Toward Mesoscale Order in Multicomponent Organic Thin Films via Hydrogen Bond Directed Supramolecular Topology

通过氢键引导的超分子拓扑实现多组分有机薄膜的介观有序

• 批准号: 1507561
• 负责人: Ronald Castellano
• 金额: $ 59.86万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1507561&HistoricalAwards=false
• 关键词: Toward; Mesoscale; Order; Multicomponent; Organic

With this award the Macromolecular, Supramolecular and Nanochemistry Program supports Professor Ronald Castellano and his collaborators at the University of Florida to study semiconducting carbon-based (organic) materials. For many downstream applications - displays, lighting, solar cells, transistors, and sensors - the three-dimensional (3-D) arrangement of organic molecules in processed thin (10-1,000 nanometer) films dictates device performance. This study is developing a general self-assembly approach to allow functional organic molecules to form useful superstructures in a self-guided way. In the broadest sense, the work contributes to a general understanding of how to control the 3-D structure of single and multi-component organic matter at the nano-/mesoscale. Broader impacts with respect to education and training come from (1) graduate and undergraduate students being exposed to multidisciplinary science that includes synthetic and physical organic chemistry, spectroscopy, computation, materials processing/characterization, and device fabrication; (2) the student participants, together with the UF Chemistry Club, disseminating standards-aligned experimental modules to K-8 classrooms that embed concepts of the chemical/materials sciences and their own research; and (3) broadening the participation of underrepresented groups in STEM research activities. While it is known how to tailor the electronic and optical properties of individual pi-conjugated molecules as well as to program the arrangements of the molecules in solution, a major bottleneck for their usage is predicting and controlling three-dimensional morphological structure in thin films. This research examines a hierarchical self-assembly approach based on hydrogen bonding to create nanoscale to mesoscale order in thin films of pi-conjugated oligomers irrespective of pi-chromophore structure. The design involves covalently linking typical pi-conjugated components to molecular recognition units capable of directing their supramolecular assembly into predictably shaped aggregates. The resulting topologies are expected to uniquely support the natural segregation of appropriately shaped additives in thin film blends, and allow desirable optoelectronic properties to be achieved. The proposed bottom-up self-assembly approach effectively decouples the morphological structure of organic semiconductor thin films from the intrinsic optoelectronic structure of the constituent pi-conjugated chromophores, allowing these aspects to be independently optimized through rational/theory-guided material design. The specific aims of this collaborative project include modular design and synthesis of pi-conjugated oligomers, evaluation of optoelectronic structure and (supra)molecular ordering in solution and in thin films, and characterization of the optoelectronic properties of and bulk ordering within the thin films using diagnostic devices.

有了这个奖项的大分子，超分子和纳米化学计划支持教授罗纳德卡斯特拉诺和他的合作者在佛罗里达大学研究半导体碳基（有机）材料。 对于许多下游应用-显示器，照明，太阳能电池，晶体管和传感器-加工薄膜（10- 1，000纳米）中有机分子的三维（3-D）排列决定了器件性能。这项研究正在开发一种通用的自组装方法，使功能有机分子以自我引导的方式形成有用的超结构。 从最广泛的意义上说，这项工作有助于对如何在纳米/中尺度上控制单组分和多组分有机物的3-D结构的一般理解。 对教育和培训的更广泛影响来自：（1）研究生和本科生接触多学科科学，包括合成和物理有机化学、光谱学、计算、材料加工/表征和器件制造;（2）学生参与者，连同UF化学俱乐部，向K-8教室传播与标准一致的实验模块，其中嵌入化学/材料科学及其自身研究的概念;以及（3）扩大代表性不足的群体在STEM研究活动中的参与。 虽然已知如何定制单个π共轭分子的电子和光学性质以及对分子在溶液中的排列进行编程，但其使用的主要瓶颈是预测和控制薄膜中的三维形态结构。 本研究探讨了一个分层的自组装方法的基础上，氢键创建纳米尺度到介观尺度的顺序在薄膜中的π共轭低聚物的π-发色团结构无关。 该设计涉及将典型的π-缀合组分共价连接到能够将其超分子组装成可预测形状的聚集体的分子识别单元。 预期所得到的拓扑结构将独特地支持薄膜共混物中适当形状的添加剂的自然分离，并允许实现期望的光电性能。 所提出的自下而上的自组装方法有效地将有机半导体薄膜的形态结构从组成π-共轭发色团的固有光电结构中分离出来，允许这些方面通过理性/理论指导的材料设计进行独立优化。 该合作项目的具体目标包括π共轭低聚物的模块化设计和合成，溶液和薄膜中的光电结构和（超）分子有序的评估，以及使用诊断设备表征薄膜内的光电特性和批量有序。