CAREER: Directed Self-Assembly of 2D Plasmonic Nanoparticles in Block Copolymer Nanofibers to Form Hierarchical Nanostructures

第一部分： 含有二维（2D）等离子体纳米颗粒的聚合物可以有助于变革性技术，例如波导、光电子器件、传感器、致动器和光响应粘合剂。这个CAREER项目解决了设计聚合物和2D等离子纳米粒子之间的界面的基本问题。该问题的解决方案将为将2D等离子纳米粒子集成到聚合物材料中并创建具有先进光学，光热和等离子特性的混合功能复合材料奠定基础。特别地，具有分层堆叠的2D等离子体纳米颗粒的聚合物的纤维和细丝可以用作用于等离子体功能构建体的增材制造的油墨。这种混合材料可以帮助设计具有上级功率转换效率的光电子器件，以及具有工业和社会重要性的能源和环境科学中的其他功能器件。其教育影响涉及阿巴拉契亚代表性不足的第一代大学生的培训。特别是，将为来自邻近的历史黑人学院和大学（HBCU）的代表性不足的学生开发一个小型夏令营，PI将担任该大学住宿学院的高级研究员，以促进STEM并提高代表性不足和第一代大学生的成功率。通过这种方式，这里所介绍的努力将培养代表性不足的当地青年，特别是孤立的阿巴拉契亚的第一代大学生，成为未来的聚合物科学家和工程师，他们将建立和重塑区域聚合物行业。 技术概述纤维具有薄膜和大块样品所缺乏的吸引人的性质，例如大表面积、低密度、高强度和外围受限的自组装。该项目的目标是利用静电纺丝和嵌段共聚物定向自组装在纤维中形成嵌段共聚物和2D等离子体纳米颗粒的分级结构，其具有迷人的结构和光热性能。主要范围是了解聚合物刷形成的机制，在2D等离子体纳米粒子和设计定制的聚合物/纳米粒子界面，在纤维中创建分层纳米结构。中心假设指出，通过利用2D等离子体纳米颗粒的独特等离子体性质，将发现聚合物刷形成机制，将制备用于纤维中的分级定向自组装的嵌段共聚物/2D等离子体纳米颗粒界面，并且将理解作为等离子体聚合物的独特特征的结构和光热性质。该目标将通过三个主要任务来实现：1）使用2D等离子体纳米粒子来揭示聚合物刷形成的机制，2）利用嵌段共聚物来指导2D等离子体纳米粒子的自组装并在纤维中形成分级结构，3）理解嵌段共聚物与2D等离子体纳米粒子混合后的域间距和光热性质。预期嵌段共聚物在纤维中表现出优选的域取向，并且2D纳米颗粒在每个嵌段共聚物域中形成具有2D纳米颗粒单层的堆叠层。该分级纳米结构将赋予聚合物新的等离子体特性，并成为波导、光致发光、粘合剂和3D打印油墨应用的积极候选者。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

PART 1: NON-TECHNICAL SUMMARYPolymers containing two-dimensional (2D) plasmonic nanoparticles could contribute to transformative technologies such as waveguides, photovoltaics, sensors, actuators, and photo-responsive adhesives. This CAREER project addresses the fundamental issue of designing the interface between polymers and 2D plasmonic nanoparticles. The solutions to this issue will lay the foundation for integrating 2D plasmonic nanoparticles into polymeric materials and creating hybrid functional composites with advanced optical, photo-thermal, and plasmonic properties. In particular, fibers and filaments of polymers with hierarchically stacked 2D plasmonic nanoparticles can be used as inks for additive manufacturing of plasmonic functional constructs. The hybrid material can help design photovoltaics with superior power conversion efficiencies, as well as other functional devices in energy and environmental sciences that are of industrial and societal importance.The educational impacts involve the training of underrepresented and first-generation college students in Appalachia. In particular, a mini summer research camp for underrepresented students from neighboring Historically Black Colleges and Universities (HBCUs)will be developed, and the PI will serve as a senior fellow in the university's Residential College to promote STEM and improve the success rate of underrepresented and first-generation college students. In this way, the effort presented here will train underrepresented local youth, especially first-generation college students in isolated Appalachia, to become future polymer scientists and engineers who will build and reshape the regional polymer industries.PART 2: TECHNICAL SUMMARYFibers possess attractive properties that thin films and bulk samples lack, for instance, large surface area, low density, high strength, and peripherally confined self-assembly. The goal of the proposed project is to exploit electrospinning and block copolymer directed self-assembly to create hierarchical structures of block copolymers and 2D plasmonic nanoparticles in fibers, which have fascinating structural and photo-thermal properties. The main scopes are to understand the mechanism of polymer brush formation on 2D plasmonic nanoparticles and design tailored polymer/nanoparticle interfaces for creating hierarchical nanostructures in fibers. The central hypothesis states that, by exploiting the unique plasmonic properties of 2D plasmonic nanoparticles, the polymer brush formation mechanism will be discovered, block copolymer/2D plasmonic nanoparticle interface for hierarchical directed self-assembly in fibers will be prepared, and structural and photothermal properties that are distinctive features of plasmonic polymers will be understood. The proposed goal will be realized via three main tasks: 1) employ 2D plasmonic nanoparticles to unveil the mechanism of polymer brush formation, 2) utilize block copolymers to direct the self-assembly of 2D plasmonic nanoparticles and form hierarchical structures in fibers, 3) understand the domain spacing and photothermal properties of block copolymers upon mixing with 2D plasmonic nanoparticles. The block copolymers are expected to exhibit preferred domain orientation in the fibers, and the 2D nanoparticles to form stacked layers with monolayers of 2D nanoparticles in each block copolymer domain. The hierarchical nanostructures will bestow on polymers novel plasmonic properties and be active candidates for applications in waveguides, photovoltaics, adhesives, and 3D printing inks.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.