Conjugated Polymer Ultrathin Films: Synthesis, Electropatterning, and Nanopatterning of Precursor Polymers

在这个项目中，我们将使用“先驱体聚合物”的方法来研究共轭聚合物材料的超薄膜形成、电图案化和纳米成膜化。这将涉及：1)合成专门的可溶性前体均聚物和共聚物，2)这些聚合物在特定位置和多层序列上的电聚合，以及3)使用微光刻(软光刻)和电化学纳米光刻(ECN)来聚合和图案化特征。基于目前的文献和最近获得的结果，有很大的潜力去寻求新的方法来合成和图案化用于半导体、显示器、传感器和其他具有微米到亚微米特征的电光应用的p-共轭聚合物超薄膜。智力影响：单体在电极上的直接电化学聚合通常会导致机械和光学质量较差的薄膜，图案化可能性有限。通过采用先驱体聚合物的方法，“主动”或“被动”先驱体聚合物主链可以指导从悬挂的电活性单体形成共轭聚合物的“交联链”。此外，使用微接触印刷(MCP)和其他压印方法也可以进行软光刻。利用ECN在聚合物薄膜和图案化特征上进行纳米刻蚀将成为可能。因此，为了在理解这些材料和方法的潜力和局限性方面产生重大的科学影响，将采取一种研究策略。这包括了解电聚合的机理和动力学、前体聚合物的大分子设计、电活性单体的构象和预取向、聚合物刷子的生长和组成、图案化的顺序、尺寸和分辨率限制，以及热机械稳定性问题。最终，挑战是成功地形成从微米到纳米(亚微米)分辨率的电聚合共轭聚合物的图案和阵列，具有独特的图案化复杂性、电光特性和器件功能。广泛的影响：该项目将直接影响当前合成共轭聚合物材料、超薄膜和图案化方法的方法。将通过出版物和合作广泛传播成果，以帮助工业和学术研究利用这些方法进行电光器件开发。该项目遵循详细的计划和时间表，包括对学生的培训以及与学术和行业合作者的互动。发现过程涉及一系列和协同的材料和方法研究。这包括：a)聚合物的新合成方法，b)创新的光谱、显微和电化学表征方法，以及c)超薄膜制备。最重要的影响是对三名有才华的学生的教育和培训，以及他们对辅导活动的参与。他们将在一个独特的环境中接受培训，在Advincula Group的一个实验室中研究新的聚合物材料合成和设备制造。此外，这将使他们能够利用科学和技术技能走向一个注重技术的社会，包括参与REU计划、SEED项目的指导活动，以及通过韦尔奇暑期学生计划面向高中生的外联活动。与首席调查员(PI)的优先事项一样，将鼓励代表人数不足的群体和少数族裔学生参加他们的研究活动。

In this project, the ultrathin film formation, electropatterning, and nanopatterning of conjugated polymer materials using the "precursor polymer" approach will be pursued. This will involve: 1) Synthesis of specialized soluble precursor homopolymers and copolymers, 2) Electropolymerization of these polymers on specific sites and multilayer sequences, and 3) Use of micro-lithography (soft-lithography) and electrochemical nanolithography (ECN) to polymerize and pattern features. Based on current literature and recent results obtained, there is a high potential to pursue new methodologies of synthesizing and patterning ultrathin films of p-conjugated polymers useful for semiconductor, display, sensor, and other electro-optical applications with micron to submicron features. Intellectual Impact: Direct electrochemical polymerizations of monomers on electrodes usually result in films of poor mechanical and optical quality with limited patterning possibilities. By taking the precursor polymer approach, "active" or "passive" precursor polymer backbones can direct the formation of conjugated polymer "cross-links" from pendant electroactive monomers. In addition, soft-lithography is possible using microcontact printing (mCP) and other imprinting methods. Nanopatterning will be possible using ECN on both polymer films and patterned features.Thus, in order to make significant scientific impact in understanding the potential and limitations of these materials and methods, a research strategy will be pursued. This includes understanding the mechanism and kinetics of electropolymerization, macromolecular design of a precursor polymer, conformation and pre-orientation of electroactive pendant monomers, growth and composition of polymer brushes, order, size, and resolution limits of patterning, and thermo-mechanical stability issues. Eventually, the challenge is to successfully form patterns and arrays of electropolymerized conjugated polymers from micron to nm (submicron) resolution with unique patterning complexities, electro-optical properties, and device function.Broad Impact: This project will directly impact current methodologies for synthesizing conjugated polymer materials, ultrathin films, and patterning methods. Wide dissemination of results through publications and collaborations will be done to aid industrial and academic research to pursue electro-optical device development using these methods. The project follows a detailed plan and timeline to incorporate the training of students and interaction with academic and industrial collaborators. The discovery process involves a tandem and synergistic materials and methods research. This includes: a) new synthesis methods for polymers, b) innovative spectroscopic, microscopic, and electrochemical characterization methods, and c) ultrathin film fabrication. The most important impact is the education and training of three talented students and their involvement in mentoring activities. They will be trained in a unique environment to investigate new polymer materials synthesis and device fabrication under one laboratory with the Advincula Group. In addition, this will allow them to harness scientific and technological skills towards a technology-minded society including participation in mentoring activities with the REU program, Project SEED, and outreach activities to high school students through the Welch Summer Student Program. As with the priorities of the Principal Investigator (PI), under-represented groups and minority students will be encouraged to participate in their research activities.