Flexoelectric Domain Walls Originated from Structural Phase Transition in Epitaxial BiVO4 Films.

Polar domain walls in centrosymmetric ferroelastics induce inhomogeneity that is the origin of advantageous multifunctionality. In particular, polar domain walls promote charge-carrier separation and hence are promising for energy conversion applications that overcome the hurdles of the rate-limiting step in the traditional photoelectrochemical water splitting processes. Yet, while macroscopic studies investigate the materials at the device scale, the origin of this phenomenon in general and the emergence of polar domain walls during the structural phase transition in particular has remained elusive, encumbering the development of this attractive system. Here, it is demonstrated that twin domain walls arise in centrosymmetric BiVO4 films and they exhibit localized piezoelectricity. It is also shown that during the structural phase transition from the tetragonal to monoclinic, the symmetry reduction is accompanied by an emergence of strain gradient, giving rise to flexoelectric effect and the polar domain walls. These results not only expose the emergence of polar domain walls at centrosymmetric systems by means of direct observation, but they also expand the realm of potential application of ferroelastics, especially in photoelectrochemistry and local piezoelectricity.

Strain engineering of optical properties in transparent VO2/muscovite heterostructures.

Transparent VO2/muscovite heterostructures have attracted considerable attention because of their unique chemical and physical properties and potential practical applications. In this paper, we investigated the influence of uniaxial mechanical strain on the optical properties of VO2/muscovite heterostructures through Raman scattering and optical transmittance measurements. Under applied strain, linear shifts in peak positions of Raman-active phonon modes at approximately 340, 309, and 391 cm-1 were observed. The extracted Grüneisen parameter values were approximately between 0.44 and 0.57. Furthermore, a pronounced strain-induced change in the metal-insulator transition (MIT) temperature was observed, which decreased under compressive strain and increased under tensile strain. The rates of MIT temperature variation reached 4.5 °C per % and 7.1 °C per % at a wavelength of 1200 nm during heating and cooling processes, respectively. These results demonstrate that the modulation of the optical properties of VO2/muscovite heterostructures is controllable and reversible through strain engineering, opening up new opportunities for applications in flexible and tunable photonic devices.

Transparent Flexible Heteroepitaxy of NiO Coated AZO Nanorods Arrays on Muscovites for Enhanced Energy Storage Application.

Transparent flexible energy storage devices are considered as important chains in the next-generation, which are able to store and supply energy for electronic devices. Here, aluminum-doped zinc oxide (AZO) nanorods (NRs) and nickel oxide (NiO)-coated AZO NRs on muscovites are fabricated by a radio frequency (RF) magnetron sputtering deposition method. Interestingly, AZO NRs and AZO/NiO NRs are excellent electrodes for energy storage application with high optical transparency, high conductivity, large surface area, stability under compressive and tensile strain down to a bending radius of 5 mm with 1000 bending cycles. The obtained symmetric solid-state supercapacitors based on these electrodes exhibit good performance with a large areal specific capacitance of 3.4 mF cm-2 , long cycle life 1000 times, robust mechanical properties, and high chemical stability. Furthermore, an AZO/NiO//Zn battery based on these electrodes is demonstrated, yielding a discharge capacity of 195 mAh g-1 at a current rate of 8 A g-1 and a discharge capacity of over 1000 cycles with coulombic efficiency to 92%. These results deliver a concept of opening a new opportunity for future applications in transparent flexible energy storage.

Deterministic optical control of room temperature multiferroicity in BiFeO3 thin films.

Controlling ferroic orders (ferroelectricity, ferromagnetism and ferroelasticity) by optical methods is a significant challenge due to the large mismatch in energy scales between the order parameter coupling strengths and the incident photons. Here, we demonstrate an approach to manipulate multiple ferroic orders in an epitaxial mixed-phase BiFeO3 thin film at ambient temperature via laser illumination. Phase-field simulations indicate that a light-driven flexoelectric effect allows the targeted formation of ordered domains. We also achieved precise sequential laser writing and erasure of different domain patterns, which demonstrates a deterministic optical control of multiferroicity at room temperature. As ferroic orders directly influence susceptibility and conductivity in complex materials, our results not only shed light on the optical control of multiple functionalities, but also suggest possible developments for optoelectronics and related applications.

Nondestructive Mapping of Long-Range Dislocation Strain Fields in an Epitaxial Complex Metal Oxide.

The misfit dislocations formed at heteroepitaxial interfaces create long-ranging strain fields in addition to the epitaxial strain. For systems with strong lattice coupling, such as ferroic oxides, this results in unpredictable and potentially debilitating functionality and device performance. In this work, we use dark-field X-ray microscopy to map the lattice distortions around misfit dislocations in an epitaxial film of bismuth ferrite (BiFeO3), a well-known multiferroic. We demonstrate the ability to precisely quantify weak, long-ranging strain fields and their associated symmetry lowering without modifying the mechanical state of the film. We isolate the screw and edge components of the individual dislocations and show how they result in weak charge heterogeneities via flexoelectric coupling. We show that even systems with small lattice mismatches and additional mechanisms of stress relief (such as mechanical twinning) may still give rise to measurable charge and strain heterogeneities that extend over mesoscopic length scales. This sets more stringent physical limitations on device size, dislocation density, and the achievable degree of lattice mismatch in epitaxial systems.

Ultrafast Giant Photostriction of Epitaxial Strontium Iridate Film with Superior Endurance.

Photostriction, optical stimulus driven mechanical deformation in materials, provides a solution toward next-generation technology. Here, the giant photostriction (∼2% change of lattice) of epitaxial strontium iridate (SrIrO3) films under illumination at room temperature is revealed via power-dependent Raman scattering, which is significantly larger as compared to conventional inorganic materials. The time scale and mechanism of this giant photostriction in SrIrO3 are further studied through time-resolved transient reflectivity measurements. The main mechanism is determined to be the electron-phonon coupling. In addition, we find that such an exotic behavior happens within few picoseconds and remains up to 107 cyclic on/off operations. The observation of giant photostriction in SrIrO3 films with superior endurance promises the advance of shape responsive solids that are sensitive to environmental stimuli, which could be widely utilized for multifunctional optoelectronics and optomechanical devices.

Depth-dependent atomic valence determination by synchrotron techniques.

The properties of many materials can be strongly affected by the atomic valence of the contained individual elements, which may vary at surfaces and other interfaces. These variations can have a critical impact on material performance in applications. A non-destructive method for the determination of layer-by-layer atomic valence as a function of material thickness is presented for La0.7Sr0.3MnO3 (LSMO) thin films. The method utilizes a combination of bulk- and surface-sensitive X-ray absorption spectroscopy (XAS) detection modes; here, the modes are fluorescence yield and surface-sensitive total electron yield. The weighted-average Mn atomic valence as measured from the two modes are simultaneously fitted using a model for the layer-by-layer variation of valence based on theoretical model Hamiltonian calculations. Using this model, the Mn valence profile in LSMO thin film is extracted and the valence within each layer is determined to within an uncertainty of a few percent. The approach presented here could be used to study the layer-dependent valence in other systems or extended to different properties of materials such as magnetism.

Atomic-Scale Mechanisms of Defect-Induced Retention Failure in Ferroelectrics.

The ability to switch the ferroelectric polarization using an electric field makes ferroelectrics attractive for application in nanodevices such as high-density memories. One of the major challenges impeding this application, however, has been known as "retention failure", which is a spontaneous process of polarization back-switching that can lead to data loss. This process is generally thought to be caused by the domain instability arising from interface boundary conditions and countered by defects, which can pin the domain wall and impede the back-switching. Here, using in situ transmission electron microscopy and atomic-scale scanning transmission electron microscopy, we show that the polarization retention failure can be induced by commonly observed nanoscale impurity defects in BiFeO3 thin films. The interaction between polarization and the defects can also lead to the stabilization of novel functional nanodomains with mixed-phase structures and head-to-head polarization configurations. Thus, defect engineering provides a new route for tuning properties of ferroelectric nanosystems.

A Strain-Driven Antiferroelectric-to-Ferroelectric Phase Transition in La-Doped BiFeO3 Thin Films on Si.

A strain-driven orthorhombic (O) to rhombohedral (R) phase transition is reported in La-doped BiFeO3 thin films on silicon substrates. Biaxial compressive epitaxial strain is found to stabilize the rhombohedral phase at La concentrations beyond the morphotropic phase boundary (MPB). By tailoring the residual strain with film thickness, we demonstrate a mixed O/R phase structure consisting of O phase domains measuring tens of nanometers wide within a predominant R phase matrix. A combination of piezoresponse force microscopy (PFM), transmission electron microscopy (TEM), polarization-electric field hysteresis loop (P-E loop), and polarization maps reveal that the O-R structural change is an antiferroelectric to ferroelectric (AFE-FE) phase transition. Using scanning transmission electron microscopy (STEM), an atomically sharp O/R MPB is observed. Moreover, X-ray absorption spectra (XAS) and X-ray linear dichroism (XLD) measurements reveal a change in the antiferromagnetic axis orientation from out of plane (R-phase) to in plane (O-phase). These findings provide direct evidence of spin-charge-lattice coupling in La-doped BiFeO3 thin films. Furthermore, this study opens a new pathway to drive the AFE-FE O-R phase transition and provides a route to study the O/R MPB in these films.

Strain Coupling of Conversion-type Fe3 O4 Thin Films for Lithium Ion Batteries.

Lithiation/delithiation induces significant stresses and strains into the electrodes for lithium ion batteries, which can severely degrade their cycling performance. Moreover, this electrochemically induced strain can interact with the local strain existing at solid-solid interfaces. It is not clear how this interaction affects the lithiation mechanism. The effect of this coupling on the lithiation kinetics in epitaxial Fe3 O4 thin film on a Nb-doped SrTiO3 substrate is investigated. In situ and ex situ transmission electron microscopy (TEM) results show that the lithiation is suppressed by the compressive interfacial strain. At the interface between the film and substrate, the existence of Lix Fe3 O4 rock-salt phase during lithiation consequently restrains the film from delamination. 2D phase-field simulation verifies the effect of strain. This work provides critical insights of understanding the solid-solid interfaces of conversion-type electrodes.

Constraining Data Mining with Physical Models: Voltage- and Oxygen Pressure-Dependent Transport in Multiferroic Nanostructures.

Development of new generation electronic devices necessitates understanding and controlling the electronic transport in ferroic, magnetic, and optical materials, which is hampered by two factors. First, the complications of working at the nanoscale, where interfaces, grain boundaries, defects, and so forth, dictate the macroscopic characteristics. Second, the convolution of the response signals stemming from the fact that several physical processes may be activated simultaneously. Here, we present a method of solving these challenges via a combination of atomic force microscopy and data mining analysis techniques. Rational selection of the latter allows application of physical constraints and enables direct interpretation of the statistically significant behaviors in the framework of the chosen physical model, thus distilling physical meaning out of raw data. We demonstrate our approach with an example of deconvolution of complex transport behavior in a bismuth ferrite-cobalt ferrite nanocomposite in ambient and ultrahigh vacuum environments. Measured signal is apportioned into four electronic transport patterns, showing different dependence on partial oxygen and water vapor pressure. These patterns are described in terms of Ohmic conductance and Schottky emission models in the light of surface electrochemistry. Furthermore, deep data analysis allows extraction of local dopant concentrations and barrier heights empowering our understanding of the underlying dynamic mechanisms of resistive switching.

In Situ Study of Fe3Pt-Fe2O3 Core-Shell Nanoparticle Formation.

We report an in situ study of Fe3Pt-Fe2O3 core-shell nanoparticle growth using liquid cell transmission electron microscopy. By controlling the Fe-to-Pt ratio in the precursor solution, we achieved the growth of nanoparticles with the formation of an iron-platinum alloy core followed by an iron oxide shell in the electron beam-induced reactions. There was no substantial change in the growth kinetics of the iron oxide shell after the Fe-Pt alloy core stopped growing. The core growth was arrested by depletion of the Pt precursor. Heteroepitaxy of Fe3Pt [101] (core)||α-Fe2O3 [111] (shell) was observed in most of the nanoparticles, while a polycrystalline iron oxide shell is developed eventually for strain relaxation. Our studies suggest that Pt atoms catalyze the reduction of Fe ions to form the Fe3Pt alloy core, and when Pt is depleted, a direct precipitation of iron oxide results in the core-shell nanostructure formation.

Self-Assembled Epitaxial Core-Shell Nanocrystals with Tunable Magnetic Anisotropy.

Epitaxial core-shell CoO-CoFe2 O4 nanocrystals are fabricated by using pulsed laser deposition with the aid of melted material (Bi2 O3 ) addition and suitable lattice mismatch provided by substrates (SrTiO3 ). Well aligned orientations among nanocrystals and reversible core-shell sequence reveal tunable magnetic anisotropy. The interfacial coupling between core and shell further engineers the nanocrystal functionality.

Topological control of nitric oxide secretion by tantalum oxide nanodot arrays.

BACKGROUND: Nitric oxide (NO) plays a very important role in the cardiovascular system as a major secondary messenger in signaling pathway. Its concentration regulates most of the important physiological indexes including the systemic blood pressure, blood flow, regional vascular tone and other cardiac functions. The effect of nanotopography on the NO secretion in cardiomyocytes has not been elucidated before. In this study, we report how the nanotopography can modulate the secretion profile of NO and attempt to elucidate the genetic pathways responsible for the same by using Tantalum Oxide nanodot arrays ranging from 10 to 200 nm. A series of nanodot arrays were fabricated with dot diameter ranging from 10 to 200 nm. Temporal NO release of cardiomyocytes was quantified when grown on different surfaces. Quantitative RT-PCR and Western blot were performed to verify the genetic pathways of NO release. RESULTS: After hours 24 of cell seeding, NO release was slowly enhanced by the increase of dot diameter from 10 nm up to 50 nm, mildly enhanced to a medium level at 100 nm, and increase rapidly to a high level at 200 nm. The temporal enhancement of NO release dropped dramatically on day 3. On day 5, a topology-dependent profile was established that maximized at 50 nm and dropped to control level at 200 nm. The NO releasing profile was closely associated with the expression patterns of genes associated with Endothelial nitric oxide synthase (eNOS) pathway [GPCR, PI3K, Akt, Bad, Bcl-2, NFκB(p65), eNOS], but less associated with Inducible nitric oxide synthase (iNOS) pathway (TNF-α, ILK, Akt, IκBα, NFκB, iNOS). Western blotting of Akt, eNOS, iNOS, and NFκB further validated that eNOS pathway was modulated by nanotopology. CONCLUSIONS: Based on the findings of the present study, 50, 100 nm can serve as the suitable nanotopography patterns for cardiac implant surface design. These two nanodot arrays promote NO secretion and can also promote the vascular smooth muscle relaxation. The results of this study can improve the heart stent design in the medical treatments.

Tuning phase stability of complex oxide nanocrystals via conjugation.

Nanocrystals (NCs) attract tremendous research interests because of their unique properties to meet the demands of functionalities. To date, hybrid NCs with multiple components are developed to meet the rising demands that could be very difficult, or even impossible to be achieved by single-component NCs. Tuning properties by strain via conjugation could be an alternative solution. Strain engineering has been discovered and widely applied to many thin-film materials for tuning physical properties. Then, there is a further question to be addressed in this study: can we take the advantages we have learned in heteroepitaxy of thin films and transfer that into the NC conjugation? In order to demonstrate this possibility, we investigated NC conjugation of BiFeO3 and LaAlO3. We found that change in either LaAlO3-NC or BiFeO3-NC size would change the stability of rhombohedral-to-tetragonal phase transition. The present results show that strain engineering is possible to be realized in not only thin film but also NC conjugation. The same concept should be applicable to other complex oxide systems in order to broaden their practical applications for the rising demands of multifunctionalities.

Magnetic mesocrystal-assisted magnetoresistance in manganite.

Mesocrystal, a new class of crystals as compared to conventional and well-known single crystals and polycrystalline systems, has captured significant attention in the past decade. Recent studies have been focused on the advance of synthesis mechanisms as well as the potential on device applications. In order to create further opportunities upon functional mesocrystals, we fabricated a self-assembled nanocomposite composed of magnetic CoFe2O4 mesocrystal in Sr-doped manganites. This combination exhibits intriguing structural and magnetic tunabilities. Furthermore, the antiferromagnetic coupling of the mesocrystal and matrix has induced an additional magnetic perturbation to spin-polarized electrons, resulting in a significantly enhanced magnetoresistance in the nanocomposite. Our work demonstrates a new thought toward the enhancement of intrinsic functionalities assisted by mesocrystals and advanced design of novel mesocrystal-embedded nanocomposites.

In situ TEM study of the Li-Au reaction in an electrochemical liquid cell.

We study the lithiation of a Au electrode in an electrochemical liquid cell using transmission electron microscopy (TEM). The commercial liquid electrolyte for lithium ion batteries (1 M lithium hexafluorophosphate LiPF6 dissolved in 1 : 1 (v/v) ethylene carbonate (EC) and diethyl carbonate (DEC)) was used. Three distinct types of morphology change during the reaction, including gradual dissolution, explosive reaction and local expansion/shrinkage, are observed. It is expected that significant stress is generated from lattice expansion during lithium-gold alloy formation. There is vigorous bubble formation from electrolyte decomposition, likely due to the catalytic effect of Au, while the bubble generation is less severe with titanium electrodes. There is an increase of current in response to electron beam irradiation, and electron beam effects on the observed electrochemical reaction are discussed.

Probing local ionic dynamics in functional oxides at the nanoscale.

A scanning probe microscopy technique for probing local ionic dynamics in electrochemically active materials based on the first-order reversal curve current-voltage (FORC-IV) method is presented. FORC-IV imaging mode is applied to a Ca-substituted bismuth ferrite (Ca-BFO) system to separate the electronic and ionic phenomena in this material and visualize the spatial variability of these behaviors. The variable-temperature measurements further demonstrate the interplay between the thermally and electric-field-driven resistance changes in Ca-BFO. The FORC-IV is shown to be a simple, powerful, and flexible method for studying electrochemical activity of materials at the nanoscale and, in conjunction with the electrochemical strain microscopy, it can be used for differentiating ferroelectric and ionic behaviors.

Nonvolatile Modulation of Bi2O2Se/Pb(Zr,Ti)O3 Heteroepitaxy.

The pursuit of high-performance electronic devices has driven the research focus toward 2D semiconductors with high electron mobility and suitable band gaps. Previous studies have demonstrated that quasi-2D Bi2O2Se (BOSe) has remarkable physical properties and is a promising candidate for further exploration. Building upon this foundation, the present work introduces a novel concept for achieving nonvolatile and reversible control of BOSe's electronic properties. The approach involves the epitaxial integration of a ferroelectric PbZr0.2Ti0.8O3 (PZT) layer to modify BOSe's band alignment. Within the BOSe/PZT heteroepitaxy, through two opposite ferroelectric polarization states of the PZT layer, we can tune the Fermi level in the BOSe layer. Consequently, this controlled modulation of the electronic structure provides a pathway to manipulate the electrical properties of the BOSe layer and the corresponding devices.