Quasi-2D n-Type Semiconducting Polymers: Novel Monomers, Synthesis, and Enhanced Electron Transport and Photovoltaic Properties

第一部分：非技术性总结为了应对为不断增长的世界人口提供低成本和无污染清洁能源的社会挑战，需要可能彻底改变能量转换和存储技术的新型半导体材料和器件。创造新一代电子设备和信息技术也需要这种材料。该项目旨在开发创建新的塑料基电子传输半导体材料所需的基础知识，这些材料将增强的电荷传输和光吸收特性与易于加工成机械坚固的柔性薄膜相结合。该项目的结果可能会导致新一代高性能半导体塑料适用于各种能量转换和存储技术。 该项目还与可持续性有关，因为电子传输半导体聚合物有望成为低成本，可持续和可规模化制造的材料，与目前广泛用于光电化学电池光阳极的无机氧化物相比，具有更好的性能，以有效生产燃料（例如水电池中的氢）。在光伏应用中，电子传输聚合物可以实现坚固的全聚合物器件，与目前更昂贵的无机器件相比，其可以大规模廉价制造。项目成果将通过经同行评审的期刊出版物和会议介绍加以传播。该项目为培训科学家和工程师，包括妇女和少数民族提供了广泛的机会，涉及半导体材料和能源科学与技术等高度跨学科领域，这些领域需要化学、物理、材料科学、数学和工程方面的知识。该项目还将通过将研究成果纳入主要研究员（PI）教授的研究生和本科生课程来改进课程。PI与日本，韩国，英国和法国的科学家在半导体材料，电子设备和能量转换设备的一般领域进行了许多研究合作，并接待了来自这些国家的高级科学家和学生的访问。该项目将加强这些国际合作，并为学生提供全球培训视角。第二部分：技术概述合适的n型半导体聚合物的缺乏限制了对这类材料中电子传输的基本理解以及用于塑料电子器件的p-n互补逻辑电路、高效全聚合物太阳能电池、用于高效制氢的光电化学电池的光阳极、用于可再充电电池中的高能量/功率密度存储的电极和p-n热电器件的开发。拟议的研究将解决n型半导体聚合物领域的基本科学挑战。 该项目的总体目标是创建和研究一类新型的n型半导体聚合物，具有准2D电子离域和增强的电子传输特性，适用于电子器件和能量转换和存储应用。计划中的研究将：（1）设计、合成和开发了适用于共轭聚合物设计的新型缺电子结构单元亚芳基双苯并咪唑类聚合物，（2）设计、合成和表征了基于亚芳基双苯并咪唑类的准二维n型半导体聚合物，（3）研究了新型亚芳基双苯并咪唑类聚合物的自组装和体相形貌、电子结构、光学和电子输运性质，（4）研究了亚芳基双苯并咪唑类聚合物的电子结构、光学和电子输运性质。（4）探索最有前途的新型n型导电聚合物作为全聚合物太阳能电池中的受体材料，并研究共混物形态、光伏性能以及潜在的结构-性能关系。拟议研究的结果可以改变对n型半导体聚合物在各种电子器件以及能量转换和存储器件中的基本理解、开发和应用，并有助于可持续发展。

PART 1: NON-TECHNICAL SUMMARYNovel semiconductor materials and devices that could potentially revolutionize energy conversion and storage technologies are needed to address society's grand challenge of supplying low cost and pollution-free clean energy for a growing world population. Such materials are also needed to create new generations of electronic devices and information technologies. This project aims to develop the basic knowledge needed for creating new plastic-based electron-transporting semiconducting materials that combine enhanced charge transport and light-absorbing properties with ease of processing into mechanically rugged flexible thin films. Results from the project may lead to new generations of high performance semiconducting plastics suitable for applications in diverse energy conversion and storage technologies. The project is also relevant to sustainability in that electron transporting semiconducting polymers show promise to be low-cost, sustainable, and scalable-manufactured materials with improved properties compared to inorganic oxides now widely used in photoanodes for photoelectrochemical cells for efficient production of fuels (e.g. hydrogen in aqueous cells). In photovoltaic applications, electron transporting polymers could enable rugged all-polymer devices which could be manufactured cheaply on a large scale compared to current more expensive inorganic devices. Project results will be disseminated through peer-reviewed journal publications and conference presentations. The project provides extensive opportunities for training scientists and engineers, including women and minorities, in the highly interdisciplinary fields of semiconductor materials and energy science and technologies, which require knowledge of chemistry, physics, materials science, mathematics, and engineering. The project will also enable curriculum improvements by integration of research findings into the graduate and undergraduate courses taught by the principal investigator (PI). The PI has many research collaborations with scientists in Japan, South Korea, UK, and France in the general areas of semiconductor materials, electronic devices, and energy conversion devices and has hosted visits by senior scientists and students from these countries. This project will strengthen those international collaborations and provide a global training perspective for the students. PART 2: TECHNICAL SUMMARYThe scarcity of suitable n-type semiconducting polymers has limited the fundamental understanding of electron transport in this class of materials and the development of p-n complementary logic circuits for plastic electronics, highly efficient all-polymer solar cells, photoanodes for photoelectrochemical cells for efficient hydrogen production, electrodes for high energy/power density storage in rechargeable batteries, and p-n thermoelectric devices. The proposed research will address the basic scientific challenges in the field of n-type semiconducting polymers. The overall goal of the project is to create and investigate a novel class of n-type semiconducting polymers with quasi-2D electronic delocalization and enhanced electron transport properties suitable for electronic devices and energy conversion and storage applications. The planned research will: (1) design, synthesize, and develop arylene bisbenzimidazoles as novel electron-deficient building block monomers suitable for the design of conjugated polymers; (2) design, synthesize, and characterize arylene bisbenzimidazole-based quasi-2D n-type semiconducting polymers; (3) investigate the self-assembly and bulk morphology, electronic structure and optical and electron transport properties of the novel arylene bisbenzimidazole polymers; and (4) explore the most promising new n-type conducting polymers as acceptor materials in all-polymer solar cells and investigate the blend morphology, photovoltaic properties, and underlying structure-property relationships. Results of the proposed study could transform the basic understanding, development and applications of n-type semiconducting polymers in diverse electronic devices as well as energy conversion and storage devices, and contribute to sustainability.