The development of fieldable laser-induced breakdown spectrometer: No limits on the horizon

In this review, new trends in the development of fieldable instrumentation based on laser-induced breakdown spectroscopy (LIBS) and its recent applications is presented. Depending on the LIBS configuration we will distinguish between portable, remote and stand-off instruments. Moreover, the development of portable systems gives greater flexibility and also increases the range of LIBS applications. In general, portable instruments are employed in close-contact applications like immovable artworks, contaminated soils and environmental diagnostic, while remote and stand-off instruments are normally used in analytical applications at distances where access to the sample is difficult or hazardous. Although remote and stand-off instruments are both used for chemical analysis at distances, the instrumental configurations are completely different. In remote analysis, an optical fiber is employed to deliver the laser energy a certain distance. This approach has been usually restricted to industrial applications, bulk analysis in water, geological measurements and chemical analysis on nuclear stations. In the case of stand-off applications, the laser beam and the returning plasma light are transmitted in an open-path configuration. In this article we also discuss the instrumental requirements in the design of remote and stand-off instruments.     

Design,construction and assessment of a field-deployable laser-induced breakdown spectrometer for remote elemental sensing

A field-deployable laser-induced breakdown spectrometer for measurements in the hundreds of meters range has been presented. The system is capable of elemental analysis with no previous preparation and in near real time, with the only requirement of a free line-of-sight between the instrument and the sample. Main factors influencing LIBS performance at stand-off distances are outlined. LIBS signal is shown to depend on range of analysis, peak power, beam quality, laser wavelength and optics dimensions. A careful control of focusing conditions has been shown to be of importance to avoid interferences from air breakdown by the stand-off focused beam.     

Laser-induced breakdown spectroscopy for space exploration applications: Influence of the ambient pressure on the calibration curves prepared from soil and clay samples

Recently, there has been an increasing interest in the laser-induced breakdown spectroscopy (LIBS) technique for stand-off detection of geological samples for use on landers and rovers to Mars, and for other space applications. For space missions, LIBS analysis capabilities must be investigated and instrumental development is required to take into account constraints such as size, weight, power and the effect of environmental atmosphere (pressure and ambient gas) on flight instrument performance. In this paper, we study the in-situ LIBS method at reduced pressure (7 Torr CO₂ to simulate the Martian atmosphere) and near vacuum (50 mTorr in air to begin to simulate the Moon or asteroids' pressure) as well as at atmospheric pressure in air (for Earth conditions and comparison). Here in-situ corresponds to distances on the order of 150 mm in contrast to stand-off analysis at distance of many meters. We show the influence of the ambient pressure on the calibration curves prepared from certified soil and clay pellets. In order to detect simultaneously all the elements commonly observed in terrestrial soils, we used an Echelle spectrograph. The results are discussed in terms of calibration curves, measurement precision, plasma light collection system efficiency and matrix effects.     

Use of the vacuum ultraviolet spectral region for laser-induced breakdown spectroscopy-based Martian geology and exploration

Several elements important to planetary geology (e.g. Br, C, Cl, P, S) and the human exploration of Mars (e.g. toxic elements such as As) have strong emission lines in the purge and vacuum ultraviolet (VUV) spectral region (100–200 nm). This spectral region has not been extensively studied for space applications using geological samples. We studied emissions from the laser-induced breakdown spectroscopy (LIBS) plasma in this region using a sample chamber filled with 7 torr (930 Pa) of CO₂ to simulate the Martian atmosphere. Pressures down to 0.02 torr were also used to evaluate the effect of the residual CO₂ on the spectra and to begin investigating the use of VUV-LIBS for airless bodies such as asteroids and the Moon. Spectra were recorded using a 0.3-m vacuum spectrometer with an intensified CCD (ICCD) camera. The effects of time delay and laser energy on LIBS detection at reduced pressure were examined. The effect of ambient CO₂ on the detection of C in soil was also evaluated. Lines useful for the spectrochemical analysis of As, Br, C, Cl, P, and S were determined and calibration curves were prepared for these elements. Although LIBS is being developed for stand-off analysis at many meters distance, the experiments reported here were aimed at in-situ (close-up) analysis.     

Laser-Induced Breakdown Spectroscopy for Mars surface analysis: capabilities at stand-off distances and detection of chlorine and sulfur elements

An international consortium is studying the feasibility of performing in situ geochemical analysis of Mars soils and rocks at stand-off distances up to several meters using the Laser-Induced Breakdown Spectroscopy (LIBS) technique. Stand-off analysis for Martian exploration imposes particular requirements on instrumentation, and it is necessary to first test the performance of such a system in the laboratory. In this paper, we test the capabilities of two different experimental setups. The first one is dedicated to the qualitative analysis of metals and rocks at distances between 3 and 12 m. With the second one, we have obtained quantitative results for aluminum alloys and developed a spectral database under Martian conditions for sulfur and chlorine, two elements that are geologically interesting but generally difficult to detect by LIBS under standard conditions (atmospheric pressure, close distance). These studies were carried out to determine an optimal instrumental design for in situ Mars analysis. The quality of analytical results affected by the optical elements and spectrometer has been particularly highlighted.     

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.     

Insights in the laser induced breakdown spectroscopy signal generation underwater using dual pulse excitation — Part II: Plasma emission intensity as a function of interpulse delay

Influence of time delay between two laser pulses on the LIBS (laser induced breakdown spectroscopy) signal inside liquids was investigated and the results are compared with data from literature. Plasma was produced by laser ablation (LA) of aluminum inside water and its emission after the second laser pulse was characterized by spectrally and time resolved detection. Light propagation through the vapor bubble formed by the first laser pulse was studied by measurements of beam scattering and transmission. Optical absorption by the evolving bubble is not significant, but its growth is accompanied by lowering of its refraction index n_b with respect to surrounding liquid; this effect increases defocusing both of the incident beam and of the out-coming plasma radiation. Collection efficiency of the secondary plasma emission rapidly degrades with the cavity growth, but close to its full expansion the LIBS signal partially recovers through Snell's reflections at the liquid–vapor interface, which produce a bright spot close to the bubble center. Such a light redistribution allows detecting of the emission from external plasma volume, otherwise deflected out of the collection system. Except for strong line transitions from the main sample constituents, self-absorbed inside the high-pressure cavity, we observed the highest LIBS signal when sending the second pulse well before the bubble is fully expanded. Transitions of the pressure wave through the focal volume, formed by the first laser pulse and reflected from the cell's walls and sample back-plane, enhances the LIBS signal importantly. The measured lifetime of the secondary plasma rapidly decreases with the bubble expansion. Here, we also discuss the optimization of the optical collection system and some analytical aspects of double-pulse (DP) LIBS inside liquids.     

Rapid in-situ analysis of liquid steel by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) denotes a technique where a pulsed laser beam is used to ablate small amounts of the target material. The characteristic optical emission line intensities of the excited species in the laser-generated plasma allow a quantitative chemical analysis of the target material. LIBS is a fast, non-contact method allowing large working distances between the sample under investigation and the detection system. These properties make LIBS applicable to process control in metallurgy. We describe an apparatus designed for rapid in-situ analysis of solid and molten metals at variable distances of up to 1.5 m. A variable lens system allows compensation for varying positions of the liquid steel surface. The LIBS signal is guided by a fiber optic bundle of 12-m length to the spectrometer. Analysis of an element's concentration takes 7 s. Laboratory experiments using an induction furnace showed that the addition of admixtures to liquid steel results in rapid response of the system. Results including the in-situ monitoring of Cr, Cu, Mn and Ni within certain concentration ranges are presented (Cr: 0.11–13.8 wt.%; Cu: 0.044–0.54 wt.%; Mn: 1.38–2.5 wt.%; Ni: 0.049–5.92 wt.%).     

Joint analyses by laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy at stand-off distances

Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS) of solid samples have both been shown to be feasible with sample-to-instrument distances of many meters. The two techniques are very useful together, as the combination of elemental compositions from LIBS and molecular vibrational information from Raman spectroscopy strongly complement each other. Remote LIBS and Raman spectroscopy spectra were taken together on a number of mineral samples including sulfates, carbonates and silicates at a distance of 8.3 m. The complementary nature of these spectra is highlighted and discussed. A factor of approximately 20 difference in intensity was observed between the brightest Raman line of calcite, at optimal laser power, and the brighter Ca I LIBS emission line measured with 55 mJ/pulse laser power. LIBS and Raman spectroscopy have several obstacles to devising a single instrument capable of both techniques. These include the differing spectral ranges and required detection sensitivity. The current state of technology in these areas is discussed.     

All-fiber-coupled laser-induced breakdown spectroscopy sensor for hazardous materials analysis

An all-fiber-coupled laser-induced breakdown spectroscopy (LIBS) sensor device is developed. A passively Q-switched Cr⁴⁺Nd³⁺:YAG microchip laser is amplified within an Yb fiber amplifier, thus generating high power laser pulses (pulse energy E_p = 0.8 mJ, wavelength λ = 1064 nm, repetition rate f_rep. = 5 kHz, pulse duration t_p = 1.2 ns). A passive (LMA) optical fiber is spliced to the active fiber of an Yb fiber amplifier for direct guiding of high power laser pulses to the sensor tip. In front of the sensor a plasma is generated on the surface to be analyzed. The plasma emission is collected by a set of optical fibers also integrated into the sensor tip. The spectrally resolved LIBS spectra are processed by application of principal component analysis (PCA) and analyzed together with the time-resolved spectra with neural networks. Such procedure allows accurate analysis of samples by LIBS even for materials with similar atomic composition. The system has been tested successfully during field measurements at the German Armed Forces test facility at Oberjettenberg.

The LIBS sensor is not restricted to anti-personnel mine detection but has also the potential to be suitable for analysis of bulk explosives and surface contaminations with explosives, e.g. for the detection of improvised explosive devices (IEDs).     

Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample.     

Evaluation of femtosecond LIBS for spectrochemical microanalysis of aluminium alloys

The analytical performance of femtosecond laser-induced breakdown spectroscopy (LIBS) for elemental microanalysis of aluminium alloys and for mapping precipitate distribution on the sample surface has been studied in detail. A Ti–sapphire laser system producing pulses of 130 fs at 800 nm was used to generate the laser-induced plasma. Multi-element microanalysis of commercially available aluminium alloys was performed in air at atmospheric pressure. Crater characteristics such as diameter and crater morphology were characterized by optical and scanning-electron microscopy. Scaling of plasma emission and limit of detection as a function of laser pulse energy was also investigated. Current experimental results are presented and are compared with previous nanosecond microLIBS measurements.     

The influence of laser-particle interaction in laser induced breakdown spectroscopy and laser ablation inductively coupled plasma spectrometry

Particles produced by previous laser shots may have significant influence on the analytical signal in laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma (LA-ICP) spectrometry if they remain close to the position of laser sampling. The effects of these particles on the laser-induced breakdown event are demonstrated in several ways. LIBS-experiments were conducted in an ablation cell at atmospheric conditions in argon or air applying a dual-pulse arrangement with orthogonal pre-pulse, i.e., plasma breakdown in a gas generated by a focussed laser beam parallel and close to the sample surface followed by a delayed crossing laser pulse in orthogonal direction which actually ablates material from the sample and produces the LIBS plasma. The optical emission of the LIBS plasma as well as the absorption of the pre-pulse laser was measured. In the presence of particles in the focus of the pre-pulse laser, the plasma breakdown is affected and more energy of the pre-pulse laser is absorbed than without particles. As a result, the analyte line emission from the LIBS plasma of the second laser is enhanced. It is assumed that the enhancement is not only due to an increase of mass ablated by the second laser but also to better atomization and excitation conditions favored by a reduced gas density in the pre-pulse plasma. Higher laser pulse frequencies increase the probability of particle-laser interaction and, therefore, reduce the shot-to-shot line intensity variation as compared to lower particle loadings in the cell. Additional experiments using an aerosol chamber were performed to further quantify the laser absorption by the plasma in dependence on time both with and without the presence of particles. The overall implication of laser-particle interactions for LIBS and LA-ICP-MS/OES are discussed.     

Calibration Measurements in laser-induced breakdown spectroscopy using nanosecond and picosecond lasers

The influence of laser pulse duration on laser-induced breakdown spectroscopy (LIBS) calibration curves is investigated in the present work. Two Nd:YAG lasers providing pulses of 35 ps and 5 ns, respectively, both operating at 1064 nm, have been used to create plasmas on aluminium, manganese, iron, and silicon targets and on prepared stoichiometric samples of these metals in a matrix. The time-resolved, space-averaged plasma temperatures have been deduced using Boltzmann plots, while the electron number density has been determined from the broadening of spectral lines. The effect of laser pulse duration on the plasma characteristics is discussed, and comparisons are made with previously reported data measured under similar experimental conditions. The optimum experimental conditions (i.e., time delay, gate width, laser energy) have been determined for reliable use of LIBS for quantitative analysis for both pulse durations. For each of the metals of interest, calibration curves have been constructed for concentrations ranging up to 2%.     

LIBS using dual- and ultra-short laser pulses

Pre-ablation dual-pulse LIBS enhancement data for copper, brass and steel using ns laser excitation are reported. Although large enhancements are observed for all samples, the magnitude of the enhancement is matrix dependent. Whereas all of the dual-pulse studies used ns laser excitation we see interesting effects when using ps and fs laser excitation for single-pulse LIBS. LIBS spectra of copper using 1.3 ps and 140 fs laser pulses show much lower background signals compared to ns pulse excitation. Also, the atomic emission decays much more rapidly with time. Because of relatively low backgrounds when using ps and fs pulses, non-gated detection of LIBS is shown to be very effective. The plasma dissipates quickly enough using ps and fs laser pulses, that high pulse rates, up to 1,000 Hz, are effective for increasing the LIBS signal, for a given measurement time. Finally, a simple near-collinear dual-pulse fiber-optic LIBS probe is shown to be useful for enhanced LIBS measurements.     

LIBS using dual- and ultra-short laser pulses

Pre-ablation dual-pulse LIBS enhancement data for copper, brass and steel using ns laser excitation are reported. Although large enhancements are observed for all samples, the magnitude of the enhancement is matrix dependent. Whereas all of the dual-pulse studies used ns laser excitation we see interesting effects when using ps and fs laser excitation for single-pulse LIBS. LIBS spectra of copper using 1.3 ps and 140 fs laser pulses show much lower background signals compared to ns pulse excitation. Also, the atomic emission decays much more rapidly with time. Because of relatively low backgrounds when using ps and fs pulses, non-gated detection of LIBS is shown to be very effective. The plasma dissipates quickly enough using ps and fs laser pulses, that high pulse rates, up to 1000 Hz, are effective for increasing the LIBS signal, for a given measurement time. Finally, a simple near-collinear dual-pulse fiber-optic LIBS probe is shown to be useful for enhanced LIBS measurements. Received: 1 August 2000 / Revised: 2 November 2000 / Accepted: 8 November 2000     

Evaluation of a compact spectrograph for in-situ and stand-off Laser-Induced Breakdown Spectroscopy analyses of geological samples on Mars missions

Laser-induced Breakdown Spectroscopy (LIBS) is actively under development for future use on surface probes to Mars. The analytical method can be deployed for in-situ and/or stand-off analysis with the latter embodiment providing the greatest advantages compared to previous and current elemental analysis methods used for planetary surface analysis. For this application, LIBS must be thoroughly investigated in terms of analytical capabilities and flight-rated instruments must be developed. Because of the low pressure of the predominantly CO₂ atmosphere on Mars, studies are needed to understand analytical requirements and to determine performance under these conditions. Stand-off analysis demands the most stringent requirements on instrumentation. Therefore, it must be determined if the high performance components that are normally used in a typical LIBS laboratory setup, which are generally not optimized for small size and weight, are essential to obtain the maximum scientific return from a mission. A key component of a LIBS apparatus is the detection system consisting of a spectrograph and a detector. Here we present an evaluation of one design of a compact spectrograph (Ocean Optics HR2000) for in-situ and stand-off LIBS analyses of geological samples under Mars atmospheric conditions.     

Influence of laser wavelength on LIBS diagnostics applied to the analysis of ancient bronzes

In this work the influence of laser wavelength upon the analytical results obtained from applying LIBS diagnostics to bronzes was investigated theoretically and experimentally at 1,064 nm and 355 nm. The laser ablation process was modeled for a set of reference samples of quaternary Cu/Sn/Pb/Zn alloys and the difference between plume composition and known target stoichiometry was estimated for both of the wavelengths considered. LIBS measurements were performed on the same set of reference samples and under the same experimental conditions to validate the model at different wavelengths. Results from the application of the model to calculate sample optical properties during laser irradiation, absorption in the plasma and plasma temperature are also presented.     

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.     

Laser-induced breakdown spectroscopy in water: Improvement of the detection threshold by signal processing

Laser-induced breakdown spectroscopy (LIBS) has been performed on immersed solid samples with different grades of surface roughness and material homogeneity and on bulk water solutions. The underwater plasma was produced by applying double-pulse excitation at 1064 nm, with different sets of laser pulse energies. LIBS spectra were recorded separately for each couple of laser pulses in order to monitor shot-to-shot plasma behavior and to apply signal post processing. The latter was aimed at improving the detection limits for elemental analyses. Except in the case of flat homogeneous solid samples at high laser pulse energies, the measurements were affected by strong shot-to-shot signal oscillations. Automatic elimination of low intensity spectra reduced the detection limit up to a factor of seven. The optimum level for spectral filtering depends strongly on sample properties. For bulk water, a poor correlation was observed between the peak line intensities and the plasma continuum emission, making the peak-to-background ratio unsuitable for internal standardization purposes. The analytical performance of LIBS for bulk liquid was also affected by the spatial fluctuations of the breakdown location, a phenomenon known as “moving breakdown” in the literature, which was responsible for the signal depletion in the detection region. In preliminary measurements on water solutions, the detection limit of 0.2 mg/l for magnesium has been obtained after applying data post processing.