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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 tet ragonal-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.
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 su ggest 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.
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