CAREER: Deciphering 2-Dimensional, Crystal-Mediated, Surface-Enhanced Raman Scattering for Quantitative Analysis

职业：破译二维、晶体介导、表面增强拉曼散射以进行定量分析

• 批准号: 1945364
• 负责人: Xi Ling
• 金额: $ 67.89万
• 依托单位: Trustees of Boston University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-03-01 至 2025-02-28
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1945364&HistoricalAwards=false
• 关键词: CAREER; Deciphering; Dimensional; Crystal; Mediated

Molecules can be detected and identified by how they absorb or emit light of different wavelengths. A technique called Raman spectroscopy reveals information about molecular structure using the light scattered by molecules as they vibrate at their unique frequencies. Over 40 years ago, it was discovered that the Raman scattering signals could be increased dramatically (more than a million times) when molecules were stuck to (adsorbed on) a roughened metal surface. That discovery improved chemical detection and analysis, however the signal improvements are not always reproducible from one surface to another and the precise reason for the enhancement is still under vigorous debate. In this project, funded by the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) Program of the Chemistry Division, Professor Xi Ling of Boston University is investigating signal enhancements in Raman spectroscopy on the surfaces of well-defined, two-dimensional (2D) crystals (e.g., tin sulfide (SnS2) and tungsten selenide (WSe2)). The structure and properties of these crystals are better defined and understood than those of roughened metal surfaces and thus, Professor Ling and her students may uncover how and why Raman signal are enhanced on surfaces. New technologies are expected to emerge from this research project, especially in the field of chemical analysis, where it may become routine to detect just a few or even a single molecule of a substance. The students engaged in this project are gaining advanced training in spectroscopy (light-matter interactions) and molecular and materials design, both of which are increasingly sought-after areas of expertise in the science and technology sector. Professor Ling will develop and implement a laser spectroscopy experience for students by collaborating with Boston University's Learning Resource Network (LERNet) and its outreach programs. This outreach program encourages young women and high schools students to enter science and engineering fields. Dr. Lin will also enhance open source education resources for high school teachers and students by developing interactive video lesson modules. The mechanisms of surface-enhanced Raman spectroscopy (SERS) are not fully understood, especially the chemical mechanism (CM), which remains relatively mysterious compared to the electromagnetic (EM) mechanism. The scientific objectives of this project are to gain a deeper understanding of chemical mechanism and explore the potential of 2D crystals to overcoming the key problem of reproducibility of SERS in practical applications. Quantitative SERS data from well-defined samples (both 2D substrate and adsorbed analytes) serve to test the CM theory in the literature. The Ling group is employing multiple analytical approaches, such as wavelength-scanned Raman measurements, micro-absorption spectroscopy, as well as rigorous group theory analysis to understand the origin of the chemical enhancement in a quantitative manner. Furthermore, toward the development of revolutionary SERS-sensing techniques, 2D crystal/metal systems are being investigated to understand how the 2D crystals influence the plasmon frequency and electromagnetic field distribution of metal nanostructures and demonstrate the high sensitivity, selectivity and reproducibility of the system in micro-sensing. Collectively, these investigations are providing a deeper understanding of the controversial CM in SERS and guide an innovative design of a better SERS platform. The broader technical impacts of this work include new knowledge of CM in SERS and the seeding of development of new technique for chemical and bio-sensing. The education plan improves the quality, retention, and diversity of STEM students in science and technology.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.

分子可以通过它们如何吸收或发射不同波长的光来检测和识别。一种叫做拉曼光谱学的技术利用分子以其独特的频率振动时散射的光来揭示分子结构的信息。40多年前，人们发现当分子附着在粗糙的金属表面时，拉曼散射信号会急剧增加（超过一百万倍）。这一发现改进了化学检测和分析，然而，信号的改进并不总是可以从一个表面复制到另一个表面，而且这种增强的确切原因仍在激烈的争论中。在这个由化学学部化学结构、动力学和机理a （CSDM-A）项目资助的项目中，波士顿大学的Xi Ling教授正在研究明确定义的二维（2D）晶体（例如，硫化锡（SnS2）和硒化钨（WSe2））表面的拉曼光谱信号增强。与粗糙金属表面相比，这些晶体的结构和性质得到了更好的定义和理解，因此，凌教授和她的学生可能会发现拉曼信号在表面上增强的方式和原因。新技术有望从这个研究项目中出现，特别是在化学分析领域，它可能成为常规检测物质的几个甚至单个分子。参与该项目的学生将获得光谱学（光-物质相互作用）和分子与材料设计方面的高级培训，这两个领域都是科学和技术领域越来越受欢迎的专业领域。凌教授将通过与波士顿大学学习资源网络（LERNet）及其外展项目合作，为学生开发和实施激光光谱学经验。这个拓展项目鼓励年轻女性和高中生进入科学和工程领域。林博士还将通过开发互动视频课程模块，为高中教师和学生提供更多的开源教育资源。表面增强拉曼光谱（SERS）的机理尚未完全了解，特别是化学机理（CM），与电磁机理（EM）相比，它仍然是一个相对神秘的机制。该项目的科学目标是深入了解二维晶体的化学机理，探索二维晶体的潜力，以克服SERS在实际应用中的再现性的关键问题。从定义良好的样品（2D底物和吸附分析物）的定量SERS数据用于测试文献中的CM理论。凌团队正在采用多种分析方法，如波长扫描拉曼测量，微吸收光谱，以及严格的群论分析，以定量的方式了解化学增强的起源。此外，为了发展革命性的sers传感技术，人们正在研究二维晶体/金属系统，以了解二维晶体如何影响金属纳米结构的等离子体频率和电磁场分布，并展示该系统在微传感中的高灵敏度、选择性和可重复性。总的来说，这些研究为SERS中有争议的CM提供了更深入的理解，并指导了更好的SERS平台的创新设计。这项工作的更广泛的技术影响包括SERS中CM的新知识和化学和生物传感新技术发展的播种。该教育计划提高了STEM学生在科学和技术领域的质量、保留率和多样性。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

项目成果

Spin-induced linear polarization of photoluminescence in antiferromagnetic van der Waals crystals

• DOI: 10.1038/s41563-021-00968-7
• 发表时间: 2020-06
• 期刊: Nature Materials
• 影响因子: 41.2
• 作者: Xingzhi Wang;Jun Cao;Zhengguang Lu;A. Cohen;Hikari Kitadai;Tianshu Li;Qishuo Tan;Matthew Wilson;C. Lui;D. Smirnov;S. Sharifzadeh;X. Ling

Deterministic Localization of Strain-Induced Single-Photon Emitters in Multilayer GaSe

• DOI: 10.1021/acsphotonics.3c00052
• 发表时间: 2022-10
• 期刊: ACS Photonics
• 影响因子: 7
• 作者: Weijun Luo;A. Puretzky;B. Lawrie;Qishuo Tan;Hongze Gao;Zhuofa Chen;A. Sergienko;A. Swan;L. Liang;X. Ling

Ultrathin GaN Crystal Realized Through Nitrogen Substitution of Layered GaS

• DOI: 10.1007/s11664-023-10670-w
• 发表时间: 2023-09
• 期刊: Journal of Electronic Materials
• 影响因子: 2.1
• 作者: Jun Cao;Tianshu Li;Hongze Gao;Xin Cong;Miao‐Ling Lin;Nicholas Russo;Weijun Luo;Siyuan Ding;Zifan Wang;Kevin E. Smith;Ping-Heng Tan;Qiong Ma;X. Ling

Resonance-Enhanced Excitation of Interlayer Vibrations in Atomically Thin Black Phosphorus

• DOI: 10.1021/acs.nanolett.1c00917
• 发表时间: 2021-05-28
• 期刊: NANO LETTERS
• 影响因子: 10.8
• 作者: Mao, Nannan;Lin, Yuxuan;Tisdale, William A.
• 通讯作者: Tisdale, William A.

Improving Strain-localized GaSe Single Photon Emitters with Electrical Doping

通过电掺杂改进应变局域 GaSe 单光子发射器

• DOI: 10.1021/acs.nanolett.3c02308
• 发表时间: 2023
• 期刊: Nano Letters
• 影响因子: 10.8
• 作者: Luo, Weijun;Puretzky, Alexander;Lawrie, Benjamin;Tan, Qishuo;Gao, Hongze;Swan, Anna K.;Liang, Liangbo;Ling, Xi
• 通讯作者: Ling, Xi