BiFeO$_3$ thin films can be epitaxially stabilized in a nearly-tetragonal phase under a high biaxial compressive strain. Here we investigate the polarized Raman spectra of constrained BiFeO$_3$ films with tetragonal-like (BFO-T), rhombohedral-like (BFO-R) and multiphase (BFO-T+R) structure. Based on analysis of the number and symmetry of the Raman lines, we provide strong experimental evidence that the nearly-tetragonal films are monoclinic ($Cc$ symmetry) and not tetragonal $(P4mm)$. Through the Raman mapping technique we show localized coexistence of BFO-T and BFO-R phases with the relative fraction dependent on the film thickness.
Highly-strained BiFeO3 exhibits a "tetragonal-like, monoclinic" crystal structure found only in epitaxial films (with an out-of-plane lattice parameter exceeding the in-plane value by >20%). Previous work has shown that this phase is properly described as a M$_{C}$ monoclinic structure at room temperature [with a (010)$_{pc}$ symmetry plane, which contains the ferroelectric polarization]. Here we show detailed temperature-dependent x-ray diffraction data that evidence a structural phase transition at ~100C to a high-temperature M$_{A}$ phase ["tetragonal-like" but with a (1-10)$_{pc}$ symmetry…
Synchrotron and lab-scale x-ray diffraction shows that tetragonal-like T'-BiFeO3 films on miscut LaAlO3 substrates (miscut < 5 deg) exhibit (00l)-planes tilted away from those of the substrate as predicted by the "Nagai model" (except for miscut <0.2 deg). Tilts as large as 1 deg are achieved even in 100 nm thick films, strikingly larger than those observed in other perovskites. We attribute this to the large c/a ratio and the high crystalline coherency of the T'-BiFeO3/LaAlO3 interface. This coherency is possible through an observed "diagonal-on-diagonal" alignment. Interestingly, the substra…
We have investigated the nanoscale switching properties of strain-engineered BiFeO3 thin films deposited on LaAlO3 substrates using a combination of scanning probe techniques. Polarized Raman spectral analysis indicate that the nearly-tetragonal films have monoclinic (Cc) rather than P4mm tetragonal symmetry. Through local switching-spectroscopy measurements and piezoresponse force microscopy we provide clear evidence of ferroelectric switching of the tetragonal phase but the polarization direction, and therefore its switching, deviates strongly from the expected (001) tetragonal axis. We also…
The anisotropic optical properties of multiferroic BiFeO$_3$ thin films have been determined with Mueller matrix ellipsometry at room-temperature. The full dielectric tensors of tetragonal-like and rhombohedral-like BiFeO$_3$ phases epitaxially grown on LaAlO$_3$ and SrTiO$_3$ single crystal substrates, respectively, within the spectral range of 0.6 and 6.5 eV are reported. Strain-driven anisotropy changes and transition shifts are observed as well as evidence of sub-band gap many-particle excitations are found. The transition shifts, mostly to higher energies for the highly strained tetragona…
Transmission electron microscopy study of tetragonal-like BiFeO3 films reveals a hitherto unreported hierarchical nanodomain structure. The 30-50 nm wide stripe domains with {110} domain walls consist of a substructure of lamellar nanodomains of 8-10 nm width in a herringbone-like arrangement. In situ heating and cooling reveals a reversible transition from the hierarchical nanodomain structure to a tweed-like domain structure which is accompanied by a first-order phase transition near 120 °C with a thermal hysteresis.
Defect engineering has been a powerful tool to enable the creation of exotic phases and the discovery of intriguing phenomena in ferroelectric oxides. However, accurate control the concentration of defects remains a big challenge. In this work, ion implantation, that can provide controllable point defects, allows us the ability to produce a controlled defect-driven true super-tetragonal (T) phase with enhanced tetragonality in ferroelectric BiFeO3 thin films. This point defect engineering is found to drive the phase transition from the as-grown mixed rhombohedral-like (R) and tetragonal-like (…
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 measure the remnant polarization of ferroelectric domains in BiFeO3 films down to 3.6 nm using low energy electron and photoelectron emission microscopy. The measured polarization decays strongly below a critical thickness of 5-7 nm predicted by continuous medium theory whereas the tetragonal distortion does not change. We resolve this apparent contradiction using first-principles-based effective Hamiltonian calculations. In ultra thin films the energetics of near open circuit electrical boundary conditions, i.e. unscreened depolarizing field, drive the system through a phase transition fro…
$\text{BiFeO}_\text{3}$ has drawn a great attention over last several decades due to its promising multiferroic character. In the ground state the bulk $\text{BiFeO}_\text{3}$ is found to be in the rhombohedral phase. However, it has been possible to stabilize $\text{BiFeO}_\text{3}$ with tetragonal structure. The importance of tetragonal phase is due to its much larger value of the electric polarization and the possible stabilization of ferromagnetism as in the rhombohedral phase. Furthermore, the tetragonal structure of $\text{BiFeO}_\text{3}$ has been reported with different $c/a$ ratio, op…
Epitaxial BiFeO3/SrRuO3 superlattices have been grown by pulsed laser deposition on a (001) oriented LaAlO3 substrate and probed by X-ray diffraction and Raman spectroscopy. To investigate the structural competition between rhombohedral BiFeO3 and orthorhombic SrRuO3 the total thickness of all SLs was kept constant and the bilayer thickness (period) Λ was varied. The interlayer strain effects are therefore tuned from large strain effects (short Λ period) to quasi-relaxed structure (large Λ). A complementary investigation using X-ray diffraction and phonon dynamics hints to change from a rhombo…
We report a Raman scattering investigation of columnar BiFeO3-CoFe2O4 (BFO-CFO) epitaxial thin film nanostructures, where BFO pillars are embedded in a CFO matrix. The feasibility of a strain analysis is illustrated through an investigation of two nanostructures with different BFO-CFO ratios. We show that the CFO matrix presents the same strain state in both nanostructures, while the strain state of the BFO pillars depends on the BFO/CFO ratio with an increasing tensile strain along the out-of-plane direction with decreasing BFO content. Our results demonstrate that Raman scattering allows mon…
In bismuth ferrite (BiFeO3), antiferromagnetic and ferroelectric order coexist at room temperature, making it of particular interest for studying magnetoelectric coupling. The mutual control of magnetic and electric properties is very useful for a wide variety of applications. This has led to an enormous amount of research into the properties of BiFeO$_3$. Nonetheless, one of the most fundamental aspects of this material, namely the symmetries of the lattice vibrations, remains controversial.We present a comprehensive Raman study of BiFeO$_3$ single crystals with the approach of monitoring the…
Magnetic ordering, as one of the most important characteristics in magnetic materials, could have significant influence on the band structure, spin dependent transport, and other important properties of materials. Its measurement, especially for the case of antiferromagnetic ordering, however, is generally difficult to be achieved. Here we demonstrate the feasibility of magnetic ordering detection using a noncontact and nondestructive optical method. Taking the compressive strained tetragonal BiFeO3 (BFO) as an example and combining density functional theory calculations with the minimal one-b…
BiFeO3 thin films with various thicknesses were grown epitaxially on (001) LaSrAlO4 single crystal substrates using pulsed laser deposition. High resolution x-ray diffraction measurements revealed that a tetragonal-like phase with c-lattice constant ~4.65 Å is stabilized by a large misfit strain. Besides, a rhombohedral-like phase with c-lattice constant ~3.99 Å was also detected at film thickness of ~50 nm and above to relieve large misfit strains. In-plane piezoelectric force microscopy studies showed clear signals and self-assembled nanoscale stripe domain structure for the tetragonal-like …
Interplay between magnetic and lattice excitations in BiFeO$_3$
我们对BiFeO $_3$单晶中的高能磁激发进行了拉曼散射研究，研究了温度和激光激发能的函数关系。在拉曼光谱中在1250 cm $^{-1}$处观察到的强特征先前已被分配给两个声子泛音。我们在这里表明，它的不寻常的频率偏移与激发能和它的非对称温度依赖的Fano线型揭示了一个强耦合的磁激发。在相同的能量范围内，我们还确定了两个磁振子激发的温度依赖性非常相似的$α$ -Fe $_2$ O $_3$赤铁矿。
(BiFeO3)(1-x)Λ/(LaFeO3)xΛ superlattices (SLs) with varying x have been grown by pulsed laser deposition on (111) oriented SrTiO3 substrates. In order to obtain good epitaxy and flat samples a conducting SrRuO3 buffer has been deposited prior to the superlattices to screen the polar mismatch for such (111) SrTiO3 orientation. X-ray diffraction reciprocal space mapping on different family of planes were collected and evidenced a room temperature structural change at x=0.5 from a rhombohedral/monoclinic structure for rich BiFeO3 to an orthorhombic symmetry for rich LaFeO3. This symmetry change ha…
The nanostructural evolution of the strain-induced structural phase transition in BiFeO3 is examined. Using high-resolution X-ray diffraction and scanning-probe microscopy-based studies we have uniquely identified and examined the numerous phases present at these phase boundaries and have discovered an intermediate monoclinic phase in addition to the previously observed rhombohedral- and tetragonal-like phases. Further analysis has determined that the so-called mixed-phase regions of these films are not mixtures of rhombohedral- and tetragonal-like phases, but intimate mixtures of highly-disto…
A highly strained BiFeO3 (BFO) thin film is transformed between phases with distinct structures and properties by nanosecond-duration applied electric field pulses. Time-resolved synchrotron x-ray microdiffraction shows that the steady-state transformation between phases is accompanied by a dynamical component that is reversed upon the removal of the field. Steady-state measurements reveal that approximately 20% of the volume of a BFO thin film grown on a LaAlO3 substrate can be reproducibly transformed between rhombohedral-like and tetragonal-like phases by electric field pulses with magnitud…
A morphotropic phase boundary driven by epitaxial strain has been observed in a lead-free multiferroic BiFeO3 thin films and the strain-driven phase transitions were widely reported to be iso-symmetric Cc-Cc ones by recent works. In this paper, we suggest that the tetragonal-like BiFeO3 phase identified in epitaxial films on (001) LaAlO3 single crystal substrates is monoclinic MC. This MC phase is different from MA type monoclinic phase reported in BiFeO3 films grown on low mismatch substrates, such as SrTiO3. This is confirmed not only by synchrotron x-ray studies but also by piezoresponse fo…
We report electrically switchable polarization and ferroelectric domain scaling over a thickness range of 5-100 nm in BiFeO3 films deposited on [110] vicinal substrates. The BiFeO3 films of variable thickness were deposited with SrRuO3 bottom layer using pulsed laser deposition technique. These films have fractal domain patterns and the domain width scales closely with the square root of film thickness, in accordance with the Landau-Lifschitz-Kittel (LLK) law. The Switching Spectroscopy Piezo-response Force Microscopy provides clear evidence for the ferroelectric switching behavior in all the …
Piezoelectrics interconvert mechanical energy and electric charge and are widely used in actuators and sensors. The best performing materials are ferroelectrics at a morphotropic phase boundary (MPB), where several phases can intimately coexist. Switching between these phases by electric field produces a large electromechanical response. In the ferroelectric BiFeO$_3$, strain can be used to create an MPB-like phase mixture and thus to generate large electric field dependent strains. However, this enhanced response occurs at localized, randomly positioned regions of the film, which potentially …
We report a study on the thermodynamic stability and structure analysis of the epitaxial BiFeO3 (BFO) thin films grown on YAlO3 (YAO) substrate. First we observe a phase transition of MC-MA-T occurs in thin sample (<60 nm) with an utter tetragonal-like phase (denoted as MII here) with a large c/a ratio (~1.23). Specifically, MII phase transition process refers to the structural evolution from a monoclinic MC structure at room temperature to a monoclinic MA at higher temperature (150oC) and eventually to a presence of nearly tetragonal structure above 275oC. This phase transition is further con…
Recent studies have reported the existence of an epitaxially-stabilized tetragonal-like ('T-like') monoclinic phase in BiFeO3 thin-films with high levels of compressive strain. While their structural and ferroelectric properties are different than those of rhombohedral-like ('R-like') films with lower levels of strain, little information exists on magnetic properties. Here, we report a detailed neutron scattering study of a nearly phase-pure film of T-like BiFeO3. By tracking the temperature dependence and relative intensity of several superstructure peaks in the reciprocal lattice cell, we co…
We present the temperature- and thickness-dependent structural and morphological evolution of strain induced transformations in highly-strained epitaxial BiFeO3 films deposited on LaAlO3 (001) substrates. Using high-resolution X-ray diffraction and temperature-dependent scanning-probe-based studies we observe a complex temperature- and thickness-dependent evolution of phases in this system. A thickness-dependent transformation from a single monoclinically distorted tetragonal-like phase to a complex mixed-phase structure in films with thicknesses up to ~200 nm is the consequence of a strain-in…
BiFeO3 (BFO) multiferroic oxide has a complex phase diagram that can be mapped by appropriately substrate-induced strain in epitaxial films. By using Raman spectroscopy, we conclusively show that films of the so-called supertetragonal T-BFO phase, stabilized under compressive strain, displays a reversible temperature-induced phase transition at about 100\circ, thus close to room temperature.
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…
Ferroelectric-based photovoltaics have shown great promise as a source of renewable energy, thanks to their in-built charge separation capability, yet their efficiency is often limited by low charge carrier mobilities. In this work, we compare the photovoltaic prospects of various phases of the multiferroic material BiFeO$_3$ by evaluating their charge carrier effective masses using first-principles simulations. We identify a tetragonal phase with the promising combination of a large spontaneous polarisation and relatively light charge carriers. From a systematic study of the octahedral distor…
The crystal structure of BiFeO3/BaxSr1-xTiO3 (BFO/BST) heterostructures with x = 0.2, 0.6 and 0.8, grown on single-crystal MgO (001) substrate was investigated by x-ray diffraction and Raman spectroscopy in order to determine the influence of mismatch-induced strains and spontaneous polarization in BST buffer layers on BFO layers. The lattice parameter of the BFO layers was shown to decrease with increasing concentration of Ba ions, despite the increasing in-plain lattice parameters of tetragonal unit cells of BST layers. The rhombohedral angle of the crystal structure of BFO layers demonstrat…
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 synchrotron grazing incidence x-ray diffraction analysis of the domain structure and polar symmetry of highly strained BiFeO3 thin films grown on LaAlO3 substrate. We revealed the existence of periodic elastic nanodomains in the pure tetragonal-like BFO ultrathin films down to a thickness of 6 nm. A unique shear strain accommodation mechanism is disclosed. We further demonstrated that the periodicity of the nanodomains increases with film thickness but deviates from the classical Kittel's square root law in ultrathin thickness regime (6 - 30 nm). Temperature-dependent experiments …
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…
Despite the technological significance of the tetragonal PbTiO3 for the piezoelectric transducer industry, its high pressure behaviour is quite controversial as two entirely different scenarios, involving pressure induced (1) morphotropic phase boundary (MPB) like structural transition with concomitant rotation of the ferroelectric polarization vector and (2) antiferrodistortive (AFD) phase transition followed by emergence of a reentrant ferroelectric phase, have been proposed in recent theoretical and experimental studies. We have attempted to address these controversies through a high resolu…
The recent discovery of a stress-induced structural phase transition in the single-component perovskite BiFeO3 has revived interest in this lead-free ferroelectric. The coexistence of different phases may lead to large piezoelectric coefficients, a property typically associated with complex solid solutions of lead-based perovskites. Here we report combined experimental and computational results showing that the stress-induced phase transitions in BiFeO3 follow the path of rhombohedral(R)-to-monoclinic(MA)-to-monoclinic(MC)-to-tetragonal(T), where both MC and T show highly enhanced c/a ratios. …
Thin films of (1-x)BiFeO<sub>3</sub>-xPbTiO<sub>3</sub> (BF-xPT) with x ~ 0.60 were fabricated on Pt/Si substrates by chemical solution deposition of precursor BF and PT layers alternately in three different multilayer configurations. These multilayer deposited precursor films upon annealing at 700°C in nitrogen show pure perovskite phase formation. In contrast to the equilibrium tetragonal structure for the overall molar composition of BF:PT::40:60, we find monoclinic structured BF-xPT phase of M<sub>A</sub> type. Piezo-force microscopy confirmed ferroelectric switching in the films and revea…
Polycrystalline ceramic samples and a single crystal of EuTiO3 have been investigated by Raman spectroscopy in the temperature range 80-300 K. Although synchrotron XRD data clearly indicated the cubic to tetragonal phase transition around 282 K, no mode from the symmetry allowed Raman active phonons was found in the tetragonal phase, contrary to the case of the homologous SrTiO3. In order to study the evolution of this unique characteristic, ceramics of EuxSr1-xTiO3 (x=0.03-1.0) characterized by synchrotron XRD for the structural phase transition have been also investigated by Raman spectrosco…
Our first-principles results show that geometric frustration can be induced in thin films of multiferroic BiFeO3. We find that competing magnetic interactions occur in the so-called super-tetragonal phase of this material, which can be grown on strongly-compressive substrates. We show that the frustration level can be tuned by appropriately choosing the substrate; in fact, the three-dimensional spin order gets totally annihilated in a narrow range of epitaxial strains. We argue that the effects revealed here are not exclusive to BiFeO3, and predict that they also occur in multiferroic BiCoO3.
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, …
The influence of La and Nd co-substitution on the structural and magnetic properties of BiFeO3 (BFO) thin films was examined. Epitaxial thin films of pure and, La and Nd co-doped BFO on the SrRuO3 buffered single crystal SrTiO3 (001) substrate were deposited using pulsed laser deposition. The structural change in co doped La and Nd BFO thin films which was caused by the changes of force constant in the crystal lattice induced by ionic radii mismatch was investigated. Raman spectroscopy studies manifest the structural change in doped BFO films from rhombohedral to monoclinic distorted phase whi…
Raman scattering experiments on LaFeAsO with splitted antiferromagnetic (T_AFM = 140 K) and tetragonal-orthorhombic (T_S = 155 K) transitions show a quasi-elastic peak (QEP) in B2g symmetry (2 Fe tetragonal cell) that fades away below ~T_AFM and is ascribed to electronic nematic fluctuations. A scaling of the reported shear modulus with the T-dependence of the QEP height rather than the QEP area indicates that magnetic degrees of freedom drive the structural transition. The large separation between T_S and T_AFM in LaFeAsO compared with their coincidence in BaFe2As2 manifests itself in slower …
We present a comprehensive study of polar and magnetic excitations in BiFeO3 ceramics and a thin film epitaxially grown on an orthorhombic (110) TbScO3 substrate. Infrared reflectivity spectroscopy was performed at temperatures from 5 to 900 K for the ceramics and below room temperature for the thin film. All 13 polar phonons allowed by the factor-group analysis were observed in theceramic samples. The thin-film spectra revealed 12 phonon modes only and an additional weak excitation, probably of spin origin. On heating towards the ferroelectric phase transition near 1100 K, some phonons soften…
Halide perovskite (HP) semiconductors exhibit unique strong coupling between the electronic and structural dynamics. The high-temperature cubic phase of HPs is known to be entropically stabilized, with imaginary frequencies in the calculated phonon dispersion relation. Similar calculations, based on the static average crystal structure, predict a stable tetragonal phase with no imaginary modes. This work shows that in contrast to standard theory predictions, the room-temperature tetragonal phase of CH$_{3} $NH$_{3} $PbI$_{3}$ is strongly anharmonic. We use Raman polarization-orientation (PO) m…
In studies using piezoresponse force microscopy, we observe a non-zero lateral piezoresponse at 180$^\circ$ domain walls in out-of-plane polarized, c-axis-oriented tetragonal ferroelectric Pb(Zr$_{0.2}$Ti$_{0.8}$)O$_3$ epitaxial thin films. We attribute these observations to a shear strain effect linked to the sign change of the $d_{33}$ piezoelectric coefficient through the domain wall, in agreement with theoretical predictions. We show that in monoclinically distorted tetragonal BiFeO$_3$ films, this effect is superimposed on the lateral piezoresponse due to actual in-plane polarization, and…
The hybrid halide perovskite CH3NH3PbI3 exhibits a complex structural behaviour, with successive transitions between orthorhombic, tetragonal and cubic polymorphs at ca. 165 K and 327 K. Herein we report first-principles lattice dynamics (phonon spectrum) for each phase of CH3NH3PbI3. The equilibrium structures compare well to solutions of temperature-dependent powder neutron diffraction. By following the normal modes we calculate infrared and Raman intensities of the vibrations, and compare them to the measurement of a single crystal where the Raman laser is controlled to avoid degradation of…
Raman Signatures of Lithium Ion Dynamics in LLZO Garnet Electrolytes: Atomistic Insights from MD-Raman Calculations
Technical University of Munich（慕尼黑工业大学）；Massachusetts Institute of Technology（麻省理工学院）；Fritz-Haber-Institut of the Max-Planck-Society（马克斯·普朗克学会弗里茨·哈伯研究所）
In this paper, we revisit the high-pressure behavior of BaZrO3 by a combination of first-principle calculations, Raman spectroscopy, and x-ray diffraction under high pressure. We confirm experimentally the cubic-to-tetragonal transition at 10 GPa and find no evidence for any other phase transition up to 45 GPa, the highest pressures investigated, at variance with past reports. We re-investigate phase stability with density functional theory considering not only the known tetragonal (I4/mcm) phase but also other potential antiferrodistortive candidates. This shows that the tetragonal phase beco…
We report a Raman scattering investigation of KTa1-xNbxO3 (x = 0.35, 0.5) thin films deposited on MgO and LaAlO3 as a function of temperature. The observed phase sequence in the range from 90 K to 720 K is similar to the structural phase transitions of the end-member material KNbO3. Although similar in the phase sequence, the actual temperatures observed for phase transition temperatures are significantly different from those observed in the literature for bulk samples. Namely, the tetragonal (ferroelectric) to cubic (paraelectric) phase transition is up to 50 K higher in the films when compar…
Among the recent discoveries of domain wall functionalities, the observation of electrical conduction at ferroelectric domain walls in the multiferroic insulator BiFeO3 has opened exciting new possibilities. Here, we report evidence of electrical conduction also at 180° ferroelectric domain walls in the simpler tetragonal ferroelectric PZT thin films. The observed conduction shows nonlinear, asymmetric current-voltage characteristics, thermal activation at high temperatures and high stability. We relate this behavior to the microscopic structure of the domain walls, allowing local defects segr…
