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Stress-induced structural phase transitions in multiferroic BiFeO3 thin films have attracted much attention for both fundamental research and promising applications in electronic devices. In this work, with the assistance of spherical aberration-corrected transmission electron microscopy, a tetragonal phase with the super large tetragonality (c/a ∼ 1.53) was found in the epitaxial BiFeO3 thin film on a LaAlO3/Si substrate. Analyses of atom positions showed that displacements of an Fe atom in this super tetragonal phase are much smaller than that in a regular tetragonal phase. First-principles calculations revealed that the structural phase transition occurs with the increasing lattice tetragonality c/a, accompanied by transitions in the atomic coordination and magnetic order.

Single-frequency piezoresponse force microscopy (PFM) images of a BiFeO3/DyScO3(110) thin film, obtained with long (kc = 0.82 N/m) and short (kc = 7.64 N/m) cantilevers, were analyzed as a function of the applied voltage frequency. For long cantilevers, the electrostatic and electrostrictive contributions were identified. These contributions were reduced with a frequency near the second mode of the contact resonance; while for short cantilevers, the first mode was necessary. A method for domain structure analyses, to discriminate a ferroelectric behavior from a non-ferroelectric, through the optimization of PFM images, is also described. The analysis can be extended to cantilevers with different spring constants and ferroelectric materials.

Flexible electronics have a great potential to impact consumer electronics and with that our daily life. Currently, no direct growth of epitaxial functional oxides on commercially available flexible substrates is possible. In this study, in order to address this challenge, muscovite, a common layered oxide, is used as a flexible substrate that is chemically similar to typical functional oxides. We fabricated epitaxial MoO2 films on muscovite via pulsed laser deposition technique. A combination of X-ray diffraction and transmission electron microscopy confirms van der Waals epitaxy of the heterostructures. The electrical transport properties of MoO2 films are similar to those of the bulk. Flexible or free-standing MoO2 thin film can be obtained and serve as a template to integrate additional functional oxide layers. Our study demonstrates a remarkable concept to create flexible electronics based on functional oxides.

A series of self-assembled WO3–BiVO4 nanostructured thin films were grown on the (001) yttria-stabilized zirconia (YSZ) substrate at the substrate temperatures of 400 °C, 500 °C, 550 °C, 600 °C, 650 °C and 700 °C by a pulsed laser deposition method. The microstructures including crystalline phases, epitaxial relationships, surface morphologies and interface structures were investigated by a combination of x-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. The sample grown at 400 °C was amorphous due to the low driving forces for nucleation and diffusion. For the samples made at 500 °C, 550 °C and 600 °C, the monoclinic BiVO4 matrix epitaxially grew on YSZ, forming the matrix, where the WO3 nanopillars were embedded in with a specific orientation relationship among BiVO4, WO3 and YSZ. However, in thin films deposited at 650 °C and 700 °C, the WO3 grains randomly grew on the YSZ substrate, which dominated the microstructures of the resultant thin films. Qua...

The growth behavior of Ba(Mg1∕3Ta2∕3)O3 (BMT) thin films on bare or Pt-coated silicon substrates and their buffering effect on the subsequently deposited Pb(Zr,Ti)O3 (PZT) films were systematically examined. The preferred orientation of BMT layer varies pronouncedly with the deposition parameters. It is (200) textured when deposited under high substrate temperature (400°C) or large laser fluence (3J∕cm2). The BMT layer not only suppresses the film-to-substrate interdiffusion but also enhances the Pb(Zr1−xTix)O3 (PZT) nucleation kinetics. The PZT films prepared on BMT layer by metal-organic-decomposition (MOD) process begin to crystallize at a substrate temperature as low as 400°C, which is lower than the reported heat treatment temperature for preparing PZT films via MOD process. However, postannealing at 550°C is required to fully crystallize the PZT films. The PZT∕BMT∕Pt(Si) thin films show high dielectric constant [(ϵr)PZT=400–425], low leakage current density (Je

Self-assembled WO3-BiVO4 nanostructured thin films were grown on a (001) yttrium stabilized zirconia (YSZ) substrate by the pulsed laser deposition method with and without the indium tin oxide (ITO) bottom electrode. Their microstructures including surface morphologies, crystalline phases, epitaxial relationships, interface structures, and composition distributions were investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray energy dispersive spectroscopy. In both samples, WO3 formed nanopillars embedded into the monoclinic BiVO4 matrix with specific orientation relationships. In the sample with the ITO bottom electrode, an atomically sharp BiVO4/ITO interface was formed and the orthorhombic WO3 nanopillars were grown on a relaxed BiVO4 buffer layer with a mixed orthorhombic and hexagonal WO3 transition layer. In contrast, a thin amorphous layer appears at the interfaces between the thin film and the YSZ substrate in the sample without the ITO electrode. I...

Heteroepitaxial ZnO and SrRuO3 were grown on SrTiO3 (111) substrates and formed a self-assembled wurtzite-perovskite nanostructure. Spontaneous orientation-tuning of the SrRuO3 pillars was observed, with the growth direction changing from [111]SRO to [011]SRO as the film thickness increased, which is attributed to a misfit strain transition from the biaxial strain imposed by the SrTiO3 substrate to the vertical strain provided by the ZnO matrix. The [011]-SrRuO3 and [0001]-ZnO combination presents a favorable matching in the nanocomposite films, resulting in higher charge carrier mobility. This vertically integrated configuration and regulation on the crystallographic orientations are expected to be employed in designing multi-functional nanocomposite systems for applications in electronic devices.

The La2/3Sr1/3MnO3/BiFeO3 (LSMO/BFO) heterostructure is studied as probed by temperature-dependent ferromagnetic resonance (FMR). Consistent with the structure analysis, two FMR modes are found for both a single LSMO layer and a LSMO/BFO bilayer grown on DyScO3, corresponding to the strained and relaxed phases of LSMO. The FMR linewidth intensity vs temperature curve shows two maxima at 200 K and 140 K in the strained phase of LSMO/BFO bilayer, which is related to the magnetic excitations in BFO. Our results demonstrate a dynamic spin interaction between LSMO and BFO, suggesting an effective route to manipulate the magnetic properties of oxide heterostructures.

Considerable attention has been paid to ferroic systems in pursuit of advanced applications in past decades. Most recently, the emergence and development of multiferroics, which exhibit the coexistence of different ferroic natures, has offered a new route to create functionalities in the system. In this manuscript, we step from domain engineering to explore a roadmap for discovering intriguing phenomena and multifunctionalities driven by periodic domain patters. As-grown periodic domains, offering exotic order parameters, periodic local perturbations and the capability of tailoring local spin, charge, orbital and lattice degrees of freedom, are introduced as modeling templates for fundamental studies and novel applications. We discuss related significant findings on ferroic domain, nanoscopic domain walls, and conjunct heterostructures based on the well-organized domain patterns, and end with future prospects and challenges in the field.

BiFeO3-LiMn2O4 (BFO-LMO) heterostructures were fabricated via pulsed laser deposition, and their ferroelectric and ferromagnetic properties were probed by magnetic force microscopy (MFM), piezoresponse force microscopy (PFM), and the newly developed piezomagnetic force microscopy (PmFM). MFM imaging shows no clear distinction between BFO and LMO phases, while PFM and PmFM mappings clearly distinguish LMO nanopillars from BFO matrix. Linear piezoelectric and piezomagnetic responses have been observed in both phases, with the effects more prominent in BFO. The strong piezomagnetic response in BFO is believed to arise from Mn doping, while piezoelectric-like response of LMO is attributed to ionic activities as well as vertical geometry of the heterostructure. The limitation of global excitation of PmFM is also discussed.

Temperature dependent magnetic and phonon anomalies in epitaxial self-assembled CoFe2O4 (CFO) rods embedded in BaTiO3 (BTO) matrix nanostructures were investigated. The temperature dependence of A1(2TO) phonon frequency of BTO indicates that the BTO matrix experiences structural transformations. The lattice strain produced during the structural transformations drives spin reorientation in CFO rods, resulting in anomalous changes of magnetization. Through correlating the phonon anomalies with the increase of in-plane spin ordering, we show the spin-phonon coupling induces the softening of A1g and A1(2TO) phonons. It suggests that spin strongly couples with lattice strain and phonons in this nanostructure.

We investigate the anisotropic stress dependent magnetic and phonon behaviors in self-assembled CoFe2O4-PbTiO3 (CFO-PTO) nanostructures deposited on SrRuO3 buffered SrTiO3 substrates of various thickness. The increased vertical compressed stress with increasing thickness enhances the vertical magnetic anisotropy of CFO while gradually reducing the vertical polarization of PTO. By applying the magnetic-field dependent Raman scattering, the CFO-A1g and T2g(1) phonon frequencies shift oppositely because of the magnetostriction. Moreover, the PTO-A1 mode intensities anomalously enhance and the A1 and E mode frequencies, respectively, increase and decrease, which prove the existence of the stress-mediated magnetoelectric (ME) effect. This study shows that the ME transmission process is dominated by interfacial stress, which is critical for enhancing the ME efficiency.

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...

Spectroscopic ellipsometry was used to investigate the strain-dependent optical properties of BiFeO3 thin films. At room temperature, the compressively strained BiFeO3/LaAlO3 thin films show the largest band gap of about 3.12 eV. It redshifts to 2.75 eV for the tensile strained BiFeO3/NdScO3 thin films. With increasing temperature, observable anomalies in the band gap for all strained thin films near 640 K indicate that antiferromagnetic transition temperature is independent of strain and close to its bulk value, which are in good agreement with the first-principles calculations. These results further suggest a complex nature of charge-spin coupling in multiferroic BiFeO3 thin films.

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C+) whilst the same films grown on the (La,Sr)CoO3-electrodes are polarized downward (C−). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C+ orientation possess a more active surface for metal reduction than their C− counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

This study reports a self-assembled multiferroic nanostructure, composed of PbTiO3 (PTO) pillars embedded in a CoFe2O4 (CFO) matrix, deposited on MgO(001) by pulsed laser deposition. The epitaxial relationship in the PTO-CFO nanostructure is (100)[101]PTO∥(001)[101]CFO∥(001)[101]MgO, confirming the in-plane aligned polarization of PTO. The perpendicular magnetic anisotropy of this thin film results from the magnetoelastic anisotropy that exceeds the shape anisotropy. The increased frequency and the enhanced intensity of the tetrahedral (T-) site phonon modes by increasing the magnetic field indicate strong magnetoelastic coupling through magnetostriction in this multiferroic nanostructure. The anisotropic Raman strength enhancement of the T-site phonon along different directions suggests the magnetoelastic coupling is most efficient in the in-plane direction.

The pattern configuration and interface structure in epitaxial BiFeO3-CoFe2O4 heterostructures grown on (010)pc NdGaO3 substrates have been investigated systematically by transmission electron microscopy and chemical analysis. The crystal orientation of CoFe2O4 variants was tuned to [111]CFO, while BiFeO3 kept [010]pc matching the substrate. Triangular prism-shaped CoFe2O4 embedded in the BiFeO3 matrix grew as an equilibrium island mode with {111}CFO as its surfaces and interfaces. Two types of BiFeO3-CoFe2O4 orientation relationships were determined as (001)[010]BFO//(0-22)[111]CFO and (101)[010]BFO//(−220)[111]CFO. The results reveal that the dominant factors controlling the growth orientation of the present vertical heterostructures are surface energy anisotropy and atomic structure continuity.

We demonstrate that thermal annealing in cation controlled environments is an effective means to obtain atomically flat and chemically single terminated surfaces of a layer structured substrate. The effectiveness of the cation controlled annealing method is proved with SrLaAlO4, which is a representative layer structured substrate of A2BO4 type. Potassium ion scattering, in particular, shows that the method allows not only single termination but also selective termination of either A- or B-site on the substrate. We further demonstrate that the chemical nature of underlying SrLaAlO4 substrates is of critical importance in the growth of SrRuO3 thin films resulting in different morphologies and transport properties.

The oxygen vacancies in the SrTiO3 (STO) single crystal with two different cap layers, CoFe2O4 (CFO) and BiFeO3 (BFO), are investigated with the technique of electron paramagnetic resonance (EPR). EPR spectra show the resonance lines of the residual oxygen vacancy in air annealed STO, STO/CFO, and STO/BFO, showing the high sensitivity of EPR to the low concentration defects. The experimental results indicate that the oxide cap layers enhance the oxygen deficiency in bulk STO and the amount of oxygen vacancy is dependent on the electronegativity of metal ion in the cap layer. Accordingly, STO/BFO has a larger amount of oxygen vacancy than that of STO/CFO.

Trilayer heterostructures consisting of a ferroelectric bismuth ferrite (BFO) film sandwiched between ferromagnetic lanthanum strontium manganese oxide (LSMO) films were fabricated using pulsed laser deposition. Both BFO thicknesses (20 nm, 5 nm) and cooling rates were varied to investigate the role of processing parameters on the chemistry of the interfaces. The interfaces were investigated using a dedicated aberration corrected scanning transmission electron microscope (STEM) operated at 100 kV via STEM-high angle annular dark field (STEM-HAADF) and STEM-electron energy loss spectroscopy (STEM-EELS) modes. Combined analysis through STEM-HAADF and STEM-EELS revealed the formation of lattice distortion in certain regions of the BFO layer for the ∼5 nm film. Piezoresponse force microscopy (PFM) studies of the ∼5 nm BFO sample revealed weak ferroelectric domain switching. Stacking fault defects with mixed valence manganese (Mn-B site cation) were formed in the top LSMO layer when the heterostructure was coo...

This report investigates the phase evolution pathway of magnetite nanocrystal synthesis on oxide-supported substrates. A template-free phase separation approach, which exploits the thermodynamic instability of ternary perovskite BiFeO3 and inherent volatility of bismuth oxide in low oxygen pressure and high temperature is presented. The formation of an intermediate hematite nanocrystal phase is found as a key step that controls the eventual size and morphology of the magnetite nanocrystals. X-ray absorption spectra measurements and X-ray magnetic circular dichroism confirm that the spectral fingerprints of the magnetite nanocrystals match with that of bulk crystals. Magnetic measurements show that magnetic anisotropy is directly attributed to the nanocrystal morphology.

The dependence of field-on and field-off hysteresis loop shape in Piezoresponse Force Microscopy (PFM) on driving voltage, Vac, is explored. A nontrivial dependence of hysteresis loop parameters on measurement conditions is observed. The strategies to distinguish between paraelectric and ferroelectric states with small coercive bias and separate reversible hysteretic and non-hysteretic behaviors are suggested. Generally, measurement of loop evolution with Vac is a necessary step to establish the veracity of PFM hysteresis measurements.

The thermodynamic parameters of domain relaxation process in the absence of external electric fields are related to the intrinsic electrostatic and stress/strain conditions inside the materials, such as the states at surface, states at interface with the electrode, and the atomic defects in the bulk. In order to perform systematical studies of these intrinsic effects, we investigated domain relaxation in a monodomain environment, which was obtained in strained epitaxial BiFeO3 (BFO)(111) films. Without as-grown domain walls and grain boundaries, the epitaxial BFO(111) film provided an ideal system for the dynamic observation of 180-degree domain wall motion. Nano-domains were initially created by writing voltage pulses under the tip of a scanning force microscope and then relaxed through time. The downward polarized domains exhibited much better retention behaviors than the upward domains. A two-step backswitching process was observed, and the behaviors varied with the initial domain sizes. Surface potential measurement showed the dissipation of surface screen charges with time, which was strongly coupled with the 1st step relaxation. The asymmetry behaviors for upward and downward backswitchings, and the two-stage relaxation processes can be explained by the mobile vacancies and the redistribution of surface charges. This study provides the basic understanding of the role of surface charges during the ferroelectric domain relaxation.

We studied ultrafast dynamics and photoinduced mechanical strain of BiFeO3 thin films by dual-color transient reflectivity measurements (ΔR/R). Anisotropic photostriction in BiFeO3 is found to be mainly driven by the optical rectification effect. Results of the photostriction at various thicknesses show that the estimated sound velocity along [110] direction of BiFeO3 is 4.76 km/s.

This study presents a direct visualization of the influences of ferroelectric polarization on the electronic properties of the Schottky contact at the Nb-SrTiO3/BiFeO3 hetero-interface using scanning tunneling microscopy and spectroscopy (STM/S). The evolution of the local density of states across the Nb-SrTiO3/BiFeO3 interface reveals the interfacial band alignment and the characteristic quantities of the metal/ferroelectric contact. The unique combination of STM and STS in this study delivers an approach to obtain critical information on the interfacial electronic configurations of ferroelectric oxide interfaces and also their variation with ferroelectric polarization switching.

We investigated the electronic reconstruction at the n-type LaAlO3/SrTiO3 interface with hard x-ray photoelectron spectroscopy (HAXPES) under grazing incidence. By exploiting the collapse of evanescent x-ray waves and the abrupt increase of x-ray absorption at the critical incidence angle, our HAXPES study reveals a 2% electronic reconstruction from Ti4+ to Ti3+ occurring near the interface. Such an electronic reconstruction also extends from the interface into SrTiO3 with a depth of about 48 A (∼12 unit cells) and an estimated total charge transfer of ∼0.24 electrons per two-dimensional unit cell.

The local dynamics of ferroelectric domain polarization are uniquely investigated with sub-20-nm resolved maps of switching times, growth velocities, and growth directions. This is achieved by analyzing movies of hundreds of consecutive high speed piezo force microscopy images, which record domain switching dynamics through repeatedly alternating between high speed domain imaging and the application of 20-nanosecond voltage pulses. Recurrent switching patterns are revealed, and domain wall velocities for nascent domains are uniquely reported to be up to four times faster than for mature domains with radii greater than approximately 100 nm. Switching times, speeds, and directions are also shown to correlate with local mechanical compliance, with domains preferentially nucleating and growing in compliant sample regions while clearly shunting around locations with higher stiffness. This deterministic switching behavior strongly supports a defect-mediated energy landscape which controls polarization reversal, and that can therefore be predicted, modeled, and even manipulated through composition, processing, and geometry. Such results have important implications for the practical performance of ferroelectric devices by enabling guided optimization of switching times and feature densities, while the methods employed provide a new means to investigate and correlate dynamic functionality with mechanical properties at the nanoscale.

A model is developed to investigate the domain pattern and piezoelectric response across the polymorphic phase transition in strained epitaxial bismuth ferrite films. The orientations of stripelike pattern of the mixed rhombohedral and tetragonal phases are predicted as the consequence of competition between elastic and depolarization energies. The abnormally large piezoelectric response is attributed to the strain-driven softening in dielectric stiffness. The results are in good agreement with recent experimental observations and provide a guidance for developing similar strain-driven polymorphic phase transition in other related perovskite material systems.

The switching kinetics in epitaxial (001)-, (110)-, and (111)-oriented BiFeO3 thin films were investigated as a function of applied field and time. It was found that the ferroelectric switching behavior obeys the Kolmogorov–Avrami–Ishibashi theory only in the high field range. The detailed behavior depends on the film orientation. A comparison with standard systems, such as epitaxial Pb(Zr0.2Ti0.8)O3 films, reveals some similarities as well as some differences. For instance, the presence of 109° and 71° ferroelastic domain walls might be ruled out as the source of the decrease in switched polarization at low applied fields, in contrast to what is the case for a/c domain walls in tetragonal Pb(Zr0.2Ti0.8)O3.

The magnetism-induced ferroelectricity in the E-type orthorhombic HoMnO3 (o-HMO) films grown on Nb-doped and undoped SrTiO3(001) substrates was studied. The temperature dependent magnetization in these films evidently exhibits an antiferromagnetic ordering around 44K and an anomalous second magnetic ordering along the c-axis near 35K. Interestingly, at this anomalous transition temperature, an associated ferroelectric polarization was probed by the P-E hysteresis measurements, indicating the intimated coupling between the ferroelectric response and the reordering of Mn spins, which has never been disclosed previously by dielectric constant measurements.

We report a photovoltaic effect in ferroelectric BiFeO3 thin films. The all-oxide heterostructures with SrRuO3 bottom and tin doped indium oxide top electrodes are characterized by open-circuit voltages ∼0.8–0.9 V and external quantum efficiencies up to ∼10% when illuminated with the appropriate light. Efficiencies are at least an order of magnitude larger than the maximum efficiency under sunlight (AM 1.5) thus far reported for ferroelectric-based devices. The dependence of the measured open-circuit voltage on film thickness suggests contributions to the large open-circuit voltage from both the ferroelectric polarization and band offsets at the BiFeO3/tin doped indium oxide interface.

We present a quantitative study of 180° domain wall motion in epitaxial BiFeO 3 (111) films, which can be treated as a nearly ideal single-domain environment. The domains were dynamically written by applying voltage pulses and examined by the piezoresponse force microscope technique. A transition of domain growth behaviors from the activated type to the nonactivated type was observed when increasing the pulse voltages. The obtained activation field was close to the ideally thermodynamic switching field of BiFeO 3 . The asymmetry of activated fields showed the preference of the downward polarization in the BiFeO 3 / SrRuO 3 films.

The ferroelectric polarization switching behavior at the 24 degrees (100) tilt grain boundary (GB) in an epitaxial multiferroic BiFeO3 bicrystal film is studied using piezoresponse force microscopy (PFM). The PFM amplitudes across positively and negatively poled GB regions suggest the presence of a frozen polarization component at the interface. The switching experiments demonstrate that the GB attracts the domain wall and acts as a pinning center. The PFM results are compared with conductive atomic force microscopy and spectroscopy, which suggest domain wall pinning at the GB can be partially attributed to increased conductance at the GB. Other funder Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC for the Office of Basic Energy Sciences, U.S. Department of Energy and the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, and U.S. Department of Energy under Contract No. DE-AC02-05CH11231. the Alexander von Humboldt Foundation and National Science Council, R.O.C., under Contract No. NSC 97-3114-M-009-001. Author has checked copyright kpw6/12/13

An atomic force microscopy (AFM) based technique is described for mapping piezoactuation with nanoscale resolution in less than a second per complete image frame. “High speed piezo force microscopy” (HSPFM) achieves this >100× increase in acquisition rates by coupling a commercial AFM with concepts of acoustics. This allows previously inaccessible dynamic studies, including measuring ferroelectric domain nucleation and growth during in situ poling. Hundreds of consecutive images are analyzed with 49 μs temporal resolution per pixel per frame, revealing 32 nucleation sites/μm2 with 36 μm/s average domain velocities. HSPFM images acquired in as fast as 1/10th s are also presented.

Lead vanadate (PbVO3) is a multifunctional material which is both polar and magnetic. Its optical properties, important for linear and nonlinear optical spectroscopy of the material, are presented. Using spectroscopic ellipsometry, the refractive index and absorption versus wavelength of lead vanadate thin films at 295K is reported. Using optical second harmonic generation, the nonlinear optical coefficients were determined to be d15∕d31=0.20±0.02, d33∕d31=316.0±4.4, and ∣d33∣=10.40±0.35pm∕V at a fundamental wavelength of 800nm.

Ferroelectric domain structures of (001)c, (101)c, and (111)c oriented epitaxial BiFeO3 thin films were studied by using the phase-field approach. Long-range elastic and electrostatic interactions were taken into account. The effects of various types of substrate constraint on the domain morphologies were systematically analyzed. It is demonstrated that domain structures of BiFeO3 thin films could be controlled by selecting proper film orientations and substrate constraint. The dependence of the {110}c-type domain wall orientation on substrate constraint for the (001)c oriented BiFeO3 thin film was also discussed.

Using spectroscopic ellipsometry, the refractive index and absorption versus wavelength of the ferroelectric antiferromagnet Bismuth Ferrite, BiFeO_3 is reported. The material has a direct band-gap at 442 nm wavelength (2.81 eV). Using optical second harmonic generation, the nonlinear optical coefficients were determined to be d_15/d_22 = 0.20 +/- 0.01, d_31/d_22 = 0.35 +/- 0.02, d_33/d_22 = -11.4 +/- 0.20 and |d_22| = 298.4 +/- 6.1 pm/V at a fundamental wavelength of 800 nm.

We have probed the role of La substitution on the ferroelectric properties of epitaxial BiFeO3 films on SrTiO3-templated Si. This provides a mechanism to engineer the rhombohedral distortion in the crystal and, thus, control domain structure and switching. With a 10% La substitution, the (Bi0.9La0.1)FeO3 film showed well-saturated ferroelectric hysteresis loops with a remanent polarization of 45μC∕cm2, a converse piezoelectric coefficient d33 of 45pm∕V, and a dielectric constant of 140. Over this range of La substitution, the coercive field systematically decreases such that a coercive voltage of 1V can been obtained in a 100nm thick film. These results show promise for the ultimate implementation of this lead-free multiferroic operating at voltages in the range of 2–3V.

The optical properties of epitaxial BiFeO3 thin films have been characterized in the visible range. Variable temperature spectra show an absorption onset near 2.17eV, a direct gap (2.667±0.005eV at 300K), and charge transfer excitations at higher energy. Additionally, we report photoconductivity in BiFeO3 films under illumination from a 100mW∕cm2 white light source. A direct correlation is observed between the magnitude of the photoconductivity and postgrowth cooling pressure. Dark conductivities increased by an order of magnitude when comparing films cooled in 760 and 0.1Torr. Large increases in photoconductivity are observed in light.

We report the growth and characterization of exchange bias and spin valve heterostructures based on the multiferroic antiferromagnet BiFeO3 on Si (001) substrates. Using Co0.9Fe0.1 as the ferromagnet, we demonstrate heterostructures with large negative exchange bias and negligible training (or a decrease in exchange bias field as a function of repeated magnetic cycling) at room temperature. We additionally report the manufacture of spin valve structures that have been found to have current in-plane magnetoresistance of over 2.25% at room temperature.

BiFeO3 thin films have been deposited on (111) SrTiO3 single crystal substrates by reactive molecular-beam epitaxy in an adsorption-controlled growth regime. This is achieved by supplying a bismuth overpressure and utilizing the differential vapor pressures between bismuth oxides and BiFeO3 to control stoichiometry. Four-circle x-ray diffraction reveals phase-pure, untwinned, epitaxial, (0001)-oriented films with rocking curve full width at half maximum values as narrow as 25arcsec (0.007°). Second harmonic generation polar plots combined with diffraction establish the crystallographic point group of these untwinned epitaxial films to be 3m at room temperature.

The authors report the integration of multiferroic BiFeO3 films with the semiconductor GaN using liquid-delivery metal-organic chemical-vapor deposition. Epitaxial BiFeO3 films were deposited via interface control using SrTiO3 buffer/template layers. The growth orientation relationship was found to be (111)[11¯0]BiFeO3‖(111)[11¯0]SrTiO3‖(0001)[112¯0]GaN, with in-plane 180° rotational twins. The C-V characteristics of a Pt∕BiFeO3∕SrTiO3∕GaN capacitor exhibited hysteresis with a memory window of ∼3V at a sweeping voltage of ±30V.

A single-domain thermodynamic theory is employed to predict the spontaneous polarizations of (001)c, (101)c, and (111)c oriented epitaxial BiFeO3 thin films grown on dissimilar substrates. The effects of various substrate-induced strains on the spontaneous polarization were studied. The dependences of the spontaneous polarization on film orientations and the types of substrate-induced strains were analyzed.

Piezoelectric force microscopy has been enhanced by coplanar epitaxial electrodes to detect and manipulate the striped ferroelectric domain structure of a multiferroic BiFeO3 thin film grown on single-crystalline DyScO3. Time-resolved imaging revealed ferroelastic (71° and 109°) switching of domains in a needlelike region that grew from one electrode toward the other in a uniform electric field, and demonstrated reversible rotation of the 71° domain stripe orientation in a nonuniform field. Purely ferroelectric (180°) switching was suppressed by the geometry of the electrodes. The extendibility of this apparatus opens the door toward magnetoelectric domain imaging.

Epitaxial growth of (0001)-oriented BiFeO3 thin films on the (0001) surface of GaN has been realized using intervening epitaxial (111) SrTiO3∕(100) TiO2 buffer layers. The epitaxial BiFeO3 thin films have two in-plane orientations: [112¯0]BiFeO3‖[112¯0]GaN plus a twin variant related by a 180° in-plane rotation. BiFeO3 shows an out-of-plane remanent polarization of ∼90μC∕cm2, which is comparable to the remanent polarization of BiFeO3 prepared on (111) SrTiO3 single crystal substrates. The orientation of BiFeO3 realized on GaN provides the maximal out-of-plane polarization of BiFeO3, which is equivalent to a surface charge of 5×1014electrons∕cm2.

The authors have studied the magnetic properties of BaTiO3–CoFe2O4 nanostructures, which were prepared using pulsed laser deposition. Such nanostructures show a large uniaxial magnetic anisotropy with an easy axis along the pillar long direction. As the growth temperature decreases, the magnetic anisotropy increases. Careful analyses reveal that heteroepitaxial strain is the primary contribution to the magnetic anisotropy.

The authors report results of transport studies on high quality, fully epitaxial BiFeO3 thin films grown via pulsed laser deposition on SrRuO3∕DyScO3 (110) substrates. Ferroelectric tests were conducted using symmetric and asymmetric device structures with either SrRuO3 or Pt top electrodes and SrRuO3 bottom electrodes. Comparison between these structures demonstrates the influence of electrode selection on the dominant transport mechanism. Analysis of film electrical response suggests Poole-Frenkel emission as the limiting leakage current mechanism in the symmetric structure. Temperature dependent measurements yield trap ionization energies of ∼0.65–0.8eV. No clear dominant leakage mechanism was observed for the asymmetric structure.

We have grown BiFeO3 thin films on SrRuO3∕SrTiO3 and SrRuO3∕SrTiO3∕Si using liquid delivery metalorganic chemical vapor deposition. Epitaxial BiFeO3 films were successfully prepared through the systematic control of the chemical reaction and deposition process. We found that the film composition and phase equilibrium are sensitive to the Bi:Fe ratio in the precursor. Fe-rich mixtures show the existence of α-Fe2O3, while Bi-rich mixtures show the presence of β-Bi2O3 as a second phase at the surface. In the optimized films, we were able to obtain an epitaxial single perovskite phase thin film. Electrical measurements using both quasistatic hysteresis and pulsed polarization measurements confirm the existence of ferroelectricity with a switched polarization of 110–120μC∕cm2, ΔP(=P*−P). Out-of plane piezoelectric (d33) measurements using an atomic force microscope yield a value of 50–60pm∕V.