Discovery of Self-Assembled Network Phases And Metallic Nanostructures Driven by Confinement

限制驱动的自组装网络相和金属纳米结构的发现

• 批准号: 2411155
• 负责人: Jeremiah Johnson
• 金额: $ 46.5万
• 依托单位: Massachusetts Institute of Technology
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-06-01 至 2027-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2411155&HistoricalAwards=false
• 关键词: Discovery; Self; Assembled; Network; Phases

NON-TECHNICAL SUMMARY:Block copolymers are a class of polymers that contain two or more chemically distinct units. As a result, these polymers can spontaneously arrange themselves to produce dense arrays of nanoscale periodic structures with spacings of ~10–100 nm. These materials are useful in a range of nanoscale technologies, including the manufacture of integrated circuits and porous membranes for filtration or separation. This proposal explores a type of block copolymer called a Janus multiblock bottlebrush copolymer, in which the molecules consist of a backbone to which sidechains of three or more different polymer compositions are attached. These materials self-assemble into nanoscale structures with unusual morphologies such as layers of mesh-like structures, which cannot be formed from common block copolymers, making the Janus polymers interesting for nanomanufacturing. The proposal has two major aims: first, testing hypotheses about the formation of novel morphologies, and second, introducing a metal-containing group into the polymer to enable the formation of useful nanostructures such as microelectronic metallization wires. Success in reaching these goals will contribute to solving longstanding needs in nanofabrication based on self-assembly; in particular, the fabrication of metallic meshes and rectilinear nanostructures. Broader impacts include training of students, public events, and outreach activities to promote diversity in science and engineering.TECHNICAL SUMMARY:This proposal explores a class of Janus multiblock bottlebrush copolymers that microphase- separate to form structures with hierarchical length scales consisting of a substructure within a superstructure such as mesh-in-lamella. The morphologies of Janus bottlebrush multiblock copolymers differ qualitatively from those of Janus bottlebrush diblock copolymers and the role of the confinement of the molecules within the superstructure on the substructure assembly will be investigated both experimentally and computationally. Furthermore, the proposal develops methods to incorporate a block consisting of metal-containing N-heterocyclic carbenes (NHC) via a poly(NHC metallopolymer) branched macromonomer route, facilitating the selective introduction of metal species within the block copolymer. Thin film morphologies and directed self-assembly of Janus bottlebrush multiblock copolymers will be investigated using solvent annealing combined with structural analysis, and metal nanostructures such as meshes will be fabricated. The proposed research will broaden the range of self-assembled morphologies obtainable from block copolymer self-assembly, as well as extending the utility of bottlebrush copolymers by introducing a metal-containing block. Morphologies relevant to semiconductor device fabrication will form a particular focus of this project. A graduate student and undergraduates including summer researchers from a local community college will be trained in an interdisciplinary field with the opportunity to interact with a computational collaborator. The results will be incorporated into classroom teaching and seminars and will be organized and archived for public access. The senior researchers and students will engage in public outreach and promotion of diversity through various programs..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.

非技术概述：嵌段共聚物是一类含有两个或更多个化学上不同的单元的聚合物。因此，这些聚合物可以自发地排列自己，以产生间距为~10-100 nm的纳米级周期性结构的密集阵列。这些材料可用于一系列纳米级技术，包括制造集成电路和用于过滤或分离的多孔膜。该提案探索了一种称为Janus多嵌段瓶刷共聚物的嵌段共聚物，其中分子由三种或更多种不同聚合物组合物的侧链连接的主链组成。这些材料自组装成具有不寻常形态的纳米级结构，例如网状结构层，这不能由常见的嵌段共聚物形成，使得Janus聚合物对纳米制造感兴趣。该提案有两个主要目的：第一，测试关于形成新形态的假设，第二，将含金属基团引入聚合物中，以形成有用的纳米结构，如微电子金属化线。成功实现这些目标将有助于解决基于自组装的纳米纤维的长期需求;特别是金属网和直线纳米结构的制造。更广泛的影响包括学生的培训，公共活动和推广活动，以促进科学和工程的多样性。技术摘要：该提案探讨了一类Janus多嵌段瓶刷共聚物，微相分离，形成具有分级长度尺度的结构，包括在上层结构，如网格层内的子结构。Janus bottlebrush多嵌段共聚物的形态不同的Janus bottlebrush二嵌段共聚物和限制的分子内的子结构组装的超结构的作用，将在实验和计算上进行研究。此外，该提案开发了通过聚（NHC金属聚合物）支化大分子单体路线并入由含金属的N-杂环卡宾（NHC）组成的嵌段的方法，促进了金属物质在嵌段共聚物内的选择性引入。薄膜形态和定向自组装Janus瓶刷多嵌段共聚物将使用溶剂退火结合结构分析进行研究，并将制造金属纳米结构，如网格。拟议的研究将拓宽范围内的自组装形态可从嵌段共聚物自组装，以及通过引入含金属的嵌段扩展瓶刷共聚物的效用。与半导体器件制造相关的形态将成为该项目的一个特别重点。一名研究生和本科生，包括来自当地社区学院的暑期研究人员，将接受跨学科领域的培训，并有机会与计算合作者进行互动。研究结果将纳入课堂教学和研讨会，并将进行整理和存档，供公众查阅。高级研究人员和学生将通过各种计划参与公共宣传和促进多样性。该奖项反映了NSF的法定使命，并被认为是值得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的支持。