Article

Applied Spectroscopy
2018, Vol. 72(S1) 35–50
! The Author(s) 2018
Laser-Induced Breakdown Spectroscopy Article reuse guidelines:
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(LIBS): Fast, Effective, and Agile Leading DOI: 10.1177/0003702818791926
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Edge Analytical Technology

Javier Laserna, José M. Vadillo, and Pablo Purohit

Introduction Standoff LIBS

Laser-induced breakdown spectroscopy (LIBS) is currently Standoff LIBS refers to spectral measurements performed
considered one of the most active research areas in the while the laser beam and the return plasma emission travel
field of analytical spectroscopy. Over the years, scientists through an open path. Although this application was
and engineers have focused on the development of LIBS as a demonstrated in the early years of LIBS, the use of lasers
tool for chemical measurements, with significant efforts in with improved beam properties, detectors with gating cap-
developing new devices, methods, and data processing algo- abilities and tailored optical designs, has resulted in a new
rithms to improve the analytical performance of LIBS. In generation of LIBS systems of unprecedented performance.
combination with tailored excitation methods using multi- Standoff LIBS is strictly a line-of-sight technology, that is,
pulse, multiwavelength laser systems, substantial improve- the laser source and the sample must ‘‘see’’ each other. In
ments in detection power, representativeness, accuracy, the so-called coaxial systems, the path traveled by the laser
and sampling throughput have been achieved. beam and the return radiation is coincident, involving sev-
Development of LIBS instruments with extended capabil- eral tens meters in some instances. In this case, it is indis-
ities for energy delivery to the sample using ultrashort laser pensable to separate the two beams, for instance using a
pulses has been undertaken, which has permitted a better dichroic mirror. Since these optical components have lim-
understanding of the underlying issues of LIBS; notably, ited transmission in some regions of the spectrum, the cor-
laser interaction with matter, plasma dynamics, and proper- responding parts of the LIBS response are blocked. The
ties. As a result, LIBS has emerged as a powerful alternative path in biaxial setups is at variable angles and thus a separ-
for chemical analysis in a wide front of applications, from ation component for the two paths is not needed.
geological exploration to industrial inspection, from envir- However, this approach requires a careful alignment of
onmental monitoring to biomedical and forensic analysis, the optics elements when the target distance changes.
from cultural heritage to homeland security. Implementation of standoff LIBS requires the use of large-
While LIBS certainly has practical utility in many labora- scale optics such as telescopes of substantial aperture when
tory-based chemical measurements, the true potential of large distances are pursued, whereas the remainder instru-
this technology becomes apparent when it is used for appli- ment components are standard to a tabletop LIBS system.
cations inaccessible to more conventional analytical tech- Figure 1 shows the optical layout of a standoff system using
niques. Inspection of the elemental composition of distant a Cassegrain telescope.1 Although optical architectures
objects and LIBS analysis underwater solids constitute with refracting telescopes have been also used,2 most
examples of the exclusive capabilities of LIBS. Since detailed reported systems use reflecting optics. Large mirrors are
account of plasma fundamentals, instruments, methods and advantageous for this application as they are less costly than
applications of LIBS can be found in the extensive literature lenses of the same size and are free from chromatic aber-
on the topic, this viewpoint focuses on the key features that ration, whereas UV-enhanced aluminum mirrors provide
contributed to the influential, problem-solving character of excellent reflectivity from the UV to the NIR.
LIBS. We take the perspective of our own work in the field Standoff LIBS offers many advantages, among them
and discuss current achievements in standoff LIBS methods, the capability for the analysis of the elemental composition
underwater solids inspection, and single nanoparticle ana- of distant objects being of topmost importance. The
lysis. We then introduce the strategies used for improving
the detection power of LIBS and discuss the use of LIBS in
combination with other spectroscopic tools. Finally, we Departamento de Quı́mica Analı́tica, Universidad de Málaga, Málaga, Spain
identify challenges that merit further attention, by under-
Corresponding author:
lining some possible ways to solve the most common Javier Laserna, Departamento de Quı́mica Analı́tica, Universidad de
impediments for advancement of LIBS towards an enabling Málaga, Málaga, Spain
analytical technology. Email: [email protected]
36 Applied Spectroscopy 72(S1)

Figure 1. Optical layout of a standoff LIBS instrument using a Cassegrain telescope. (1) Diverging lens, (2) converging lens, (03)
dichroic mirror, (4) primary mirror, (5) secondary mirror, (6) flip mirror, (7) folding mirror, (8) optical fiber, and (9) CCD. Reprinted
from Laserna et al.1 with permission from The Optical Society of America.

distinctive character of standoff LIBS is that this method According to the ChemCam team:12 no sample prepar-
allows chemical measurements in extreme environments ation, analysis within the sample petrological context,
not approachable by regular laboratory technologies. dust removal, sub-millimeter scale investigation, multipoint
Examples of applications are industrial production lines,3–5 analysis, the ability to carry out statistical surveys, whole-
urban scenarios6,7 and remote field operations.8,9 rock analyses, and rapid data acquisition. The satisfactory
One of the most successful demonstrations of the cap- system performance in the context of the limited capabil-
abilities of standoff LIBS is the ChemCam instrument of the ities of time-integrated detectors as those used in
Mars Science Laboratory (MSL) deployed and operating on ChemCam, the inherent difficulties in handling a robotized
the red planet since 2012. With the difficulties of a working instrument from Earth with a largely delayed response
temperature often below 0  C and an atmosphere of carbon because of the large distance, together with the changing
dioxide at 10 torr in the presence of strong solar radiation, conditions of the rover surroundings, including the inher-
the MSL rover uses standoff LIBS to measure the atomic ently dusty and harsh Mars environment, and finally the
composition of rocks and soils at distances from 2 to 7 m, unavoidable sample effects derived from variable surface
using an 15 mJ per pulse laser source and a set of miniature texture and grain size, constitute an extraordinary demon-
spectrometers fitted with unintensified CCD detectors. stration of instrumental maturity. ChemCam is now close
Compared to measurements in a laboratory on Earth, the to 550 000 laser shots on Mars.13
ChemCam instrument faces an additional number of chal- In closed ranges, the analytical performance of standoff
lenges, some of them difficult to predict. For instance, solar LIBS at short distances has been demonstrated to follow
absorption lines on Mars make it difficult the processing of closely that of laboratory measurements. However, as the
hydrogen lines. The spectral background level is variable distance to the target increases, significant effects caused by
because the target albedo changes slightly after each laser atmospheric turbulence on the outgoing laser beam and on
shot. As a result, the quantitative treatment of intensities the atomic emission signal return have been observed. On a
needs careful treatment and refinement. Apart from the microscopic scale, turbulent eddies of variable size and dur-
effects associated to the propagation of light beams through ation, from seconds to minutes, are formed in the atmos-
the atmosphere discussed below, the LIBS signal dependence phere. These currents lead to small temperature gradients
with the target distance defies the comparison of data that cause micro fluctuations in the atmosphere’s refractive
derived from variable observation ranges. Several methods index. As a result, three different phenomena affect the
of limited success to correct for the distance effect have laser beam, namely beam wandering, beam spreading, and
been attempted.10,11 In essence, the methods use calibration scintillation. Beam wandering refers to random variations
curves from a set of spectral variables derived from dust in the position of the beam centroid of the laser pulses
measurements of many Martian targets and the average on the distant target caused by large turbulent eddies,
behavior of a large suite of laboratory standards. Using par- whereas beam spreading is the distortion of the wave
tial least square tests in combination with multivariate cali- front in the laser pulse, usually due to micro eddies in the
bration, the method yields an improved agreement between beam path. Scintillation is a fluctuation in the irradiance at
ChemCam spectral intensities of the same target obtained at the central beam position. Figure 2 shows the effect caused
variable distances. The success of the method is heavily by these phenomena as noticed in the imprints left on a
dependent on the number of spectral lines considered and target placed at 120 m.1 When a single laser shot is deliv-
only works properly for the range of distances tested. ered to the sample as in Fig. 2a, the originally Gaussian
The capabilities of the ChemCam sensor in operation on beam is noticeably distorted showing hot spots and areas
Mars constitute an archetype of the advantages of LIBS. of null radiation. Subsequent laser shots result in
Laserna et al. 37

Figure 2. Imprints left on an aluminum target by a Gaussian Nd:YAG laser focused at 120 m after (a) 1 shot, (b) 20 shots, (c) 100 shots,
and (d) 1000 shots. Reprinted from Laserna et al.1 with permission from The Optical Society of America.

increasingly larger imprints as observed in Fig. 2b–d as a vaporization of the surrounding liquid follow thus causing
result of beam wandering. These effects are magnified in the the formation of an expanding cavitation bubble. This
presence of adverse weather conditions such as windy or bubble contains a dense particle cloud and vapors from
high temperature environments, where extensive gradients the solid sample. The emitting material in the plasma is
in the index of refraction of air often occur. irregularly distributed and shows very weak emission
These phenomena affect in a larger extent to beams except for a thin layer near the original surface. The
propagating parallel and close to the ground as is the case plasma exhibits an intense continuum and broadened
in many standoff LIBS experiments. When the analyte of lines, which are of little use for analytical purposes. The
interest is homogeneously distributed across the surface bubble front moves towards the bulk liquid until the pres-
inspected or when the sample is a massive pure material, sure exerted by the surrounding liquid stops the expansion.
beam wander tends to average the responses of the The second phase involves the collapse of the cavitation
sampled area, which is favorable for the identification pur- bubble and the re-excitation of the ablated material to
poses or for a quantitative treatment of the signal. For result in a second expanding front. Formation of this sec-
heterogeneous materials, though, increasing the signal-to- ondary plasma has been explained by complex interaction
noise ratio (SNR) by ensemble averaging the signal from of the hot plasma front with the surroundings, which leads
multiple laser shots is adversely affected by beam wander to the propagation of a high temperature and high pressure
as every laser shot may be hitting a position of different region back to the target.16 This second plasma is charac-
composition. The problem gets more severe as the distance terized by a lower electron number density and a much
and turbulence increase. Beam spreading and scintillation lower continuum emission, and is consequently useful for
induce increased intensity fluctuations by changing the analytical purposes. The sequence of events has been docu-
irradiance at the target. A fourfold increase in the uncer- mented in a recent report17 and is presented in Figure 3.
tainty has been observed when increasing the target dis- A collinear second pulse has been used to excite the
tance from 35 m to 90 m.14 When considering the return material inside the bubble. This material is in form of nano-
emission radiation, a plasma moving on the target as a particles, which tend, from one side, to shield the surface
result of beam wander will cause changes in the image pos- from the incoming beam, but favors evaporation and exci-
ition of the plasma on the telescope focal plane by changing tation to emitting states due to its smaller energy demand.
the angle of arrival on the receiving optics. Although this The role of nanoparticles is complex and not yet fully
effect may change the magnitude and the noise level of the understood, however a significant enhancement of the ana-
observed signal, the imaging capabilities of telescopes tend lytical signal is observed after the second pulse.18
to reduce the scale of the effect.15 The progression of events observed in underwater LIBS
using single or double pulses depends to a large extent
on the interplay of several experimental variables, especially
LIBS of Underwater Solids the absolute and relative energy of the laser pulses and the
The study of laser induced plasmas of solids submerged in sequencing of the energy delivery. Formation of the cavita-
water constitutes an area of broad interest as the simple tion bubble requires usually a lower energy than the exci-
but unique operation of LIBS permits the chemical analysis tation of the secondary plasma, whereas the delayed
of materials in challenging environments such as the sea second pulse produces the best signal-to-background
bed. A single ns laser shot induces a series of complex ratio from several tens microseconds to a few hundred
processes involving the sample and the surrounding microseconds, depending on the pulse energies delivered
water, which proceed typically in two phases. After to the sample. Observation of the analytical signal requires
plasma ignition, emission of strong shock waves and a further set of instrumental settings so that the whole
38 Applied Spectroscopy 72(S1)

Figure 3. Superimposed images of plasma photography (false colour) and shadowgraphy of an aluminum target inside water.
The acquisition delay (ms) with respect to the laser pulse is reported on each photograph. Reprinted from Lazic et al.15 with permission
from Elsevier.

experiment entails a very careful selection of parameters to instrument is preserved. This approach has been used for
result in consistent and comparable results with other inspection of shipwrecks of archeological interest.22,23
measurements. Figure 4 shows pictures of a survey in the Mediterranean
Significant gains in signal quality can be achieved for Sea to identify and sort the materials found in the wreck.
metals, rocks and sediments submerged in water if lasers The unique capability of LIBS for the chemical analysis of
of long-pulse duration are used.19 An increase of hydro- submerged solids is of great interest to basic science and
static pressure up to 30 MPa (300 atm) does not have a to tackle the challenges of extreme measurements such as
significant influence on the quality of the observed spectra. in situ assessment of corrosion in line pipes, evaluation
In this approach, the energy of the pulse is only of a few of underwater steel and concrete structures, identification
tens mJ, whereas the pulse length may be as long as 250 ms. of unknown objects, and exploration of deep-sea mineral
Self-absorption reduces the observed intensity of the emis- resources. In the harsh environment existing in aquatic
sion lines and becomes more evident as the ablated mass masses, the measurement precision is determined by extra-
increases. Preferential evaporation of elements has shown neous circumstances, beyond the capacity of LIBS technol-
to have no influence on the quantitative analysis of brass ogy, ultimately by currents, water turbidity, and by the
samples submerged in water.20 presence of sediments, concretion layers and algal deposits
Single or multiple laser pulses can be used to acquire on the materials. In deep waters, some of these factors are
improved spectra if an air purge at the solid surface absent. Nevertheless, even in this case, the ability to keep
removes the water layer close to the sample. The complex- the laser irradiance-dependent LIBS signal within the data
ity associated to the cavitation bubble and to the successive quality objectives of the measurement constitutes a most
expansions and contractions of the ablated material is thus difficult challenge.
circumvented. Furthermore, particulate matter and bubbles
resulting from previous ablation events are flushed away LIBS for the Analysis of Particulate Matter:
from the light path, thus avoiding potential sources of meas-
urement uncertainty. This solution, pioneered by Beddows
From Aerosols to Single Nanoparticles
et al., 21 has been utilized in combination with fiber optics Since early development stages, the scarce amount of
beam delivery for inspection of archeological materials in sample required to perform LIBS analysis has been high-
coastal waters.22,23 A handheld probe was operated under- lighted as one of the major advantages of the technology.24
water and connected to a surface LIBS instrument by an In fact, nowadays, characterization of masses in the nano
umbilical cable containing the optical fiber and the com- and femtogram range has become routine in LIBS labora-
pressed air tubing. The probe contains the optics needed tories.25,26 This feature, combined with simultaneous multi-
for laser beam focusing and plasma light collection. Apart element detection, makes LIBS a strong asset for nanoin-
from removing water from the sample surface, the air spection, turning the field of single particle studies a topic of
supply maintains a positive purging and prevents the admit- continuously increasing interest. Although some prelimin-
tance of seawater to the interior of the probe. Interestingly, ary uses of high power laser sources for chemical charac-
the jet of compressed air does not degrade the signal terization of airborne material date from 1979,27 the first
repeatability and thus the performance of the LIBS ad hoc steps of LIBS for the analysis of particulate matter
Laserna et al. 39

hand, it is necessary to direct the reader’s attention

toward the relative standard deviations (RSDs) reported
in Radziemski et al.,28 with results ranging from 10% Na
to 30% Be, which the authors attributed to possible
inhomogeneity of the samples under evaluation. In fact,
the size and, subsequently, the mass distribution of the par-
ticles are the major sources of uncertainty in aerosol
experiments, and RSD values in this range are still
common in LIBS for particulate matter analysis, despite
the use of improved experimental setups and sampling
schemes. The efficiency of particle atomization in laser-
induced plasmas, intimately tied to particle size, ultimately
governs the number of atoms available for excitation to
emitting levels. This is briefly discussed in Cremers
et al.,29 but it was not until some years later that this crucial
concept of the dual role played by the sampling laser, ser-
ving at the same time as a source of particle atomization
and as an excitation source, was thoroughly explored.
Hahn and co-workers paved the way towards single par-
ticle LIBS in a series of works covering fundamental aspects
of the particle–plasma interaction. Guidelines for condi-
tional data analysis are provided in order to improve the
sampling rates in aerosol LIBS based on the number of real
hits, i.e., recorded plasma events containing sample infor-
mation, when analyzing airborne particles.30 This approach
prevents analyte signals from being diluted in the averaging
process, widely used for treatment of aerosol data bulks
frequently consisting in hundreds to thousands LIBS spec-
tra, by discarding those results corresponding to plasmas
formed in absence of particles, thus only featuring back-
ground or signals originating from air ionized by the laser
pulse. Conditional analysis has played a major part in the
successful implementation of LIBS for standoff analysis of
aerosols in industrial environments,31 one of the main goals
Figure 4. (a) Photographic detail of the structure of the ship- behind the inception of this application, and, more pertin-
wreck, and (b) diver operating the LIBS probe. ent to this subsection, the quantitative analysis of discrete
aerosol particles.32
Size threshold for complete particle dissociation was
can be traced back to the publication by Radziemski et al. in among the first questions encompassed in single particle
1983.28 In this work, the authors introduced the use of LIBS LIBS (SP-LIBS) as it marks the limit from which particles
for in situ direct detection of aerosols in ambient air. Limits cannot be reliably quantified.33 Further work by different
of detection (LODs) were established for Na, P, As, Hg, and authors explored the complete dissociation threshold for a
Be in air, the latter being 0.6 ng per gram of air. Several variety of samples such as glucose and NaHCO3.34
remarkable conclusions, which served as stepping-stones Providing a general threshold value or a compilation related
for the development of the research topic during the to particle composition are ambitious, if not unfeasible,
1990s, could be drawn from this paper. The work show- tasks since the number of parameters that must be stan-
cased the adaptability of LIBS to off-lab scenarios, an unfeas- dardized may well be exceedingly large. Hence, only illus-
ible situation for well-established analytical techniques such trative ranges35 can be used to direct new experimental
as inductively coupled plasma–optical emission spectros- work, hampering the establishment of LIBS as a robust
copy (ICP-OES), and the low absolute LODs accessible to tool for real time and in situ quantitative analysis of
LIBS, despite having rather high concentration LODs usu- aerosols.
ally in the order of ppm. Absolute LODs are the main When it comes to single particle analysis, unambiguous
analytical figure of merit reported in Cremers et al.,29 attribution of spectra to single entities becomes a chimera
where Cl and F were detected in air with minimum that researchers must tame, the sooner the better. Imaging
masses of 80 ng and 2 mg, respectively. On the other of particle plasmas can be of great help in tying the emission
40 Applied Spectroscopy 72(S1)

charged particles, which are attracted to the center of

the balance. The mass of the trappable particles may be
discriminated by adjusting the AC field. Tuning of the elec-
tric field also allows for particle manipulation and precise
positioning regarding focus of the sampling laser, ensuring
particle interception at maximum energy density and, sub-
sequently, under optimum dissociation and excitation con-
ditions. Aqueous aerosol particles diffused into the EDB
and dried upon trapping, forming spherical particles with
sizes ranging between 1 and 20 mm of salts dissolved in the
nebulized solution. Solutes are subsequently pre-concen-
trated in the dry droplets. This, besides the good particle
size repeatability, largely contributing to reduced RDS
values, resulted in LODs that are rarely, if ever, seen in
LIBS. To name a few examples, the LOD of 60 parts per
billion (ppb) was calculated for Ni and Pb, and 50 ppb for
Zn.37 EDB-LIBS has been proved as a robust method for
characterizing single microparticles: yet, its applicability to
Figure 5. Time- and wavelength-resolved plasma imaging sub-mm or nanometric particles has not been demon-
showing a borosilicate glass particle engulfed by the plasma as it strated, leaving a highly important territory to be explored.
dissociates and its components diffuse in the laser-produced
Moreover, the implementation of EDB-LIBS to routine in
plasma. Reprinted from Hohreiter and Hahn36 with permission
situ analysis looks complicated, given the chamber and
from the American Chemical Society.
experimental configuration required for it to yield its full
potential.
The second pathway merged LIBS with optical catapult-
to its source.36 Figure 5 depicts the temporal evolution of a ing (OC) and optical trapping (OT) resulting in OC-OT-
plasma that engulfed a single borosilicate microparticle in LIBS, first introduced in 2014.40 This combination allowed
the peripheral area. Particle dissociation and diffusion of its SP-LIBS to work directly on powdered solid samples, avoid-
components through the plasma cloud is clearly indicated ing particle suspension in aqueous media prior to analysis.
by intensity distribution. These images are among the most OC was used to put the sample in solid aerosol state by
crucial results reported in particle-LIBS since they also pro- ejection from its support mediated by a laser-produced
vide a basis for discussing mechanisms leading to particle shockwave. Then, particles were optically trapped in the
dissociation and excitation, and illustrate the greater rele- focal region of a tightly focused continuous wave (CW)
vance of plasma–particle interaction as opposed to pulse– laser, where an electromagnetic force, known as the gradi-
particle interaction, as further remarked in Figure 6. While ent force, attracts the particles to the peak intensity of the
plasma imaging can be of great help in assessing the ques- radiation and confines them to a small volume by overcom-
tion posed earlier in this paragraph and in the fundamental ing the repulsive extinction forces, i.e., scattering and
aspects of SP-LIBS, it is not exempt of drawbacks. Namely, absorption. Once a single particle is trapped (and the aero-
it can only be used after the sample has been probed, sol relaxed), a single shot LIBS spectrum can be recorded.
implying that a particle cluster cannot be discarded before- Additionally, the authors developed a calibration scheme to
hand, and, specifically for single particles, it is limited to relate the net signal recorded to the number of photons
relatively large particle sizes (1–2 mm), as smaller ones produced by particles, therefore evaluating the excitation
are not likely to produce enough light to be discriminated efficiency. Figure 7 sums up the most relevant results
from the air plasma. Therefore, complementary pre-LIBS reported so far using OC-OT-LIBS, i.e., successful direct
diagnostic approaches are required to verify the presence detection and characterization of sub-100 nm single Cu par-
of single particles, expand the size range of application ticles,41 with the smallest particle size being 25 nm in diam-
while maintaining or improving aerosol sampling rates; eter, equivalent to a mass of 73 ag. An absolute LOD of
ultimately, to allow SP-LIBS to delve into the nanoworld. approximately 59 ag was estimated for Cu, a limit never
It is indeed in this field that the great synergy LIBS has come been reported before by an optical emission technique. The
in handy. photon yield shows that the excitation efficiency increases
Notably, two different combinations have been evaluated as the particle size decreases.40–42 This behavior has been
as platforms to stably isolate, hold and recognize single proposed as the reason behind the extreme sensitivity of
particles before LIBS studies. The first of them is the elec- this approach.
trodynamic balance (EDB).37–39 The EDB makes use of a The above examples prove that LIBS can already be con-
superposition of DC and AC electric fields to levitate sidered as a suitable tool for single particle characterization
Laserna et al. 41

Figure 6. Characteristic time,  crit, delimiting direct laser-particle interaction deduced from pulse irradiation–plasma ignition threshold
comparison.39

Pushing the Sensitivity of LIBS

Analytical techniques are subject to the constant examin-
ation of their detection power and LIBS it is not an excep-
tion. It seems clear that in direct solid analysis techniques it
is more difficult to cope with a criteria to determine the
sensitivity if we compare them with classic wet chemistry
techniques. However, it is important not to fall in the mis-
take of comparing trace analysis and microanalysis.43 What
can be said beyond any reasonable doubt is that LIBS may
routinely achieve absolute detection limits in the femto-
gram range with a single pulse vaporizing low ng of sample.
Laser-induced breakdown spectroscopy researchers
Figure 7. Correlation between averaged single Cu nanoparticle must face the physical barriers associated to perform bulk
LIBS signal and particle mass (straight line). Absolute photon sub-micrometric characterization and compositional ana-
production per mass unit for each particle size is shown by the lyses. The primary impediment relies on the minimum
dashed line. Typical examples of averaged single particle spectra laser fluence (fluence threshold, Fth) required to generate
are provided in the inset. Reprinted from Purohit et al.41 with a detectable optical emission of the analyte. In the process
permission from John Wiley and Sons, Inc. of generating laser pulse energies sufficient to overcome
the excitation and ionization thresholds of the sample,
the process also leads to the removal of unexcited ablated
and nanoinspection. Moreover, it has an exciting near future material. Despite the considerable advances in fundamental
ahead, as the gates to the restricted field of cutting-edge physics of laser plasmas and the understanding of the phe-
nanomaterial analysis have just been merely opened and a nomena occurring during its expansion, one cannot predict
long path ahead can be predicted. the amount of mass that will be ablated, the mass fraction
42 Applied Spectroscopy 72(S1)

efficient generation of particles of small diameter that are

efficiently atomized in the second step. At gentle LIBS con-
ditions, the population of aerosols is shifted to diam-
eters < 1 mm, that may experience complete atomization
by a secondary source, yielding more free atoms and ions
for LIBS analysis.46 Further work related to the population
of laser-induced nanoparticles as a function of experimental
conditions must be conducted in the future, as such basic
knowledge will elucidate the reasons of the behavior of the
laser plasma and its analytical performance. This is an inter-
disciplinary work that demands a shift of knowledge from
spectroscopy moving away from spectroscopy to aerosols
science and related areas. New generation mobility ana-
lyzers with the capability to filter and count nanoparticles
from streams could be helpful in the understanding of all
the particle-release related processes.
A second body of experimental approaches involves
excitation of the vapor phase or of the particles induced
by the ablation pulse with sources other than a laser. The
most common approaches are based on excitation with
high-voltage electrical pulses (Figure 8e),47 microwave cav-
Figure 8. Sketch of different approaches to enhance the LIBS ities (Figure 8f),48 or glow-discharges (Figure 8g).49 In the
signal. (a) Collinear double pulse, (b) convergent double pulse, (c) latter two situations, there is a need of a plasmogen gas (Ar
reheated double pulse, (d) pre-pulse double pulse, (e) spark/arc
or He) to support the secondary plasma. In all cases, excel-
assisted, (f) microwave assisted, (g) glow-discharge assisted, and
lent improvements in sensitivity have been found. Again, it
(h) nanoparticle enhanced.
is difficult to establish a common ground between them due
to differences in the experimental set-ups, the excitation
transformed into gas-phase, the size distribution of par- laser or the sample used. However, it seems evident in all
ticles in the ablated mass (also considering the tiny particles situations that the decoupling of the material sampling
generated by nucleation or condensation from the gas induced by the ablation laser from the re-excitation of
phase), the percentage of free atoms and ions per unit of the ablated material improves and stabilizes the signal,
ablated mass, and the percentage of atoms excited to dif- making it less dependent on the matrix. Another important
ferent electronic levels. Despite these unknown answers issue is the increase in the persistence of the emission,
affecting the quantitative aspects of the technique—a wide- which allows the acquisition of signals at longer delays,
spread problem in surface analysis techniques—experimen- reducing the need of fast-gating detectors.50
tal work in LIBS shows that: (a) the atomization efficiency is The modification of the ablation surface with the cover-
low, and (b) the particle distribution of the ablated mass is age with metallic nanoparticles (so-called nanoparticle-
wide and affected by the ablation conditions. enhanced LIBS, or NE-LIBS) is a simple but quite efficient
There has been a wide interest to enhance the LIBS way of improving the analytical signal in LIBS without modi-
detection power by different methods.44 The most success- fication of the experimental set-up or introduction of sec-
ful approach involves excitation with a secondary plasma. ondary sources.51 Enhancement factors up to two orders
Thus, double-laser pulse schemes, excitation with micro- of magnitude in conductors has been reported, together
waves plasmas, sparks/arcs, glow-discharges, or modifica- with a clear improvement in the reproducibility. NE-LIBS
tions in the interrogated surface (Figure 8) are found in is a topic where further development in understanding its
the literature with significant success. In general, all of fundamentals is definitely warranted, and where a significant
them operate by improving the atomization of the particu- number of applications are expected in the near future.
late matter induced in LIBS, if the LIBS conditions do not
generate large particles, which would point at fragmentary
and incomplete evaporation. Strategies based on double
Fusion with LIBS
pulse excitation are commonly found in the literature The information contained in a LIBS spectrum is mostly
(Figure 8a–d) with different combinations of operating par- elemental since the emission process derives from the
ameters such as wavelength, pulse width and fluence range, relaxation of the valence electrons promoted to higher
making difficult to standardize the results. The so-called electronic states. As in other atomic emission spectro-
pre-pulse approach (Figure 8d) has shown excellent scopic techniques, molecular information in LIBS is limited
results.45 The reason seems to be related to a more to the presence of emitting diatomic species. Such
Laserna et al. 43

Figure 9. Gating strategy required to obtain Raman spectra from a laser pulse. Under energy conditions above the plasma formation
threshold, the temporal window allowing the recording of the scattered photons is confined to the first nanoseconds before the onset
of a phase-change occurring in the sample surface.

discriminant capabilities. The synergistic effect in the

sequential or simultaneous combination of two or more
analytical systems has been largely exploited in applied
spectroscopy. The success in the approach relies on the
degree of orthogonality between the techniques used.52
Between the surface laser spectroscopy approaches, the
combination of LIBS and Raman spectroscopy represents
a solid marriage that warrants further exploitation. As
pointed out in Wiens et al.,53 both techniques make use
of similar high-intensity laser beams and use spectrographs
to disperse the signal over overlapping spectral ranges.
Importantly, both techniques may record the signals over
a similar time-scale, can be used in close vicinity or in stand-
off configurations, and are fully orthogonal in the chemical
information provided. Thus, while LIBS provides detailed
information on elemental composition, Raman offers the
power associated to molecular (vibrational) spectra. The
Figure 10. Spatially localized strategy required to obtain Raman
combination of both sources of information in a single
spectra from a laser pulse. Considering a laser pulse with a
instrument allows much more complete identification of
Gaussian distribution of energy along its radial axis, the periphery
will be more suitable for the collection of scattered photons. samples than with only one technique. The potential of
the happy marriage between LIBS and Raman has been
explored several times in the literature, although it can
be said without doubt that the decisive demonstration
information is not very relevant from a structural point of came with homeland security applications54 and geochem-
view in the case of metals or inorganic compounds. ical research. In the latter one, the research has ended up
However, the presence of species as CH, OH, NH, CN, with the developing of a prototype that will be integrated in
and C2 owns relevance in LIBS of organics. This importance the SuperCam instrument in the next Mars 2020 mission.55
is twofold: first, the species are indicative of the presence of Aside from discussions about the power of the LIBS-Raman
species-specific bonds in the native molecule, and second, combination, there are still some open questions about the
they are by-products derived from the arrangement of free right experimental configuration to be used that should be
atoms present in the reaction volume, where the con- clarified in the near future. On top of complexity, a two-
course of the ambient molecules plays a significant role. lasers (CW þ pulsed) approach for the excitation and two
The addition of a second analysis method (in a simultan- independent detectors for Raman and LIBS represents the
eous or consecutive arrangement) providing molecular best way to obtain higher performances, with the under-
information represents an advantage that levels up the standing that both approaches can be independently
44 Applied Spectroscopy 72(S1)

Figure 11. Experimental set-up for a simultaneous ion-photon collection. The plasma expands to the reader, while ions are pushed
away to the right by means of an electrical pulse and analyzed using a TOF mass spectrometer. The photons are collected by means of a
fiber optic outside the vacuum chamber. The iCCD and the transient recorder are synchronized by the laser.

optimized. Such excitation and detection scheme has been thermal-induced effects are expected.57 However, add-
used by Hoehse et al.56 in combination with a double-arm itional work is required to test that effect in different
echelle spectrograph, demonstrating to be competitive in samples.
sensitivity and resolution to top-ranked commercial grating An approach for coincident Raman-LIBS acquisition
instruments. Simplifying the set-up by using a single-excita- without the need of precise detector gating sequence con-
tion source is also feasible. In this case, the main concern is sists of taking advantage of the radial distribution of the
keeping the irradiance under the required values for each laser irradiance profile on the sample. Thus, the collection
excitation mode. The laser irradiance required for Raman is of the scattered or emitted photons from specific regions
much lower than that for LIBS, as the plasma formation of the excited surface (Figure 10) allows the simultaneous
threshold does not have to be reached (Figure 9, left acquisition of the atomic or molecular information if the
panel), something incompatible with LIBS, which clearly collection device can be precisely offset spatially. In con-
requires plasma formation. Thus, simultaneous Raman- secutive pulses on the same surface, the effect of the geom-
LIBS spectra from identical laser events can just be rec- etry of the generated crater must be accounted for, as the
orded using two different detectors with tailored gating. scattering signal from the periphery will be compromised
For Raman, the scattered photons will be collected at by the Gaussian shape. This spatially resolved approach has
times earlier than the starting of plasma formation (Figure been successfully demonstrated,58 allowing single-pulse rec-
9, right panel). Such approach implies limiting the integra- ording of Raman, LIBS, and even Raman-LIBS signals.
tion time to a few nanoseconds, compromising the quality Differential Raman or LIBS spectra making use of the irradi-
of the Raman spectra recorded. Under practical situations, ance gradient along the radial axis of the incoming front of
where data with a satisfactory SNR are required, the work- the laser beam has also been recently reported for the
flow implies the acquisition of N successive low-fluence surveillance of Mars mineralogy. 59
spectra to obtain the Raman spectra from the specific From our perspective, the Raman-LIBS fusion approach
zone, followed by the required LIBS spectra with the is clearly a trend exhibiting impressive capabilities. The
laser energy adjusted to higher fluences. An interesting hyphenated LIBS–Raman instrument has the potential to
question arises at this point: how will the accumulative become an important field tool for a full atomic/molecular
laser energy dose (fluence) for Raman affect the sample screening of any sample and matrix in any ambient con-
for the subsequent LIBS analysis? For micron-size silicates text. Further improvements are expected to combine
expected to be analyzed in the Mars 2020 mission, no these two techniques into a single instrument with small
Laserna et al. 45

Figure 12. Single-shot spectra of DNT recorded in a pulse-paired fashion using a first low-fluence pulse to record the mass spectra,
followed by a second pulse at larger energy for the LIBS spectra. Both spectra were recorded in vacuum at 10–6 mbar with 266 nm
excitation.

size, low mass, low power consumption, and low trans- controlling the energy dose required to get excellent non-
portation with in-field capabilities. Expanded spectral can destructive Raman analysis on a selected sample location
be obtained with arrays of monolithic monochromators/ prior to a LIBS analysis on the same location. The option
detectors. A variable attenuator provides the option of of laser fiber delivery opens the door for new unexplored
46 Applied Spectroscopy 72(S1)

The merging of LIBS and LIMS can be easily done

through viewports with direct optical access to the
sample or by fiber optic feedthroughs (Figure 11). In both
situations, the direct light from the laser plasmas can be
recorded out of the vacuum chamber. The addition of a
TOF-MS analyzer in a concurrent/simultaneous detection
scheme adds a second orthogonal dimension to the infor-
mation gathered by LIBS, as well as the additional informa-
tion provided by the isotopic capabilities.
As in the Raman-LIBS approach, the undoubted advan-
tages of the simultaneous LIBS/LIMS detection are somehow
exposed to experimental constraints, as the optimum con-
ditions for LIBS may diverge from those required for LIMS.
The key aspect again relies in the determination of the dif-
Figure 13. Discriminant function analysis applied to DNT– ferent ion and photons formation threshold,60 as the high
isomers samples from mass/emission spectral features obtained electron and ion number density associated to plasma for-
in a pairing-pulse approach.
mation is way off that required for an optimum focusing of
the laser-generated ions. Specific excitation conditions allow
options for both. The inclusion of a Raman device within the for simultaneous ion–photon detection (Figure 12) although
optical axis of a laser-sampling device for laser ablation at expense of sacrificing the spectral performance.61,62
inductively coupled plasma mass spectrometry (LA-ICP- Under tailored conditions, it is possible to perform LIMS
MS) is also conceivable. Doubtlessly, the best is yet to come. and LIBS in a paired-shot scheme with two different fluence
Mass spectrometry has not been unaffected by the conditions optimized for each detection mode. As with
temptation to be hybridized with LIBS systems to improve Raman-LIBS, the sample entity is preserved using a first
its versatility. The power and virtues of mass spectrometry laser shot well below the plasma formation threshold to
are out of question and out of the scope of this article. It is induce sample ionization, while the second pulse hits the
only important to remember a few aspects: (a) mass spec- sample on the same position at a larger fluence, allowing
trometry information (molecular/atomic) is highly depend- the recording of a LIBS spectrum under high vacuum con-
ent on the ionization type, (b) time-of-flight mass ditions. The combined information of full range mass and
spectrometers (TOF-MS) are the mass analyzers better optical emission spectra allows tackling challenging prob-
fitted to pulsed ionization sources, and (c) a TOF-MS may lems as the discrimination of DNT isomers (2,3-, 2-4-,
record in a single run all the transient ions produced during and 2-6-DNT) using a single-laser shot excitation design
a single ionization event. For the above reasons, the cou- with the help of the spectral information and chemometric
pling of a pulsed laser as ionization source and a TOF-MS as tools (Figure 13).
mass analyzer (coined generically as laser-ionization mass The information provided by mass spectrometry is fully
spectrometry or LIMS) has been a marriage of convenience complementary with that of LIBS, and even with that of
since long. It is also important to stress that mass spec- Raman. In a research lab, the idea of a ‘‘Swiss Army
trometry implies high vacuum and so, in the merging of LIBS knife’’ instrument where the individual performances of
and LIMS the sample is no longer in air at atmospheric each technique had to be balanced in favor of the integra-
pressure, limiting (but not impairing) some of the most tion is not well accepted. However, new challenging situ-
desirable properties of LIBS related to its experimental ations where a full atomic/molecular/isotopic information is
flexibility. From the authors’ point of view, operating LIBS required with a single instrument can be next door and may
under vacuum conditions (or under inert/reactive atmos- help to change the present analytical mindset. In the mean-
pheres) expands its capabilities by introducing unique fea- time, the extraordinary flexibility of an atomic spectroscopy
tures to the recorded spectra (particularly when working technique as LIBS is allowing astonishing alliances with
with organics) as the favorable expansion of the plume nar- molecular spectroscopy and with mass spectrometry.
rows the emission lines, reduces the background and
restricts the molecular emission to that resulting from pri- Paving the Way for Present and Future
mary mechanisms, since the recombination cross section is
low. The absence of secondary mechanisms is advanta-
Challenges
geous, as the spectral information can be exclusively related Quantitative analysis by LIBS is perhaps the less transcend-
to direct fragments or rearrangements between them. ent feature of the analytical capabilities of this outstanding
Working under high vacuum conditions also allows the pos- technology. LIBS can be used as a fast quantitative and
sibility to extend LIBS spectral coverage to VUV or even to semiquantitative method when a rapid screening of labora-
the X-ray range. tory samples is required. However, from a conventional
Laserna et al. 47

Figure 14. Spider charts comparing LIBS versus solution ICPMS.

48 Applied Spectroscopy 72(S1)

standpoint, laboratory methods such as atomic absorption basis, when compared to laser pulses of longer duration,
spectroscopy, ICP-OES, and ICP-MS would be the pre- the short pulse decreases the mass of ablated material.
ferred methods because of the better concentration detec- Because of the high temperature of the early plasma, line
tion limits and superior precision. Figure 14 shows a emission is buried in a strong background with the added
comparison of the analytical figures of merit of LIBS and consequence of broadened lineshapes. In spite of this fun-
solution ICP-MS. A semiquantitative scale has been used in damental limitation, a judicious choice of the observation
which 10 represents the maximum performance. time window and laser pulse energy allows to manage the
Operational and added value parameters are also con- large gradients in plasma temperature and electron number
sidered. As visually shown, ICP-MS overtakes LIBS in core density. Dealing with all these aspects is, and will remain,
features such as detection power, linear dynamic range crucial for advancing in the goal of reaching better limits of
(LDR), and selectivity. However, LIBS shows clear advan- detection, representativeness, and reduced measurement
tages when practical features such as fieldability, portability, uncertainty.
and analysis speed are considered. Recent investigation has
shown that LIBS may face analytical problems of remarkable Acknowledgments
complexity such as isotopic analysis of solid materials.63 Authors acknowledge financial support from the Spanish
Here, the non-contact nature of standoff LIBS may play a Ministerio de Economı́a y Competitividad under Research
key role, although the need of suitable limits of detection Project CTQ2014-56058P. The authors would like to thank the
for minor isotopes represents a major challenge to this Society for Applied Spectroscopy for giving them the opportunity
technology. The recent findings that quality spectra of levi- to contribute to this special Supplement. The authors are also
tated individual nanoparticles of mass in the attogram thankful to Professor Nicoló Omenetto for his continuous inter-
regime can be acquired in just a single laser shot in an est and discussions of the material presented.
open air atmosphere and at room temperature, are promis-
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From left: James Devlin, Secretary 1957-64; Edwin Hodge,

Treasurer 1957-61; Isabel Tipton, Treasurer 1962-64; Neil
Gordon (in the back), President 1961; Donald Johnson, President
1963; John Hansen, President 1962.
SAS 50th Anniversary Atomic Spectroscopy Symposium Speakers
and Organizer

SAS Members Event (Lake Tahoe): Steve Rehse, Genevieve Isshak,

Diane Errigo (photo bombing), and other members. Steve Ray and Gary Hieftje