An analytical technique operating at the nanoscale must be flexible regarding variable experimental conditions while ideally also being highly specific, extremely sensitive, and spatially confined. In this respect, tip-enhanced Raman scattering (TERS) has been demonstrated to be ideally suited to, e.g., elucidating chemical reaction mechanisms, determining the distribution of components and identifying and localizing specific molecular structures at the nanometre scale. TERS combines the specificity of Raman spectroscopy with the high spatial resolution of scanning probe microscopies by utilizing plasmonic nanostructures to confine the incident electromagnetic field and increase it by many orders of magnitude. Consequently, molecular structure information in the optical near field that is inaccessible to other optical microscopy methods can be obtained. In this general review, the development of this still-young technique, from early experiments to recent achievements concerning inorganic, organic, and biological materials, is addressed. Accordingly, the technical developments necessary for stable and reliable AFM- and STM-based TERS experiments, together with the specific properties of the instruments under different conditions, are reviewed. The review also highlights selected experiments illustrating the capabilities of this emerging technique, the number of users of which has steadily increased since its inception in 2000. Finally, an assessment of the frontiers and new concepts of TERS, which aim towards rendering it a general and widely applicable technique that combines the highest possible lateral resolution and extreme sensitivity, is provided.

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尖端增强的拉曼光谱–从早期发展到最新进展

在纳米尺度上运行的分析技术必须在可变的实验条件下具有灵活性，同时理想情况下还必须具有高度的特异性，极高的敏感性和空间限制。在这方面，尖端增强拉曼散射（TERS）已被证明非常适合于例如，阐明化学反应机理，确定组分的分布以及识别和定位纳米级的特定分子结构。TERS通过利用等离子体纳米结构限制入射电磁场并将其增加许多数量级，将拉曼光谱法的特异性与扫描探针显微镜的高空间分辨率结合在一起。因此，可以获得其他光学显微镜方法无法获得的光学近场中的分子结构信息。在本篇综述中，探讨了这项仍处于年轻阶段的技术的发展，从早期的实验到有关无机，有机和生物材料的最新成果，一应俱全。因此，回顾了稳定，可靠的基于AFM和STM的TERS实验所必需的技术发展，以及在不同条件下仪器的特殊性能。该评论还重点介绍了一些实验，这些实验说明了这项新兴技术的功能，自2000年推出以来，其用户数量一直在稳步增长。最后，对TERS的前沿领域和新概念进行了评估，旨在使TERS具有通用性和提供了一种结合了尽可能高的横向分辨率和极高灵敏度的广泛应用的技术。