摘要
以钙钛矿为代表的共点配位多面体晶体(CSCPC)具有独特而丰富的光、电、磁性质,在多铁材料、快离子导体、光电催化等方面具有广阔的应用前景.在众多CSCPC中,具有优异理化性质的相只是极少数.因此,如何通过结构调控获得这些相,一直是相关领域的研究热点和“卡脖子”问题.受此启发,本文从相结构的角度评述了近年来高性能CSCPC的合成研究,以期明确相转变的内在规律,并揭示其中所蕴藏的相调控机制.首先系统地总结了CSCPC中常见的多面体和晶格骨架的类型,并将多面体畸变大致分为偏移、转动、变形三大类.以此为基础,对各类材料合成方案进行分析和归纳,发现传统的合成方案多依赖于宏观尺度上对温度、压力、组分等外部物理条件的改变.近年来,新兴的合成方案聚焦于对多面体几何和拓扑结构的微观调控,如利用容忍因子和基板趋近效应来构造相结构.它们在本质上都遵循着共同的相调控机制,即通过引发多面体的畸变来诱导晶体转变成具有目标属性的相结构.不同的是,后者具有更强的目标导向性,但其适用面还局限在配位八面体的转动体系,如何拓展其应用范围尚存挑战性.此外,“明确引发畸变的根源及各畸变间相互作用”以及“基于计算机科学的定制化指导”都是优化合成方案的未来方向.本文所做的调研和评述以期为高性能CSCPC材料的设计和制备提供一些思路和启发.
Corner-shared coordination polyhedral crystals(CSCPCs)represented by perovskites have unique and various properties in optics,electrics,and magnetism,leading to their broad applications such as in serving as ferroelectric material,fast ionic conductors,and electro/photo-catalysts.However,the excellent properties are owned only by a very small fraction of CSCPS phases.How to obtain such phases through structural operation has always been a research hotspot and a bottleneck in related fields.Herein,we review the recent research progress of the synthesis of high-performance CSCPC materials from the perspective of phase structure,in order to clarify the intrinsic rules of phase evolution and reveal the mechanism behind the phase manipulation.We first systematically summarize the types of polyhedra and crystal frameworks in CSCPCs and classify the polyhedral distortions as three main types,i.e.cation displacements,polyhedral rotations,and deformations.Based on that,we further analyze and conclude different material synthesis methods.We find that most traditional synthesis methods rely on the phase transitions induced by the change of external physical conditions at a macroscopic level,such as composition,temperature,and pressure.Recently,there was an emerging synthesis method focusing on the microscopic manipulation of polyhedral geometry and topology,such as phase constructions according to tolerance-factor and substrate-proximity effects.The macroscopic synthesis methods and the microscopic synthesis methods share the same phase manipulation mechanism:making crystals transit into the structure-specified phases by inducing polyhedral distortions.The only difference is that the latter is more target-oriented,but its applications are currently limited to octahedral coordination tilt/rotation systems.Expanding its application scope is still a challenge.In addition,we propose two aspects that may be useful in optimizing the synthesis method:one is to clarify the origin of induced distortions and the interaction between d
作者
方成
汪洪
施思齐
Fang Cheng;Wang Hong;Shi Si-Qi(State Key Laboratory of Green Building Materials,China Building Materials Academy,Beijing 100024,China;Beijing Key Laboratory of Solar Energy and Building Energy-saving Glass Materials Processing Technology,China Building Materials Academy,Beijing 100024,China;Materials Genome Initiative Center,Shanghai Jiao Tong University,Shanghai 200240,China;School of Materials Science and Engineering,Shanghai Jiao Tong University,Shanghai 200240,China;Zhang Jiang Institute for Advanced Study,Shanghai Jiao Tong University,Shanghai 201203,China;School of Materials Science and Engineering,Shanghai University,Shanghai 200444,China;Materials Genome Institute,Shanghai University,Shanghai 200444,China)
出处
《物理学报》
SCIE
EI
CAS
CSCD
北大核心
2023年第18期159-169,共11页
Acta Physica Sinica
关键词
共点配位多面体晶体
多面体畸变
相转变
属性调控
合成方案
corner-shared coordination polyhedral crystal
polyhedral distortion
phase evolution
property manipulation
synthesis method
