnetic and electrical properties of La_1?x Ca_xMnO_3?x/2 reduced manganites with 0≤x≤0.5 are established. These investigations contribute to the understanding of magnetic interactions in manganites without Mn⁴⁺ ions. It is found that these manganites show a long-range antiferromagnetic order up to x=0.09 and transform into spin glasses at 0.09<x≤0.35. The compositions in the range 0.35<x≤0.5 show a strong increase in the spontaneous magnetization and critical point associated with the appearance of spontaneous magnetization and can therefore be viewed as inhomogenious ferromagnets. The magnetic and crystal structure peculiarities of La_0.5Ca_0.5MnO_2.75 are established by the neutron diffraction method. The strongly reduced samples show a large magnetoresistance below the point where the spontaneous magnetization develops. The magnetic phase diagram of La_1?x Ca_xMnO_3?x/2 is established by magnetization measurements. The magnetic behavior is interpreted assuming that the Mn³⁺-O-Mn³⁺ magnetic interaction is anisotropic (positive-negative) in the orbitally ordered phase and isotropic (positive) in the orbitally disordered phase. Introduction of the oxygen vacancies changes the magnetic interaction sign from positive to negative, thereby leading to a spin glass state in strongly reduced compounds. The results obtained reveal unusual features of strongly reduced manganites such as a large ferromagnetic component, a high magnetic ordering temperature, and a large magnetoresistance despite the absence of Mn³⁺-Mn⁴⁺ pairs. In order to explain these results, the oxygen vacancies are supposed to be ordered.     

Magnetization studies of TbFeO3

The spontaneous magnetization and principal magnetic susceptibilities of TbFeO₃ were measured from 4.2 to 300 K. The weak ferromagnetic moment is along the c crystallographic axis in the entire temperature range. The field dependence of the magnetization at 4.2 K was also studied. The magnetic behavior is interpreted in terms of an interaction between the ordered Fe³⁺ spin system and the electrons occupying the lowest lying “accidental” doublet of the Tb³⁺ ions. The FeTb interaction and the Tb³⁺ Van Vl eck susceptibility along the c axis play significant roles in determining the magnetic configuration of the Fe³⁺ spin system. No indication was found that the TbTb interaction plays a significant role in the magnetic behavior of TbFeO₃ at temperature above 4.2 K.     

Structure, transport and magnetic properties in La2xSr2−2xCo2xRu2−2xO6

The perovskite solid solutions of the type La_2xSr_2−2xCo_2xRu_2−2xO₆ with 0.25≤x≤0.75 have been investigated for their structural, magnetic and transport properties. All the compounds crystallize in double perovskite structure. The magnetization measurements indicate a complex magnetic ground state with strong competition between ferromagnetic and antiferromagnetic interactions. Resistivity of the compounds is in confirmation with hopping conduction behaviour though differences are noted especially for x=0.4 and 0.6. Most importantly, low field (50 Oe) magnetization measurements display negative magnetization during the zero field cooled cycle. X-ray photoelectron spectroscopy measurements indicate the presence of Co²⁺/Co³⁺ and Ru⁴⁺/Ru⁵⁺ redox couples in all compositions except x=0.5. Presence of magnetic ions like Ru⁴⁺ and Co³⁺ gives rise to additional ferromagnetic (Ru-rich) and antiferromagnetic sublattices and also explains the observed negative magnetization.     

Magnetic properties of rare earth ion (Sm) added nanocrystalline Mg-Cd ferrites, prepared by oxalate co-precipitation method

Nanocrystalline ferrite powder having the general formula Mg_1−xCd_xFe₂O₄+5% Sm³⁺ (x=0, 0.2, 0.4, 0.6, 0.8 and 1.0) was synthesized by chemical oxalate co-precipitation technique. The synthesized powder was characterized by X-ray, IR and SEM techniques. The XRD analysis confirms cubic spinel phase with orthoferrite secondary phase. The lattice constant increases with increase in Cd²⁺ content (x). It is smaller than that for pure Mg-Cd ferrites. The average crystallite size lies in the range 28.69-32.66 nm. Saturation magnetization and magnetic moment increase with cadmium content up to x=0.4 and decrease thereafter. This is attributed to the existence of localized canted spin. The decrease in saturation magnetization and magnetic moment beyond x=0.4 is due to the presence of triangular spin arrangement on B-site. Coercivity and remanent magnetization decrease while Y-K angles increase with Cd²⁺ content. The Sm³⁺ addition improves the magnetic properties.     

Behavior of the magnetic subsystems in Nd2BaNiO5

The temperature dependences of the heat capacity, the magnetic susceptibility, and the splitting of the ground Kramers doublet of the Nd³⁺ ion in the chain magnet Nd₂BaNiO₅ are studied. An antiferromagnetic phase transition manifests itself as anomalies in all these dependences. The parameters of the Nd-Ni and Nd-Nd interactions are estimated. The field dependence of the magnetization has two anomalies. A strong magnetic anisotropy prevents the magnetic moments of the Nd³⁺ ion from deviating from axis c in the crystal even in an external magnetic field. The processes of magnetization and the internal specific features of a chain of spins S = 1 are discussed.     

Magnetization and electron spin resonance of Fe impurities in (TMTSF)2AsF6: magnetic-field-dependent interaction between impurity spins and spin-density waves

A new spin-density-wave (SDW) system with magnetic impurities (TMTSF)₂(AsF₆)_1−x(FeCl₄)_x was prepared and its magnetic properties were studied by means of magnetization and electron-spin-resonance measurements. The anisotropic g-value and comparison of the Fe concentration with the Curie constant indicate that the Fe³⁺ ions are in a low-spin state. We also found that the magnetization curve of the impurity spins in this compound shows an anomalous behavior. This behavior can be explained if one assumes a field-dependent magnetic interaction between the Fe³⁺ spins and the SDW moment. We suppose that the field dependence of the SDW pinning potential is responsible for this phenomenon.     

The magnetization of PrFeAsO0.60F0.12 superconductor

The magnetization of the PrFeAsO_0.60F_0.12 polycrystalline sample has been measured as functions of temperature and magnetic field (H). The observed total magnetization is the sum of a superconducting irreversible magnetization and a paramagnetic magnetization. Analysis of dc susceptibility χ(T) in the normal state shows that the paramagnetic component of magnetization comes from the Pr³⁺ magnetic moments. The intragrain critical current density (J_L) derived from the magnetization data is large. The J_L(H) curve displays a second peak which shifts towards the high-field region with decreasing temperature. In the low-field region, a plateau up to a field H^* followed by a power law H^?5/8 behavior of J_L(H) is the characteristic of the strong pinning. A vortex phase diagram for the present superconductor has been obtained from the magnetization and resistivity data.     

Modifications in magnetic anisotropy of M—type strontium hexaferrite crystals by swift heavy ion irradiation.

Using vibrating sample magnetometery (VSM) 50 MeV Li³⁺ ion irradiation effects on magnetic properties of single crystals of SrGa_xIn_yFe_12−(x+y)O₁₉ (where x=0, 5, 7, 9; y=0, 0.8, 1.3, 1.0), are reported. The substitution of Ga and In in strontium hexaferrite crystals decreases the value of magnetization sharply, which is attributed to shifting of collinear magnetic order to a non-collinear one. Reduction of magnetization is also explained to be as a result of the occupation of the crystallographic sites of Fe³⁺ by Ga³⁺ and In³⁺. The Li³⁺ ion irradiation decreases the value of magnetization, irrespective of whether the crystals are Ga–In substituted or unsubstituted crystals of SrFe₁₂O₁₉. The result is interpreted in terms of the occurrence of a paramagnetic doublet in crystals replacing magnetic sextuplet as a result of irradiation. Substitution of Ga–In in Strontium hexaferrite decreases the value of anisotropy constant. Irradiation with Li³⁺ ions increases the values of anisotropy field for both substituted as well as unsubstituted crystals. Substitution with Ga–In also decreases the Curie temperature (T_c) but the irradiation with Li³⁺ ions does not affect the curie temperature of either Ga–In substituted or pure SrFe₁₂O₁₉ crystals.     

Effect of indium addition on the structure and magnetic properties of YIG

In this work we report the structure and magnetic properties of a series of single-phase indium-substituted yttrium iron garnet (In-YIG) nanoparticles with nominal composition of Y₃In_xFe_5−xO₁₂ (x=0.1, 0.2, 0.3 and 0.4) prepared by conventional mixed oxide route. Based on XRD results, the lattice parameters of the samples increased with increase in In³⁺ content due to its larger ionic radius. Mössbauer results confirmed the substitution of In³⁺ for Fe³⁺ in [a] site of YIG structure. Further, the magnitudes of the magnetic hyperfine field (MHF) were seen to reduce due to indium substitution. Moreover, a rising trend was observed for saturation magnetization (M_S) of the samples with x>0.2 owing to the substitution of non-magnetic In³⁺ for Fe³⁺. However, the observed initial drop of M_S for the sample with x=0.2 compared to that with x=0.1 is possibly attributed to the dominance of spin canting over the net magnetization rise caused by In³⁺ in [a] sites.     

Spin reversal and magnetization jumps in ErMexMn1−xO3 perovskites (Me=Ni,Co)

The erbium-based manganite ErMnO₃ has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni)=0.2–0.5 in the nickel-based solid solution ErNi_xMn_1−xO₃, while it can be extended up to x(Co)=0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co³⁺. Presence of different magnetic entities (i.e., Er³⁺, Ni²⁺, Co²⁺, Co³⁺, Mn³⁺, and Mn⁴⁺) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNi_xMn_1−xO₃, a critical concentration x_crit(Ni)=1/3 separates two regimes: spin-canted AF interactions predominate at x<x_crit, while the ferromagnetic behavior is enhanced for x>x_crit. Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at T_c, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T⁻¹, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo_0.50Mn_0.50O₃ was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50=Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co²⁺ and Co³⁺ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate.     

Understanding the magnetic ground state of rare-earth intermetallic compound Ce4Sb3: Magnetization and neutron diffraction studies

Magnetization and neutron diffraction studies have been performed on Ce₄Sb₃ compound (cubic Th₃P₄-type, space group I4¯3d, no. 220). Magnetization of Ce₄Sb₃ reveals a ferromagnetic transition at ∼5 K, the temperature below which the zero-field-cooled and field-cooled magnetization bifurcate in low applied fields. However, a saturation magnetization (M_S) value of only ∼0.93μ_B/Ce³⁺ is observed at 1.8 K, suggesting possible presence of crystal field effects and a paramagnetic/antiferromagnetic Ce³⁺ moment. Magnetocaloric effect in this compound has been computed using the magnetization vs. field data obtained in the vicinity of the magnetic transition, and a maximum magnetic entropy change, −ΔS_M, of ∼8.9 J/kg/K is obtained at 5 K for a field change of 5 T. Inverse magnetocaloric effect occurs at ∼2 K in 5 T indicating the presence of antiferromagnetic component. This has been further confirmed by the neutron diffraction study that evidences commensurate antiferromagnetic ordering at 2 K in zero magnetic field. A magnetic moment of ∼1.24μ_B/Ce³⁺ is obtained at 2 K and the magnetic moments are directed along Z-axis.     

Crossover effects in scheelite DyLiF4

The Zeeman effect, magnetization, and differential susceptibility of a DyLiF₄ crystal in a pulsed magnetic field are studied experimentally and theoretically. It is found that Dy³⁺ ion levels in DyLiF₄ approach each other and a crossover occurs in a magnetic field H ‖ [001], which leads to a smearing of peaks in the differential magnetic susceptibility dM/dH and to inflection points in the magnetization curves M(H) at low temperatures. It is demonstrated that magnetic anomalies that accompany the crossover in DyLiF₄ in a field H ‖[001] are sensitive to the electronic structure of the Dy³⁺ ion. Therefore, these anomalies can be used to refine the crystal-field parameters. The effects of variations in the crystal field and temperature and of a deviation of the direction of the magnetic field from the symmetry axis on the magnitude and character of the magnetic anomalies associated with the crossover are investigated. The crystal field and crossover effects in the scheelite structure are compared with those in the zircon structure.     

Neutron diffraction study of the crystallographic and magnetic structures of the BaFe12−xMnxO19 m-type hexagonal ferrites

The cationic distributions, ionic valencies and magnetic structures of the magnetoplumbite-like BaFe_12-xMn_xO₁₉ hexagonal ferrites have been studied from powder diffraction data in the paramagnetic and ferrimagnetic phases. The paramagnetic diagrams show that the Mn cations enter all the sublattices of the M-type structure except the pseudo-tetrahedral one within the R-block. It is also concluded that, in the spinel block, the tetrahedral site is occupied by Fe³⁺ and Mn²⁺ ions whereas in the remaining octahedral sites are located Fe³⁺, Mn³⁺, Mn⁴⁺ cations in a selective way and with a hierarchy of preferences. From the magnetic diagrams it is concluded that even if the long range magnetic ordering has a collinear ferrimagnetic character, the 12k and 2a octahedral sublattices present a random moment canting which decreases further the saturation magnetization.     

Magnetic and electrical transport properties in the self-doped manganite La0.9Mn0.9M0.1O3 (M=Mn,Zn and Ti)

The magnetic and electrical transport properties of La_0.9Mn_0.9M_0.1O₃ (M=Mn, Zn and Ti) were investigated. The temperature and magnetic field dependence of electrical resistivity (ρ) and dc magnetization were studied. All the compounds are found in rhombohedral structure. The excess oxygen in all three compounds was detected through iodometric titration. A modification in resistivity is observed when M=Mn is replaced by M=Zn and Ti. The high temperature resistivity above T_C follow variable range hopping model for both Zn and Ti compounds. For Zn doping, the observation of large field-cool effect and decrease in resistivity at room temperature and is assumed to be due to the implant of Mn⁴⁺ in Mn³⁺ matrix, which favor Mn³⁺/Mn⁴⁺ double exchange. The ferromagnetic behavior below T_C for the compound with M=Ti is correlated to the excess oxygen in it, which implants Mn⁴⁺ and thus incorporates ferromagnetic interactions. The substitutions lead to a reduction of T_c and magnetization.     

On the mixed valence of the chromium ions in the noncollinear ferrimagnetic spinels Mn1−xCuxCr2S4 (Where x = 0.85, 0.90, 0.95)

For the polycrystalline samples of Mn_1?xCu_xCr₂S₄ (x = 0.85, 0.90, 0.95) the magnetization was measured in the temperature range between 77 K and the Curie temperature, T_C, using a magnetic balance (Faraday's method) and pulsed magnetic fields up to 2.0 T. The magnetic susceptibility was measured between T_C and about 600 K. The Curie temperatures were obtained using the kink point method.In the temperature range between 4.2 and 77 K the magnetization was measured in stationary magnetic fields up to 14 T. The data indicate a noncollinear ferrimagnetic structure. The compounds under investigation can be treated as CuCr₂S₄ slightly doped with Mn, with a valence distribution Mn²⁺_1?xCu¹⁺_xCr³⁺_2?xCr⁴⁺_xS^2?₄.     

Causes of the Metamagnetism in a Disordered EuMn<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>O<Subscript>3</Subscript> Perovskite

The magnetic properties of the EuMn_0.5Co_0.5O₃ perovskite synthesized under various conditions are studied in fields up to 140 kOe. The sample synthesized at T = 1500°C is shown to exhibit a metamagnetic phase transition, which is irreversible below T = 40 K, and the sample synthesized at T = 1200°C demonstrates the field dependence of magnetization that is typical of a ferromagnet. Both samples have T_C = 123 K and approximately the same magnetization in high magnetic fields. The metamagnetism is assumed to be related to a transition from a noncollinear ferromagnetic phase to a collinear phase, and the presence of clusters with ordered Co²⁺ and Mn⁴⁺ ions leads to ferromagnetism. The noncollinear phase is formed due to the competition between positive Co²⁺–Mn⁴⁺ and negative Mn⁴⁺–Mn⁴⁺ and Co²⁺–Co²⁺ interactions, which make almost the same contributions, and to the existence of a high magnetic anisotropy.     

Synthesis of a new magnetic Y2Mn2/3Re4/3O7 with pyrochlore-like structure

A complex oxide of the Y₂Mn_2/3Re_4/3O₇ composition with pyrochlore-like structure and parameters of hexagonal unit cell _a=14.91(1) Å _c=17.53(1) Å was synthesized. The magnetic susceptibility and magnetization measurements showed that below 190 K this oxide possesses spontaneous magnetic moment. In the paramegnetic region, the magnetic susceptibility obeys the Curie-Weiss law χ=C/(T?Θ), with C=2.07 cm³ K mol^?1 and Θ=?160 K, and the effective magnetic moment corresponding to the cationic combination Mn²⁺-Re⁵⁺. The data obtained allow one to assume that the compound has a noncollinear antiferromagnetic structure.     

151Eu Mössbauer Spectroscopy in La0.38Eu0.29Ca0.33MnO3

Electrical conductivity with and without magnetic field, d.c. magnetization and ¹⁵¹Eu Mössbauer studies were carried out in La_0.38Eu_0.29Ca_0.33MnO₃ perovskite manganite system. An insulating ground state is found throughout the temperature range with charge ordered (CO) state emerging at T _CO ～ 140 K, where as an external magnetic field of 6 T induces metal-insulator transition at ～120 K. D.C. magnetization measurements show the antiferromagnetic (AFM) transition occurring at T _N ≈ 48 K. The temperature dependent ¹⁵¹Eu Mössbauer measurements showed that the substituted Eu replaces La³⁺ in the 3+ charge state and a small magnetic moment gets induced at the Eu nucleus at low temperatures. The anomalous variation of the f- factor with temperature occurring around T _N and T _CO corroborates the occurrence of antiferromagnetic (AFM) and charge ordering (CO) transition, respectively.     

Magnetic exchange interactions induced by Cr-doping in perovskite manganites

The effect of Cr-doping on the structural, magnetic and transport properties of perovskite manganites La_0.8Ca_0.2Mn_1−xCr_xO₃ (0≤x≤0.7) has been investigated. The Curie temperature (T_C) of the Cr-doped samples is almost unchanged up to 30% of Cr-doping. The Cr-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_C. The dc and ac magnetization data suggest that ferromagnetic clusters induced by double exchange interaction between Cr³⁺ and Mn³⁺ ions and antiferromagnetic components driven by Cr³⁺/Mn⁴⁺ and Cr³⁺/Cr³⁺ interactions are present in the Cr-doped system, which is supported by comparative studies on magnetic and transport properties of LaMnO_3+δ and LaMn_0.75Cr_0.25O_3+δ.     

Effect of illumination on magnetization and microwave absorption of La1−xCaxMnO3 (x<0.2) films

Light-induced changes of the hysteresis loops of magnetization and microwave absorption are investigated in low-doped La_1−xCa_xMnO₃ (x<0.2) thin films. The width of the hysteresis loops decreases clearly under illumination with visible or near-infrared light at temperatures below 50 K. The microwave conductivity has a minimum value at magnetic fields corresponding to the magnetization reversal and is shifted towards weaker fields under illumination. These effects show complex nonexponential time evolution and dependence on strength of the magnetic field. The results can be explained by assuming that small ferromagnetic metallic regions exist within the insulating ferromagnetic phase of the sample, and that these regions are expanded by optically induced charge transfer between Jahn–Teller split e_g states of neighboring Mn³⁺ ions. Decrease of the Mn³⁺ XPS core level spectrum is observed in the samples under illumination with a HeNe laser.