Hazard detection systems must be evaluated with appropriate test material concentrations under controlled conditions in order to accurately identify and quantify unknown residues commonly utilized in theater. The existing assortment of hazard reference sample preparation methods/techniques presents a range of variability and reproducibility concerns, making it increasingly difficult to accurately assess optically- based detection technologies. To overcome these challenges, we examined the optimization, characterization, and calibration of microdroplets from a drop-on-demand microdispenser that has a proven capability for the preparation of energetic reference materials. Research presented herein focuses on the development of a simplistic instrument calibration technique and sample preparation protocol for explosive materials testing based on drop-on-demand technology. Droplet mass and reproducibility were measured using ultraviolet-visible (UV-Vis) absorption spectroscopy. The results presented here demonstrate the operational factors that influence droplet dispensing for specific materials (e.g., energetic and interferents). Understanding these parameters permits the determination of droplet and sample uniformity and reproducibility (typical R² values of 0.991, relative standard deviation or RSD ≤ 5%), and thus the demonstrated maturation of a successful and robust methodology for energetic sample preparation.

Detection and identification of unknown and possibly hazardous materials is a vital area of research to which infrared (IR) spectroscopy is ideally suited. Infrared absorption spectra can be measured with many sensing paradigms of which photoacoustic spectroscopy (PAS) is a sensitive and flexible variant. The flexibility of PAS allows for the construction of narrowly tailored spectroscopic sensors that are designed for specific tasks. We discuss the evaluation of an interferometric PAS sensor by the measurement of common explosive hazards from a standoff distance of 1 m. Reproduction of IR absorption spectra for 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), pentaerythritol tetranitrate (PETN), and 2,4,6-trinitrotoluene (TNT) demonstrate the capabilities of the interferometric sensor for standoff explosives detection.

Approaches to provide chip-scale aqueous chemical sensing for environmental and health monitoring via Photonic Integrated Circuit (PIC) technology are showing promise. To meet future Army demand we have investigated waveguide structures compatible with feature sizes offered by modern mass-manufacturing PIC foundries. We have found that wide subwavelength grating (SWG) waveguide structures can maximally interact with an encapsulating analyte capture material with low propagation loss. We describe the analyte/light interaction component of our general integrated photonics chemical detector sensitivity model and use it to compare the effectiveness of waveguide geometries for sensing. The structures we have investigated afford superior detection to strip and slot waveguides. Lastly, we introduce a novel tapered SWG waveguide geometry with improved transmission and similar sensitivity to non-tapered SWG designs.

Traditionally, chemical sensing platforms have been hampered by the opposing concerns of increasing sensor capability while maintaining a minimal package size. Current sensors, although reasonably sized, are geared to more classical chemical threats, and the ability to expand their capabilities to a broader range of emerging threats is uncertain. Recently, photoacoustic spectroscopy, employed in a sensor format, has shown enormous potential to address these ever-changing threats. Photoacoustic spectroscopy is one of the more flexible infrared spectroscopy variants, and that flexibility allows for the construction of sensors that are designed for specific tasks. The Army Research Laboratory has, for the past 14 years, engaged in research into the development of photoacoustic sensing platforms with the goal of sensor miniaturization and the detection of a variety of chemical targets both proximally and at range. This paper reviews this work.

We report on the development of a photoacoustic device for the detection of condensed-phase materials. A mid-infrared quantum cascade laser (QCL) was used for depth-profiling studies to distinguish among glycerol films and tetraethoxysilane (TEOS) films deposited on photoresist-coated silicon wafers. The QCL was continuously tunable from 1015 cm⁻¹ to 1240 cm⁻¹, allowing for collection of photoacoustic vibrational spectra for these materials. Variation of the laser pulse repetition rate allowed for identification and molecular discrimination of glycerol, TEOS, and photoresist based solely on photoacoustic spectra collected at different film depths.