Voltage-Dependent FTIR and 2D Infrared Spectroscopies within the Electric Double Layer Using a Plasmonic and Conductive Electrode.
Voltage-Dependent FTIR and 2D Infrared Spectroscopies within the Electric Double Layer Using a Plasmonic and Conductive Electrode.
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DOI：
10.1021/acs.jpcb.2c08431
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发表时间：
2023-03-09
影响因子：
3.3
通讯作者：
Zanni, Martin T.
中科院分区：
文献类型：
--
作者：
Yang, Nan;Ryan, Matthew J.;Son, Minjung;Mavric, Andraz;Zanni, Martin T.
双电层和带电表面之间存在很强的电场。这些场影响界面上的分子结构和化学。我们已经开发了一种具有红外等离子体增强的透明电极，足以测量电压可以施加到的表面上亚单层覆盖的FTIR和二维红外光谱。我们的器件由红外透明衬底、10-20 nm导电氧化铟锡(ITO)层、3-5 nm Al_2O_3电阻层和3 nm非导电等离子体金组成。材料和厚度被设置为最大限度地增加单层分子的表面数密度、导电性和等离子体增强，同时最小化背景信号和避免Fano线形扭曲。通过用原子力显微镜和电子显微镜反复表征材料的粗糙度和厚度，并用光谱学监测等离子体共振增强，优化了设计。这种设计对重复制造具有很强的耐用性。用4-巯基苯甲腈为单分子膜测试了该电极的氰基官能团，并用4-巯基苯甲酸甲酯进行了CO和CC伸缩模式的测试。在这两种单分子膜上都观察到了与电压相关的斯塔克位移。我们还观察到CN模的跃迁偶极子强度与外加电压成线性关系，提供了测量表面电场强度的第二种方法。我们预计，该电池将在外加电压下实现许多新的电压依赖红外实验。
Strong electric fields exist between the electric double layer and charged surfaces. These fields impact molecular structures and chemistry at interfaces. We have developed a transparent electrode with infrared plasmonic enhancement sufficient to measure FTIR and two-dimensional infrared spectra at submonolayer coverages on the surface to which a voltage can be applied. Our device consists of an infrared transparent substrate, a 10–20 nm layer of conductive indium tin oxide (ITO), an electrically resistive layer of 3–5 nm Al2O3, and a 3 nm layer of nonconductive plasmonic gold. The materials and thicknesses are set to maximize the surface number density of the monolayer molecules, electrical conductivity, and plasmonic enhancement while minimizing background signals and avoiding Fano line shape distortions. The design was optimized by iteratively characterizing the material roughness and thickness with atomic force microscopy and electron microscopy and by monitoring the plasmon resonance enhancement with spectroscopy. The design is robust to repeated fabrication. This new electrode is tested on nitrile functional groups using a monolayer of 4-mercaptobenzonitrile as well as on CO and CC stretching modes using 4-mercaptobenzoic acid methyl ester. A voltage-dependent Stark shift is observed on both monolayers. We also observe that the transition dipole strength of the CN mode scales linearly with the applied voltage, providing a second way of measuring the surface electric field strength. We anticipate that this cell will enable many new voltage-dependent infrared experiments under applied voltages.
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