【作者】 郭丽玲；

【导师】 刘韩星；

【作者基本信息】 武汉理工大学 ， 材料学， 2006， 博士

【摘要】 钙钛矿或类钙钛矿结构是功能材料的一类重要母体结构，不仅因为很多新发现的功能材料具有这类结构，还因为这类结构具有非凡的结构畸变自调和能力。人们可以按照器件对材料性能的具体要求对三维钙钛矿进行低维度的拆分与组装，层状类钙钛矿结构的有机-无机杂合物就是指由有机、无机物通过软化学法组装而得的、分子水平上的有机-无机复合物，具有层状类钙钛矿结构。该类杂合物的独特性能使它们在微电子领域中有广泛的应用前景。 层状类钙钛矿结构的有机-无机杂合物不仅使有机、无机材料的优势性能在分子尺度上的结合成为可能，还为深入研究材料的结构形成规律、结构与性能的关系提供了前所未有的机会。而材料的结构是性能的决定因素之一，因此系统地研究层状类钙钛矿杂合物的结构及形成规律，对获得该类材料的结构与性能的关系，获得其结构设计原则和实现性能控制有重要的理论意义与实际意义。 本文对预期具有层状类钙钛矿结构、化学式为(C_nH_2n+1NH₃)₂MCl₄（其中M=Mn，Fe，Co，Ni，Cu，Zn；n=2，4，6，8，10，12）的有机-无机杂合物晶体的合成与结构进行了系统研究，用液相反应成功合成出M=Mn，Fe，Co，Cu，Zn五个系列共30种杂合物，并得到了各系列杂合物的最佳合成条件。 用常温下的X射线衍射谱、扫描电镜、傅立叶变换红外谱和热重分析对各系列杂合物的常温结构，对各组分间的相互作用进行了系统的研究。研究发现，各杂合物都具有典型的层状结构，同金属系列杂合物的层间距随有机链长的增加而线性增加。而且M=Mn，Fe，Cu的杂合物组与M=Co，Zn的杂合物组存在组内的结构相似性和组间的结构差异性。结构的相似性与差异性既来自于有机元在空间排列的组内相同和组间不同，也来自于无机元结构的组内相同和组间不同：M=Mn，Fe，Cu组内无机层由共顶连接的[MCl₆]八面体构成，而M=Co，Zn组内无机层由不共用任何几何元素的[MCl₄]四面体构成。金属-氯离子、有机-无机元、有机-有机元之间相互作用的不同对杂合物的结构形成及稳定性都有影响。 在相变温度附近的变温条件下，用X射线衍射谱、傅立叶变换红外谱和激光拉曼谱对n=12的杂合物相变的结构进行了研究。研究发现，相变是可逆的。相变后杂合物层间距增大，层间距增大是杂合物中有机元的构象变化造成的，无机元的结构在相变前后保持了相对稳定。这一点又由相变前后杂合物在可见光区吸收谱没有能带的变化只有吸光度的变化所证实。根据层间距大小可合理推测旁式-反式键间隔的构象和全旁式构象是高温相最可能的构象。更多还原

【Abstract】 The perovskite-type structure is one of the most important parent structures of functional materials. This is not only because of the numerical superiority of the new functional materials with this structure but also because of the self-harmonic variation of the structure distortions. The 3-dimensional perovskite structure can be cut into low-dimensional structural units and be assembled according to the specific property requirements of the materials in kinds of devices. Layered perovskite-type organic-inorganic hybrids are sort of the assembly of the organic and inorganic units by employing the soft chemistry methods. In the assembly, the organic and the inorganic units were hybridized on the molecular scale and formed the layered perovskite structure. In the microelectronics field, the potential application of the hybrids is in good prospect for their novel properties.The layered perovskite-type hybrids give the possibilities of combining the useful properties of the organic and inorganic compounds. Moreover, they provide a new substantial opportunity for deeply understand the laws of the structure forming and the relationship of the structures and properties. The properties of materials strongly depend on their structures. In order to get the principles and to get to the realization of the structure and property design or control, it is quite necessary to systematically study the layered perovskite hybrids on the structures and the structure forming and it is very significant both in the theories and in the realities.This dissertation focuses on the synthesis and the structures of the organic-inorganic hybrids with chemical formula (C_nH_2n+1NH₃)₂MCl₄ and the expected layered perovskite-type structure, where M=Mn,Fe,Co,Ni,Cu,Zn and n=2,4,6,8,10,12. The 5 series hybrids, 30 compounds of M= Mn,Fe,Co,Cu,Zn were successfully synthesized by the reactions in solutions and the optimum synthetic conditions were found out.The structures of the 5 series hybrids at room temperature and the interactions between the different components in the hybrids were characterized and analyzed by XRD, SEM, FTIR and TG-DSC. The results demonstrate that all hybrids feature layered structures and the interlayer distance increases depend linearly on the increasing of the organic alkyl chain lengths. The results also suggest that the structures of the hybrids are very similar inside the group of M=Mn,Fe,Cu and inside the group of M=Co,Zn, respectively. But they are different between the two groups. The structure similarity inside the groups and the difference between the groups are更多还原