An electron paramagnetic resonance study of phase segregation in Nd0.5Sr0.5MnO3

We present results of an electron paramagnetic resonance (EPR) study of Nd_1−xSr_xMnO₃ with x=0.5 across the paramagnetic to ferromagnetic, insulator to metal transition at 260 K (T_c) and the antiferromagnetic, charge ordering transition (T_N=T_co) at 150 K. The results are compared with those on Nd_0.45Sr_0.55MnO₃ which undergoes a transition to a homogeneous A-type antiferromagnetic phase at T_N=230 K and on La_0.77Ca_0.23MnO₃ which undergoes a transition to coexisting ferromagnetic metallic and ferromagnetic insulating phases. For x=0.5, the EPR signals below T_c consist of two Lorentzian components attributable to the coexistence of two phases. From the analysis of the temperature dependence of the resonant fields and intensities, we conclude that in the mixed phase ferromagnetic and A-type antiferromagnetic (AFM) phases coexist. The x=0.55 compound shows a single Lorentzian throughout the temperature range. The signal persists for a few degrees below T_N. The behaviour of the A-type AFM phase is contrasted with that of the two ferromagnetic phases present in La_0.77Ca_0.23MnO₃. The comparison of behaviour of A-type AFM signal observed in both Nd_0.5Sr_0.5MnO₃ and Nd_0.45Sr_0.55MnO₃ with the two FM phases of La_0.77Ca_0.23MnO₃, vis-à-vis the shift of resonances with respect to the paramagnetic phases and the behaviour of EPR intensity as a function of temperature conclusively prove that the Nd_0.5Sr_0.5MnO₃ undergoes phase separation into A-type AFM and FM phases.     

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.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.     

Electronic structure and half-metallicity of the new Heusler alloys PtZrTiAl,PdZrTiAl and Pt0.5Pd0.5ZrTiAl

The electronic structure and magnetic properties of the PtZrTiAl, PdZrTiAl and Pt_0.5Pd_0.5ZrTiAl Heusler alloys were investigated using the full-potential linearized augmented plane wave (FPLAPW) within the generalized gradient approximation (GGA). For the PtZrTiAl, and PdZrTiAl alloys, the results showed that these Heusler alloys were stable in the Type I structure. The (Pt, Pd)ZrTiAl Heusler alloys are found to exhibit half-metallic ferromagnetism for both the Type I and Type II structure. The total magnetic moments of the PtZrTiAl and PdZrTiAl alloys were obtained to be 3 μ_B per formula unit, which are in agreement with the Slater-Pauling rule m_tot = (Nv ? 18). The half-metalliciy characteristic exists in the relatively wide ranges of 6.06–6.78 Å, and 6.13–6.73 Å for the PtZrTiAl and PdZrTiAl alloys, respectively. To complete the fundamental characteristics of these alloys, Pt_0.5Pd_0.5ZrTiAl is predicted to be a half-metallic ferromagnet with an energy gap of 0.90 eV in the minority spin and a complete spin polarization at the Fermi level. These new Heusler alloys may become ideal candidate material for future spintronic applications.     

Domain structure of the antiferromagnetic insulating state in Nd0.5Sr0.5MnO3

Optical reflectivity studies of the ferromagnetic metal (FMM) to antiferromagnetic insulator (AFI) phase transition were performed on Nd_0.5Sr_0.5MnO₃ single crystals in a wide temperature and magnetic field range. The formation of a domain structure in the AFI state was observed. On the basis of the experimental results and symmetry analysis we conclude that these domains are crystal twins, confirming the symmetry lowering of the crystal at this phase transition. The twin domain structure of the AFI state in the Nd_0.5Sr_0.5MnO₃ is visible in reflected unpolarized light due to a different tilting of the surface of the domains. We find no evidence for intermediate FMM+AFI stripe phase.     

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.     

Preparation and characteristics of Pr1.6Sr0.4NiO4+YSZ as composite cathode of solid oxide fuel cells

Composite cathodes of (1?x wt%)Pr_1.6Sr_0.4NiO₄+(x wt%)Y₂O₃-stabilized ZrO₂ (YSZ; x=0, 10, 20, 30, 40) abbreviated as Pr_1.6Sr_0.4NiO₄+xYSZ, were prepared. The composite cathodes with x>0 matched with electrolyte YSZ in thermal expansion coefficient (TEC) better than the cathode Pr_1.6Sr_0.4NiO₄ did. Pr_1.6Sr_0.4NiO₄+20YSZ exhibited the best performance on cathode overpotential and impedance. When the cathode overpotential was 0.1 V, the polarization current density of Pr_1.6Sr_0.4NiO₄+20YSZ was 0.28 A cm^?2, which is about 5.6 times higher than that of Pr_1.6Sr_0.4NiO₄, 0.05 A cm^?2. The area-specific resistance (ASR) for Pr_1.6Sr_0.4NiO₄+20YSZ was about 17.7% of that for Pr_1.6Sr_0.4NiO₄ at 750 °C.     

Phase transitions in La0.5Sr0.5FeO3−δ investigated by mechanical spectrum

The mechanical spectrum measurement was performed in ceramic La_0.5Sr_0.5FeO_3?δ from liquid nitrogen temperature to room temperature at kilohertz frequencies. From temperature dependent reduced modulus, a kink (corresponding temperature labeled as T_M) was observed which evidenced a phase transition by the mechanical spectrum at two flexural resonance frequencies. This elastic manifested phase transition is a charge disproportionation transition. Around 170 K, an internal friction peak (labeled as P1) was observed accompanied with a large modulus hardening with the decrease in temperature. Two mechanisms are proposed for P1 peak, one is elastic manifestation of magnetic freezing, and the other is the ordering or freezing of oxygen vacancies.     

The nature of magnetoelastic anomalies in Nd<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> upon suppression of charge ordering by a magnetic field

This paper reports on the results of investigations into the magnetic and magnetoelastic properties of Nd_0.5Sr_0.5MnO₃ single crystals in pulsed magnetic fields up to 250 kOe, the magnetic and kinetic properties of these crystals in weak static magnetic fields, and their thermal expansion. It is demonstrated that the studied properties exhibit a number of anomalies due to a transition from the antiferromagnetic semiconducting state to the ferromagnetic metallic state upon suppression of charge ordering.     

Magnetocaloric effect in polycrystalline (La0.5Gd0.2)Sr0.3MnO3

In this paper, we present a study of magnetocaloric effect in the colossal magnetoresistance material (La_0.5Gd_0.2)Sr_0.3MnO₃. From the measurements of isothermal magnetization at different temperatures, we have discovered a large magnetic entropy change with a broad peak around Curie temperature (270.5 K) in (La_0.5Gd_0.2)Sr_0.3MnO₃ polycrystalline sample. Moreover, the maximum of magnetic entropy change exhibits a nearly linear dependence with applied high magnetic field. These results suggest that this material is a suitable candidate as working substance in magnetic refrigeration near room temperature.     

Structure and oxygen stoichiometry of SrCo0.8Fe0.2O3−δ and Ba0.5Sr0.5Co0.8Fe0.2O3−δ

High temperature X-ray diffraction (HT-XRD), temperature programmed desorption (TPD), thermogravimetric analysis–differential thermal analysis (TGA/DTA) and neutron diffraction were combined to determine the structure and oxygen stoichiometry of SrCo_0.8Fe_0.2O_3−δ (SCF) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) up to 1273 K in the pO₂ range of 1 to 10^− 5 atm. Formation of the vacancy-ordered brownmillerite phase, SrCo_0.8Fe_0.2O_2.5, was observed as a region of zero oxygen release in the TPD measurements and confirmed by HT-XRD and TGA/DTA. No ordering was observed in the BSCF system by any of the techniques utilized in this work. The oxygen vacancy concentration of BSCF was found to be considerably higher than that of SCF and always higher than that of the ordered brownmillerite phase of SCF, δ = 0.5. The combination of a high vacancy concentration and absence of ordering leads to higher oxygen permeation fluxes through BSCF membranes in comparison to SCF.     

X-ray photoelectron spectroscopy analysis of (Ln1−xSrx)CoO3−δ (Ln: Pr,Nd and Sm)

The chemical states of the surface of (Ln_0.5Sr_0.5)CoO_3?δ (Ln (lanthanides) = Pr, Nd and Sm) used for cathode materials of intermediate temperature operating solid oxide fuel cells (IT-SOFCs) were investigated by X-ray photoelectron spectroscopy (XPS). Oxygen peaks comprised of lower binding energy (LBE) and higher binding energy (HBE) peaks from (Ln_0.5Sr_0.5)CoO_3?δ and Pr_0.3Sr_0.7CoO_3?δ (PSC37) showed that some merged oxygen peak behavior is a function of the Sr and lanthanide concentrations. By investigating the oxygen peaks, it was determined that more oxygen vacancies were generated on the surface of the cathodes when the lanthanides and Sr were substituted into perovskite oxides. When comparing the binding energies (BEs) of PSC37 with Pr_0.5Sr_0.5CoO_3?δ (PSC55), the LBE and HBE of the Sr peaks both increased when Sr was substituted at the A-site of a perovskite. Surface analysis of the Co peak on the surface of the cathode materials showed that the Co exists mainly as Co³⁺ and partially oxidized to Co⁴⁺ on the cathode materials. The partial existence of Co⁴⁺ can provide some polaron hopping providing electronic conduction for the solid oxide fuel cell.     

Synthesis and characterization of (Pr0.75Sr0.25)1 − xCr0.5Mn0.5O3 − δ as anode for SOFCs

The complex perovskite (Pr_0.75Sr_0.25)_1 − xCr_0.5Mn_0.5O_3 − δ (PSCM) has been prepared and studied as possible anode material for high-temperature solid oxide fuel cells (SOFCs). PSCM exhibits GdFeO₃-type structure and is both physically and chemically compatible with the conventional YSZ electrolyte. The reduction of PSCM resulted in structural change from orthorhombic Pbnm to cubic Pm-3m. Selected area electron diffraction (SAED) analysis on the reduced phases indicated the presence of a √2 × √2 × 2 superlattice. The total conductivity values of ∼ 75% dense Pr_0.75Sr_0.25Cr_0.5Mn_0.5O_3 − δ at 900 °C in air and 5% H₂/Ar are 9.6 and 0.14 S cm^− 1 respectively. The conductivity of PSCM drops with decreasing Po₂ and is a p-type conductor at all studied Po₂. The average TEC of Pr_0.75Sr_0.25Cr_0.5Mn_0.5O_3 − δ is 9.3 × 10^− 6 K^− 1, in the temperature range of 100–900 °C and is close to that of YSZ electrolyte. The anode polarization resistance of PSCM in wet 5%H₂ is 1.31 Ω cm² at 910 °C and in wet CH₄ at 930 °C; the polarization resistance is 1.29 Ω cm². PSCM was unstable at 900 °C in unhumidified hydrogen. Cell performance measurements carried out using graded PSCM and La_0.8Sr_0.2MnO₃ as anode and cathode respectively yielded a maximum power density of 0.18 W cm^− 2 in wet 5%H₂/Ar at 910 °C and the corresponding current density was 0.44 A cm^− 2 at 0.4 V. The activation energy for the electrochemical cell operating in wet (3% H₂O) 5%H₂/Ar fuel is 85 kJ mol^− 1.     

Electronic properties of the polycrystalline tin dioxide interface with conjugated organic layers

The results on the electronic structure of the unoccupied electronic states of the polycrystalline SnO₂ in the energy range from 5 eV to 25 eV above the Fermi level are presented. The modification of the electronic structure and of the surface potential upon deposition of the ultrathin films of copper phthalocyanine (CuPc) and of perylene tetracarboxylic acid dianhydride (PTCDA) film onto the SnO₂ surface were studied using the very low energy electron diffraction (VLEED) method and the total current spectroscopy (TCS) measurement scheme. A substantial attenuation of the TCS signal coming from the SnO₂ surface was observed upon formation of a 1.5–2 nm thick organic deposit layer while no new spectral features from the deposit were distinguishable. It was observed that the electronic structure typical for the organic films was formed within the organic deposit thickness range from 2 nm to 7 nm. The interfacial charge transfer was characterized by the formation of the polarization layer up to 5 nm thick in the organic films. The PTCDA deposition on SnO₂ was accompanied by the negative charge transfer onto the organic layer and to the 0.65 eV increase the surface work function. At the CuPc/SnO₂ interface, the negative charge was transferred to the SnO₂ surface and the overall surface work function decreased by 0.15 eV.     

Thermal and chemical expansion of mixed conducting La0.5Sr0.5Fe1−xCoxO3−δ materials

Oxygen deficiency, thermal and chemical expansion of La_0.5Sr_0.5Fe_1−xCo_xO_3−δ (x = 0, 0.5, 1) have been measured by thermogravimetry, dilatometry and high temperature X-ray diffraction. The rhombohedral perovskite materials transformed to a cubic structure at 350 ± 50 °C. The thermal expansion of the materials up to the onset of thermal reduction was 14–18 × 10^− 6 K^− 1. Above 500 °C in air (400 °C in N₂), chemical expansion contributed to the thermal expansion and the linear thermal expansion coefficients were significantly higher, 16–35 × 10^− 6 K^− 1. The chemical expansion, ε_c, showed a maximum of 0.0045 for x = 0.5 and 0.0041 for x = 1 at 800–900 °C. The normalized chemical expansion, ε_c/Δδ, was 0.036 for x = 0.5 and 0.035 for x = 1 at 800 °C. The chemical expansion can be correlated with an increasing ionic radius of the transition metals with decreasing valence state.     

Charge ordering and structural transitions in Pr0.5Sr0.41Ca0.09MnO3

The structural and magnetic transitions in Pr_0.5Sr_0.41Ca_0.09MnO₃ have been investigated by neutron diffraction and electron microscopy. Two structural transitions, Imma to I4/mcm and I4/mcm to Pmmn, are observed by decreasing the temperature. Two magnetic transitions, from a paramagnetic insulating to a ferromagnetic metallic and from a ferromagnetic metallic to an antiferromagnetic insulating states at T_C=250 K and T_N=180 K, respectively, are also observed. The structures of these three forms have been determined from neutron powder diffraction data. The first important result concerns the low temperature antiferromagnetic CE type and charge ordered structure, which has been refined in the Pmmn space group, without any constraint. This structure is completely long range ordered, with two Mn-sites, Mn³⁺ in tetragonally elongated octahedra, and Mn⁴⁺, off-centered in nearly regular octahedra. The second important point concerns the abrupt character of the structural transition from the I4/mcm to the Pmmn structure, without any appearance of incommensurability. The magnetic and transport properties of this compound are compared with those of Pr_0.5Sr_0.5MnO₃.     

Structure and electrochemical properties of Sm0.5Sr0.5Co1 − xFexO3 − δ cathodes for solid oxide fuel cells

Crystal structure, thermal expansion coefficient, electrical conductivity and cathodic polarization of compositions in the system Sm_0.5Sr_0.5Co_1 − xFe_xO_3 − δ with 0 ≤ x ≤ 0.9 were studied as function of Co / Fe ratio and temperature, in air. Two phases, including an Orthorhombic symmetry for 0 ≤ x ≤ 0.4 and a cubic symmetry for 0.5 ≤ x ≤ 0.9, were observed in samples of Sm_0.5Sr_0.5Co_1 − xFe_xO_3 − δ at room temperature. The adjustment of thermal expansion coefficient (TEC) to electrolyte, which is one of the main problems of SSC, could be achieved to lower TEC values with more Fe substitution. High electrical conductivity above 100 S/cm at 800 °C was obtained for all specimens, so they could be good conductors as cathodes of IT-SOFC. The polarization behavior of SSCF as a function of Fe content was evaluated by means of AC impedance using LSGM electrolyte. It was discovered that the Area Specific Resistance (ASR) of SSCF increased as the amount of substitution of Fe for Co increased. When the amount of Fe reached to 0.4, the highest ASR was obtained and then the resistance started decreasing above that. The electrode with a composition of Sm_0.5Sr_0.5Co_0.2Fe_0.8O_3 − δ showed high catalytic activity for oxygen reduction operating at temperature ranging from 700 to 800 °C.     

Fabrication of Gd0.5Sr0.5CoO3 film for SOFC cathode by pulsed laser deposition

Gd_0.5Sr_0.5CoO₃ (GSCO) film has been fabricated by pulsed laser deposition (PLD) to be used as the cathode of the solid oxide fuel cell (SOFC). The GSCO thin film obtained has a columnar crystalline structure so that it will have a high permeation property. The PLD technique has been found suitable for growing a film of complex composition because of its good control of stoichiometry and thus for fabricating a GSCO film used as the cathode of the SOFC. The GSCO film has been studied for porosity electrical conductivity and power density. The GSCO film grown at a substrate temperature of 1100 K and oxygen gas pressure of 100 Pa has high electrical conductivity which is 820 S cm^− 1 at 973 K with post annealing at a rather low temperature (1000 K). This value is higher than that of the GSCO film prepared by RF-sputtering with post annealing at a higher temperature (1273 K).     

Electron paramagnetic resonance studies on manganite Pr0.5Sr0.5Mn1−x Ga x O3 (x=0 and 0.05)

In this paper, we present the investigations of electron paramagnetic resonance on perovskite manganite Pr_0.5Sr_0.5MnO₃ and Ga-doped Pr_0.5Sr_0.5Mn_0.95Ga_0.05O₃. The temperature dependent paramagnetic resonance spectra parameters (effective g-factor, peak-to-peak linewidth ΔH _pp and double integrated intensities) have been used to study the paramagnetic spin correlations and spin dynamics. The gradual increase of effective g-factor is attributed to the presence of orbital ordering above T _C. The model fittings of temperature dependent double integrated intensities reveal Arrhenius law is appropriate for describing Pr_0.5Sr_0.5Mn_0.95Ga_0.05O₃ instead of Pr_0.5Sr_0.5MnO₃ system. As for Pr_0.5Sr_0.5MnO₃, the broadening of linewidth with the temperature increase origins from the contribution of small polaron hopping in the PM regime. However, as for Pr_0.5Sr_0.5Mn_0.95Ga_0.05O₃, the broadening of EPR linewidth can be understood with the spin-lattice relaxation mechanism.     

Magnetostructural phase separation and giant isotope effect in R<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript>

Results of neutron diffraction studies of R_0.5Sr_0.5MnO₃ manganites (R = Sm, Nd_0.772Tb_0.228, and Nd_0.544Tb_0.456) performed to reveal the microscopic origins of the giant oxygen isotope effect recently discovered in Sm_0.5Sr_0.5MnO₃ are presented. It is shown that two crystalline phases differing in the type of Jahn-Teller distortions of oxygen octahedra and in the type of magnetic ordering coexist at low temperatures in all the studied compositions. A scenario for the observed phase transitions is suggested based on the diffraction data. It is found that the percolation transition from the metallic to insulating state in compositions with Sm upon substitution of ¹⁸O for ¹⁶O is associated with a sharp (from 65 to 13%) decrease in the volume of the ferromagnetic metallic phase.