Periodic elastic nanodomains in ultrathin tetrogonal-like BiFeO3 films

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 Kittels square root law in ultrathin thickness regime (6 - 30 nm). Temperature-dependent experiments also reveal the disappearance of periodic modulation above 90C due to a MC-MA structural phase transition.

Large tensile strain induced monoclinic MB phase in BiFeO3 epitaxial thin films on PrScO3 substrate

Crystal and domain structures of tensile-strained BiFeO3 films grown on orthorhombic (110)o PrScO3 substrates were investigated. All films possess a MB-type monoclinic structure with 109o stripe domains oriented along the [=i10]o direction. For films thicknesses less than ~40 nm, presence of well-ordered domains is proved by the detection of satellite peaks in synchrotron x-ray diffraction studies. For thicker films, For thicker films, only the Bragg reflections from tilted domains were detected. This is attributed to the broader domain size distribution in thicker films.Using planar electrodes,the in-plane polarization of the MB phase is determined to be 85 uC/cm2, which is much larger than that of compressive strained BiFeO3 films. Our results further reveal that the substrate monoclinic distortion plays a major role in determining the stripe domain formation of the rhombohedral ferroic epitaxial thin films, which sheds light to the understanding of elastic domain structure evolution in many other functional oxide thin films as well.

Study of strain effect on in-plane polarization in epitaxial BiFeO3 thin films using planar electrodes

Epitaxial strain plays an important role in determining physical properties of perovskite ferroelectric oxide thin films. However, it is very challenging to directly measure properties such as polarization in ultrathin strained films using traditional sandwich capacitor devices, because of high leakage current. We employed a planar electrode device with different crystallographical orientations between electrodes along different electric field orientation to directly measure the in-plane polarization-electric field (P-E) hysteresis loops in fully strained thin films. At high misfit strains such as -4.4%, the pure Tetrogonal-like phase is obtained and its polarization vector is constrained to lie in the (010) plane with a significantly large in-plane component, ~44 {mu}C/cm2. First-principle calculations are carried out in parallel, and provide a good agreement with the experimental results. Our results pave the way to design in-plane devices based on T-like BFO and the strategy proposed here can be expanded to study all other similar strained multiferroic ultrathin films.

Characterization and manipulation of mixed phase domains in highly-strained BiFeO3 thin films

The novel strain-driven morphotropic phase boundary (MPB) in highly-strained BiFeO3 thin film is featured by ordered mixed phase nanodomains (MPNs). Through scanning probe microscopy and synchrotron X-ray diffraction, eight structural variants of the MPNs are identified. Detailed polarization configurations within the MPNs are resolved using angular-dependent piezoelectric force microscopy. Guided by the obtained results, deterministic manipulation of the MPNs has been demonstrated by controlling the motion of the local probe. These findings are important for in-depth understanding of the ultrahigh electromechanical response arising from phase transformation between competing phases, enabling future explorations on the electronic structure, magnetoelectricity and other functionalities in this new MPB system.

Temperature-driven evolution of hierarchical nanodomain structure in tetragonal-like BiFeO3 films

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 {deg}C with a thermal hysteresis.

Coexistence of Ferroelectric Triclinic Phases and Origin of Large Piezoelectric Responses in Highly Strained BiFeO3 films

The structural evolution of the strain-driven morphotropic phase boundary (MPB) in BiFeO3 films has been investigated using synchrotron x-ray diffractometry in conjunction with scanning probe microscopy. Our results demonstrate the existence of mixed-phase regions that are mainly made up of two heavily tilted ferroelectric triclinic phases. Analysis of first-principles computations suggests that these two triclinic phases originate from a phase separation of a single monoclinic state accompanied by elastic matching between the phase-separated states. These first-principle calculations further reveal that the intrinsic piezoelectric response of these two low-symmetry triclinic phases is not significantly large, which thus implies that the ease of phase transition between these two energetically close triclinic phases is likely responsible for the large piezoelectric response found in the BiFeO3 films near its MPB. These findings not only enrich the understandings of the lattice and domain structure of epitaxial BiFeO3 films but may also shed some light on the origin of enhanced piezoelectric response near MPB.

Nanoscale domains in strained epitaxial BiFeO3 thin Films on LaSrAlO4 Substrate

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 {AA} is stabilized by a large misfit strain. Besides, a rhombohedral-like phase with c-lattice constant ~3.99 {AA} 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 regions. These findings suggest a complex picture of nanoscale domain patterns in BiFeO3 thin films subjected to large compressive strains.

Low-Symmetry Monoclinic Phases and Polarization Rotation Path Mediated By Epitaxial Strain in Multiferroic BiFeO3 Thin Films

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 force microscopy measurements. The polarization vectors of the tetragonal-like phase lie in the (100) plane, not the (110) plane as previously reported. A phenomenological analysis was proposed to explain the formation of MC Phase. Such a low symmetry MC phase, with its linkage to MA phase and the multiphase coexistence open an avenue for large piezoelectric response in BiFeO3 films and shed light on a complete understanding towards possible polarization rotation paths and enhanced multiferroicity in BiFeO3 films mediated by epitaxial strain. This work may also aid the understanding of developing new lead-free strain-driven morphotropic phase boundary in other ferroic systems.