The complex interplay of spin, charge, orbital and lattice degrees of freedom provides a plethora of exotic phases and physical phenomena. In recent years, complex spin topologies have emerged as a ...consequence of the electronic band structure and the interplay between spin and spin-orbit coupling in materials. Here we produce complex topologies of electrical polarization--namely, nanometre-scale vortex-antivortex (that is, clockwise-anticlockwise) arrays that are reminiscent of rotational spin topologies--by making use of the competition between charge, orbital and lattice degrees of freedom in superlattices of alternating lead titanate and strontium titanate layers. Atomic-scale mapping of the polar atomic displacements by scanning transmission electron microscopy reveals the presence of long-range ordered vortex-antivortex arrays that exhibit nearly continuous polarization rotation. Phase-field modelling confirms that the vortex array is the low-energy state for a range of superlattice periods. Within this range, the large gradient energy from the vortex structure is counterbalanced by the corresponding large reduction in overall electrostatic energy (which would otherwise arise from polar discontinuities at the lead titanate/strontium titanate interfaces) and the elastic energy associated with epitaxial constraints and domain formation. These observations have implications for the creation of new states of matter (such as dipolar skyrmions, hedgehog states) and associated phenomena in ferroic materials, such as electrically controllable chirality.
Systems that exhibit phase competition, order parameter coexistence, and emergent order parameter topologies constitute a major part of modern condensed-matter physics. Here, by applying a range of ...characterization techniques, and simulations, we observe that in PbTiO
/SrTiO
superlattices all of these effects can be found. By exploring superlattice period-, temperature- and field-dependent evolution of these structures, we observe several new features. First, it is possible to engineer phase coexistence mediated by a first-order phase transition between an emergent, low-temperature vortex phase with electric toroidal order and a high-temperature ferroelectric a
/a
phase. At room temperature, the coexisting vortex and ferroelectric phases form a mesoscale, fibre-textured hierarchical superstructure. The vortex phase possesses an axial polarization, set by the net polarization of the surrounding ferroelectric domains, such that it possesses a multi-order-parameter state and belongs to a class of gyrotropic electrotoroidal compounds. Finally, application of electric fields to this mixed-phase system permits interconversion between the vortex and the ferroelectric phases concomitant with order-of-magnitude changes in piezoelectric and nonlinear optical responses. Our findings suggest new cross-coupled functionalities.
Domains and domain walls are critical in determining the response of ferroelectrics, and the ability to controllably create, annihilate, or move domains is essential to enable a range of ...next-generation devices. Whereas electric-field control has been demonstrated for ferroelectric 180° domain walls, similar control of ferroelastic domains has not been achieved. Here, using controlled composition and strain gradients, we demonstrate deterministic control of ferroelastic domains that are rendered highly mobile in a controlled and reversible manner. Through a combination of thin-film growth, transmission-electron-microscopy-based nanobeam diffraction and nanoscale band-excitation switching spectroscopy, we show that strain gradients in compositionally graded PbZr1-xTixO3 heterostructures stabilize needle-like ferroelastic domains that terminate inside the film. These needle-like domains are highly labile in the out-of-plane direction under applied electric fields, producing a locally enhanced piezoresponse. This work demonstrates the efficacy of novel modes of epitaxy in providing new modalities of domain engineering and potential for as-yet-unrealized nanoscale functional devices.
Flexoelectricity refers to electric polarization generated by heterogeneous mechanical strains, namely strain gradients, in materials of arbitrary crystal symmetries. Despite more than 50 years of ...work on this effect, an accurate identification of its coupling strength remains an experimental challenge for most materials, which impedes its wide recognition. Here, we show the presence of flexoelectricity in the recently discovered polar vortices in PbTiO3/SrTiO3 superlattices based on a combination of machine-learning analysis of the atomic-scale electron microscopy imaging data and phenomenological phase-field modeling. By scrutinizing the influence of flexocoupling on the global vortex structure, we match theory and experiment using computer vision methodologies to determine the flexoelectric coefficients for PbTiO3 and SrTiO3. Our findings highlight the inherent, nontrivial role of flexoelectricity in the generation of emergent complex polarization morphologies and demonstrate a viable approach to delineating this effect, conducive to the deeper exploration of both topics.
Stimulation with ultrafast light pulses can realize and manipulate states of matter with emergent structural, electronic and magnetic phenomena. However, these non-equilibrium phases are often ...transient and the challenge is to stabilize them as persistent states. Here, we show that atomic-scale PbTiO
/SrTiO
superlattices, counterpoising strain and polarization states in alternate layers, are converted by sub-picosecond optical pulses to a supercrystal phase. This phase persists indefinitely under ambient conditions, has not been created via equilibrium routes, and can be erased by heating. X-ray scattering and microscopy show this unusual phase consists of a coherent three-dimensional structure with polar, strain and charge-ordering periodicities of up to 30 nm. By adjusting only dielectric properties, the phase-field model describes this emergent phase as a photo-induced charge-stabilized supercrystal formed from a two-phase equilibrium state. Our results demonstrate opportunities for light-activated pathways to thermally inaccessible and emergent metastable states.
We report dramatic variations in cation stoichiometry in SrTiO3 thin films grown via pulsed laser deposition and the implications of this nonstoichiometry for structural, dielectric, and thermal ...properties. The chemical composition of SrTiO3 thin films was characterized via X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry. These studies reveal that deviations in laser fluence and deposition geometry can result in deviations of cation stoichiometry as large as a few percent. Additionally, X-ray diffraction was used to probe structural evolution and revealed an asymmetric strain relaxation mechanism in which films possessing Sr-excess undergo relaxation before those possessing Sr-deficiency. Furthermore, the dielectric constant decreases and the loss tangent increases with increasing nonstoichiometry with intriguing differences between Sr-excess and -deficiency. Thermal conductivity is also found to be sensitive to nonstoichiometry, with Sr-excess and -deficiency resulting in 65% and 35% reduction in thermal conductivity, respectively. These trends are explained by the expected defect structures.
We demonstrate a link between the growth process, the stoichiometry of LaAlO(3), and the interfacial electrical properties of LaAlO(3)/SrTiO(3) heterointerfaces. Varying the relative La:Al cation ...stoichiometry by a few atomic percent in films grown at 1×10(-3) Torr results in a 2 and 7 order-of-magnitude change in the 300 and 2 K sheet resistance, respectively, with highly conducting states occurring only in La-deficient or Al-excess films. Further reducing the growth pressure results in an increase of the carrier density and a dramatic change in mobility. We discuss the relative contributions of intrinsic and extrinsic effects in controlling the physical properties of this widely studied system.
► We developed a method by which ferroelectric domains can be imaged in situ in real time. ► We examine effects of changing applied electric field on ferroelectric domain behavior. ► Quantitative ...domain kinetics information provides a view of device performance. ► Imaging domain dynamics provides new insight on device limitations in varying electric field.
In situ Transmission Electron Microscopy (TEM) techniques can potentially fill in gaps in the current understanding interfacial phenomena in complex oxides. Select multiferroic oxide materials, such as BiFeO3 (BFO), exhibit ferroelectric and magnetic order, and the two order parameters are coupled through a quantum–mechanical exchange interaction. The magneto-electric coupling in BFO allows control of the ferroelectric and magnetic domain structures via applied electric fields. Because of these unique properties, BFO and other magneto-electric multiferroics constitute a promising class of materials for incorporation into devices such as high-density ferroelectric and magnetoresistive memories, spin valves, and magnetic field sensors. The magneto-electric coupling in BFO is mediated by volatile ferroelastically switched domains that make it difficult to incorporate this material into devices.
To facilitate device integration, an understanding of the microstructural factors that affect ferroelastic relaxation and ferroelectric domain switching must be developed. In this article, a method of viewing ferroelectric (and ferroelastic) domain dynamics using in situ biasing in TEM is presented. The evolution of ferroelastically switched ferroelectric domains in BFO thin films during many switching cycles is investigated. Evidence of partial domain nucleation, propagation, and switching even at applied electric fields below the estimated coercive field is revealed. Our observations indicate that the occurrence of ferroelastic relaxation in switched domains and the stability of these domains is influenced the applied field as well as the BFO microstructure. These biasing experiments provide a real time view of the complex dynamics of domain switching and complement scanning probe techniques. Quantitative information about domain switching under bias in ferroelectric and multiferroic materials can be extracted from in situ TEM to provide a predictive tool for future device development.
Summary
Background
In both acute graft‐versus‐host disease (GVHD) and lupus erythematosus (LE), the patient's own tissues are subjected to immunological assault via complex mechanisms influenced by ...interferon (IFN) and other cytokines. Although not typically confused clinically, these entities have overlapping histopathological findings in the skin.
Aim
To assess whether GVHD can be differentiated from LE using molecular methods on skin specimens.
Methods
We developed a quantitative reverse transcription PCR assay based on previously identified tissue‐based biomarkers of cutaneous GVHD, and compared gene expression in GVHD with that in LE.
Results
Both entities showed robust expression of IFN‐induced genes and of genes encoding proteins involved in antigen presentation, cell signalling and tissue repair. Levels of gene expression differed significantly in GVHD compared with LE, particularly those of IFN‐induced genes such as MX1, OAS3, TAP1 and STAT3 (P < 0.01). Three logistic regression models could differentiate the two entities with a high degree of certainty (receiver operating characteristic area under the curve of 1.0).
Conclusion
The study demonstrates the feasibility of distinguishing between microscopically similar inflammatory dermatoses using tissue‐based molecular techniques.
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