ABSTRACT
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.
ABSTRACT
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 â¼ 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.
ABSTRACT
A refractive index of dielectrics was modified by several methods and was known to have direct influence on optical forces in nanophotonic structures. The present contribution shows that isomerization of photoswitching molecules can be used to regulate refractive index of dielectrics in-situ. In particular, spectroscopic study of a polydimethylsiloxane-arylazopyrazole (PDMS-AAP) composite revealed that refractive index of the composite shifts from 2.0 to 1.65 in trans and cis states, respectively, of the embedded AAP. Based on this, a proposition is made for a waveguide structure, in which external UV/Vis source reversibly regulates the conformation of the PDMS-AAP core. Computational study is performed using Maxwell's equations on buried waveguide structure. The simulation, implemented in PYTHON, sequentially utilizes empirical refractive indices of the composite in the isomeric states in lieu of regulation by a source. The simulation revealed highly confined wave propagations for injected signals of 340 and 450 nm wavelengths. It is observed that the cis state suppresses higher order mode when propagating UV wavelength but allows it for visible light. This modal tuning demonstrated that single mode can be selectively excited with appropriate waveguide dimensions. Further impact of the tuning is seen in the optical force between waveguide pair where the forces shift between attractive and repulsive in relation to the isomeric state of the PDMS-AAP core. These effects which stem from the adjustment of refractive index by photoisomerization suggests that in-situ regulation of index is achievable by successful integration of photoswitching molecules in host materials, and the current PDMS-AAP composites investigated in this study can potentially enhance nanophotonic and opto-mechanical platforms.
ABSTRACT
Evidence is presented that a "three-for-one" process based on two cross-relaxations between Pr3+ ions efficiently populates the mid-infrared-emitting 3H5 manifold in a Pr3+-doped low-maximum-phonon-energy host. The concentration dependence of infrared fluorescence spectra and lifetimes of polycrystalline Pr:KPb2Cl5 initially excited to the 3F3,4 manifolds indicate that the 3500-5500-nm fluorescence becomes strongly favored over shorter-wavelength infrared emission bands in the higher-concentration sample. The strong concentration dependence of the 3F3 and 3H6 manifold lifetimes suggests that both of these decay by cross-relaxation processes, resulting in more than one ion excited to 3H5 for each ion initially excited to 3F3. Indeed, modeling and accounting for all possible decay paths indicate that, on average, about 2.3 ions are excited to 3H5 for each initially-excited ion. This confirms that the three-for-one excitation process must occur and contribute significantly to the total excitation efficiency. These results indicate that the two distinct cross-relaxation processes observed between Pr ions result in substantially higher excitation quantum efficiency, 230%, than any ever reported in rare-earth doped materials.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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; â¼5.6-10 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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
A mercury-cadmium-telluride linear array detection system that is capable of rapidly capturing (â¼1-5 s) a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the long-wave infrared region (LWIR, â¼5.6-10 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 (â¼millisecond). 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.
ABSTRACT
In this work, we develop a mercury-cadmium-telluride linear array detection system that is capable of rapidly capturing (â¼1-5 s) a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the long-wave infrared (LWIR) region (â¼5.6-10 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.
Subject(s)
Cadmium Compounds , Lasers , Mercury Compounds , Spectrum Analysis/methods , Chemical Warfare Agents/chemistry , Infrared Rays , Optical Phenomena , Organic Chemicals/chemistry , Perchlorates/chemistry , Potassium/chemistry , Quaternary Ammonium Compounds/chemistry , Spectrophotometry, Atomic/methodsABSTRACT
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.
Subject(s)
Pharmaceutical Preparations/analysis , Pharmaceutical Preparations/chemistry , Spectrophotometry, Infrared/methods , Aspirin/chemistry , Equipment Design , Lasers , Models, Chemical , Organic Chemicals/analysis , Organic Chemicals/chemistry , Spectrophotometry, Infrared/instrumentationABSTRACT
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.
Subject(s)
Infrared Rays , Spectrophotometry, Atomic/methods , Lasers , Quaternary Ammonium Compounds/chemistryABSTRACT
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.
Subject(s)
Carbon Dioxide/chemistry , Carbon/chemistry , Lasers , Oxygen/chemistry , Spectrophotometry, Infrared/methods , Feasibility Studies , Reproducibility of Results , Sensitivity and SpecificityABSTRACT
In this work we present a detailed analysis of the infrared to visible upconversion in Nd(3+)-doped KPb(2)Br(5) low phonon crystal by using both steady-state and time-resolved luminescence spectroscopy. Efficient blue, green, orange, and red emissions have been observed under excitation into the (4)F(5/2) and (4)F(3/2) states. The low phonon energy of this crystal leads to a significant reduction of the multiphonon relaxation rates which allows most of the excited states to relax radiatively. To investigate the nature of the upconversion processes, emission spectroscopy and lifetime measurements for the visible fluorescence, performed by using one photon excitation, have been compared to the upconverted emissions and lifetimes obtained under infrared pulsed excitation. The analysis of the experimental results indicates that the upconverted emissions occur via energy-transfer upconversion.
