In this study, plasma-polymerized films are evaluated as enrichment membranes deposited at the surface of mid-infrared transparent waveguides for liquid-phase chemical sensing utilizing evanescent field absorption spectroscopy. Fluorocarbon films were deposited onto zinc selenide (ZnSe) waveguides from plasma-polymerized pentafluoroethane (CF(3)CHF(2)) vapor. Excellent optical transmission of ZnSe waveguides after plasma deposition confirms compatibility of the infrared transparent substrate with this low-temperature, solvent-free film deposition process. The liquid-phase enrichment characteristics for plasma membranes were investigated via evanescent field absorption spectroscopy of a model analyte (tetrachloroethylene); the limits of detection were below 300 ppb (v/v) in water. Plasma-polymerized films are known for their excellent mechanical and chemical stability, while offering tunable chemical and physical characteristics during the deposition process. Future application of this coating strategy for depositing robust enrichment membranes with tunable batch production capability imparts an attractive route toward application-oriented development of next-generation mid-infrared chemical sensors applicable in harsh environments.
A combined experimental and spectral ray tracing approach for identifying and evaluating evanescent field interactions with discrete surface deposits along a horizontal attenuated total reflection (HATR) element is presented. By experimentally depositing poly(styrene-co-butadiene) (PSCB) residues at fixed intervals along the measurement surface of a HATR crystal, distinct regions of evanescent field interaction with the surface deposits along the multi-reflection waveguide are visualized via infrared absorption features of PSCB. The infrared-attenuated total reflection (IR-ATR) measurements were confirmed by spectral ray tracing analysis simulating transmission-absorption spectra after modeling the polymeric surface deposits as thin-film IR absorbing cylinders. The presented analytical procedures and simulations provide a generic strategy for identifying and evaluating "active" sensing regions along ATR elements. Additionally, the simulated ATR setup along with the presented spectral ray tracing procedures provide a virtual platform aiding the development, optimization, and integration of deep-sea IR-ATR sensor probes with submersible mid-infrared spectrometers for in situ marine monitoring applications, which was the initial motivation for these studies.
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