Flexoelectricity in Solid Dielectrics: From Theory to Applications

Flexoelectricity phenomenologically describes the universal electromechanical coupling effect between electric polarization and strain gradient, and electric field gradient and elastic strain. In contrast to piezoelectricity which is invalid in materials with inversion symmetry, flexoelectricity exists, commonly, in all solid dielectrics. In this paper, a summary of the research on flexoelectricity is presented to illustrate the development of this topic. Flexoelectricity still have many open questions and unresolved issues in the developing field, although it has attracted a surge of attention recently. Here we review the theoretical investigations and experimental studies on flexoelectricity, and the aim of the current paper is to look into the potential applications of this electromechanical coupling effect.     

Towards local electromechanical probing of cellular and biomolecular systems in a liquid environment

Electromechanical coupling is ubiquitous in biological systems, with examples ranging from simple piezoelectricity in calcified and connective tissues to voltage-gated ion channels, energy storage in mitochondria, and electromechanical activity in cardiac myocytes and outer hair cell stereocilia. Piezoresponse force microscopy (PFM) originally emerged as a technique to study electromechanical phenomena in ferroelectric materials, and in recent years has been employed to study a broad range of non-ferroelectric polar materials, including piezoelectric biomaterials. At the same time, the technique has been extended from ambient to liquid imaging on model ferroelectric systems. Here, we present results on local electromechanical probing of several model cellular and biomolecular systems, including insulin and lysozyme amyloid fibrils, breast adenocarcinoma cells, and bacteriorhodopsin in a liquid environment. The specific features of PFM operation in liquid are delineated and bottlenecks on the route towards nanometre-resolution electromechanical imaging of biological systems are identified.     

Flexoelectricity in Bones

Bones generate electricity under pressure, and this electromechanical behavior is thought to be essential for bone's self‐repair and remodeling properties. The origin of this response is attributed to the piezoelectricity of collagen, which is the main structural protein of bones. In theory, however, any material can also generate voltages in response to strain gradients, thanks to the property known as flexoelectricity. In this work, the flexoelectricity of bone and pure bone mineral (hydroxyapatite) are measured and found to be of the same order of magnitude; the quantitative similarity suggests that hydroxyapatite flexoelectricity is the main source of bending‐induced polarization in cortical bone. In addition, the measured flexoelectric coefficients are used to calculate the (flexo)electric fields generated by cracks in bone mineral. The results indicate that crack‐generated flexoelectricity is theoretically large enough to induce osteocyte apoptosis and thus initiate the crack‐healing process, suggesting a central role of flexoelectricity in bone repair and remodeling.     

Electromechanical responses of piezoelectric nanoplates with flexoelectricity

Flexoelectricity, representing the coupling between electrical polarizations and strain gradients, should be taken into account in the analysis of electromechanical responses of nanostructures where large strain gradients are expected. In this paper, we will explore the influence of flexoelectricity on the electromechanical coupling behavior of a simply supported piezoelectric nanoplate by using the Kirchhoff plate theory. The governing equations and corresponding boundary conditions are deduced from Hamilton’s principle, and the analytical solutions are obtained for the deflection and natural frequency. The results indicate that the deflections predicted by the present model are smaller than those calculated by the classical one which only considers piezoelectricity, while the frequencies exhibit the opposite trend. In addition, the flexoelectric effect is more prominent for thinner plates; the differences of the deflections or frequencies between the two models are gradually diminishing with an increase in the plate thickness. The current work may contribute to the understanding of the higher-order electromechanical coupling mechanism. Moreover, the modified plate model can be utilized to accurately design novel piezoelectric nanoplate-based sensors in nanoelectromechanical systems.     

A decade of piezoresponse force microscopy: progress, challenges, and opportunities

Coupling between electrical and mechanical phenomena is a near-universal characteristic of inorganic and biological systems alike, with examples ranging from piezoelectricity in ferroelectric perovskites to complex, electromechanical couplings in electromotor proteins in cellular membranes. Understanding electromechanical functionality in materials such as ferroelectric nanocrystals and thin films, relaxor ferroelectrics, and biosystems requires probing these properties on the nanometer level of individual grain, domain, or protein fibril. In the last decade, piezoresponse force microscopy (PFM) was established as a powerful tool for nanoscale imaging, spectroscopy, and manipulation of ferroelectric materials. Here, we present principles and recent advances in PFM, including vector and frequency-dependent imaging of piezoelectric materials, briefly review applications for ferroelectric materials, discuss prospects for electromechanical imaging of local crystallographic and molecular orientations and disorder, and summarize future challenges and opportunities for PFM emerging in the second decade since its invention     

In Situ TEM Electromechanical Testing of Nanowires and Nanotubes

The emergence of one‐dimensional nanostructures as fundamental constituents of advanced materials and next‐generation electronic and electromechanical devices has increased the need for their atomic‐scale characterization. Given its spatial and temporal resolution, coupled with analytical capabilities, transmission electron microscopy (TEM) has been the technique of choice in performing atomic structure and defect characterization. A number of approaches have been recently developed to combine these capabilities with in‐situ mechanical deformation and electrical characterization in the emerging field of in‐situ TEM electromechanical testing. This has enabled researchers to establish unambiguous synthesis‐structure‐property relations for one‐dimensional nanostructures. In this article, the development and latest advances of several in‐situ TEM techniques to carry out mechanical and electromechanical testing of nanowires and nanotubes are reviewed. Through discussion of specific examples, it is shown how the merging of several microsystems and TEM has led to significant insights into the behavior of nanowires and nanotubes, underscoring the significant role in‐situ techniques play in the development of novel nanoscale systems and materials.     

Exploring nanoscale magnetism in advanced materials with polarized X-rays

Nanoscale magnetism is of paramount scientific interest and high technological relevance. To control magnetization on a nanoscale, both external magnetic fields and spin polarized currents, which generate a spin torque onto the local spin configuration, are being used. Novel ideas of manipulating the spins by electric fields or photons are emerging and benefit from advances in nano-preparation techniques of complex magnetic materials, such as multiferroics, ferromagnetic semiconductors, nanostructures, etc.Advanced analytical tools are needed for their characterization. Polarized soft X-rays using X-ray dichroism effects are used in a variety of spectroscopic and microscopic techniques capable of quantifying in an element, valence and site-sensitive way basic properties of ferro(i)- and antiferromagnetic systems, such as spin and orbital moments, nanoscale spin configurations and spin dynamics with sub-ns time resolution. Future X-ray sources, such as free electron lasers will provide an enormous increase in peak brilliance and open the fs time window to studies of magnetic materials. Thus fundamental magnetic time scales with nanometer spatial resolution can be addressed.This review provides an overview and future opportunities of analytical tools using polarized X-rays by selected examples of current research with advanced magnetic materials.     

Immunogold FIB‐SEM: Combining Volumetric Ultrastructure Visualization with 3D Biomolecular Analysis to Dissect Cell–Environment Interactions

Volumetric imaging techniques capable of correlating structural and functional information with nanoscale resolution are necessary to broaden the insight into cellular processes within complex biological systems. The recent emergence of focused ion beam scanning electron microscopy (FIB‐SEM) has provided unparalleled insight through the volumetric investigation of ultrastructure; however, it does not provide biomolecular information at equivalent resolution. Here, immunogold FIB‐SEM, which combines antigen labeling with in situ FIB‐SEM imaging, is developed in order to spatially map ultrastructural and biomolecular information simultaneously. This method is applied to investigate two different cell–material systems: the localization of histone epigenetic modifications in neural stem cells cultured on microstructured substrates and the distribution of nuclear pore complexes in myoblasts differentiated on a soft hydrogel surface. Immunogold FIB‐SEM offers the potential for broad applicability to correlate structure and function with nanoscale resolution when addressing questions across cell biology, biomaterials, and regenerative medicine.     

Machine Detection of Enhanced Electromechanical Energy Conversion in PbZr0.2Ti0.8O3 Thin Films

Many energy conversion, sensing, and microelectronic applications based on ferroic materials are determined by the domain structure evolution under applied stimuli. New hyperspectral, multidimensional spectroscopic techniques now probe dynamic responses at relevant length and time scales to provide an understanding of how these nanoscale domain structures impact macroscopic properties. Such approaches, however, remain limited in use because of the difficulties that exist in extracting and visualizing scientific insights from these complex datasets. Using multidimensional band‐excitation scanning probe spectroscopy and adapting tools from both computer vision and machine learning, an automated workflow is developed to featurize, detect, and classify signatures of ferroelectric/ferroelastic switching processes in complex ferroelectric domain structures. This approach enables the identification and nanoscale visualization of varied modes of response and a pathway to statistically meaningful quantification of the differences between those modes. Among other things, the importance of domain geometry is spatially visualized for enhancing nanoscale electromechanical energy conversion.     

Multiscale Soft–Hard Interface Design for Flexible Hybrid Electronics

Emerging next-generation soft electronics will require versatile properties functioning under mechanical compliance, which will involve the use of different types of materials. As a result, control over material interfaces (particularly soft/hard interfaces) has become crucial and is now attracting intensive worldwide research efforts. A series of material and structural interface designs has been devised to improve interfacial adhesion, preventing failure of electromechanical properties under mechanical deformation. Herein, different soft/hard interface design strategies at multiple length scales in the context of flexible hybrid electronics are reviewed. The crucial role of soft ligands and/or polymers in controlling the morphologies of active nanomaterials and stabilizing them is discussed, with a focus on understanding the soft/hard interface at the atomic/molecular scale. Larger nanoscopic and microscopic levels are also discussed, to scrutinize viable intrinsic and extrinsic interfacial designs with the purpose of promoting adhesion, stretchability, and durability. Furthermore, the macroscopic device/human interface as it relates to real-world applications is analyzed. Finally, a perspective on the current challenges and future opportunities in the development of truly seamlessly integrated soft wearable electronic systems is presented.     

Self‐Assembly of Functional Molecules into 1D Crystalline Nanostructures

Self‐assembled functional nanoarchitectures are employed as important nanoscale building blocks for advanced materials and smart miniature devices to fulfill the increasing needs of high materials usage efficiency, low energy consumption, and high‐performance devices. One‐dimensional (1D) crystalline nanostructures, especially molecule‐composed crystalline nanostructures, attract significant attention due to their fascinating infusion structure and functionality which enables the easy tailoring of organic molecules with excellent carrier mobility and crystal stability. In this review, we discuss the recent progress of 1D crystalline self‐assembled nanostructures of functional molecules, which include both a small molecule‐derived and a polymer‐based crystalline nanostructure. The basic principles of the molecular structure design and the process engineering of 1D crystalline nanostructures are also discussed. The molecular building blocks, self‐assembly structures, and their applications in optical, electrical, and photoelectrical devices are overviewed and we give a brief outlook on crucial issues that need to be addressed in future research endeavors.     

Phase Stability in Nanostructures

Nanostructured materials provide access to tailor‐made materials properties by microstructural design. Excellent mechanical properties such as high strength or wear resistance are often found in nanocrystalline materials. For magnetic materials, the design of nanostructured composites offers advantages if the structural scales match the intrinsic magnetic length scales. In some cases, as in the new nanocrystalline soft magnetic alloys, the combination of amorphous and nanocrystalline phases is necessary to obtain the desired properties. This rises the question of the limiting size for a stable crystalline structure, especially in contact with an amorphous phase. These considerations, which have been of interest for basic research in the context of the microcrystalline model for amorphous materials, are of technical importance for the optimization of nanostructured composites. Recent model experiments about the stability of thin Fe‐based glass forming alloy films are reviewed. A relationship between phase stability, composition, and interface density has been established. The implications of the results for the design of nanostructured alloy systems are discussed.     

Boundary element formulation for plane problems in size‐dependent piezoelectricity

A new boundary element formulation is developed to analyze two‐dimensional size‐dependent piezoelectric response in isotropic dielectric materials. The model is based on the recently developed consistent couple stress theory, in which the couple‐stress tensor is skew‐symmetric. For isotropic materials, there is no classical piezoelectricity, and the size‐dependent piezoelectricity or flexoelectricity effect is solely the result of coupling of polarization to the skew‐symmetric mean curvature tensor. As a result, the size‐dependent effect is specified by one characteristic length scale parameter l, and the electromechanical effect is specified by one flexoelectric coefficient f. Interestingly, in this size‐dependent multi‐physics model, the governing equations are decoupled. However, the problem is coupled, because of the existence of a flexoelectric effect in the boundary couple‐traction and normal electric displacement. We discuss the boundary integral formulation and numerical implementation of this size‐dependent piezoelectric boundary element method, which provides a boundary‐only formulation involving displacements, rotations, force‐tractions, couple‐tractions, electric potential, and normal electric displacement as primary variables. Afterwards, we apply the resulting BEM formulation to several computational problems to confirm the validity of the numerical implementation and to explore the physics of the flexoelectric coupling. Copyright © 2016 John Wiley & Sons, Ltd.     

Amorphous Quantum Nanomaterials

In quantum materials, macroscopic behavior is governed in nontrivial ways by quantum phenomena. This is usually achieved by exquisite control over atomic positions in crystalline solids. Here, it is demonstrated that the use of disordered glassy materials provides unique opportunities to tailor quantum material properties. By borrowing ideas from single‐molecule spectroscopy, single delocalized π‐electron dye systems are isolated in relatively rigid ultrasmall (<10 nm diameter) amorphous silica nanoparticles. It is demonstrated that chemically tuning the local amorphous silica environment around the dye over a range of compositions enables exquisite control over dye quantum behavior, leading to efficient probes for photodynamic therapy (PDT) and stochastic optical reconstruction microscopy (STORM). The results suggest that efficient fine‐tuning of light‐induced quantum behavior mediated via effects like spin‐orbit coupling can be effectively achieved by systematically varying averaged local environments in glassy amorphous materials as opposed to tailoring well‐defined neighboring atomic lattice positions in crystalline solids. The resulting nanoprobes exhibit features proven to enable clinical translation.     

Advances in Biological Liquid Crystals

Biological liquid crystals, a rich set of soft materials with rod‐like structures widely existing in nature, possess typical lyotropic liquid crystalline phase properties both in vitro (e.g., cellulose, peptides, and protein assemblies) and in vivo (e.g., cellular lipid membrane, packed DNA in bacteria, and aligned fibroblasts). Given the ability to undergo phase transition in response to various stimuli, numerous practices are exercised to spatially arrange biological liquid crystals. Here, a fundamental understanding of interactions between rod‐shaped biological building blocks and their orientational ordering across multiple length scales is addressed. Discussions are made with regard to the dependence of physical properties of nonmotile objects on the first‐order phase transition and the coexistence of multi‐phases in passive liquid crystalline systems. This work also focuses on how the applied physical stimuli drives the reorganization of constituent passive particles for a new steady‐state alignment. A number of recent progresses in the dynamics behaviors of active liquid crystals are presented, and particular attention is given to those self‐propelled animate elements, like the formation of motile topological defects, active turbulence, correlation of orientational ordering, and cellular functions. Finally, future implications and potential applications of the biological liquid crystalline materials are discussed.     

One‐step Preparation of Monodisperse Multifunctional Macroporous Particles through a Spontaneous Physical Process

Macroporous particles that combine the property features of spherical structures and porous materials are expected to find use over micro‐ and macroscopic length scales from miniaturized systems such as cell imaging, drug and gene delivery to industrial applications. However, the capacity for de novo design of such materials is still limited. Here, a spontaneous process to fabricate monodisperse multifunctional macroporous particles (MMMPs) by high internal phase emulsion templating is reported. An interesting physical phenomenon involving self‐emulsification and synergistic effects between nanoparticles and amphiphilic diblock copolymers is observed in this process. These MMMPs, featured with tailor‐made pore structures, pH responsiveness, and magnetic response, could be used as stimuli‐responsive carriers for multiple functional molecules with a high loading and releasing efficiency. This new understanding regarding the underlying phenomena that control self‐emulsification behavior and synergistic action in emulsion systems provides a unique outlook and a novel approach to the design of potentially multifunctional porous materials for controllable release and delivery processes.     

Hydrogels and Scaffolds for Immunomodulation

For over two decades, immunologists and biomaterials scientists have co‐existed in parallel world with the rationale of understanding the molecular profile of immune responses to vaccination, implantation, and treating incurable diseases. Much of the field of biomaterial‐based immunotherapy has relied on evaluating model antigens such as chicken egg ovalbumin in mouse models but their relevance to humans has been point of much discussion. Nevertheless, such model antigens have provided important insights into the mechanisms of immune regulation and served as a proof‐of‐concept for plethora of biomaterial‐based vaccines. After years of extensive development of numerous biomaterials for immunomodulation, it is only recently that an experimental scaffold vaccine implanted beneath the skin has begun to use the human model to study the immune responses to cancer vaccination by co‐delivering patient‐derived tumor lysates and immunomodulatory proteins. If successful, this scaffold vaccine will change the way we approached untreatable cancers, but more importantly, will allow a faster and more rational translation of therapeutic regimes to other cancers, chronic infections, and autoimmune diseases. Most materials reviews have focused on immunomodulatory adjuvants and micro‐nano‐particles. Here we provide an insight into emerging hydrogel and scaffold based immunomodulatory approaches that continue to demonstrate efficacy against immune associated diseases.     

3D Printed Tubulanes as Lightweight Hypervelocity Impact Resistant Structures

Lightweight materials with high ballistic impact resistance and load‐bearing capabilities are regarded as a holy grail in materials design. Nature builds these complementary properties into materials using soft organic materials with optimized, complex geometries. Here, the compressive deformation and ballistic impact properties of three different 3D printed polymer structures, named tubulanes, are reported, which are the architectural analogues of cross‐linked carbon nanotubes. The results show that macroscopic tubulanes are remarkable high load‐bearing, hypervelocity impact‐resistant lightweight structures. They exhibit a lamellar deformation mechanism, arising from the tubulane ordered pore structure, manifested across multiple length scales from nano to macro dimensions. This approach of using complex geometries inspired by atomic and nanoscale models to generate macroscale printed structures allows innovative morphological engineering of materials with tunable mechanical responses.     

The feedback loop between theory,simulation and experiment for plasticity and property modeling

Recent advances in theory, simulation and experiment are leading to new capabilities for understanding and characterizing the relation between dislocation substructure evolution and materials properties and performance. With the emergence of large-scale computational capabilities, techniques such as three-dimensional discrete dislocation dynamics simulations are providing new insights to a range of materials deformation phenomena. Such simulations provide direct measures of dislocation motion and substructure development at small and continuously increasing length scales and time scales. Concurrently, the advent of new experimental techniques promises to revolutionize our ability to directly characterize dislocation substructures and their relationship to the microstructure of a range of material systems. Taken by themselves, the simulations and experiments will greatly advance our understanding of materials behavior. We argue, however, that close linkage of the two will provide critically needed validation and enable progress in solving some of the most challenging problems of plasticity, thereby profoundly impacting our ability to predict properties and performance of materials in engineered systems.