LIBS Signal Research Articles

Laser-Induced Breakdown Spectroscopy Applied on Liquid Films: Effects of the Sample Thickness and the Laser Energy on the Signal Intensity and Stability

Droplets of organic liquids on aluminum substrate were probed by an Nd:YAG laser, both in a steady state and during rotation at speeds 18–150 rpm. Rotation transforms the droplet into film, which estimated thickness at high speeds was below 3 μm and 20 μm for diesel and peanut oil, respectively. Line intensities from the liquid (C I) and the support (Al I) material were tracked as a function of the film thickness and the laser energy. By film thinning, the line intensities from liquid sample were enhanced up to a factor 100x; simultaneously, the LIBS signal fluctuations were reduced 5–10 times with respect to the steady droplet. In certain experimental conditions, the line intensities from the support material become very weak with respect to the C I line, indicating an efficient screening of the substrate by highly excited plasma from the liquid layer. At a fixed rotation speed, there is a laser energy threshold, dependent on the liquid thickness, above which the LIBS signal becomes stable. Here, we discuss the relative processes and optimization of the experimental conditions for the LIBS measurements frome one laser shot to another.

Improvement of the Laser-Induced Breakdown Spectroscopy method sensitivity by the usage of combination of Ag-nanoparticles and vacuum conditions

In this work we studied the effect of vacuum (low pressure) conditions on the behavior of laser-induced plasma (LIP) created on a sample surface covered with silver nanoparticles (Ag-NPs), i.e. Nanoparticles-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) experiment in a vacuum. The focus was put on the step by step optimization of the measurement parameters, such as energy of the laser pulse, temporally resolved detection, ambient pressure, and different content of Ag-NPs applied on the sample surface. The measurement parameters were optimized in order to achieve the greatest enhancement represented as the signal-to-noise ratio (SNR) of NELIBS signal to the SNR of LIBS signal. The presence of NPs involved in the ablation process enhances LIP intensity; hence the improvement in the analytical sensitivity was yielded. A leaded brass standard was analyzed with the emphasis on the signal enhancement of Pb traces. We gained enhancement by a factor of four. Although the low pressure had no significant influence on the LIP signal enhancement compared to that under ambient conditions, the SNR values were noticeably improved with the implementation of the NPs.

Development of a Stand-off Laser Induced Breakdown Spectroscopy (ST-LIBS) system for the analysis of complex matrices

In the present work, we discuss the evaluation and optimization of a stand-off laser induced breakdown spectroscopy (ST-LIBS) system, developed indigenously for remote analysis of heavy elements in soil. A compact Q-switched Nd:YAG laser operating at fundamental wavelength 1064 nm was used for plasma generation at distances up to 6 meters. Techniques for optimal experimental results were evaluated for detection of Cd, Cr, Pb, Mo and Ni in soil. The system was evaluated with two NIST certified soil samples. The effect of working distance on the LIBS signal is also discussed briefly. Results confirm the capabilities of the system for remote monitoring.

Femtosecond Laser-Induced Breakdown Spectroscopy Studies of Nitropyrazoles: The Effect of Varying Nitro Groups.

The technique of femtosecond laser-induced breakdown spectroscopy (FLIBS) was employed to investigate seven explosive molecules of nitropyrazole in three different atmospheres: ambient air, nitrogen, and argon. The FLIBS data illustrated the presence of molecular emissions of cyanide (CN) violet bands, diatomic carbon (C2) Swan bands, and atomic emission lines of C, H, O, and N. To understand the plasma dynamics, the decay times of molecular and atomic emissions were determined from time-resolved spectral data obtained in three atmospheres: air, argon, and nitrogen. The CN decay time was observed to be longest in air, compared to nitrogen and argon atmospheres, for the molecules pyrazole (PY) and 4-nitropyrazole (4-NPY). In the case of C2 emission, the decay time was observed to be the longest in argon, compared to the air and nitrogen environments, for the molecules PY, 4-NPY, and 1-methyl-3,4,5-trinitropyrazole. The intensities of the CN, C2, C, H, O, and N emission lines and various molecular/atomic intensity ratios such as CN/C2, CN(sum)/C2(sum), CN/C, CN(sum)/C, C2/C, C2(sum)/C, (C2 + C) / CN, (C2(sum) + C)/CN(sum), O/H, O/N, and N/H were also deduced from the LIBS spectra obtained in argon atmosphere. A correlation between the observed decay times and molecular emission intensities with respect to the number of nitro groups, the atmospheric nitrogen content, and the oxygen balance of the molecules was investigated. The relationship among the LIBS signal intensity, the molecular/atomic intensity ratios, and the oxygen balance of these organic explosives was also explored.

Influence of oxygen addition to the carrier gas on laser-induced breakdown spectroscopy measurements on aerosols

In this work, laser-induced breakdown spectrosopy is implemented on aerosol particles for absolute concentration analysis. The aim of this work is the investigation of the effect of the bath gas used for nebulizing the aerosol. Nitrogen, air, and 50% O2 in N2 mixture have been chosen as carrier gasses in order to analyze the effect of oxygen addition to the gas. LIBS measurements have been carried out on aerosol particles produced from CuCl2 2H2O solutions, and the 324.7nm Cu line is considered. As a first analysis, plasma parameters, such as temperature and electron density, have been evaluated changing the carrier gas. Measurements to derive the LIBS calibration curve of the 324.7nm Cu line are carried out in air and in N2. The significant difference in the slope of the resulting calibration curves has to be attributed to the oxygen addition to the bath gas. To explore such behavior, time-resolved measurements of the Cu line and peak/base ratio have been performed. The presence of two competitive effects have been observed that becomes significant increasing the amount of oxygen in the carrier gas. One is the oxygen-quenching effect, already observed in the literature, and the other one is the enhancement of the Cu LIBS signal, expecially at short delay times. These effects have been observed also at other Cu lines and changing the analyte source. The results are presented and widely discussed.

The effects of laser repetition rate on femtosecond laser ablation of dry bone: a thermal and LIBS study.

The aim of this study is to understand the effect of varying laser repetition rate on thermal energy accumulation and dissipation as well as femtosecond Laser Induced Breakdown Spectroscopy (fsLIBS) signals, which may help create the framework for clinical translation of femtosecond lasers for surgical procedures. We study the effect of repetition rates on ablation widths, sample temperature, and LIBS signal of bone. SEM images were acquired to quantify the morphology of the ablated volume and fsLIBS was performed to characterize changes in signal intensity and background. We also report for the first time experimentally measured temperature distributions of bone irradiated with femtosecond lasers at repetition rates below and above carbonization conditions. While high repetition rates would allow for faster cutting, heat accumulation exceeds heat dissipation and results in carbonization of the sample. At repetition rates where carbonization occurs, the sample temperature increases to a level that is well above the threshold for irreversible cellular damage. These results highlight the importance of the need for careful selection of the repetition rate for a femtosecond laser surgery procedure to minimize the extent of thermal damage to surrounding tissues and prevent misclassification of tissue by fsLIBS analysis.

An Improving Method for Background Correction in Laser Induced Breakdown Spectroscopy

Background correction is an essential part in LIBS signal analysis. The interpolation method of background correction has major drawbacks. This paper introduces an interpolation method to overcome the shortcomings of linear and cubic spline interpolation methods. Finally, we compare different interpolation methods to verify the proposed interpolation method.

A method for improving wavelet threshold denoising in laser-induced breakdown spectroscopy

The wavelet threshold denoising method is an effective noise suppression approach for noisy laser-induced breakdown spectroscopy signal. In this paper, firstly, the noise sources of LIBS system are summarized. Secondly, wavelet multi-resolution analysis and wavelet threshold denoising method are introduced briefly. As one of the major factors influencing the denoising results in the process of wavelet threshold denoising, the optimal decomposition level selection is studied. Based on the entropy analysis of noisy LIBS signal and noise, a method of choosing optimal decomposition level is presented. Thirdly, the performance of the proposed method is verified by analyzing some synthetic signals. Not only the denoising results of the synthetic signals are analyzed, but also the ultimate denoising capacity of the wavelet threshold denoising method with the optimal decomposition level is explored. Finally, the experimental data analysis implies that the fluctuation of the noisy LIBS signals can be decreased and the weak LIBS signals can be recovered. The optimal decomposition level is able to improve the performance of the denoising results obtained by wavelet threshold denoising with non-optimal wavelet functions. The signal to noise ratios of the elements are improved and the limit of detection values are reduced by more than 50% by using the proposed method.

Laser-induced Breakdown Spectroscopy and ablation threshold analysis using a megahertz Yb fiber laser oscillator

A LIBS system is demonstrated using a 100m cavity Yb fiber oscillator producing ~70ps, 320nJ clusters of 50–100fs sub-pulses at 2MHz. A new empirical model for femtosecond ablation is presented to explain the LIBS signal intensity's non-linear dependence on pulse fluence by accounting for the Gaussian beam's spatial distribution. This model is compared to experimental data and found to be superior to linear threshold fits. This model is then used to measure the ablation threshold of Cu using a typical amplified Ti:sapphire system, and found to reproduce previously reported values to within ~20%. The ablation threshold of Cu using the Yb fiber oscillator system was measured to be five times lower than on the amplified Ti:sapphire system. This effect is attributed to the formation of nanostructures on the surface, which have previously been shown to decrease the ablation threshold. The plasma lifetime is found to be ~1ns, much shorter than that of nanosecond ablation, further indicating that the decreased threshold results from surface effects rather than laser–plasma interaction. The low threshold and high pulse energy of the Yb fiber oscillator allows the acquisition of LIBS spectra at megahertz repetition rates. This system could potentially be developed into a compact, fiber-based portable LIBS device taking advantage of the benefits of ultrafast pulses and high repetition rates.

Analysis of Enhanced Laser-Induced Breakdown Spectroscopy with Double Femtosecond Laser Pulses

In this paper, an experimental study of collinear geometry double-pulse femtosecond LIBS was performed on a Ni sample in ambient air in an effort to clarify the contributing processes responsible for the signal enhancement observed in comparison with the single-pulse case. Double-pulse LIBS spectra show a very clear enhancement when an optimum inter-pulse delay was used. The influences of the inter-pulse delay between two pulses on the LIBS signal intensity, electron temperature and density were investigated. It is most remarkable that the evolutions of signal enhancement and electron temperature versus the inter-pulse delay showed the same behavior and revealed two main regimes of interaction. These results provide additional insight into the possible emission enhancement mechanisms in the double pulse configuration.

Characterization of laser ablation of copper in the irradiance regime of laser-induced breakdown spectroscopy analysis

The LIBS signal depends both on the ablated mass and on the plasma excitation temperature. These fundamental parameters depend in a complex manner on laser ablation and on laser–plasma coupling. As several works in the literature suggest that laser ablation processes play a predominant role compared to plasma heating phenomena in the LIBS signal variations, this paper focuses on the study of laser ablation. The objective was to determine an interaction regime enabling to maximally control the laser ablation. Nanosecond laser ablation of copper at 266nm was characterized by scanning electron microscopy and optical profilometry analysis, in air at 1bar and in the vacuum. The laser beam spatial profile at the sample surface was characterized in order to give realistic values of the irradiance. The effect of the number of accumulated laser shots on the crater volume was studied. Then, the ablation crater morphology, volume, depth and diameter were measured as a function of irradiance between 0.35 and 96GW/cm². Results show that in the vacuum, a regular trend is observed over the whole irradiance range. In air at 1bar, below a certain irradiance, laser ablation is very similar to the vacuum case, and the ablation efficiency of copper was estimated at 0.15±0.03atom/photon. Beyond this irradiance, the laser beam propagation is strongly disrupted by the expansion of the dense plasma, and plasma shielding appears. The fraction of laser energy used for laser ablation and for plasma heating is estimated in the different irradiance regimes.

Angular-based spatially resolved laser-induced breakdown spectroscopy: a new technique for the effective enhancement of signals without an external time delay system

In this study, we developed a novel angularbased spatially resolved laser-induced breakdown spectroscopy (ABSR-LIBS) technique. This new method allows the spatially resolved spectroscopic properties of laserinduced plasma to be investigated using different angles and polar distances with a spatially adjustable fiber optics probe. The experimental evaluations suggested that the intensity of the Al signal distributions in the "side-view" depended greatly on the angle of the collection probe. The location of a collection probe at 50° would facilitate efficient spectral collection and minimize the disturbance of the plasma plume. The spectral signals in the plasma emissions had different distribution at various polar distances using the same collection angle, and the highest signal intensity was observed between 15 and 35 mm polar distances. This ABSR-LIBS technique improved both the LIBS signal and the maximum emission intensity of Al atoms by several times at the best spatial position in our experimental conditions. Furthermore, we successfully obtained well-resolved line emission spectroscopy signals without any external time delay using a nongated spectrometer based on the ABSR-LIBS system. We consider that the ABSR-LIBS technique has great potential for obtaining new insights with laser-induced plasma instruments and it could facilitate the development of a low-cost instrument.

Combination of cylindrical confinement and spark discharge for signal improvement using laser induced breakdown spectroscopy

Spark discharge has been proved to be an effective way to enhance the LIBS signal while moderate cylindrical confinement is able to increase the signal repeatability with limited signal enhancement effects. In the present work, these two methods were combined together not only to improve the pulse-to-pulse signal repeatability but also to simultaneously and significantly enhance the signal as well as SNR. Plasma images showed that the confinement stabilized the morphology of the plasma, especially for the discharge assisted process, which explained the improvement of the signal repeatability.

Temperature effect on the optical emission intensity in laser induced breakdown spectroscopy of super alloys

In this paper, the influence of heating and cooling samples on the optical emission spectra and plasma parameters of laser-induced breakdown spectroscopy for Titanium 64, Inconel 718 super alloys, and Aluminum 6061 alloy is investigated. Samples are uniformly heated up to approximately 200°C and cooled down to -78°C by an external heater and liquid nitrogen, respectively. Variations of plasma parameters like electron temperature and electron density with sample temperature are determined by using Boltzmann plot and Stark broadening methods, respectively. Heating the samples improves LIBS signal strength and broadens the width of the spectrum. On the other hand, cooling alloys causes fluctuations in the LIBS signal and decrease it to some extent, and some of the spectral peaks diminish. In addition, our results show that electron temperature and electron density depend on the sample temperature variations.

Optimization of a Laser Induced Breakdown Spectroscopy Method for the Analysis of Liquid Samples

A laser-induced breakdown spectrometer has been developed and optimized for the measurement of trace content of metals in Zamzam and in water processed by a Leveluck water machine. Zamzam water was frozen into ice using liquid nitrogen to overcome the LIBS diffi culties, specifi c to the detection of LIBS signal in liquid samples. The laser-produced plasma from the frozen ice sample was then analyzed using this LIBS spectrometer. The important parameters that can influence the sensitivity of the LIBS system, including the laser pulse width and energy, the sample homogeneity and the sampling geometry were optimized.

Effect of ambient conditions on laser-induced breakdown spectra

The role of different ambient conditions on LIBS signal intensity was investigated for better understanding and performance of LIBS as a quantitative and qualitative analytical technique. For this purpose, the relative LIBS signal intensities were measured for a standard Cr line (520.8 nm) at different gas pressures of Ar, He, and air. The plasma was generated using a Q-switched pulsed Nd:YAG laser having wavelength of 1064 nm and pulse duration of 8 ns. The analysis revealed that the intensities of the spectral atomic Cr line (520.8 nm) were strongly enhanced under the argon environment in 10–40 mbar range. The electron excitation temperature (T e ) and number density (n e ) were estimated by using a Boltzmann plot and a Stark broadening profile, respectively. For optimum dependence of LIBS, laser energy and pressure dependence was also studied. The electron temperature and number density showed an increase with increase in ambient gas pressure.

Characterization of organic materials by LIBS for exploration of correlation between molecular and elemental LIBS signals

The present study is performed for the preparation of a database by accumulating LIBS spectra of 4-nitroaniline and 4-nitrotoluene in air and argon. Changes in the behavior of the molecular bands of the C2 Swan system and CN violet system as well as of atomic lines of C, H and N in the LIBS signal are appreciable in argon. In order to explore the correlation between observed LIBS signal and molecular composition of these materials, normalized intensities of the emission lines have been estimated for each compound. It has been found that the relative rates of increase/decrease in the normalized intensities for all sets are higher for 4-nitrotoluene in argon. The cause of the higher rate for 4-nitrotoluene might be due to the possession of a distinctive functional group. The ultimate goal behind the whole study is to use this data-base as input for the discrimination of energetic materials.

Detection of explosives in traces by laser induced breakdown spectroscopy: Differences from organic interferents and conditions for a correct classification

With the aim to study and to improve LIBS capability for detecting residues of energetic compounds in air surrounding, nine types of explosives and some potential interferents, placed in small quantities on a metallic support, were interrogated by a laser. Shot-to-shot behavior of the line intensities relative to the sample constituents was studied. The detected plasma was not stoichiometric and the line intensities, as well as their ratios, were changing even for an order of magnitude from one sampling point to another, particularly in the case of aromatic compounds. We explained some sources of such LIBS signal's behavior and this allowed us to establish a data processing procedure, which leads to a good linearization among the data sets. In this way, it was possible to determine some real differences between the LIBS spectra from explosives and interferents, and to correlate them with molecular formulas, with some known pathways for the molecule's decomposition and with successive chemical reactions in the plasma. Number spectral parameters, which distinguish the each studied explosive from other organic materials, were also determined and compared with previously published results relative to percentages of correct classifications for the same explosives. Experimental conditions for reliable recognition of the explosives by LIBS in air are also suggested, together with the parameters that should be considered or discarded from the classification procedure.

Design and construction of Q-switched Nd:YAG laser system for LIBS measurements

A passive, Q-switched pulsed, Nd:YAG laser system was designed and built, which can provide a potential compact robust laser source for portable laser induced breakdown spectroscopy systems. The developed laser system operates at 1064 nm. Each laser shot contains a train of pulses having maximum total output energy of 170 mJ. The number of pulses varies from 1–6 pulses in each laser shot depending on the pump energy. The pulse width of each pulse ranges from 20 to 30 ns. The total duration of the output pulse train is within 300 μs. The multi-pulse nature of the laser shots was employed to enhance the LIBS signal. To validate the system, LIBS measurements and analysis were performed on ancient ceramic samples collected from Al-Fustat excavation in Old Cairo. The samples belong to different Islamic periods in Egypt history. The results obtained are highly indicative that useful information can be provided to archeologists for use in restoring and repairing of precious archeological objects.

Spatial confinement of laser-induced plasma to enhance LIBS sensitivity for trace elements determination in soils

To improve analytical figures-of-merit of the single-pulse LIBS for determination of trace elements in soil samples, a new configuration for spatial confinement based on a special designed device described recently in our work (A.M. Popov, F. Colao and R. Fantoni, J. Anal. At. Spectrom., 2009, 24, 602–604) was studied. The confinement tool realized is a small chamber (about 4 mm in diameter) equipped with polished brass walls and high efficiency collecting optics. A specific analytical procedure was developed to clean the chamber from impurities of microparticles deposited on surface of its walls after each experiment. Investigating the influence of focusing conditions on the stability of LIBS emission signal we have found that the relative standard deviation (RSD) of LIBS signal decreased as the distance between the focus position and the sample surface increased. So, the optimal position of the focus was found below the sample surface as a compromise between the need of collecting intense emission signals and of avoiding breakdown from the ejected microparticles. A significant intensity enhancement was observed inside the chamber, its use as an analytical tool was deeply investigated. The intensity enhancement, obtained on several major (Fe, Mg, Si) and trace elements (As, Ba, Cr, Hg, Mn, Ni, P, Pb, Ti, V) in the examined samples was significantly larger than the decrease of signal-to-noise ratio associated with the slightly worst statistics in the reproducibility of single-shot spectra inside the chamber. The 3σ-limits of detection (LOD) of As, Hg, Pb, Mn, V and Ba in soil by using the confined plasma were 30, 25, 90, 140, 1 and 50 ppm, respectively, resulting 2–5 times lower than LODs obtained for a free-expanding plasma under the same experimental conditions.