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Laser-induced breakdown spectroscopy

Abstract

Laser-induced breakdown spectroscopy (LIBS) is an atomic optical-emission technique with the attractive characteristics of performing spectroscopic analysis ‘at a distance’, on an untreated sample and on very short timescales. Further advantages are high spatial resolution and microdestructivity; also LIBS can be performed on samples in the solid, liquid or gaseous state. All of these advantages arise from the use of a pulsed laser that both samples and excites the material under study, through the mechanism of laser ablation. However, analysis of the resulting optical-emission spectra is complex, and is probably the main reason that LIBS is only slowly being adopted as a viable analytical technique. Nevertheless, LIBS provides excellent elemental imaging, and is finding applications across a range of fields, including in industrial processes, environmental and biomedical analyses, geology and mining, and in cultural heritage. This Primer discusses the key points to consider before, during and after a LIBS measurement, to optimize the experimental conditions, acquire and analyse representative spectra, and properly communicate the results. The most promising current applications of LIBS are described, as are future directions for the development of LIBS that could make it an effective competitor to mainstream analytical techniques.

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Fig. 1: Experimental set-up for laser-induced breakdown spectroscopy.

Fig. 2: Baseline correction using a polynomial function.

Fig. 3: Deconvolution of a low-spectral-resolution spectrum from laser-induced breakdown spectroscopy using the Richardson–Lucy algorithm.

Fig. 4: High-resolution elemental images from laser-induced breakdown spectroscopy on breccia.

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Acknowledgements

I.A.U. acknowledges the financial support of the Scientific Grant Agency of the Slovak Republic (contract number VEGA-1/0803/21) and the Slovak Research and Development Agency (contract number APVV-22-0548). F.O.B. thanks the Comisión de Investigaciones Científicas de la Provincia de Buenos Aires for support.

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Authors and Affiliations

Applied and Laser Spectroscopy Laboratory, Institute of Chemistry of Organometallic Compounds, Research Area of CNR, Pisa, Italy

Vincenzo Palleschi, Stefano Legnaioli & Francesco Poggialini

Centro de Investigaciones Ópticas, La Plata, Argentina

Fausto Osvaldo Bredice

Department of Experimental Physics, Comenius University, Bratislava, Slovakia

Ivan Alexander Urbina

Quantum Electronics Laboratory, University of Science and Technology Houari Boumediene, Algiers, Algeria

Noura Lellouche

Center for Development of Advanced Technologies, Algiers, Algeria

Sabrina Messaoud Aberkane

Authors

Vincenzo Palleschi

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2. Stefano Legnaioli

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3. Francesco Poggialini

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4. Fausto Osvaldo Bredice

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5. Ivan Alexander Urbina

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6. Noura Lellouche

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7. Sabrina Messaoud Aberkane

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Contributions

Introduction (V.P.); Experimentation (F.O.B.); Results (N.L. and S.M.A.); Applications (S.L.); Reproducibility and data deposition (F.P.); Limitations and optimizations (I.A.U.); Outlook (V.P.); overview of the Primer (V.P.).

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Correspondence to Vincenzo Palleschi.

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Glossary

Breakdown

The mechanism that produces an electrical discharge in a non-conducting medium subject to a high electric field, such as the electric field of a high-power laser beam in atmosphere or in other gases.

Charge-coupled device

A solid-state photoelectric 2D detector that produces an electrical signal proportional to the number of photons striking the detector.

Cross-talk

An effect that can occur in laser-induced breakdown spectroscopy measurements, where the residual material from one pulse (ablated material particles or vapours) interacts with the subsequent laser pulse.

Dark current

Light detectors (photodiodes, photomultiplier, charge-coupled device cameras) generate small currents even in the absence of light: these ‘dark currents’ are indistinguishable from a real signal. Dark current increases with sensor temperature, and hence can be reduced by cooling the detector to temperatures close to zero degrees Celsius.

Electron continuum emission

In the early stages of plasma evolution, the temperature is very high and there are many free electrons that can be decelerated by interacting with ions in the plasma. This deceleration causes the emission of radiation with a continuum spectrum (free–free transitions). A further contribution to the continuum radiation comes from the capture of free electrons by ions (free–bound transitions).

Fluence

Defined as the laser-beam energy divided by the surface area of the laser beam spot at the focus and determines the ablation or breakdown thresholds. Fluence is usually expressed in units of J cm−2.

Instrumental broadening

The spectrometers and detectors used in laser-induced breakdown spectroscopy cause a broadening of spectral lines, which can be viewed as the convolution of the intrinsic broadening of the emission line and a Gaussian function of a characteristic width.

Intensified charge-coupled device

(ICCD). Realized by integrating an image intensifier with a charge-coupled device. The intensifier boosts the incoming light on the detector, enabling the detection of low-intensity signals. ICCDs are particularly useful for capturing signals within narrow time windows, down to the nanosecond scale — making them essential for analysing rapidly varying laser-induced breakdown spectroscopy signals.

Irradiance

Defined as the laser-pulse power divided by the surface area of the laser beam spot at the focus.

Laser ablation

The mechanism by which some minimal quantity of material is removed from the sample under the effect of a high-power laser beam.

Optical emission

Emission of radiation in the optical region, comprised from near ultraviolet to near infrared wavelengths. Hot material ablated and brought to the plasma state by a laser pulse is characterized by strong optical emission.

Plasma

Highly ionized gas in which the interactions between ions and electrons are dominant and determine its physical and chemical properties; also known as the fourth state of matter.

Stark effect

The fluctuating electric field generated by fast, free electrons around atoms and ions perturbs atomic energy levels and causes a broadening of emission lines. For most elements, the broadening is proportional to the electron number density; the proportionality factor is called the Stark coefficient.

Wavelet transform

Conceptually similar to the Fourier transform; whereas in a Fourier transform the signal (here, the laser-induced breakdown spectroscopy spectrum) is decomposed into a series of sines and cosines across the whole spectrum, in a wavelet transform, the decomposition is done using localized functions (called wavelets), which better fits the peaks in the spectrum.

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Palleschi, V., Legnaioli, S., Poggialini, F. et al. Laser-induced breakdown spectroscopy. Nat Rev Methods Primers 5, 17 (2025). https://doi.org/10.1038/s43586-025-00388-w

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Accepted:30 January 2025

Published:20 March 2025

DOI:https://doi.org/10.1038/s43586-025-00388-w

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