Standoff Deep Ultraviolet Raman Spectrometer for Trace Detection

We developed a state-of-the-art, high-sensitivity, low-stray-light standoff deep-ultraviolet (DUV) Raman spectrometer for the trace detection of resonance Raman-enhanced chemical species. As an excitation source for Raman measurements, we utilized our recently developed, second-generation, miniaturized, diode-pumped, solid-state neodymium-doped gadolinium orthovanadate (Nd:GdVO₄) laser that generates quasi-continuous wave 228 nm light. This 228 nm excitation enhances the Raman intensities of vibrations of NO_x groups in explosive molecules, aromatic groups in biological molecules, and various aromatic hydrocarbons. Our DUV Raman spectrograph utilizes a custom DUV f/8 Cassegrain telescope with an ∼200 mm diameter primary mirror, high-efficiency DUV transmission gratings, custom DUV mirrors, and a custom 228 nm Rayleigh rejection filter. We utilized our new standoff DUV Raman spectrometer to measure high signal-to-noise ratio spectra of ∼50 μg/cm² drop-cast explosives: ammonium nitrate (AN), trinitrotoluene, pentaerythritol tetranitrate as well as aromatic biological molecules: lysozyme, tryptophan, tyrosine, deoxycytidine monophosphate, deoxyadenosine monophosphate at an ∼3 m distance within 10-30 s accumulation times. We roughly estimate the average ultraviolet resonance Raman (UVRR) detection limits for the relatively homogeneous drop-cast films of explosives and biological molecules to be ∼1 μg/cm² when utilizing a continuous raster scanning that averages Raman signal over ∼1 cm² sample area to avoid quick analyte depletion due to ultraviolet (UV) photolysis. We determined 3 m standoff UVRR detection limits for drop-cast AN films and identified factors impacting UVRR detection limits such as analyte photochemistry and analyte morphology. We found a detection limit of ∼0.5 μg/cm² for drop-cast AN films on glass substrates when the Raman signal is averaged over ∼0.5 cm² of sample surface using a continuous raster scan. For a step raster scan, when the probed sample area is limited to the laser spot size, the detection limit is approximately tenfold higher (∼5 μg/cm²) due to the impact of UV photochemistry.