Ei Brown

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, 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.

Spectroscopic characterization and upconversion processes under ~1.5 μm pumping in Er doped Yttria ceramics

We report on the spectroscopic characteristics and upconversion emission in Er3+ doped Yttria (Y2O3) transparent ceramics prepared by a modified two-step sintering method. The near-infrared (1.5 μm) emission properties were evaluated as a function of Er3+ concentration. Judd-Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were calculated and compared with results reported for Er3+ doped Y2O3 single crystal and nanocrystals. Following pumping at 1.532 μm, weak blue (~0.41 μm, 2H9/2→4I15/2), strong green (~0.56 μm, 2H11/2, 4S3/2→4I15/2) and red (~0.67 μm, 4F9/2→4I15/2) emission bands were observed as well as weak near-infrared emissions at 0.8 μm (4I9/2→4I15/2) and 0.85 μm (4S3/2→4I13/2) at room temperature. The upconversion emission properties under ~1.5 μm pumping were further investigated through pump power dependence and decay time studies. Sequential two-photon absorption leads to the 4I9/2 upconversion emission while energy transfer upconversion is responsible for the emission from the higher excited states 2H9/2, 2H11/2, 4S3/2, and 4F9/2. The enhanced red emission with increasing Er3+ concentration most likely occurred via the cross-relaxation process between (4F7/2 → 4F9/2) and (4I11/2 → 4F9/2) transitions, which increased the population of the 4F9/2 level.

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.

Eye-safe infrared laser-induced breakdown spectroscopy (LIBS) emissions from energetic materials

Laser-induced breakdown spectroscopy is a powerful diagnostic tool for detection of trace elements by monitoring the atomic and ionic emission from laser-induced plasmas. Besides elemental emissions from conventional UV-Vis LIBS, molecular LIBS emission signatures of the target compounds were observed in the long-wave infrared (LWIR) region in recent studies. Most current LIBS studies employ the fundamental Nd:YAG laser output at 1.064 μm, which has extremely low eye-damage threshold. In this work, comparative LWIR-LIBS emissions studies using traditional 1.064 μm pumping and eye-safe laser wavelength at 1.574 μm were performed on several energetic materials for applications in chemical, biological, and explosive (CBE) sensing. A Q-switched Nd: YAG laser operating at 1.064 μm and the 1.574 μm output of a pulsed Nd:YAG pumped Optical Parametric Oscillator were employed as the excitation sources. The investigated energetic materials were studied for the appearance of LWIR-LIBS emissions (4-12 μm) that are directly indicative of oxygenated breakdown products as well as partially dissociated and recombination molecular species. The observed molecular IR LIBS emission bands showed strong correlation with FTIR absorption spectra of the studied materials for 1.064 μm and 1.574 μm pump wavelengths.

Infrared absorption and fluorescence properties of Ho-doped KPb2Br5

Spectroscopic properties of the 2 μm infrared (IR) emission (5I7 → 5I8) from trivalent holmium (Ho3+) doped potassium lead bromide (KPb2Br5) are presented. The investigated Ho3+ doped KPb2Br5 (KPB) material was synthesized through purification of starting materials including multi-pass zone-refinement, bromination, and subsequently grown using horizontal Bridgman technique. The bromination process was critical for removing oxidic impurities and enhancing the quality of the crystal. Judd-Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were calculated and compared with results reported for Ho3+ doped KPb2Cl5 (KPC). Under resonant pumping (~1.907 μm), Ho: KPB showed a broad IR emission centered at ~2 μm with an exponential decay time of 7.1 ms at room temperature. The nearly temperature independent emission lifetime is consistent with a negligibly small non-radiative decay rate for the 5I7 excited state of Ho3+, as predicted by the multiphonon energy gap law. The optical absorption, emission and gain cross-sections of Ho: KPB were determined for the 2 μm transition. The Ho: KPB crystal was also evaluated as a potential solid-state material for laser cooling applications.

Mid infrared emission spectroscopy of carbon plasma

Mid infrared time-resolved emission spectra were recorded from laser-induced carbon plasma. These spectra constitute the first study of carbon materials LIB spectroscopy in the mid infrared range. The carbon plasma was induced using a Q-switched Nd: YAG laser. The laser beam was focused to high purity graphite pellets mounted on a translation stage. Mid infrared emission from the plasma in an atmospheric pressure background gas was detected by a cooled HgCdTe detector in the range 4.4-11.6μm, using long-pass filters. LIB spectra were taken in argon, helium and also in air. Despite a gate delay of 10μs was used there were strong backgrounds in the spectra. Superimposed on this background broad and noisy emission bands were observed, the form and position of which depended somewhat on the ambient gas. The spectra were digitally smoothed and background corrected. In argon, for instance, strong bands were observed around 4.8, 6.0 and 7.5μm. Using atomic spectral data by NIST it could be concluded that carbon, argon, helium and nitrogen lines from neutral and ionized atoms are very weak in this spectral region. The width of the infrared bands supports molecular origin. The infrared emission bands were thus compared to vibrational features of carbon molecules (excluding C2) of various sizes on the basis of previous carbon cluster infrared absorption and emission spectroscopic analyses in the literature and quantum chemical calculations. Some general considerations are given about the present results.

Optical spectroscopy of rare-earth doped ternary lead based halides

Spectroscopic properties of Pr3+ and Er3+ -doped KPb2Br5 crystals were investigated for possible applications in eye-safe lasers as well as Ce3+-doped KPb2Cl5 and Eu2+-doped KPb2Cl5/KPb2Br5 for potential radiation detectors. The studied materials were synthesized through careful purification of starting materials including multi-pass zone-refinement and halogenation. The growth of the purified materials was then carried out through the vertical or horizontal Bridgman technique. Under resonant excitation, infrared (IR) emissions at ~1.5 μm and ~1.6 μm were observed from Er:KPb2Br5 and Pr:KPb2Br5 corresponding to the 4f-4f transitions of 4I13/2→4I15/2 and 3F4,3F3→3H4, respectively. Emission characteristics of the ~1.5 μm Er3+ and ~1.6 μm Pr3+ transitions including IR to visible upconversion emission studies were also discussed. Under xenon lamp excitation, spectroscopic results showed allowed 5d-4f Ce3+ emission centered at ~375 nm in Ce3+-doped KPb2Cl5. Fast photoluminescence decay time of ~30-50 ns was attained from Ce:KPb2Cl5, while X-ray excited emission at ~530 nm appeared to originate from the host KPb2Cl5 crystal. In addition, a commercial Ce:YAP (yttrium aluminum perovskite, YAlO3) crystal was included in this study for comparison. Eu2+ 5d-4f emissions were not observed from Eu2+-doped KPb2Cl5 and KPb2Br5 crystals.