Brian E. Lemoff

Deep-ultraviolet Raman spectroscopy is a very useful approach for standoff detection of explosive traces. Using two simultaneous excitation wavelengths improves the specificity and sensitivity to standoff explosive detection. The High Technology Foundation developed a highly compact prototype of resonance Raman explosives detector. In this work, we discuss the relative performance of a dual-excitation sensor compared to a single-excitation sensor. We present trade space analysis comparing three representative Raman systems with similar size, weight, and power. The analysis takes into account, cost, spectral resolution, detection/identification time and the overall system benefit.

A promising approach to stand-off detection of explosive traces is using resonance Raman spectroscopy with Deepultraviolet (DUV) light. The DUV region offers two main advantages: strong explosive signatures due to resonant and λ^{- 4} enhancement of Raman cross-section, and lack of fluorescence and solar background. For DUV Raman spectroscopy, continuous-wave (CW) or quasi-CW lasers are preferable to high peak powered pulsed lasers because Raman saturation phenomena and sample damage can be avoided. In this work we present a very compact DUV source that produces greater than 1 mw of CW optical power. The source has high optical-to-optical conversion efficiency, greater than 5 %, as it is based on second harmonic generation (SHG) of a blue/green laser source using a nonlinear crystal placed in an external resonant enhancement cavity. The laser system is extremely compact, lightweight, and can be battery powered. Using two such sources, one each at 236.5 nm and 257.5 nm, we are building a second generation explosive detection system called Dual-Excitation-Wavelength Resonance-Raman Detector (DEWRRED-II). The DEWRRED-II system also includes a compact dual-band high throughput DUV spectrometer, and a highly-sensitive detection algorithm. The DEWRRED technique exploits the DUV excitation wavelength dependence of Raman signal strength, arising from complex interplay of resonant enhancement, self-absorption and laser penetration depth. We show sensor measurements from explosives/precursor materials at different standoff distances.

A key challenge for standoff explosive sensors is to distinguish explosives, with high confidence, from a myriad of unknown background materials that may have interfering spectral peaks. To meet this challenge a sensor needs to exhibit high specificity and high sensitivity in detection at low signal-to-noise ratio levels. We had proposed a Dual-Excitation- Wavelength Resonance-Raman Detector (DEWRRED) to address this need. In our previous work, we discussed various components designed at WVHTCF for a DEWRRED sensor. In this work, we show a completely assembled laboratory prototype of a DEWRRED sensor and utilize it to detect explosives from two standoff distances. The sensor system includes two novel, compact CW deep-Ultraviolet (DUV) lasers, a compact dual-band high throughput DUV spectrometer, and a highly-sensitive detection algorithm. We choose DUV excitation because Raman intensities from explosive traces are enhanced and fluorescence and solar background are not present. The DEWRRED technique exploits the excitation wavelength dependence of Raman signal strength, arising from complex interplay of resonant enhancement, self-absorption and laser penetration depth. We show measurements from >10 explosives/pre-cursor materials at different standoff distances. The sensor showed high sensitivity in explosive detection even when the signalto- noise ratio was close to one (~1.6). We measured receiver-operating-characteristics, which show a clear benefit in using the dual-excitation-wavelength technique as compared to a single-excitation-wavelength technique. Our measurements also show improved specificity using the amplitude variation information in the dual-excitation spectra.

Raman spectroscopy is a widely used spectroscopic technique with a number of applications. During the past few years, we explored the use of simultaneous multiple-excitation-wavelengths (MEW) in resonance Raman spectroscopy. This approach takes advantage of Raman band intensity variations across the Resonance Raman spectra obtained from two or more excitation wavelengths. Amplitude variations occur between corresponding Raman bands in Resonance Raman spectra due to complex interplay of resonant enhancement, self-absorption and laser penetration depth. We have developed a very sensitive algorithm to estimate concentration of an analyte from spectra obtained using the MEW technique. The algorithm uses correlations and least-square minimization approach to calculate an estimate for the concentration. For two or more excitation wavelengths, measured spectra were stacked in a two dimensional matrix. In a simple realization of the algorithm, we approximated peaks in the ideal library spectra as triangles. In this work, we present the performance of the algorithm with measurements obtained from a dual-excitation-wavelength Resonance Raman sensor. The novel sensor, developed at WVHTCF, detects explosives from a standoff distance. The algorithm was able to detect explosives with very high sensitivity even at signal-to-noise ratios as low as ~1.6. Receiver operating characteristics calculated using the algorithm showed a clear benefit in using the dual-excitation-wavelength technique over single-excitation-wavelength techniques. Variants of the algorithm that add more weight to amplitude variation information showed improved specificity to closely resembling spectra.

Deep-ultraviolet resonance Raman spectroscopy (DUVRRS) is a promising approach to stand-off detection of explosive traces due to: 1) resonant enhancement of Raman cross-section, 2) λ^-4-cross-section enhancement, and 3) fluorescence and solar background free signatures. For trace detection, these signal enhancements more than offset the small penetration depth due to DUV absorption. A key challenge for stand-off sensors is to distinguish explosives, with high confidence, from a myriad of unknown background materials that may have interfering spectral peaks. To address this, we are developing a stand-off explosive sensor using DUVRRS with two simultaneous DUV excitation wavelengths. Due to complex interplay of resonant enhancement, self-absorption and laser penetration depth, significant amplitude variation is observed between corresponding Raman bands with different excitation wavelengths. These variations with excitation wavelength provide an orthogonal signature that complements the traditional Raman signature to improve specificity relative to single-excitation-wavelength techniques. As part of this effort, we are developing two novel CW DUV lasers, which have potential to be compact, and a compact dual-band high throughput DUV spectrometer, capable of simultaneous detection of Raman spectra in two spectral windows. We have also developed a highly sensitive algorithm for the detection of explosives under low signal-to-noise situations.