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-cubic beta-gamma transition around 950C. This transition is similar to the metal-insulator transition in Ba0.6K0.4BiO3.
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…
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.
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 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.
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…
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…
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…
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…
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…
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 …
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 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 …
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…
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 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…
Sol-gel deposited (010) textured polycrystalline thin films of gallium ferrite (GaFeO3 or GFO) on n-Si(100) and Pt/Si(111) substrates are characterized for room temperature multiferroism. Structural characterization using X-ray diffraction and Raman spectroscopy confirms formation of single phase with nano-sized crystallites. Temperature dependent magnetization study demonstrates ferri to paramagnetic transition at ~300 K. Room temperature piezoresponse force microscopic analysis reveals local 180 degree phase switching of ferroelectric domains at very high coercive field EC, ~ 1350 kV/cm cons…
Multiferroics in which giant ferroelectric polarization and magnetism coexist are of tremendous potential for engineering disruptive applications in information storage and energy conversion. Yet the functional properties of multiferroics are thought to be affected detrimentally by the presence of point defects, which may be abundant due to the volatile nature of some constituent atoms and high temperatures involved in materials preparation. Here, we demonstrate with theoretical methods that oxygen vacancies may enhance the functionality of multiferroics by radically changing their magnetic in…
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.
In this paper, the photocatalytic activity of multiferroics BiFeO3 (BFO) and Bi0.8La0.2FeO3 (BLFO) nanocrystals with two different morphologies which were synthesized by two different sol-gel (SG) and hydrothermal (HT) methods have been studied. All the obtained samples were characterized using X-ray diffractometer, Fourier transform infrared spectroscopy, transmission electron microscopy, UV-vis spectroscopy and vibrating sample magnetometer. Differential thermal analysis (DTA) measurements were probed ferroelectric- paraelectric first-order phase transition (TC) for all samples. Addition of …
Using the theory of symmetry and the microscopic model we predicted the possibility of a linear roto-antiferromagnetic effect in the perovskites with structural antiferrodistortive and antiferromagnetic long-range ordering and found the necessary conditions of its occurrence. The main physical manifestations of this effect are the smearing of the antiferromagnetic transition and the jump of the specific heat near it. In the absence of external fields linear roto-antiferromagnetic coupling can induce a weak antiferromagnetic ordering above the Neel temperature, but below the temperature of anti…
We present a microscopic theory that shows the importance of spin-orbit coupling in perovskite compounds with heavy ions. In BiFeO3 (BFO) the spin-orbit coupling at the bismuth ion sites results in a special kind of magnetic anisotropy that is linear in the applied E-field. This interaction can convert the cycloid ground state into a homogeneous antiferromagnet, with a weak ferromagnetic moment whose orientation can be controlled by the E-field direction. Remarkably, the E-field control of magnetism occurs without poling the ferroelectric moment, providing a pathway for reduced energy dissipat…
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…
We report X-ray structural studies of the metal-insulator phase transition in bismuth ferrite, BiFeO3, both as a function of temperature and of pressure (931 oC at atmospheric pressure and ca. 45 GPa at ambient temperature). Based on the experimental results, we argue that the metallic gamma-phase is not rhombohedral but is instead the same cubic Pm3m structure whether obtained via high temperature or high pressure, that the MI transition is second order or very nearly so, that this is a band-type transition due to semi-metal band overlap in the cubic phase and not a Mott transition, and that …
Multiferroic bismuth ferrite (BiFeO3) thin films were prepared by pulsed laser deposition (PLD) technique. Electronic structures of the film have been studied by in situ photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). Both the Fe 2p PES and XAS spectra show that Fe ion is formally in +3 valence state. The Fe 2p and O K edge XAS spectra indicate that the oxygen octahedral crystal ligand field splits the unoccupied Fe 3d state to t2g and eg states. Valence band Fe 2p-3d resonant photoemission results indicate that hybridization between Fe 3d and O 2p plays important rol…
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 combine a wide variety of experimental techniques to analyze two heretofore mysterious phase transitions in multiferroic bismuth ferrite at low temperature. Raman spectroscopy, resonant ultrasound spectroscopy, EPR, X-ray lattice constant measurements, conductivity and dielectric response, specific heat and pyroelectric data have been collected for two different types of samples: single crystals and, in order to maximize surface/volume ratio to enhance surface phase transition effects, BiFeO3 nanotubes were also studied. The transition at T=140.3K is shown to be a surface phase transition, …
Bismuth ferrite (BiFeO$_3$) is one of the very few known single-phase multiferroic materials. While the bulk compound is rhombohedral (R), the discovery of an epitaxial strain-induced structural transition into a so-called 'super tetragonal-phase' (T-phase) in this material incited a flurry of research activity focused on gaining an understanding of this phase transition and its possible functionalities. This metastable phase of BiFeO$_3$ is also multiferroic, with giant ferroelectric polarization and coexisting antiferromagnetic order, but above all it is the strain relaxation-induced phase m…
We demonstrate room temperature ferroelectricity in the epitaxial thin films of magnetoelectric GaFeO3. Piezo-force measurements show a 180o phase shift of piezoresponse upon switching the electric field indicating nanoscale ferroelectricity in epitaxial thin films of gallium ferrite. Further, temperature dependent impedance analysis with and without the presence of an external magnetic field clearly reveals a pronounced magneto-dielectric effect across the magnetic transition temperature. In addition, our first principles calculations show that Fe ions are not only responsible for ferrimagnet…
We calculate the effect of epitaxial strain on the structure and properties of multiferroic bismuth ferrite, BiFeO3, using first-principles density functional theory. We find that, while small strains cause only quantitative changes in behavior from the bulk material, compressive strains of greater than 4% induce an isosymmetric phase transition accompanied by a dramatic change in structure. In striking contrast to the bulk rhombohedral perovskite, the highly strained structure has a c/a ratio of ~1.3 and five-coordinated Fe atoms. We predict a rotation of polarization from [111] (bulk) to nea…
Spatially modulated morphotropic phase boundaries in a compressively strained multiferroic thin film
University of Southern California（南加州大学）；University of Michigan, Dearborn（密歇根大学迪尔伯恩分校）；University of California, Berkeley（加州大学伯克利分校）；Cornell University（康奈尔大学）
In bismuth ferrite thin films the cycloidal spiral spin structure is suppressed, and as a result the spin-wave magnon branches of long wavelength are reduced from a dozen to one, at ω= 19.2 cm-1 (T=4K). This spin wave has not been measured previously above room temperature, but in the present work we show via Raman spectroscopy that it is an underdamped propagating wave until 455 K. This has important room-temperature device implications. The data show that ω(T) follows an S=5/2 Brillouin function and hence its Fe+3 ions are in the high-spin 5/2 state and not the low-spin S=1/2 state. The spin…
Helium implantation in epitaxial thin films is a way to control the out-of-plane deformation independently from the in-plane strain controlled by epitaxy. In particular, implantation by means of a helium microscope allows for local implantation and patterning down to the nanometer resolution, which is of interest for device applications. We present here a study of bismuth ferrite (BiFeO3) films where strain was patterned locally by helium implantation. Our combined Raman, XRD and TEM study shows that the implantation causes an elongation of the BiFeO3 unit cell and ultimately a transition towa…
We report a Raman scattering investigation of multiferroic bismuth ferrite BiFeO3 epitaxial (c-axis oriented) thin films from -192 to 1000C. Phonon anomalies have been observed in three temperature regions: in the gamma-phase from 930C to 950C; at ~370C, Neel temperature (TN), and at ~123C, due to a phase transition of unknown type (magnetic or structural). An attempt has been made to understand the origin of the weak phonon-magnon coupling and the dynamics of the phase sequence. The disappearance of several Raman modes at ~820C (Tc) is compatible with the known structural phase transition and…
Polycrystalline La and Ti co-substituted ceramics were synthesized by the tartaric acid modified sol-gel technique. It was observed that the co-substitution of La & Ti at Bi & Fe sites in BiFeO3 suppress the impurity phase formation which is a common problem in bismuth ferrite. The quantitative crystallographic phase analysis was performed with the help of FULLPROF program which suggests the existence of compositional driven crystal structure transition from rhombohederal (space group R3c) to the orthorhombic (space group Pbnm). The changes in the phonon frequencies as well as line widths of A…
Composition-driven structural transitions in Bi1-xCaxFe1-xMnxO3 ceramics prepared by the tartaric acid modified sol-gel technique have been studied to analyze its effect on the magnetic properties of bismuth ferrite (BiFeO3). It was observed that the co-substitution of Ca & Mn at Bi & Fe sites in BiFeO3 (BFO) significantly suppress the impurity phases. The quantitative crystallographic phase analysis has been carried out by double phase Rietveld analysis of all the XRD patterns which indicates the existence of compositional driven crystal structure transformation from rhombohederal (R3c space …
