功能有机分子固态结晶与相变过程研究

To clearly understand the mechanism of crystal formation and phase-transition is a long-standing challenge in the whole scientific fields, especially for those processes that occur in the solid-state. Because such crystallization and phase-transition occurring in confined environments is difficult to observe directly, we know little about the basic model and the key transform mechanism of these fundamental process. However, it will help a lot to illuminate the mechanism for both the universal value in the chemistry,biology, geology and material science, and the precise controlling over the morphology and arrangement of the crystals. We developed an in situ and in real time imaging protocol to record the interfaces revolution in a solid-state crystallization of molecular amorphous particles, based on the optoelectronic information from the functional organic molecules. The details of the morphology revolution during the transformation from one phase to another can be monitored by the changing of the optical respond, because such organic compounds exhibit distinguishable fluorescence in different morphologies. The project is proposed based on plenty of preliminary relevant researches, aiming to get a real picture and to acquaint the influence factors of the whole dynamic process of crystal formation and phase-transition in soled state. And furthermore, we hope this facile and direct method can be developed into an effective way to probe the inner structural process of a molecular solids.

晶体成核、生长和相变一直都是科学界努力探索的根本问题，特别是对于固态过程，由于无法通过常规的手段直接观察到晶体界面的变化情况，其基本模型和关键转换机制大多还未搞清。阐明这些机制不仅在化学、生物、地质和材料科学等领域具有普遍的科学意义，更有助于精确调控晶体材料的生长形貌和排布，充分发挥有机分子的功能特性。本课题以功能有机分子为研究对象，通过有机分子自身的光电信号传递固体内部发生的分子组装和晶体相变过程信息，借助功能分子自身的荧光信号在相变时的变化反映相转变细节，以原位、实时、无损的方式，研究有机材料的晶化与相变过程，揭示各内因和外因对结晶和相变进程的影响。本项目的提出建立在大量相关研究基础之上，希望可以从实验上揭示分子材料固态晶化相变的真实动态过程和影响因素，发展成为一个探究分子固体内部结构转变的有效方法。

阐明晶体的成核、生长和相变机制不仅在化学、生物、地质和材料科学等领域具有普遍的科学意义，更有助于精确调控晶体材料的生长形貌和排布，充分发挥有机分子的功能特性。本课题以功能有机分子为研究对象，在功能有机分子固态结晶与相变过程研究中，通过设计原位、实时的观察方法，较为深入地阐明了多种典型有机及有机-无机晶体的生长和相变过程和机理。发明了微距升华晶体生长方法，受到了广泛国际关注，两次入选美国化学会ACS Editors' Choice，多次入选30日和年度（2018，2020）阅读下载量排行榜以及“2018阅读量最高的十佳中国投稿文章”第一名，2020年度晶体生长类论文阅读下载排行榜第一名；被Nature Communications选为亮点论文；全球化学化工领域著名新闻杂志《化学化工新闻》（Chemical & Engineering News）专题报道。该方法目前已被国内外数十家科研机构采用。研制了恒温控速反溶剂扩散系统新型生长设备，突破了大尺寸、高质量有机-无机复合钙钛矿单晶生长工艺，生长的溴铅甲胺等单晶创造了国际报道最大尺寸、最高质量记录。生长的大尺寸有机掺杂单晶为我国相关部门的装备预研提供了关键材料。在Nature Communications，Chemistry of Materials等期刊发表SCI收录论文 > 15 篇，授权专利1项，培养博士生4名，获得山东省优秀博士论文。申请人获得山东省杰出青年基金资助。