We review the concept of surface charge, first in the context of the polarization in ferroelectric materials, and second in the context of layers of charged ions in ionic insulators. While the former is traditionally discussed in the ferroelectrics community, and the latter in the surface science community, we remind the reader that the two descriptions are conveniently unified within the modern theory of polarization. In both cases, the surface charge leads to electrostatic instability - the so-called "polar catastrophe" - if it is not compensated, and we review the range of phenomena that arise as a result of different compensation mechanisms. We illustrate these concepts using the example of the prototypical multiferroic bismuth ferrite, BiFeO3, which is unusual in that its spontaneous ferroelectric polarization and its layer charges can be of the same magnitude. As a result, for certain combinations of polarization orientation and surface terminationits surface charge is self-compensating. We use density functional calculations of BiFeO3 slabs and superlattices, analysis of high-resolution transmission electron micrographs as well as examples from the literature to explore the consequences of this peculiarity.
Micro-Raman studies show that under ~700 kV/cm of d.c. voltage stressing for a few seconds, thin-film bismuth ferrite BiFeO3 phase separates into magnetite Fe3O4. No evidence is found spectroscopically of hemite alpha-Fe2O3, maghemite gamma-Fe2O3, or of Bi2O3. This relates to the controversy regarding the magnitude of magnetization in BiFeO3.
We have investigated the Faraday rotation of in-plane magnetized bismuth - substituted ferrite garnet films grown by liquid phase epitaxy on (100) oriented gadolinium gallium garnet substrates. The Faraday spectra were measured for photon energies between 1.7 - 2.6 eV. To interprete the spectra, we use a model based on two electric dipole transitions, one tetrahedral and one octahedral. Furthermore, the Faraday rotation sensitivity was measured at 2.3 eV, and found to be in good agreement with the theoretical predicitions. In particular, we find that the sensitivity increases linearly with the…
We investigate, using density functional theory, how the interaction between the ferroelectric polarization and the chemical structure of the (001) surfaces of bismuth ferrite influences the surface properties and reactivity of this material. A precise understanding ofthe surface behavior of ferroelectrics is necessary for their use in surface science applications such as catalysis as well as for their incorporation in microelectronic devices. Using the (001) surface of bismuth ferrite as a model system we show that the most energetically favoured surface geometries are combinations of surface…
Hexagonal ferrites (h-RFeO$_3$, R=Y, Dy-Lu) have recently been identified as a new family of multiferroic complex oxides. The coexisting spontaneous electric and magnetic polarizations make h-RFeO$_3$ rare-case ferroelectric ferromagnets at low temperature. Plus the room-temperature multiferroicity and predicted magnetoelectric effect, h-RFeO$_3$ are promising materials for multiferroic applications. Here we review the structural, ferroelectric, magnetic, and magnetoelectric properties of h-RFeO$_3$. The thin film growth is also discussed because it is critical in making high quality single cr…
Low-temperature magnetic properties of epitaxial BiFeO3 thin films grown on (111)-SrTiO3 substrates have been studied. ZFC and FC magnetization curves show a large discrepency beginning at a characteristic temperature Tf that is dependent on the magnetic-field strengh. Tf(H) varies according to the well known de Aleimda-Thouless line (varies in Hexp(2/3)) suggesting an acentric long rnage spin-glass behavior and mean field system.
Single crystalline films of bismuth-substituted ferrite garnets have been synthesized by the liquid phase epitaxy method where GGG substrates are dipped into the flux. The growth parameters are controlled to obtain films with in-plane magnetization and virtually no domain activity, which makes them excellently suited for magnetooptic imaging. The Faraday rotation spectra were measured across the visible range of wavelengths. To interprete the spectra we present a simple model based on the existence of two optical transitions of diamagnetic character, one tetrahedral and one octahedral. We find…
The method of microwave assisted hydrothermal synthesis of bismuth ferrite multiferroic nanoflowers, their mechanism of growth, magnetic as well as dielectric properties are presented. The nanoflowers are composed of numerous petals formed by BiFeO3 (BFO) nanocrystals and some amount of amorphous phase. The growth of the nanoflowers begins from the central part of calyx composed of only few petals towards which subsequent petals are successively attached. The nanoflowers exhibit enhanced magnetization due to size effect and lack of spin compensation in the spin cycloid. The dielectric properti…
This study reports on the synthesis of ball-like bismuth ferrite BiFeO3 nanoflowers by means of microwave assisted hydrothermal process and also on their composition and mechanism of growth. It turns out that the petals of the nanoflowers are composed of the nanocrystals with the size about 35-39 nm whereas their thickness and size depends on the concentration of surfactants. The petals contain BiFeO3 phase and traces of Bi2O3 oxide and metallic Bi and Fe deposited mainly at their surface. Amounts of impurity phases are more pronounced in nanoflowers synthesized during short time, and become a…
This review devoted to multiferroic properties of Bismuth-based perovskites falls into two parts. The first part focuses on BiFeO3 and summarizes the recent progress made in the studies of its pressure-temperature phase diagram and magnetoelectric coupling phenomena. The second part discusses in a more general way the issue of polar - and multiferroic - phases in BiBO3 perovskites and the competition between ferroelectricity and other structural instabilities, from an inventory of recently synthetized compounds.
A new chiral phase of ferric ions in bismuth ferrite, the only material known to support multiferroic behaviour at room temperature, is inferred from extensive sets of data gathered by resonant x-ray Bragg diffraction. Values of all ferric multipoles participating in a minimal model of Fe electronic structure are deduced from azimuthal-angle scans. Extensive sets of azimuthal-angle data, gathered by resonant x-ray Bragg diffraction, yield values of all ferric multipoles participating in a minimal model of Fe electronic structure. Paramagnetic (700 K) and magnetically ordered (300 K) phases of …
In complex oxide heteroepitaxy, strain engineering is a powerful tool to obtain phases in thin films that may be otherwise unstable in bulk. A successful example of this approach is mixed phase bismuth ferrite (BiFeO3) epitaxial thin films. The coexistence of a tetragonal-like (T-like) matrix and rhombohedral-like (R-like) striations provides an enhanced electromechanical response, along with other attractive functional behaviors. In this paper, we compare the energetics associated with two thickness dependent strain relaxation mechanisms in this system: domain walls arising from monoclinic di…
There is a profound analogy between inhomogeneous magnetoelectric effect in multiferroics and flexoelectric effect in liquid crystals. This similarity gives rise to the flexomagnetoelectric polarization induced by spin modulation. The theoretical estimations of flexomagnetoelectric polarization agree with the value of jumps of polarization in magnetoelectric dependences (~20muC/m^2) observed at spin cycloid suppression at critical magnetic field 200kOe.
Single phase barium titanate-bismuth ferrite ((1-x)BaTi$_3$-(x)BiFe$_3$, BTO-BFO) solid solutions were prepared using citric acid and ethylene glycol assisted sol-gel synthesis method. Depending on the dopant content the samples are characterized by tetragonal, tetragonal-pseudocubic, pseudocubic and rhombohedral structure as confirmed by Raman spectroscopy and XRD measurements. An increase of the BFO content leads to a reduction in the cell parameters accompanied by a decrease in polar distortion of the unit cell wherein an average particle size increases from 60 up to 350 nm. Non zero piezor…
The process of magnetic relaxation was studied in bismuth ferrite BiFeO3 multiferroic micro-cubes obtained by means of microwave assisted Pechini process. Two different mechanisms of relaxation were found. The first one is a rapid magnetic relaxation driven by the domain reorientations and/or pinning and motion of domain walls. This mechanism is also responsible for the irreversible properties at low temperatures. The power-law decay of the magnetic moment confirms that this relaxation takes place in the system of weakly interacting ferromagnetic or superferromagnetic domains. The second mecha…
We show that epitaxial (001) thin films of multiferroic bismuth ferrite BiFeO3 are monoclinic at room temperature instead of tetragonal or Rhombohedral as reported earlier . We report a orthorhombic order-disorder beta-phase between 820C and 950C contrary to the earlier report. The transition sequence monoclinic-orthorhombic phase in (001)BiFeO3 thin film (rhombohedral-orthorhombic transition in single crystal) resembles that of BaTiO3 or PbSc1/2Ta1/2O3. The transition to the cubic $γ$-phase causes an abrupt collapse of the bandgap toward zero (insulator-metal transition) at the orthorhombic-c…
The dependencies on strain and oxygen vacancies of the ferroelectric polarization and the weak ferromagnetic magnetization in the multiferroic material bismuth ferrite, BiFeO_3, are investigated using first principles density functional theory calculations. The electric polarization is found to be rather independent of strain, in striking contrast to most conventional perovskite ferroelectrics. It is also not significantly affected by oxygen vacancies, or by the combined presence of strain and oxygen vacancies. The magnetization is also unaffected by strain, however the incorporation of oxygen…
Bismuth ferrite (BiFeO3) is one of the most promising multiferroics with a sufficiently high ferroelectric (FE) and antiferromagnetic transition temperatures, and magnetoelectric (ME) coupling coefficient at room temperature, and thus it is highly sensitive to the impact of cross-influence of applied electric and magnetic fields. According to the urgent demands of nanotechnology miniaturization for ultra-high density data storage in advanced nonvolatile memory cells, it is very important to reduce the sizes of multiferroic nanoparticles in the self-assembled arrays without serious deterioratio…
University of Duisburg-Essen（杜伊斯堡-埃森大学）；European Organization for Nuclear Research (CERN)（欧洲核子研究组织（CERN））；Universidade de Aveiro（阿威罗大学）；Institute for Research in Fundamental Sciences (IPM)（基础科学研究所（IPM））
We report visible light detection with in-plane BiFeO3 (BFO) thin films grown on pre-patterned inter-digital electrodes. In-plane configured BFO film displayed photocurrents with a 40:1 photo-to-dark-current ratio and improved photo-sensing ability for >15000 s (4 hrs) under small bias voltage (42V). Nearly sixty percent of the photo-induced charge carriers decay in 1.0 s and follow a double-exponential decay model. At 373 K the effect of light does not significantly increase the dark current, probably due to reduced mobility. Sub-bandgap weak monochromatic light (1 mw/cm2) shows one fold incr…
We studied the ultrafast third-order optical nonlinearity in a single crystal of multiferroic bismuth ferrite (BiFeO3) in the near-infrared range of 0.5-1.0 eV, where the material is fundamentally transparent,at room temperature. With pump pulses at 1.55 eV, which is off-resonant to the strong inter-band charge transfer (CT) transition, we observed instantaneous transient absorption with pencil-like temporal profile originating from the two-photon CT transition from the oxygen 2p to the iron 3p levels. In contrast, under pumping with 3.10-eV photons, the pencil-like absorption change was not o…
We have used first-principles methods to investigate the phase diagram of multiferroic bismuth ferrite (BiFeO3 or BFO), revealing the energetic and vibrational features that control the occurrence of various relevant structures. More precisely, we have studied the relative stability of four low-energy BFO polymorphs by computing their free energies within the quasi-harmonic approximation, introducing a practical scheme that allows us to account for the main effects of spin disorder. As expected, we find that the ferroelectric ground state of the material (with R3c space group) transforms into …
We analyze the coupling between the ferroelectric and magnetic order parameters in the magnetoelectric multiferroic BiFeO_3 using density functional theory within the local spin density approximation and the LSDA+U method. We show that weak ferromagnetism of the Dzyaloshinskii-Moriya type occurs in this material, and we analyze the coupling between the resulting magnetization and the structural distortions. We explore the possibility of electric-field-induced magnetization reversal and show that, although it is unlikely to be realized in BiFeO_3, it is not in general impossible. Finally we out…
Magnetoelectric Coupling in Nickel-Cobalt Ferrite and Lanthanum Ferrite Heterostructure Composites: Experimental Evidence and Simulation-Driven Insights
In this study we have compared magnetic, magnetostrictive and piezomagnetic properties of isotropic and anisotropic cobalt ferrite pellets. The isotropic sample was prepared by the ceramic method while the sample exhibiting uniaxial anisotropy was made by reactive sintering using Spark Plasma Sintering (SPS). This technique permits to induce a magnetic anisotropy in cobalt ferrite in the direction of the applied pressure during SPS process. Sample with uniaxial anisotropy revealed a higher longitudinal magnetostriction and piezomagnetism compared to the isotropic sample, but the transversal ma…
We present a first-principles density functional study of the structural, electronic and magnetic properties of the ferroelectric domain walls in multiferroic BiFeO3. We find that domain walls in which the rotations of the oxygen octahedra do not change their phase when the polarization reorients are the most favorable, and of these the 109 degree domain wall centered around the BiO plane has the lowest energy. The 109 degree and 180 degree walls have a significant change in the component of their polarization perpendicular to the wall; the corresponding step in the electrostatic potential is …
We have carried out the powder x-ray diffraction and dielectric studies on multiferroic particulate composite xNi0.9Zn0.1Fe2O4/(1-x)PbZr0.52Ti0.48O3 with x=0.15, 0.30, 0.45, 0.60, 0.75 and 0.90 to explore the structural and ferroelectric properties. A conventional double sintering method was used to prepare the xNi0.9Zn0.1Fe2O4/(1-x)PbZr0.52Ti0.48O3 composites. The structure of one of the component Ni0.9Zn0.1Fe2O4 is spinel cubic with space group Fd3m, while the other component PbZr0.52Ti0.48O3 is selected around the morphotropic phase boundary region in which the tetragonal and monoclinic pha…
There have been a large number of papers on bismuth ferrite (BiFeO3) over the past few years, trying to exploit its room-temperature magnetoelectric multiferroic properties. Although these are attractive, BiFeO3 is not the ideal multiferroic, due to weak magnetization and the difficulty in limiting leakage currents. Thus there is an ongoing search for alternatives, including such materials as gallium ferrite (GaFeO3). In the present work we report a comprehensive study of the perovskite PbTi1-xPdxO3 with 0 < x < 0.3. Our study includes dielectric, impedance and magnetization measurements, cond…
Bismuth ferrite is one of the most widely studied multiferroic materials because of its large ferroelectric polarisation coexisting with magnetic order at room temperature. Using density functional theory (DFT), we identify several previously unknown polar and non-polar structures within the low-energy phase space of perovskite-structure bismuth ferrite, BiFeO$_3$. Of particular interest is a series of non-centrosymmetric structures with polarisation along one lattice vector, combined with anti-polar distortions, reminiscent of ferroelectric domains, along a perpendicular direction. We discuss…
Implementation of antiferromagnetic compounds as active elements in spintronics has been hindered by their insensitive nature against external perturbations which causes difficulties in switching among different antiferromagnetic spin configurations. Electrically-controllable strain gradient can become a key parameter to tune the antiferromagnetic states of multiferroic materials. We have discovered a correlation between an electrically-written straight-stripe mixed-phase boundary and an in-plane antiferromagnetic spin axis in highly-elongated La-5%-doped BiFeO$_{3}$ thin films by performing p…
We report the nanoscale electrical imaging results in hexagonal $Lu_{0.6}Sc_{0.4}FeO_3$ single crystals using conductive atomic force microscopy (C-AFM) and scanning microwave impedance microscopy (MIM). While the dc and ac response of the ferroelectric domains can be explained by the surface band bending, the drastic enhancement of domain wall (DW) ac conductivity is clearly dominated by the dielectric loss due to DW vibration rather than mobile-carrier conduction. Our work provides a unified physical picture to describe the local conductivity of ferroelectric domains and domain walls, which …
The possibility of multiferroicity arising from charge ordering in LuFe2O4 and structurally related rare earth ferrites is reviewed. Recent experimental work on macroscopic indications of ferroelectricity and microscopic determination of coupled spin and charge order indicates that this scenario does not hold. Understanding the origin of the experimentally observed charge and spin order will require further theoretical work. Other aspects of recent research in these materials, such as geometrical frustration effects, possible electric-field-induced transitions, or orbital order are also briefl…
Magnetic phase transitions in multiferroic bismuth ferrite (BiFeO3) induced by magnetic field, epitaxial strain, and composition modification are considered. These transitions from a spatially modulated spin spiral state to a homogenous antiferromagnetic one are accompanied by the release of latent magnetization and a linear magnetoelectric effect that makes BiFeO3-based materials efficient room-temperature single phase multiferroics.
Several Niobium oxides of formula Ba2LnFeNb4O15 (Ln = La, Pr, Nd, Sm, Eu, Gd) with the Tetragonal Tungsten Bronze (TTB) structure have been synthesised by conventional solid-state methods. The Neodymium, Samarium and Europium compounds are ferroelectric with Curie temperature ranging from 320 to 440K. The Praseodymium and Gadolinium compounds behave as relaxors below 170 and 300 K respectively. The Praseodymium, Neodymium, Samarium, Europium and Gadolinium compounds exhibit magnetic hysteresis loops at room temperature originating from traces of a barium ferrite secondary phase. The presence o…
In this article, we perform the symmetry analysis of perovskite-based multiferroics: bismuth ferrite (BiFeO3)-like, orthochromites (RCrO3), and Ruddlesden-Popper perovskites (Ca3Mn2O7-like), being the typical representatives of multiferroics of the trigonal, rhombic, and tetragonal crystal families and explore the effect of crystallographic distortions on magnetoelectric properties. We determine the principal order parameters for each of the considered structures and obtain their invariant combinations consistent with the particular symmetry. This approach allowed us to analyze the features of…
We report on low-energy electron microscopy imaging of ferroelectric domains with submicron resolution. Periodic strips of 'up' and 'down'-polarized ferroelectric domains in bismuth ferrite -a room temperature multiferroic- serve as a model system to compare low-energy electron microscopy with the established piezoresponse force microscopy. The results confirm the possibility of full-field imaging of ferroelectric domains with short acquisition times by exploiting the sensitivity of ultraslow electrons to small variations of the electric potential near surfaces in the "mirror" operation mode.
Most multiferroic materials with coexisting ferroelectric and magnetic order exhibit cycloidal antiferromagnetism with wavelength of several nanometers. The prototypical example is bismuth ferrite (BiFeO$_3$ or BFO), a room-temperature multiferroic considered for a number of technological applications. While most applications require small sizes such as nanoparticles, little is known about the state of these materials when their sizes are comparable to the cycloid wavelength. This work describes a microscopic theory of cycloidal magnetism in nanoparticles based on Hamiltonian calculations. It …
Bismuth ferrite, BiFeO3, is the only known room-temperature 'multiferroic' material. We demonstrate here, using neutron scattering measurements in high quality single crystals, that the antiferromagnetic and ferroelectric orders are intimately coupled. Initially in a single ferroelectric state, our crystals have a canted antiferromagnetic structure describing a unique cycloid. Under electrical poling, polarisation re-orientation induces a spin flop. We argue here that the coupling between the two orders may be stronger in the bulk than that observed in thin films where the cycloid is absent.
We present results of an {\it ab initio} density functional theory study of three bismuth-based multiferroics, BiFeO$_{3}$, Bi$_{2}$FeCrO$_{6}$, and BiCrO$_{3}$. We disuss differences in the crystal and electronic structure of the three systems, and we show that the application of the LDA+$U$ method is essential to obtain realistic structural parameters for Bi$_{2}$FeCrO$_{6}$. We calculate the magnetic nearest neighbor coupling constants for all three systems and show how Anderson's theory of superexchange can be applied to explain the signs and relative magnitudes of these coupling constants…
Remarkably high values of polarization as well as a significant magnetic susceptibility have been observed in multiferroic Bismuth Ferrite (BFO) in the form of nanorods protruding out. These were developed on porous Anodised Alumina (AAO) templates using wet chemical technique. Diameters of nanorods are in the range of 20-100 nm. The high values of polarization and magnetic susceptibility are attributed to the BFO nanorod structures giving rise to the directionality. There is no leakage current in P-E loop examined at various frequencies. Magnetocapacitance measurements reflect a significant e…
We propose a device model that elucidates the role of domain walls in the photovoltaic effect in multi-domain ferroelectric perovskites. The model accounts for the intricate interplay between ferroelectric polarization, space charges, photo-generation and electronic transport. When applied to bismuth ferrite, results show a significant electric potential step across both 71-degree and 109-degree domain walls, which in turn contributes to the photovoltaic (PV) effect. We also find a strong correlation between polarization and oxygen octahedra tilts, which indicates the nontrivial role of the la…
Epitaxial thin film fabrication of iron oxides including magnetite Fe3O4 and epsilon-ferrite epsilon-Fe2O3 with the potential for advancing electromagnetic devices has been investigated, which led to the first ever epsilon-ferrite epitaxial layer being synthesized in the conventional sputtering process. Concerning Fe3O4 (100) / MgO (100) films, a cube-on-cube epitaxial relationship and sharp rocking curves with FWHM of 50 - 350 arcsec were confirmed regardless of the small amount of Ge additions. Sputtering Ar gas pressure PAr heavily influenced their magnetic and transport properties. High PA…
The question of how ferroelectric polarization is coupled to magnetism in magnetoelectric multiferroics, in which both types of order are simultaneously present, is of considerable scientific and practical interest. A recent Letter \cite{fennie} presents an analysis of the important ``ABO$_3$'' class of perovskite multiferroics. This Letter argues that antiferromagnetic multiferroics with magnetic ions on the B site, such as the well-studied room-temperature multiferroic bismuth ferrite (A=Bi, B=Fe), cannot show linear magnetoelectric coupling of the form ${\bf P} \cdot ({\bf L} \times {\bf M}…
Hybridization of semiconducting and magnetic materials into a single heterostructure is believed to be potentially applicable to the design of novel functional spintronic devices. In the present work we report epitaxial stabilization of four magnetically ordered iron oxide phases (Fe3O4, γ-Fe2O3, α-Fe2O3 and most exotic metastable ε-Fe2O3) in the form of nanometer sized single crystalline films on GaN(0001) surface. The epitaxial growth of as many as four distinctly different iron oxide phases is demonstrated within the same single-target Laser MBE technological process on a GaN semiconductor …
While piezoelectrics and ferroelectrics are playing a key role in many everyday applications, there are still a number of open questions related to the physics of those materials. In order to foster the understanding of piezoelectrics and ferroelectric and pave the way to future applications, the nanoscale characterization of these materials is essential. In this light, we have developed a novel AFM based mode that obtains a direct quantitative analysis of the piezoelectric coefficient d33. This nanoscale tool is capable of detecting and reveal piezo-charge generation through the direct piezoe…
First-principles calculations were performed to investigate the ferroelectric properties of barium titanate and bismuth ferrite, as well as phonon dispersion of BaTiO3, using density functional theory and density functional perturbation theory. Results show that the strong hybridization of Ti-O and Bi-O lead to the corresponding mechanisms for stabilizing the distorted structure. The spontaneous polarization of 59.4 μC/cm2 and 27.6 μC/cm2 were calculated for BiFeO3 and BaTiO3 respectively, using berry phase method within the modern theory of polarization. The stereochemical activity of Bi-6s l…
