Two-photon Absorption Laser-induced Fluorescence Measurements Research Articles

Spatially resolved TALIF investigation of atomic oxygen in the effluent of a CO2 microwave discharge

A diagnostic setup for one-dimensionally spatially resolved two-photon absorption laser-induced fluorescence (TALIF) detection of ground state oxygen atoms ( 2p43P2,1,0 ) is developed. The goal of this study is to investigate the evolution of temperatures and absolute number densities of oxygen atoms along the effluent of a low-pressure CO2 microwave discharge in order to gain insights into some of the mechanisms governing the post-discharge regime. The plasma source is operated at conditions of 600 W– 1200 W of absorbed power with flow rates of 74 sccm and 370 sccm pure CO2 at pressures between 1.2 mbar and 5 mbar with specific energy inputs up to 111.9 eV/molecule. These operating conditions exhibit high CO2 conversions (up to 90%) at low energy efficiencies (2%–7.4%), due to direct electron impact dissociation driving the conversion process resulting in splitting of CO2 into CO and metastable oxygen atoms. The TALIF measurements yield spatially resolved translational temperatures between 1000 K– 1600 K for most operating conditions and axial positions along the effluent. Reference measurements with xenon 6p′[3/2]2 are used for absolute number density calibration. The resulting axially resolved number density profiles of ground state atomic oxygen increase along the effluent, even at considerable distances of several centimeters from the active discharge, before they reach a maximum between 5×1020 m−3 and 2.2×1021 m−3 depending on the condition, and decrease after that. This behavior indicates the potential significance of quenching of metastable oxygen atoms within the post-discharge regime of the investigated CO2 discharges. The measured spatially resolved number density evolutions are qualitatively consistent with quenching via wall collisions being the dominant deactivation mechanism, underlining the importance of particle-wall interactions.

Absolute atomic nitrogen density spatial mapping in three MHCD configurations

In this work, nanosecond two-photon absorption laser induced fluorescence (TALIF) is used to perform spatial mappings of the absolute density of nitrogen atoms generated in a micro-hollow cathode discharge (MHCD). The MHCD is operated in the normal regime, with a DC discharge current of 1.6 mA and the plasma is ignited in a 20% Ar/ 80% N2 gas mixture. A 1-inch diameter aluminum substrate, acting as a third electrode (second anode), is placed further away from the MHCD to emulate a deposition substrate. The spatial profile of the N atoms is measured in three MHCD configurations. First, we study a MHCD having the same pressure (50 mbar) on both sides of the anode/cathode electrodes and the N atoms simply diffuse in three dimensions from the MHCD. The recorded N atoms density profile in this case satisfies our expectations, i.e. the maximal density is found at the axis of the hole, close to the MHCD. However, when we introduce a pressure differential, thus creating a plasma jet, an unexpected N atoms distribution is measured with maximum densities away from the jet axis. This behavior cannot be simply explained by the TALIF measurements. Then, as a first simplified approach in this work, we turn our attention to the role of the gas flow pattern. Compressible gas flow simulations show a correlation between the jet width and the radial distribution of the N atoms at different axial distances from the gap. Finally, a DC positive voltage is applied to the third electrode (second anode), which ignites a micro cathode sustained discharge (MCSD). The presence of the pressure differential unveils two stable working regimes depending on the current repartition between the two anodes. The MCSD enables an homogenization of the density profile along the surface of the substrate, which is suitable for nitride deposition applications.

Two-photon absorption laser induced fluorescence measurements of absolute neutral deuterium density, temperature, and bulk flow in Proto-MPEX

Neutral particle control is critical for fusion fueling and confinement. Neutral diagnostics for fusion-relevant plasmas are commonly restricted to line-integrated or ex situ methods. A non-perturbative, two-photon absorption laser induced fluorescence (TALIF) diagnostic is implemented on the Prototype Material Plasma Exposure eXperiment (Proto-MPEX) to probe neutral atomic deuterium in a fusion-relevant plasma at 1 cm intervals along the radius of the vacuum vessel. The diagnostic is situated ∼20 m from the vacuum vessel, and a signal is collected along the laser injection axis, requiring only one line-of-sight. TALIF measurements are absolutely calibrated using xenon and krypton. Absolute atomic densities derived from xenon calibration are compared to absolute atomic densities derived from krypton calibration. Here, preliminary measurements of absolute atomic deuterium density, temperature, and local bulk flow dependence on radial location and input power in Proto-MPEX are presented. Neutral atomic deuterium velocity distribution functions are measured throughout a one-second plasma pulse with a time resolution of 250 ms.

Measurement of the two-photon excitation cross-section of the 6p′[3/2]2 and 6p′[1/2]0 levels of Xe I at the wavelengths 224.3 and 222.6 nm

The two-photon excitation cross-section is a key parameter for the two-photon absorption laser induced fluorescence (TALIF) method, which is commonly used to measure atomic densities in gaseous media, especially for plasma diagnostics. The method consists in recording the fluorescence signal that follows the resonant absorption of two photons of UV light. Calibration often relies on comparing the signal recorded in the studied sample with the fluorescence produced, at a similar wavelength, in a noble gas vapor, the density of which can be easily known. The ratio of the involved cross-sections however plays an essential role for the accuracy of such measurements. Yet the two-photon excitation cross-section of atomic xenon, which is often used as the reference for oxygen density measurements, was measured only once, at the wavelengths of interest. The aim of the present study has been to consolidate the experimental value of that key parameter. The cross-section is found equal to and for the 6p′[3/2]2 and 6p′[1/2]0 levels, respectively. For the 6p′[3/2]2 level this is more than twice smaller than previously admitted. Even though the necessarily large relative uncertainty of a non-linear cross-section attaches a relatively large uncertainty to this factor of one half, the result suggests that atomic densities already measured by Xe-calibrated TALIF may have to be revised to significantly lower values. The experiments performed also provide an opportunity to revisit the validity of the approximations used for quantitative TALIF measurements and the collisional broadening and pressure shift of the two-photon 6p′[1/2]0 line. A new formula has been used to describe the two-photon absorption of a Gaussian beam in a long gas cell, which makes the decrease of the beam intensity a simple analytic expression even in strong absorption regime, based on a polylogarithmic function of the absorption rate variable.

TALIF measurements of hydrogen and deuterium surface loss probabilities on quartz in low pressure high density plasmas

This article deals with surface loss on quartz of atomic hydrogen (H) and its isotope deuterium (D) in a low-pressure (10 Pa) pulsed inductively coupled plasma. The atomic temporal decay in the post discharge is measured by two-photon absorption laser-induced fluorescence (TALIF). From the loss rate, the atomic surface loss probability is determined. In pure hydrogen or pure deuterium gas, no isotopic effect on surface kinetics has been observed and the surface loss probabilities of H and D were found to be almost identical and equal to ∼1.8%. However, despite the lack of difference in surface loss probability, a net isotopic effect on surface loss rate due to the mass difference between the isotopes is measured. Hydrogen atoms diffuse faster and have higher flux to the plasma chamber walls than deuterium atoms. Hydrogen atoms are therefore lost at higher rate than deuterium atoms. Based on the observed isotopic difference and on the comparison between H and D TALIF signals, the isotopic effects on H and D atom production are discussed.

Radar resonance-enhanced multiphoton ionization for measurement of atomic oxygen in non-equilibrium pulsed plasmas

In this work, coherent microwave Rayleigh scattering for the detection of resonance-enhanced multiphoton ionization (Radar REMPI) was used for the measurement of atomic oxygen in a nonequilibrium pulsed plasma discharge. Specifically, the detection of atomic oxygen is demonstrated in a pulsed discharge at 100 Torr in a molecular oxygen and helium gas mixture. REMPI was conducted using Nd:YAG pumped dye radiation at 618.9 nm mixed with the Nd:YAG 355 nm radiation, generating 225.6 nm laser light, of which two photons match the energy of the 2P33p(3P) electronically excited intermediate state of atomic oxygen. A third photon from the laser source then readily ionizes the atom in the 2 + 1 photon REMPI scheme. The Radar REMPI results are compared to two-photon absorption laser-induced fluorescence measurements from the literature, which shows reasonable agreement.

Two-Photon Laser-Induced Fluorescence Measurements of Atomic Oxygen Density in Hypersonic Plasma Flow

An experimental investigation of high-enthalpy air flow generated by L2K arc-jet facility of DLR is carried out by means of two-photon absorption laser-induced fluorescence (TALIF) measurements of atomic oxygen at transition. The experiment has been conducted with an arc current of 600 A, a mass flow rate of , and a total pressure of , resulting in both mass-specific enthalpy of and a reservoir temperature of 4200 K. Atomic oxygen has been characterized in terms of translational temperature and absolute number density either in the freestream or behind a shock wave upstream a blunt body. A calibration method based on TALIF measurements of xenon at transition has been used. The results highlight that in the freestream the fluorescence signal exhibits a peak activity lower with respect to that inspected in the shock layer. The measured lifetimes of and indicate that, in the shock layer, the depletion of the atomic oxygen excited state occurs mainly via quenching. The analysis of the line broadening of the spectral profile of atomic oxygen reveals an increment of the translational temperature in the shock layer with respect to that measured in the freestream, resulting in and , respectively. It is found that in the freestream the absolute number density attains and the presence of the shock wave induces an increment of the number density of , that is, 4.85 times higher than that detected in the freestream.

Plasma-assisted CO2 conversion: optimizing performance via microwave power modulation

Significant improvement in the energy efficiency of plasma-assisted CO2 conversion is achieved with applied power modulation in a surfaguide microwave discharge. The obtained values of CO2 conversion and energy efficiency are, respectively, 0.23 and 0.33 for a 0.95 CO2 + 0.05 N2 gas mixture. Analysis of the energy relaxation mechanisms shows that power modulation can potentially affect the vibrational–translational energy exchange in plasma. In our case, however, this mechanism does not play a major role, likely due to the low degree of plasma non-equilibrium in the considered pressure range. Instead, the gas residence time in the discharge active zone together with plasma pulse duration are found to be the main factors affecting the CO2 conversion efficiency at low plasma pulse repetition rates. This effect is confirmed experimentally by the in situ time-resolved two-photon absorption laser-induced fluorescence measurements of CO molecular density produced in the discharge as a result of CO2 decomposition.

Fluorescence measurement of atomic oxygen concentration in a dielectric barrier discharge

Concentration of atomic oxygen was measured in a volume dielectric barrier discharge (DBD) ignited in mixtures of Ar + O2(+ H2) at atmospheric pressure. Two-photon absorption laser induced fluorescence (TALIF) of atomic oxygen was used and this method was calibrated by TALIF of Xe in a mixture of argon and a trace of xenon. The calibration was performed at atmospheric pressure and it was shown that quenching by three-body collisions has negligible effect on the life time of excited Xe atoms. The concentration of atomic oxygen in the DBD was around 1021 m−3 and it was stable during the whole discharge period. The concentration did not depend much on the electric power delivered to the discharge provided that the power was sufficiently high so that the visible discharge filled the whole reactor volume. Both the addition of hydrogen or replacing of argon by helium led to a significant decrease of atomic oxygen concentration. The TALIF measurements of O concentration levels in the DBD plasma performed in this work are made use of e.g. in the field analytical chemistry. The results contribute to understanding the processes of analyte hydride preconcentration and subsequent atomization in the field of trace element analysis where DBD plasma atomizers are employed.

Pressure broadening of atomic oxygen two-photon absorption laser induced fluorescence

Atomic oxygen, considered to be a determining reactant in plasma applications at ambient pressure, is routinely detected by two-photon absorption laser induced fluorescence (TALIF). Here, pressure broadening of the (2p4 3P2 → 3p 3PJ=0,1,2) two-photon transition in oxygen atoms was investigated using a high-resolution TALIF technique in normal and Doppler-free configurations. The pressure broadening coefficients determined were = 0.40 ± 0.08 cm−1/bar for oxygen molecules and = 0.46 ± 0.03 cm−1/bar for helium atoms. These correspond to pressure broadening rate constants = 9 · 10–9 cm3 s−1 and = 4 · 10−9 cm3 s−1, respectively. The well-known quenching rate constants of O(3p 3PJ) by O2 and He are at least one order of magnitude smaller, which signifies that non-quenching collisions constitute the main line-broadening mechanism. In addition to providing new insights into collisional processes of oxygen atoms in electronically excited 3p 3PJ state, reported pressure broadening parameters are important for quantification of oxygen TALIF line profiles when both collisional and Doppler broadening mechanisms are important. Thus, the Doppler component (and hence the temperature of oxygen atoms) can be accurately determined from high resolution TALIF measurements in a broad range of conditions.

Novel xenon calibration scheme for two-photon absorption laser induced fluorescence of hydrogen.

Two photon absorption laser induced fluorescence (TALIF) measurements of neutral hydrogen and its isotopes are typically calibrated by performing TALIF measurements on krypton with the same diagnostic system and using the known ratio of the absorption cross sections [K. Niemi et al., J. Phys. D 34, 2330 (2001)]. Here we present the measurements of a new calibration method based on a ground state xenon scheme for which the fluorescent emission wavelength is nearly identical to that of hydrogen, thereby eliminating chromatic effects in the collection optics and simplifying detector calibration. We determine that the ratio of the TALIF cross sections of xenon and hydrogen is 0.024 ± 0.001.

TALIF measurements of oxygen atom density in the afterglow of a capillary nanosecond discharge

The atomic oxygen density has been measured in the afterglow of a capillary nanosecond discharge in 24–30 mbar synthetic air (N2 : O2 = 4 : 1) by the two-photon absorption laser-induced fluorescence (TALIF) technique, combined with absolute calibration by comparison with xenon TALIF. The discharge was initiated by a train of 30 ns FWHM pulses of alternating positive–negative–positive polarity, separated by 250 ns, with a train repetition frequency of 10 Hz. The amplitude of the first pulse was 10 kV in the cable. A flow of synthetic air through the tube provided complete gas renewal between pulse trains. The O-atom density measurements were made over the time interval 200 ns–2 µs after the initial pulse. The gas temperature was determined by analysis of the molecular nitrogen second positive system optical emission spectrum. The influence of the gas temperature on the atom density measurements, and the reactions producing O atoms, are discussed.

Two-Photon Absorption Laser-Induced Fluorescence Investigation of Plasmas for Mars Entry

Two-photon absorption laser-induced fluorescence measurements have been conducted to investigate atomic oxygen temperature and number density in a plasma relevant to Martian entry. The high-enthalpy plasma flow has been produced by an inductively heated plasma generator. This paper describes the experimental setup and shows the applicability of laser diagnostics to Mars-relevant plasmas. Particular emphasis is put on the use of the generated data for the numerical simulation of the aerothermal chemistry of a Martian entry. Relative fluorescence signals are calibrated by a procedure using xenon as a reference. This calibration method allows the in situ experimental determination of the instrumental broadening of the spectroscopic setup and thus an accurate temperature measurement. The acquired, highly resolved line profiles of the fluorescence signal yield a translational temperature of and a mean number density of .

Two photon absorption laser induced fluorescence measurements of neutral density in a helicon plasma

We have developed a new diagnostic based on two-photon absorption laser induced fluorescence (TALIF). We use a high intensity (5 MW/cm2), narrow bandwidth (0.1 cm−1) laser to probe the ground state of neutral hydrogen, deuterium and krypton with spatial resolution better than 0.2 cm, a time resolution of 10 ns, and a measurement cadence of 20 Hz. Here, we describe proof-of-principle measurements in a helicon plasma source that demonstrate the TALIF diagnostic is capable of measuring neutral densities spanning four orders of magnitude; comparable to the edge neutral gradients predicted in the DIII-D tokamak pedestal. The measurements are performed in hydrogen and deuterium plasmas and absolute calibration is accomplished through TALIF measurements in neutral krypton. The optical configuration employed is confocal, i.e., both light injection and collection are accomplished with a single lens through a single optical port in the vacuum vessel. The wavelength resolution of the diagnostic is sufficient to separate hydrogen and deuterium spectra and we present measurements from mixed hydrogen and deuterium plasmas that demonstrate isotopic abundance measurements are feasible. Time resolved measurements also allow us to explore the evolution of the neutral hydrogen density and temperature and effects of wall recycling. We find that the atomic neutral density grows rapidly at the initiation of the discharge, reaching the steady-state value within 1 ms. Additionally, we find that neutral hydrogen atoms are born with 0.08 eV temperatures, not 2 eV as is typically assumed.

Atomic oxygen TALIF measurements in an atmospheric-pressure microwave plasma jet with in situ xenon calibration

Two-photon absorption laser-induced fluorescence (TALIF) is used to measure the absolute density of atomic oxygen (O) in a coaxial microwave jet in ambient air at atmospheric pressure, operated with a mixture of He and a few per cent of air. The TALIF signal is calibrated using a gas mixture containing Xe. A novel method to perform calibration in situ, at atmospheric pressure, is introduced. The branching ratios of several Xe mixtures are reported, to enable us to perform the Xe calibration without the need for a vacuum vessel. The O densities are measured spatially resolved, and as a function of admixed air to the He, and microwave power. The electron density and temperatures are measured using Thomson scattering, and the N2 and O2 densities are measured using Raman scattering. O densities are found to have a maximum of (4–6) × 1022 m−3, which indicate that O2 is close to fully dissociated in the plasma. This is confirmed by the Raman scattering measurements. O is found to recombine mainly into species other than O2 in the afterglow, which is suggested to consist of O3 and oxidized components of NO.

Two-photon absorption laser-induced fluorescence measurements of atomic nitrogen in a radio-frequency atmospheric-pressure plasma jet

The first direct measurements of atomic nitrogen species in a radio-frequency atmospheric-pressure plasma jet (APPJ) are presented. Atomic nitrogen radicals play a key role in new plasma medicine applications of APPJs. The measurements were performed with a two-photon absorption laser-induced fluorescence diagnostic, using 206.65 nm laser photons for the excitation of ground-state N atoms and observing fluorescence light around 744 nm. The APPJ was run with a helium gas flow of 1 slm and varying small admixtures of molecular nitrogen of 0–0.7 vol%. A maximum in the measured N concentration was observed for an admixture of 0.25 vol% N2.

Modeling and experimental study of molecular nitrogen dissociation in an Ar–N2 ICP discharge

The dissociation of nitrogen molecules in an Ar–N2 inductively coupled plasma (ICP) discharge is studied both experimentally and theoretically. To measure the absolute N atom density and emission intensity of Ar and N2 excited levels, two-photon absorption laser-induced fluorescence (TALIF) spectroscopy and optical emission spectroscopy are used. We observe an increase in N atom density with increasing pressure whereas the N atom density decreases for pressures higher than 100 mTorr in a pure nitrogen discharge. On adding argon to the mixture, we observe that the dissociation rate is enhanced when going from a pure nitrogen discharge to an argon mixed discharge. To calculate the plasma parameters, a global (volume-averaged) model is developed. The variation of the electron temperature and the particle densities are calculated by solving the particle and energy balance equations. The model calculations are compared with the measurement results and the production and loss rates of each species are described under each discharge condition. From the model calculation, the dissociation of N2 molecules in the Ar–N2 mixed discharge occurs mainly by electron impact dissociation at low pressures, while at high pressures the dissociative recombination is enhanced by charge transfer between Ar+ and N2(X) as well as metastable–metastable pooling dissociation due to the high density. In addition, the surface sticking coefficient of nitrogen atoms in a planar ICP discharge (including glass and stainless steel walls) is deduced from TALIF measurements and is estimated to be 0.02 under our set-up conditions.

Comparison of TALIF and catalytic probes for the determination of nitrogen atom density in a nitrogen plasma afterglow

The density of neutral nitrogen atoms in a glass reactor was measured by two absolute methods: two-photon absorption laser induced fluorescence (TALIF) and catalytic probes. The source of N atoms was nitrogen plasma created in a quartz tube by surfatron microwave generator operating at 2.45 GHz and adjustable output power up to 300 W. The TALIF measurements were performed using a dye laser which was pumped by a YAG laser. At the exit of the dye laser, the beam frequency was doubled through a KDP crystal and then mixed in a BBO crystal. The wavelength of the output laser beam was chosen at 206.65 nm so two-photon absorption was suitable to excite nitrogen atoms from the ground state to the 5d 2D state. Absolute N density was determined by using calibration with krypton. Simultaneously, the N atom density was measured with a fiber optics catalytic probe (FOCP) with a well-activated iron catalytic tip. Measurements were performed by both methods at nitrogen flows between 0.2 and 2 l min−1, and discharge powers between 60 and 300 W. At rather high nitrogen flows, the N atom density increased monotonically with increasing discharge power, while at lower flow saturation was observed. TALIF showed somewhat higher values than FOCP which was attributed to the accuracy of both methods. The main advantage of TALIF is a broader detection range, while FOCP is an extremely simple and inexpensive technique.

Atomic hydrogen densities in capacitively coupled very high-frequency plasmas in H2: Effect of excitation frequency

Absolute hydrogen atom densities in pure hydrogen capacitive discharges were measured as a function of excitation frequency (13.56, 27.12, and 40.68 MHz), nominal electrical power, and gas pressure (between 0.1 and 1 Torr). Quantitative measurements were made using two-photon absorption laser-induced fluorescence (TALIF), put on an absolute scale by comparison with the TALIF signal from a known density of krypton gas, as proposed by Niemi, Schultz von Gathen, and Döbele [J. Phys. D 34, 2330 (2001)]. The H atom density increases with gas pressure and electrical power, and at a given power and pressure it increases significantly with excitation frequency. The latter can be attributed in part to increased electron density. However, time-resolved TALIF measurements in the afterglow showed that the H atom surface loss probabilities are not constant, becoming somewhat smaller when the sheath voltage is lowered, as is the case when the excitation frequency is increased, contributing to the increase in H density.