Electronic transport and magnetic studies of La1−xCax−0.08Sr0.04Ba0.04MnO3

Lanthanum based mixed valence manganite system La_1−xCa_x−0.08Sr_0.04Ba_0.04MnO₃ (LCSBMO; x=0.15, 0.24 and 0.33) synthesized through the sol-gel route is systematically investigated in this paper. The electronic transport and magnetic susceptibility properties are analyzed and compared, apart from the study of unit cell structure, microstructure and composition. Second order phase transition is observed in all the samples and significant difference is observed between the insulator to metal transition temperature (T_MI) and paramagnetic (PM) to ferromagnetic (FM) transition temperature (T_C). In contrast to the insulating FM behaviour usually observed in La_1−xCa_xMnO₃ (LCMO) for x=0.15, a clear insulator to metal transition is observed for LCSBMO for the same percentage of lanthanum. The temperature dependent resistivity of polycrystalline pellets, when obeying the well studied law ρ=ρ_o+ρ₂T² for T<T_MI, is observed to differ significantly in the values of ρ_o and ρ₂, with the electrical conductivity increasing with x. The variable range hopping model has been found to fit resistivity data better than the small polaron model for T>T_MI. AC magnetic susceptibility study of the polycrystalline powders of the manganite system shows the highest PM to FM transition of 285 K for x=0.33.     

Structural and magnetic phase diagram and room temperature CMR effect of La1−xAgxMnO3

The study of the structural and magnetic phase diagram of the manganites La_1−xAg_xMnO₃ shows similarity with the La_1−x′Sr_x′MnO₃ series, involving a metallic ferromagnetic domain at relatively high temperature (≈300 K). The Ag-system differs from the Sr-one by a much smaller homogeneity range (x≤1/6) and the absence of charge ordering. But the most important feature of the Ag-manganites deals with the exceptionally high magnetoresistance (−25%) at room temperature under 1.2 T, that appears for the composition x=1/6. The latter is interpreted as the coincidence of the optimal double exchange condition (Mn³⁺:Mn⁴⁺=2) with T_max=300 K (maximum of the ρ(T) curve in zero field).     

Phase separation, ferromagnetism and magnetic irreversibility in La1−xSrxMn1−yFeyO3

Magnetic susceptibility, χ(T), is investigated in ceramic La_1−xSr_xMn_1−yFe_yO₃ (LSMFO) samples with x=0.3 and y=0.15−0.25. A ferromagnetic (FM) transition observed in LSMFO is accompanied with an appreciable decrease of the transition temperature with increasing y, which is connected to breaking of the FM double-exchange interaction by doping with Fe. Strong magnetic irreversibility, observed in low (B=10 G) field, gives evidence for frustration of the magnetic state of LSMFO. The FM transition, which is expanded with increasing B, is more pronounced in the samples with y=0.15-0.20 and broadens considerably at y=0.25, where the irreversibility is increased. Well above the transition, χ(T) exhibits a Curie-Weiss asymptotic behavior, yielding very large values of the effective Bohr magneton number per magnetic ion, incompatible with those of Mn or Fe single ions. At y=0.15 and 0.20 a critical behavior of χ⁻¹(T)∼(T/T_C−1)^γ in the region of the FM transition is characterized by influence of two different magnetic systems, a 3D percolative one with γ₌γ_p≈1.8 and T_C=T_C^(p), and a non-percolative 3D Heisenberg spin system, with γ=γ_H≈1.4 and T_C=T_C^(H), where T_C^(p)<T_C^(H). At y=0.25 the percolative contribution to the critical behavior of χ(T) is not observed. The dependence of χ on T and y gives evidence for phase separation, with onset already near the room temperature, leading to generation of nanosize FM particles in the paramagnetic host matrix of LSMFO. The ferromagnetism of LSMFO is attributable to percolation over the system of such particles and generation of large FM clusters, whereas the frustration is governed presumably by a system of smaller weakly-correlated magnetic units, which do not enter the percolative FM clusters.     

Room temperature magnetic entropy change and magnetoresistance in La0.70(Ca0.30−xSrx)MnO3:Ag 10% (x=0.0−0.10)

The magnetic and magnetocaloric properties of polycrystalline La_0.70(Ca_0.30−xSr_x)MnO₃:Ag 10% manganite have been investigated. All compositions are crystallized in single phase orthorhombic Pbnm space group. Both, the insulator–metal transition temperature (T^IM) and Curie temperature (T_c) are observed at 298 K for x=0.10 composition. Though both T^IM and T_c are nearly unchanged with Ag addition, the MR is increased. The MR at 300 K is found to be as large as 31% with magnetic field change of 1 T, whereas it reaches up to 49% at magnetic field of 3 T for the La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample. The maximum entropy change (ΔS_Mmax) at near its T_c (300.5 K) is 7.6 J kg⁻¹ K⁻¹ upon the magnetic field change of 5 T. The La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample having good MR (31%^1 T, 49%^3 T) and reasonable change in magnetic entropy (7.6 J kg⁻¹.K⁻¹, 5 T) at 300 K can be a potential magnetic refrigerant material at ambient temperatures.     

Anomalous paramagnetic behavior in the paramagnetic phase of La2/3−xYxCa1/3MnO3 studied through EPR and its relation to colossal magnetoresistance

Electron paramagnetic resonance on La_2/3−xY_xCa_1/3MnO₃ in the paramagnetic (PM) regime is presented for 0≤x≤0.133. The resonance linewidth (ΔH_pp) decreases with cooling, reaches the minimum at T_min, and then anomalously increases with further cooling toward T_c. Our analysis on ΔH_pp(T) below T_min shows that the anomalous PM behavior below T_min is due to the appearance of a ferromagnetic (FM) phase within the PM matrix caused by the applied magnetic fields. The correlation between the anomalous PM and the colossal magnetoresistance is discussed. We argue that both are caused by the phase segregation in which the compound is phase-separated into a mixture of FM and PM regions.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).     

Band-edge exciton transitions temperature in multiple stacked self-assembled (In1−xMnx)As quantum dot arrays

Multiple stacked self-assembled (In_1−xMn_x)As quantum-dot (QD) arrays were grown on GaAs (100) substrates by using molecular-beam epitaxy with a goal of producing (In_1−xMn_x)As QDs with a semiconductor phase and a high ferromagnetic transition temperature (T_c). Atomic force microscopy, magnetic force microscopy, high-resolution transmission electron microscopy, and energy dispersive X-ray fluorescence measurements showed that crystalline multiple stacked (In_0.84Mn_0.16)As with symmetric single-domain particle were formed on GaAs substrates. Near-field scanning optical spectroscopy spectra at 10 K for the (In_0.84Mn_0.16)As multiple stacked QDs showed that the band-edge exciton transitions were observed. The magnetization curve as a function of the magnetic field at 5 and 300 K indicated that the multiple stacked (In_0.84Mn_0.16)As QDs were ferromagnetic, and the magnetization curve as a function of the temperature showed that the T_c was as high as 400 K. These results provide important information on the optical and magnetic properties for enhancing the T_c of (In_1−xMn_x)As-based nanostructures.     

Influence of Ce doping on electrical and thermal properties of La0.7−xCexCa0.3MnO3 (0.0≤x≤0.7) manganites

The effect of Ce-doping on structural, magnetic, electrical and thermal transport properties in hole-doped manganites La_0.7−xCe_xCa_0.3MnO₃ (0.0≤x≤0.7) is investigated. The structure of the compounds was found to be crystallized into orthorhombically distorted perovskite structure. dc Susceptibility versus temperature curves reveal various magnetic transitions. For x≤0.3, ferromagnetic regions (FM) were identified and the magnetic transition temperature (T_C) was found to be decreasing systematically with increasing Ce concentration. The electrical resistivity ρ(T) separates the well-define metal-semiconducting transition (T_MS) for low Ce doping concentrations (0.0≤x≤0.3) consistent with magnetic transitions. For the samples with 0.4≤x≤0.7, ρ(T) curves display a semiconducting behavior in both the high temperature paramagnetic (PM) phase and low temperature FM or antiferromagnetic phase. The electron–phonon and electron–electron scattering processes govern the low temperature metallic behavior, whereas small polaron hopping model is found to be operative in PM phases for all samples. These results were broadly corroborated by thermal transport measurements for metallic samples (x≤0.3) in entire temperature range we investigated. The complicated temperature dependence of Seebeck coefficient (S) is an indication of electron–magnon scattering in the low temperature magnetically ordered regime. Specific heat measurements depict a broadened hump in the vicinity of T_C, indicating the existence of magnetic ordering and magnetic inhomogeneity in the samples. The observation of a significant difference between ρ(T) and S(T) activation energies and a positive slope in thermal conductivity κ(T) implying that the conduction of charge carriers were dominated by small polaron in PM state of these manganites.     

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.     

Effect of electron-beam irradiation on the magnetic properties of Ga1−xMnxAs thin films grown on GaAs (100) substrates

The effect of electron-beam irradiation on the magnetic properties of (Ga_1−xMn_x)As thin films grown on GaAs (100) substrates by using molecular beam epitaxy was investigated. The ferromagnetic transition temperature (T_c) of the annealed (Ga_0.933Mn_0.067)As thin films was 160 K. The T_c value for the as-grown (Ga_0.933Mn_0.067)As thin films drastically decreased with increasing electron-beam current. This significant decrease in the T_c value due to electron-beam irradiation originated from the transformation of Mn substituted atoms, which contributed to the ferromagnetism, into Mn interstitials or Mn-related clusters. These results indicate that the magnetic properties of (Ga_1−xMn_x)As thin films grown on GaAs (100) substrates are significantly affected by electron-beam irradiation.     

Structure and magnetization studies of Nd0.5−xPrxSr0.5MnO3 system

The structural and magnetic properties of Nd_0.5−xPr_xSr_0.5MnO₃ (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) system have been investigated. With the substitution of Pr in Nd_0.5Sr_0.5MnO₃, it shows a gradual structure transformation from the Imma orthorhombic symmetry to the tetragonal I4/mcm phase, and the crystallographic transition remains incomplete, even in Pr_0.5Sr_0.5MnO₃. A large bifurcation between zero-field-cooled (ZFC) and field-cooled (FC) susceptibility has been observed below Curie temperature (T_C), which is characteristic of coexistence of ferromagnetism (FM) and antiferromagnetism (AFM) at low temperature region. The magnetization of Pr_0.5Sr_0.5MnO₃ is larger than that of Nd_0.5Sr_0.5MnO₃, while Nd_0.5Sr_0.5MnO₃ with more CE-type AFM shows larger magnetization than Nd_0.3Pr_0.2Sr_0.5MnO_3, which mixed with CE-type (majority) and A-type (minority) AFM at low temperature, indicating that the magnetization of Nd_0.5−xPr_xSr_0.5MnO₃ system is affected by A-site disorder combined with orbital ordering of A-type AFM and CE-type AFM.     

The effect of Gd-doping on the charge ordering state of Bi0.3−xGdxCa0.7MnO3 (0≤x≤0.30)

The effect of Gd-doping on the charge ordering (CO) state in perovskite-type manganates Bi_0.3−xGd_xCa_0.7MnO₃ with x=0, 0.02, 0.05, 0.1, 0.3 has been investigated by transport and magnetic property measurements. It is found that CO temperature (T_CO) and antiferromagnetic (AFM) ordering temperature T_N occurring below T_CO decrease obviously with increasing Gd-doping level. Accompanying the variation of T_CO, the increased magnetization and the decreased resistivity are observed. In addition, the increased magnetic inhomogeneity has been also observed in the samples based on the difference between the zero-field-cooling (ZFC) magnetization M_ZFC and field-cooling (FC) magnetization M_FC, which is ascribed to the competition between ferromagnetic (FM) phase induced by Gd-doping and CO AFM phase. The experimental results indicate that the Bi³⁺ lone pair electron with 6s² character plays a dominating role on the CO state of Bi_0.3Ca_0.7MnO₃.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Double metal-insulator peaks and effect of Sm substitution on magnetic and transport properties of hole-doped La0.85Ag0.15MnO3

La_0.85−xSm_xAg_0.15MnO₃ (x=0−0.2) ceramics were prepared using the conventional solid-state synthesis method to investigate the effect of Sm³⁺ substitution on magnetic and electrical transport properties. Magnetic susceptibility versus temperature measurements showed all samples exhibit ferromagnetic to paramagnetic transition with Curie temperature, T_c decreasing from 283 K (x=0) to 164 K (x=0.2) with increasing Sm³⁺. The observed slope in susceptibility, χ′ versus temperature curves below T_c indicates the possible presence of FM and AFM phases in the metallic region. In addition, a deviation from the Curie-Weiss law above T_c in 1/χ′ versus T curves indicates the existence of a Griffith's phase in the x=0.05−0.2 samples due to the Sm³⁺ ion substitution. The Griffith temperature, T_G was found to decrease from 295 K (x=0.05) to 229 K (x=0.2). Electrical resistivity measurements of the samples in zero field showed transition from metallic behavior to insulating behavior as the temperature was increased. For x=0, two metal-insulator, MI transition peaks were observed at T_p1=282 K and at T_p2=250 K. Both peaks shifted to lower temperatures with the increase in Sm³⁺. The relative resistivity of the first peak to the second peak decreases with increasing Sm³⁺ for x>0.05 while at x=0.2 the T_p1 peak was strongly suppressed. Magnetoresistance, MR was observed to weaken with Sm³⁺ substitution. The metallic region of the ρ(T) curve of the x=0−0.15 samples was fitted to the model of electron-electron and electron-magnon scattering while the insulating region was fitted to the variable range hopping, VRH model. The resistivity behavior indicated that the substitution of Sm³⁺ weakened the double exchange process and enhanced the Jahn-Teller effect. Our results indicated that the T_p1 peak is strongly related to the double-exchange mechanism while the T_p2 peak is suggested to originate from magnetic inhomogeneity.     

Doping dependence of the superconducting gap by Andreev reflection in Au/La2−xSrxCuO4 point-contact junctions

We studied the doping dependence of the superconducting gap in La_2−xSr_xCuO₄ (LSCO) by means of Andreev reflection measurements in Au/LSCO point-contact junctions. The Andreev reflection features were found to disappear at T_c^A close to the bulk T_c. The fit of the conductance curves with the BTK-Tanaka-Kashiwaya model gives good results if a (s+d)-wave gap symmetry is used. The low-temperature dominant isotropic gap component Δ_s follows very well the T_c vs. x curve, while the gap-like features observed by angle-resolved photoemission spectroscopy and tunneling scale with T^∗. This confirms the different origin of these two energy scales at T<T_c.     

Magnetocaloric effect of GdCo2−xAlx compounds

The structure, magnetic property and magnetocaloric effect of GdCo_2−xAl_x (x=0, 0.06, 0.12, 0.18, 0.24, 0.4) compounds have been investigated by X-ray diffraction (XRD) and magnetic measurement techniques. The experimental results show that the GdCo_2−xAl_x (x≤0.4) compounds are single phase with a Laves-phase MgCu₂-type structure. The Curie temperature T_c initially increases, and then decreases with increasing Al content. The maximum value of T_c, 418 K, is reached for the compound with x=0.06. The magnetic entropy change, which is determined from the temperature and field dependence of the magnetization by the Maxwell relation, decreases almost linearly with increasing Al content.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

As-NQR study of superconductivity in LaRAsO1−xFx (R=Fe and Ni)

We report ⁷⁵As nuclear quadrupole resonance (NQR) studies on oxypnictide superconductors LaFeAsO_1−xF_x (x=0.08, 0.15) and LaNiAsO_1−xF_x (x=0, 0.06, 0.10, 0.12). In LaFeAsO_0.92F_0.08 (T_c=23 K), nuclear spin-lattice relaxation rate 1/T₁ shows no coherence peak just below T_c and decreases with decreasing temperature accompanied by a hump structure at T∼0.4T_c, which is a characteristic of the multigap superconductivity. In the normal state, the quantity 1/T₁T increases with decreasing temperature to T_c, indicating that the existence of antiferromagnetic correlation originating from its multiple electronic band structure. On the other hand, LaNiAsO_1−xF_x shows a clear Hebel-Slichter (coherence) peak just below T_c, evidencing that the LaNiAsO_1−xF_x is a BCS superconductor. In the normal state, 1/T₁T is constant in the temperature range for all LaNiAsO_1−xF_x, which indicates electron correlations are weak. We suggest that the contrasting behavior of both superconductivity and electron correlations in LaFeAsO_0.92F_0.08 and LaNiAsO_1−xF_x between them relate to the difference of electronic band structure configuration. We also provide a possible interpretation for the pseudogap-like behavior in the normal state observed in both compounds.     

Occurrence of re-entrant ferromagnetic transitions in rare-earth manganates on cooling the charge-ordered states

Some of the compositions of the half-doped rare-earth manganates, La_0.5−xLn_xCa_0.5MnO₃ (Ln=Nd, Pr) and Nd_0.5Ca_0.5−xSr_xMnO₃ with relatively small A-cation radii, 〈r_A〉, show an unusual behavior wherein they become ferromagnetic (FM) on cooling the charge ordered (CO) state (T_CO>T_C). With increase in 〈r_A〉, however, the T_C becomes greater than T_CO. Thus, plots of T_C and T_CO against 〈r_A〉 for La_0.5−xLn_xCa_0.5MnO₃ (Ln=Nd, Pr) and Nd_0.5Ca_0.5−xSr_xMnO₃ show cross-over from the T_CO>T_C regime to the T_C>T_CO regime around 〈r_A〉 values of 1.195±0.003 and 1.200±0.005 Å, respectively. Between T_C and T_CO, the CO and FM phases are likely to coexist. In Nd_0.5Ca_0.5Mn_1−xM_xO₃ (M=Cr, Ru), T_CO>T_C when x≤0.10, suggesting the re-entrant nature of the FM transition.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.