Magnetic and magnetocaloric results of magnetic field-induced transitions in La1−xCexMn2Si2 (x=0.35 and 0.45) compounds

The La_1−xCe_xMn₂Si₂ compounds (x=0.35 and 0.45) exhibit an antiferromagnetic-ferromagnetic transition caused by the changes in distance between Mn atoms due to temperature changes. A field-induced transition from antiferromagnetic state to ferromagnetic state at a critical field, which decreases with increase in temperature, can also be induced by applying a magnetic field. In this paper our aim is to study the magnetization and magnetocaloric effect, close to transition temperatures. Our subsidiary aim is to examine the temperature dependence of critical field and ferromagnetic fraction of compounds. The variation of magnetocaloric effect with temperature is correlated with the ferromagnetic-antiferromagnetic phase coexistence. Our final aim is to examine the harmony between magnetocaloric effect values calculated both by the Maxwell theory and by the Landau theory.     

Magnetic properties of electron-doped Y1−xCexMnO3 compounds

Cerium-doped Y_1−xCe_xMnO₃ compounds have been prepared in single-phase form for x=0 to 0.10. X-ray diffraction (XRD) patterns could be analyzed by using P6₃cm space group. Temperature variations of ac susceptibility and magnetization measurements show that these Ce-doped materials exhibit weak ferromagnetic transition. The observed ferromagnetic transition is attributed to the double exchange ferromagnetic interaction between Mn²⁺ and Mn³⁺ ions due to electron doping. The M–H loops exhibit hysteresis along with linear contribution and were analyzed based on bound magnetic polaron (BMP) model. Increase in saturation magnetization and decrease in BMP concentrations have been observed with increase in Ce doping.     

Magnetic study of phase separation and charge ordering in La1−xSrxMnO3 near x=0.5

We have investigated the magnetic phase diagram of polycrystalline and single-crystal La_1−xSr_xMnO₃ near 0.46≤x≤0.50. It turns out that for x<0.48, the polycrystalline material is ferromagnetic (FM), but for x≥0.48, incipient charge ordering takes place along with antiferromagnetism. At x=0.48, the ferromagnetic-antiferromagnetic phase transition in ceramics occurs at less than 85 kOe but requires significantly larger field for increasing x. These observations are in contrast to what is found in the single crystals, which are all FM.     

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.     

The correlation between structure and magnetic properties in the manganites La0.7Ca0.3−xTexMnO3 (0≤x≤0.15)

The effect of Te-doping at La-site on structural, magnetic and transport properties in the manganites La_0.7Ca_0.3−xTe_xMnO₃ (0≤x≤0.15) has been investigated. All samples show an orthorhombic structure (O′-Pbnm) at room temperature. It shows that the Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase in the Te content. All samples exhibit an insulator-metal (I-M) transition and the resistivity increases with the increase in the Te-doping level. Additionally, the Curie temperature T_c decreases and the transition becomes broader with increasing Te-doping level, in contrast, the magnetization of Te-doping samples at low temperatures decrease with increasing x as x≤0.10 and then increase with further increasing x to 0.15. The results are discussed in terms of Jahn-Teller (JT) vibrational anisotropy Q₃/Q₂ and the opening of the new DE channel between Mn²⁺-O-Mn³⁺ due to the introduction of Mn²⁺ ions because of the substitution of Te⁴⁺ ions for Ca²⁺ ions.     

Study of structural, transport and magneto-resistive properties of La0.7Ca0.3−xCexMnO3 (0≤x≤0.2)

We have synthesized a series of La_0.7(Ca_0.3−xCe_x)MnO₃ (0≤x≤0.2) by standard solid-state reaction method. X-ray diffraction (XRD) measurement was carried out for structural studies and Rietveld refinement was done for structural analysis. The transport properties were studied using four probe technique. The temperature dependence of the resistivity was measured in the temperature range of 20 K to room temperature. It is found that all samples show a systematic variation in metal to insulator transition at transition temperature (T_P) and resistivity (ρ) with the relative concentration of hole and electron doping in the system. The samples showed varying amounts of colossal magnetoresistance depending upon temperature and applied magnetic field. The magnetoresistance values as high as 72% were observed in x=0 sample.     

Magnetism, magnetocaloric effect and positive magnetoresistance in Fe-doped antipervoskite compounds SnCMn3−xFex (x=0.05-0.20)

The effects of Fe substitution on the structure, magnetic properties, magnetocaloric effect and positive magnetoresistance (MR) effect in antipervoskite compounds SnCMn_3−xFe_x (x=0.05-0.20) have been investigated systematically. Partial substitution of Fe for Mn leads to the monotonic reduction in both the Curie temperature T_C and saturated magnetization (M_S). It can be attributed to the reduction of electronic density of state at the Fermi energy by Fe-doping. The maximum values of magnetic entropy change (−ΔS_M) and positive MR gradually decrease as x increases, due to the broadening of magnetic phase transition. The refrigerant capacity increases initially with x≤0.05, then decreases gradually as x increases further, which is suggested to originate from the competition between the decreasing −ΔS_M and broadening temperature span. Our result indicates that the chemical doping on Mn site is an effective method for manipulating the properties of antiperovskite compounds AXMn₃.     

Electron-doped Sm1−xSrxMnO3 perovskite manganites: Crystal and magnetic structures and physical properties

We present the results of a study of electron-doped Sm_1−xSr_xMnO₃ (x>0.5) perovskite manganites by combining high-resolution neutron powder diffraction with measurements of resistivity, magnetization and magnetic susceptibility. Although investigated Sm_0.45Sr_0.55MnO₃ and Sm_0.37Sr_0.63MnO₃ compounds belonging to the same phase diagram area differ significantly in the strontium content, they are homogeneous antiferromagnetic (AF) insulators and do not exhibit CMR. They have different crystallographic symmetries (orthorhombic Pbnm and tetragonal I4/mcm, respectively) in the entire temperature range under study (1.5-288 K), differ in the type of spin ordering at low temperatures (AF-A and AF-C), are characterized by different orbital polarizations (d_x²_−y² and d_3z²_−r²), and possess two- and one-dimensional magnetic properties, respectively. The lack of magnetoresistance for these compositions is explained by the lack of coexisting magnetic phases involving double exchange ferromagnetism, in contrast to what is observed for the magnetoresistive Sm_1−xSr_xMnO₃ compounds, that is with x?0.52.     

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.     

Structural, transport, and magnetic properties in the Ti-doped manganites LaMn1−xTixO3 (0≤x≤0.2)

The magnetism and transport properties of the samples LaMn_1−xTi_xO₃ (0≤x≤0.2) were investigated. All samples show a rhombohedral structure () at room temperature. The sample with x=0 undergoes the paramagnetic-ferromagnetic (PM-FM) transition accompanied by an insulator-metal (I-M) transition due to the oxygen excess. The doped samples show ferromagnetism and cluster behavior at low temperatures. Though no I-M transition associated with the PM-FM transition appears, the magnetoresistance (MR) effect was observed especially at low temperatures under the applied fields of 0.5 T. Due to the fact that the oxygen content in the Ti-doped samples is nearly stochiometry (3.01) and the Hall resistivity at room temperature is negative, the ferromagnetism in LaMn_1−xTi_xO₃ (0.05≤x≤0.2) is believed to be consistent with the Mn²⁺-O-Mn³⁺ double exchange (DE) mechanism. These results suggest that DE can be obtained by direct Mn-site doping.     

Structural, magnetic and transport properties in the manganites La0.7Sr0.3−xTexMnO3 (0≤x≤0.15)

The effect of Te-doping at La-site on structural, magnetic and transport properties in the manganites La_0.7Sr_0.3−xTe_xMnO₃ (0≤x≤0.15) has been investigated. All samples show a rhombohedral structure with the space group . It shows that the Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase of Te content. The Curie temperature T_C decreases with increasing Te-doping level, in contrast, the magnetization magnitude of Te-doping samples at low temperatures increase with increasing x as x≤0.05 and then decrease with further increasing x to 0.15. The results are discussed in terms of the combined effects of the opening of the new double exchange (DE) channel between Mn²⁺-O-Mn³⁺ due to the introduction of Mn²⁺ ions because of the substitution of Te⁴⁺ for Sr²⁺ and the reduction of the transfer integral b due to the decrease of the Mn-O-Mn bond angle.     

Magnetic anisotropy of Tb1−xGdxMn6Sn6 compounds

Magnetization curves of Tb_1−xGd_xMn₆Sn₆ compounds (0?x?1) have been measured for aligned powder samples in the temperature range 4.2–300 K in pulsed magnetic fields up to 30 T. Temperature and concentration dependences of the magnetocrystalline anisotropy constants K₁ and K₂ and concentration dependence of the temperature of spontaneous spin-reorientation transition have been determined. Using these data, we estimated the contribution of the manganese and terbium atoms to the magnetic anisotropy of Tb_1−xGd_xMn₆Sn₆ and analyzed the origin of the appearance of field-induced first-order magnetic phase transition in these compounds.     

Magnetocaloric effect of Gd5SixSn4−x Alloys

The crystal structure and magnetocaloric effect of Gd₅Si_xSn_4−x   (with x=2.4$x=2.4$, 2.6 and 2.8) alloys were studied by means of X-ray power diffraction (XRD) and magnetic measurements. From the XRD results, these alloys adopt a Gd₅Si₄-type structure for x=2.8$x=2.8$, Gd₅Si₄-type and Gd₅Si₂Ge₂-type mixed structures for x=2.4$x=2.4$ and 2.6, while some minor phases can also be found. The Curie temperatures of the Gd₅Si_xSn_4−x increases gradually when x increases from 276 K for x=2.4$x=2.4$, to 301.5 K for x=2.8$x=2.8$. Magnetic entropy changes of these alloys at a magnetic field change of 0–1.8 T are 1.88, 2.26 and 1.69 J/kg K for x=2.4$x=2.4$, 2.6 and 2.8, respectively. The temperature-dependent XRD analysis shows that there is no crystallographic transition for these alloys, which can explain their low magnetic entropy changes.     

The effect of Fe doping on structural, magnetic and electrical transport properties of CaMn1−xFexO3 (x=0-0.35)

A comprehensive study of the effect of Fe doping on CaMnO₃ is carried out by means of experiments on the structural, transport conduction, and magnetic properties of CaMn_1−xFe_xO₃ (0≤x≤0.35). With a sol-gel process for sample preparation, Fe is substituted for Mn up to x=0.35. This substitution substantially brings out the lattice expansion and gradually suppresses the antiferromagnetism. For x=0.08 and 0.10 in particular, the magnetization curves with a field-cooled mode under the field of 1 kOe behave as those of a ferrimagnetic-like system and present low-temperature negative magnetization. For x≥0.15, the negative magnetization phenomenon disappears, and a ferromagnetic component coexists with an antiferromagnetic one, but the antiferromagnetic interaction still dominates in these compounds. Electrical transport measurements show insulating behavior for all compositions. Fe doping, even at a level as low as x=0.02, can cause a marked resistivity increase in the temperature range studied. Further increasing the Fe content causes the resistivity to gradually decrease due to the increasing carrier presence.     

Investigation on the magnetocaloric effect in DyNi2, DyAl2 and Tb1−nGdnAl2 (n=0, 0.4, 0.6) compounds

The magnetocaloric effect (MCE) in the DyNi₂, DyAl₂ and Tb_1−nGd_nAl₂ (n=0, 0.4, 0.6) was theoretically investigated in this work. The DyNi₂ and DyAl₂ compounds are described considering a model Hamiltonian which includes the crystalline electrical field anisotropy. The anisotropic MCE was calculated changing the magnetic field direction from 〈1 1 1〉 to 〈0 0 1〉 in DyNi₂ and from 〈1 0 0〉 to 〈0 1 1〉 in DyAl₂. The influence of the second- and first-order spin-reorientation phase transitions on the MCE that occurs in these systems is discussed. For the calculations of the MCE thermodynamic quantities in the Tb_1−nGd_nAl₂ systems we take into account a two sites magnetic model, and good agreement with the available experimental data was obtained.     

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.     

Magnetic and transport properties in Sr1−xLaxFe1−xMnxO3

The magnetic and transport properties in the perovskite Sr_1−xLa_xFe_1−xMn_xO₃ have been explored. As x rises, the systemic ferromagnetism increases gradually and cluster-spin-glass state occurs in the low-temperature region. For 0.3?x?0.7, the ferromagnetic phase separation from the paramagnetic phase was observed from the results of electron-spin-resonance measurement. Although all samples show a semiconducting behavior, their transport properties are dominated by two different mechanisms, namely, the electronic transport of x?0.5 samples is realized by thermal activation but the variable-range hopping is applied in x?0.7 ones. The different transport mechanism can be understood from the Mn/Fe ions interaction.     

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.     

Low field magnetoresistance and conduction noise in layered manganite La1.4Ca1.6Mn2O7

Temperature dependence of conduction noise and low field magnetoresistance of layered manganite La_1.4Ca_1.6Mn₂O₇ (DLCMO) are reported and compared with the infinite layered manganite La_0.7Ca_0.3MnO₃ (LCMO). The double layered manganite was prepared using standard solid state reaction method and had a metal-insulator transition temperature (T_M-I) of 155 K. The temperature dependence of susceptibility showed evolution of ferromagnetic ordering at 168 K. The observed voltage noise spectral density (S_V) shows 1/f^α type of behaviour at all temperatures from 77 K to 300 K. In the ferromagnetic region (T<168 K), S_V/V² shows two peaks at 164 K and 114 K. The observed two peaks in normalised conduction noise of DLCMO is attributed to the excess noise generated due to setting up of short range 2D-ferromagnetic ordering and long range 3D-ferromagnetic ordering at two different temperatures T_C2 and T_C1. In temperature range between T_C1 and T_C2, the magnetoresistance (MR) showed a gradual increase with the magnetic field. The observed MR has been explained in the framework of the two phase model [ferromagnetic (FM) domains and paramagnetic (PM) regions].