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A simple model is worked out to investigate laser-induced fluorescence in media of arbitrary optical thicknesses at the excitation wavelength. Close-form expressions are obtained for laser fluence, absorbed energy density and emitted fluorescence signal as a function of optical thickness and incident laser fluence. It is shown that in optically thick media saturation curves are not proportional to density of the species excited by the laser, except at saturation, and that the saturation fluence increases with optical thickness. Experimental saturation curves of lead in laser-produced plasmas of brass are discussed in the light of this model.

Laser-induced breakdown spectroscopy (LIBS) has demonstrated its high potential in measurement of material composition in many areas including space exploration. LIBS instruments will be parts of payloads for the 2011 Mars Science Laboratory NASA-led mission and the ExoMars mission planned by ESA. This paper considers application of artificial neural networks (ANN) for material identification based on LIBS spectra that may be obtained with a portable instrument in ambient conditions. The several classes of materials used in this study included those selected to represent the sites analogues to Mars. In addition, metals and aluminum alloys were used to demonstrate ANN capabilities. Excellent material classification is achieved with single-shot measurements in real time.

The combination of the laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF) techniques was investigated to improve the limit of detection (LOD) of trace elements in solid matrices. The influence of the main experimental parameters on the LIF signal, namely the ablation fluence, the excitation energy, and the inter-pulse delay, was studied experimentally and a discussion of the results was presented. For illustrative purpose we considered detection of lead in brass samples. The plasma was produced by a Q-switched Nd:YAG laser and then re-excited by a nanosecond Optical Parametric Oscillator (OPO) laser. The experiments were performed in air at atmospheric pressure. We found out that the optimal conditions were obtained for our experimental set-up using relatively weak ablation fluence of 2-3 J/cm² and an inter-pulse delay of abuot 5-10 µs. Also, a few tens of microjoules was typically required to maximize the LIF signal. Using the LIBS-LIFS technique, a single-shot LOD for lead of about 1.5 part per million (ppm) was obtained while a value of 0.2 ppm was obtained after accumulating over 100 shots. These values represent an improvement of about two orders of magnitude with respect to LIBS., available, unlimited, public

We consider the application of the differential absorption imaging technique in the soft X-ray region. The surface-density maps of test samples containing bromine, resulting from the application of the differential absorption imaging technique, are presented. Images of the samples were obtained in an X-ray monochromatic projection imaging scheme based on a spherically bent crystal using line emission close to the $L_2$ edge of bromine from a microplasma produced by focusing a nanosecond laser on the surface of an aluminum target.

In this work, the assumption of local thermodynamic equilibrium (LTE) for a laser-induced plasma in ambient air is examined experimentally using two different laser systems, namely an infrared short-pulse Ti:Sapphire laser and an ultraviolet long-pulse XeCl excimer laser. The LTE assumption is investigated by examining the plasma produced at a laser fluence of 10 J/cm2 from aluminum targets containing iron and magnesium impurities. The excitation temperature is deduced from Boltzmann diagrams built from a large number of spatially integrated neutral iron lines distributed from 3.21 to 6.56 eV. It is shown that at any time after the end of the laser pulse, the neutral excited states are in excellent Boltzmann equilibrium. Detailed investigation of Boltzmann equilibrium further validates previous temperature measurements using less accurate diagrams. However, observations of ion lines provide some evidence that the ionized species do not obey Saha equilibrium, thereby indicating departure from LTE. This could be explained by the fact that the plasma cannot be considered as stationary for these species.

The differential X-ray imaging technique is a powerful tool for the detection of small concentrations of contrast agents in samples, as demonstrated recently by many biological and medical applications using synchrotron radiation. In this paper, we present an implementation of this technique using a laser-plasma soft X-ray source combined with an X-ray imaging system based upon a spherically bent Bragg crystal. Using a test sample containing a solution of LiBr of known concentration, we demonstrate that the use of our table-top configuration is suitable to detect Br inside our sample via differential imaging at the L 2 edge of Br at 7.7684 A .

Ray-tracing simulations of an optical X-ray system based on a spherically bent crystal operating in Bragg configuration for monochromatic projection imaging of thin samples are presented, obtained using a code developed for that purpose. The code is particularly suited for characterizing experimental arrangements routinely used with laser-produced plasma X-ray sources. In particular, the spatial resolution of the imaging system was investigated and a careful study of the complex pattern of the X-ray backlighting beam was performed.

In this paper, the expansion in ambient air of a plasma produced by laser ablation from an aluminum target is studied with the help of a one-dimensional fluid code that includes a consistent description of ablation and of the subsequent plasma expansion. Two limiting cases for the expansion geometry have been considered: Cartesian and hemispheric. The plasma temperature and electron density as a function of the space coordinate and time have been obtained for laser pulse durations of 100 fs, 200 ps, and 5 ns, and laser fluences up to a few tens of J/cm2. Simulation results are in good agreement with experiments. The code shows that for times typically longer than 1 μs, the plasma space-averaged temperature and electron density are nearly independent of the laser parameters and of the chosen expansion geometry. For a given pulse duration the plasma temperature first increases with the fluence and then reaches a saturation value. It is shown that most of the observed plasma behavior can be explained by radiative cooling.

In the framework of laser-induced plasma spectroscopy (LIPS) applications, time-resolved characteristics of laser-produced aluminium plasmas in air at atmospheric pressure are investigated for laser pulse durations ranging from 100 fs to 270 ps. Measurements show that for delays after the laser pulse longer than ~100 ns, the plasma temperature increases slightly with the laser pulse duration, while the electron density is independent of it. In addition, as the pulse duration increases, the plasma radiation emission lasts longer and the spectral lines arise later from the continuum emission. The time dependence of the continuum emission appears to be similar whatever the duration of the laser pulse is, while the temporal evolution of the line emission seems to be affected mainly by the plasma temperature. Finally, as far as spectrochemical applications (such as LIPS) of laser-produced plasmas are concerned, this study highlights the importance of the choice of appropriate temporal gating parameters for each laser pulse duration.

In this study, various results are presented for laser ablation experiments on aluminum and silicon, made in ambient air by means of subpicosecond laser pulses. These results include threshold fluences for plasma formation and for the appearance of various spectral lines, and the single shot fluence required to remove aluminum layers of various specific thicknesses (ranging from 10 to 500 nm) deposited on a silicon substrate. The threshold fluence for plasma formation is of the order of 0.1 J/cm2. Threshold fluences for the appearance of the spectral lines considered vary from 0.1 to about 5 J/cm2. Finally, our results suggest that for high fluences, even for ultrashort laser pulses, the ablation depth is essentially determined by a long-range process, such as thermal conduction in the solid, rather than by the short range optical depth.

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.

This paper reports studies on time-resolved space-integrated laser induced breakdown spectroscopy (LIBS) of plasmas produced by ultrashort laser pulses at atmospheric pressure, on aluminum alloy targets. The temporal behavior of specific ion and neutral emission lines of Al, Mg and Fe has been characterized. The results show a faster decay of continuum and spectral lines, and a shorter plasma lifetime than in the case of longer laser pulses. Spectroscopic diagnostics were used to determine the time-resolved electron density, as well as the excitation and ionization temperatures. In comparison with plasmas produced by ns laser pulses, the plasma generated by ultrashort pulses exhibits a faster thermalization. Analytical performances of fs-LIBS were also evaluated. Linear calibration curves for minor elements (Mg, Fe, Si, Mn, Cu) presented in aluminum alloys were obtained. The limits of detection are in the parts per million (ppm) range and are element-dependent.

Laser ablation due to an ultrashort laser pulse on a massive aluminum target was investigated by means of a one-dimensional fluid code. Clear separation between the ablated matter and the unablated target is seen to occur through spinodal decomposition involving thermodynamic instabilities near the critical point of aluminum. The code also shows that the end of the ablation process is preceded by the ejection of droplets, which form about $15%$ of the total ejected mass.

Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) was performed for quantitative analysis of three metallic trace elements: Fe, Pb and Au in aqueous solutions. The plasma was generated using a UV (266 nm) frequency-quadrupled Q-switched Nd:YAG laser (7 ns) and then reheated by a 1064 nm Q-switched Nd:YAG laser (7 ns) in a quasi-collinear geometrical configuration. In order to improve the reproducibility of LIBS measurements, a circulation cell was used, providing a reproducibility of about 4% with a laser repetition rate of 0.3 Hz. The influence of the inter-pulse delay and the fluence of the second laser pulse on the signal-to-noise ratio (SNR) for the analytical lines was investigated and optimized. Analytical figures of merit of DP-LIBS and conventional single-pulse LIBS (SP-LIBS) were evaluated by establishing the calibration curves for the Fe I 358.12 nm, Pb I 405.78 nm and Au I 267.60 nm lines. The signal was greatly enhanced in DP-LIBS while the noise level did not vary as much. An improvement of the relative limit of detection of about 10 was achieved using DP-LIBS when compared to UV SP-LIBS in all cases. Measurement of the electron density as a function of time indicates that the plasma plume lifetime is longer in DP-LIBS. Similar trends in the excitation temperature were not observed for reasons that we attribute to larger uncertainties related to the Boltzmann plot method.

Resonance-enhanced laser-induced breakdown spectroscopy (RELIBS) was investigated with the aim to improve the limit of detection of trace elements in the context of elemental analysis of aluminium alloys. A Q-switched Nd:YAG laser pulse (7 ns, 1064 nm) was used for ablation of the samples and was followed, after a suitable delay, by an Optical Parametric Oscillator (OPO) laser pulse (7 ns), tuned at 396.15 nm, to resonantly excite the aluminium host atoms. In particular, the Mg I 285.21 nm and Si I 288.16 nm lines were observed in the acquisition spectral window. We investigated the influence of the main experimental parameters, namely, the excitation wavelength, the interpulse delay and the ablation and excitation fluences, on the signal-to-noise ratio for the Mg I 285.21 nm line. We found that, at low ablation fluences, typically less than a few J cm−2, the Mg signal at 285.21 nm achieved using RELIBS was significantly enhanced when compared to LIBS using the same ablation fluence. At fluences higher than 8 J cm−2, the effect of the excitation pulse became unnoticeable and similar results were observed for both approaches. The optimum conditions were achieved for an interpulse delay of about 30 ns, an ablation fluence of about 3.8 J cm−2 and an excitation fluence of about 1.1 J cm−2. The corresponding absolute LoDs were 0.7 and 50 fg, for Mg and Si, respectively, using RELIBS. When using LIBS, they were 4 and 128 fg, instead. Finally, the applicability of RELIBS in the context of a minimally destructive elemental analysis is discussed.

The combination of laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF) was investigated to improve the limit of detection (LoD) of trace elements in liquid water, while preserving the distinctive on-line monitoring capabilities of LIBS analysis. The influence of the main experimental parameters, namely the ablation fluence, the excitation fluence, and the inter-pulse delay was studied to maximize the fluorescence signal. The plasma was produced by a 266 nm frequency-quadrupled Q-switched Nd:YAG laser and the trace elements under investigation were then re-excited by a nanosecond optical parametric oscillator (OPO) laser, delivering pulses in the sub-mJ energy range, and tuned to strong absorption lines of the trace elements. The reproducibility of the measurements was improved using a home-made flow-cell, and relative standard deviations as low as 6.7 percent for a series of 100 shots were attained with a repetition rate of 0.7 Hz. Using the LIBS-LIF technique, we demonstrated LoDs of 39 ppb and 65 ppb for Pb and Fe, respectively, accumulating over 100 laser shots only, which correspond to an improvement of about 500 times with respect to LIBS.

We investigate the use of a second laser with a selected wavelength to improve the limit of detection (LoD) of trace elements in the Laser-Induced Breakdown Spectroscopy (LIBS) technique. We consider the combination of LIBS with Laser-Induced Fluorescence (LIF), in which the second laser is used to excite trace elements in the plasma. The influence of the main experimental parameters on the trace elements LIF signal, namely the ablation fluence, the excitation energy, and the inter-pulse delay, was studied experimentally and a physical interpretation of the results was presented. For illustrative purpose we considered detection of Pb in brass samples and in water. The plasma was produced by a Q-switched Nd:YAG laser and then re-excited by a nanosecond optical parametric oscillator laser. We found out that the optimal conditions for our experimental set-up were obtained for relatively weak ablation fluence of 2–3 J/cm2 and inter-pulse delay of 5–10 μs. Using the LIBS-LIFS technique, a single-shot LoD for detection of lead of about 1.5 part per million (ppm) was obtained for solids and 0.5 ppm for liquids. These LoDs represent an improvement of about two orders of magnitude with respect to LIBS. We also discuss resonance-enhanced LIBS (RELIBS), in which the second laser excites the main plasma component instead of the impurities. For the set of parameters used the RELIBS, Pb signal does not differ significantly from the LIBS signal except at low ablation fluence., First International Conference on Laser Plasma Applications in Materials Science - LAPAMS'08, Algiers, Algeria, June 23-26, 2008, 2008-06-23, Algiers, Algeria, Series: AIP conference proceedings

Laser-Induced Breakdown Spectroscopy (LIBS) has been successfully applied for multi-elemental analysis of solidified mineral melt samples containing several oxides present in various concentrations. The plasma was generated using a Nd:YAG laser and the spectra were acquired using an Echelle spectrometer, coupled to an ICCD detector, which covers a spectral range from 200 to 780 nm. Using a set of 19 calibration samples, we first established univariate calibration curves for the major elements (Al, Fe, Mg, Ca, Ti and Si). We found out that the presence of matrix effects makes such a model, traditionally used in LIBS, not satisfying for quantitative analysis of such samples. Indeed, no sufficiently linear trends can be extracted from the calibration curves for the elements of interest considering all the samples. Instead, a much more robust calibration approach was obtained by considering a multivariate model. The matrix effects are then taken into account by correcting the spectroscopic signals emitted by a given species due the presence of the others ones. More specifically, we established here a calibration model using a 2nd order polynomial linear multivariate inverse regression. The capability of this approach was then checked using a 2nd set of samples with an unknown composition. A good agreement was observed between the analysis provided by X-ray fluorescence (XRF) and the LIBS measurements coupled to the multivariate model for the unknown samples.

A promising way of improving the sensitivity of the LIBS (Laser-Induced Breakdown Spectroscopy) technique consists in using basically two successive laser pulses instead of only one as in conventional LIBS: the first pulse generates the plasma and the second pulse selectively excites a specific quantum level of a given trace atomic species inside the plasma. The effect of this second laser pulse is to increase the emission of the atomic species of interest and therefore enhance the signal-to-noise ratio, leading to an improved detection. As a first step toward the detection of Pb in various materials, we present in this work a study of the resonant excitation and decay paths of Pb atoms in a laser-produced plasma. The ablation was performed using a Nd:YAG laser and the 2 nd pulse provided by an Optical Parametric Oscillator (OPO) laser was launched several μs afterwards.

Quantitative analysis of aluminum and copper alloys by means of laser-induced plasma spectroscopy (LIPS) has been investigated for three representative laser pulse durations (80 fs, 2 ps, and 270 ps). The experiments were carried out in air at atmospheric pressure with a constant energy density of 20 J/cm2. Because the decay rate of the spectral emission depends on the laser pulse duration, the optimum detection requires an optimization of the temporal gating acquisition parameters. LIPS calibration (sensitivity and nonlinearity) and the limit of detection (LOD) are discussed in detail. While the LOD of minor elements embedded in alloy samples obtained by sub-picosecond or sub-nanosecond laser pulses are both time and element dependent, provided an appropriate temporal window is chosen, the optimum LODs (several parts per million (ppm)) prove to be independent of the laser pulse duration. Finally, it is found that for elements such as those detected here, gated LIPS spectra using picosecond or sub-picosecond laser pulses provide much better LOD values than non-gated spectra.

The differential imaging technique is particularly suitable for the detection of small concentrations of contrasts agents for biological and medical applications in samples using X-ray radiography. In this paper, we present an application of this technique using a laser-plasma soft X-ray source combined with a bent crystal. Using a Fresnel plate as a test object, we were able to obtain spatial resolutions of the order of a few tens of microns. The use of our configuration to perform differential imaging of a test-sample at the L2 edge of Br at 1,596 eV is finally demonstrated.

Summary form only given, as follows. Of the few studies that have been devoted to examining departure from LTE conditions, several suggest that laser produced plasmas at low fluences could be far from LTE at early times (before typically 1 /spl mu/s). The present work addresses this issue by investigating the departure from LTE conditions in Al plasmas created by a 10 ns excimer laser pulse at a wavelength of 308 nm with fluences of about 10 J/cm/sup 2/. The Boltzmann diagram method is applied to a few lines emitted by iron impurities contained in an Al matrix. Time evolution of the LTE departure is investigated by probing the plume at various delays after the laser pulse interaction with the target.

Time-resolved x-ray spectroscopy has been used to investigate ionization dynamics of a micrometer-sized nanosecond laser-plasma during the plasma start-up phase. Experimental results are modeled using two-dimensional hydrodynamic simulations and time-dependent collisional-radiative calculations. The study clearly shows that, due to the rapid expansion cooling, x-ray emission originates predominantly from a well-localized plasma region characterized by rapidly evolving hydrodynamic conditions. In this region, ionization dynamics is found to depart substantially from the steady-state regime. The measurements provide clear evidence of this transient ionization regime showing good agreement with the time-dependent calculations.

Laser ablation of an aluminum target as a function of the pulse duration, for fluences up to 30 J/cm(2) and a wavelength of 0.8 microm, is investigated by means of a fluid code. For a given fluence, the ablation depth shows a minimum for a pulse duration of approximately 10 ps between a maximum obtained for pulses shorter than approximately 1 ps and a lower maximum obtained for pulses in the nanosecond range, in qualitative agreement with published experimental results. The decrease in ablation depth with increase in pulse duration observed between 1 and 10 ps results from the reduced temperature rise near the surface due to increased inward heat transport. The increase in the ablation depth above approximately 10 ps is due to the increase in electron density gradient length while the laser pulse intensity is close to maximum, which thus enables the plasma to absorb more of the laser pulse energy for increased ablation.

Resonant laser-induced breakdown spectroscopy (RLIBS) was investigated to improve the limit of detection (LoD) of lead traces in copper alloys. A 5-ns optical parametric oscillator laser pulse was used to ablate the sample (front edge of the pulse) and resonantly excite the lead atoms in the vapor plume (rear edge of the pulse). The laser was tuned to the Pb I 283.31 nm line and the Stokes direct-line fluorescence signal at 405.78 nm was recorded. The experiments were performed in air at atmospheric pressure. The influence of the main experimental parameters, namely the laser wavelength, laser fluence and acquisition delay, on the signal-to-noise ratio (SNR) for the Pb I 405.78 nm line was studied experimentally. We found that the best SNR for the Pb I 405.78 nm line was achieved for a laser fluence of about 1.4 J cm-2, corresponding to the onset of visible damage on the sample, and an acquisition delay of about 5 ns. When the laser was on resonance a Pb I 405.78 nm signal could however be observed for a fluence as low as 0.25 J cm-2. For fluences greater than about 5 J cm-2, similar results were obtained whether the laser wavelength was tuned on resonance or not. Under these optimal conditions, the relative LoD for lead was estimated to be about 8 parts per million, accumulating over 500 laser shots. This amounts to an improvement of about 11-fold when compared to non-resonant LIBS in typical conditions. The corresponding absolute LoD was estimated to be about 0.8 femtograms and was calculated from optical coherence tomography measurements of the crater profiles. The fact that the best performances of RLIBS were obtained near the onset of visible damage on the sample indicates that this approach is particularly suitable for minimally destructive elemental analysis. © 2011 The Royal Society of Chemistry.

The ablated depth and volume per laser pulse from an aluminum target were measured for pulse durations that ranged from 80 fs to 270 ps at an average fluence of approximately 100 J/cm2 and a wavelength of 0.8 microm. The ablated volume showed a flat maximum for subpicosecond pulses and a minimum for approximately 6 ps. The crater diameters were rather constant up to pulse durations of approximately 6 ps and increased for larger pulse durations. As a result, the ablated depth also showed a plateau for subpicosecond pulses but decreased monotonically with pulse duration. A physical interpretation of these results and their consequences for laser applications are discussed.