Dielectric Stack Filters for Ex Situ and In Situ UV Optical-Fiber Probe Raman Spectroscopic Measurements

Dielectric stack interference filters can be used in conjunction with a high-throughput single-stage spectrograph to facilitate the measurement of high signal-to-noise (S/N) ultraviolet (UV) Raman spectra with 228.9-nm and 244-nm excitation wavelengths. Placed between the sample and the spectrograph, these filters reflect Rayleigh scattering while transmitting Stokes-shifted Raman scattering. We have measured UV Raman bands from solid, highly scattering samples down to a 290-cm−1 shift from the Rayleigh line. The high throughput of the filtered single-stage spectrograph enables the measurement of UV Raman spectra from photo-labile samples, including DNA and the energetic materials pentaerythritol tetranitrate (PETN) and trinitrotoluene (TNT), with sufficiently low excitation powers and short accumulation times to minimize photo-alteration. High S/N UV preresonance and resonance Raman are obtained for PETN and TNT within 1 s, indicating the possible application of UV Raman spectroscopy as a rapid, highly selective screening methodology for the detection of trace levels of contraband explosives. Furthermore, the incorporation of these dielectric filters within a UV optical-fiber Raman probe head provides simultaneous Rayleigh rejection and removal of background silica Raman scattering. With the use of a 244-nm UV optical-fiber probe, we measured Raman spectra from 100 nM to 10 μM concentrations of polycyclic aromatic hydrocarbon (PAH) in water, even in the presence of an equimolar concentration of the visible fluorophore rhodamine 6G (R6G). Thus, we demonstrate the potential of UV Raman optical-fiber probes for minimally invasive in situ real-time monitoring at low analyte concentrations and within environments in which fluorescence backgrounds would prevent measurements with visible Raman optical-fiber probes.