化学学报 ›› 2000, Vol. 58 ›› Issue (2): 178-183. 上一篇    下一篇

研究论文

铅基复合钙钛矿型弛豫铁电单晶的生长基元与生长机理: II.成 分、结构起伏与 同型生长基元的分异和组装

许桂生;罗豪Su;仲维卓;殷之文;刘克   

  1. 湘潭工学院;中国科学院上海硅酸盐研究所.上海(200050);中国科学院无机功 能材料开放实验室
  • 发布日期:2000-02-15

Growth units and growth mechanism of lead-based complex perovskite relaxor ferroelectric single crystals: II. Splitting and assembling of the same type of growth units related to the fluctuation in composition nad structure

Xu Guisheng;LUO HAO;Zhong Weizhao;Yin Zhiwen;Liu Ke   

  1. Shanghai Inst Ceram., CAS.Shanghai(200050)
  • Published:2000-02-15

铅基复合钙钛矿型弛豫铁电单晶体PMNT,PZNT的生长基元为多种[BO~6]配位八面体。这些同型生长基元受本身稳定性的制约而在熔体中存在的几率不同。相对于[MgO~6]^1^0^-,[ZnO~6]^1^0^-八面体基元来说,[NbO~6]^7^-,[TiO~6]^8^-是更为有利的八面体基元。在基元组装过程中,各种[BO~6]八面体基元在稳定性、尺寸大小与电价上的分异致使生长界面对基元有一定的选择性,从而造成了晶体生长时成分与结构的短程起伏,并为有序畴及其它化学缺陷团簇的形成提供了条件。当加入掺质PbTiO~3时,由于[TiO~6]^8^-与[NbO~6]^7^-两种基元在组装时的类聚性及[TiO~6]^8^-对晶体稳定性的贡献,晶体的微区成分与结构得以调制,焦发石相得以抑制,这构成了用Bridgman法能直接从熔体中生长出纯钙钛矿相PMNT单晶的基础。而[MgO~6]^1^0^-与[ZnO~6]^1^0^-八面体基元的差致使PMNT,PZNT两单晶的生长难度有别,这在选择合适的生长方法时需加以考虑。

关键词: 钙钛矿型结构, 铁电晶体, 晶体生长, 弛豫, 钛酸铅, 氧化镁, 氧化铌, 氧化铅

This paper discusses the relation between the splitting and assembling of the same type growth units and the fluctuation in composition and structure in relaxor ferroelectric single crystals PMNT and PZNT, which belong to lead-based complex perovskite structures. Their growth units are considered as coordination octahedra [BO~6]. Depending on their stability, different [BO~6] growth units in the melt may have different probability to exist. [NbO~6]^7^- and [TiO~6]^8^- are more stable or more favorable octahedral units than [MgO~6]^1^0^- and [ZnO~6]^1^0^-. Various [BO~6] units exhibit remarkable difference in stability, ion size and ion electrovalence. Therefore, the growth interfaces with electric charges would make a choice among those [BO~6] growth units, resulting in the short range of fluctuation in composition and structure at the stage of crystal growth and preparing for the subsequent formation of ordered domains and other chemical defect clusters. Adding the dopant PbTiO~3 to solid solution could adjust the composition and structure of micro-regions and suppress the formation of pyrochlore, which could contribute to the resemblance between the octahedral units [TiO~6]^8^- and [NbO~6]^7^- and the stability effect of [TiO~6]^8^- in crystal structures. This become an important basis for using the modified Bridgman technique to grow pure perovskite PMNT single crystals directly from melt. The evident distinction in growth difficulty between PMNT and PZNT crystals is attributed to the differences between the growth units [MgO~6]^1^0^- and [ZnO~6]^1^0^-. The stability of growth units or structure ones should be taken into consideration when choosing the growth methods.

Key words: PEROVSKITE TYPE STRUCTURE, FERROELECTRIC CRYSTALS, CRYSTAL GROWTH, RELAXATION, MAGNESIUM OXIDE, NIOBIUM OXIDE, LEAD OXIDE

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