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Robust ferroelectricity in HfO2-based ultrathin films has the potential to revolutionize nonvolatile memory applications in nanoscale electronic devices because of their compatibility with the existing Si technology. However, to fully exploit the potential of ferroelectric HfO2-based thin films, it is crucial to develop strategies for the controlled stabilization of various HfO2-based polymorphs in nanoscale heterostructures. This study demonstrates how substrate-orientation-induced anisotropic strain can engineer the crystal symmetry, structural domain morphology, and growth orientation of ultrathin Hf0.5Zr0.5O2 (HZO) films. Epitaxial ultrathin HZO films were grown on the heterostructures of (001)- and (110)-oriented La2/3Sr1/3MnO3/SrTiO3 (LSMO/STO) substrate. Various structural analyses revealed that the (110)-oriented substrate promotes a higher degree of structural order (crystallinity) with improved stability of the (111)-oriented orthorhombic phase (Pca21) of HZO. Conversely, the (001)-oriented substrate not only induces a distorted orthorhombic structure but also facilitates the partial stabilization of nonpolar phases. Electrical measurements revealed robust ferroelectric properties in epitaxial thin films without any wake-up effect, where the well-ordered crystal symmetry stabilized by STO(110) facilitated better ferroelectric characteristics. This study suggests that tuning the epitaxial growth of ferroelectric HZO through substrate orientation can improve the stability of the metastable ferroelectric orthorhombic phase and thereby offer a better understanding of device applications.
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In2 Se3 , 2D ferroelectric-semiconductor, is a promising candidate for next-generation memory device because of its outstanding electrical properties. However, the large-area manufacturing of In2 Se3 is still a big challenge. In this work, spray pyrolysis technique is introduced for the growth of large-area In2 Se3 thin film. A polycrystalline γ-In2 Se3 layer can be grown on 15 cm × 15 cm glasss at the substrate temperature of 275 °C. The In2 Se3 ferroelectric-semiconductor field effect transistor (FeS-FET) on glass substrate demonstrates a large hysteresis window of 40.3 V at the ±40 V of gate voltage sweep and excellent uniformity. The FeS-FET exhibits an electron field effect mobility of 0.97 cm2 V-1 s-1 and an on/off current ratio of >107 in the transfer curves. The memory behavior of the large-area, In2 Se3 FeS-FETs for next-generation memory is demonstrated.
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Since facile routes to fabricate freestanding oxide membranes were previously established, tremendous efforts have been made to further improve their crystallinity, and fascinating physical properties have been also reported in heterointegrated freestanding membranes. Here, we demonstrate our synthetic recipe to manufacture highly crystalline perovskite SrRuO3 freestanding membranes using new infinite-layer perovskite SrCuO2 sacrificial layers. To accomplish this, SrRuO3/SrCuO2 bilayer thin films are epitaxially grown on SrTiO3 (001) substrates, and the topmost SrRuO3 layer is chemically exfoliated by etching the SrCuO2 template layer. The as-exfoliated SrRuO3 membranes are mechanically transferred to various nonoxide substrates for the subsequent BaTiO3 film growth. Finally, freestanding heteroepitaxial junctions of ferroelectric BaTiO3 and metallic SrRuO3 are realized, exhibiting robust ferroelectricity. Intriguingly, the enhancement of piezoelectric responses is identified in freestanding BaTiO3/SrRuO3 heterojunctions with mixed ferroelectric domain states. Our approaches will offer more opportunities to develop heteroepitaxial freestanding oxide membranes with high crystallinity and enhanced functionality.
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Conventional antiferroelectric materials with atomic-scale anti-aligned dipoles undergo a transition to a ferroelectric (FE) phase under strong electric fields. The moiré superlattice formed in the twisted stacks of van der Waals crystals exhibits polar domains alternating in moiré length with anti-aligned dipoles. In this moiré domain antiferroelectic (MDAF) arrangement, the distribution of electric dipoles is distinguished from that of two-dimensional FEs, suggesting dissimilar domain dynamics. Here we performed an operando transmission electron microscopy investigation on twisted bilayer WSe2 to observe the polar domain dynamics in real time. We find that the topological protection, provided by the domain wall network, prevents the MDAF-to-FE transition. As one decreases the twist angle, however, this transition occurs as the domain wall network disappears. Exploiting stroboscopic operando transmission electron microscopy on the FE phase, we measure a maximum domain wall velocity of 300 µm s-1. Domain wall pinnings by various disorders limit the domain wall velocity and cause Barkhausen noises in the polarization hysteresis loop. Atomic-scale analysis of the pinning disorders provides structural insight on how to improve the switching speed of van der Waals FEs.
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A polar tetragonal tungsten bronze, Pb1.91 K3.22 â¡0.85 Li2.96 Nb10 O30 (â¡: vacancies), has been successfully synthesized by a high temperature solid-state reaction. Single crystal and powder X-ray diffraction indicate that the structure of Pb1.91 K3.22 â¡0.85 Li2.96 Nb10 O30 crystallizing in the noncentrosymmetric (NCS) space group, P4bm, consists of 3D framework with highly distorted NbO6 , LiO9 , PbO12 , and (Pb/K)O15 polyhedra. While NCS Pb1.91 K3.22 â¡0.85 Li2.96 Nb10 O30 undergoes a reversible phase transition between polar (P4bm) and nonpolar (P4/mbm) structure at around 460 °C, the material decomposes to centrosymmetric Pb1.45 K3.56 Li3.54 Nb10 O30 (P4/mbm) once heated to 1200 °C. Powder second-harmonic generation (SHG) measurements with 1064 nm radiation indicate that Pb1.91 K3.22 â¡0.85 Li2.96 Nb10 O30 exhibits a giant phase-matchable SHG intensity of ≈71.5 times that of KH2 PO4 , which is the strongest intensity in the visible range among all nonlinear optical materials reported to date. The observed colossal SHG should be attributable to the synergistic effect of dipole moments from the well-aligned NbO6 octahedra, the constituting distortive channels with vacancies, and highly polarizable cations.
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Boosting dielectric permittivity representing electrical polarizability of dielectric materials has been considered a keystone for achieving scientific breakthroughs as well as technological advances in various multifunctional devices. Here, we demonstrate sizable enhancements of low-frequency dielectric responses in oxygen-deficient oxide ceramics through specific treatments under humid environments. Ultrahigh dielectric permittivity (~5.2 × 106 at 1 Hz) is achieved by hydrogenation, when Ni-substituted BaTiO3 ceramics are exposed to high humidity. Intriguingly, thermal annealing can restore the dielectric on-state (exhibiting huge polarizability in the treated ceramics) to the initial dielectric off-state (displaying low polarizability of ~103 in the pristine ceramics after sintering). The conversion between these two dielectric states via the ambient environment-mediated treatments and the successive application of external stimuli allows us to realize reversible control of dielectric relaxation characteristics in oxide ceramics. Conceptually, our findings are of practical interest for applications to highly efficient dielectric-based humidity sensors.
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Vanadium dioxide (VO2) is one of the extensively studied strongly correlated oxides due to its intriguing insulator-metal transition near room temperature. In this work, we investigated temperature-dependent nanoscale conduction in an epitaxial VO2 film grown on an Al2O3 substrate using conductive-atomic force microscopy (C-AFM). We observed that only the regions near the grain boundaries are conductive, producing intriguing donut patterns in C-AFM images. Such donut patterns were observed in the entire measured temperature range (300-355 K). The current values near the grain boundaries increased by approximately two orders of magnitude with an increase in the temperature, which is consistent with the macroscopic transport data. The spatially-varied conduction behavior is ascribed to the coexistence of different monoclinic phases, i.e., M1 and M2 phases, based on the results of temperature-dependent Raman spectroscopy. Furthermore, we investigated the conduction mechanism in the relatively conductive M1 phase regions at room temperature using current-voltage (I-V) spectroscopy and deep data analysis. Bayesian linear unmixing and k-means clustering showed three distinct types of conduction behavior, which classical C-AFM cannot resolve. We found that the conduction in the M1 phase regions can be explained by the Poole-Frenkel mechanism. This work provides deep insight into IMT behavior in the epitaxial VO2 thin film at the nanoscale, especially the coexistence and evolution of the M1 and M2 phases. This work also highlights that I-V spectroscopy combined with deep data analysis is very powerful in investigating local transport in complex oxides and various material systems.
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Interaction between dipoles often emerges intriguing physical phenomena, such as exchange bias in the magnetic heterostructures and magnetoelectric effect in multiferroics, which lead to advances in multifunctional heterostructures. However, the defect-dipole tends to be considered the undesired to deteriorate the electronic functionality. Here, deterministic switching between the ferroelectric and the pinched states by exploiting a new substrate of cubic perovskite, BaZrO3 is reported, which boosts the square-tensile-strain to BaTiO3 and promotes four-variants in-plane spontaneous polarization with oxygen vacancy creation. First-principles calculations propose a complex of an oxygen vacancy and two Ti3+ ions coins a charge-neutral defect-dipole. Cooperative control of the defect-dipole and the spontaneous polarization reveals ternary in-plane polar states characterized by biased/pinched hysteresis loops. Furthermore, it is experimentally demonstrated that three electrically controlled polar-ordering states lead to switchable and nonvolatile dielectric states for application of nondestructive electro-dielectric memory. This discovery opens a new route to develop functional materials via manipulating defect-dipoles and offers a novel platform to advance heteroepitaxy beyond the prevalent perovskite substrates.
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The ferroelectricity in ultrathin HfO2 offers a viable alternative to ferroelectric memory. A reliable switching behavior is required for commercial applications; however, many intriguing features of this material have not been resolved. Herein, we report an increase in the remnant polarization after electric field cycling, known as the "wake-up" effect, in terms of the change in the polarization-switching dynamics of a Si-doped HfO2 thin film. Compared with a pristine specimen, the Si-doped HfO2 thin film exhibited a partial increase in polarization after a finite number of ferroelectric switching behaviors. The polarization-switching behavior was analyzed using the nucleation-limited switching model characterized by a Lorentzian distribution of logarithmic domain-switching times. The polarization switching was simulated using the Monte Carlo method with respect to the effect of defects. Comparing the experimental results with the simulations revealed that the wake-up effect in the HfO2 thin film is accompanied by the suppression of disorder.
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The manipulation of local ionic behavior via external stimuli in oxide systems is of great interest because it can help in directly tuning material properties. Among external stimuli, mechanical force has attracted intriguing attention as novel stimulus for ionic modulation. Even though effectiveness of mechanical force on local ionic modulation has been validated in terms of static effect, its real-time i.e., dynamic, behavior under an application of the force is barely investigated in spite of its crucial impact on device performance such as force or pressure sensors. In this study, we explore dynamic ionic behavior modulated by mechanical force in NiO thin films using electrochemical strain microscopy (ESM). Ionically mediated ESM hysteresis loops were significantly varied under an application of mechanical force. Based on these results, we were able to investigate relative relationship between the force and voltage effects on ionic motion and, further, control effectively ionic behavior through combination of mechanical and electrical stimuli. Our results can provide comprehensive information on the effect of mechanical forces on ionic dynamics in ionic systems.
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Flexoelectricity is an electromechanical coupling between electrical polarization and a strain gradient 1 that enables mechanical manipulation of polarization without applying an electrical bias2,3. Recently, flexoelectricity was directly demonstrated by mechanically switching the out-of-plane polarization of a uniaxial system with a scanning probe microscope tip3,4. However, the successful application of flexoelectricity in low-symmetry multiaxial ferroelectrics and therefore active manipulation of multiple domains via flexoelectricity have not yet been achieved. Here, we demonstrate that the symmetry-breaking flexoelectricity offers a powerful route for the selective control of multiple domain switching pathways in multiaxial ferroelectric materials. Specifically, we use a trailing flexoelectric field that is created by the motion of a mechanically loaded scanning probe microscope tip. By controlling the SPM scan direction, we can deterministically select either stable 71° ferroelastic switching or 180° ferroelectric switching in a multiferroic magnetoelectric BiFeO3 thin film. Phase-field simulations reveal that the amplified in-plane trailing flexoelectric field is essential for this domain engineering. Moreover, we show that mechanically switched domains have a good retention property. This work opens a new avenue for the deterministic selection of nanoscale ferroelectric domains in low-symmetry materials for non-volatile magnetoelectric devices and multilevel data storage.
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Quantum mechanical tunneling of electrons across ultrathin insulating oxide barriers has been studied extensively for decades due to its great potential in electronic-device applications. In the few-nanometers-thick epitaxial oxide films, atomic-scale structural imperfections, such as the ubiquitously existed one-unit-cell-high terrace edges, can dramatically affect the tunneling probability and device performance. However, the underlying physics has not been investigated adequately. Here, taking ultrathin BaTiO3 films as a model system, an intrinsic tunneling-conductance enhancement is reported near the terrace edges. Scanning-probe-microscopy results demonstrate the existence of highly conductive regions (tens of nanometers wide) near the terrace edges. First-principles calculations suggest that the terrace-edge geometry can trigger an electronic reconstruction, which reduces the effective tunneling barrier width locally. Furthermore, such tunneling-conductance enhancement can be discovered in other transition metal oxides and controlled by surface-termination engineering. The controllable electronic reconstruction can facilitate the implementation of oxide electronic devices and discovery of exotic low-dimensional quantum phases.
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With recent trends on miniaturizing oxide-based devices, the need for atomic-scale control of surface/interface structures by pulsed laser deposition (PLD) has increased. In particular, realizing uniform atomic termination at the surface/interface is highly desirable. However, a lack of understanding on the surface formation mechanism in PLD has limited a deliberate control of surface/interface atomic stacking sequences. Here, taking the prototypical SrRuO3/BaTiO3/SrRuO3 (SRO/BTO/SRO) heterostructure as a model system, we investigated the formation of different interfacial termination sequences (BaO-RuO2 or TiO2-SrO) with oxygen partial pressure (PO2) during PLD. We found that a uniform SrO-TiO2 termination sequence at the SRO/BTO interface can be achieved by lowering the PO2 to 5 mTorr, regardless of the total background gas pressure (Ptotal), growth mode, or growth rate. Our results indicate that the thermodynamic stability of the BTO surface at the low-energy kinetics stage of PLD can play an important role in surface/interface termination formation. This work paves the way for realizing termination engineering in functional oxide heterostructures.
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The atomic-scale synthesis of artificial oxide heterostructures offers new opportunities to create novel states that do not occur in nature. The main challenge related to synthesizing these structures is obtaining atomically sharp interfaces with designed termination sequences. In this study, it is demonstrated that the oxygen pressure (PO2) during growth plays an important role in controlling the interfacial terminations of SrRuO3 /BaTiO3 /SrRuO3 (SRO/BTO/SRO) ferroelectric (FE) capacitors. The SRO/BTO/SRO heterostructures are grown by a pulsed laser deposition method. The top SRO/BTO interface, grown at high PO2 (around 150 mTorr), usually exhibits a mixture of RuO2 -BaO and SrO-TiO2 terminations. By reducing PO2, the authors obtain atomically sharp SRO/BTO top interfaces with uniform SrO-TiO2 termination. Using capacitor devices with symmetric and uniform interfacial termination, it is demonstrated for the first time that the FE critical thickness can reach the theoretical limit of 3.5 unit cells.
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Energy technologies of the 21(st) century require an understanding and precise control over ion transport and electrochemistry at all length scales - from single atoms to macroscopic devices. This short review provides a summary of recent studies dedicated to methods of advanced scanning probe microscopy for probing electrochemical transformations in solids at the meso-, nano- and atomic scales. The discussion presents the advantages and limitations of several techniques and a wealth of examples highlighting peculiarities of nanoscale electrochemistry.
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Voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When the grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag(+)/Ag redox reaction to Ag(+)-ion diffusion with the increase in the applied voltage and pulse duration. This study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.
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Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO2 embedded in supporting matrices of SrTiO3. The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeO2 films. By using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness.
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Fundamental understanding of domain dynamics in ferroic materials has been a longstanding issue because of its relevance to many systems and to the design of nanoscale domain-wall devices. Despite many theoretical and experimental studies, a full understanding of domain dynamics still remains incomplete, partly due to complex interactions between domain-walls and disorder. We report domain-shape-preserving deterministic domain-wall motion, which directly confirms microscopic return point memory, by observing domain-wall breathing motion in ferroelectric BiFeO3 thin film using stroboscopic piezoresponse force microscopy. Spatial energy landscape that provides new insights into domain dynamics is also mapped based on the breathing motion of domain walls. The evolution of complex domain structure can be understood by the process of occupying the lowest available energy states of polarization in the energy landscape which is determined by defect-induced internal fields. Our result highlights a pathway for the novel design of ferroelectric domain-wall devices through the engineering of energy landscape using defect-induced internal fields such as flexoelectric fields.
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Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically nonlocal cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and nonlocal) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.
Assuntos
Eletroquímica , Umidade , Nanotecnologia , Prata/química , Microscopia de Varredura por SondaRESUMO
The development of electron and scanning probe microscopies in the second half of the twentieth century has produced spectacular images of the internal structure and composition of matter with nanometer, molecular, and atomic resolution. Largely, this progress was enabled by computer-assisted methods of microscope operation, data acquisition, and analysis. Advances in imaging technology in the beginning of the twenty-first century have opened the proverbial floodgates on the availability of high-veracity information on structure and functionality. From the hardware perspective, high-resolution imaging methods now routinely resolve atomic positions with approximately picometer precision, allowing for quantitative measurements of individual bond lengths and angles. Similarly, functional imaging often leads to multidimensional data sets containing partial or full information on properties of interest, acquired as a function of multiple parameters (time, temperature, or other external stimuli). Here, we review several recent applications of the big and deep data analysis methods to visualize, compress, and translate this multidimensional structural and functional data into physically and chemically relevant information.