Petefish Joseph W, Hillier Andrew C
Department of Chemical and Biological Engineering, Iowa State University , Ames, Iowa 50011, United States.
Anal Chem. 2014 Mar 4;86(5):2610-7. doi: 10.1021/ac4038398. Epub 2014 Feb 17.
Surface enhanced infrared absorption (SEIRA) spectroscopy is an attractive method for increasing the prominence of vibrational modes in infrared spectroscopy. To date, the majority of reports associated with SEIRA utilize localized surface plasmon resonance from metal nanoparticles to enhance electromagnetic fields in the region of analytes. Limited work has been performed using propagating surface plasmons as a method for SEIRA excitation. In this report, we demonstrate angle-tunable enhancement of vibrational stretching modes associated with a thin poly(methyl methacrylate) (PMMA) film that is coupled to a silver-coated diffraction grating. Gratings are fabricated using laser interference lithography to achieve precise surface periodicities, which can be used to generate surface plasmons that overlap with specific vibrational modes in the polymer film. Infrared reflection absorption spectra are presented for both bare silver and PMMA-coated silver gratings at a range of angles and polarization states. In addition, spectra were obtained with the grating direction oriented perpendicular and parallel to the infrared source in order to isolate plasmon enhancement effects. Optical simulations using the rigorous coupled-wave analysis method were used to identify the origin of the plasmon-induced enhancement. Angle-dependent absorption measurements achieved signal enhancements of more than 10-times the signal in the absence of the plasmon.
表面增强红外吸收(SEIRA)光谱法是一种在红外光谱中增强振动模式显著性的颇具吸引力的方法。迄今为止,与SEIRA相关的大多数报告都利用金属纳米颗粒的局域表面等离子体共振来增强分析物区域的电磁场。利用传播表面等离子体作为SEIRA激发方法的工作还很有限。在本报告中,我们展示了与耦合到镀银衍射光栅的聚甲基丙烯酸甲酯(PMMA)薄膜相关的振动拉伸模式的角度可调增强。使用激光干涉光刻技术制造光栅以实现精确的表面周期性,可用于产生与聚合物薄膜中特定振动模式重叠的表面等离子体。给出了裸银光栅和PMMA涂覆银光栅在一系列角度和偏振态下的红外反射吸收光谱。此外,为了分离等离子体增强效应,在光栅方向垂直和平行于红外源的情况下获得了光谱。使用严格耦合波分析方法进行的光学模拟用于确定等离子体诱导增强的起源。角度相关的吸收测量实现了比不存在等离子体时的信号增强超过10倍的信号增强。