Two-photon Absorption Laser-induced Fluorescence Research Articles

Quantitative measurements of ground state atomic oxygen in atmospheric pressure surface micro-discharge array

The generation of atomic oxygen in an array of surface micro-discharge, working in atmospheric pressure He/O2 or Ar/O2 mixtures, is investigated. The absolute atomic oxygen density and its temporal and spatial dynamics are studied by means of two-photon absorption laser-induced fluorescence. A high density of atomic oxygen is detected in the He/O2 mixture with up to 10% O2 content in the feed gas, whereas the atomic oxygen concentration in the Ar/O2 mixture stays below the detection limit of 1013 cm−3. The measured O density near the electrode under the optimal conditions in He/1.75% O2 gas is 4.26 × 1015 cm−3. The existence of the ground state O (2p4 3P) species has been proven in the discharge at a distance up to 12 mm away from the electrodes. Dissociative reactions of the singlet O2 with O3 and deep vacuum ultraviolet radiation, including the radiation of excimer , are proposed to be responsible for O (2p4 3P) production in the far afterglow. A capability of the surface micro-discharge array delivering atomic oxygen to long distances over a large area is considered very interesting for various biomedical applications.

Two-photon-absorption line strengths for nitric oxide: Comparison of theory and sub-Doppler, laser-induced fluorescence measurements.

We discuss the results of high-resolution, sub-Doppler two-photon-absorption laser-induced fluorescence (TPALIF) spectroscopy of nitric oxide at low pressure and room temperature. The measurements were performed using the single-longitudinal mode output of a diode-laser-seeded optical parametric generator (OPG) system with a measured frequency bandwidth of 220 MHz. The measurements were performed using a counter-propagating pump beam geometry, resulting in sub-Doppler TPALIF spectra of NO for various rotational transitions in the (0,0) vibrational band of the A2Σ+ - X2Π electronic transition. The experimental results are compared with the results of a perturbative treatment of the rotational line strengths for the 20 different rotational branches of the X2Π(v″ = 0) → A2Σ+(v' = 0) two-photon absorption band. In the derivation of the expressions for the two-photon transition absorption strength, the closure relation is used for rotational states in the intermediate levels of the two-photon transition in analogy with the Placzek treatment of Raman transitions. The theoretical treatment of the effect of angular momentum coupling on the two-photon rotational line strengths features the use of irreducible spherical tensors and 3j symbols. The final results are expressed in terms of the Hund's case (a) coupling coefficients aJ and bJ for the X2Π(v″ = 0) rotational level wavefunctions, which are intermediate between Hund's case (a) and case (b). Considerable physical insight is provided by this final form of the equations for the rotational line strengths. Corrections to the two-photon absorption rotational line strength for higher order effects such as centrifugal stretching can be included in a straightforward fashion in the analysis by incorporating higher order terms in these coupling coefficients aJ and bJ, although these corrections are essentially negligible for J < 50. The theoretical calculations of relative line intensities are in good agreement both with our experiment and with published experimental results. In addition, the calculated line shapes and relative intensities for closely spaced main branch and satellite transitions are in excellent agreement with our experimental measurements.

Comparison of femtosecond- and nanosecond-two-photon-absorption laser-induced fluorescence (TALIF) of atomic oxygen in atmospheric-pressure plasmas

Absolute number densities of atomic species produced by nanosecond (ns)-duration, repetitively pulsed electric discharges are measured by two-photon-absorption laser-induced fluorescence (TALIF). Unique to this work is the development of femtosecond-laser-based TALIF (fs-TALIF) that offers a number of advantages over more conventional nanosecond (ns)-pulse-duration laser techniques, such as higher-fidelity quenching rate measurements over a wide pressure range, significantly reduced photolytic interference (including photo-dissociation and photo-ionization), ability to collect two-dimensional images of atomic-species number densities with high spatial resolution aided by higher signal level, and efficient and accurate measurements of atomic-species number densities due to the higher repetition rates of the laser. For full quantification of these advantages, atomic-oxygen TALIF signals are collected from an atmospheric-pressure plasma jet employing both ns- and fs-duration laser-excitation pulses and the results are compared and contrasted.

Ground state atomic oxygen in high-power impulse magnetron sputtering: a quantitative study

The ground state density of oxygen atoms in reactive high-power impulse magnetron sputtering discharges has been studied quantitatively. Both time-resolved and space-resolved measurements were conducted. The measurements were performed using two-photon absorption laser-induced fluorescence (TALIF), and calibrated by optical emission actinometry with multiple Ar emission lines. The results clarify the dynamics of the O ground state atoms in the discharge afterglow significantly, including their propagation and fast decay after the plasma pulse, as well as the influence of gas pressure, O2 admixture, etc.

Measurements of Absolute Atomic Nitrogen Density by Two-Photon Absorption Laser-Induced Fluorescence Spectroscopy in Hot Air Plasma Generated by Microwave Resonant Cavity

For the first time, absolute densities of atomic nitrogen in its ground state (N4S) have been measured in hot dry and humid air plasma columns under post-discharge regime. The determination of space-resolved absolute densities leads to obtain the dissociation degrees of molecular nitrogen in the plasma. The hot plasmas are generated inside an upstream gas-conditioning cell at 600 mbar when the air gas flow is directly injected at 10 slm in a microwave resonant cavity (2.45 GHz, 1 kW) placed in the downstream side. Density measurements based on laser induced fluorescence spectroscopy with two-photon excitation (TALIF), are more particularly performed along the radial and axial positions of the plasma column. Calibration of TALIF signals is performed in situ (i.e. in the same gas-conditioning cell but without plasma) using an air gas mixture containing krypton. Optical emission spectroscopy is considered to estimate the rotational gas temperature by adding a small amount of H2 in dry air to better detect OH (A-X) spectra. The rotational temperatures in humid air plasma column (50% of humidity) are larger than those of dry air plasma column by practically 30% near the nozzle of resonant cavity on the axis of the plasma column. This is partly due to attachment heating processes initiated by water vapor. A maximum of the measured absolute nitrogen density is also observed near the nozzle which is also larger for humid air plasma column. The obtained dissociation degrees of molecular nitrogen in both dry and humid air plasma along the air plasma column are lower than the cases where only thermodynamic equilibrium is assumed. This is characteristic of the absence of chemical and energetic equilibria not yet reached in the air plasma column dominated by recombination processes.

The effect of three different methods of adding O2 additive on O concentration of atmospheric pressure plasma jets (APPJs)

In order to maximize the O concentration generated by the atmospheric pressure plasma jets (APPJs), several different methods of adding O2 additive to working gas have been proposed. However, it is not clear, which method is capable of generating the highest concentration of O atom. In this paper, the concentration of O atoms in an APPJs by adding O2 to (1) the working gas, to (2) the downstream inside the tube, and (3) to the shielding gas is investigated by two-photon absorption laser-induced fluorescence spectrometry. The results clearly demonstrate that the highest O density is achieved when 1.5% of O2 is added to the working gas rather than the other two methods. In other words, the most effective way to generate O atoms is by premixing O2 with the working gas. Further investigation suggests that O atoms are mainly generated around the electrode region, where the electric field is highest. In addition, when O2 is added to the working gas, if in the meantime extra O2 is added to the downstream inside the tube, a significant decrease of O density is observed.

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.

Time-Selective TALIF Spectroscopy of Atomic Oxygen Applied to an Atmospheric Pressure Argon Plasma Jet

Two-photon laser excitation diagnostics is applied to characterize the atomic oxygen production in an atmospheric pressure Ar+O2% plasma jet. The plasma jet device is driven by a 13.56-MHz radio-frequency power supply. It is found that in addition to the fast decaying two-photon absorption laser-induced fluorescence (TALIF), unexpected emissions from excited atomic argon and oxygen species with a long decay time are existent in TALIF processes. This phenomenon is believed to be common in TALIF diagnostics of atomic oxygen, especially in high-pressure plasmas because of intense collisional energy transfer processes. In order to avoid the influence of extra emissions on TALIF performance, time-selective detection is utilized to capture the pure atomic oxygen fluorescence through nanosecond imaging for characterizing the spatial distribution of O atoms in the plasma effluent. An approximate method for the absolute density calibration based on the atomic oxygen fluorescence in the open air, due to the laser-induced photodissociation of O2 molecules, is applied to the TALIF signal from a plasma jet. The 2-D spatial distributions of the ground state density of atomic oxygen are built in the plasma effluent under different O2 contents. With the increase in O2 admixtures, the generation of atomic oxygen is constricted to the plasma core area close to the gas outlet, and a maximum O density is obtained with 0.3% O2 in the core area.

Mechanisms behind surface modification of polypropylene film using an atmospheric-pressure plasma jet

Plasma treatments are common for increasing the surface energy of plastics, such as polypropylene (PP), to create improved adhesive properties. Despite the significant differences in plasma sources and plasma properties used, similar effects on the plastic film can be achieved, suggesting a common dominant plasma constituent and underpinning mechanism. However, many details of this process are still unknown. Here we present a study into the mechanisms underpinning surface energy increase of PP using atmospheric-pressure plasmas. For this we use the effluent of an atmospheric-pressure plasma jet (APPJ) since, unlike most plasma sources used for these treatments, there is no direct contact between the plasma and the PP surface; the APPJ provides a neutral, radical-rich environment without charged particles and electric fields impinging on the PP surface. The APPJ is a RF-driven plasma operating in helium gas with small admixtures of O2 (0–1%), where the effluent propagates through open air towards the PP surface. Despite the lack of charged particles and electric fields on the PP surface, measurements of contact angle show a decrease from 93.9° to 70.1° in 1.4 s and to 35° in 120 s, corresponding to a rapid increase in surface energy from 36.4 mN m−1 to 66.5 mN m−1 in the short time of 1.4 s. These treatment effects are very similar to what is found in other devices, highlighting the importance of neutral radicals produced by the plasma. Furthermore, we find an optimum percentage of oxygen of 0.5% within the helium input gas, and a decrease of the treatment effect with distance between the APPJ and the PP surface. These observed effects are linked to two-photon absorption laser-induced fluorescence spectroscopy (TALIF) measurements of atomic oxygen density within the APPJ effluent which show similar trends, implying the importance of this radical in the surface treatment of PP. Analysis of the surface reveals a two stage mechanism for the production of polar bonds on the surface of the polymer: a fast reaction producing carboxylic acid, or a similar ketone, followed by a slower reaction that includes nitrogen from the atmosphere on the surface, producing amides from the ketones.

Fluorescence (TALIF) measurement of atomic hydrogen concentration in a coplanar surface dielectric barrier discharge

Spatially and temporally resolved measurements of atomic hydrogen concentration above the dielectric of coplanar barrier discharge are presented for atmospheric pressure in 2.2% H2/Ar. The measurements were carried out in the afterglow phase by means of two-photon absorption laser-induced fluorescence (TALIF). The difficulties of employing the TALIF technique in close proximity to the dielectric surface wall were successfully addressed by taking measurements on a suitable convexly curved dielectric barrier, and by proper mathematical treatment of parasitic signals from laser–surface interactions. It was found that the maximum atomic hydrogen concentration is situated closest to the dielectric wall from which it gradually decays. The maximum absolute concentration was more than 1022 m−3. In the afterglow phase, the concentration of atomic hydrogen above the dielectric surface stays constant for a considerable time (10 μs–1 ms), with longer times for areas situated farther from the dielectric surface. The existence of such a temporal plateau was explained by the presented 1D model: the recombination losses of atomic hydrogen farther from the dielectric surface are compensated by the diffusion of atomic hydrogen from regions close to the dielectric surface. The fact that a temporal plateau exists even closest to the dielectric surface suggests that the dielectric surface acts as a source of atomic hydrogen in the afterglow phase.

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.

Two-photon absorption laser induced fluorescence measurement of atomic oxygen density in an atmospheric pressure air plasma jet

Atomic oxygen number density [O] is measured in an air atmospheric pressure plasma jet (APPJ) using two-photon absorption laser induced fluorescence (TALIF). Gas flow is fixed at 8 slpm, the RF power coupled into the plasma jet varied between 5 W and 20 W, and the resulting changes in atomic oxygen density measured. Photolysis of molecular oxygen is employed to allow in situ calibration of the TALIF system. During calibration, O2 photo-dissociation and two-photon excitation of the resulting oxygen atoms are achieved within the same laser pulse. The atomic oxygen density produced by photolysis is time varying and spatially non-uniform which needs to be corrected for to calibrate the TALIF system for measurement of atomic oxygen density in plasma. Knowledge of the laser pulse intensity I0(t), wavelength, and focal spot size allows correction factors to be determined using a rate equation model. Atomic oxygen is used for calibration and measurement, so the laser intensity can be increased outside the TALIF quadratic laser power dependence region without affecting the calibration reliability as the laser power dependence will still be the same for both. The atomic O density results obtained are not directly benchmarked against other known density measurement techniques. The results show that the plasma jet atomic oxygen content increases as the RF power coupled into the plasma increases.

Absolute OH and O radical densities in effluent of a He/H2O micro-scaled atmospheric pressure plasma jet

The effluent of a micro-scaled atmospheric pressure plasma jet (μ-APPJ) operated in helium with admixtures of water vapor ( ppm) has been analyzed by means of cavity ring-down laser absorption spectroscopy and molecular beam mass spectrometry to measure hydroxyl (OH) radical densities, and by two-photon absorption laser-induced fluorescence spectroscopy to measure atomic oxygen (O) densities. Additionally, the performance of the bubbler as a source of water vapor in the helium feed gas has been carefully characterized and calibrated. The largest OH and O densities in the effluent of and , respectively, have been measured at around 6000 ppm. The highest selectivity is reached around 1500 ppm, where the OH density is at ∼63% of its maximum value and is 14 times larger than the O density. The measured density profiles and distance variations are compared to the results of a 2D axially symmetric fluid model of species transport and reaction kinetics in the plasma effluent. It is shown that the main loss of OH radicals in the effluent is their mutual reaction. In the case of O, reactions with other species than OH also have to be considered to explain the density decay in the effluent. The results presented here provide additional information for understanding the plasma-chemical processes in non-equilibrium atmospheric pressure plasmas. They also open the way to applying μ-APPJ with He/H2O as a selective source of OH radicals.

Fast, downstream removal of photoresist using reactive oxygen species from the effluent of an atmospheric pressure plasma Jet

In the semiconductor industry the plasma removal of photoresist (PR) between processing steps (so-called plasma ashing) is a critical issue in enabling the creation of advanced wafer architectures associated with the next generation of devices. We investigated the feasibility of a novel atmospheric-pressure plasma jet (APPJ) to remove PR. Our device operates at atmospheric pressure, eliminating the need for low-pressure operation used in conventional plasma ashing. Also, our method uses the downstream effluent of the source, avoiding issues relating to ion bombardment, a known hinderance to atomic precision manufacturing. Two-photon absorption laser induced fluorescence (TALIF) measurements of the system has shown that the PR removal rate is directly correlated with the atomic oxygen flux to the surface. The maximum removal rates achieved were 10 μm min−1, a factor of 100 improvement over typical low-pressure methods, while the quality of the etch, as assessed by attenuated total reflection fourier transform infrared spectroscopy, was found to be equal to low-pressure standards.

Quantitative Determination of Density of Ground State Atomic Oxygen from Both TALIF and Emission Spectroscopy in Hot Air Plasma Generated by Microwave Resonant Cavity

Two experimental techniques have been used to quantify the atomic oxygen density in the case of hot air plasma generated by a microwave (MW) resonant cavity. The latter operates at a frequency of 2.45 GHz inside a cell of gas conditioning at a pressure of 600 mbar, an injected air flow of 12 L/min and an input MW power of 1 kW. The first technique is based on the standard two photon absorption laser induced fluorescence (TALIF) using xenon for calibration but applied for the first time in the present post discharge hot air plasma column having a temperature of about 4500 K near the axis of the nozzle. The second diagnostic technique is an actinometry method based on optical emission spectroscopy (OES). In this case, we compared the spectra intensities of a specific atomic oxygen line (844 nm) and the closest wavelength xenon line (823 nm). The two lines need to be collected under absolutely the same spectroscopic parameters. The xenon emission is due to the addition of a small proportion of xenon (1% Xe) of this chemically inert gas inside the air while a further small quantity of H2 (2%) is also added in the mixture in order to collect OH(A-X) and NH(A-X) spectra without noise. The latter molecular spectra are required to estimate gas and excitation temperatures. Optical emission spectroscopy measurements, at for instance the position z=12 mm on the axis plasma column that leads to a gas measured temperature equal to 3500 K, an excitation temperature of about 9500 K and an atomic oxygen density 2.09×1017±0.2×1017 cm−3. This is in very good agreement with the TALIF measurement, which is equal to 2.0×1017 cm−3.

Kinetics of NO formation and decay in nanosecond pulse discharges in Air, H2-Air, and C2H4-Air mixtures

Time-resolved, absolute NO and N atom number densities are measured by NO Laser Induced Fluorescence (LIF) and N Two-Photon Absorption LIF in a diffuse plasma filament, nanosecond pulse discharge in dry air, hydrogen-air, and ethylene-air mixtures at 40 Torr, over a wide range of equivalence ratios. The results are compared with kinetic modeling calculations incorporating pulsed discharge dynamics, kinetics of vibrationally and electronically excited states of nitrogen, plasma chemical reactions, and radial transport. The results show that in air afterglow, NO decay occurs primarily by the reaction with N atoms, NO + N → N2 + O. In the presence of hydrogen, this reaction is mitigated by reaction of N atoms with OH, N + OH → NO + H, resulting in significant reduction of N atom number density in the afterglow, additional NO production, and considerably higher NO number densities. In fuel-lean ethylene-air mixtures, a similar trend (i.e. N atom concentration reduction and NO number density increase) is observed, although [NO] increase on ms time scale is not as pronounced as in H2-air mixtures. In near-stoichiometric and fuel-lean ethylene-air mixtures, when N atom number density was below detection limit, NO concentration was measured to be lower than in air plasma. These results suggest that NO kinetics in hydrocarbon-air plasmas is more complex compared to air and hydrogen-air plasmas, additional NO reaction pathways may well be possible, and their analysis requires further kinetic modeling calculations.

Gas temperature measurements in oxygen plasmas by high-resolution Two-Photon Absorption Laser-induced Fluorescence

One of the most important, and difficult to measure, parameters of laboratory discharges in molecular gases is the gas translational temperature. We propose a novel technique to measure directly, with excellent spatial and temporal resolution, the velocity distribution of ground-state atoms (oxygen atoms in this case) in plasmas from the Doppler broadening of their laser excitation spectra. The method is based on the well-known Two-Photon Laser-induced Fluorescence (TALIF) technique, but uses a specially-built pulsed tunable ultraviolet laser with very narrow bandwidth which allows the Doppler profiles to be measured with high precision. This laser consists of a pulsed Nd:YAG-pumped Ti:Sapphire ring cavity which is injection-seeded by a single-mode cw Ti:sapphire laser. The single-mode infrared output pulses are frequency quadrupled by two non-linear crystals to reach the necessary UV wavelength (226 nm, 0.2 mJ) for TALIF excitation. This technique should be applicable to a wide range of discharges, ranging from low-pressure RF plasmas for surface processing to atmospheric pressure plasmas. Results of preliminary tests on low-pressure O2 DC discharges are presented.

Surface charge dynamics and OH and H number density distributions in near-surface nanosecond pulse discharges at a liquid / vapor interface

The present work provides insight into surface charge dynamics and kinetics of radical species reactions in nanosecond pulse discharges sustained at a liquid-vapor interface, above a distilled water surface. The near-surface plasma is sustained using two different discharge configurations, a surface ionization wave discharge between two exposed metal electrodes and a double dielectric barrier discharge. At low discharge pulse repetition rates (~100 Hz), residual surface charge deposition after the discharge pulse is a minor effect. At high pulse repetition rates (~10 kHz), significant negative surface charge accumulation over multiple discharge pulses is detected, both during alternating polarity and negative polarity pulse trains. Laser induced fluorescence (LIF) and two-photon absorption LIF (TALIF) line imaging are used for in situ measurements of spatial distributions of absolute OH and H atom number densities in near-surface, repetitive nanosecond pulse discharge plasmas.Both in a surface ionization wave discharge and in a double dielectric barrier discharge, peak measured H atom number density, [H] is much higher compared to peak OH number density, due to more rapid OH decay in the afterglow between the discharge pulses. Higher OH number density was measured near the regions with higher plasma emission intensity. Both OH and especially H atoms diffuse out of the surface ionization wave plasma volume, up to several mm from the liquid surface. Kinetic modeling calculations using a quasi-zero-dimensional H2O vapor / Ar plasma model are in qualitative agreement with the experimental data. The results demonstrate the experimental capability of in situ radical species number density distribution measurements in liquid-vapor interface plasmas, in a simple canonical geometry that lends itself to the validation of kinetic models.

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.

Energy resolved actinometry for simultaneous measurement of atomic oxygen densities and local mean electron energies in radio-frequency driven plasmas

A diagnostic method for the simultaneous determination of atomic oxygen densities and mean electron energies is demonstrated for an atmospheric pressure radio-frequency plasma jet. The proposed method is based on phase resolved optical emission measurements of the direct and dissociative electron-impact excitation dynamics of three distinct emission lines, namely, Ar 750.4 nm, O 777.4 nm, and O 844.6 nm. The energy dependence of these lines serves as basis for analysis by taking into account two line ratios. In this frame, the method is highly adaptable with regard to pressure and gas composition. Results are benchmarked against independent numerical simulations and two-photon absorption laser-induced fluorescence experiments.