钠钨青铜Na2W4O13的孪晶结构与辐照相变

钠钨青铜Na₂W₄O₁₃的孪晶结构与辐照相变

林泽圣^#，刘曦^#，蒋仁辉，李佩，赵培丽，唐真，王怀远，王桢源，黄天龙，吴姗姗，贾双凤，郑赫^*，王建波

（1. 武汉大学物理科学与技术学院，电子显微镜中心，人工微结构教育部重点实验室和高等研究院，湖北武汉430072；2. 武汉大学科研公共服务条件平台，湖北武汉430072）

摘 要   本文采用热氧化法制备了Na₂W₄O₁₃纳米片，并利用球差校正扫描透射电子显微技术对其孪晶畴结构进行了原子尺度表征，发现样品中存在大量镜面孪晶结构。结合群论中的母子群关系理论，解析了Na₂W₄O₁₃中畴结构形成的原因，并预测了9种可能的畴结构，其中type3镜面孪晶与实验中观察到取向关系为[010]//[0 0]_T、(100)//(100)_T的(100)孪晶一致。经过电子束辐照，三斜结构的Na₂W₄O₁₃可以相变为立方结构的Na_xWO₃（x< 0.5）。而有孪晶存在的样品中，相变过程中容易出现缺陷，这可能是由晶格失配导致的。论文结果为理解钠钨青铜材料的结构与性能提供借鉴。

关键词   钠钨青铜Na₂W₄O₁₃；过渡金属层状氧化物；取向畴；群论；透射电子显微学     中图分类号：TG115. 21⁺ 5. 3; O766⁺. 1; O753⁺. 1; O722⁺. 4; O761; O763 文献标识码: Adoi：10.3969/j.issn.1000-6281.2024.03.003

Twin structure and irradiation-induced phase transition in sodium tungsten bronzeNa₂W₄O₁₃

LIN Zesheng^1#, LIU Xi^1#, JIANG Renhui¹, LI Pei¹, ZHAO Peili¹, TANG Zhen¹, WANG Huaiyuan¹,WANG Zhenyuan¹, HUANG Tianlong¹,WU Shanshan¹, JIA Shuangfeng¹, ZHEN He^1*, WANG Jianbo^1,2*

（1. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan Hubei 430072；2. Core Facility of Wuhan University, Wuhan Hubei430072）

Abstract    In this paper, Na₂W₄O₁₃ nanosheets were prepared by thermal oxidation method and characterized by scanning transmission electron microscopy at the atomic scale. Typical twin structures were observed in most samples. The formation of domain structure in Na₂W₄O₁₃ was analyzed by group theory. Nine possible domain structures were predicted. Among them, the type3 mirror twin is consistent with the (100) twin with the orientation relationship of [010]//[0 0]_T and (100)//(100)_T. Additionally, the electron beam irradiation on single crystalline and twinning-structure nanomaterials was studied. The phase-transition from triclinic-structure Na₂W₄O₁₃ to cubic-phase Na_xWO₃（x< 0.5）occurred in both types of samples. The samples with twinning structure showed the nucleation of point defect caused by lattice mismatch between twin variant and substrate. Our results shed light on the microstructure in layered Na₂W₄O₁₃ materials, which may facilitate the basic understanding of the structure-property interplay in tungsten bronzes. 

keywords    sodium tungsten bronze Na₂W₄O₁₃; transition metal layer oxide; orientation domain; group theory; transmission electron microscope

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