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

第1部分：非技术性总结需要可能彻底改变能源转换和存储技术的新型半导体材料和器件，以应对社会面临的重大挑战，即为日益增长的世界人口提供低成本、无污染的清洁能源。这种材料也是创造新一代电子设备和信息技术所必需的。该项目旨在开发创造新的基于塑料的电子传输半导体材料所需的基本知识，这种材料将增强的电荷传输和光吸收性能与易于加工成机械坚固的柔性薄膜相结合。该项目的成果可能会导致新一代高性能半导体塑料，适用于各种能源转换和存储技术。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、可持续和可扩展的制造材料，与目前广泛用于光电化学电池的光电阳极以高效生产燃料(例如，水电池中的氢)的无机氧化物相比，具有更好的性能。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，这种器件可以大规模制造，成本低廉。项目成果将通过同行评议的期刊出版物和会议发言进行传播。该项目为包括妇女和少数族裔在内的半导体材料和能源科学与技术等高度跨学科领域的科学家和工程师提供了广泛的培训机会，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首席调查员(PI)教授的研究生和本科课程来改进课程。国际和平研究所与日本、韩国、英国和法国的科学家在半导体材料、电子设备和能源转换设备等一般领域进行了许多研究合作，并接待了这些国家的资深科学家和学生访问。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：技术综述由于缺乏合适的n型半导体聚合物，限制了对这类材料中电子传输的基本了解，并限制了塑料电子的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、可充电电池中高能量/功率密度存储的电极以及p-n热电器件的开发。这项拟议的研究将解决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造和研究一类新型的n型半导体聚合物，具有准2D电子离域和增强的电子传输性能，适合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、合成和开发适合于设计共轭聚合物的新型缺乏电子的构建块单体；(2)设计、合成和表征基于芳基双苯并咪唑的准2D n型半导体聚合物；(3)研究新型芳纶双苯并咪唑聚合物的自组装和本体形态、电子结构以及光学和电子传输性能；以及(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的受体材料，并研究其共混形态、光伏性能和潜在的结构-性能关系。拟议的研究结果可以改变n型半导体聚合物在各种电子设备以及能量转换和存储设备中的基本理解、开发和应用，并有助于可持续性。

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.