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An Aurivillius-phase multiferroic material Bi 1.25 AlMnO 3.25 embedded with Au NPs displays tunable functionalities at various deposition temperatures.
Here, combining the experimental techniques of high-resolution X-ray diffraction, magnetometry, specific heat measurement, and X-ray photoelectron, Raman and dielectric spectroscopy techniques, we have studied the influence of La and Cr doping on the crystal structure and magnetism of the room temperature Aurivillius multiferroic Bi 5 Ti 3 FeO 15 by investigating the physical properties of (Bi 4 La)Ti 3 FeO 15 and Bi 5 Ti 3 (Fe 0.5 Cr 0.5 )O 15 . The parent (Bi 5 Ti 3 FeO 15 ) and the doped ((Bi 4 La)Ti 3 FeO 15 and Bi 5 Ti 3 (Fe 0.5 Cr 0.5 )O 15 ) compounds crystallize in the A2 1 am space group, which is confirmed through our analysis of high-resolution synchrotron X-ray diffraction data obtained on phase-pure polycrystalline powders. We determined the oxidation states of the metal atoms in the studied compounds as Fe 3+ , Ti 4+ , Cr 3+ , and La 3+ through the analysis of X-ray photoelectron spectroscopy data. The magnetic susceptibilities of the three compounds are marked by the absence of a long-range ordered ground state, but dominated by superparamagnetic clusters with dominant antiferromagnetic interactions. This signature of short-range magnetism is also seen in specific heat as a low temperature enhancement which is suppressed upon the application of external magnetic fields up to 8 T. Our dielectric spectroscopy experiments showed that the three studied compounds display similar features in the dielectric constant measured as a function of frequency. However, upon doping La at the Bi site, the width of the ferroelectric hysteresis loop increases for (Bi 4 La)Ti 3 FeO 15 compared to that of the parent compound Bi 5 Ti 3 FeO 15 , and with Cr doping, Bi 5 Ti 3 (Fe 0.5 Cr 0.5 )O 15 becomes a leaky dielectric. The resilience of the Aurivillius crystal structure towards doping of La at the Bi site and Cr at the Fe site is clearly seen in the bulk properties of magnetic susceptibility, specific heat and the average crystal structure. The relevance of changes in the local structure is evident from our Raman spectroscopy and X-ray pair distribution function studies.
We report the crystal structure, magnetic, ferroelectric, dielectric, and magneto-dielectric properties of [Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3}]{sub (1−x)}[Co{sub 0.65}Zn{sub 0.35}Fe{sub 2}O{sub 4}]{sub x}: (x = 0.1, 0.2, 0.3, and 0.4) composites. Rietveld refinement results of X-ray diffraction patterns confirm the formation of these composites for all x values. All the composites show well-saturated ferroelectric and ferromagnetic hysteresis (multiferroic-composite behavior) at room temperature. With increase in Co{sub 0.65}Zn{sub 0.35}Fe{sub 2}O{sub 4} (CZFO) content an increase in saturation magnetization, and decrease in saturation polarization, remanent polarization, and dielectric constant are observed. The ferroelectric phase transition temperature increases with increase in CZFO content. All of the compositions undergo second-order ferroelectric phase transitions, which can be explained by Landau-Devonshire theory. The recoverable energy density (∼0.20 to 0.04 J/cm{sup 3}) and charge-curve energy density (∼0.84 to 0.11 J/cm{sup 3}) decrease with increase in the CZFO content. The room-temperature magneto-dielectric measurements provide direct evidence of magneto-electric coupling via strain at room temperature.
Aurivillius Bi{sub 5}Ti{sub 3}FeO{sub 15} (BTFO) multiferroic ceramics with different Cr-doped concentrations have been synthesized by the conventional solid state reaction method. The influences of Cr-doping concentrations on the structural, magnetic, dielectric, and ferroelectric properties of BTFO ceramics are investigated in detail. All these sintered Cr-substituted BTFO ceramics are determined to be layered perovskite Aurivillius structure by X-ray diffraction, as well as the lattice parameters a, b, and c are in good accordance with Vegard's law along with the Cr-doping concentration. The lattice distortion a/b for Aurivillius family decreases with increasing Cr-doping concentration. Moreover, Cr-doping can promote greatly the grain growth of BTFO samples confirmed from field emission scanning electron microscopy characterization. However, no obvious signs of the improvement in ferroelectric properties are found in Cr-doped BTFO ceramics, and abnormal ferroelectric polarization versus electric field (P-E) loops are observed as Cr-doping content is beyond 0.1. Similar ε (tanδ) versus frequency plots to those of the BTFO sample are exhibited when Cr-doping concentration is less than 0.1. Nevertheless, obvious dielectric dispersion phenomena are shown as the Cr-doping concentration is beyond 0.1, and this dispersion behavior becomes strong with further increasing Cr-doping concentration, which are clearly indicated by the appearance of dielectric loss relaxation peaks in the measurement frequency from 10{sup 2} Hz to 10{sup 6} Hz. In addition, the corresponding frequency to relaxation peak shifts towards high frequencies with the Cr-doping concentration. Finally, the same magnetic orderings for all these Cr-doped BTFO ceramics as those of the BTFO one, i.e., superparamagnetic state dominated with antiferromagnetic interaction, are unambiguously found, signifying that the predicted Fe{sup 3+}-O-Cr{sup 3+} 180° ferromagnetic superexchange interaction based on the Goodenough-Kanamori (G-K) rule might not be achieved in BTFO ceramics through Cr substitution by the conventional solid state reaction.
Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ∼2 nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions and depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient is significant enough to drive the cation migration across the interface, thereby mitigating the misfit strain. Our results offer new insights on how chemical roughening at oxide interfaces can be effective in stabilizing the structural integrity of the interface without the need for misfit dislocations. These findings offer a general formalism for understanding cation intermixing at highly strained oxide interfaces that are used in nanoelectronic devices.
DyFe{sub 0.5}Cr{sub 0.5}O{sub 3} has been synthesized using a sol-gel method. It exhibits ferroelectricity at the antiferromagnetic ordering temperature T{sub N1}∼261 K. Large magnetocaloric effect (MCE) (11.3 J/kg K at 4.5 T) enhanced by magnetoelectric coupling due to magnetic field and temperature induced magnetic transition was observed. Temperature-dependent Raman study shows an anomalous behavior near T{sub N1} in the phonon modes related to the vibration of Dy atoms and stretching of CrO{sub 6}/FeO{sub 6} octahedra, suggesting the ferroelectricity in DyFe{sub 0.5}Cr{sub 0.5}O{sub 3} is associated with the spin-phonon coupling with respect to both Dy and Cr/Fe ions. These results suggest routes to obtain high-temperature multiferroicity and large MCE for practical applications.
PbZr{sub 0.52}Ti{sub 0.48}O{sub 3}/CoFe{sub 2}O{sub 4}/La{sub 0.7}Sr{sub 0.3}MnO{sub 3} (PZT/CFO/LSMO) and PZT/LSMO heterostructures were grown on single-crystal MgO (100) substrates using the dual-laser ablation technique. X-ray diffraction confirmed the epitaxial relationship between the layers in the heterostructures. Magnetization measurements showed in-plane uniaxial magnetic anisotropy in PZT/CFO/LSMO with enhanced saturation magnetization of 288 emu/cm{sup 3} as compared to 244 emu/cm{sup 3} for PZT/LSMO. With the introduction of the hard magnetic CFO, the low coercivity of PZT/LSMO increased from 0.1 kOe to 1.4 kOe. Polarization measurements showed well-saturated square hysteresis loops for PZT/CFO/LSMO with enhanced remanent polarization (P{sub r}) values of 69 μC/cm{sup 2} at a coercive field (E{sub c}) of 88 kV/cm as compared to P{sub r} = 51 μC/cm{sup 2} at E{sub c} = 39 kV/cm for PZT/LSMO. The improved hard ferromagnetic and ferroelectric properties in PZT/CFO/LSMO as compared to PZT/LSMO make it desirable for multiferroic device applications.
Ferromagnetic-ferroelectric composites show strain mediated coupling between the magnetic and electric sub-systems due to magnetostriction and piezoelectric effects associated with the ferroic phases. We have synthesized core-shell multiferroic nano-composites by functionalizing 10–100 nm barium titanate and nickel ferrite nanoparticles with complementary coupling groups and allowing them to self-assemble in the presence of a catalyst. The core-shell structure was confirmed by electron microscopy and magnetic force microscopy. Evidence for strong strain mediated magneto-electric coupling was obtained by static magnetic field induced variations in the permittivity over 16–18 GHz and polarization and by electric field induced by low-frequency ac magnetic fields.
We propose a microscopic model in order to study the multiferroic properties of Cu{sub 2}OSeO{sub 3} taking into account the ferrimagnetic interaction, frustration, linear magnetoelectric (ME) coupling, and anharmonic spin-phonon interaction. We have shown that the dielectric constant and the phonon energy and damping have a kink near the magnetic phase transition T{sub C} = 58 K which disappears with increasing of an external magnetic field. This behavior is an evidence for a strong ME coupling and in qualitative agreement with the experimental data.
Thermal evolution and an intermediate phase between ferroelectric orthorhombic and paraelectric tetragonal phase of multiferroic Bi{sub 5}Ti{sub 3}FeO{sub 15} ceramic have been investigated by temperature-dependent spectroscopic ellipsometry and Raman scattering. Dielectric functions and interband transitions extracted from the standard critical-point model show two dramatic anomalies in the temperature range of 200–873 K. It was found that the anomalous temperature dependence of electronic transition energies and Raman mode frequencies around 800 K can be ascribed to intermediate phase transformation. Moreover, the disappearance of electronic transition around 3 eV at 590 K is associated with the conductive property.
We investigate the effects of slight Dy/Mn off-stoichiometry on the multiferroic behaviors of DyMnO{sub 3} (Dy{sub 1−x}Mn{sub 1+x}O{sub 3}). It is revealed that the distorted lattice structure and ferroelectric property exhibit higher stability against the Mn deficiency than the Dy deficiency. Since the electric polarization includes the contributions from the Mn-Mn and Dy-Mn interactions, the measured polarization exhibits different dependence on the Mn deficiency from that on the Dy deficiency. The present work suggests that the Dy/Mn off-stoichiometry is detrimental to the ferroelectricity, owing to the modulated spin interactions and reshuffled spin frustration.
Optical phonons of multiferroic Bi{sub 4}Ti{sub 3}O{sub 12}-BiFeO{sub 3} ceramic have been investigated by low temperature Raman scattering and infrared reflectance spectra. Anomalies at about 85 K can be observed from the temperature dependence of the Raman and infrared modes, which arise from spin-phonon interaction during antiferromagnetic to paramagnetic phase transition. It was found that the change of exchange interaction in magnetic phase transition can be induced by Fe-O-Fe octahedral tilting driven from the A-site atoms. Moreover, ferroelectricity-related displacement of Bismuth atoms suggests the coupling of magnetic and ferroelectric orders.
Thin film of BaTiO{sub 3} doped with 0.1 at. % Cr (Cr:BTO) has been prepared by pulsed laser deposition technique. Film was deposited on Pt/SrTiO{sub 3} substrate at 500 °C in 50 mTorr Oxygen gas pressure using KrF (298 nm) laser. Polycrystalline growth of single phase Cr:BTO thin film has been confirmed by grazing angle X-ray diffraction. Cr:BTO film exhibited remnant polarization 6.4 μC/cm{sup 2} and 0.79 MV/cm coercivity. Magnetization measurement of Cr:BTO film showed magnetic moment 12 emu/cc. Formation of weakly magnetic domains has been captured by magnetic force microscopy. Theoretical impedance equation fitted to experimental data in Cole-Cole plot for thin film in presence of transverse magnetic field resolved the increase in grain capacitance from 4.58 × 10{sup −12} to 5.4 × 10{sup −11} F. Film exhibited high value 137 mV/cm-Oe magneto-electric (ME) coupling coefficient at room temperature. The high value of ME coupling obtained can reduce the typical processing steps involved in multilayer deposition to obtain multiferrocity in thin film. Barium titanate being best ferroelectric material has been tailored to be multiferroic by non ferromagnetic element, Cr, doping in thin film form opens an avenue for more stable and reliable spintronic material for low power magnetoelectric random excess memory applications.
Bi{sub 0.8}La{sub 0.15}RE{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3} (where RE = Pr and Nd) have been prepared via conventional solid state route. The Rietveld refinement of X-ray diffraction patterns shows that both systems crystallize in orthorhombic Pnma space group. Raman modes observed for these two systems indicate that both systems are very close to orthorhombic Pnma structure. Appearance of prominent A{sub 1}-3 and weak E-2 modes in Bi{sub 0.8}La{sub 0.15}Nd{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3} indicate the presence of chemically more active Bi-O covalent bonds (which favors stereochemical activity of Bi lone pair electrons) in comparison to Bi{sub 0.8}La{sub 0.15}Pr{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3}. Moreover, Bi{sub 0.8}La{sub 0.15}Nd{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3} system shows higher dielectric constant, low dielectric loss, and higher magnetization value in comparison to Bi{sub 0.8}La{sub 0.15}Pr{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3} system. Ferroelectric transition temperature decreases to 460 °C for both systems in comparison to 710 °C of Bi{sub 0.8}La{sub 0.2}Fe{sub 0.9}Mn{sub 0.1}O{sub 3}. The improved dielectric and magnetic response suggests Bi{sub 0.8}La{sub 0.15}Nd{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3} a better multiferroic system than Bi{sub 0.8}La{sub 0.15}Pr{sub 0.05}Fe{sub 0.9}Mn{sub 0.1}O{sub 3}.
The ultrafast carrier dynamics of the multiferroic BiFeO{sub 3} film in a broad temperature range is investigated using optical pump-probe spectroscopy. The photoexcited electrons release their energy with optical phonons emission through electron-phonon coupling in about 1 ps. The following intermediate process is identified as dynamical spin-lattice coupling in several picoseconds. Furthermore, the peak values of the optical reflectivity and the time constants of carrier relaxation channels show significant changes while the temperature varies from 137.5 K to around 195 K, this aligns with the previously reported hidden phase transition. Our study demonstrates that ultrafast spectroscopy is a sensitive method to look into the dynamical interactions among the on-site high-energy electrons accumulated in the p conduction band of Bi, coherent optical phonon, as well as the spin degree of freedom. These features play crucial roles in the characterization of phase transitions.
Crystal structure, microstructure, local ferroelectric, and magnetic properties of the Bi{sub 0.9}Nd{sub 0.1}Fe{sub 1−x}Ti{sub x}O{sub 3} samples have been investigated at room temperature to reveal the effect of Ti{sup 4+} doping on the multiferroic behavior of the lanthanide-modified compound representing a polar (space group R3c) antiferromagnetic phase of the Bi{sub 1−x}Ln{sub x}FeO{sub 3} perovskites. Ti doping results in a gradual suppression of the rhombohedral distortions, however, symmetry of the crystal structure remains the same in the entire concentration range allowing the single-phase perovskites to be obtained (x ≤ 0.08). The doping tends to reduce existing lone-pair cation-driven polar displacements, thus giving rise to a decrease of the ferroelectric polarization in the Bi{sub 0.9}Nd{sub 0.1}Fe{sub 1−x}Ti{sub x}O{sub 3} (x→0.08) series. A drastic (from ∼10 μm for x = 0 to ∼1 μm for 0.02 ≤ x ≤ 0.08) decrease of the average grain size induced by the doping is accompanied by the formation of a ferroelectric domain structure with the average domain width of ∼40 nm. Finally, the doping was shown to induce an antiferromagnetic to weak ferromagnetic transformation. The maximum remanent magnetization observed in the Bi{sub 0.9}Nd{sub 0.1}Fe{sub 1−x}Ti{sub x}O{sub 3} series at x ∼ 0.05 coincides with the locked magnetization releasing upon the magnetic field-induced suppression of the magnetic cycloid in pure BiFeO{sub 3}.
Low-thickness La{sub 0.66}Sr{sub 0.34}MnO{sub 3} (LSMO)/BiFeO{sub 3} (BFO) thin film samples deposited on SrTiO{sub 3} were imaged by high resolution x-ray microscopy at different temperatures. The ultra-thin thickness of the top layer allows to image both the ferromagnetic domain structure of LSMO and the multiferroic domain structure of the buried BFO layer, opening a path to a direct observation of coupling at the interface on a microscopic level. By comparing the domain size and structure of the BFO and LSMO, we observed that, in contrast to LSMO single layers, LSMO/BFO multilayers show a strong temperature dependence of the ferromagnetic domain structure of the LSMO. Particularly, at 40 K, a similar domain size for BFO and LSMO is observed. This indicates a persistence of exchange coupling on the microscopic scale at a temperature, where the exchange bias as determined by magnetometer measurements is vanishing.
Magnetic structure evolution of multiferroic hexagonal YMn{sub 1−x}Fe{sub x}O{sub 3} (x = 0, 0.05, and 0.1) has been studied by carrying out detailed temperature-dependent neutron diffraction at zero and 5 T fields. Thermodynamic data confirm antiferromagnetic ordering at T{sub N} in all the compositions. Our sub-T{sub N} neutron diffraction results assign the magnetic structure of pure YMnO{sub 3} to Γ{sub 1} irreducible representation. Over the perturbative-doping range, magnetic structure changes via Γ{sub 1} + Γ{sub 2} for YMn{sub 0.95}Fe{sub 0.05}O{sub 3} on to Γ{sub 2} for YMn{sub 0.9}Fe{sub 0.1}O{sub 3}, as the maiden compositional analogue of spin-reorientation; its occurrence in temperature-domain already reported for several manganites. Moreover, while the large thermal isostructural changes observed above T{sub N} are subdued in the ordered state, small alterations by the applied 5 T-field are relatively uniform across, confirming strong magneto-elastic nature of the system. Decrease of the ordered magnetic moment (μ{sub ord}) and planar magnetic frustration noted with Fe-doping is enhanced by the applied field, apparently through canting.