Clayton S.-C. Yang

Mid-Infrared Emission from Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique for detecting and identifying trace elemental contaminants by monitoring the visible atomic emission from small plasmas. However, mid-infrared (MIR), generally referring to the wavelength range between 2.5 to 25 μm, molecular vibrational and rotational emissions generated by a sample during a LIBS event has not been reported. The LIBS investigations reported in the literature largely involve spectral analysis in the ultraviolet–visible–near-infrared (UV-VIS-NIR) region (less than 1 μm) to probe elemental composition and profiles. Measurements were made to probe the MIR emission from a LIBS event between 3 and 5.75 μm. Oxidation of the sputtered carbon atoms and/or carbon-containing fragments from the sample and atmospheric oxygen produced CO2 and CO vibrational emission features from 4.2 to 4.8 μm. The LIBS MIR emission has the potential to augment the conventional UV-VIS electronic emission information with that in the MIR region.

Long-wave, infrared laser-induced breakdown (LIBS) spectroscopy emissions from energetic materials.

Laser-induced breakdown spectroscopy (LIBS) has shown great promise for applications in chemical, biological, and explosives sensing and has significant potential for real-time standoff detection and analysis. In this study, LIBS emissions were obtained in the mid-infrared (MIR) and long-wave infrared (LWIR) spectral regions for potential applications in explosive material sensing. The IR spectroscopy region revealed vibrational and rotational signatures of functional groups in molecules and fragments thereof. The silicon-based detector for conventional ultraviolet–visible LIBS operations was replaced with a mercury–cadmium–telluride detector for MIR–LWIR spectral detection. The IR spectral signature region between 4 and 12 μm was mined for the appearance of MIR and LWIR–LIBS emissions directly indicative of oxygenated breakdown products as well as dissociated, and/or recombined sample molecular fragments. Distinct LWIR–LIBS emission signatures from dissociated-recombination sample molecular fragments between 4 and 12 μm are observed for the first time.

Mid-Infrared Laser-Induced Breakdown Spectroscopy Emissions from Alkali Metal Halides

CLAYTON S.-C. YANG,* E. BROWN, UWE HOMMERICH, SUDHIR B. TRIVEDI, ALAN C. SAMUELS, and A. PETER SNYDER Battelle Eastern Science and Technology Center, Aberdeen, Maryland 21001 (C.S.-C.Y.); Department of Physics, Hampton University, Hampton, Virginia 23668 (E.B., U.H.); Brimrose Corporation of America, Baltimore, Maryland 21152 (S.B.T.); and Edgewood Chemical Biological Center, Aberdeen Proving Ground, Maryland 21010-5424 (A.C.S., A.P.S.)

Mid-Infrared, Long Wave Infrared (4–12 μm) Molecular Emission Signatures from Pharmaceuticals Using Laser-Induced Breakdown Spectroscopy (LIBS)

In an effort to augment the atomic emission spectra of conventional laser-induced breakdown spectroscopy (LIBS) and to provide an increase in selectivity, mid-wave to long-wave infrared (IR), LIBS studies were performed on several organic pharmaceuticals. Laser-induced breakdown spectroscopy signature molecular emissions of target organic compounds are observed for the first time in the IR fingerprint spectral region between 4–12 μm. The IR emission spectra of select organic pharmaceuticals closely correlate with their respective standard Fourier transform infrared spectra. Intact and/or fragment sample molecular species evidently survive the LIBS event. The combination of atomic emission signatures derived from conventional ultraviolet–visible-near-infrared LIBS with fingerprints of intact molecular entities determined from IR LIBS promises to be a powerful tool for chemical detection.

Nonlinear polarization switching near half the band gap in semiconductors

Experimental results of nonlinear polarization switching based on the phenomenon of power-dependent polarization evolution in an AlGaAs strip-loaded waveguide are reported. At 1550 nm, an input peak intensity of 28 GW/cm2 (before the waveguide) results in 30% power switching in a 2-cm-long waveguide. Numerical studies show that we can make the nonlinear switching more efficient by using the nonlinear anisotropy in a multiple-quantum-well waveguide.

Infrared laser-induced breakdown spectroscopy emissions from energetic materials

There is a current need for an active standoff system that can detect and classify surfaces that have been contaminated with chemical, biological, and explosive materials. Laser-Induced Breakdown Spectroscopy (LIBS) has shown great promise for applications in biological and chemical (CB) sensing [1] and has significant potential for real time standoff detection and analysis. However, nearly all previous LIBS experiments were limited to spectral measurements in the UV-VIS and near-infrared (NIR) regions (∼200–980 nm). It is well known, however, that molecules exhibit spectroscopic signatures or “fingerprints” in the mid-IR (MIR) to long wave IR (LWIR) regions due to vibrational and rotational transitions.

Time resolved long-wave infrared laser-induced breakdown spectroscopy of inorganic energetic materials by a rapid mercury–cadmium–telluride linear array detection system

A mercury-cadmium-telluride linear array detection system that is capable of rapidly capturing (∼1-5 s) a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the long-wave infrared region (LWIR, ∼5.6-10 μm) was recently developed. Similar to the conventional ultraviolet-visible LIBS, a broadband emission spectrum of condensed phase samples covering a 5.6-10 μm spectral region could be acquired from just a single laser-induced micro-plasma. Intense and distinct atomic and molecular LWIR emission signatures of various solid inorganic energetic materials were readily observed and identified. Time resolved emissions of inorganic energetic materials were studied to assess the lifetimes of LWIR atomic and molecular emissions. The LWIR atomic emissions generally decayed fast on the scale of tens of microseconds, while the molecular signature emissions from target molecules excited by the laser-induced plasma appeared to be very long lived (∼millisecond). The time dependence of emission intensities and peak wavelengths of these signature emissions gave an insight into the origin and the environment of the emitting target species. Moreover, observed lifetimes of these LWIR emissions can be utilized for further optimization of the signal quality and detection limits of this technique.

Concentration Dependent Studies on the Laser-Induced Mid-Infrared Emission from KCl-NaCl Tablets

The paper presents the way that colour can serve solving the problem of calibration points indexing in a camera geometrical calibration process. We propose a technique in which indexes of calibration points in a black-and-white chessboard are represented as sets of colour regions in the neighbourhood of calibration points. We provide some general rules for designing a colour calibration chessboard and provide a method of calibration image analysis. We show that this approach leads to obtaining better results than in the case of widely used methods employing information about already indexed points to compute indexes. We also report constraints concerning the technique. Nowadays we are witnessing an increasing need for camera geometrical calibration systems. They are vital for such applications as 3D modelling, 3D reconstruction, assembly control systems, etc. Wherever possible, calibration objects placed in the scene are used in a camera geometrical calibration process. This approach significantly increases accuracy of calibration results and makes the calibration data extraction process easier and universal. There are many geometrical camera calibration techniques for a known calibration scene [1]. A great number of them use as an input calibration points which are localised and indexed in the scene. In this paper we propose the technique of calibration points indexing which uses a colour chessboard. The presented technique was developed by solving problems we encountered during experiments with our earlier methods of camera calibration scene analysis [2]-[3]. In particular, the proposed technique increases the number of indexed points points in case of local lack of calibration points detection. At the beginning of the paper we present a way of designing a chessboard pattern. Then we describe a calibration point indexing method, and finally we show experimental results. A black-and-white chessboard is widely used in order to obtain sub-pixel accuracy of calibration points localisation [1]. Calibration points are defined as corners of chessboard squares. Assuming the availability of rough localisation of these points, the points can be indexed. Noting that differences in distances between neighbouring points in calibration scene images differ slightly, one of the local searching methods can be employed (e.g. [2]). Methods of this type search for a calibration point to be indexed, using a window of a certain size. The position of the window is determined by a vector representing the distance between two previously indexed points in the same row or column. However, experiments show that this approach has its disadvantages, as described below. * E-mail: A.Nowakowski@ire.pw.edu.pl Firstly, there is a danger of omitting some points during indexing in case of local lack of calibration points detection in a neighbourhood (e.g. caused by the presence of non-homogeneous light in the calibration scene). A particularly unfavourable situation is when the local lack of detection effects in the appearance of separated regions of detected calibration points. It is worth saying that such situations are likely to happen for calibration points situated near image borders. Such points are very important for the analysis of optical nonlinearities, and a lack of them can significantly influence the accuracy of distortion modelling. Secondly, such methods may give wrong results in the case of optical distortion with strong nonlinearities when getting information about the neighbouring index is not an easy task. Beside this, the methods are very sensitive to a single false localisation of a calibration point. Such a single false localisation can even result in false indexing of a big set of calibration points. To avoid the above-mentioned problems, we propose using a black-and-white chessboard which contains the coded index of a calibration point in the form of colour squares situated in the nearest neighbourhood of each point. The index of a certain calibration point is determined by colours of four nearest neighbouring squares (Fig.1). An order of squares in such foursome is important. Because the size of a colour square is determined only by the possibility of correct colour detection, the size of a colour square can be smaller than the size of a black or white square. The larger size of a black or white square is determined by the requirements of the exact localisation step which follows the indexing of calibration points [3]. In this step, edge information is extracted from a blackand-white chessboard. This edge information needs larger Artur Nowakowski, Wladyslaw Skarbek Institute of Radioelectronics, Warsaw University of Technology, Nowowiejska 15/19, 00-665 Warszawa, A.Nowakowski@ire.pw.edu.pl Received February 10, 2009; accepted March 27, 2009; published March 31, 2009 http://www.photonics.pl/PLP

Comparative studies of long-wave laser-induced breakdown spectroscopy emissions excited at 1064 µm and eye-safe 1574 µm

In this work, comparative long-wave infrared (LWIR) laser-induced breakdown spectroscopy (LIBS) emission studies of two excitation sources: conventional 1.064 μm and eye-safe laser wavelength at 1.574 μm were performed to analyze several widely-used inorganic energetic materials such as ammonium and potassium compounds as well as the organic liquid chemical warfare agent simulant, dimethyl methylphosphate (DMMP). LWIR LIBS emissions generated by both excitation sources were examined using three different detection systems: a single element liquid nitrogen cooled Mercury Cadmium Telluride (MCT) detector, an MCT linear array detection system with multi-channel preamplifiers + integrators, and an MCT linear array detection system with readout integrated circuit. It was observed that LWIR LIBS studies using an eye-safe pump laser generally reproduced atomic and molecular IR LIBS spectra as previously observed under 1.064 µm laser excitation.

Long-Wave Infrared (LWIR) Molecular Laser-Induced Breakdown Spectroscopy (LIBS) Emissions of Thin Solid Explosive Powder Films Deposited on Aluminum Substrates:

Thin solid films made of high nitro (NO2)/nitrate (NO3) content explosives were deposited on sand-blasted aluminum substrates and then studied using a mercury–cadmium–telluride (MCT) linear array detection system that is capable of rapidly capturing a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the long-wave infrared region (LWIR; ∼5.6–10 µm). Despite the similarities of their chemical compositions and structures, thin films of three commonly used explosives (RDX, HMX, and PETN) studied in this work can be rapidly identified in the ambient air by their molecular LIBS emission signatures in the LWIR region. A preliminary assessment of the detection limit for a thin film of RDX on aluminum appears to be much lower than 60 µg/cm2. This LWIR LIBS setup is capable of rapidly probing and charactering samples without the need for elaborate sample preparation and also offers the possibility of a simultaneous ultraviolet visible and LWIR LIBS measurement.