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Probing the Role of Environmental and Sample Characteristics in Gap Mode Tip-Enhanced Raman Spectroscopy
Analytical Chemistry ( IF 6.7 ) Pub Date : 2023-06-01 , DOI: 10.1021/acs.analchem.3c00410 Yashashwa Pandey 1 , Daniel F Abbott 1 , Victor Mougel 1 , Naresh Kumar 1 , Renato Zenobi 1
Analytical Chemistry ( IF 6.7 ) Pub Date : 2023-06-01 , DOI: 10.1021/acs.analchem.3c00410 Yashashwa Pandey 1 , Daniel F Abbott 1 , Victor Mougel 1 , Naresh Kumar 1 , Renato Zenobi 1
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Tip-enhanced Raman spectroscopy (TERS) has emerged as a powerful analytical tool for nondestructive and label-free molecular characterization at the nanoscale. However, the influence of environmental factors and sample characteristics on the occurrence of spurious signals, enhancement of TERS signals, and longevity of TERS probes is not well understood yet. Herein, we present a detailed investigation of the influence of oxygen, humidity, and atmospheric carbon contaminants on scanning tunneling microscopy-TERS (STM-TERS) measurements of self-assembled monolayer systems in ambient and inert environments. Our results reveal a consistent increase of TERS signals, significant reduction of spurious signals, and drastically improved longevity of TERS probes in the inert environment. Additionally, sample characteristics such as molecular packing, chemisorption behavior, and hydrophilicity are found to have a direct impact on signal enhancement in the TERS measurements of molecular self-assembled monolayers (SAMs). The novel insights gained in this study are expected to pave the way for a more robust data analysis and improved experimental design in the future gap mode STM- and atomic force microscopy-TERS (AFM-TERS) studies.
中文翻译：
探索环境和样品特征在间隙模式尖端增强拉曼光谱中的作用
尖端增强拉曼光谱 (TERS) 已成为一种强大的分析工具，可用于纳米级的无损和无标记分子表征。然而，环境因素和样本特性对杂散信号的发生、TERS 信号的增强以及 TERS 探针寿命的影响尚不清楚。在此，我们详细研究了氧气、湿度和大气中碳污染物对环境和惰性环境中自组装单层系统的扫描隧道显微镜-TERS (STM-TERS) 测量的影响。我们的结果表明 TERS 信号持续增加，杂散信号显着减少，并且 TERS 探针在惰性环境中的寿命显着提高。此外，样品特征，如分子堆积，发现化学吸附行为和亲水性对分子自组装单层 (SAM) 的 TERS 测量中的信号增强有直接影响。在这项研究中获得的新见解有望为未来间隙模式 STM 和原子力显微镜-TERS (AFM-TERS) 研究中更强大的数据分析和改进的实验设计铺平道路。
更新日期：2023-06-01
中文翻译：
探索环境和样品特征在间隙模式尖端增强拉曼光谱中的作用
尖端增强拉曼光谱 (TERS) 已成为一种强大的分析工具，可用于纳米级的无损和无标记分子表征。然而，环境因素和样本特性对杂散信号的发生、TERS 信号的增强以及 TERS 探针寿命的影响尚不清楚。在此，我们详细研究了氧气、湿度和大气中碳污染物对环境和惰性环境中自组装单层系统的扫描隧道显微镜-TERS (STM-TERS) 测量的影响。我们的结果表明 TERS 信号持续增加，杂散信号显着减少，并且 TERS 探针在惰性环境中的寿命显着提高。此外，样品特征，如分子堆积，发现化学吸附行为和亲水性对分子自组装单层 (SAM) 的 TERS 测量中的信号增强有直接影响。在这项研究中获得的新见解有望为未来间隙模式 STM 和原子力显微镜-TERS (AFM-TERS) 研究中更强大的数据分析和改进的实验设计铺平道路。
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