Influence of the laser parameters on the space and time characteristics of an aluminum laser-induced plasma

In this work, an aluminum laser plasma produced in ambient air at atmospheric pressure by laser pulses at a fluence of 10 J/cm² is characterized by time- and space-resolved measurements of electron density and temperature. Varying the laser pulse duration from 6 ns to 80 fs and the laser wavelength from ultraviolet to infrared only slightly influences the plasma properties. The temperature exhibits a slight decrease both at the plasma edge and close to the target surface. The electron density is found to be spatially homogeneous in the ablation plume during the first microsecond. Finally, the plasma expansion is in good agreement with the Sedov's model during the first 500 ns and it becomes subsonic, with respect to the velocity of sound in air, typically 1 μs after the plasma creation. The physical interpretation of the experimental results is also discussed to the light of a one-dimensional fluid model which provides a good qualitative agreement with measurements.     

A comparison of single and double pulse laser-induced breakdown spectroscopy of aluminum samples

Single and double pulse laser-induced breakdown spectroscopy (LIBS) was carried out on aluminum samples in air. In the case of double pulse excitation, experiments were conducted by using the same laser source operated at the same wavelength (1064 nm in most cases here presented). A lowering of the second pulse plasma threshold was observed, together with an overall enhancement in line emission for the investigated time delay between the two pulses (40–60 μs). The laser-induced plasma originated by a single and double pulse was investigated near ignition threshold with the aim to study possible dynamical mechanisms in different regimes. Currently available spectroscopic diagnostics of plasma, such as the line broadening and shift due Stark effects, have been used in the characterization in order to retrieve electron densities, while standard temperature measurements were based on Boltzmann plot. Plasma relevant parameters, such as temperature and electron density, have been measured in the plasma decay on a long time scale, and compared with crater shape (diameter and inferred volume). The comparison of double with single pulse laser excitation was carried out while keeping constant the energy per pulse; the influence of laser energy was investigated as well. Results here obtained suggest that use of the double pulse technique could significantly improve the analytical capabilities of LIBS technique in routine laboratory experiments.     

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.     

Curves of growth of spectral lines emitted by a laser-induced plasma: influence of the temporal evolution and spatial inhomogeneity of the plasma

The curves of growth (COG) of five Fe I lines emitted from a laser-induced plasma, generated with Fe–Ni alloys in air at atmospheric pressure, have been investigated. Spectral lines with different energy levels and line widths, emitted with a broad range of optical depths, have been included in the study in order to check the validity of theoretical models proposed for COG generation, based in the radiative transfer within a plasma in local thermodynamic equilibrium. The COGs have been measured at time windows of 4–5 μs and 15–18 μs. The Stark widths of the Fe I lines have been obtained, and the line widths have been determined by measuring the plasma electron density at the time windows selected. It is shown that at a time window of 4–5 μs, the inhomogeneity of the plasma magnitudes has an important influence on the COGs of intense lines. For this time window, a two-region model of the plasma has been used to generate theoretical COGs that describe satisfactorily the experimental curves of all the lines using a single set of plasma parameters. The results reveal the existence of considerable gradients between the inner and the outer plasma regions in the temperature (9400–7800 K) and in the density of Fe atoms (4×10¹⁶–0.02×10¹⁶ cm⁻³ for a sample with 100% Fe). On the contrary, at the time window 15–18 μs, at which the plasma has suffered most of its expansion and cooling process, the COGs of all the lines may be described by a single-region model, corresponding to a plasma with uniform temperature (6700 K) and density of Fe atoms (0.06×10¹⁶ cm⁻³ for a sample with 100% Fe). It is also shown that at initial times, the plasma inhomogeneity has an important effect in the line profiles of intense spectral lines, which are described by using the two-region model of the laser-induced plasma.     

Analytical characterization of sample entraining multi-electrode plasma sources for atomic emission spectroscopy–II. Interelement effects and excitation temperature measurements

Interelement effects are reported for a vertical 4-electrode plasma source. The magnitude and direction of the interelement effects are influenced by the experimental conditions. For a 30-mm plasma length, the interference effect of either phosphate or aluminum on calcium emission is insignificant over the entire vertical region of the plasma observed. Ionization interference effects on Ca(II) emission produced by an easily ionized element (EIE) are in general agreement with observations in an inductively coupled plasma (ICP). Nine Fe(I) lines were used to determine the excitation temperature from the slope of a Boltzmann plot. The excitation temperature in the center of the 25-mm plasma at 6mm above the quartz tube is 5800 ± 600 K. As the plasma length increases from 25 to 30 mm, the maximum excitation temperature in the sample aerosol channel increases by 2000 K and changes spatially. The electron number density increases by a factor of 10. Under the assumption of local thermal equilibrium (LTE), the electron number density obtained from the Saha-Eggert equation is about 1.0 × 10¹⁵ cm⁻³ for a 30-mm plasma. As the sample carrier gas flow rate decreases from 0.85 to 0.711/min, the maximum excitation temperature for a 30-mm plasma increases by 1000 K.     

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.     

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.     

Excitation temperature,degree of ionization of added iron species,and electron density in an exploding thin film plasma

Time and spacially resolved spectra of a cylindrically symmetric exploding thin film plasma were obtained with a rotating mirror camera and astigmatic imaging. These spectra were decouvolved to obtain relative spectral emissivity profiles for nine Fe(II) and two Fe(I) lines. The effective (electronic) excitation temperature at various positions in the plasma and at various times during the first current halfcycle was computed from the Fe(II) emissivity values using the Boltzmann graphical method. The Fe(II)/Fe(I) emissivity ratios together with the temperature were used to determine the degree of ionization of Fe. Finally, the electron density was estimated from the Saha equilibrium. Electronic excitation temperatures range from 10,000–15,000 K near the electrode surface at peak discharge current to 7000–10,000 K at 6–10 mm above the electrode surface at the first current zero. Corresponding electron densities range from 10¹⁷-10¹⁸ cm^?3 at peak current to 10¹⁵-10¹⁶cm^?3 near zero current. Error propagation and criteria for thermodynamic equilibrium are discussed.     

Cathodoluminescence efficiency dependence on excitation density in n-type gallium nitride.

Cathodoluminescence (CL) spectra from silicon doped and undoped wurtzite n-type GaN have been measured in a SEM under a wide range of electron beam excitation conditions, which include accelerating voltage, beam current, magnification, beam diameter, and specimen temperature. The CL intensity dependence on excitation density was analyzed using a power-law model (I CL proportional, variant J m ) for each of the observed CL bands in this material. The yellow luminescence band present in both silicon and undoped GaN exhibits a close to cube root (m = 0.33) dependence on electron beam excitation at both 77 K and 300 K. However, the blue (at 300 K) and donor-acceptor pair (at 77 K) emission peaks observed in undoped GaN follow power laws with exponents of m = 1 and m = 0.5, respectively. As expected from its excitonic character, the near band edge emission intensity depends linearly (m = 1) in silicon doped GaN and superlinearly (m = 1.2) in undoped GaN on the electron beam current. Results show that the intensities of the CL bands are highly dependent not only on the defect concentration but also on the electron-hole pair density and injection rate. Furthermore, the size of the focussed electron beam was found to have a considerable effect on the relative intensities of the CL emission peaks. Hence SEM parameters such as the objective lens aperture size, astigmatism, and the condenser lens setting must also be considered when assessing CL data based on intensity measurements from this material.     

Spatial distributions of metastable argon,temperature and electron number density in an inductively coupled argon plasma

Spatially resolved radial distributions of excitation temperature and electron number density in an argon ICP were obtained. The argon excitation temperature and electron number density near the plasma center were found to 7000 K and 5 × 10¹⁵ cm^?3, respectively, at an RF power of 1.5 kW and a carrier argon flow rate 0.65 1 min^?1.Various distributions of the absorbance at the Ar I 811.5 nm line, which has one of the metastable levels as the lower level, were obtained with and without carrier argon flow, where an MIP was used as a light source. Introduction of a large amount of potassium did not influence the distribution of the absorbance. The emission intensities at Ar I 811.5 nm were also measured for comparison.     

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.     

Study of CN emission from a laser induced plasma of graphite in air

Emission of neutral N atoms and CN molecules has been studied in the plasma produced by focusing a 200 mJ Nd: YAG laser onto a graphite target in air. Emission of atomic fines appears at early times. The Stark broadening of these lines is strongly time dependent due to the evolution of electron density in the plasma. At later times the spectrum is dominated by the CN violet system B₂Σ-X₂Σ. In the range from 1 to 20 μs the population of B₂Σ rovibrational levels can be described by a temperature of about 8500 K.     

Spectroscopic Diagnostics of Enhanced Magnetron and Mesh Separation Effects in Cyclonic Atmospheric Pressure Plasma Surface Modification of Polyethylene Terephthalate

The correlation of plasma surface modification consequence and the electron characteristics in plasma state with the enhanced magnetron source and metal mesh screen are studied by cyclonic-atmospheric-pressure plasma on polyethylene terephthalate (PET) surface. The contact angle measurement is employed to examine the plasma modified PET surface hydrophilicity. Optical emission spectroscopy is used to detect the electronic excitation temperature and electron density in cyclonic atmospheric pressure plasma. The electronic excitation temperature and the electron density are measured as the operational conditions of adding magnetron source and metal mesh separation. Boltzmann plot method is employed to estimate the electronic excitation temperature whereas electron density measurement by the Voigt profile. The results show that both electronic excitation temperature and electron density have similar trend i.e., both increasing with the enhanced magnetron source while decreasing trend is observed with passing through the metal mesh.     

On the electron temperatures and densities in plasmas produced by the “torche à injection axiale”

The electron temperature and the electron density of plasmas created by the “Torche à Injection Axiale” (TIA) are determined using Thomson scattering. In the plasma with helium as the main gas, temperatures of around 25 000 K and densities of between 0.64 and 5.1 × 10²⁰m⁻³ are found. In an argon plasma the electron temperature is lower and the electron density is higher: 17 000 K and around 10²¹ m⁻³ respectively. From these results it can be established that the ionisation rates of both plasmas are much larger than the recombination rates, which means that the plasmas are far from Saha equilibrium. However, deviations from a Maxwell electron energy distribution function, as reported for the “Microwave Plasma Torch” (MPT), are not found in the TIA. The excitation and ionisation power of the TIA appears to be stronger than that of the MPT.     

Appreciation of a collisional-radiative model for the description of an inductively coupled argon plasma

The collisional-radiative model has been applied to the argon ICP discharge in order to elucidate the excitation mechanism in the plasma. The population density distributions of 25 argon energy levels were calculated under a steady-state approximation by using the literature values of electron number density, 5 × 10 ¹⁴cm^?3 and electron temperature, 9000 K. In the case of an optically thin plasma, in which the induced absorption can be neglected, the calculated population densities showed an overpopulation for low lying states, and were very close to LTE values for the upper levels. These results suggest the following excitation mechanisms in the argon ICP; corona model for lower levels and ladder-like excitation and ionization by electron impact for upper levels. According to the present calculation, the non-overpopulation of argon metastable can be interpreted by the interconversion between metastable and radiative states. It has been found that the induced absorption of resonance lines in an optically thick plasma and the motion of species in an inhomogeneous plasma have significant effects on the population densities. The non-linear processes by collision between heavy particles were not predominant compared to electron impact processes.     

Non-thermal features of atmospheric-pressure argon and helium microwave-induced plasmas observed by laser-light Thomson scattering and Rayleigh scattering

Laser-light Thomson scattering and Rayleigh scattering have been measured from a microwave-induced plasma sustained at atmospheric pressure, using both argon and helium as a support gas. The measurements were performed at several spatial positions in each plasma, and at forward microwave power levels of 350 W for argon, and at 350 W and 100 W for helium. It was found from these measurements that both argon and helium plasmas deviate substantially from local thermodynamic equilibrium (LTE), Measured electron temperatures range from 13 000–21 500 K, whereas gas temperatures are generally lower by a factor of 2 to 10, depending on the support gas and the spatial position in the discharge. At the same forward microwave power, the electron temperature of the helium plasma is about 3500–7000 K higher than that of the argon plasma. Yet, the argon plasma has a higher electron number density than the helium plasma. Electron number densities in both argon and helium plasmas are roughly two to three orders of magnitude lower than what LTE would predict, based on the measured electron temperatures and the Saha Equation. Even more interestingly, signals in the far-wing portion of the Thomson-scattering spectrum were found to be significantly higher than are predicted by a fitted Maxwellian curve, indicating that there exists an over-population of high-energy electrons. It is concluded that, compared to the inductively coupled plasma, the microwave-induced plasma is highly non-thermal and remains in an ionizing mode in the analytical zone.     

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.     

The first ionization potential of uranium and thorium measured in a d.c. arc plasma

Tha Saha relationship was used to derive the ionization potentials of uranium and thorium from measurements of temperature or of electron density in a plasma in thermodynamic equilibrium. Introducing into the plasma elements with well defined ionization potentials, such as Ba, Al, V, Cr, Zr, Mo, Cu, Si and some of the rare-earths, as matrices, the temperature and electron density were measured in the central region of the arc plasma. A relation was established between the different ionization potentials and the plasma temperature or the electron density. From this relation the values of 6.3 ± 0.3 and 7.5 ± 0.3 eV were found for the ionization potentials of U and Th respectively.     

A crossover from metal to plasma in dense fluid hydrogen

Thermodynamic properties in dense fluid hydrogen are studied by using a density-functional theory for electron-proton binary mixtures that is called quantal hypernetted-chain (QHNC) integral equation. A nonlocal approximation for the exchange-correlation potential in a finite-temperature Kohn-Sham equation is presented. Results obtained from the QHNC with the nonlocal approximation are compared with those obtained from the QHNC with a local density approximation. Temperature variation of thermodynamic quantities between 10(4) and 10(6) K are investigated along an isochor specified by a dimensionless density parameter of rs=0.5. These quantities obtained from the QHNCs show that a crossover from metal to plasma occurs around a temperature of T=1.78 x 10(5) K. Electrical resistivity Re of the dense fluid hydrogen evaluated from a Ziman formula [The Properties of Liquid Metals, edited by S. Takenohi (Wiley, New York, 1973)] extended to finite temperature is about 0.7 muOmega cm at T=10(4) K. The dense fluid hydrogen at the temperature can be considered as a metallic fluid, because the value is smaller than typical values of Re in alkali metals at room temperature. The Re slightly increases with the temperature increase, and the temperature valuation of Re is monotonic. We clearly show that the contribution from the electronic excited states plays an important role for the sharp crossover from the metal to the plasma, and that the crossover is interpreted as a crossover from degenerate electron gas to nondegenerate electron gas.     

Diagnostics of silicon plasmas produced by visible nanosecond laser ablation

The second harmonic of a pulsed Nd:YAG laser (532 nm) has been used for the ablation of silicon samples in air at atmospheric pressure. In order to study the interaction for silicon targets, the laser-induced plasma characteristics were examined in detail with the use of a space- and time-resolved technique. Electron temperatures, ionic temperatures and electron number densities were determined. A discussion of thermodynamic equilibrium status of the silicon-microplasma is presented. Electron number densities are deduced from the Stark broadening of the line profiles of atomic silicon. Plasma ionization and excitation temperatures were determined from the Boltzmann plot and the Saha–Boltzmann equation, respectively. A limited number of suitable silicon lines for the studies of temperatures were found and the effect of these lines on the temperature measurements is discussed. Electron temperatures in the range of 6000–9000 K and ionic temperatures of 12 000–17 000 K with electron number densities of the order of 10¹⁸ cm⁻³ were observed. The breakdown threshold fluence has been also measured. Silicon plasmas were also characterized in terms of their morphology (shape and size) as a function of laser energy and delay time.