High-resolution Piezoresponse Force Microscopy Research Articles

Ferroelectric solitons crafted in epitaxial bismuth ferrite superlattices

In ferroelectrics, complex interactions among various degrees of freedom enable the condensation of topologically protected polarization textures. Known as ferroelectric solitons, these particle-like structures represent a new class of materials with promise for beyond-CMOS technologies due to their ultrafine size and sensitivity to external stimuli. Such polarization textures have scarcely been demonstrated in multiferroics. Here, we present evidence for ferroelectric solitons in (BiFeO3)/(SrTiO3) superlattices. High-resolution piezoresponse force microscopy and Cs-corrected high-angle annular dark-field scanning transmission electron microscopy reveal a zoo of topologies, and polarization displacement mapping of planar specimens reveals center-convergent/divergent topological defects as small as 3 nm. Phase-field simulations verify that some of these structures can be classed as bimerons with a topological charge of ±1, and first-principles-based effective Hamiltonian computations show that the coexistence of such structures can lead to non-integer topological charges, a first observation in a BiFeO3-based system. Our results open new opportunities in multiferroic topotronics.

Room-temperature electric field-induced out-of-plane ferroelectric polarization in strain-free freestanding 2D SrTiO3 membranes

SrTiO3 (STO), a room-temperature paraelectric material in bulk form, has been a rich playground for emergent phenomena for decades. As an emerging material, great attention has been paid to freestanding 2D STO thin films. Recently, the room-temperature ferroelectricity has been unveiled in strained STO thin films; however, it remains an open question whether the strain-free freestanding 2D STO thin film is room-temperature ferroelectric or not. Here, we report the electric field-induced out-of-plane ferroelectric polarization in large-scale, freestanding, and strain-free 2D STO membranes at room temperature. High-resolution piezoresponse force microscopy measurements show that polarization in freestanding strain-free STO membranes can be switched by electric field and persist for an hour. The first-principles calculations suggest that the intrinsic defects such as oxygen vacancies could be linked to the observed spontaneous out-of-plane polarization in 2D STO membranes, which could be further enhanced by external electric field due to the induced symmetry breaking. Our work reports the unprecedented room-temperature ferroelectric polarization in strain-free freestanding 2D STO membranes, unlocking the great potential of freestanding 2D STO for the applications in novel electronic and logic-in-memory devices.

Direct observation of room-temperature out-of-plane ferroelectricity and tunneling electroresistance at the two-dimensional limit

Out-of-plane ferroelectricity with a high transition temperature in nanometer-scale films is required to miniaturize electronic devices. Direct visualization of stable ferroelectric polarization and its switching behavior in atomically thick films is critical for achieving this goal. Here, ferroelectric order at room temperature in the two-dimensional limit is demonstrated in tetragonal BiFeO3 ultrathin films. Using aberration-corrected scanning transmission electron microscopy, we directly observed robust out-of-plane spontaneous polarization in one-unit-cell-thick BiFeO3 films. High-resolution piezoresponse force microscopy measurements show that the polarization is stable and switchable, whereas a tunneling electroresistance effect of up to 370% is achieved in BiFeO3 films. Based on first-principles calculations and Kelvin probe force microscopy measurements, we explain the mechanism of polarization stabilization by the ionic displacements in oxide electrode and the surface charges. Our results indicate that critical thickness for ferroelectricity in the BiFeO3 film is virtually absent, making it a promising candidate for high-density nonvolatile memories.

Nanoscale Bubble Domains and Topological Transitions in Ultrathin Ferroelectric Films.

Observation of a new type of nanoscale ferroelectric domains, termed as "bubble domains"-laterally confined spheroids of sub-10 nm size with local dipoles self-aligned in a direction opposite to the macroscopic polarization of a surrounding ferroelectric matrix-is reported. The bubble domains appear in ultrathin epitaxial PbZr0.2 Ti0.8 O3 /SrTiO3 /PbZr0.2 Ti0.8 O3 ferroelectric sandwich structures due to the interplay between charge and lattice degrees of freedom. The existence of the bubble domains is revealed by high-resolution piezoresponse force microscopy (PFM), and is corroborated by aberration-corrected atomic-resolution scanning transmission electron microscopy mapping of the polarization displacements. An incommensurate phase and symmetry breaking is found within these domains resulting in local polarization rotation and hence impart a mixed Néel-Bloch-like character to the bubble domain walls. PFM hysteresis loops for the bubble domains reveal that they undergo an irreversible phase transition to cylindrical domains under the electric field, accompanied by a transient rise in the electromechanical response. The observations are in agreement with ab-initio-based calculations, which reveal a very narrow window of electrical and elastic parameters that allow the existence of bubble domains. The findings highlight the richness of polar topologies possible in ultrathin ferroelectric structures and bring forward the prospect of emergent functionalities due to topological transitions.

Mechanical stress-induced switching kinetics of ferroelectric thin films at the nanoscale

We investigate ferroelectric domain structure and piezoelectric response under variable mechanical compressive stress in Pb(Zr0.2TiO0.8)O3 (PZT) thin films using high-resolution piezoresponse force microscopy (PFM) and an in situ sample bending stage. Measurements reveal a drastic change in the ferroelectric domain structure which is presented along with details of the mediating switching process involving domain wall motion, nucleation, and domain wall roughening under an applied external mechanical stimulus. Furthermore, local PFM hysteresis loops reveal significant changes in the observed coercive biases under applied stress. The PFM hysteresis loops become strongly imprinted under increasing applied compressive stress.

High Resolution Piezoresponse Force Microscopy Study of Self-Assembled Peptide Nanotubes

ABSTRACT Peptide nanotubes based on short dipeptide diphenylalanine (FF) attract a lot of attention due to their unique physical properties ranging from strong piezoelectricity to extraordinary mechanical rigidity. In this work, we present the results of high-resolution Piezoresponse Force Microscopy (PFM) measurements in FF microtubes prepared from the solution. First in-situ temperature measurements show that the effective shear piezoelectric coefficient d15 (proportional to axial polarization) significantly decreases (to about half of the initial value) under heating up to 100 oC. The piezoresponse becomes inhomogeneous over the surface being higher in the center of the tubes. Further, PFM study of a composite consisting of FF microtubes and reduced graphene oxide (rGO) was performed. We show that piezoelectric properties of peptide microtubes are significantly modified and radial (vertical) piezoresponse appears in the presence of rGO as confirmed via PFM analysis. The results are rationalized in terms of molecular approach in which π – π molecular interaction between rGO and dipeptide is responsible for the appearance of radial component of polarization in such hybrid structures.

Coplanar switching of polarization in thin films of vinylidene fluoride oligomers

Switching of vinylidene fluoride oligomer thin with molecular chains aligned normal to the substrate and exhibiting a preferential in-plane have been investigated using coplanar geometry of inter-digital via high-resolution It has been shown that in-plane switching proceeds via non-180° rotation of dipoles mediated by non-stochastic expansion, and coalescence of domains. As-grown multidomain configuration is found to be strongly pinned aided by charged and the electrically induced (in-plane) mono-domain states relax to the as-grown state. The observed (approximately 0.6 MV/m) is two to three orders of magnitude smaller than that for the oligomer with out-of-plane It is suggested that the low steric hindrance to the rotation of molecular dipoles gives rise to the observed low

Anisotropic polarization response of polar nanostructures in relaxor-type lead lanthanum zirconate titanate ferroelectric ceramics

Polar nanoregions (PNRs) in relaxor-type PLZT ferroelectric ceramics and their response to the out-of-plane, in-plane electric fields were investigated by the high-resolution piezoresponse force microscopy. Anisotropic polarization switching kinetic behaviors of PNRs were found in relaxor PLZT ceramics. Normal, stable ferroelectric domain states were formed through the coalescence of PNRs in the out-of-plane field, while in the high in-plane electric field, the polarization dynamic behaviors of PNRs show spatial inhomogeneity due to the anisotropy random fields in the ferroelectric PLZT ceramics.

Uncovering Nanoscale Electromechanical Heterogeneity in the Subfibrillar Structure of Collagen Fibrils Responsible for the Piezoelectricity of Bone

Understanding piezoelectricity, the linear electromechanical transduction, in bone and tendon and its potential role in mechanoelectric transduction leading to their growth and remodeling remains a challenging subject. With high-resolution piezoresponse force microscopy, we probed piezoelectric behavior in relevant biological samples at different scale levels: from the subfibrillar structures of single isolated collagen fibrils to bone. We revealed that, beyond the general understanding of collagen fibril being a piezoelectric material, there existed an intrinsic piezoelectric heterogeneity within a collagen fibril coinciding with the periodic variation of its gap and overlap regions. This piezoelectric heterogeneity persisted even for the collagen fibrils embedded in bone, bringing about new implications for its possible roles in structural formation and remodeling of bone.

Ferroelectric domain phenomena and growth kinetics of BaMgF4 single crystal by piezoresponse force microscopy

Static and dynamic domain behavior of ferroelectric fluoride BaMgF4 single crystal was investigated using high-resolution piezoresponse force microscopy. High domain wall anisotropy was found in the as-grown BaMgF4 crystal. Antiparallel domain wall strain phenomena due to defects across the domain boundary were directly observed. The lateral domain growth in the inhomogeneous AFM tip field revealed the activation mechanism of the domain wall motion.

Nanoscale polarization relaxation kinetics in polycrystalline ferroelectric thin films

We report on the nanoscale kinetics of ferroelectric domain wall motion in polycrystalline ferroelectric thin films. High-resolution piezoresponse force microscopy is employed to investigate the changes that occur at the domain wall surface during the polarization relaxation process. 50×50nm2 domain images reveal that domain wall motion is a very jerky process. The domain wall motion shows two distinct cycles—one where it breaks into several segments to advance, following which it recombines to form a continuous surface. This “pinning-depinning” cycle continues throughout the relaxation process. A kinetic model based on the concept of domain wall mobility and a thermodynamic driving force is developed to explain this jagged motion.

High-resolution piezoresponse force microscopy investigation of imprint in ferroelectric thin films

High-resolution piezoresponse force microscopy is used to visualize imprint in polycrystalline PbZr0.25Ti0.75O3 thin films. Three-dimensional domain images show the formation of a thin bright band (∼8nm in width) running along the grain boundary after local application of a negative bias. Such bands extend completely over the region under local bias thereby forming networks. Cross-section profile analysis reveals that these are not pinned regions, rather they are formed during the switching process. This demonstrates an active role of grain boundaries in pinning a preferential polarization state. Piezoresponse hysteresis loops confirm that these regions are imprinted.