Comparative Long-Wave Infrared Laser-Induced Breakdown Spectroscopy Employing 1-D and 2-D Focal Plane Array Detectors.

Long-wave infrared (LWIR) emissions of laser-induced plasma on solid potassium chloride and acetaminophen tablet surfaces were studied using both a one-dimensional (1-D) linear array detection system and, for the first time, a two-dimensional (2-D) focal plane array (FPA) detection system. Both atomic and molecular infrared emitters in the vicinity of the plasma were identified by analyzing the detected spectral signatures in the infrared region. Time- and space-resolved long-wave infrared emissions were also studied to assess the temporal and spatial behaviors of atomic and molecular emitters in the plasma. These pioneer temporal and spatial investigations of infrared emissions from laser-induced plasma would be valuable to the modeling of plasma evolutions and the advances of the novel LWIR laser-induced breakdown spectroscopy (LIBS). When integrated both temporally (≥200 µs) and spatially using a 2-D FPA detector, the observed intensities and signal-to-noise-ratio (SNR) of single-shot LWIR LIBS signature emissions from intact molecules were considerably enhanced (e.g., with enhancement factors up to 16 and 3.76, respectively, for a 6.62 µm band of acetaminophen molecules) and, in general, comparable to those from the atomic emitters. Pairing LWIR LIBS with conventional ultraviolet-visible-near infrared (UV/Vis/NIR) LIBS, a simultaneous UV/Vis/NIR + LWIR LIBS detection system promises unprecedented capability of in situ, real-time, and stand-off investigation of both atomic and molecular target compositions to detect and characterize a range of chemistries.

Long-wave infrared laser-induced breakdown spectroscopy of complex gas molecules in the vicinity of a laser-induced plasma.

Vibration-rotation signatures of intact water and complex organic molecules in vapor phase were detected, identified, and mode-assigned in the long-wave infrared emissions of laser-induced plasma. Time resolved long-wave infrared emissions were also studied to assess the temporal behaviors of these gaseous molecular emitters. The temperatures of these molecular vapors in the hot and transient vapor-plasma plume of the laser-induced plasma were estimated to be well above room temperatures during their existence. The temperatures of the water vapors in the vapor-plasma plume were found to be evolving with time and ranging from > 2700 K at 10 µs to âˆ¼ 1500 K at 200 µs after plasma initiations using HITRAN/HAPI based molecular spectral analysis. The observations in the present study comprise (to our knowledge) the first direct evidence of hot water and intact complex organic gas molecules in the vicinity of the laser-induced plasma. The findings presented in this work serve as an important step forward in improving the understanding of the thermodynamic characteristics (such as temperatures and phases) of intact complex molecules in a hot and intricate system such as the vapor-plasma plume of a laser-induced plasma, which is essential in both fundamental studies of plasmas and of laser-induced plasma based analytical applications.

Ultrasound Signal Detection with Multi-bounce Laser Microphone.

The multi-bounce laser microphone utilizes optical methods to detect the displacement of a gold-covered thin film diaphragm caused by ultrasound signal pressure waves. This sensitive all-optical sensing technique provides new opportunities for advanced ultrasound imaging as it is expected to achieve a higher detection signal-to-noise ratio (SNR) in a broader spectrum, as compared to conventional ultrasonic transducers. The technique does not involve signal time-averaging and the real-time enhancement in detection SNR stems from the amplification of signal strength due to multiple bouncing off the diaphragm. The system was previously developed for detecting acoustic signatures generated by explosives and were limited to lower than 10 kHz in frequency. To demonstrate its feasibility for biomedical imaging applications, preliminary experiments were conducted to show high fidelity detection of ultrasound waves with frequencies ranging from 100 kHz to in excess of 1 MHz. Experimental results are also presented in this work demonstrating the improved detection sensitivity of the multi-bounce laser microphone in detecting ultrasound signals when compared with a commercial Fabry-Perot type optical hydrophone. Furthermore, we also applied the multi-bounce laser microphone to detect photoacoustic signatures emitted by India ink when a LED bar is used as the excitation source without signal averaging.

In situ chemical analysis of geology samples by a rapid simultaneous ultraviolet/visible/near-infrared (UVN) + longwave-infrared laser induced breakdown spectroscopy detection system at standoff distance.

The standoff detection range of the simultaneous ultraviolet/visible/near-infrared (UVN) + longwave-Infrared (LWIR) Laser Induced Breakdown Spectroscopy (LIBS) detection system has been successfully extended from merely 10 cm to ≥ 1 meter by adopting a reflecting telescope collection scheme and UVN + LWIR LIBS emission signatures were acquired in various atmospheres from soil and mineral samples. This system simultaneously captured emission signatures from atomic, and simple and complex molecular target species existing in or near the same laser-induce plasma plume within micro-seconds. These pioneer standoff measurements of UVN + LWIR LIBS signatures have revealed an abundance of plasma-generated sample molecular emitting species in their vapor state along with atomic ones which gave intense and distinct signature emissions in both UVN (conventional LIBS) and LWIR (LWIR LIBS) spectral regions. A HITRAN simulation estimates the temperatures of those vapor molecular species to be around 2500 K. Laser-induced plasma emissions in the LWIR region provided direct information on the molecular components of the sample substances. The demonstrable capability of the LWIR LIBS on in situ characterization of carbon- and oxygen-rich materials is expected to find important applications in water discovery and organic materials signatures detection and identification. As a result laser ablation spectroscopy will be greatly augmented in both fundamental knowledge of and capability for chemical analysis.

Comprehensive study of solid pharmaceutical tablets in visible, near infrared (NIR), and longwave infrared (LWIR) spectral regions using a rapid simultaneous ultraviolet/visible/NIR (UVN) + LWIR laser-induced breakdown spectroscopy linear arrays detection system and a fast acousto-optic tunable filter NIR spectrometer.

This is the first report of a simultaneous ultraviolet/visible/NIR and longwave infrared laser-induced breakdown spectroscopy (UVN + LWIR LIBS) measurement. In our attempt to study the feasibility of combining the newly developed rapid LWIR LIBS linear array detection system to existing rapid analytical techniques for a wide range of chemical analysis applications, two different solid pharmaceutical tablets, Tylenol arthritis pain and Bufferin, were studied using both a recently designed simultaneous UVN + LWIR LIBS detection system and a fast AOTF NIR (1200 to 2200 nm) spectrometer. Every simultaneous UVN + LWIR LIBS emission spectrum in this work was initiated by one single laser pulse-induced micro-plasma in the ambient air atmosphere. Distinct atomic and molecular LIBS emission signatures of the target compounds measured simultaneously in UVN (200 to 1100 nm) and LWIR (5.6 to 10 µm) spectral regions are readily detected and identified without the need to employ complex data processing. In depth profiling studies of these two pharmaceutical tablets without any sample preparation, one can easily monitor the transition of the dominant LWIR emission signatures from coating ingredients gradually to the pharmaceutical ingredients underneath the coating. The observed LWIR LIBS emission signatures provide complementary molecular information to the UVN LIBS signatures, thus adding robustness to identification procedures. LIBS techniques are more surface specific while NIR spectroscopy has the capability to probe more bulk materials with its greater penetration depth. Both UVN + LWIR LIBS and NIR absorption spectroscopy have shown the capabilities of acquiring useful target analyte spectral signatures in comparable short time scales. The addition of a rapid LWIR spectroscopic probe to these widely used optical analytical methods, such as NIR spectroscopy and UVN LIBS, may greatly enhance the capability and accuracy of the combined system for a comprehensive analysis.

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.

Comparative studies of long-wave laser-induced breakdown spectroscopy emissions excited at 1.064 µm and eye-safe 1.574 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.

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.

Rapid long-wave infrared laser-induced breakdown spectroscopy measurements using a mercury-cadmium-telluride linear array detection system.

In this work, we develop 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 (LWIR) region (∼5.6-10 µm). Similar to the conventional UV-Vis LIBS, a broadband emission spectrum of condensed phase samples covering the whole 5.6-10 µm region can be acquired from just a single laser-induced microplasma or averaging a few single laser-induced microplasmas. Atomic and molecular signature emission spectra of solid inorganic and organic tablets and thin liquid films deposited on a rough asphalt surface are observed. This setup is capable of rapidly probing samples "as is" without the need of elaborate sample preparation and also offers the possibility of a simultaneous UV-Vis and LWIR LIBS measurement.

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.

Standoff photoacoustic detection of explosives using quantum cascade laser and an ultrasensitive microphone.

Standoff detections of explosives using quantum cascade lasers (QCLs) and the photoacoustic (PA) technique were studied. In our experiment, a mid-infrared QCL with emission wavelength near 7.35 µm was used as a laser source. Direct standoff PA detection of trinitrotoluene (TNT) was achieved using an ultrasensitive microphone. The QCL output light was focused on explosive samples in powder form. PA signals were generated and detected directly by an ultrasensitive low-noise microphone with 1 in. diameter. A detection distance up to 8 in. was obtained using the microphone alone. With increasing detection distance, the measured PA signal not only decayed in amplitude but also presented phase delays, which clearly verified the source location. To further increase the detection distance, a parabolic sound reflector was used for effective sound collection. With the help of the sound reflector, standoff PA detection of TNT with distance of 8 ft was demonstrated.

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.

Measurement of the effective nonlinear and dispersion coefficients in optical fibers by the induced grating autocorrelation technique.

The induced grating autocorrelation technique, a technique based on temporally resolved two-beam coupling in a photorefractive crystal, was used to measure the nonlinear coefficient γ of three photonic crystal fibers (PCFs): a 30-cm long highly nonlinear PCF, and two large mode area PCFs of 4.5-m and 4.9-m lengths. The measurement used intense 2-ps, 800-nm (850-nm in one case) pulses from a Ti: sapphire laser that experienced self-phase modulation and group velocity dispersion as it travels inside the fibers. This technique was also expanded to measure γ and the dispersion coefficient ß2 simultaneously.

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 microm, 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 microm) to probe elemental composition and profiles. Measurements were made to probe the MIR emission from a LIBS event between 3 and 5.75 microm. Oxidation of the sputtered carbon atoms and/or carbon-containing fragments from the sample and atmospheric oxygen produced CO(2) and CO vibrational emission features from 4.2 to 4.8 microm. The LIBS MIR emission has the potential to augment the conventional UV-VIS electronic emission information with that in the MIR region.

Pump-induced nonlinear refractive-index change in erbium- and ytterbium-doped fibers: theory and experiment.

A 980-nm pump-induced nonlinear refractive-index (n2) change in erbium-doped (20-m) and ytterbium-doped (20-m) fibers has been measured at 1064 nm by time-delayed photorefractive beam coupling in a co-propagating and counterpropagating geometry. It was found that n2 decreases at the wavelength of the probe beam when the pump beam is present. We present a semiclassical theory based on a four-state system that accounts for the pump-induced change of n2. Both theoretical and experimental results show that a significant index change, of the order of 10%, can be obtained for cw pump powers as small as 10 mW.

New approach to the measurement of the nonlinear refractive index of short (<25 m) lengths of silica and erbium-doped fibers.

The nonlinear refractive index n2 of silica fiber (24 m) and erbium-doped fiber (10 m) is measured to within an accuracy of 5% by use of time-delayed photorefractive beam coupling of intense 53-ps, 1.064-microm pulses that experience self-phase modulation in the fibers. The resultant induced grating autocorrelation response yields a value of n2/A(eff) and a calibration standard for the fiber. A phase shift of the order of 0.19pi can be detected and is limited only by laser amplitude fluctuations. A unique advantage of this technique is its ability to measure n2 accurately in short lengths (z < or = 25 m) of fiber, whereas other approaches typically use much longer lengths of fiber (z > or = 100 m).

Cost-effective low timing jitter passively Q-switched diode-pumped solid-state laser with composite pumping pulses.

A novel scheme that combines gain switching with passive Q switching of a miniature diode-pumped solid-state laser is proposed and implemented. A composite pumping pulse, consisting of a long, low-intensity pulse and a following short, high-intensity pulse, is used to reduce the timing jitter. A greater-than-tenfold reduction in timing jitter is demonstrated.