Electron Impact Excitation-Cavity Ringdown Spectroscopy

Electron impact excitation phenomena play an important role in atomic and molecular physics. The different energy levels of an atom or molecule interact differently with incoming electrons with different energies and that affects the excitation of the energy levels of the atoms and molecules. Studies involving electron impact excitation process are generally conducted with optical emission techniques or by the electron energy loss method. In the present study, for the first time, cavity ringdown spectroscopy (CRDS) has been used to investigate electron impact excitation phenomena of electronatom collision processes. The technique, i.e., electron impact excitation-cavity ringdown spectroscopy (EIE-CRDS), was employed for the purposes of fundamental study and of real-time applications. The fundamental study which was carried out in terms of determining electron impact excitation cross section (EIECS) has been demonstrated by measuring EIECS of a few excited levels of mercury (Hg) atom. For the application side, the EIE-CRDS technique has been employed for trace element detection. This dissertation first describes the fundamentals of electron impact excitationcavity ringdown spectroscopy (EIE-CRDS); afterwards its applications are demonstrated. A novel method of measuring excitation cross sections using this EIE-CRDS technique has been explained. In this method, first the excitation of atoms are achieved by electron impact excitation process, subsequently, CRDS measured absolute number density is utilized to determine the absolute EIECS values. Steps of the method are described in detail. Applicability of the method is demonstrated by measuring EIECS of three different energy levels of Hg, namely 6s6p 3P0, 6s6p 3P1, and 6s7s 3S1, and the obtained values are in agreement with those reported in the literature. Secondly, the EIE-CRDS technique was employed to investigate the absorption spectrum of mercury atom in the vicinity of 404.65 nm, corresponding to the transition 6s7s 3S1 -\u3e 6s6p 3P0 levels of mercury. Elemental mercury was measured using a laser of wavelength 404.65 nm. The technological feasibility of developing a portable size instrument for mercury detection was explored. Subsequently, a portable size, dual-mode, plasma-CRDS based prototype instrument, capable of real-time trace element monitoring, was developed. The design, functioning, and specifications of the instrument are also explained

Electron Impact Excitation-Cavity Ringdown Spectroscopy

Electron impact excitation phenomena play an important role in atomic and molecular physics. The different energy levels of an atom or molecule interact differently with incoming electrons with different energies and that affects the excitation of the energy levels of the atoms and molecules. Studies involving electron impact excitation process are generally conducted with optical emission techniques or by the electron energy loss method. In the present study, for the first time, cavity ringdown spectroscopy (CRDS) has been used to investigate electron impact excitation phenomena of electronatom collision processes. The technique, i.e., electron impact excitation-cavity ringdown spectroscopy (EIE-CRDS), was employed for the purposes of fundamental study and of real-time applications. The fundamental study which was carried out in terms of determining electron impact excitation cross section (EIECS) has been demonstrated by measuring EIECS of a few excited levels of mercury (Hg) atom. For the application side, the EIE-CRDS technique has been employed for trace element detection. This dissertation first describes the fundamentals of electron impact excitationcavity ringdown spectroscopy (EIE-CRDS); afterwards its applications are demonstrated. A novel method of measuring excitation cross sections using this EIE-CRDS technique has been explained. In this method, first the excitation of atoms are achieved by electron impact excitation process, subsequently, CRDS measured absolute number density is utilized to determine the absolute EIECS values. Steps of the method are described in detail. Applicability of the method is demonstrated by measuring EIECS of three different energy levels of Hg, namely 6s6p 3P0, 6s6p 3P1, and 6s7s 3S1, and the obtained values are in agreement with those reported in the literature. Secondly, the EIE-CRDS technique was employed to investigate the absorption spectrum of mercury atom in the vicinity of 404.65 nm, corresponding to the transition 6s7s 3S1 -\u3e 6s6p 3P0 levels of mercury. Elemental mercury was measured using a laser of wavelength 404.65 nm. The technological feasibility of developing a portable size instrument for mercury detection was explored. Subsequently, a portable size, dual-mode, plasma-CRDS based prototype instrument, capable of real-time trace element monitoring, was developed. The design, functioning, and specifications of the instrument are also explained

Laser Spectroscopy for Atmospheric and Environmental Sensing

Lasers and laser spectroscopic techniques have been extensively used in several applications since their advent, and the subject has been reviewed extensively in the last several decades. This review is focused on three areas of laser spectroscopic applications in atmospheric and environmental sensing; namely laser-induced fluorescence (LIF), cavity ring-down spectroscopy (CRDS), and photoluminescence (PL) techniques used in the detection of solids, liquids, aerosols, trace gases, and volatile organic compounds (VOCs)

Sensor for monitoring plasma parameters

A spectrally tunable VCSEL (vertical cavity surface-emitting laser) was used as part of sensing hardware for measurements of the radial-integrated gas temperature inside an inductively coupled plasma reactor. The data were obtained by profiling the Doppler-broadened absorption of metastable Ar atoms at 763.51 nm in argon and argon/nitrogen plasmas (3, 45, and 90% N2 in Ar) at pressure 0.5-70 Pa and inductive power of 100 and 300 W. The results were compared to rotational temperature derived from the N2 emission at the (0,0) transition of the C - B system. The differences in integrated rotational and Doppler temperatures were attributed to non-uniform spatial distributions of both temperature and thermometric species (Ar* and N2*) that varied depending on conditions. A two-dimensional, two-temperature fluid plasma simulation was employed to explain these differences. This work should facilitate further development of a miniature sensor for non-intrusive acquisition of data (temperature and densities of multiple plasma species) during micro- and nano-fabrication plasma processing, thus enabling the diagnostic-assisted continuous optimization and advanced control over the processes. Such sensors would also enable tracking the origins and pathways of damaging contaminants, thereby providing real-time feedback for adjustment of processes. Our work serves as an example of how two line-of-sight integrated temperatures derived from different thermometric species make it possible to characterize the radial non-uniformity of the plasma.Comment: Presented at the Photonics West conference, Lasers and Applications in Science and Technology, San Jose, CA, January 2004. This version gives a more detailed introduction on diode lasers as diagnostic tool for micro/nano-fabrication. A follow-up paper published in Plasma Sources Sci. Technol., v.13, 691-700 (2004) featured improvements in plasma simulatio

Laser Induced Incandescence and Laser Induced Breakdown Spectroscopy based Sensor Development

In this doctoral dissertation, two laser-based sensors were evaluated for different applications. Laser Induced Incandescence (LII) is a technique which can provide nonintrusive quantitative measurement of soot and it provides a unique diagnostic tool to characterize engine performance. Since LII is linearly proportional to the soot volume fraction, it can provide in situ, real time measurement of soot volume fraction with high temporal and spatial resolution. LII has the capability to characterize soot formation during combustion. The soot volume fraction from both flames and a soot generator was investigated with LII. The effects of experimental parameters, such as laser fluence, gate delay, gate width and various laser beam focusing, on LII signal was studied. Laser Induced Breakdown Spectroscopy (LIBS), a diagnostic tool for in situ elemental analysis, has been evaluated for on-line, simultaneous, multi-species impurity monitoring in hydrogen. LIBS spectra with different impurity levels of nitrogen, argon, and oxygen were recorded and the intensity of the spectral lines of Ar, O, N, and H observed were used to form calibration plots for impurities in hydrogen measurements. An ungated detection method for LIBS has been developed and applied to equivalence ratio measurements of CH4/air and biofuel/air. LIBS has also been used to quantitatively analyze the composition of a slurry sample. The quenching effect of water in slurry samples causes low LIBS signal quality with poor sensitivity. Univariate and multivariate calibration was performed on LIBS spectra of dried slurry samples for elemental analysis of Mg, Si and Fe. Calibration results show that the dried slurry samples give good correlation between spectral intensity and elemental concentration

Measurement of Trace Environmental Contaminants Using Cavity Ringdown Spectroscopy

Environmental contamination has become a significant threat to the health and well-being of mankind as well as to the environment, prompting the establishment and implementation of stringent environmental regulations. The ability to accurately detect and quantify contaminants, such as mercury (Hg), uranium (U), and volatile organic compounds (VOCs), in real-time, in situ is of significant importance to monitoring and remediation efforts. In an effort to develop a real-time, fast-response detector that is portable, highly sensitive, and cost efficient, this research explored the feasibility of utilizing cavity ringdown spectroscopy (CRDS) in conjunction with various plasma sources and vacuum cavities to accurately detect trace quantities of contaminants. The feasibility of detecting Hg with a low power, low temperature candle-shaped microwave-induced plasma (MIP) and a copper surfatron microwave cavity with various plasma discharge tube configurations in conjunction with cavity ringdown spectroscopy (MIP-CRDS) is discussed. Detection limits were on the order of 221 ppt Hg in the vapor phase for the candle-shaped MIP and improved by a factor of 10 with the tube-shaped plasma. The ability to detect elemental Hg naturally-evaporating from contaminated soils and solutions was evaluated, and 10’s of ppt were consistently obtained. Additionally, the fine structure of the Hg 253.65 nm transition was observed with each iteration of this approach. The potential of effectively generating uranium atoms and ions with a low-power, lowlow rate microwave-induced plasma was evaluated. Uranium emission spectra covering 320 – 430 nm were obtained, labeled, and compared to the available literature values. Calibration curves were generated, and the detection limits were determined to be ~0.4 ppm. The feasibility of measuring U incorporating diode laser-plasma-CRDS was explored. The preliminary studies clearly show the ability to detect U vapor with this technique and sub-ppm detection limits were obtained. A continuous wave cavity ringdown spectroscopy system (CW-CRDS) incorporating commercially available telecommunications diode lasers was constructed, and the overall sensitivity of this system was evaluated by utilizing the absorption of the asymmetric C-H stretch overtones of several VOCs, including benzene, chlorobenzene, 1,2-dichlorobenzene, toluene, and acetone. Detection limits are determined to be in the ppb’s for each of the organics examined