Sub-nanometer Optical Imaging and Self-Assembly on Plasmonic Metals

等离子金属的亚纳米光学成像和自组装

• 批准号: RGPIN-2022-03088
• 负责人: McLean, Alastair
• 金额: $ 2.04万
• 依托单位: Queen's University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=763251
• 关键词: Sub; nanometer; Optical; Imaging; Self

My group's long-term goal is to use the capabilities of scanning probes, such as the two new state-of-the-art scanning probe microscopes described in this proposal, to address critical research questions in nanophotonics and surface chemistry/physics. In this proposal, two research questions/themes are identified and described. Theme 1: Towards atomic optical imaging with quantum optical plasmonics By combining scanning tunnelling microscopy with optical spectroscopy, it has been demonstrated that photoluminescence and also Raman images of single molecules can be acquired with sub--nanometer spatial resolution. These results dramatically illustrate how plasmonic materials can enhance optical processes and they also represent an important step towards atomic optical resolution. With theorists at Queen's, our goal is to develop and test a quantum mechanical model of the optical enhancement in photoluminescence and tip---enhanced Raman imaging that includes the opto-mechanical coupling between the vibrating molecules and the plasmon resonance. We will perform optical imaging of model systems, including molecules and atomically precise nano-clusters, using a cryogenic nano--optical microscope. Atomically sharp tips will be selected using non-contact atomic force microscopy with a qPlus sensor. The impact will be fundamental insights into plasmon enhancement that could potentially have applications for nanoscale optical devices, an important technology market in North America. Theme 2: Self--assembly of N--heterocylic carbenes on plasmonic metals Although the self--assembly of organic molecules on metallic surfaces is one of the most powerful methods for patterning at the nanometer scale, the thermal and oxidative instability of commonly used thiol-based self-assembled monolayers are significant impediments to their widespread commercial use in plasmonic optical devices. With collaborators in Chemistry, we have demonstrated that N--heterocyclic carbenes (NHCs) represent a viable alternative to thiols. Our goal is to optimize the stability of these new overlayer systems by systematically modifying the structure of the NHCs and concurrently developing a molecular--level understanding of their surface chemistry, self--assembly methods and protocols. The impact will be an optimized next generation functionalizing agent for metal surfaces based on NHCs that can be used as a surface modifier with applications in molecular electronics, microcontact printing, biosensing and surface protection. The insights gained through the study of NHC self-assembly on surfaces will also inform the synthesis of NHC-stabilized metal nanoclusters that are used in medicine and catalysis. This proposal will provide training for a total of 18 students at the following levels: 2 PhD, 6 MSc, 5 undergraduate summer students, and 5 final year honours theses.

我小组的长期目标是使用扫描探针的能力，例如本提案中描述的两个新的最新扫描探针显微镜，以解决纳米素质和表面化学/物理学中的关键研究问题。在此提案中，确定并描述了两个研究问题/主题。主题1：通过将扫描隧道显微镜与光谱相结合，朝着与量子光学等离子间的原子成像迈进，已经证明，光致发光以及单分子的拉曼图像可以通过亚纳米表空间分辨率获取。这些结果极大地说明了等离子材料如何增强光学过程，它们也代表了朝着原子光学分辨率迈出的重要一步。 借助皇后区的理论家，我们的目标是开发和测试光致发光和尖端的光学增强的量子机械模型 - 增强的拉曼成像，其中包括振动分子和等离子体共振之间的光学机械耦合。我们将使用低温纳米 - 光学显微镜对模型系统进行光学成像，包括分子和原子精确的纳米簇。使用QPLUS传感器的非接触原子力显微镜选择原子尖端。 这种影响将是对等离子体增强的基本见解，这可能会在北美的重要技术市场纳米级光学设备上应用。 主题2：N-近氧化碳烯在等离子金属上的自我组装，尽管有机分子在金属表面上的自我组装是纳米尺度上构图的最有力的方法之一，但基于硫醇基于硫醇的自组装单层的热和氧化不稳定性是在其基于硫醇的无限型单体上的优势。 与化学合作者一起，我们证明了N-杂环碳烯（NHC）代表了可行的硫醇替代品。我们的目标是通过系统地修改NHC的结构并同时发展分子的理解，对它们的表面化学，自我组装方法和协议来优化这些新叠加层系统的稳定性。 影响将是基于NHC的金属表面的优化下一代功能化剂，该剂可用作表面修饰符，并在分子电子，微接合印刷，生物传感和表面保护中应用。通过在表面上对NHC自组装的研究获得的见解也将为医学和催化中使用的NHC稳定金属纳米簇的合成。 该建议将在以下级别上为总共18个学生提供培训：2个博士学位，6个MSC，5名本科夏季学生和5个最后一年的荣誉。