铁电材料的极化疲劳:基本机理和最新进展

简要回顾了铁电材料中极化疲劳现象的基本机理和最新进展.详细地介绍了作者和其合作者最近创立的LPD-SICI模型(LPD-SICI是指极化翻转引起的电荷注入导致的局域相分离).LPD-SICI模型认为导致铁电材料中极化疲劳的主要原因是:在极化翻转早期形成的针状畴顶端的非屏蔽束缚电荷在电极-薄膜界面处会导致强烈的电荷注入(主要是电子),引起局域的焦耳热,最后在畴成核位置引发局域相分离.通过回顾过去几年在铁电材料电学极化疲劳方面实验研究的最新进展,得出LPD-SICI模型与过去三年中文献上发表的大多数实验观测相一致,并可以解释这些现象的起因.因此,极化翻转导致的局域相分离可能是各种类型铁电材料极化疲劳的共同起因.     

Giant Ferroelectric Polarization in Ultrathin Ferroelectrics via Boundary‐Condition Engineering

Tailoring and enhancing the functional properties of materials at reduced dimension is critical for continuous advancement of modern electronic devices. Here, the discovery of local surface induced giant spontaneous polarization in ultrathin BiFeO₃ ferroelectric films is reported. Using aberration‐corrected scanning transmission electron microscopy, it is found that the spontaneous polarization in a 2 nm‐thick ultrathin BiFeO₃ film is abnormally increased up to ≈90–100 µC cm^?2 in the out‐of‐plane direction and a peculiar rumpled nanodomain structure with very large variation in c /a ratios, which is analogous to morphotropic phase boundaries (MPBs), is formed. By a combination of density functional theory and phase‐field calculations, it is shown that it is the unique single atomic Bi₂O_3?x layer at the surface that leads to the enhanced polarization and appearance of the MPB‐like nanodomain structure. This finding clearly demonstrates a novel route to the enhanced functional properties in the material system with reduced dimension via engineering the surface boundary conditions.     

Light‐Induced Reversible Control of Ferroelectric Polarization in BiFeO3

Manipulation of ferroic order parameters, namely (anti‐)ferromagnetic, ferroelectric, and ferroelastic, by light at room temperature is a fascinating topic in modern solid‐state physics due to potential cross‐fertilization in research fields that are largely decoupled. Here, full optical control, that is, reversible switching, of the ferroelectric/ferroelastic domains in BiFeO₃ thin films at room temperature by the mediation of the tip‐enhanced photovoltaic effect is demonstrated. The enhanced short‐circuit photocurrent density at the tip contact area generates a local electric field well exceeding the coercive field, enabling ferroelectric polarization switching. Interestingly, by tailoring the photocurrent direction, via either tuning the illumination geometry or simply rotating the light polarization, full control of the ferroelectric polarization is achieved. The finding offers a new insight into the interactions between light and ferroic orders, enabling fully optical control of all the ferroic orders at room temperature and providing guidance to design novel optoferroic devices for data storage and sensing.     

钛酸铅陶瓷的介电和极化翻转特性研究

以水热纳米粉为前驱粉料,采用传统烧结工艺在950℃制备了致密性高、具有亚微米尺寸晶粒的钛酸铅(PbTiO3)陶瓷,并对其介电温谱和压电响应特性进行了系统的研究。结果表明,PbTiO3陶瓷在低温下的相对介电常数与测试频率无关,在室温以上,随着频率的增加,介电峰值向低温方向移动;压电力显微镜研究结果显示PbTiO3陶瓷中具有明显的微区极化翻转,表明具有较好的铁电性能。     

铁电极化诱导的PbTiO3薄膜的取向聚集生长和晶粒尺寸调控

用溶胶凝胶法制备了PbTiO₃薄膜。将含量为0.2%、0.5%和0.8%(摩尔比)的钙钛矿铁电PbTiO₃纳米片加入溶胶体系中,利用纳米片的自发极化调控薄膜的生长。结果表明,纳米片的加入显著影响了薄膜的生长过程和结晶学取向,可制备出(100)高度取向的PbTiO₃薄膜;改变纳米片的浓度,可将薄膜晶粒尺寸由100 nm调控到2 μm。扫描电子显微镜(SEM)、透射电子显微镜(TEM)观测和原位X射线衍射(in-situ XRD)的结果表明,固态薄膜中的晶粒表现出类液相的取向聚集生长特征。其原因可能是,铁电纳米片极化表面的静电力诱导小晶粒的吸附和取向排列,调控了薄膜的(100)取向和晶粒尺寸。     

Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Viewpoint: From Responsive to Adaptive and Interactive Materials and Materials Systems: A Roadmap

Soft matter systems and materials are moving toward adaptive and interactive behavior, which holds outstanding promise to make the next generation of intelligent soft materials systems inspired from the dynamics and behavior of living systems. But what is an adaptive material? What is an interactive material? How should classical responsiveness or smart materials be delineated? At present, the literature lacks a comprehensive discussion on these topics, which is however of profound importance in order to identify landmark advances, keep a correct and noninflating terminology, and most importantly educate young scientists going into this direction. By comparing different levels of complex behavior in biological systems, this Viewpoint strives to give some definition of the various different materials systems characteristics. In particular, the importance of thinking in the direction of training and learning materials, and metabolic or behavioral materials is highlighted, as well as communication and information-processing systems. This Viewpoint aims to also serve as a switchboard to further connect the important fields of systems chemistry, synthetic biology, supramolecular chemistry and nano- and microfabrication/3D printing with advanced soft materials research. A convergence of these disciplines will be at the heart of empowering future adaptive and interactive materials systems with increasingly complex and emergent life-like behavior.     

The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [R‐ and S‐1‐(4‐Chlorophenyl)ethylammonium]2PbI4

2D organic–inorganic lead iodide perovskites have recently received tremendous attention as promising light absorbers for solar cells, due to their excellent optoelectronic properties, structural tunability, and environmental stability. However, although great efforts have been made, no 2D lead iodide perovskites have been discovered as ferroelectrics, in which the ferroelectricity may improve the photovoltaic performance. Here, by incorporating homochiral cations, 2D lead iodide perovskite ferroelectrics [R‐1‐(4‐chlorophenyl)ethylammonium]₂PbI₄ and [S‐1‐(4‐chlorophenyl)ethylammonium]₂PbI₄ are successfully obtained. The vibrational circular dichroism spectra and crystal structural analysis reveal their homochirality. They both crystalize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition with transition temperature as high as 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. They also possess semiconductor characteristics with a direct bandgap of 2.34 eV. Nevertheless, their racemic analogue adopts a centrosymmetric space group P2₁/c at room temperature, exhibiting no high‐temperature phase transition. The homochirality in 2D lead iodide perovskites facilitates crystallization in polar space groups. This finding indicates an effective way to design high‐performance 2D lead iodide perovskite ferroelectrics with great application prospects.     

Better,Faster, and Less Biased Machine Learning: Electromechanical Switching in Ferroelectric Thin Films

Machine-learning techniques are more and more often applied to the analysis of complex behaviors in materials research. Frequently used to identify fundamental behaviors within large and multidimensional datasets, these techniques are strictly based on mathematical models. Thus, without inherent physical or chemical meaning or constraints, they are prone to biased interpretation. The interpretability of machine-learning results in materials science, specifically materials’ functionalities, can be vastly improved through physical insights and careful data handling. The use of techniques such as dimensional stacking can provide the much needed physical and chemical constraints, while proper understanding of the assumptions imposed by model parameters can help avoid overinterpretation. These concepts are illustrated by application to recently reported ferroelectric switching experiments in PbZr_0.2Ti_0.8O₃ thin films. Through systematic analysis and introduction of physical constraints, it is argued that the behaviors present are not necessarily due to exotic mechanisms previously suggested, but rather well described by classical ferroelectric switching superimposed by non-ferroelectric phenomena, such as electrochemical deformation, electrostatic interactions, and/or charge injection.     

From Flatland to Spaceland: Higher Dimensional Patterning with Two‐Dimensional Materials

The creation of three‐dimensional (3D) structures from two‐dimensional (2D) nanomaterial building blocks enables novel chemical, mechanical or physical functionalities that cannot be realized with planar thin films or in bulk materials. Here, we review the use of emerging 2D materials to create complex out‐of‐plane surface topographies and 3D material architectures. We focus on recent approaches that yield periodic textures or patterns, and present four techniques as case studies: (i) wrinkling and crumpling of planar sheets, (ii) encapsulation by crumpled nanosheet shells, (iii) origami folding and kirigami cutting to create programmed curvature, and (iv) 3D printing of 2D material suspensions. Work to date in this field has primarily used graphene and graphene oxide as the 2D building blocks, and we consider how these unconventional approaches may be extended to alternative 2D materials and their heterostructures. Taken together, these emerging patterning and texturing techniques represent an intriguing alternative to conventional materials synthesis and processing methods, and are expected to contribute to the development of new composites, stretchable electronics, energy storage devices, chemical barriers, and biomaterials.     

Dielectric Polarization in Inverse Spinel-Structured Mg2TiO4 Coating to Suppress Oxygen Evolution of Li-Rich Cathode Materials

High-energy Li-rich layered cathode materials (≈900 Wh kg⁻¹) suffer from severe capacity and voltage decay during cycling, which is associated with layered-to-spinel phase transition and oxygen redox reaction. Current efforts mainly focus on surface modification to suppress this unwanted structural transformation. However, the true challenge probably originates from the continuous oxygen release upon charging. Here, the usage of dielectric polarization in surface coating to suppress the oxygen evolution of Li-rich material is reported, using Mg₂TiO₄ as a proof-of-concept material. The creation of a reverse electric field in surface layers effectively restrains the outward migration of bulk oxygen anions. Meanwhile, high oxygen-affinity elements of Mg and Ti well stabilize the surface oxygen of Li-rich material via enhancing the energy barrier for oxygen release reaction, verified by density functional theory simulation. Benefited from these, the modified Li-rich electrode exhibits an impressive cyclability with a high capacity retention of ≈81% even after 700 cycles at 2 C (≈0.5 A g⁻¹), far superior to ≈44% of the unmodified counterpart. In addition, Mg₂TiO₄ coating greatly mitigates the voltage decay of Li-rich material with the degradation rate reduced by ≈65%. This work proposes new insights into manipulating surface chemistry of electrode materials to control oxygen activity for high-energy-density rechargeable batteries.