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High-speed electronics require epitaxial films with exceptionally high carrier mobility at room temperature (RT). Alkaline-earth stannates with high RT mobility show outstanding prospects for oxide electronics operating at ambient temperatures. However, despite significant progress over the last few years, mobility in stannate films has been limited by dislocations because of the inability to grow fully coherent films. Here, we demonstrate the growth of coherent, strain-engineered phases of epitaxial SrSnO3 (SSO) films using a radical-based molecular beam epitaxy approach. Compressive strain stabilized the high-symmetry tetragonal phase of SSO at RT, which, in bulk, exists only at temperatures between 1062 and 1295 K. We achieved a mobility enhancement of over 300% in doped films compared with the low-temperature orthorhombic polymorph. Using comprehensive temperature-dependent synchrotron-based X-ray measurements, electronic transport, and first principles calculations, crystal and electronic structures ...

Hydrogenation, an effective way to tune the properties of transition metal oxide (TMO) thin films, has been long awaited to be performed safely and without an external energy input. Recently, metal-acid-TMO has been reported to be an effective approach for hydrogenation, but the requirement of acid limits its application. In this work, the reversible and rapid hydrogen doping of WO

The transformation from crystalline SrIrO3 to active amorphous iridium oxide electrocatalyst occurs via the lattice oxygen redox., The use of renewable electricity to prepare materials and fuels from abundant molecules offers a tantalizing opportunity to address concerns over energy and materials sustainability. The oxygen evolution reaction (OER) is integral to nearly all material and fuel electrosyntheses. However, very little is known about the structural evolution of the OER electrocatalyst, especially the amorphous layer that forms from the crystalline structure. Here, we investigate the interfacial transformation of the SrIrO3 OER electrocatalyst. The SrIrO3 amorphization is initiated by the lattice oxygen redox, a step that allows Sr2+ to diffuse and O2− to reorganize the SrIrO3 structure. This activation turns SrIrO3 into a highly disordered Ir octahedral network with Ir square-planar motif. The final SryIrOx exhibits a greater degree of disorder than IrOx made from other processing methods. Our results demonstrate that the structural reorganization facilitated by coupled ionic diffusions is essential to the disordered structure of the SrIrO3 electrocatalyst.

Engineering magnetic anisotropy in two-dimensional systems has enormous scientific and technological implications. The uniaxial anisotropy universally exhibited by two-dimensional magnets has only two stable spin directions, demanding 180 degrees spin switching between states. We demonstrate a novel eightfold anisotropy in magnetic SrRuO3 monolayers by inducing a spin reorientation in (SrRuO3)1/(SrTiO3)N superlattices, in which the magnetic easy axis of Ru spins is transformed from uniaxial direction (N = 1 and 2) to eightfold directions (N = 3, 4 and 5). This eightfold anisotropy enables 71 and 109 degrees spin switching in SrRuO3 monolayers, analogous to 71 and 109 degrees polarization switching in ferroelectric BiFeO3. First-principle calculations reveal that increasing the SrTiO3 layer thickness induces an emergent correlation-driven orbital ordering, tuning spin-orbit interactions and reorienting the SrRuO3 monolayer easy axis. Our work demonstrates that correlation effects can be exploited to substantially change spin-orbit interactions, stabilizing unprecedented properties in two-dimensional magnets and opening rich opportunities for low-power, multi-state device applications., 15+13 pages, 5+10 figures, including supplementary materials

Heterostructures composed of superconductor and ferroelectrics (SC/FE) are very important for manipulating the superconducting property and applications. However, growth of high-quality superconducting iron chalcogenide films is challenging because of their volatility and FE substrate with rough surface and large lattice mismatch. Here, we report a two-step growth approach to get high-quality FeSe

Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO 3 (Li-SNO) contains a large amount of mobile Li + located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li + conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na + . The results highlight the potential of quantum materials and emergent physics in design of ion conductors.

Memristive devices are an emerging technology that enables both rich interdisciplinary science and novel device functionalities, such as nonvolatile memories and nanoionics-based synaptic electronics. Recent work has shown that the reproducibility and variability of the devices depend sensitively on the defect structures created during electroforming as well as their continued evolution under dynamic electric fields. However, a fundamental principle guiding the material design of defect structures is still lacking due to the difficulty in understanding dynamic defect behavior under different resistance states. Here, we unravel the existence of threshold behavior by studying model, single-crystal devices: resistive switching requires that the pristine oxygen vacancy concentration reside near a critical value. Theoretical calculations show that the threshold oxygen vacancy concentration lies at the boundary for both electronic and atomic phase transitions. Through operando, multimodal X-ray imaging, we show that field tuning of the local oxygen vacancy concentration below or above the threshold value is responsible for switching between different electrical states. These results provide a general strategy for designing functional defect structures around threshold concentrations to create dynamic, field-controlled phases for memristive devices.

The rapid growth of internet based ride-sharing brings great changes to residents' travel and city traffic. However, few studies had employed empirical data to examine the unique travel patterns of internet based ride-sharing trips. In this paper, we compare taxi trip records and internet based ride-sharing trip records provided by DiDi company. Results reveal many interesting findings that had never been reported before. From the viewpoint of service patterns, ride-sharing mainly increases supplies in hot areas and peak hours. By applying a non-negative matrix factorization method, we find that ride-sharing principally serves as an approach for commuting. So, as an effective supplement to traditional taxi service, it regulates spatial and temporal supply-demand imbalance, especially during morning and evening rush periods. From the viewpoint of individual behavior patterns, we use a clustering method to identify two kinds of internet based ride-sharing drivers. The first kind of drivers usually provides ride-sharing along daily home-work commuting. Trips served by these drivers have relatively constant origin-designation (OD) pairs. The second kind of drivers does not serve regularly and roams around the city even in working hours. Therefore, there are no constant OD pairs in their ride-sharing trips. Counterintuitively, we find that home-work commuting drivers account for only a small part of total drivers and they only serve a small number of commuting trips. In addition, internet based ride-sharing is not just traditional hitchhiking worked through mobile internet. We find that internet based ride-sharing drivers intend to make long distance trips, and they intend to detour further to pick up or drop off passengers than traditional hitchhike drivers since they are paid. All these findings are helpful for policy makers at all levels to make informed decisions about deployment of internet based ride-sharing service. This paper also verifies that big data analytics is particularly useful and powerful in the analysis of ride-sharing and taxi service patterns.

Multiferroics with simultaneous electric and magnetic orderings are highly desirable for sensing, actuation, data storage, and bio-inspired systems, yet developing flexible materials with robust multiferroic properties at room temperature is a long-term challenge. Utilizing water-soluble Sr3 Al2 O6 as a sacrificial layer, the authors have successfully self-assembled a freestanding BaTiO3 -CoFe2 O4 heteroepitaxial nanostructure via pulse laser deposition, and confirmed its epitaxial growth in both out-of-plane and in-plane directions, with highly ordered CoFe2 O4 nanopillars embedded in a single crystalline BaTiO3 matrix free of substrate constraint. The freestanding nanostructure enjoys super flexibility and mechanical integrity, not only capable of spontaneously curving into a roll, but can also be bent with a radius as small as 4.23 µm. Moreover, piezoelectricity and ferromagnetism are demonstrated at both microscopic and macroscopic scales, confirming its robust multiferroicity at room temperature. This work establishes an effective route for flexible multiferroic materials, which have the potential for various practical applications.

Antiferroelectric PbZrO3 is being considered for a wide range of applications where the competition between centrosymmetric and noncentrosymmetric phases is important to the response. Here, we focus on the epitaxial growth of PbZrO3 thin films and understanding the chemistry–structure coupling in Pb1+δZrO3 (δ = 0, 0.1, 0.2). High-quality, single-phase Pb1+δZrO3 films are synthesized via pulsed-laser deposition. Although no significant lattice parameter change is observed in X-ray studies, electrical characterization reveals that while the PbZrO3 and Pb1.1ZrO3 heterostructures remain intrinsically antiferroelectric, the Pb1.2ZrO3 heterostructures exhibit a hysteresis loop indicative of ferroelectric response. Further X-ray scattering studies reveal strong quarter-order diffraction peaks in PbZrO3 and Pb1.1ZrO3 heterostructures indicative of antiferroelectricity, while no such peaks are observed for Pb1.2ZrO3 heterostructures. Density functional theory calculations suggest the large cation nonstoichiometry ...

The polarization of $\mathrm{PbZ}{\mathrm{r}}_{0.52}\mathrm{T}{\mathrm{i}}_{0.48}{\mathrm{O}}_{3}$ thin film is switched by changing film thickness through the competition between the strain relaxation-induced flexoelectric fields and the interfacial effects. Without an applied electric field, this reversal of polarization is exploited to control the magnetic properties of $\mathrm{L}{\mathrm{a}}_{0.67}\mathrm{S}{\mathrm{r}}_{0.33}\mathrm{Mn}{\mathrm{O}}_{3}$ by the competition/cooperation between the charge-mediated and the strain-mediated effects. Scanning transmission electron microscopy, polarized near-edge x-ray absorption spectroscopy, and half-integer diffraction measurements are employed to decode the intrinsic magnetoelectric effects in the $\mathrm{L}{\mathrm{a}}_{0.67}\mathrm{S}{\mathrm{r}}_{0.33}\mathrm{Mn}{\mathrm{O}}_{3}/\mathrm{PbZ}{\mathrm{r}}_{0.52}\mathrm{T}{\mathrm{i}}_{0.48}{\mathrm{O}}_{3}$ heterostructures. With $\mathrm{PbZ}{\mathrm{r}}_{0.52}\mathrm{T}{\mathrm{i}}_{0.48}{\mathrm{O}}_{3}$ films $l48\phantom{\rule{0.16em}{0ex}}\mathrm{nm}$, the polarization-driven carrier density modulation around the $\mathrm{L}{\mathrm{a}}_{0.67}\mathrm{S}{\mathrm{r}}_{0.33}\mathrm{Mn}{\mathrm{O}}_{3}/\mathrm{PbZ}{\mathrm{r}}_{0.52}\mathrm{T}{\mathrm{i}}_{0.48}{\mathrm{O}}_{3}$ interface and the strain-mediated Mn $3d$ orbital occupancy work together to enhance the magnetism of 14-unit-cell $\mathrm{L}{\mathrm{a}}_{0.67}\mathrm{S}{\mathrm{r}}_{0.33}\mathrm{Mn}{\mathrm{O}}_{3}$ film; with $\mathrm{PbZ}{\mathrm{r}}_{0.52}\mathrm{T}{\mathrm{i}}_{0.48}{\mathrm{O}}_{3}$ layers $g48\phantom{\rule{0.16em}{0ex}}\mathrm{nm}$, the strain-induced change of bond length/angle of $\mathrm{Mn}{\mathrm{O}}_{6}$ accompanied with a modified spin configuration are responsible for the decrease in the Curie temperature and magnetization of 14-unit-cell $\mathrm{L}{\mathrm{a}}_{0.67}\mathrm{S}{\mathrm{r}}_{0.33}\mathrm{Mn}{\mathrm{O}}_{3}$ film.

Ferroelastic switching in ferroelectric/multiferroic oxides plays a crucial role in determining their dielectric, piezoelectric, and magnetoelectric properties. In thin films of these materials, however, substrate clamping is generally thought to limit the electric-field- or mechanical-force-driven responses to the local scale. Here, we report mechanical-force-induced large-area, non-local, collective ferroelastic domain switching in PbTiO3 epitaxial thin films by tuning the misfit-strain to be near a phase boundary wherein c/a and a1/a2 nanodomains coexist. Phenomenological models suggest that the collective, c-a-c-a ferroelastic switching arises from the small potential barrier between the degenerate domain structures, and the large anisotropy of a and c domains, which collectively generates much larger response and large-area domain propagation. Large-area, non-local response under small stimuli, unlike traditional local response to external field, provides an opportunity of unique response to local stimuli, which has potential for use in high-sensitivity pressure sensors and switches., Clamping effects in ferroelestastic thin films limits their usefulness for applications such as sensitive mechanical sensors. Here, the authors report on non-local mechanical force induced switching in PbTiO3 thin films by tuning the material to a state of nearly energetically degenerate co-existing domains.

This work presents a systematic study of stress and strain of AlxGa1-xN/AlN with composition ranging from GaN to AlN, grown on a c-plane sapphire by metal-organic chemical vapor deposition, using synchrotron radiation high-resolution X-ray diffraction and reciprocal space mapping. The c-plane of the AlxGa1-xN epitaxial layers exhibits compressive strain, while the a-plane exhibits tensile strain. The biaxial stress and strain are found to increase with increasing Al composition, although the lattice mismatch between the AlxGa1-xN and the buffer layer AlN gets smaller. A reduction in the lateral coherence lengths and an increase in the edge and screw dislocations are seen as the AlxGa1-xN composition is varied from GaN to AlN, exhibiting a clear dependence of the crystal properties of AlxGa1-xN on the Al content. The bandgap of the epitaxial layers is slightly lower than predicted value due to a larger tensile strain effect on the a-axis compared to the compressive strain on the c-axis. Raman characteristics of the AlxGa1-xN samples exhibit a shift in the phonon peaks with the Al composition. The effect of strain is also discussed on the optical phonon energies of the epitaxial layers. The techniques discussed here can be used to study other similar materials., 14 pages, 5 figures, 2 tables

Anderson localization in phonon heat conduction is observed in GaAs/AlAs superlattices with ErAs nanodots., Nondiffusive phonon thermal transport, extensively observed in nanostructures, has largely been attributed to classical size effects, ignoring the wave nature of phonons. We report localization behavior in phonon heat conduction due to multiple scattering and interference events of broadband phonons, by measuring the thermal conductivities of GaAs/AlAs superlattices with ErAs nanodots randomly distributed at the interfaces. With an increasing number of superlattice periods, the measured thermal conductivities near room temperature increased and eventually saturated, indicating a transition from ballistic to diffusive transport. In contrast, at cryogenic temperatures the thermal conductivities first increased but then decreased, signaling phonon wave localization, as supported by atomistic Greenșs function simulations. The discovery of phonon localization suggests a new path forward for engineering phonon thermal transport.

High-speed electronics require epitaxial films with exceptionally high carrier mobility at room temperature (RT). Alkaline-earth stannates with high RT mobility show outstanding prospects for oxide electronics operating at ambient temperatures. However, despite significant progress over the last few years, mobility in stannate films has been limited by dislocations because of the inability to grow fully coherent films. Here, we demonstrate the growth of coherent, strain-engineered phases of epitaxial SrSnO

It is a great challenge to maintain thermally stable luminescence of red phosphors in white light-emitting diodes (LEDs), because of the large Stokes shift. For the purpose of overcoming this challenge, this work elucidates the intrinsic mechanism of the thermal quenching luminescence of CaAlSiN3:Eu2+. The empty 5d orbital of Eu2+ is partly filled with electrons upon Eu2+ increasing, as observed using XANES; and the exceptional expansion of the local Eu–N bond length, the ratio of which is far larger than the volume expansion of crystal lattice brought by doping Eu2+, is measured using EXAFS. The shift of Fermi level predicted with the first-principles calculations is confirmed by the valence band spectra. Therefore, the changeable distribution of electrons on the excited substates and then thermal delocalization to the conduction band are the intrinsic mechanisms of thermal quenching luminescence of CaAlSiN3:Eu2+. The results provide a solid basis for exploring the methods to enhance the thermal stable l...

Epitaxial strain can be used to tune the properties of complex oxides with perovskite structure. Beyond just lattice mismatch, the use of octahedral rotation mismatch at heterointerfaces could also provide an effective route to manipulate material properties. Here, we examine the evolution of the structural motif (i.e., lattice parameters, symmetry, and octahedral rotations) of SrRuO3 films grown on substrates engineered to have the same lattice parameters, but different octahedral rotations. SrRuO3 films grown on SrTiO3 (001) (no octahedral rotations) and GdScO3-buffered SrTiO3 (001) (with octahedral rotations) substrates are found to exhibit monoclinic and tetragonal symmetry, respectively. Electrical transport and magnetic measurements reveal that the tetragonal films exhibit higher resistivity, lower magnetic Curie temperatures, and more isotropic magnetism as compared to those with monoclinic structure. Synchrotron-based quantification of the octahedral rotation network reveals that the tilting pattern in both film variants is the same (albeit with slightly different magnitudes of in-plane rotation angles). The abnormal rotation pattern observed in tetragonal SrRuO3 indicates a possible decoupling between the internal octahedral rotation and lattice symmetry, which could provide new opportunities to engineer thin-film structure and properties.

In this letter, a series of vanadium dioxide (VO2) epitaxial films were deliberately deposited on TiO2 substrates with different orientations [(001), (110), and (101)], in an attempt to gain insights into the strained VO2 epitaxial film. We found in-plane [100] and [1-10] directions, obviously anisotropic metal-insulator transition (MIT) in (110)-oriented VO2 films. In combination with synchrotron radiation high-resolution x-ray diffraction characterizations, electronic transport data reveal that the critical temperature of MIT depends on the strain state of the dimeric vanadium atomic chain along the c axis of the rutile phase. The anisotropy of MIT is closely related to the orientation of the VO2 films, which is caused by the varied orientation configuration of V-V atomic chain dimerization in the films. Soft x-ray absorption spectroscopy results further indicate that this anisotropy may be driven by the directional hybridization of O 2p and V 3d orbitals with respect to the orientation of VO2 thin films. The polarization-dependent V L-edge and O K-edge XAS data suggest that the elongation of the apical V-O bond length increases the p-d orbital overlap; thus, the energy level of the d// orbital is raised relative to that of the π* orbital. These anisotropic MIT behaviors will help us to understand how the strain engineering depends on the strain state of vanadium dimers in VO2 films.

Facing the current gaps with regard to the momentum effect in Chinese securities market, a momentum strategy was constructed to compare the securities market price under the effective market theory with under the non-effective market theory by the Hushen 300 index from 2006 to 2015 and a stock price residual measurement model. An important result was that the root cause of the momentum effect was systematic irrational behavior. On this basis, a new momentum strategy was constructed based on RSP (Residual of Stock Price), and the performance of that strategy was tested in different ranking and holding periods. The new momentum strategies were obtained positive average cumulative abnormal returns in the super short-term, short term and medium term. This finding confirmed the significant existence of the momentum effect in China’s stock market and the validity of the RSP momentum strategy. Therefore, this finding can be contributed to effectively addressed the current gaps and examine the applicability of classic asset pricing theory and behavioral finance theory in China's stock market. Finally, after considering the transaction costs, the momentum strategy is effective in both theory and practice.

Solid-oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure-property relationships that would enable the rational design of better materials. Here, using epitaxial thin-film growth, synchrotron radiation, impedance spectroscopy, and density-functional theory, the impact of structural parameters (i.e., unit-cell volume and octahedral rotations) on ionic conductivity is delineated in La0.9 Sr0.1 Ga0.95 Mg0.05 O3- δ . As compared to the zero-strain state, compressive strain reduces the unit-cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit-cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit-cell volumes and octahedral rotations decrease migration barriers and create low-energy migration pathways, respectively. The desired combination of large unit-cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit-cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion-conducting perovskite electrolytes.

The van der Waals (vdW) bond is traditionally believed to be orders of magnitude lower than the typical chemical bond (i.e., ionic, metallic, or covalent), and hence the effects caused by a vdW interface are thought to be trivial. In this paper, by investigating the vdW epitaxial growth of a mechanically soft perovskite on the vdW substrate, we obtained the solid proof of strong non-negligible vdW interaction. The experimental results illustrate the formation of cracks and holes for the relaxation of the vdW strain as well as a lattice-constant-dependent epitaxial angle evolution and a pronounced band-structure change. The first-principles calculations indicate that the contribution of the vdW interaction energy at the epitaxial interface reaches up to more than a quarter of the overall interaction energy far exceeding the traditionally recognized vdW bonding strength. Both the experimental and the theoretical work show that given the appropriate material system, the vdW interaction could be strong enough to significantly manipulate material properties.

Control over the oxygen octahedral framework is widely recognized as key to the design of functional properties in perovskite oxide heterostructures. Although the oxygen octahedral framework can be manipulated during synthesis, the as-grown oxygen octahedra generally remain fixed, preventing the development of adaptive behavior in electronic and ionotronic systems. Here, it is demonstrated that the oxygen octahedral framework can be dynamically and reversibly manipulated by an electric field through the coupling with oxygen vacancies. Studying model WO3 heterostructures during ionic liquid gating with a combination of in situ X-ray scattering and spectroscopy, it is shown that large changes in electronic properties can arise due to the increased flexibility of the octahedral network at high vacancy concentrations. The results describe a generic framework for the construction of dynamic systems and devices with an array of field-tunable properties.

The desire for low-power/voltage operation of devices is driving renewed interest in understanding scaling effects in ferroelectric thin films. As the dimensions of ferroelectrics are reduced, the properties can vary dramatically, including the robust scaling relationship between coercive field ( Ec) and thickness ( d), also referred to as the Janovec-Kay-Dunn (JKD) law, wherein Ec ∝ d-2/3. Here, we report that whereas (001)-oriented heterostructures follow JKD scaling across the thicknesses range of 20-330 nm, (111)-oriented heterostructures of the canonical tetragonal ferroelectric PbZr0.2Ti0.8O3 exhibit a deviation from JKD scaling wherein a smaller scaling exponent for the evolution of Ec is observed in films of thickness ≲ 165 nm. X-ray diffraction reveals that whereas (001)-oriented heterostructures remain tetragonal for all thicknesses, (111)-oriented heterostructures exhibit a transition from tetragonal-to-monoclinic symmetry in films of thickness ≲ 165 nm as a result of the compressive strain. First-principles calculations suggest that this symmetry change contributes to the deviation from the expected scaling, as the monoclinic phase has a lower energy barrier for switching. This structural evolution also gives rise to changes in the c/ a lattice parameter ratio, wherein this ratio increases and decreases in (001)- and (111)-oriented heterostructures, respectively, as the films are made thinner. In (111)-oriented heterostructures, this reduced tetragonality drives a reduction of the remanent polarization and, therefore, a reduction of the domain-wall energy and overall energy barrier to switching, which further exacerbates the deviation from the expected scaling. Overall, this work demonstrates a route toward reducing coercive fields in ferroelectric thin films and provides a possible mechanism to understand the deviation from JKD scaling.

To investigate the epitaxial strain effect on local electronic structure of FeO6octahedron of BiFeO3epitaxial film, polarization-dependent FeL23-edge x-ray absorption spectroscopy studies were performed on both tetragonal (T)-like BFO/LAO and rhombohedral (R)-like BFO/STO epitaxial films. Charge transfer multiplet theory based fittings were also performed to reveal the local electronic structure difference. Due to dramatic structural difference caused by epitaxial strain between these two samples, significant electronic structure differences were observed between these two specimens. For BFO/LAO, anisotropic electronic structure appears in vertically-elongated FeO6octahedron and an additional shift of Fe ion off the central position is suggested. For BFO/STO, electronic structure is almost isotropic.

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>3/SrTiO>3 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>1/a>2 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., A.R.D. acknowledges support from the Army Research Office under grant W911NF-14-1-0104 and the Department of Energy, Office of Science, Office of Basic Energy Sciences under grant no. DE-SC0012375 for synthesis and structural study of the materials. Z.H. acknowledges support from NSF-MRSEC grant number DMR-1420620 and NSF-MWN grant number DMR-1210588. A.K.Y. acknowledges support from the Office of Basic Energy Sciences, US Department of Energy DE-AC02-05CH11231. C.T.N. acknowledge support from the Office of Basic Energy Sciences, US Department of Energy DE-AC02-05CH11231. S.L.H. acknowledges support from the National Science Foundation under the MRSEC programme (DMR-1420620). M.R.M. acknowledges support from the National Science Foundation Graduate Research Fellowship under grant number DGE-1106400. K.-D.P., V.K. and M.B.R. acknowledge support from the US Department of Energy, Office of Basic Sciences, Division of Material Sciences and Engineering, under Award No. DE-SC0008807. A.F. acknowledges support from the Swiss National Science Foundation. P.G.-F. and J.J. acknowledge financial support from the Spanish Ministry of Economy and Competitiveness through grant number FIS2015-64886-C5-2-P. J.I. is supported by the Luxembourg National Research Fund (Grant FNR/C15/MS/10458889 NEWALLS). L.-Q.C. is supported by the US Department of Energy, Office of Basic Energy Sciences under Award FG02-07ER46417. R.R. and L.W.M. acknowledge support from the Gordon and Betty Moore Foundation’s EPiQS Initiative, under grant GBMF5307. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-C02-05CH11231. Nanodiffraction measurements were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Electron microscopy of superlattice structures was performed at the Molecular Foundry at Lawrence Berkeley National Laboratory, supported by the Office of Science, Office of Basic Energy Sciences, US Department of Energy (DE-AC02-05CH11231).

Ferroelectric-dielectric superlattices consisting of alternating layers of ferroelectric ${\mathrm{PbTiO}}_{3}$ and dielectric ${\mathrm{SrTiO}}_{3}$ exhibit a disordered striped nanodomain pattern, with characteristic length scales of 6 nm for the domain periodicity and 30 nm for the in-plane coherence of the domain pattern. Spatial disorder in the domain pattern gives rise to coherent hard $x$-ray scattering patterns exhibiting intensity speckles. We show here using variable-temperature Bragg-geometry $x$-ray photon correlation spectroscopy that $x$-ray scattering patterns from the disordered domains exhibit a continuous temporal decorrelation due to spontaneous domain fluctuations. The temporal decorrelation can be described using a compressed exponential function, consistent with what has been observed in other systems with arrested dynamics. The fluctuation speeds up at higher temperatures and the thermal activation energy estimated from the Arrhenius model is $0.35\ifmmode\pm\else\textpm\fi{}0.21\text{ }\text{ }\mathrm{eV}$. The magnitude of the energy barrier implies that the complicated energy landscape of the domain structures is induced by pinning mechanisms and domain patterns fluctuate via the generation and annihilation of topological defects similar to soft materials such as block copolymers.

Functional oxide superlattices offer new and exciting possibilities for the exploration of emergent properties at the nanoscale. While the behavior of La1−xSrxFeO3 films has been extensively investigated at low temperatures, few studies have been carried out at high temperatures, particularly for LaFeO3/SrFeO3 superlattice systems. Here, we investigate the transport behavior and optical properties of (LaFeO3)n/(SrFeO3)1 superlattices at 373 K and above. Using optical spectroscopy, we observe a low energy excitation at ∼1 eV, attributable to charge transfer between the O 2p and Fe 3d states of the δ-doped single SrFeO3 layer. From in-plane conductivity measurements on the superlattices, we determine activation energies that are much lower than those of alloyed samples and vary with the total number of SrFeO3 layers. This suggests that polaronic transport is confined near the SrFeO3 regions, permitting mobilities significantly enhanced over those in alloyed thin films.

We investigated the microstructure of PbTiO3 films epitaxially grown on DyScO3 (110) substrates using synchrotron-based 3D reciprocal space mapping and X-ray reflection interface microscopy. The results show that an in-plane anisotropic mixture domain state (a* + a/c) exists in the PbTiO3 films, where a* domains reside between a/c twin stripe domains. Furthermore, when compared with traditional a domains in a/c twins, the a* domain is found to possess a similar in-plane lattice parameter but a much smaller out-of-plane lattice (∼0.5%). We also discovered a temperature-driven transition between a* and a/c pointing to potential applications in functional devices due to the huge mechanical response (4.85%) and polarization rotation between the a* and c domains.We investigated the microstructure of PbTiO3 films epitaxially grown on DyScO3 (110) substrates using synchrotron-based 3D reciprocal space mapping and X-ray reflection interface microscopy. The results show that an in-plane anisotropic mixture domain state (a* + a/c) exists in the PbTiO3 films, where a* domains reside between a/c twin stripe domains. Furthermore, when compared with traditional a domains in a/c twins, the a* domain is found to possess a similar in-plane lattice parameter but a much smaller out-of-plane lattice (∼0.5%). We also discovered a temperature-driven transition between a* and a/c pointing to potential applications in functional devices due to the huge mechanical response (4.85%) and polarization rotation between the a* and c domains.

Understanding and controlling the domain evolution under external stimuli in multiferroic thin films is critical to realizing nanoelectronic devices, including for non-volatile memory, data storage, sensors, and optoelectronics. In this article, we studied the shear-strain effect on the domain evolution with temperature in highly strained BiFeO3 thin films on rhombohedral LaAlO3 substrates using a high-resolution synchrotron X-ray diffraction three dimensional-reciprocal space mapping (3D-RSM) technique. The results revealed significant biaxial, anisotropic, evolution behaviors of the mixed-phase (MC + R′/T′ phases) BiFeO3 ferroelectric domains along the in-plane [100] and [010] axes. These biaxial, anisotropic, evolution behaviors were attributed to the shear-strain-modulated transition pathways of the mixed-phase ferroelectric domains. This viewpoint was further verified in the BiFeO3/LaSrAlO4 (001) system in which no anisotropic evolution behaviors of the mixed-phase domains were found. This work sheds light on the quantitative analysis of domain evolution in multi-domain systems and demonstrates that the shear-strain effect could act as an effective tool to manipulate the domain behavior and control novel functionalities of ferroelectric thin films.

Perovskite oxide superlattices are of particular interest due to novel phenomena emerging at interfaces which are beyond the bulk properties of the constituent layers. However, building perovskite superlattices comprised of stoichiometric layers with sharp interfaces has proven challenging. Here, the synthesis of a series of high quality (SrTiO3)n/(CaTiO3)n superlattice structures grown on LSAT substrates is demonstrated by employing hybrid molecular beam epitaxy, where Ti was supplied using metal-organic titanium tetraisopropoxide (TTIP), and Sr and Ca were supplied using conventional effusion cells. By careful adjustment of the cation fluxes of Sr and Ca with respect to the TTIP flux, the growth windows of SrTiO3 and CaTiO3 were overlapped, allowing us to grow the individual superlattice layers with self-regulated stoichiometry. Stable and repeatable reflection high-energy electron diffraction oscillations during the entire ∼2.5 h growth period indicated good source flux stability. The structural quality of the superlattice films were determined by scanning transmission electron microscopy and synchrotron-based X-ray diffraction, revealing periodic, phase pure, homogenous superlattice structures with abrupt interfaces. Utilization of perovskite stoichiometric growth windows offers great potential for accessing and realizing interface driven phenomena in versatile perovskite superlattice materials with chemistries beyond titanates.

Ferroelectric-dielectric superlattices consisting of alternating layers of ferroelectric PbTiO_{3} and dielectric SrTiO_{3} exhibit a disordered striped nanodomain pattern, with characteristic length scales of 6 nm for the domain periodicity and 30 nm for the in-plane coherence of the domain pattern. Spatial disorder in the domain pattern gives rise to coherent hard x-ray scattering patterns exhibiting intensity speckles. We show here using variable-temperature Bragg-geometry x-ray photon correlation spectroscopy that x-ray scattering patterns from the disordered domains exhibit a continuous temporal decorrelation due to spontaneous domain fluctuations. The temporal decorrelation can be described using a compressed exponential function, consistent with what has been observed in other systems with arrested dynamics. The fluctuation speeds up at higher temperatures and the thermal activation energy estimated from the Arrhenius model is 0.35±0.21 eV. The magnitude of the energy barrier implies that the complicated energy landscape of the domain structures is induced by pinning mechanisms and domain patterns fluctuate via the generation and annihilation of topological defects similar to soft materials such as block copolymers.

The records generated by taxicabs which are equipped with GPS devices is of vital importance for studying human mobility behavior, however we are focusing on taxi drivers' operation patterns in this paper. We identify a group of valuable characteristics, which are simple but effective, through large scale drivers' behavior in a complex metropolis environment. Based on the daily operations of 31,000 taxi drivers in New York City which covers over 14 million of trip records during Jan 1 to Jan 31 in 2013, we classify drivers into top, ordinary and low income groups according to monthly working load, daily income and daily ranking. Then, we apply big data analysis and visualization methods to compare the different characteristics among top, ordinary and low income drivers in selecting of working time, working area as well as driving routes. The results verify that top drivers do have special operation tactics to help themselves serve more passengers, travel faster thus make more money per unit time. This research provides new possibilities for fully utilizing the information obtained from urban taxicab data for estimating human behavior, which is not only very useful for individual taxicab driver but also to those policy-makers in city authorities.

Mechanism of metal-insulator transition (MIT) in strained VO2 thin films is very complicated and incompletely understood despite three scenarios with potential explanations including electronic correlation (Mott mechanism), structural transformation (Peierls theory) and collaborative Mott-Peierls transition. Herein, we have decoupled coactions of structural and electronic phase transitions across the MIT by implementing epitaxial strain on 13-nm-thick (001)-VO2 films in comparison to thicker films. The structural evolution during MIT characterized by temperature-dependent synchrotron radiation high-resolution X-ray diffraction reciprocal space mapping and Raman spectroscopy suggested that the structural phase transition in the temperature range of vicinity of the MIT is suppressed by epitaxial strain. Furthermore, temperature-dependent Ultraviolet Photoelectron Spectroscopy (UPS) revealed the changes in electron occupancy near the Fermi energy EF of V 3d orbital, implying that the electronic transition triggers the MIT in the strained films. Thus the MIT in the bi-axially strained VO2 thin films should be only driven by electronic transition without assistance of structural phase transition. Density functional theoretical calculations further confirmed that the tetragonal phase across the MIT can be both in insulating and metallic states in the strained (001)-VO2/TiO2 thin films. This work offers a better understanding of the mechanism of MIT in the strained VO2 films.

Instability of emerging perovskite organometallic halide in humidity environment is the biggest obstacle for its potential applications in solar energy harvest and electroluminescent display. Understanding the detailed decay mechanism of these materials in moisture is a critical step towards the final appropriate solutions. As a model study presented in this work, in situ synchrotron radiation x-ray diffraction was combined with microscopy and gravimetric analysis to study the degradation process of CH3NH3PbI3 in moisture and the results reveal that: 1) intermediate monohydrated CH3NH3PbI3·H2O is detected in the degradation process of CH3NH3PbI3 and the final decomposition products are PbI2 and aqueous CH3NH3I; 2) the aqueous CH3NH3I could hardly further decompose into volatile CH3NH2, HI or I2; 3) the moisture disintegrate CH3NH3PbI3 and then alter the distribution of the decomposition products, which leads to an incompletely-reversible reaction of CH3NH3PbI3 hydrolysis and degrades the photoelectric properties. These findings further elucidate the picture of hydrolysis process of perovskite organometallic halide in humidity environment.

The photophysical and photochemical properties of hypocrellins (HA and HB) are examined with two-photon excitations at 800 nm using femtosecond pulses from a Ti:sapphire laser. The two-photon excited fluorescence spectra of HA and HB are very similar to those obtained by one-photon excitation, which may indicate that the two-photon induced photodynamic processes of hypocrellins are similar to one-photon induced photodynamic processes. The two-photon excitation cross sections of HA and HB are measured at 800 nm as about 34.8×10 −50 cm 4 s/photon and 21.3×10 −50 cm 4 s/photon, respectively. The large two-photon cross sections of both HA and HB, suggest that the hypocrellins can be potential two-photon phototherapeutic agents. As an example for two-photon photodynamic therapy of hypocrellins, we also further examine the cell-damaging effects of HA upon two-photon illumination. Our preliminary results of cell viability test indicate hypocrellins can effectively damage the Hela cells under two-photon illumination.

The crystalline phases and domain configuration in the morphotropic phase boundary composition Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 (PMN-0.34PT) single crystal have been investigated by synchrotron-based X-ray 3D Reciprocal Space Mapping (3D-RSM) and Piezoresponse Force Microscopy. The coexistence of tetragonal (T) and monoclinic MC phases in this PMN-0.34PT single crystal is confirmed. The affiliation of each diffraction spot in the 3D-RSM was identified with the assistance of qualitative simulation. Most importantly, the twinning structure between different domains in such a mixed phase PMN-PT crystal is firmly clarified, and the spatial distribution of different twin domains is demonstrated. In addition, the lattice parameters of T and MC phases in PMN-0.34PT single crystal as well as the tilting angles of crystal lattices caused by the interfacial lattice mismatch are determined.

A controllable metal-insulator transition (MIT) of VO2 has been highly desired due to its huge potential applications in memory storage, smart windows or optical switching devices. Recently, interfacial strain engineering has been recognized as an effective approach to tuning the MIT of epitaxial VO2 films. However, the strain-involved structural evolution during the MIT process is still not clear, which prevents comprehensively understanding and utilizing interfacial strain engineering in VO2 films. In this work, we have systematically studied the epitaxial VO2 thick films grown on TiO2 (001) single crystal substrate and the structural transition at the boundary of MIT region. By using in situ temperature-dependent high-resolution x-ray diffractions, a tetragonal-like ('T-like') to 'rutile' structural phase transition is identified during the MIT process. The room-temperature crystal phase of epitaxial VO2/TiO2 (001) thick film is clarified to be tetragonal-like, neither strained-rutile phase nor monoclinic phase. The calculated atomic structure of this T-like phase VO2 resembles that of the M1 phase VO2, which has been verified by their similar Raman spectra. More, the crystal lattices of the coexisted phases in the MIT region were revealed in detail. The current findings will not only show some clues on the MIT mechanism study from the structural point of view, but also favor the interface engineering assisted VO2-based devices and applications in the future.

We studied using organic liquids (cyclohexane, n-butanol, and ethylene glycol) to modulate the transport properties at room temperature of an epitaxial VO2 film on a VO2/Al2O3 heterostructure. The resistance of the VO2 film increased when coated with cyclohexane or n-butanol, with maximum changes of 31% and 3.8%, respectively. In contrast, it decreased when coated with ethylene glycol, with a maximum change of −7.7%. In all cases, the resistance recovered to its original value after removing the organic liquid. This organic-liquid-induced reversible resistance switching suggests that VO2 films can be used as organic molecular sensors.

Electric-field control of non-volatile magnetization switching in the absence of external-magnetic-field bias has been investigated in multiferroic Co40Fe40B20/0.7Pb(Mg1/3Nb2/3)-0.3PbTiO3 (CoFeB/PMN-0.3PT) heterostructure at room temperature. The two non-volatile magnetic states are achieved without magnetic-field bias and can be switched in a reversible and reproducible manner by an electric field. These results are attributed to the modulation of the magnetic anisotropy of the CoFeB layer by as-grown magnetic field and electric-field?induced non-volatile strain through unipolar-electric-field cycling. High-resolution X-ray diffraction studies on the (022) peaks under in situ electric field indicate that the non-volatile strain is closely related to the 71? ferroelastic domain switching ( to ) of the PMN-0.3PT substrate. The corresponding ratio of the ferroelastic domain is electrically changed by 14.1% between the two non-volatile magnetic states. Our results provide a promising path to non-magnetically operating magnetic bits by pure electric field at room temperature.