Ferroelectric materials exhibit the largest dielectric permittivities and piezoelectric responses in nature, making them invaluable in applications from supercapacitors or sensors to actuators or electromechanical transducers. The origin of this behavior is their proximity to phase transitions. However, the largest possible responses are most often not utilized due to the impracticality of using temperature as a control parameter and to operate at phase transitions. This has motivated the design of solid solutions with morphotropic phase boundaries between different polar phases that are tuned by composition and that are weakly dependent on temperature. Thus far, the best piezoelectrics have been achieved in materials with intermediate (bridging or adaptive) phases. But so far, complex chemistry or an intricate microstructure has been required to achieve temperature-independent phase-transition boundaries. Here, we report such a temperature-independent bridging state in thin films of chemically simple BaTiO 3 . A coexistence among tetragonal, orthorhombic, and their bridging low-symmetry phases are shown to induce continuous vertical polarization rotation, which recreates a smear in-transition state and leads to a giant temperature-independent dielectric response. The current material contains a ferroelectric state that is distinct from those at morphotropic phase boundaries and cannot be considered as ferroelectric crystals. We believe that other materials can be engineered in a similar way to contain a ferroelectric state with gradual change of structure, forming a class of transitional ferroelectrics. Similar mechanisms could be utilized in other materials to design low-power ferroelectrics, piezoelectrics, dielectrics, or shape-memory alloys, as well as efficient electro-and magnetocalorics.
Very sensitive responses to external forces are found near phase transitions. However, phase transition dynamics and pre-equilibrium phenomena are difficult to detect and control. We have directly observed that the equilibrium domain structure following a phase transition in BaTiO3, a ferroelectric and ferroelastic material, is attained by halving of the domain periodicity, sequentially and multiple times. The process is reversible, displaying periodicity doubling as temperature is increased. This observation is backed theoretically and can explain the fingerprints of domain period multiplicity observed in other systems, strongly suggesting this as a general model for pattern formation during phase transitions in ferroelastic materials. TEXT (INTRODUCTION)The current interest in adaptable electronics calls for new paradigms of material systems with multiple metastable states. Functional materials with modulated phases 1 bring interesting possibilities in this direction, as long as we are able to tune the stability of these available states.Ferroic materials are good prospective candidates because the modulation can be controlled by external magnetic, electric or stress fields. In magnetic materials, the presence of competing interaction between spins can lead to commensurate or incommensurate modulated structures,
To obtain crystalline thin films of alpha-Quartz represents a challenge due to the tendency for the material towards spherulitic growth. Thus, understanding the mechanisms that give rise to spherulitic growth can help regulate the growth process. Here the spherulitic type of 2D crystal growth in thin amorphous Quartz films was analyzed by electron back-scatter diffraction (EBSD). EBSD was used to measure the size, orientation, and rotation of crystallographic grains in polycrystalline SiO2 and GeO2 thin films with high spatial resolution. Individual spherulitic Quartz crystal colonies contain primary and secondary single crystal fibers, which grow radially from the colony center towards its edge, and fill a near circular crystalline area completely. During their growth, individual fibers form so-called rotational crystals, when some lattice planes are continuously bent. The directions of the lattice rotation axes in the fibers were determined by an enhanced analysis of EBSD data. A possible mechanism, including the generation of the particular type of dislocation(s), is suggested.
Despite its potential for CMOS applications, atomic layer deposition (ALD) of GeO2 thin films, by itself or in combination with SiO2, has not been widely investigated yet. Here, we report the ALD growth of SiO2/GeO2 multilayers on si1icon substrates using a so far unexplored Ge precursor. The characterization of multilayers with various periodicities reveals layer-by-layer growth with electron density contrast and the absence of chemical intermixing, down to a periodicity of two atomic layers.
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