Nanostructured surfaces for surface plasmon resnonance spectroscopy and imaging

Surface plasmon resonance (SPR) has achieved widespread recognition as a sensitive, label-free, and versatile optical method for monitoring changes in refractive index at a metal-dielectric interface. Refractive index deviations of 10-6 RIU are resolvable using SPR, and the method can be used in real-time or ex-situ. Instruments based on carboxymethyl dextran coated SPR chips have achieved commercial success in biological detection, while SPR sensors can also be found in other fields as varied as food safety and gas sensing. Chapter 1 provides a physical background of SPR sensing. A brief history of the technology is presented, and publication data are included that demonstrate the large and growing interest in surface plasmons. Numerous applications of SPR sensors are listed to illustrate the broad appeal of the method. Surface plasmons (SPs) and surface plasmon polaritions (SPPs) are formally defined, and important parameters governing their spatial behavior are derived from Maxwell\u27s equations and appropriate boundary conditions. Physical requirements for exciting SPs with incident light are discussed, and SPR imaging is used to illustrate the operating principle of SPR-based detection. Angle-tunable surface enhanced infrared absorption (SEIRA) of polymer vibrational modes via grating-coupled SPR is demonstrated in Chapter 2. Over 10-fold enhancement of C-H stretching modes was found relative to the absorbance of the same film in the absence of plasmon excitation. Modeling results are used to support and explain experimental observations. Improvements to the grating coupler SEIRA platform in Chapter 2 are explored in Chapters 3 and 4. Chapter 3 displays data for two sets of multipitch gratings: one set with broadly distributed resonances with the potential for multiband IR enhancement and the other with finely spaced, overlapping resonances to form a broadband IR enhancement device. Diffraction gratings having multiple periods were fabricated using a Lloyd\u27s mirror interferometer to perform multiple exposures at multiple angles before developing. Precise control of the resonance position is shown by locating three SPR dips at predetermined wavenumbers of 5000, 4000, and 3000 cm-1, respectively. A set of three gratings, each having four closely spaced resonances is employed to show how the sensor response could be broadened. The work in Chapter 3 shows potential for simultaneous enhancement of multiple vibrational modes; the multiband approach might find application for modes at disparate locations within the IR spectrum, while the broadband approach may allow concurrent probing of of broad single modes or clusters of narrow modes within a particular neighborhood of the spectrum. Chapter 4 uses the rigorous coupled-wave analysis (RCWA) method to numerically explore another facet of the nanostructure-based tunability of grating-baed SPR sensing. The work in this chapter illustrates how infrared signal enhancement could be tailored by through adjustment of the grating amplitude. Modeled infrared reflection absorption (IRRAS) spectra and electric field distributions were generated for several nanostructured grating configurations. It was found that there exists a critical amplitude value for a given grating pitch where the plasmon response achieves a maximum. Amplitudes greater than this critical value produce a broader and attenuated plasmon peak, while smaller amplitudes produce a plasmon resonance that is not as intense. Field simulations show how amplitudes nearer the critical amplitude resulted in large increases in the electric field within an analyte film atop the sensor surface, and the relative strength of the increased field is predictable based on the appearance of the IRRAS spectra. It is believed that these larger fields are the cause of observed enhanced absorption. Published reports pertaining to interactions of SPs with molecular resonance and to diffraction-based tracking of plasmons without a spectrometer are included in the Appendix to this thesis. In the first of the two reports, it is shown that plasmons coupling to dye molecular resonance can be quenched due to the effects of the high extinction coefficient of the dye. In the second report, the thickness of nanometer-scale SiO films on a gold-coated grating is evaluated by tracking the plasmon using a Bertrand lens and camera. Model results show close agreement with observations in both works. This work aims to show the versatility of SPR sensing in multiple applications. The inherent angle- and wavelength-tunability of plasmon responses is a distinct advantage for sensing phenomena over a wide range of conditions. SPR sensing is also highly dependent on the nanostructure at and near the metal-dielectric interface. The thickness of thin metal coatings, as well as the pitch, amplitude, and shape of metallic gratings all affect the behavior of SPPs in profound ways. Gratings provide an especially information-rich avenue for SPR sensing, as data is contained in multiple diffracted orders over a wide range of angles and wavelengths