Piezoresponse Force Microscopy Research Articles

Tape‐Casting Lead‐Free Dielectrics Permit Superior Capacitive Energy Storage Performance

AbstractDielectric capacitors have garnered significant attention for their promising attributes in advanced pulse power systems of the future, owing to their rapid charge/discharge capabilities, high power density, and remarkable stability. Whereas environmentally friendly lead‐free ceramics are facing serious challenges of low breakdown strength, poor energy storage density, and/or conversion efficiency, which has been an obstacle to developing desirable dielectric capacitors. In this study, high‐quality ultrathin (<20 µm) lead‐free ceramic dielectrics are successfully produced via the tape‐casting method. The local structural characteristics of these ceramics are verified using piezoresponse force microscopy and aberration‐corrected scanning transmission electron microscopy. By introducing Ta5+ ions into Bi0.39Na0.36Sr0.25TiO3 ceramics, the polar clusters tend to decrease together while the maximum applied electric field tends to increase. This phenomenon can be attributed to the decreased grain size and complex polar structure characterized by extremely small polar clusters, enabling the simultaneous achievement of high applied electric field, large polarization, and minimized polarization hysteresis. Notably, the tape‐casted lead‐free ceramics exhibited exceptional comprehensive energy storage performance with a recoverable energy storage density of ≈10.06 J cm−3 and an efficiency of ≈93% under a high electric field of 915 kV cm−1, surpassing the capabilities of most reported lead‐free ceramics. This work offers a viable solution for developing lead‐free ceramic dielectrics with outstanding energy storage capabilities.

Atomic-Scale Characterization of 180° Conductive Domain Walls in PbZr0.1Ti0.9O3.

Conductive domain walls (DWs) in ferroic materials have emerged as promising candidates for applications in nanoelectronics due to their unique properties such as high conductivity and nonvolatility. In this study, we investigate the atomic structure and conductivity of nominally neutral 180° DWs artificially created in an epitaxial thin film of tetragonal PbZr0.1Ti0.9O3. Using piezoresponse force microscopy and scanning transmission electron microscopy, we elucidate the complex structure of these 180° DWs and their coupling with ferroelastic domains, revealing that they exhibit a complex structure due to the strain-mediated interplay with the ferroelastic domains. Our results demonstrate that the 180° DWs conductivity is associated with the emergence of polar discontinuities, including the formation of tail-to-tail charged segments, which has been further confirmed by electron energy loss spectroscopy. Additionally, we investigated the long-term performance of these domain boundaries, demonstrating their unique mobility and structural stability. Our findings provide insights into the atomic-scale mechanisms that turn nominally neutral DWs into highly conductive channels, paving the way for their use in advanced nanoelectronic devices.

Direct laser poling of lithium niobate on insulator with femtosecond laser

We demonstrated experimentally direct femtosecond writing of ferroelectric domains in lithium niobate on insulator. The fabricated ferroelectric domain structures were characterized using Cherenkov second harmonic microscopy and piezoresponse force microscopy. We also experimentally explored the far-field second harmonic generation from the laser-induced ferroelectric domain structures. This study opens the door for direct laser writing of lithium niobate-based integrated photonic circuits, which typically require on-chip frequency conversion and wavefront control.

Nanoscale Mapping of Carrier Distribution Regulated by Polarization in 2D FeFETs.

The emergence of 2D ferroelectrics, sliding ferroelectrics, and 2D ferroelectric semiconductors has greatly expanded the potential applications of two-dimensional ferroelectric field-effect transistors (2D FeFETs) in nonvolatile memory, neuromorphic synapses, and negative capacitance. However, the interaction between ferroelectric and semiconductor layers remains not well understood, and characterization methods to correlate carriers and polarization dynamics at the nanoscale are still lacking. Utilizing in situ scanning microwave impedance microscopy and piezoresponse force microscopy measurements, we employed a Pb(Zr0.2Ti0.8)O3/MoS2-based 2D FeFET as an example to reveal, with high spatial resolution, the microscopic redistribution of carriers. This study uncovers the microscopic behavior of ferroelectric-semiconductor heterojunctions, paving the way for a deeper understanding of ferroelectric-gating effects and retention issues at the nanoscale in 2D FeFETs.

Giant Modulation of Second-Harmonic Generation in CuInP2S6 by Interfacing with MoS2 Atomic Layers.

Probing and manipulating the intriguing nonlinear optical responses in van der Waals (vdW) ferroelectrics offer opportunities for their applications in nanophotonics. Here, we report the observation of giant and tunable second-harmonic generation (SHG) in ferroelectric CuInP2S6 (CIPS) and CIPS/MoS2 heterostructures. The results show that CIPS, ranging from multilayer to bulk-like samples, all exhibit strong SHG with giant anisotropy. The SHG anisotropy is attributed to the local strain along the a-axis that naturally exists in CIPS, as evidenced by piezoresponse force microscopy measurement. We further realized the strong modulation of SHG in CIPS by interfacing with monolayer MoS2. A combination of polarization, temperature, and thickness-dependent SHG and photoluminescence analyses shows that the nonlinear optical signal control in CIPS/MoS2 heterostructures is unrelated to the polar symmetry of CIPS and MoS2 but is driven by light absorption-mediated interfacial coupling. Our study provides a material platform based on vdW ferroelectric heterostructures for achieving dynamic control of nonlinear optical responses, which shows great potential applications in modern nanophotonics.

Single-crystal ferroelectric LiNbO3 thin film-based synaptic devices enabled with tunable domain wall current for neuromorphic computing

Neuromorphic devices can emulate the human brain to process information, which receives lots of attention in the field of artificial intelligence. Synaptic devices based on ferroelectric thin films feature low-power consumption, multifunctionality, and scalability. Among them, ferroelectric charged domain wall (CDW) devices have attracted intensive interest for the implementation of memristive devices due to their ultrahigh integration ability inherited from the nanoscale domain wall thickness. In particular, the preparation of wafer-scale single-crystalline ferroelectric thin films via ion-sliced heterogeneous wafer bonding lays a good foundation for large-scale integration of ferroelectric devices with functional circuits. However, the biomimic synaptic characteristics and the systematic demonstration of synaptic devices are largely unexplored for this material system. Here, we demonstrate a model synaptic device based on a single-crystal ferroelectric LiNbO3 thin film, which provides the desired characteristics for neuromorphic computing. The conductance modulation demonstrates good linearity for efficient neuromorphic computing applications. Simulations using the Modified National Institute of Standards and Technology handwritten recognition dataset prove that LiNbO3-based synaptic devices can operate with an online learning accuracy of 95.1%. The injection and annihilation of the CDW are proposed as the basis of the conductivity modulation by combining with the piezoresponse force microscopy and conductive atomic force microscopy mapping measurements. With the mature fabrication process of the ultrathin high-quality ferroelectric thin films, LiNbO3-based synaptic devices have an extensive application prospect for future neuromorphic computing systems.

Rational design of ZnO/SrTiO3 S-scheme heterojunction for photo-enhanced piezocatalytic hydrogen production

Photopiezocatalysis have been frequently investigated for hydrogen evolution reactions in recent years. Herein, ZnO, SrTiO3 and ZnO/SrTiO3 S-scheme heterojunction were investigated for photo/piezocatalytic hydrogen production. Piezocatalytic hydrogen production under ultrasonic vibration by using ZnO, SrTiO3 and ZnO/SrTiO3 was obtained as 270 µmol g-1h−1, 200 µmol g-1h−1 and 1265 µmol g-1h−1, respectively. In addition, ZnO/SrTiO3 S-scheme heterojunction showed 2200 µmol g-1h−1 photopiezocatalytic hydrogen production under simultaneous exposure to white LED light and ultrasonic sound. ZnO/SrTiO3 heterojunction displayed significantly higher hydrogen production rate due to the decreased charge recombination, increased charge transfer with strong piezoelectric polarization and internal electrical field. The piezoelectric effect of ZnO/SrTiO3 heterojunction is also confirmed by piezoresponse force microscope technique with butterfly and phase hysteresis loops. Also, piezoelectric coefficient of ZnO/SrTiO3 found about 2-folds higher than those of their pristine forms. Electron transfer and reaction mechanism of ZnO/SrTiO3 and activity differences are confirmed by advanced optical and electrochemical techniques such as diffuse reflectance spectroscopy, electronic impedance spectroscopy, Mott-Schottky calculation and chronoamperometry. The whole electrochemical measurements have been performed with or without mechanical stress and light irradiation, which signify their band bending properties, electron transfer mechanism and catalytic activities.

Investigation of Microstructure and Physical Characteristics of Eco-Friendly Piezoelectric Composite Thin Films Based on Chitosan and Ln2O3-Doped Na0.5Bi0.5TiO3-BaTiO3 Nanoparticles.

This paper investigates the synthesis and characterization of eco-friendly piezoelectric composite thin films composed of chitosan and Ln2O3-doped Na0.5Bi0.5TiO3-BaTiO3 (NBT-BT) nanoparticles. The films were fabricated using a solution-casting technique, successfully embedding the particles into the chitosan matrix, which resulted in enhanced piezoelectric properties compared to pure chitosan. Characterization methods, such as photoluminescence spectroscopy and piezo-response force microscopy (PFM) which revealed strong electromechanical responses, with notable improvements in piezoelectric performance due to the inclusion of NBT-BT nanoparticles. X-ray diffraction (XRD) analysis revealed a pure perovskite phase with the space group R3c for NBT-BT and NBT-BT-Ln particles. Scanning electron microscopy (SEM) images showed a non-uniform distribution of NBT-BT particles within the chitosan matrix. The results also suggest that the incorporation of rare earth elements further enhances the electrical and piezoelectric properties of the composites, highlighting their potential in flexible and smart device applications. Overall, these findings underscore the potential of chitosan-based composites in addressing environmental concerns while offering effective solutions for energy harvesting and biomedical applications.

Magnetic Field-Induced Polar Order in Monolayer Molybdenum Disulfide Transistors.

In semiconducting monolayer transition metal dichalcogenides (ML-TMDs), broken inversion symmetry and strong spin-orbit coupling result in spin-valley lock-in effects so that the valley degeneracy may be lifted by external magnetic fields, potentially leading to real-space structural transformation. Here, magnetic field (B)-induced giant electric hysteretic responses to back-gate voltages are reported in ML-MoS2 field-effect transistors (FETs) on SiO2/Si at temperatures <20 K. The observed hysteresis increases with |B| up to 12 T and is tunable by varying the temperature. Raman spectroscopic and scanning tunneling microscopic studies reveal significant lattice expansion with increasing |B| at 4.2 K, and this lattice expansion becomes asymmetric in ML-MoS2 FETs on rigid SiO2/Si substrates, leading to out-of-plane mirror symmetry breaking and the emergence of a tunable out-of-plane ferroelectric-like polar order. This broken symmetry-induced polarization in ML-MoS2 shows typical ferroelectric butterfly hysteresis in piezo-response force microscopy, adding ML-MoS2 to the single-layer material family that exhibits out-of-plane polar order-induced ferroelectricity, which is promising for such technological applications as cryo-temperature ultracompact non-volatile memories, memtransistors, and ultrasensitive magnetic field sensors. Moreover, the polar effect induced by asymmetric lattice expansion may be further generalized to other ML-TMDs and achieved by nanoscale strain engineering of the substrate without magnetic fields.

Mapping domain structures near a grain boundary in a lead zirconate titanate ferroelectric film using X-ray nanodiffraction

The effect of an electric field on local domain structure near a 24° tilt grain boundary in a 200 nm-thick Pb(Zr0.2Ti0.8)O3 bi-crystal ferroelectric film was probed using synchrotron nanodiffraction. The bi-crystal film was grown epitaxially on SrRuO3-coated (001) SrTiO3 24° tilt bi-crystal substrates. From the nanodiffraction data, real-space maps of the ferroelectric domain structure around the grain boundary prior to and during application of a 200 kV cm−1 electric field were reconstructed. In the vicinity of the tilt grain boundary, the distributions of densities of c-type tetragonal domains with the c axis aligned with the film normal were calculated on the basis of diffracted intensity ratios of c- and a-type domains and reference powder diffraction data. Diffracted intensity was averaged along the grain boundary, and it was shown that the density of c-type tetragonal domains dropped to ∼50% of that of the bulk of the film over a range ±150 nm from the grain boundary. This work complements previous results acquired by band excitation piezoresponse force microscopy, suggesting that reduced nonlinear piezoelectric response around grain boundaries may be related to the change in domain structure, as well as to the possibility of increased pinning of domain wall motion. The implications of the results and analysis in terms of understanding the role of grain boundaries in affecting the nonlinear piezoelectric and dielectric responses of ferroelectric materials are discussed.

Strain-Engineered Ferroelectricity in 2H Bilayer MoS2.

The exploration of two-dimensional (2D) materials exhibiting out-of-plane ferroelectric and piezoelectric properties through interlayer twist/translation or strain, known as sliding ferroelectricity, has become a focal point in the quest for low-power electronic devices, capitalizing on weak van der Waals interactions. Herein, we delve into the behavior of strained bilayer molybdenum disulfide (2L-MoS2) transferred onto a nanocone-patterned substrate. An intriguing observation is the emergence of unexpected vertical ferroelectricity in MoS2, irrespective of whether it was prepared using chemical vapor deposition or mechanical exfoliation from the bulk crystal. Such an observation underscores the versatility and reproducibility of the emerging ferroelectricity across different preparation methods. Furthermore, the piezoelectric coefficients recorded are exceptionally high, with the values of 37.54 and 24.80 pm V-1 for monolayer and bilayer MoS2, respectively, outperforming most currently discovered 2D piezoelectrics. The presence of room-temperature out-of-plane ferroelectricity in strained 2L-MoS2 is confirmed through first-principles calculations and piezoresponse force microscopy. This ferroelectric behavior can be attributed to the symmetry breaking and interlayer sliding within the strained 2L-MoS2 structure. Our findings not only deepen the understanding of ferroelectricity in 2D materials but also offer insights for the design of 2D ferroelectrics, thereby enabling diverse functionalities and applications in ferroelectricity.

Superior Piezoelectric Performance in Textured CaBi2Nb2O9 Ferroelectric Ceramics through Rare-Earth Gadolinium Doping and Spark Plasma Sintering.

High-performance piezoelectric ceramics with excellent thermal stability are crucial for high-temperature piezoelectric sensor applications. However, conventional fabrication processes offer limited enhancements in piezoelectric performance. In this study, we achieved a significant breakthrough in the piezoelectric performance of highly textured CaBi2Nb2O9 (CBN) ceramics by incorporating rare-earth gadolinium doping and utilizing spark plasma sintering. The resulting Ca0.97Gd0.03Bi2Nb2O9 (CBN-3Gd) ceramics exhibited superior piezoelectric properties, with a high piezoelectric constant d33 of 26 pC/N and a high Curie temperature TC of 946 °C. We employed piezoresponse force microscopy (PFM) to observe the morphology and dimensions of the ferroelectric domains, revealing a rod-shaped 3D domain configuration. This configuration facilitated polarization rotation in the textured ceramics, as analyzed using X-ray photoelectron spectroscopy (XPS) and polarization-electric field (P-E) hysteresis loops. Furthermore, the textured CBN-3Gd ceramics demonstrated exceptional thermal stability and reliability. The piezoelectric constant d33 decreased by only 11.8% over a temperature range of room temperature to 500 °C, and the DC electrical resistivity remained at 6.7 × 105 Ω cm at 600 °C. This work not only highlights the great potential of textured CBN-based ceramics for high-temperature piezoelectric sensors but also provides a viable strategy for enhancing the performance of piezoelectric materials with large aspect ratio micromorphology.

Topological Polar Networks in Twisted Rhombohedral-Stacked Bilayer WSe2 Moiré Superlattices.

Sliding ferroelectricity enables materials with intrinsic centrosymmetric symmetry to generate spontaneous polarization via stacking engineering, extending the family of ferroelectric materials and enriching the field of low-dimensional ferroelectric physics. Vertical ferroelectric domains, where the polarization is perpendicular to atomic motion, have been discovered in twisted bilayers of inversion symmetry broken systems such as hexagonal boron nitride, graphene, and transition metal chalcogenides. In this study, we demonstrate that this symmetry breaking also induces lateral polar networks in twisted bilayer rhombohedral-stacked WSe2, as determined through symmetry considerations and vector piezoresponse force microscopy (V-PFM) results. Lateral polarization (LP) in saddle point (SP) regions forms head-to-tail triangular vortices, exhibiting elliptical domain shapes with widths up to 40 nm. The LP encloses the vertical polarization (VP), forming a network of Bloch-type merons and antimerons. Our work enhances the understanding of domain distribution and polarization orientation in moiré ferroelectrics.

Eliminating interface shielding effect endowed by piezoelectric polarization in S-scheme heterojunction for high-efficiency H2 evolution

Eliminating the interface shielding effect within step-scheme (S-scheme) heterojunctions which can attenuate the separation driving force of built-in electric field plays a vital role in enhancing the photocatalytic performance. Herein, an extra driving force induced by piezoelectric field is introduced to mitigate such predicament in S-scheme, thereby facilitating the charge separation. Specifically, the piezoelectric CuInS2-BiFeO3 S-scheme heterojunction which with powerful piezoelectric field endowed by the piezoelectric BiFeO3 is constructed via a facile electrostatic self-assembly strategy and served as the touchstone to verify that hypothesis. The direction of built-in field between the heterojunction interface that is orienting from CuInS2 to BiFeO3 has been confirmed by in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance. Furthermore, the obviously piezo-field at the interface of CuInS2-BiFeO3 which can tilt energy band to enhance the built-in field under external force is also revealed by piezoresponse force microscopy. Consequently, benefiting from the highly-efficient charge separation offered by the synergy of piezoelectric field and S-scheme built-in electric field, a remarkably H2 production rate of 1465.1 µmol/g is achieved under simultaneous visible light and ultrasonic vibration irradiation. This work sheds light on the role of external field in enhancing the efficient separation of carriers in S-scheme heterojunctions.

Realizing Ultrahigh Energy Storage Density in (Bi0.5Na0.5)0.94Ba0.06TiO3-Based Ceramics via Manipulating the Domain Configuration and Grain Boundary Density.

Dielectric capacitors with a high power density are widely used in various pulsed power electronic systems. However, their low comprehensive energy storage performance severely limits the development of these systems in terms of miniaturization and lightweight design. Herein, we achieved decent energy storage performance in a class of (Bi0.5Na0.5)0.94Ba0.06TiO3 (BNTBT)-based ceramics by synergistically manipulating domain configurations and grain boundary densities. High-resolution transmission electron microscopy and piezoresponse force microscopy confirm that composition-driven refined domain configurations with weak polarity effectively improve the polarization response of BNTBT-based ceramics. The results of experimental and phase-field simulation analysis indicate that the refined grain size contributes to its high breakdown electric strength (Eb). Benefiting from the high polarization difference (ΔP) of 32.62 μC/cm2, delayed saturation polarization behavior, and an ultrahigh Eb of 815.00 kV/cm, BNT-based ceramics simultaneously achieve a high energy storage density (Wrec) of ∼12.25 J/cm3 and an efficiency (η) of ∼86.90%. Because of these structure-induced advantages, the ceramics also exhibit good energy storage temperature stability in the range of 30-150 °C. We believe that the findings of this work may provide practical guidance for the development of high-performance energy storage ceramics.

Multistate Ferroelectric Diodes with High Electroresistance Based on van der Waals Heterostructures.

Some van der Waals (vdW) materials exhibit ferroelectricity, making them promising for novel nonvolatile memories (NVMs) such as ferroelectric diodes (FeDs). CuInP2S6 (CIPS) is a well-known vdW ferroelectric that has been integrated with graphene for memory devices. Here we demonstrate FeDs with self-rectifying, hysteretic current-voltage characteristics based on vertical heterostructures of 10 nm thick CIPS and graphene. By using vdW indium-cobalt top electrodes and graphene bottom electrodes, we achieve a high electroresistance (on- and off-state resistance ratios) of ∼106, an on-state rectification ratio of 2500 for read/write voltages of 2 V/0.5 V, and a maximum output current density of 100 A/cm2. These metrics compare favorably with state-of-the-art FeDs. Piezoresponse force microscopy measurements show that stabilization of intermediate net polarization states in CIPS leads to stable multibit data retention at room temperature. The combination of two-terminal design, multibit memory, and low-power operation in CIPS-based FeDs is potentially interesting for compute-in-memory and neuromorphic computing applications.

Analyzing flexoelectric polarization of suspended membrane by nonlinear bending theory of plate

Strain gradient breaks inversion symmetry and induces flexoelectric polarization as well as electromechanical coupling in all material systems, though the effect is usually only significant at the nanoscale. Two-dimensional (2D) materials and thin membranes thus provide an ideal platform to explore flexoelectricity, which has been widely pursued, yet quantitative theoretical analysis is needed to guide the rapid experimental developments. In this work, we develop 2D flexoelectric model for suspended membrane based on von Kármán plate theory, and implement it into finite element computation using conforming BCIZ element. Numerical results and discussions on flexoelectric polarization in suspended membrane under uniform pressure or concentrated load are presented, which are validated by piezoresponse force microscopy (PFM) experiments under a range of membrane thicknesses and loading forces showing good agreement with computations. Since large strain gradient often exists in samples with small size in one or two dimensions, the method we develop provides a powerful tool to study a wide range of low-dimensional materials and structures with flexoelectric effect.

Mapping Sliding Ferroelectricity in Bulk (PbS)1.11VS2 Crystals

The recent discovery of sliding ferroelectricity opens up the field of 2D ferroelectricity. However, the limitation to switching the polarization due to the topological protection of the domain walls limits the potential of these heterostructures. Here, the switching of sliding ferroelectric bulk misfit layer compound (PbS)1.11VS2 crystals is studied using switching spectroscopy piezoresponse force microscopy. A large number of measured hysteresis loops can be efficiently analyzed using unsupervised machine‐learning tools. Different switching behavior of the domains is observed on different types of domain structures, and it is shown that full domain switching can be observed for the right type of dislocation structure in the PbS layer.

Growth and thickness effect of -oriented ternary 0.06Pb(Mn1/3Nb2/3)O3-0.94Pb(Zr0.48Ti0.52)O3 ferroelectric thin films on silicon substrate by RF sputtering

The development of advanced piezoelectric thin films with large piezoelectric response on silicon substrate is a crucial technology for piezoelectric microelectromechanical systems applications. In this work, high-quality <100>-oriented 0.06Pb(Mn1/3Nb2/3)O3-0.94Pb(Zr0.48Ti0.52)O3 (PMN-PZT) thin films were grown on the Pt/Ti/SiO2/Si substrate by sputtering. X-ray diffraction, scanning electron microscopy, and piezoresponse force microscopy were utilized to characterize the phase, morphologies, and domain structures. The growth parameters were optimized and thickness-dependent electrical properties were established. Well-crystalized micron-thick PMN-PZT films with high remnant polarization of 49 μC/cm2 and giant piezoelectric coefficient (d33) up to 484 pC/N (about twice of the polycrystalline PMN-PZT thin film and thrice of the Pb(Zr0.52Ti0.48)O3 thin film) were obtained. The excellent electrical properties make it highly advantageous for applications in MEMS devices.

On-demand nanoengineering of in-plane ferroelectric topologies.

Hierarchical assemblies of ferroelectric nanodomains, so-called super-domains, can exhibit exotic morphologies that lead to distinct behaviours. Controlling these super-domains reliably is critical for realizing states with desired functional properties. Here we reveal the super-switching mechanism by using a biased atomic force microscopy tip, that is, the switching of the in-plane super-domains, of a model ferroelectric Pb0.6Sr0.4TiO3. We demonstrate that the writing process is dominated by a super-domain nucleation and stabilization process. A complex scanning-probe trajectory enables on-demand formation of intricate centre-divergent, centre-convergent and flux-closure polar structures. Correlative piezoresponse force microscopy and optical spectroscopy confirm the topological nature and tunability of the emergent structures. The precise and versatile nanolithography in a ferroic material and the stability of the generated structures, also validated by phase-field modelling, suggests potential for reliable multi-state nanodevice architectures and, thereby, an alternative route for the creation of tunable topological structures for applications in neuromorphic circuits.