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

Ultra-Trace Chemical Sensing with Long-Wave Infrared Cavity-Enhanced Spectroscopic Sensors
Author:
Publisher:
Total Pages:
Release: 2003
Genre:
ISBN:

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.

Cavity-Enhanced Spectroscopy and Sensing

Cavity-Enhanced Spectroscopy and Sensing
Author: Gianluca Gagliardi
Publisher: Springer
Total Pages: 537
Release: 2013-10-19
Genre: Science
ISBN: 3642400035

The book reviews the dramatic recent advances in the use of optical resonators for high sensitivity and high resolution molecular spectroscopy as well as for chemical, mechanical and physical sensing. It encompasses a variety of cavities including those made of two or more mirrors, optical fiber loops, fiber gratings and spherical cavities. The book focuses on novel techniques and their applications. Each chapter is written by an expert and/or pioneer in the field. These experts also provide the theoretical background in optics and molecular physics where needed. Examples of recent breakthroughs include the use of frequency combs (Nobel prize 2005) for cavity enhanced sensing and spectroscopy, the use of novel cavity materials and geometries, the development of optical heterodyne detection techniques combined to active frequency-locking schemes. These methods allow the use and interrogation of optical resonators with a variety of coherent light sources for trace gas detection and sensing of strain, temperature and pressure.

Long Wave Infrared Cavity Enhanced Sensors

Long Wave Infrared Cavity Enhanced Sensors
Author:
Publisher:
Total Pages:
Release: 2004
Genre:
ISBN:

The principal goal of Pacific Northwest National Laboratory's (PNNL's) long wave infrared (LWIR) cavity enhanced sensor (CES) project is to explore ultra-sensitive spectroscopic techniques and apply them to the development of LWIR chemical sensors needed for detecting weapons proliferation. This includes detecting not only the weapons of mass destruction (WMDs) themselves, but also signatures of their production and/or detonation. The LWIR CES project is concerned exclusively with developing point sensors; other portions of PNNL's IR Sensors program address stand off detection. PNNL's LWIR CES research is distinguished from that done by others by the use quantum cascade lasers (QCLs) as the light source. QCLs are novel devices, and a significant fraction of our research has been devoted to developing the procedures and hardware required to implement them most effectively for chemical sensing. This report details the progress we have made on our LWIR CES sensor development. During FY02, PNNL investigated three LWIR CES implementations beginning with the easiest to implement, direct cavity-enhanced detection (simple CES), including a technique of intermediate difficulty, cavity-dithered phase-sensitive detection (FM recovery CES) through to the most complex technique, that of resonant sideband cavity-enhanced detection also known as noise-immune cavity-enhanced optical heterodyne molecular spectroscopy, or NICE-OHMS.

Cavity Ring-Down Spectroscopy

Cavity Ring-Down Spectroscopy
Author: Giel Berden
Publisher: John Wiley & Sons
Total Pages: 344
Release: 2009-08-11
Genre: Science
ISBN: 9781444308242

Cavity Ring-Down Spectroscopy: Techniques and Applications provides a practical overview of this valuable analytical tool, explaining the fundamental concepts and experimental methods, and illustrating important applications. Designed as both an introductory text and a reference source, this book is relevant for scientists unfamiliar with CRDS who are interested in using the technique in their research, as well as experienced users.

New Enhanced Sensitivity Infrared Laser Spectroscopy Techniques Applied to Reactive Plasmas and Trace Gas Detection

New Enhanced Sensitivity Infrared Laser Spectroscopy Techniques Applied to Reactive Plasmas and Trace Gas Detection
Author: Stefan Welzel
Publisher: Logos Verlag Berlin GmbH
Total Pages: 198
Release: 2009
Genre: Science
ISBN: 3832523456

Infrared laser absorption spectroscopy (IRLAS) employing both tuneable diode and quantum cascade lasers (TDLs, QCLs) has been applied with both high sensitivity and high time resolution to plasma diagnostics and trace gas measurements. TDLAS combined with a conventional White type multiple pass cell was used to detect up to 13 constituent molecular species in low pressure Ar/H2/N2/O2 and Ar/CH4/N2/O2 microwave discharges, among them the main products such as H2O, NH3, NO and CO, HCN respectively. The hydroxyl radical has been measured in the mid infrared (MIR) spectral range in-situ in both plasmas yielding number densities of between 1011 ... 1012 cm-3. Strong indications of surface dominated formation of either NH3 or N2O and NO were found in the H2-N2-O2 system. In methane containing plasmas a transition between deposition and etching conditions and generally an incomplete oxidation of the precursor were observed. The application of QCLs for IRLAS under low pressure conditions employing the most common tuning approaches has been investigated in detail. A new method of analysing absorption features quantitatively when the rapid passage effect is present is proposed. If power saturation is negligible, integrating the undisturbed half of the line profile yields accurate number densities without calibrating the system. By means of a time resolved analysis of individual chirped QCL pulses the main reasons for increased effective laser line widths could be identified. Apart from the well-known frequency down chirp non-linear absorption phenomena and bandwidth limitations of the detection system may significantly degrade the performance and accuracy of inter pulse spectrometers. The minimum analogue bandwidth of the entire system should normally not fall below 250 MHz. QCLAS using pulsed lasers has been used for highly time resolved measurements in reactive plasmas for the first time enabling a time resolution down to about 100 ns to be achieved. A temperature increase of typically less than 50 K has been established for pulsed DC discharges containing Ar/N2 and traces of NO. The main NO production and depletion reactions have been identified from a comparison of model calculations and time resolved measurements in plasma pulses of up to 100 ms. Considerable NO struction is observed after 5 ... 10 ms due to the impact of N atoms. Finally, thermoelectrically cooled pulsed and continuous wave (cw) QCLs have been employed for high finesse cavity absorption spectroscopy in the MIR. Cavity ring down spectroscopy (CRDS) has been performed with pulsed QCLs and was found to be limited by the intrinsic frequency chirp of the laser suppressing an efficient intensity build-up inside the cavity. Consequently the accuracy and advantage of an absolute internal absorption calibration is not achievable. A room temperature cw QCL was used in a complementary cavity enhanced absorption spectroscopy (CEAS) configuration which was equipped with different cavities of up to 1.3 m length. This spectrometer yielded path lengths of up to 4 km and a noise equivalent absorption down to 4 x 10-8 cm-1Hz-1/2. The corresponding molecular concentration detection limit (e.g. for CH4, N2O and C2H2 at 1303 cm-1/7.66 Aem) was generally below 1 x 1010 cm-3 for 1 s integration times and one order of magnitude less for 30 s integration times. The main limiting factor for achieving even higher sensitivity is the residual mode noise of the cavity. Employing a 0.5 m long cavity the achieved sensitivity was good enough for the selective measurement of trace atmospheric constituents at 2.2 mbar.

Laser Spectroscopy for Sensing

Laser Spectroscopy for Sensing
Author: Matthieu Baudelet
Publisher: Elsevier
Total Pages: 601
Release: 2014-02-15
Genre: Technology & Engineering
ISBN: 085709873X

Laser spectroscopy is a valuable tool for sensing and chemical analysis. Developments in lasers, detectors and mathematical analytical tools have led to improvements in the sensitivity and selectivity of spectroscopic techniques and extended their fields of application. Laser Spectroscopy for Sensing examines these advances and how laser spectroscopy can be used in a diverse range of industrial, medical, and environmental applications. Part one reviews basic concepts of atomic and molecular processes and presents the fundamentals of laser technology for controlling the spectral and temporal aspects of laser excitation. In addition, it explains the selectivity, sensitivity, and stability of the measurements, the construction of databases, and the automation of data analysis by machine learning. Part two explores laser spectroscopy techniques, including cavity-based absorption spectroscopy and the use of photo-acoustic spectroscopy to acquire absorption spectra of gases and condensed media. These chapters discuss imaging methods using laser-induced fluorescence and phosphorescence spectroscopies before focusing on light detection and ranging, photothermal spectroscopy and terahertz spectroscopy. Part three covers a variety of applications of these techniques, particularly the detection of chemical, biological, and explosive threats, as well as their use in medicine and forensic science. Finally, the book examines spectroscopic analysis of industrial materials and their applications in nuclear research and industry. The text provides readers with a broad overview of the techniques and applications of laser spectroscopy for sensing. It is of great interest to laser scientists and engineers, as well as professionals using lasers for medical applications, environmental applications, military applications, and material processing. Presents the fundamentals of laser technology for controlling the spectral and temporal aspects of laser excitation Explores laser spectroscopy techniques, including cavity-based absorption spectroscopy and the use of photo-acoustic spectroscopy to acquire absorption spectra of gases and condensed media Considers spectroscopic analysis of industrial materials and their applications in nuclear research and industry

Modern Techniques of Spectroscopy

Modern Techniques of Spectroscopy
Author: Dheeraj Kumar Singh
Publisher: Springer Nature
Total Pages: 663
Release: 2021-04-01
Genre: Technology & Engineering
ISBN: 9813360844

The book highlights recent developments in the field of spectroscopy by providing the readers with an updated and high-level of overview. The focus of this book is on the introduction to concepts of modern spectroscopic techniques, recent technological innovations in this field, and current examples of applications to molecules and materials relevant for academia and industry. The book will be beneficial to researchers from various branches of science and technology, and is intended to point them to modern techniques, which might be useful for their specific problems. Spectroscopic techniques, that are discussed include, UV-Visible absorption spectroscopy, XPS, Raman spectroscopy, SERS, TERS, CARS, IR absorption spectroscopy, SFG, LIBS, Quantum cascade laser (QCL) spectroscopy, fluorescence spectroscopy, ellipsometry, cavity-enhanced absorption spectroscopy, such as cavity ring-down spectroscopy (CRDS) and evanescent wave-CRDS both in gas and condensed phases, time-resolved spectroscopy etc. Applications introduced in the different chapters demonstrates the usefulness of the spectroscopic techniques for the characterization of fundamental properties of molecules, e.g. in connection with environmental impact, bio-activity, or usefulness for pharmaceutical drugs, and materials important e.g. for nano-science, nuclear chemistry, or bio-applications. The book presents how spectroscopic techniques can help to better understand substances, which have also great impact on questions of social and economic relevance (environment, alternative energy, etc.).

Cavity-enhanced Spectroscopies for Applications of Remote Sensing, Chemical Kinetics and Detection of Radical Species

Cavity-enhanced Spectroscopies for Applications of Remote Sensing, Chemical Kinetics and Detection of Radical Species
Author: Thinh Quoc Bui
Publisher:
Total Pages: 390
Release: 2015
Genre: Electronic dissertations
ISBN:

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O2 and CO2 for obtaining laboratory reference data in support of NASA's OCO-2 mission. FS-CRDS is highly sensitive (>10 km absorption path length) and precise (>10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and 13C/12C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(1D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.