Ultra-Trace Chemical Sensing with Long-Wave Infrared Cavity-Enhanced Spectroscopic Sensors

The infrared sensors task of Pacific Northwest National Laboratory's (PNNL's) Remote Spectroscopy Project (Task B of Project PL211) is focused on the science and technology of remote and in-situ spectroscopic chemical sensors for detecting proliferation and coun-tering terrorism. Missions to be addressed by remote chemical sensor development in-clude detecting proliferation of nuclear or chemical weapons, and providing warning of terrorist use of chemical weapons. Missions to be addressed by in-situ chemical sensor development include countering terrorism by screening luggage, personnel, and shipping containers for explosives, firearms, narcotics, chemical weapons, or chemical weapons residues, and mapping contaminated areas. The science and technology is also relevant to chemical weapons defense, air operations support, monitoring emissions from chemi-cal weapons destruction or industrial activities, law enforcement, medical diagnostics, and other applications. Sensors for most of these missions will require extreme chemical sensitivity and selectiv-ity because the signature chemicals of importance are expected to be present in low con-centrations or have low vapor pressures, and the ambient air is likely to contain pollutants or other chemicals with interfering spectra. Cavity-enhanced chemical sensors (CES) that draw air samples into optical cavities for laser-based interrogation of their chemical content promise real-time, in-situ chemical detection with extreme sensitivity to specified target molecules and superb immunity to spectral interference and other sources of noise. PNNL is developing CES based on quantum cascade (QC) lasers that operate in the mid-wave infrared (MWIR - 3 to 5 microns) and long-wave infrared (LWIR - 8 to 14 mi-crons), and CES based on telecommunications lasers operating in the short-wave infrared (SWIR - 1 to 2 microns). All three spectral regions are promising because smaller mo-lecular absorption cross sections in the SWIR are offset by the superior performance, ma-turity, and robustness of SWIR lasers, detectors, and other components, while the reverse is true for the MWIR and LWIR bands. PNNL's research activities include identification of signature chemicals and quantification of their spectroscopy, exploration of novel sensing techniques, and experimental sensor system construction and testing. In FY02, experimental QC laser systems developed with DARPA funding were used to explore continuous-wave (cw) CES in various forms culminating in the NICE-OHMS technique [1-3] discussed below. In FY02 PNNL also built an SWIR sensor to validate utility of the SWIR spectral region for chemical sensing, and explore the science and engineering of CES in field environments. The remainder of this report is devoted to PNNL's LWIR CES research. During FY02 PNNL explored the performance and limitations of several detection tech-niques in the LWIR including direct cavity-enhanced absorption, cavity-dithered phase-sensitive detection and resonant sideband cavity-enhanced detection. This latter tech-nique is also known as NICE-OHMS, which stands for Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectroscopy. This technique, pioneered in the near infra-red (NIR) by Dr J. Hall and coworkers at the University of Colorado, is one of the most sensitive spectroscopic techniques currently known. In this report, the first demonstra-tion of this technique in the LWIR is presented.