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A study of the phase transition and magnetocaloric effect in multiferroic La{sub 2}MnNiO{sub 6} single crystals

Magnetic and magnetocaloric properties of single crystal double perovskite La{sub 2}MnNiO{sub 6} have been investigated in details. Its ordered phase with a high Curie temperature (T{sub C} = 280 K) exhibits a significant refrigerant capacity around room temperature. A model based on the mean field theory approximation has been used in order to quantify the magnetic and magnetocaloric properties in the ordered La{sub 2}MnNiO{sub 6}. The magnetization and entropy changes were satisfactorily simulated as a function of temperature and magnetic field. On the other hand, the presence of cationic disorder in La{sub 2}MnNiO{sub 6} phases allows to shift the Curie point to low temperature without a significant change in the magnetocaloric performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Dy-substitution on the structural, vibrational, and multiferroic properties of BiFeO{sub 3} nanoparticles

Dysprosium (Dy) modified BiFeO{sub 3} [Bi{sub 1−x}Dy{sub x}FeO{sub 3} (x = 0.05, 0.10, and 0.15)] nanoparticles have been synthesized by a low temperature co-precipitation method. Rietveld analysis of X-ray diffraction data reveals a transformation from rhombohedral structure to orthorhombic structure with increase in the Dy concentration. From the transmission electron microscopy analysis, it is observed that the particle sizes of Bi{sub 1−x}Dy{sub x}FeO{sub 3} (x = 0.05, 0.10, and 0.15) nanoparticles range between 50–70, 40–50, and 30–50 nm, respectively. Raman spectra of Bi{sub 1−x}Dy{sub x}FeO{sub 3} (x = 0.05) belonging to rhombohedral (R3c) structure show 4A{sub 1} and 7E fundamental Raman modes in the range of 100–650 cm{sup −1} and two-phonon scattering modes such as 2A{sub 4} (longitudinal optical), 2E8 (transverse optical (TO)), and 2E{sub 9} (TO) in the range of 950–1270 cm{sup −1}. Suppression, broadening, and shifting of Raman modes have been observed with further increase in Dy concentration. The fundamental Raman modes of Bi{sub 1−x}Dy{sub x}FeO{sub 3} (x = 0.15) are assigned under orthorhombic (pnma) rather than rhombohedral (R3c) as the Rietveld analysis of X-ray diffraction data predicts a structural transformation for this particular composition. A complete suppression of two phonon modes has been noticed for this composition. An anomaly in the temperature dependent dielectric studies has been observed in all the samples at the vicinity of Neel temperature indicating a magnetic ordering, and an increase in magnetization with increase of Dy concentration in BiFeO{sub 3} is noticed from the room temperature magnetic studies. P–E hysteresis loop studies show a decrease of remnant polarization (P{sub r}) with the increase in Dy concentration and disappearance of hysteresis loop occurs for Bi{sub 1−x}Dy{sub x}FeO{sub 3} (x = 0.15) depicting a transformation from non-centrosymmetric (R3c) to centrosymmetric (Pnma) system.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Multiferroicity and magneto-electric effect in Gd{sub 2}BaNiO{sub 5}

We report the observation of electric polarization in the magnetically ordered state of the Haldane chain compound, Gd{sub 2}BaNiO{sub 5}, with strongly correlated magnetic and dielectric properties. The results of dc magnetic susceptibility and heat capacity measurements indicate two magnetic transitions, one corresponding to the anti-ferromagnetic order at T{sub N} ∼ 55 K and the other to spin-reorientation transition at T{sub SR} ∼ 24 K. The dielectric permittivity (ϵ{sub r}{sup ′}) and loss (tanδ) also exhibit anomalies in the vicinity of T{sub SR} and T{sub N}, respectively. Below the spin-reorientation transition, concurrently magnetic-field-induced spin-flop and the meta-electric transitions are observed at a critical magnetic field in isothermal magnetization and magneto-dielectric results, respectively. Another interesting finding is that Δϵ{sub r}{sup ′} (=(ϵ{sub r}{sup ′}(H)−ϵ{sub r}{sup ′}(0))/ϵ{sub r}{sup ′}(0)) changes its sign at the critical magnetic field. The origin of the observed magneto-electric effect is discussed on the basis of spin–phonon coupling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Spin and phonon anomalies in epitaxial self-assembled CoFe{sub 2}O{sub 4}-BaTiO{sub 3} multiferroic nanostructures

Temperature dependent magnetic and phonon anomalies in epitaxial self-assembled CoFe{sub 2}O{sub 4} (CFO) rods embedded in BaTiO{sub 3} (BTO) matrix nanostructures were investigated. The temperature dependence of A{sub 1}(2TO) phonon frequency of BTO indicates that the BTO matrix experiences structural transformations. The lattice strain produced during the structural transformations drives spin reorientation in CFO rods, resulting in anomalous changes of magnetization. Through correlating the phonon anomalies with the increase of in-plane spin ordering, we show the spin-phonon coupling induces the softening of A{sub 1g} and A{sub 1}(2TO) phonons. It suggests that spin strongly couples with lattice strain and phonons in this nanostructure.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Topology breaking of the vortex in multiferroic Y{sub 0.67}Lu{sub 0.33}MnO{sub 3}

Although topological defects, such as domain walls (DWs) or vortices, are naturally protected by topological invariance, yet, we discover an exception that the six-state topology of the vortex with Z2 × Z3 symmetry is broken by a partial edge dislocation (PED) in hexagonal Y{sub 0.67}Lu{sub 0.33}MnO{sub 3}, where the topologies of the four-state vortex or closed DWs emerges. Using aberration-corrected scanning transmission electron microscopy, we found that the PED plays an important role in changing the phase of translation domain. The PED at the vortex core leads to the formation of the four-state vortex, while the ones at closed DWs connect different types of DWs, both corresponding to continuous phase changes. These results indicate that PEDs can change the topology of translation-related domain vortices and more vortices with even domains can be expected.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Scandium induced structural transformation and B′:B″ cationic ordering in Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} multiferroic ceramics

The current study explores non-magnetic Sc{sup 3+} induced structural transformation, evolution of local B-site cation ordering and associated effect on ferroelectric phase transition temperature T{sub max} (temperature corresponding to dielectric maxima) on increasing the atom percent of Sc substitution in [Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} (PFN)] ceramics. In this regard, the phase pure Pb[(Fe{sub 0.5−x}Sc{sub x})Nb{sub 0.5}]O{sub 3} ceramics with x varying from 0 to 0.5 were synthesized through solid state reaction route. The detailed structural analysis through Rietveld refinement confirms the room temperature transformation from a monoclinic Cm to rhombohedral R3m structure at x = 0.3 mol. % of Sc. Absorption spectra studies show that there is a considerable increment in the bandgap at higher scandium content. Most interestingly, the T{sub max} exhibited an increment for lower scandium contents (x = 0.1 to 0.25) followed by a drop in T{sub max} (x = 0.3 to 0.5). Such anomalous behavior in T{sub max} is expected to arise due to the onset of B′, B″ local cation ordering beyond Sc content x = 0.25. The B-site cation ordering at and beyond x = 0.3 was also confirmed by the evolution of cation order induced Pb-O coupled vibrational mode in Raman scattering studies. In addition, the Mössbauer spectra of PFN (x = 0) and Pb(Fe{sub 0.4}Sc{sub 0.1}Nb{sub 0.5})O{sub 3} (x = 0.1) are reported to verify the spin state and oxidation state of iron. The lattice distortion due to the radius ratio difference between a Sc{sup 3+} cation and Fe{sup 3+} cation in low spin state is responsible for the structural transformation, which in turn facilitates a B′:B″ cation ordering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ferroic characterizations, phase transformation, and internal bias field in 0.75Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3}–0.25PbTiO{sub 3} multiferroic ceramic

The complex perovskite of 0.75Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3}–0.25PbTiO{sub 3} (0.75PFW-0.25PT) ceramic was prepared by the conventional oxide mixing method. The detailed microstructure of 0.75PFW-0.25PT ceramic was investigated. At room temperature, the TEM analysis reveals that only cubic structure (nonpolar) exists, which is different from the phase coexistence of cubic (66%) and tetragonal (34%) structure revealed by XRD. A mechanism dominated by a temperature rise due to electron-beam irradiation has been proposed. The XPS measurement confirms the mixed balance state of Fe{sup 2+} and Fe{sup 3+} in the as-prepared 0.75PFW-0.25PT specimen, which facilitates the formation of the defect dipoles with oxygen vacancies, in turn resulting in the internal-bias field (E{sub i}) phenomenon. The appearance of weak magnetic interactions is believed relating to the presence of noncompensated magnetic moments in Fe-rich islands. These results provide key information for understanding the composition, defect, ferroelectric, and ferromagnetic properties in 0.75PFW-0.25PT ceramic.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multiferroic CuCrO₂ under high pressure: In situ X-ray diffraction and Raman spectroscopic studies

The compression behavior of delafossite compound CuCrO₂ has been investigated by in situ x-ray diffraction (XRD) and Raman spectroscopic measurements up to 23.2 and 34 GPa, respectively. X-ray diffraction data show the stability of ambient rhombohedral structure up to ~23 GPa. Material shows large anisotropy in axial compression with c-axis compressibility, κ{sub c} = 1.26 × 10⁻³(1) GPa⁻¹ and a-axis compressibility, κ{sub a} = 8.90 × 10⁻³(6) GPa⁻¹. Our XRD data show an irreversible broadening of diffraction peaks. Pressure volume data when fitted to 3rd order Birch-Murnaghan equation of state give the value of bulk modulus, B₀ = 156.7(2.8) GPa with its pressure derivative, B₀{sup ’} as 5.3(0.5). All the observed vibrational modes in Raman measurements show hardening with pressure. Appearance of a new mode at ~24 GPa indicates the structural phase transition in the compound. Our XRD and Raman results indicate that CuCrO{sub 2} may be transforming to an ordered rocksalt type structure under compression.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electric field induced cubic to monoclinic phase transition in multiferroic 0.65Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-0.35PbTiO{sub 3} solid solution

The results of x-ray diffraction studies on 0.65Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-0.35PbTiO{sub 3} solid solution poled at various electric fields are presented. After poling, significant value of planar electromechanical coupling coefficient (k{sub P}) is observed for this composition having cubic structure in unpoled state. The cubic structure of 0.65Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-0.35PbTiO{sub 3} transforms to monoclinic structure with space group Pm for the poling field ≥5 kV/cm. Large c-axis microscopic lattice strain (1.6%) is achieved at 30 kV/cm poling field. The variation of the c-axis strain and unit cell volume with poling field shows a drastic jump similar to that observed for strain versus electric field curve in (1 − x)Pb(Mg{sub 1/3}Nb{sub 2/3}) O{sub 3}-xPbTiO{sub 3} and (1 − x)Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}-xPbTiO{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Local geometric and electronic structures and origin of magnetism in Co-doped BaTiO{sub 3} multiferroics

We have prepared polycrystalline samples BaTi{sub 1−x}Co{sub x}O{sub 3} (x = 0–0.1) by solid-state reaction. X-ray diffraction and Raman-scattering studies reveal the phase separation in crystal structure as changing Co-doping content (x). The samples with x = 0–0.01 are single phase in a tetragonal structure. At higher doping contents (x > 0.01), there is the formation and development of a secondary hexagonal phase. Magnetization measurements at room temperature indicate a coexistence of paramagnetic and weak-ferromagnetic behaviors in BaTi{sub 1−x}Co{sub x}O{sub 3} samples with x > 0, while pure BaTiO{sub 3} is diamagnetic. Both these properties increase with increasing x. Analyses of X-ray absorption spectra recorded from BaTi{sub 1−x}Co{sub x}O{sub 3} for the Co and Ti K-edges indicate the presence of Co{sup 2+} and Co{sup 3+} ions. They locate in the Ti{sup 4+} site of the tetragonal and hexagonal BaTiO{sub 3} structures. Particularly, there is a shift of oxidation state from Co{sup 2+} to Co{sup 3+} when Co-doping content increases. We believe that the paramagnetic nature in BaTi{sub 1−x}Co{sub x}O{sub 3} samples is due to isolated Co{sup 2+} and Co{sup 3+} centers. The addition of Co{sup 3+} ions enhances the paramagnetic behavior. Meanwhile, the origin of ferromagnetism is due to lattice defects, which is less influenced by the changes caused by the variation in concentration of Co{sup 2+} and Co{sup 3+} ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Direct band gaps in multiferroic h-LuFeO{sub 3}

We measured the optical properties of epitaxial thin films of the metastable hexagonal polymorph of LuFeO{sub 3} by absorption spectroscopy, magnetic circular dichroism, and photoconductivity. Comparison with complementary electronic structure calculations reveals a 1.1 eV direct gap involving hybridized Fe 3d{sub z{sup 2}}+O 2p{sub z}→Fe d excitations at the Γ and A points, with a higher energy direct gap at 2.0 eV. Both charge gaps nicely overlap the solar spectrum.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A study of magnetic ordering in multiferroic hexagonal Ho{sub 1-x}Dy{sub x}MnO{sub 3}

This paper investigates the magnetic properties of Ho{sub 1-x}Dy{sub x}MnO{sub 3} by considering the inter-planar Mn{sup 3+}-O-O-Mn{sup 3+} interaction. The theoretical analysis shows that the asymmetric in-plane exchange interaction couples the in-plane and inter-planar Mn{sup 3+} spin structures via asymmetry parameter δ. This leads to the existence of both the in-plane and inter-planar ordering, which in turn restricted the allowed magnetic space groups to Γ{sub 1} and Γ{sub 4}. The experimental studies confirmed the concomitant nature of the in-plane and the inter-planar ordering at T{sub N}, T{sub SR}, and T{sub 2}. It also showed that the magnetic phase diagram is dominated by the allowed magnetic structures Γ{sub 1} and Γ{sub 4}. Furthermore, an effort is made to resolve the inconsistency regarding the T{sub SR} (32 or 40 K). The studies revealed that the antiferromagnetic inter-planar interaction is switched to the ferromagnetic interaction (40 K) upon cooling, which in turn drives the spin reorientation at 32 K. The Mn{sup 3+} spin structure is seen to be coupled to rare earth sub-lattice through the modulation of the inter-planar interaction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Lattice dynamics and broad-band dielectric properties of multiferroic Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} ceramics

Complex dielectric properties of Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} ceramics were investigated in a broad frequency range from 100 Hz up to 90 THz. A broad dielectric anomaly was observed near the temperature of the ferroelectric phase transition (T{sub C1} = 376 K). Below 1 MHz, the anomaly is strongly influenced by conductivity of the sample, but higher frequency data taken up to 81 MHz reveal a broad and frequency independent peak at T{sub C1} typical for a diffuse ferroelectric phase transition. Surprisingly, dielectric permittivity measured at 37 GHz exhibits a peak shifted by 25 K above T{sub C1}, which indicates polar nanoregions with dynamics in microwave frequency region. A dielectric relaxation, which appears in THz region below 700 K, slows down towards T{sub C1} and again hardens below T{sub C2} = 356 K. This central mode drives both phase transitions, so they belong to order–disorder type, although the polar phonons exhibit anomalies near both phase transitions. In the paraelectric phase, infrared reflectivity spectra correspond to local Fm3{sup ¯}m structure due to short-range chemical ordering of Fe and Nb cations on the B perovskite sites. Moreover, each polar phonon is split due to two different cations on the B sites. Recently, Manley et al. [Nat. Commun. 5, 3683 (2014)] proposed a new mechanism of creation of polar nanoregions in relaxor ferroelectrics. They argued, based on their inelastic neutron scattering studies of PMN–PT, that the TO1 phonon is split and interaction of both components gives rise to so called Anderson phonon localization, which can produce regions of trapped standing waves and these waves induce polar nanoregions in relaxors. We cannot exclude or confirm this mechanism, but we show that the splitting of polar phonons is a common feature for all complex perovskites with relaxor ferroelectric behavior and it can be also observed in canonical ferroelectric BaTiO{sub 3}, where the soft mode is split in paraelectric phase due to a strong lattice anharmonicity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Size effect on multiferroic TbMn{sub 2}O{sub 5} nanorods

The effect of the size of TbMn{sub 2}O{sub 5} on their magnetoelectric properties is studied using a field emission transmission electron microscope, ac magnetic susceptibility, relative dielectric constant, specific heat capacity, and x-ray diffraction at various temperatures. A bulk sample and nanorods with two axial lengths, 〈L{sub C}〉, are investigated. Nanorods with 〈L{sub C}〉 of 216 nm and 64 nm crystallize with orthorhombic Pbam symmetry as the bulk material. The axial direction of the two sizes of nanorod is parallel to the c axis of the crystal. No particular radial direction is observed. The critical size for the magnetic ordering of TbMn{sub 2}O{sub 5} is found to be between 〈L{sub C}〉 = 64 nm and 216 nm. Experiments on specific heat capacity verified these results. No similar phenomenon concerning the ferroelectric property is observed. At T = 30 K and 35 K, the 〈L{sub C}〉 = 216 nm sample yields a charge-ordering-like x-ray diffraction peak, which may be associated with the magnetically induced charge ordering superlattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The magnetic origin of multiferroic Y{sub 2}CoMnO{sub 6}

It has been found experimentally that the ferroelectricity in Y{sub 2}CoMnO{sub 6} is driven by a magnetic ordering of collinear up-up-down-down (↑↑↓↓). Here, the origin of the magnetism and thereby ferroelectricity is studied using first-principles calculations. We first confirm that the experimentally observed ↑↑↓↓ antiferromagnetic structure is the ground state of Y{sub 2}CoMnO{sub 6}. Additionally, both the Co{sup 2+} and Mn{sup 4+} are in the high-spin state. By analyzing the exchange coupling and corresponding pathways, we conclude that the ↑↑↓↓ spin order in Y{sub 2}CoMnO{sub 6} originates from a subtle competition between the ferromagnetic Co-O-Mn super-exchange and antiferromagnetic Co-Mn direct-exchange along c axis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multiferroic properties of Pb{sub 0.90}Sr{sub 0.10}TiO{sub 3}-CoFe{sub 2}O{sub 4} nanostructured bilayered thin film

Pb{sub 0.90}Sr{sub 0.10}TiO{sub 3}-CoFe{sub 2}O{sub 4}(PST10-CFO) nanostructured bilayered thin film were grown on Si (100) substrate by using metallo-organic decomposition chemical route and spin coating technique. Results show that PST (pervoskite structure) and CFO (spinel) phase coexist in the bilayered thin films, annealed at 650°C for 2hr and no obvious impurity phase can be detected. The structural, surface morphology and micro structural properties were confirmed by X-Ray diffraction (XRD), atomic force microscope (AFM) respectively. Excellent ferroelectric behavior at different voltage was observed, with two platinum electrodes only at surface of the bilayer thin film. A room temperature ferromagnetic behavior was observed in the bilayered Pb{sub 0.90}Sr{sub 0.10}TiO{sub 3}-CoFe{sub 2}O{sub 4} nanostructured thin film. The saturation magnetization and variation in coercivity value of the bilayer thin film is lower than that of the pure CFO film in the presence of non ferromagnetic PST layer which is the attributed that the significant coupling between the two phases.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Study of microstructure, dielectric and ferromagnetic properties of the (1-x)Ba{sub 0.95}Sr{sub 0.05}TiO{sub 3}-(x)CoFe{sub 1.8}Mn{sub 0.2}O{sub 4} multiferroic composites

In the present work, (1-x)Ba{sub 0.95}Sr{sub 0.05}TiO{sub 3}-(x)CoFe{sub 1.8}Mn{sub 0.2}O{sub 4} composites are prepared by standard solid state reaction method. The X-ray diffraction measurement of the composites shows that both the phases coexist in the composite, individually. The morphology of the composites were examined by field emission scanning electron microscopy and reveals homogeneous microstructure with two types of grains, smaller grains of the Ba{sub 0.95}Sr{sub 0.05}TiO{sub 3} (BST) and bigger grains of the CoFe{sub 1.8}Mn{sub 0.2}O{sub 4} (CFM). The dielectric studies show that all the composites exhibit dispersion in the lower frequency region attributable to the interfacial polarization. In addition, at lower frequencies, the dielectric constant (ε´) is found to increase with increase in CFM content in the composites. The ferromagnetic properties of the composites improve with the increase in the CFM content.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural and multiferroic properties of self doped yttrium manganites YMn{sub 1+X}O{sub 3}

We have prepared the polycrystalline samples of compositions YMn{sub 1+x}O{sub 3} (x =0, 0.17) and studied their structural properties using x-ray diffraction and Raman spectroscopy measurements. The sample with composition Y:Mn = 1:1 showed the antiferromagnetic transition in the magnetization verses temperature (M-T) measurements near 70 K similar to standard YMnO{sub 3}. But the sample with composition Y:Mn = 1:1.17 showed glass like magnetic transition around 42 K in the M-T measurements. Also, a hysteresis in the isothermal magnetization curve at 2K was observed for the Mn rich sample, while the linear trend of magnetization with magnetic field was noted for the sample with equal Y/Mn ratio at 2K. We understood that the Mn excess in Mn rich sample results in the formation of Mn{sup 2+} ions and the magnetic exchange among the Mn{sup 3+/}Mn{sup 2+} ions is responsible for the observed magnetic behaviour. The room temperature ferroelectric properties of the studied samples were also investigated by measuring P-E loops.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗