Department of Chemistry, Iowa State University, 1605 Gilman Hall, 2415 Osborn Drive, Ames, IA, 50011, USA.
The Ames Laboratory, U.S. Department of Energy, Ames, IA, 50011, USA.
Anal Bioanal Chem. 2020 Sep;412(24):6009-6022. doi: 10.1007/s00216-020-02510-1. Epub 2020 Mar 16.
Total internal reflection (TIR) optical spectroscopies have been widely used for decades as non-destructive and surface-sensitive measurements of thin films and interfaces. Under TIR conditions, an evanescent wave propagates into the sample layer within a region approximately 50 nm to 2 μm from the interface, which limits the spatial extent of the optical signal. The most common TIR optical spectroscopies are fluorescence (i.e., TIRF) and infrared spectroscopy (i.e., attenuated total reflection infrared). Despite the first report of TIR Raman spectroscopy appearing in 1973, this method has not received the same attention to date. While TIR Raman methods can provide chemical specific information, it has been outshined in many respects by surface-enhanced Raman spectroscopy (SERS). TIR Raman spectroscopy, however, is garnering more interest for analyzing the chemical and physical properties of thin polymer films, self-assembled monolayers (SAMs), multilayered systems, and adsorption at an interface. Herein, we discuss the early experimental and computational work that laid the foundation for recent developments in the use of TIR Raman techniques. Recent applications of TIR Raman spectroscopy as well as modern TIR Raman instruments capable of measuring monolayer-sensitive vibrational modes on smooth metallic surfaces are also discussed. The use of TIR Raman spectroscopy has been on a rise and will continue to push the limits for chemical specific interfacial and thin film measurements. Graphical abstract Total internal reflection (TIR) Raman spectroscopy can extract the chemical and physical information from thin films and adsorbates.
全内反射（TIR）光学光谱学作为一种非破坏性和表面敏感的薄膜和界面测量方法，已经得到了广泛的应用几十年。在 TIR 条件下，倏逝波在界面附近约 50nm 到 2μm 的区域内传播到样品层，这限制了光学信号的空间范围。最常见的 TIR 光学光谱学是荧光（即 TIRF）和红外光谱学（即衰减全反射红外）。尽管 TIR 拉曼光谱的首次报道出现在 1973 年，但迄今为止，这种方法并没有得到同样的关注。虽然 TIR 拉曼方法可以提供化学特异性信息，但在许多方面它已经被表面增强拉曼光谱（SERS）所超越。然而，TIR 拉曼光谱在分析聚合物薄膜、自组装单层（SAM）、多层系统和界面吸附的化学和物理性质方面越来越受到关注。本文讨论了为 TIR 拉曼技术的最新发展奠定基础的早期实验和计算工作。还讨论了 TIR 拉曼光谱的最新应用以及能够测量光滑金属表面单层敏感振动模式的现代 TIR 拉曼仪器。TIR 拉曼光谱的使用一直在增加，并将继续推动化学特异性界面和薄膜测量的极限。
