Optical emission spectroscopy and modeling of plasma produced by laser ablation of titanium oxides

In the present study, the time evolution of electron number density, of electron, atom and ion temperatures, of plasma produced by KrF excimer laser ablation of titanium dioxide and monoxide targets, are investigated by temporally and spatially resolved optical emission spectroscopy over a wide range of laser fluence from 1.7 to 6 J cm⁻², oxygen pressures of 10⁻²–10⁻¹ torr and in a vacuum. A state-to-state collisional radiative model is proposed for the first time to interpret the experimental results at a distance of 0.6 mm from the target surface, in vacuum and for a time delay from 100 to 300 ns from the beginning of the laser pulse. In particular, we concentrate our attention on problems concerning the existence of the local thermodynamic conditions in the laser-induced plasma and deviation from them, as observed in our experiment. The numerical model proposed for calculating the electron number density and the population densities of atoms and ions in excited states give good quantitative agreement with the experimental results of the optical emission spectroscopy measurements.     

Study of early laser-induced plasma dynamics: Transient electron density gradients via Thomson scattering and Stark Broadening,and the implications on laser-induced breakdown spectroscopy measurements

To further develop laser-induced breakdown spectroscopy (LIBS) as an analytical technique, it is necessary to better understand the fundamental processes and mechanisms taking place during the plasma evolution. This paper addresses the very early plasma dynamics (first 100 ns) using direct plasma imaging, light scattering, and transmission measurements from a synchronized 532-nm probe laser pulse. During the first 50 ns following breakdown, significant Thomson scattering was observed while the probe laser interacted with the laser-induced plasma. The Thomson scattering was observed to peak 15–25 ns following plasma initiation and then decay rapidly, thereby revealing the highly transient nature of the free electron density and plasma equilibrium immediately following breakdown. Such an intense free electron density gradient is suggestive of a non-equilibrium, free electron wave generated by the initial breakdown and growth processes. Additional probe beam transmission measurements and electron density measurements via Stark broadening of the 500.1-nm nitrogen ion line corroborate the Thomson scattering observations. In concert, the data support the finding of a highly transient plasma that deviates from local thermodynamic equilibrium (LTE) conditions during the first tens of nanoseconds of plasma lifetime. The implications of this early plasma transient behavior are discussed in the context of plasma–analyte interactions and the role on LIBS measurements.     

Numerical simulations of ultrashort laser pulse ablation and plasma expansion in ambient air

Using a self-consistent one-dimensional Cartesian Lagrangian fluid code, we modeled the ultrashort laser pulse ablation of solid aluminum and the subsequent plasma expansion in ambient air. A laser fluence of approximately 10 J/cm² is considered. The code axial plasma temperature and density are strongly inhomogeneous and the maximum radiation emission generally occurs in the front of the plasma. The code average plasma temperature is in good agreement with the experiments for all times, while larger discrepancies with respect to the experiments are observed at late times for the plasma density. Experimental results are in reasonable agreement with the condition of thermodynamic equilibrium, which is an important assumption in the model.     

Measurement of electron density utilizing the Hα-line from laser produced plasma in air

The electron density in a laser produced plasma experiment was measured utilizing the Stark broadening of the H_α-line at 656.27 nm. This line results from the interaction of the Nd:YAG laser at the fundamental wavelength of 1.06 μm with a plane solid aluminum target in a humid air. The measurements were repeated at several delay times (0–10 μs) and at a fixed gate time of 1 μs. The electron density from the optically thin Al II-line at 281.62 nm was measured in parallel from the same spectra. The electron density was found in the range from 10¹⁸ cm^− 3 down to 6 × 10¹⁶ cm^− 3 at longer delay time. The electron density from the H_α-line using the Griem's standard theory was compared with the predictions of other model due to Gigosos et al. The agreement between the measured electron density from both the H_α-line and the Al II-line would confirm the reliability of utilizing the H_α-line as an electron density standard reference line in LIBS experiments. Several important features characterize the H_α-line: it is a well isolated line, it gives large signal to background ratio, it lasts a long time after the termination of the laser (up to 10 μs), its Stark width is relatively large and does not exhibit self-absorption.     

Early phase laser induced plasma diagnostics and mass removal during single-pulse laser ablation of silicon

The electron number density and temperature during the early phase (<300 ns) of laser-induced plasmas from silicon using a 266-nm, 3-ns Nd:YAG laser were deduced via spectroscopic methods. These parameters were measured as a function of delay time vs. irradiance in the range of 2–80 GW/cm², and compared with crater volume measurements. A dramatic change in plasma characteristics (electron number density, temperature, and degree of ionization) as well as a sharp increase of mass removal was observed when the irradiance was increased beyond a threshold of 20 GW/cm². Possible mechanisms such as inverse bremsstrahlung and self-regulation were used to describe these data in the low irradiance region. Laser self-focusing and critical temperature are discussed to explain the dramatic changes after the irradiance reaches the threshold.     

Early stage emission spectroscopy study of metallic titanium plasma induced in air by femtosecond- and nanosecond-laser pulses

In this work the laser induced plasma obtained in air at atmospheric pressure by the interaction of a fs (femtosecond) or a ns (nanosecond) laser pulse with a metallic titanium target has been investigated by optical emission spectroscopy. The temporal evolution of plasma parameters such as electron number density and excitation temperature has been determined in order to highlight the processes involved when the emission spectra are acquired at short time delays from the ablating laser pulse. A survey of elementary processes implicated during plasma formation and expansion of ns- and fs-Laser Induced Plasma has been performed. Departures from equilibrium conditions are even discussed. The dynamic aspects corresponding to ns- and fs-LIP have been investigated by optical time of flight (TOF) and by fast emission imaging. The overall results have been used for clarifying the basic mechanisms occurring during plasma expansion due to either ns or fs laser source when experimental conditions usually used for laser-induced breakdown spectroscopy (LIBS) applications are employed.     

Diagnostics in an air inductively coupled plasma

Radial temperature distributions in an air inductively coupled plasma discharge, operated at atmospheric pressure, are calculated from measurements of the absolute intensities of two atomic nitrogen lines (746.9 and 493.5 nm), the first negative band system of the nitrogen molecular ion at 391.4 nm, and the air continuum at 560.0 nm. The radial intensity distribution of the Mg I 285.2 and Mg II 279.6 nm lines are employed with the determined radial temperature distribution to calculate the radial electron number density throughout the normal analytical zone. The temperatures ranged from about 6000 to 10,000 K, and the electron number density varied from 5 × 10¹³ to 2 × 10¹⁶ cm^?3 in the regions above the induction coil where differences of less than 3 fold were observed between experimental and calculated Ca II to Ca I intensity ratios. On the basis of agreement among the measured temperatures and calcium ion-to-atom intensity ratios, the extent of local thermodynamic equilibrium is evaluated.     

Measurement of the properties of a CO2 laser induced air-plasma by double floating probe and spectroscopic techniques

The laser-induced breakdown spark has recently been advanced as a method for real-time, in-situ spectrochemical analysis of gases. Many of these analyses take place in ambient air. To better characterize this source, we have measured the temporal variation of temperature and electron density in an air plasma induced by a CO₂ laser operating at 0.5 and 0.8 J/pulse. The electron temperature was measured by the double floating-probe technique (DFP). An excitation temperature for oxygen atoms was determined spectroscopically by Boltzmann plots. Electron density in the plasma was measured from the Stark broadening of the 715.6-nm line of 01. At 0.5 J/pulse, the DFP temperature ranged from 175000 K at 5 μs to less than 10000 K at 25 μs, while the 01 excitation temperature ranged from 19000 K at 1 μs to above 11 000 K at 25 μs. The excitation temperature and electron density agree with values calculated by others from local thermodynamic equilibrium models of an air plasma. While the electron temperature from the DFP method is much higher than the excitation temperature at 5 μs, at times greater than 25 μs the two have converged, implying thermodynamic equilibration between the species.     

Laser Based Optical Emission Studies of Zinc Oxide (ZnO) Plasma

We present the optical emission characteristics of the zinc oxide (ZnO) plasma produced by the first (1,064 nm) and second (532 nm) harmonics of a Q switched Nd: YAG laser. The target material was placed in front of laser beam in air (at atmospheric pressure).The experimentally observed line profiles of neutral zinc (Zn I) have been used to extract the electron temperature using the Boltzmann plot method, whereas, the electron number density has been determined from the Stark broadening. The electron temperature is calculated by varying distance from the target surface along the line of propagation of plasma plume and also by varying the laser irradiance. Beside we have studied the variation of number density as a function of laser irradiance as well as its variation with distance from the target surface. It is observed that electron temperature and electron number density increases as laser energy is increased.     

Double pulse laser ablation and laser induced breakdown spectroscopy: A modeling investigation

A numerical model, describing laser–solid interaction (i.e., metal target heating, melting and vaporization), vapor plume expansion, plasma formation and laser–plasma interaction, is applied to describe the effects of double pulse (DP) laser ablation and laser induced breakdown spectroscopy (LIBS). Because the model is limited to plume expansion times in the order of (a few) 100 ns in order to produce realistic results, the interpulse delay times are varied between 10 and 100 ns, and the results are compared to the behavior of a single pulse (SP) with the same total energy. It is found that the surface temperature at the maximum is a bit lower in the DP configuration, because of the lower irradiance of one laser pulse, but it remains high during a longer time, because it rises again upon the second laser pulse. Consequently, the target remains for a longer time in the molten state, which suggests that laser ablation in the DP configuration might be more efficient, through the mechanism of splashing of the molten target. The total laser absorption in the plasma is also calculated to be clearly lower in the DP configuration, so that more laser energy can reach the target and give rise to laser ablation. Finally, it is observed that the plume expansion dynamics is characterized by two separate waves, the first one originating from the first laser pulse, and the second (higher) one as a result of the second laser pulse. Initially, the plasma temperature and electron density are somewhat lower than in the SP case, due to the lower energy of one laser pulse. However, they rise again upon the second laser pulse, and after 200 ns, they are therefore somewhat higher than in the SP case. This is especially true for the longer interpulse delay times, and it is expected that these trends will be continued for longer delay times in the μs-range, which are most typically used in DP LIBS, resulting in more intense emission intensities.     

Spectroscopic and shadowgraphic analysis of laser induced plasmas in the orthogonal double pulse pre-ablation configuration

This work focuses on the study of the plumes obtained in the double pulse orthogonal Laser Induced Breakdown Spectroscopy (LIBS) in the pre-ablation configuration using both spectroscopic and shadowgraphic approaches. Single and double pulse LIBS experiments were carried out on a brass sample in air. Both the distance of the air plasma from the target surface and the interpulse delay were varied (respectively in the range 0.1–4.2 mm and up to 50 μs) revealing a significant variation of the plasma emission and of the plume-shock wave dynamical expansion in different cases. The intensity of both atomic and ionized zinc lines was measured in all the cases, allowing the calculation of the spatially averaged temperature and electron density and an estimation of the ablated mass. The line intensities and the thermodynamic parameters obtained by the spectroscopic measurements were discussed bearing in mind the dynamical expansion characteristics obtained from the shadowgraphic approach. All the data seem to be consistent with the model previously proposed for the double pulse collinear configuration where the line enhancement is mainly attributed to the ambient gas rarefaction produced by the first laser pulse, which causes a less effective shielding of the second laser pulse.     

Influence of sample temperature on the expansion dynamics and the optical emission of laser-induced plasma

We investigate the influence of sample temperature on the dynamics and optical emission of laser induced plasma for various solid materials. Bulk aluminum alloy, silicon wafer, and metallurgical slag samples are heated to temperature T_S ≤ 500 °C and ablated in air by Nd:YAG laser pulses (wavelength 1064 nm, pulse duration approx. 7 ns). The plasma dynamics is investigated by fast time-resolved photography. For laser-induced breakdown spectroscopy (LIBS) the optical emission of plasma is measured by Echelle spectrometers in combination with intensified CCD cameras. For all sample materials the temporal evolution of plume size and broadband plasma emission vary systematically with T_S. The size and brightness of expanding plumes increase at higher T_S while the mean intensity remains independent of temperature. The intensity of emission lines increases with temperature for all samples. Plasma temperature and electron number density do not vary with T_S. We apply the calibration-free LIBS method to determine the concentration of major oxides in slag and find good agreement to reference data up to T_S = 450 °C. The LIBS analysis of multi-component materials at high temperature is of interest for technical applications, e.g. in industrial production processes.     

Evaluation of the continuous optical discharge for spectrochemical analysis

The continuous optical discharge (COD) has been studied as a spectrochemical excitation source for atomic emission spectroscopy. The COD was generated by focusing a 45-W cw-CO₂ laser beam in Xe gas at pressures between 1150 and 3200 torr. The high temperature ( 10 000 K) and electron density (~10 ¹⁷ cm ^?3) of the plasma should provide good excitation for elements difficult to excite by more conventional sources. Some characteristics of the plasma were examined as a function of laser power and gas pressure. The design of a gas cell for analytical measurements which increases plasma stability is presented. Linear calibration curves for O₂; and Cl₂ introduced into the plasma were obtained and detection limits established. Detection limits were also determined for solid materials laser ablated into the COD. Because the COD operates at pressures above atmospheric, gas samples are most easily introduced for analysis. To prevent contamination of optical components by analyte dissociation products, the COD should be operated as a plasmatron.     

Laser Induced Surface Morphology of Molybdenum Correlated with Breakdown Spectroscopy

Surface modifications of laser irradiated molybdenum have been correlated with plasma parameters. Nd:YAG laser (1064 nm, 10 ns) was employed at various laser irradiances ranging from 6 to 50 GW/cm² under argon environment. The ablation efficiency has been investigated by measuring the crater depth using surface profilometry analysis. Scanning electron microscope (SEM) analysis reveals the formation of coarse grains along with cracked boundaries, cavities and cones at the central ablated areas. Whereas, uplifted re-solidified material, cavities, ridges, droplets and cones were observed at boundary regions. Laser Induced Breakdown Spectroscopy (LIBS) analysis has been performed to evaluate electron temperature and number density of molybdenum plasma. Electron temperature and electron density varies from 6670 to 9305 K and 0.62 × 10¹⁸ to 0.72 × 10¹⁸ cm^?3 respectively. Both the parameters showed similar trend in variation with laser irradiance i.e. an initial increase from 13 to 19 GW/cm² followed by a decrease from 19 to 25 GW/cm² and then a saturation from 25 to 50 GW/cm². The initial increasing trend is attributed to the enhanced excited vapor content of the ablated material, confinement effects of the surrounding argon and absorption of laser energy into the molybdenum vapor plasma during the trailing part of laser pulse leading to ignition of laser supported combustion (LSW) waves. The decreasing trend is attributed to the shielding effect and saturation is explainable on the basis of the formation of a self-regulating regime. Surface modifications of laser irradiated molybdenum were correlated with the plasma parameters.     

Time-resolved optical emission spectroscopic measurements of He plasma induced by a high-power CO2 pulsed laser

Laser-induced breakdown spectroscopy of helium plasma, initially at room temperature and pressures ranging from 12 to 101 kPa was investigated using a transverse excitation atmospheric CO₂ pulsed laser (λ = 9.621 and 10.591 μm, a full width at half maximum of 64 ns, and an intensity from 1.5 to 5.36 GW cm⁻²). The helium breakdown spectrum is mainly due to electronic relaxation of excited He, He⁺ and H. Plasma characteristics were examined in detail on the emission lines of He and He⁺ by the time-integrated and time-resolved optical emission spectroscopy technique. Optical breakdown threshold intensities, ionization degree and plasma temperatures were obtained. An auxiliary metal mesh target was used to analyze the temporal evolution of the species in the plasma. The results show a faster decay of the continuum emission and He⁺ species than in the case of neutral He atoms. The velocity and kinetic energy distributions for He and He⁺ species were obtained from time-of-flight measurements. Electron density in the laser-induced plasma was estimated from the analysis of spectral data at various times from the laser pulse incidence. Temporal evolution of electron density has been used for the estimation of the three-body electron-ion recombination rate constant.     

Stark broadening of Mg I and Mg II spectral lines and Debye shielding effect in laser induced plasma

We report Stark broadening parameters for three Mg I lines and one Mg II line in the electron number density range (0.67–1.09) · 10¹⁷ cm^− 3 and electron temperature interval (6200–6500) K. The electron density is determined from the half width of hydrogen impurity line, the H_α, while the electron temperature is measured from relative intensities of Mg I or Al II lines using Boltzmann plot technique. The plasma source was induced by Nd:YAG laser radiation at 1.06 μm having pulse width 15 ns and pulse energy 50 mJ. Laser induced plasma is generated in front of a solid state surface. High speed photography is used to determine time of plasma decay with good homogeneity and then applied line self-absorption test and Abel inversion procedure. The details of data acquisition and data processing are described and illustrated with typical examples. The experimental results are compared with two sets of semiclassical calculations and the results of this comparison for Mg I lines are not unambiguous while for Mg II 448.1 nm line, the results of Dimitrijević and Sahal-Bréchot calculations agree well with our and other experimental results in the temperature range (5000–12,000) K and these theoretical results are recommended for plasma diagnostic purposes. The study of line shapes within Mg I 383.53 nm multiplet shows that the use of Debye shielding correction improves the agreement between theoretical and experimental Stark broadening parameters.     

Semiempirical model for analysis of inhomogeneous optically thick laser-induced plasmas

In this paper, a more realistic approach of a non-uniform optically thick plasma in local thermodynamic equilibrium was applied to describe self-reversal of Co I 340.51 nm emission line recorded from a laser-induced plasma generated on a Co–Cr–Mo metallic alloy. This line was selected because it is one of the most absorbed of the major elements in air at atmospheric pressure.The model describes the behavior of the plasma after the breakdown, and it was semiempirical thus, some information was taken from the experiment. A cylinder-symmetrical plasma column with a parabolic temperature distribution having a maximum at the center and decreasing toward the edges was considered. The input parameters were the plasma length, the temperature in the plasma core, and the Co total density, which were estimated from measurements and previous work. Moreover, the distribution of electron density depended on the temperature, and the ionization degree was taken into account through Saha equation. Then, plasma parameters were adjusted in such a way calculations reproduced the experimentally measured line profiles.The effect of varying laser power on plasma homogeneity and its evolution in time were investigated. Moreover, preliminary results of spatial distribution of plasma parameters were obtained that confirmed the practical application of the model on plasma diagnostics.     

Comparison of active and passive spectroscopic methods to investigate atmospheric inductively coupled plasmas

A comparison of Thomson and Rayleigh scattering, diode laser absorption and line emission measurements is performed on a 100 MHz atmospheric argon-flowing inductively coupled plasma. The parameters, which are measured in two or more ways, are the electron density, the electron temperature and the heavy particle temperature. The optimized diagnostics show the same behavior for the electron density and temperature. Nevertheless, the Thomson scattering diagnostic is the best at retrieving the radial profile. The heavy particle temperature, as measured by using both Rayleigh scattering and diode laser absorption, is identical within the estimated errors. The technique of measuring the temperature during power interruption, with both Thomson scattering and emission spectroscopy, shows that the electron and heavy particle temperatures are not equal during the period of power interruption.     

Temporal behavior of neutral and ionic lines emitted from a laser induced plasma on an aqueous surface

The temporal behavior of spectral lines emitted from a laser induced plasma has been studied. The plasma was created by using a Nd:YAG pulsed laser in air at atmospheric pressure focused on the surface of an aqueous solution. This work is an extension of previous published work [J. Ben Ahmed, Z. Ben Lakhdar, G. Taieb, Kinetics of laser induced plasma on an aqueous surface, Laser chem. 20 (2002) 123–134.]. The time evolution of lines intensities emitted from Ca, Ca⁺, Mg and Mg⁺ has been experimentally observed and simulated using a simple theoretical approach based on electron–ion recombination. It was shown that the plasma temperature and electron density are correlated to the dynamics of plasma emission. Finally, the time evolution of the optical depth of Ca⁺ resonance line at 393.4 nm was also studied.     

Optical emission spectroscopy of electron-cyclotron-resonance-heated helium mirror plasmas

In this experiment emission spectroscopy in the 3000–5000 Å range has been utilized to determine the electron temperature (15–60 eV) and ion density (2–5 x 10¹¹ cm^–3) of helium plasmas produced by the Michigan mirror machine⁽¹⁾ (MIMI). The plasma is generated and heated by whistler-mode electron-cyclotron resonance (ECR) waves at 7.43 GHz with 400–900 W power in 80-ms-long pulses. Gas fueling is provided at the midplane region by a leak valve with a range in pressure of 3 x 10 to 2 x 10⁴ Torr. Emission line intensities are interpreted using a model of the important collisional and radiative processes occurring in the plasma. The model examines secondary processes such as radiation trapping, excitation transfer between levels of the carne principle quantum number, and excitation front metastable states for plasmas in the parameter range of MIMI (n _c = 1–6 x 10¹¹ cm^–3). Front the analysis of line intensity ratios for neutral helium, the electron temperature is measured and its dependence upon the gas pressure and microwave power is determined. These temperatures agree with those obtained by Langmuir probe measurements. Art analysis of the line intensity ratio between singly ionized helium and neutral helium yields a measurement of the ion density which is in good agreement with electron density measurements made by a microwave interferometer.