Mutual Synthesis of Conjugated Polymers and Dopants for Well-Ordered Self-Assemblies

共轭聚合物和掺杂剂的相互合成以实现有序自组装

基本信息

批准号：
1708245
负责人：
Howard Katz
金额：
$ 39.97万
依托单位：
Johns Hopkins University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2017
资助国家：
美国
起止时间：
2017-08-01 至 2021-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1708245&HistoricalAwards=false
关键词：
Mutual Synthesis Conjugated Polymers Dopants

项目摘要

This award is funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry. Professor Howard E. Katz of Johns Hopkins University is supported to explore the idea that the main components of conducting plastics - the polymeric material and the dopants -- can be designed simultaneously for best performance. This requires that their molecule-sized subunits fit well together, continuous paths for conducting electricity are created, and the dopants maintain their ability to stabilize the electrical charges that move when the electricity is conducted. A fundamental issue to be explored is whether it is better for dopants to be mixed equally through the entire volume of the plastics, or whether it is better for separate parts of a mixture to be rich in the plastic and others be rich in the dopant. New ways to make plastics and dopants, more detailed understanding of how they fit together and promote electrical conduction in the plastic mixtures, and computer-based models for predicting the properties of the plastics in advance of making them are expected outcomes of this project. Conducting plastics are the basis of numerous emerging technologies such as plastic solar cells and light emitters for more efficient use of energy, detectors for dangerous chemicals important for defense operations, and medical devices to detect diseases. All of these technologies have created new economic opportunities. Integrating the research with education and outreach trains graduate students as future members of the plastic electronics workforce, and brings the opportunities of plastic electronics to elementary school, high school, and art institute students in the City of Baltimore. The main objective of this project is to design and synthesize pairs of conjugated, high-charge-carrier-mobility polymers and corresponding chemical dopants that induce charges in those polymers, such that the pairs form assemblies that retain favorable charge-transporting molecular organization. The supramolecular structure of the original polymer is a consequence of pi-interactions among the conjugated polymer main chains and regular spacing caused by alkyl side chains. The idea is to explore different chemical design elements in the polymer and dopant components so that the dopants become accommodated in the supramolecular structure, or even enhance the structure. These design strategies are compared to the extreme cases of dopants covalently attached to main chains, known as "self-doped polymers", and dopants that would be expected to phase segregate from the charge-transporting polymers and thus exist in separate domains. The molecular packing of the polymer-dopant assemblies is elucidated using x-ray and neutron scattering techniques. Absorbance, photoelectron, and electron spin resonance spectroscopy indicate the formation of charge carriers. Computational modeling creates a theoretical basis for both the packing and charge transfer efficiency. The outcome of this project guides the design of polymers that conduct electricity with high efficiency using only electrons or holes as charge carriers, without ionic contributions. The project may resolve the uncertainty about whether structures with dopant functionality adjacent to main chains or remote from main chains lead to better defined crystallinity and higher electronic conductivity. A theoretical basis for selecting among various assembly types for future designs is developed. Because the polymers are assembled from blends with dopants, the dopant concentration is tunable for the maximum conductivity, or alternatively for optimization of other functions such as charge injection into optoelectronic devices or matrices for thermoelectric composites.

该奖项由化学系高分子、超分子和纳米化学项目资助。约翰·霍普金斯大学的 Howard E. Katz 教授得到支持，探索导电塑料的主要成分（聚合物材料和掺杂剂）可以同时设计以获得最佳性能的想法。这要求它们的分子大小的亚基很好地配合在一起，创建连续的导电路径，并且掺杂剂保持其稳定导电时移动的电荷的能力。需要探讨的一个基本问题是，掺杂剂是否均匀地混合在塑料的整个体积中更好，或者混合物的单独部分富含塑料而其他部分富含掺杂剂是否更好。制造塑料和掺杂剂的新方法，更详细地了解它们如何组合在一起并促进塑料混合物中的导电，以及在制造塑料之前预测塑料性能的基于计算机的模型是该项目的预期成果。导电塑料是众多新兴技术的基础，例如用于更有效利用能源的塑料太阳能电池和光发射器、对国防行动重要的危险化学品探测器以及用于检测疾病的医疗设备。所有这些技术都创造了新的经济机会。将研究与教育和推广相结合，将研究生培养为塑料电子劳动力的未来成员，并为巴尔的摩市的小学、高中和艺术学院的学生带来塑料电子的机会。该项目的主要目标是设计和合成成对的共轭高电荷载流子迁移率聚合物以及相应的化学掺杂剂，这些掺杂剂在这些聚合物中诱导电荷，使得这些对形成保留有利的电荷传输分子组织的组件。原始聚合物的超分子结构是共轭聚合物主链之间的π相互作用和烷基侧链引起的规则间距的结果。这个想法是探索聚合物和掺杂剂成分中的不同化学设计元素，使掺杂剂适应超分子结构，甚至增强结构。这些设计策略与共价连接到主链的掺杂剂（称为“自掺杂聚合物”）的极端情况进行比较，并且掺杂剂预计会与电荷传输聚合物相分离，从而存在于不同的域中。使用 X 射线和中子散射技术阐明了聚合物-掺杂剂组件的分子堆积。吸收光谱、光电子光谱和电子自旋共振光谱表明载流子的形成。计算模型为堆积和电荷转移效率奠定了理论基础。该项目的成果指导了聚合物的设计，该聚合物仅使用电子或空穴作为电荷载体，无需离子贡献即可高效导电。该项目可以解决以下不确定性：具有邻近主链或远离主链的掺杂功能的结构是否会导致更好的结晶度和更高的电子电导率。为未来设计中选择各种装配类型奠定了理论基础。由于聚合物是由与掺杂剂的共混物组装而成，因此掺杂剂浓度可调节以获得最大电导率，或者优化其他功能，例如将电荷注入光电器件或热电复合材料的基质中。

项目成果

期刊论文数量（13）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

3,4,5‐Trimethoxy Substitution on an N‐DMBI Dopant with New N‐Type Polymers: Polymer‐Dopant Matching for Improved Conductivity‐Seebeck Coefficient Relationship

用新型 N-型聚合物对 N-DMBI 掺杂剂进行 3,4,5-三甲氧基取代：聚合物-掺杂剂匹配以改善电导率-塞贝克系数关系

DOI：
10.1002/anie.202110505
发表时间：
2021-11
期刊：
Angewandte Chemie International Edition
影响因子：
0
作者：
Han, Jinfeng;Chiu, Arlene;Ganley, Connor;McGuiggan, Patty;Thon, Susanna M.;Clancy, Paulette;Katz, Howard E.
通讯作者：
Katz, Howard E.

A chemical kinetics perspective on thermoelectric transport

热电输运的化学动力学视角

DOI：
10.1063/5.0055367
发表时间：
2021-08-11
期刊：
Applied Physics Letters
影响因子：
4
作者：
Nanxian Chen;Juan Pino;H. Katz
通讯作者：
H. Katz

Dichlorinated Dithienylethene‐Based Copolymers for Air‐Stable n‐Type Conductivity and Thermoelectricity

用于空气的二氯化二噻吩乙烯共聚物 - 稳定的 n 型电导率和热电性

DOI：
10.1002/adfm.202005901
发表时间：
2020-10-23
期刊：
Advanced Functional Materials
影响因子：
19
作者：
Jinfeng Han;Huidong Fan;Qingyang Zhang;Qin Hu;T. Russell;H. Katz
通讯作者：
H. Katz

Blended Conjugated Host and Unconjugated Dopant Polymers Towards N‐type All‐Polymer Conductors and High‐ZT Thermoelectrics

混合共轭主体和非共轭掺杂聚合物以实现 N 型全聚合物导体和高 ZT 热电材料

DOI：
10.1002/anie.202219313
发表时间：
2023-04
期刊：
Angewandte Chemie International Edition
影响因子：
0
作者：
Han, Jinfeng;Jiang, Yufeng;Tiernan, Emma;Ganley, Connor;Song, Yunjia;Lee, Taein;Chiu, Arlene;McGuiggan, Patty;Adams, Nicholas;Clancy, Paulette;et al
通讯作者：
et al

Suppression of Ionic Doping by Molecular Dopants in Conjugated Polymers for Improving Specificity and Sensitivity in Biosensing Applications

通过共轭聚合物中的分子掺杂剂抑制离子掺杂，提高生物传感应用的特异性和灵敏度