Laser-induced breakdown spectroscopy (LIBS) is a type of atomic emission spectroscopy which uses a highly energetic laserpulse as the excitation source. The laser is focused to form a plasma, which atomizes and excites samples. The formation of the plasma only begins when the focused laser achieves a certain threshold for optical breakdown, which generally depends on the environment and the target material. In principle, LIBS can analyze any matter regardless of its physical state, be it solid, liquid or gas. Because all elements emit light of characteristic frequencies when excited to sufficiently high temperatures, LIBS can (in principle) detect all elements, limited only by the power of the laser as well as the sensitivity and wavelength range of the spectrograph & detector. If the constituents of a material to be analyzed are known, LIBS may be used to evaluate the relative abundance of each constituent element, or to monitor the presence of impurities. In practice, detection limits are a function of a) the plasma excitation temperature, b) the light collection window, and c) the line strength of the viewed transition. LIBS makes use of optical emission spectrometry and is to this extent very similar to arc/spark emission spectroscopy.
LIBS operates by focusing the laser onto a small area at the surface of the specimen; when the laser is discharged it ablates a very small amount of material, in the range of nanograms to picograms, which generates a plasma plume with temperatures in excess of 100,000 K. During data collection, typically after local thermodynamic equilibrium is established, plasma temperatures range from 5,000–20,000 K. At the high temperatures during the early plasma, the ablated material dissociates (breaks down) into excited ionic and atomic species. During this time, the plasma emits a continuum of radiation which does not contain any useful information about the species present, but within a very small timeframe the plasma expands at supersonic velocities and cools. At this point the characteristic atomic emission lines of the elements can be observed. The delay between the emission of continuum radiation and characteristic radiation is in the order of 10 µs, this is why it is necessary to temporally gate the detector.
LIBS can often be referred to as its alternative name: laser-induced plasma spectroscopy (LIPS). The term LIPS has alternative meanings that are outside the field of analytical spectroscopy, therefore the term LIBS is preferred.
LIBS is technically very similar to a number of other laser-based analytical techniques, sharing much of the same hardware. These techniques are the vibrational spectroscopic technique of Raman spectroscopy, and the fluorescence spectroscopic technique of laser-induced fluorescence (LIF). In fact devices are now being manufactured which combine these techniques in a single instrument, allowing the atomic, molecular and structural characterisation of a specimen as well as giving a deeper insight into physical properties.
Schematic of a LIBS system – Courtesy of US Army Research Laboratory
Because such a small amount of material is consumed during the LIBS process the technique is considered essentially non-destructive or minimally-destructive, and with an average power density of less than one watt radiated onto the specimen there is almost no specimen heating surrounding the ablation site. Due to the nature of this technique sample preparation is typically minimised to homogenisation or is often unnecessary where heterogeneity is to be investigated or where a specimen is known to be sufficiently homogeneous, this reduces the possibility of contamination during chemical preparation steps. One of the major advantages of the LIBS technique is its ability to depth profile a specimen by repeatedly discharging the laser in the same position, effectively going deeper into the specimen with each shot. This can also be applied to the removal of surface contamination, where the laser is discharged a number of times prior to the analysing shot. LIBS is also a very rapid technique giving results within seconds, making it particularly useful for high volume analyses or on-line industrial monitoring.
LIBS is an entirely optical technique, therefore it requires only optical access to the specimen. This is of major significance as fiber optics can be employed for remote analyses. And being an optical technique it is non-invasive, non-contact and can even be used as a stand-off analytical technique when coupled to appropriate telescopic apparatus. These attributes have significance for use in areas from hazardous environments to space exploration. Additionally LIBS systems can easily be coupled to an optical microscope for micro-sampling adding a new dimension of analytical flexibility.
With specialised optics or a mechanically positioned specimen stage the laser can be scanned over the surface of the specimen allowing spatially resolved chemical analysis and the creation of ‘elemental maps’. This is very significant as chemical imaging is becoming more important in all branches of science and technology.
Portable LIBS systems are more sensitive, faster and can detect a wider range of elements (particularly the light elements) than competing techniques such as portable x-ray fluorescence. And LIBS does not use ionizing radiation to excite the sample, which is both penetrating and potentially carcinogenic.
LIBS, like all other analytical techniques is not without limitations. It is subject to variation in the laser spark and resultant plasma which often limits reproducibility. The accuracy of LIBS measurements is typically better than 10% and precision is often better than 5%. The detection limits for LIBS vary from one element to the next depending on the specimen type and the experimental apparatus used. Even so, detection limits of 1 to 30 ppm by mass are not uncommon, but can range from >100 ppm to <1 ppm.
Courtesy of Wikipedia, the free encyclopedia