Vacuum ultraviolet laser-induced breakdown spectroscopy analysis of polymers

Laser-induced breakdown spectroscopy (LIBS) in the vacuum ultraviolet range (VUV, λ < 200 nm) is employed for the detection of trace elements in polyethylene (PE) that are difficult to detect in the UV/VIS range. For effective laser ablation of PE, we use a F₂ laser (wavelength λ = 157 nm) with a laser pulse length of 20 ns, a pulse energy up to 50 mJ, and pulse repetition rate of 10 Hz. The optical radiation of the laser-induced plasma is measured by a VUV spectrometer with detection range down to λ = 115 nm. A gated photon-counting system is used to acquire time-resolved spectra. From LIBS measurements of certified polymer reference materials, we obtained a limit of detection (LOD) of 50 µg/g for sulphur and 215 µg/g for zinc, respectively.The VUV LIBS spectra of PE are dominated by strong emission lines of neutral and ionized carbon atoms. From time-resolved measurements of the carbon line intensities, we determine the temporal evolution of the electronic plasma temperature, T_e. For this, we use Saha–Boltzmann plots with the electron density in the plasma, N_e, derived from the broadening of the hydrogen H-α line. With the parameters T_e and N_e, we calculate the intensity ratio of the atomic sulphur and carbon lines at 180.7 nm and at 175.2 nm, respectively. The calculated intensity ratios are in good agreement with the experimentally measured results.     

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.     

Fast vacuum slag analysis in a steel works by laser-induced breakdown spectroscopy

Samples taken from the liquid slag layer in a vacuum degasser station of a steel works are analyzed after solidification by laser-induced breakdown spectroscopy (LIBS) without any further sample preparation. The mass fractions of the major components of the vacuum slags are in the range of 50–60% for CaO, 0.5–12% for SiO₂ and 20–40% for Al₂O₃. The species are distributed heterogeneously in the solid samples having diameters of 35 mm. Furthermore the color and structure of the samples is varying significantly. A fast spatial averaging of representative sample areas is realized by spatial laser beam shaping. Multivariate calibration and its validation is carried out with calibration and validation sets of production samples which are analyzed by X-ray fluorescence measurements or as borate beads for reference. The laser-induced breakdown spectroscopy instrument is installed in the steel works at a distance of about 10 m from the vacuum degasser. The laser-induced breakdown spectroscopy analysis runs automatically after the sample placement and it takes 80 s including data transfer to the host computer of the steel works. Operational tests are carried out to demonstrate the feasibility of a fast slag analysis in the harsh environment of the vacuum degasser plant.     

A theoretical study of atmospheric propagation of laser and return light for stand-off laser induced breakdown spectroscopy purposes

A theoretical study of atmospheric extinction mechanisms of optical radiation (molecular/aerosol scattering and absorption) has been carried out in order to assess their influences on stand-off laser-induced breakdown spectroscopy (LIBS) measurements. The atmospheric extinction of laser radiation at wavelengths commonly used in laser-induced breakdown spectroscopy (1064 nm and 532 nm) and of the laser-induced breakdown spectroscopy plasma emission beyond 250 nm is small compared to the attenuation with range due to the inverse square law. The fundamental problem with light propagation through the atmosphere is that the atmospheric transmittance does not remain constant within the whole spectral interval, and that this variation results in a change in the spectral distribution of the light received by the detector. Knowledge of atmospheric transmittance would allow for compensation of this effect.     

Effect of atmosphere on collinear double-pulse laser-induced breakdown spectroscopy

Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) has been shown to enhance LIBS spectra. Several researchers have reported significant increases in signal-to-noise and/or spectral intensity compared to single-pulse (SP) LIBS. In addition to DP-LIBS, atmospheric conditions can also increase sensitivity. Thus, in this study, a collinear DP-LIBS scheme was used along with manipulation of the atmospheric conditions. The DP-LIBS scheme consisted of an initial 45-mJ pulse at 1,064-nm fired into a sample contained in a controlled atmospheric/vacuum chamber. A second analytical 45-mJ pulse at 1,064-nm was then fired 0 to 200 μs after and along the same path of the first pulse. Ar, He, and air at pressures ranging from atmospheric pressure to 1 Torr are introduced during DP-LIBS and SP-LIBS experiments. For a brass sample, significant increases in the spectral intensities of Cu and Zn lines were observed in DP-LIBS under Ar compared to DP-LIBS in air. It was also found that Cu and Zn lines acquired with SP-LIBS in Ar are nearly as intense as DP-LIBS in air. While collinear DP-LIBS is effective for increasing the sensitivity for some reduced atmospheres (i.e., Ar and air at 630 to 100 Torr and He at 300 Torr), the enhanced spectral intensity ultimately dropped off as the pressure was reduced below 10 Torr for all atmospheric compositions in the experimental arrangement used in this study. At all pressures of air and Ar, the plasma temperature remained rather constant with increased inter-pulse delays; however, the plasma temperature was more variable for different He gas pressures and inter-pulse delays.     

Detection of zinc and lead in water using evaporative preconcentration and single-particle laser-induced breakdown spectroscopy

A novel laser-induced breakdown spectroscopy (LIBS)-based measurement method for metals in water is demonstrated. In the presented technology a small amount of sodium chloride is dissolved in the sample solution before spraying the sample into a tubular oven. After water removal monodisperse dry NaCl aerosol particles are formed where trace metals are present as additives. A single-particle LIBS analysis is then triggered with a scattering based particle detection system. Benefits are the highly increased metal concentration in the LIBS focal volume and the static NaCl-matrix which can be exploited in the signal processing procedure. Emitted light from the emerged plasma plume is collected with wide angle optics and dispersed with a grating spectrometer. In an aqueous solution, the respective limits of detection for zinc and lead were 0.3 ppm and 0.1 ppm using a relatively low 14 mJ laser pulse energy. Zn/Na peak intensity ratio calibration curve for zinc concentration was also determined and LIBS signal dependence on laser pulse energy was investigated.     

Nanosecond and femtosecond Laser Induced Breakdown Spectroscopic analysis of bronze alloys

In the present work we are studying the influence of pulse duration (nanosecond (ns) and femtosecond (fs)) at λ = 248 nm on the laser-induced plasma parameters and the quantitative analysis results for elements such as Sn, Zn and Pb, in different types of bronze alloys adopting LIBS in ambient atmosphere. Binary (Sn–Cu), ternary (Sn–Zn–Cu or Sn–Pb–Cu) and quaternary (Sn–Zn–Pb–Cu) reference alloys characterized by a chemical composition and metallurgical features similar to those used in Roman times, were employed in the study. Calibration curves, featuring linear regression coefficients over 98%, were obtained for tin, lead and zinc, the minor elements in the bronze alloys (using the internal standardization method) as well as for copper, the major element. The effects of laser pulse duration and energy on laser-induced plasma parameters, namely the excitation temperature and the electron density have been studied in our effort to optimize the analysis. Finally, LIBS analysis was carried on three real metal objects and the spectra obtained have been used to estimate the type and elemental composition of the alloys based on the calibration curves produced with the reference alloys. The results obtained are very useful in the future use of portable LIBS systems for in situ qualitative and quantitative elemental analysis of bronze artifacts in museums and archaeological sites.     

Time-resolved characterization of laser-induced plasma from fresh potatoes

Optical emission of laser-induced plasma on the surface of fresh vegetables provides sensitive analysis of trace elements for in situ or online detection of these materials. This emergent technique promises applications with expected outcomes in food security or nutrition quality, as well as environment pollution detection. Characterization of the plasma induced on such soft and humid materials represents the first step towards quantitative measurement using this technique. In this paper, we present the experimental setup and protocol that optimize the plasma generation on fresh vegetables, potatoes for instance. The temporal evolution of the plasma properties are investigated using time-resolved laser-induced breakdown spectroscopy (LIBS). In particular, the electron density and the temperatures of the plasma are reported as functions of its decay time. The temperatures are evaluated from the well known Boltzmann and Saha-Boltzmann plot methods. These temperatures are further compared to that of the typical molecular species, CN, for laser-induced plasma from plant materials. This comparison validates the local thermodynamic equilibrium (LTE) in the specific case of fresh vegetables ablated in the typical LIBS conditions. A study of the temporal evolution of the signal to noise ratio also provides practical indications for an optimized detection of trace elements. We demonstrate finally that, under certain conditions, the calibration-free LIBS procedure can be applied to determine the concentrations of trace elements in fresh vegetables.     

Atomic and molecular emissions in laser-induced breakdown spectroscopy

This article summarizes measurements and analysis of hydrogen Balmer series atomic lines following laser-induced optical breakdown. Electron number density on the order of 1 × 10²⁵ m^− 3 can be measured using H_α Stark width and shift in the analysis of breakdown plasma in 1 to 1.3 × 10⁵ Pa, gaseous hydrogen. The H_β line can be utilized for electron number density up to 7 × 10²³ m^− 3. The historic significance is elaborated of accurate H_β measurements. Electron excitation temperature is inferred utilizing Boltzmann plot techniques that include H_γ atomic lines and further members of the Balmer series. Laser ablation of aluminum is discussed in view of limits of application of the Balmer series. H_β and H_γ lines show presence of molecular carbon in a 2.7 and 6.5 × 10⁵ Pa, expanding methane flow. Diagnostic of such diatomic emission spectra is discussed as well. Laser-induced breakdown spectroscopy historically embraces elemental analysis, or atomic spectroscopy, and to a lesser extent molecular spectroscopy. Yet occurrence of superposition spectra in the plasma decay due to recombination or due to onset of chemical reactions necessitates consideration of both atomic and molecular emissions following laser-induced optical breakdown. Molecular excitation temperature is determined using so-called modified Boltzmann plots and fitting of spectra from selected molecular transitions. The primary interest is micro-plasma characterization during the first few micro-seconds following optical breakdown, including shadowgraph visualizations.     

Calibration free laser-induced breakdown spectroscopy of oxide materials

The quantitative determination of oxide concentration by laser-induced breakdown spectroscopy is relevant in various fields of applications (e.g.: analysis of ores, concrete, slag). Calibration free laser-induced breakdown spectroscopy and the multivariate calibration are among the methods employed for quantitative concentration analysis of complex materials. We measured the intensity of neutral and ionized atomic emission lines of oxide materials by laser-induced breakdown spectroscopy and we modified the calibration free laser-induced breakdown spectroscopy method to increase the accuracy. The concentration of oxides was obtained by using stoichiometric relations. Sample materials were prepared from oxide powder (Fe₂O₃, MgO, CaO) by mixing and pressing. The concentration was 9.8–33.3 wt.% Fe₂O₃, 7.6–33.3 wt.% MgO and 33.3–81.2 wt.% CaO for different samples. Nd:YAG laser (wavelength 1064 nm, pulse duration ≈ 6 ns) ablation was performed in air. The laser-induced plasma emission was measured by an Echelle spectrometer equipped with a sensitivity calibrated ICCD camera. The numerical calibration free laser-induced breakdown spectroscopy algorithm included the fast deconvolution of instrumental function, and the correction of self-absorption effects. The oxide concentration C_CF calculated from calibration free laser-induced breakdown spectroscopy results and the nominal concentration C_N were very close for all samples investigated. The relative error in concentration, |C_CF–C_N|/C_N, was < 10%, < 20%, and < 5% for Fe₂O₃, MgO, and CaO, respectively. The results indicate that this method can be employed for the analysis of major elements in multi-component technical materials.     

Parametric study of a fiber-optic laser-induced breakdown spectroscopy probe for analysis of aluminum alloys

In the present work we demonstrate a fiber-optic laser-induced breakdown spectroscopy (FO LIBS) system for delivering laser energy to a sample surface to produce a spark as well as to collect the resulting radiation from the laser-induced spark. In order to improve the signal/background (S/B) ratio, various experimental parameters, such as laser energy, gate delay and width, detector gain, lenses of different focal lengths and sample surface, were tested. In order to provide high reliability and repeatability in the analysis, we also measured plasma parameters, such as electron density and plasma temperature, and determined their influence on the measurement results. The performance of FO LIBS was also compared with that of a LIBS system that does not use a fiber to transmit the laser beam. LIBS spectra with a good S/B were recorded at 2-μs gate delay and width. LIBS spectra of six different Al alloy samples were recorded to obtain calibration data. We were able to obtain linear calibration data for numerous elements (Cr, Zn, Fe, Ni, Mn, Mg and Cu). A linear calibration curve for LIBS intensity ratio vs. concentration ratio reduces the effect of physical variables (i.e. shot-to-shot power fluctuation, sample-to-surface distance, and physical properties of the samples). Our results reveal that this system may be useful in designing a high-temperature LIBS probe for measuring the elemental composition of Al melt.     

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.     

Preliminary studies of laser-induced breakdown spectrometry for the determination of Ba,Cd, Cr and Pb in toys

The performance of laser-induced breakdown spectrometry (LIBS) for the determination of Ba, Cd, Cr and Pb in toys has been evaluated by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with intensified charge-coupled device detector. Samples were purchased in different cities of São Paulo State market and analyzed directly without sample preparation. Laser-induced breakdown spectrometry experimental conditions (number of pulses, delay time, integration time gate and pulse energy) were optimized by using a Doehlert design. Laser-induced breakdown spectrometry signals correlated reasonably well with inductively coupled plasma optical emission spectrometry (ICP OES) concentrations after microwave-assisted acid digestion of selected samples. Thermal analysis was used for polymer identification and scanning electron microscopy to visualize differences in crater geometry of different polymers employed for toy fabrication. Results indicate that laser-induced breakdown spectrometry can be proposed as a rapid screening method for investigation of potentially toxic elements in toys. The unique application of laser-induced breakdown spectrometry for identification of contaminants in successive layers of ink and polymer is also demonstrated.     

Characterization of nano-composite oxide ceramics and monitoring of oxide thin film growth by laser-induced breakdown spectroscopy

Multi-component oxide ceramics and epitaxial oxide thin films are analyzed by laser-induced breakdown spectroscopy (LIBS). Furthermore, pulsed-laser deposition (PLD) of thin films is investigated by long-term monitoring of the optical plasma emission. Both nano-composite high-temperature superconductors (HTS) consisting of YBa₂Cu₃O_7 − δ bulk and Y₂Ba₄MCuO_x (M-2411, M = Ag, Nb) nano-particles, and semiconducting ZnO doped with Aluminum and Lithium are ablated by nano-second laser pulses. The plasma emission is recorded using grating spectrometers with intensified gated detectors. The LIBS signals of nano-particles correlate with the nominal content of the M-2411 phase (0–15 mol%) and reveal a strong signal of Ytterbium impurity (3–35 ppm). In situ monitoring of the PLD process shows element signals that are stable for more than 10,000 laser pulses for both HTS and ZnO ceramics. The relative concentration of elements in thin films and ceramics as determined by LIBS is almost the same.     

Doubly ionized ion emission in laser-induced breakdown spectroscopy in air

The emission from doubly ionized species in laser-induced plasmas has not been properly investigated before since most analytical measurements were made at relatively long delays. This work proves that doubly ionized species, such as boron (B) III and iron (Fe) III, can exist during the first 150–200 ns of the plasma lifetime in plasmas produced in air by typical lasers with irradiances of 10⁹–10¹¹ W/cm². The emission from these ions was detected using both the double- and single-pulse excitations. The sum of the second ionization potential and the energy of corresponding excited states is approximately 30 eV. The presence of doubly charged ions in the early plasma was additionally confirmed by computer simulations using a collision-dominated plasma model. The emission from doubly ionized species may be used for analytical purpose. For example, in the spectrum from a B–Fe ore, the B III analytical line at 206.6 nm is free from Fe spectral interference thus enabling the online laser-induced breakdown spectroscopy sorting of ores into three products with high, medium, and low B₂O₃ contents.     

Review: Applications of single-shot laser-induced breakdown spectroscopy

As applications for laser-induced breakdown spectroscopy (LIBS) become more varied with a greater number of field and industrial LIBS systems developed and as the technique evolves to be more quantitative that qualitative, there is a more significant need for LIBS systems capable of analysis with the use of a single laser shot. In single-shot LIBS, a single laser pulse is used to form a single plasma for spectral analysis. In typical LIBS measurements, multiple laser pulses are formed and collected and an ensemble-averaged method is applied to the spectra. For some applications there is a need for rapid chemical analysis and/or non-destructive measurements; therefore, LIBS is performed using a single laser shot. This article reviews in brief several applications that demonstrate the applicability and need for single-shot LIBS.     

Fast and sensitive trace metal analysis in aqueous solutions by laser-induced breakdown spectroscopy using wood slice substrates

To perform fast and sensitive trace metal analysis in aqueous solutions by laser-induced breakdown spectroscopy (LIBS) based on only one single-pulse laser system, a wood slice has been used as a liquid absorber to transform liquid sample analysis to solid sample analysis using LIBS. High detection sensitivity and good reproducibility can be achieved with this approach. Calibration curves for five metal elements, Cr, Mn, Cu, Cd, and Pb under trace concentrations, have been obtained, and the limits of their detection were determined to be in the range of 0.029–0.59 mg L^− 1, 2–3 orders better than those obtained by directly analyzing liquid samples where the laser was focused on a liquid surface. The wood slice was very easy to handle and thus, the whole analysis process took only 4–5 min for each sample. This approach provides a more practical approach for fast and sensitive metal element analysis in aqueous solutions using LIBS, which is especially useful for monitoring toxic heavy metals in water.     

Emission enhancement using two orthogonal targets in double pulse laser-induced breakdown spectroscopy

The enhancement of emission intensity resulting from the interaction between two laser-induced plasmas on two orthogonal targets was investigated using double pulse laser-induced breakdown spectroscopy (LIBS) at 0.7 Pa, by means of time-resolved spectroscopy and fast photography. The results showed that the interaction between both plasmas improved carbon emission intensity in comparison to a single laser-induced plasma. For all the carbon lines of interest 477.2 nm (CI), 426.7 nm (CII), and 473.4 nm (C₂ Swan band head), the intensity enhancement showed a maximum at a delay between lasers in the range from 2 to 5 μs; moreover it increased with the fluence of the first laser. On the other hand, in the case of C₂ the intensity enhancement reached a maximum at 5 mm from the target; however it decreased with increasing fluence of the second laser. The largest intensity enhancement found was twofold for atomic species and sixfold for molecular species.     

Sampling statistics and considerations for single-shot analysis using laser-induced breakdown spectroscopy

A statistical analysis of single-shot spectral data is reported for laser-induced breakdown spectroscopy (LIBS). Fluctuations in both atomic emission and plasma continuum emission are investigated in concert for a homogenous gaseous flow, and fluctuations in plasma temperature are reported based on iron atomic emission in an aerosol-seeded flow. Threshold irradiance for plasma initiation and plasma absorption were investigated for pure gaseous and aerosol streams, with detailed statistical measurements performed as a function of pulse energy in the breakdown regime. The ratio of the analyte atomic emission intensity to the continuum emission intensity (peak/base) provided a robust signal for single-shot LIBS analysis. Moreover, at optimal temporal delay, the precision of the LIBS signal was maximized for pulse energies within the saturation regime with respect to plasma absorption of incident energy. Finally, single-shot temperature measurements were analyzed, leading to the conclusion that spatial variations in the plasma volume formation and subsequent plasma emission collection, play important roles in the overall shot-to-shot precision of the LIBS technique for gaseous and aerosol analysis.     

Laser-induced fluorescence detection of lead atoms in a laser-induced plasma: An experimental analytical optimization study

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 about 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.