Spectrochimica Acta Part B 57 (2002) 1115–1130

Review
Quantitative micro-analysis by laser-induced breakdown
spectroscopy: a review of the experimental approaches夞
E. Tognoni*, V. Palleschi, M. Corsi, G. Cristoforetti
Istituto per i Processi Chimico-Fisici (IPCF) del CNR, Area della Ricerca di Pisa, Via G. Moruzzi 1, 56124 Pisa, Italy

Received 10 January 2002; accepted 21 March 2002

Abstract

The laser-induced breakdown spectroscopy (LIBS) technique has shown in recent years its great potential for rapid
qualitative analysis of materials. Because of the lack of pre-treatment of the material, as well as the speed of analysis,
not mentioning the possibility of in situ analysis, this technique offers an attractive solution for a wide range of
industrial applications. As a consequence, a lot of work has been devoted towards the application of LIBS technique
for quantitative micro-analysis. The purpose of this paper is to give a review of the current experimental approaches
used for obtaining quantitative micro-analysis using the LIBS technique. The influence on LIBS analytical
performances of laser power, wavelength and pulse length, the proper choice of experimental geometry, the importance
of ambient gas choice and the role of detectors for improving the precision of LIBS analysis are among the topics
discussed in this paper.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: LIBS; Micro-analysis; Analytical instruments

1. Introduction erties that conquer more and more new LIBS

In recent years the application of the laser-
induced breakdown spectroscopy (LIBS) tech-
nique w1x to ‘real life’ problems (industrial process,
environmental monitoring, etc.) have greatly
grown in number and in variety. The feasibility of
rapid multi-elemental analysis and the lack of a
direct contact with the sample are appealing prop-
夞 This paper was presented at the 1st Euro-Mediterranean
Symposium on Laser-Induced Breakdown Spectroscopy, Cairo,
Egypt, November 2001, and is published in the Special Issue
of Spectrochimica Acta Part B, dedicated to that conference.
*Corresponding author. Fax: q39-050-315-22-30.
E-mail address: tognoni@ifam.pi.cnr.it (E. Tognoni).
users. Some commercial LIBS instruments are
available on the market, offering to the end user
the possibility of direct measurements without
worrying about the setting up and assembly of
single instrumental components. However, even
these commercial instruments are still not suffi-
cient to guarantee the final user the achievement
of reproducible and precise quantitative results.
In fact, the analytical performances of the LIBS
technique depend strongly on the choice of exper-
imental conditions, which have to be carefully
studied in each particular application. Main para-
meters affecting the performance are the laser
wavelength, the pulse energy, the time interval of

0584-8547/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 Ž 0 2 . 0 0 0 5 3 - 8
1116 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
observation and the geometrical set-up of the
collecting optics. The choice of the experimental
arrangement should be aimed at optimizing the
reproducibility of the measurements, while at the
same time achieving plasma conditions where the
hypotheses of LTE, stoichiometric ablation and
thin plasma are fulfilled.
The best indication that LIBS has not yet over-
come the experimentation stage to become a rou-
tine methodology is perhaps given by the variety
of different experimental configurations reported
in the literature. Each different arrangement is the
answer to a different analytical problem: while this
testifies to the versatility of the LIBS technique,
at the same time the use of many different exper-
imental conditions makes difficult a meaningful
comparison between results obtained in different
laboratories.
The purpose of this paper is to give a review of
the studies that have investigated the effect of the
main experimental parameters on the quality of
LIBS measurements. We produced this review due
to the lack (to our knowledge) of a similar
reference in the existing literature. We will not
describe the history of LIBS applications, nor
mention the best results achieved by LIBS in terms
of precision or sensitivity. To this regard we refer
the reader to previous reviews, which cover differ-
ent aspects of the LIBS technique w2–5x. Among
these earlier reviews, the work by Rusak et al. w4x
is organized in three different sections regarding
solids, liquids and gases, respectively; each section
is in turn divided into theoretical studies and
experimental studies. For each element the lowest
detection limit achieved is listed. The review by
Song et al. w5x, on the other hand, presented a
brief overview of the basic LIBS principles and of
the instrumentation used in this technique, though
the main focus was devoted to the LIBS applica-
tions to a wide variety of samples and elements.
In the following sections we will focus instead
on the effects of experimental parameters on LIBS
analytical performance, referring mostly to exper-
imental studies appearing in the literature in the
last decade. Though a typical review should cover
the most recent publications in the field, due to
the specific focus on experimental parameters we
also had to include in this summary some of the
first systematic studies, which dated from the late
1980s to the early 1990s. This summary provides
a source for researchers who wish to retrieve
information regarding previous experimental stud-
ies on measurement parameters. In the literature
there is also a corresponding series of theoretical
works dealing with the basic physical principles
that describe the laser–matter interaction and plas-
ma evolution. Since the focus of the current review
is imprinted to the experimental aspects, we refer
the reader to other works w1,6–8x for the investi-
gation of theoretical models.
The organization of the present manuscript was
devised in order to deal with the effect of single
parameters separately. On some occasions during
the course of the discussion it is concluded that a
particular condition can be favorable to achieve a
particular effect, however, in our opinion it is very
hard to express a definite preference for a particular
configuration over another one. In fact the prob-
lems faced in a specific application are always
different. Since one of our aims is to help the
beginner LIBS user, we think that giving an
overview of the existing knowledge is an effective
help, whilst indicating which is better the other
could be misleading.
On the other hand, the reader interested in the
discussion of the accuracy of LIBS quantitative
analysis, is referred to some recent works where a
more critical discussion is proposed w9–11x.
2. Choice of experimental parameters in LIBS
measurements
2.1. Laser characteristics
Different kinds of lasers are used in laser-
induced plasma spectroscopy, typically ranging
from UV excimer lasers to infrared solid-state
lasers. The different laser–material coupling char-
acteristics of different laser sources strongly affect
the behavior of the resulting plasma. This issue
has been the object of many studies that lead to a
satisfactory knowledge of the problem, so that we
are now able to choose the most suitable laser
depending on the task to be accomplished.
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
In the following paragraphs some recent works
are reviewed, describing the effect of different
laser parameters on plasma formation.
2.1.1. Fluence and power density
For the formation of a plasma, the laser fluence
should exceed a threshold value, typically of the
order of several Joules per square centimeter for
nanosecond laser pulses. These values are easily
attained by proper focusing of the laser beam. At
diffraction limit, the diameter w2 of the laser beam
at the focus of the focusing lens can be calculated
as:
f sample composition was different, too).
w2f2.44l (1)
w1
where w1 is the diameter of the laser beam before
focalization, f is the focal length of the lens and
l the laser wavelength.
Cabalin and Laserna w12x made a systematic
study for determining the threshold fluence for
plasma formation in a set of nine metals, largely
spread in physical and thermal properties, like
melting and boiling temperatures, thermal conduc-
tivity, etc. Fluence thresholds correlated fairly well
with thermal properties such as melting and boiling
temperature, suggesting that thermal effects must
play a significant role during laser ablation with
nanosecond pulses, for fluences close to the thresh-
old. The authors also investigated the behavior of
line emission intensity vs. incident fluence and
found an initial linear correlation, probably due to
the increase of ablated material; subsequently for
higher fluence values, the emission signal reaches
a saturation regime, attributed to the absorption of
the laser beam by the plasma formed in front of
the sample. The starting point of the saturation
regime is element-dependent, and correlated with
the value of the threshold. Milan and Laserna w13x
also reported a similar behavior for silicon.
The same behavior of coupling efficiency was
found in dependence of the power density, for
nanosecond and picosecond lasers, by Russo w14x:
the mass ablation rate increases linearly with pow-
er density, then undergoes a regime change, fol-
lowed by saturation. In order to obtain the
maximum efficiency in mass removal, a study by
Chan and Russo suggested the use of power
1117
densities of the order of 1 GWycm2 for a copper
target w15x. Higher power densities produced con-
stant mass ablation rate, due to the shielding of
the laser energy acted by the plasma itself. How-
ever, in a similar range, between 0.6 and 1.2 GWy
cm2, Chaleard
´ et al. w16x found a linear dependence
of the ablated mass on the power density for an
aluminum sample, indicating the presence of a
unique ablation regime in the specified range. The
authors explained this difference with the difficulty
of comparing experiments carried out with differ-
ent laser sources, having different energy distri-
bution (it should be also noted, however, that the
The mass ablation rate is not the only significant
parameter in the quest for good reliable experi-
mental data. The dissociation and excitation of the
ablated mass and therefore the spectral emission
intensity are dependent on the plasma temperature.
The actual plasma temperature is significantly
increased by higher laser power density. Therefore,
higher power density may be beneficial to improve
the analytical sensitivity w17x.
As a consequence of the strong dependence of
the plasma conditions on the fluence or power
density, many arrangements have been described,
devised to fine-adjust the laser power delivered on
the sample. Some authors w18x prefer to adjust the
pulse energy with the help of attenuators along the
path, instead of adjusting the supply voltage, in
order to prevent changes of energy distribution in
the laser beam. Aragon et al. w19x, for example,
used for that reason a half-wave plate that rotates
the plane of polarization and a polarizing beam
splitter cube.
Another straightforward way to reduce the pow-
er density on the target surface consists in displac-
ing the focusing lens with respect to the target, in
order to change the dimensions of the focal spot
over which the pulse energy is distributed.
´
Chaleard et al. w16x used to spatially filter the
laser beam before focusing it on the sample sur-
face, in order to obtain a more homogeneous
energy distribution and consequently a more reg-
ular crater.
Indeed, the ideal situation for laser ablation
experiments would be a ‘flat-top’ distribution of
the laser beam energy, because each point of the
1118 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
target surface would receive the same amount of
energy. This is obviously not the case when the
laser exhibits an uncontrolled energy beam distri-
bution, in particular with the use of a multi-mode
laser source, for which the variation is generally
very high. This can induce a highly complex
ablation process, in which the ablation regime may
not be the same at each point of the ablated
surface.
The effect of pulse-to-pulse laser stability on
the emission intensity has been investigated by
Castle et al. w20x by simultaneously monitoring
the analyte (Cu) signal and the laser pulse energy
by means of a photodiode. No significant correla-
tion was observed, indicating that the laser pulse
variance played a small role in the overall variance
of LIBS measurement.
Wisbrun et al. w21x measured the behavior of
the signal-to-noise ratio in sand and soil samples
depending on the laser pulse energy which was
varied between 0 and 320 mJ. In their experimental
conditions, the signal-to-noise ratio increased with
pulse energy until approximately 100 mJ, and then
remained almost constant. This result was consid-
ered particularly encouraging in view of the field
application of the technique, for a possible use of
a fiber optic to deliver the laser beam further to
the signal collection, without a degradation of the
signal.
2.1.2. Wavelength and pulse duration
In the case of solids ablation, Kim w22x pointed
out the importance for LIBS measurements of the
leading-edge rise-time of the laser pulse, which
should be fast enough to remove the surface layers
at a speed at least equal to that of the thermal
conduction front moving into the bulk.
Amoruso et al. w23x evaluated the efficiency of
the mechanisms of energy absorption in the plasma
for a visible and a UV laser wavelength during
ablation of an aluminum sample. In a nanosecond
laser ablation process, target evaporation begins
just after the impact of the leading edge of the
laser pulse on the surface. The interaction of the
following part of the laser beam with the vapor in
the vicinity of the target surface leads to a strong
heating and ionization of the vapor and plasma
formation. Although some species can be directly
vaporized as ionized particles, plasma formation
can be mainly ascribed to processes involved in
the laser–vapor interaction. There are two domi-
nant photon absorption processes in the aluminum
vapor for visible and UV photons. One is inverse
Bremsstrahlung (IB) absorption, by which free
electrons gain kinetic energy from the laser beam,
thus promoting plume ionization and excitation
through collision with excited and ground-state
neutrals. The second mechanism is photoionization
(PI) of excited species and, at sufficiently high
laser intensity, multiphoton ionization (MPI) of
excited or ground-state atoms. The authors
observed that the primary mechanism of laser
absorption and ionization of the relatively cold
neutral vapor formed by the leading edge of the
ablating laser pulse depends strongly on the radi-
ation wavelength: at ls532 nm, the ionization
can be mainly ascribed to electron-neutral IB
processes, and consequent electronic ionization,
whereas at 355 nm direct PI of excited states in
the vapor seems to be the most effective process
(the IB process is less efficient in the UV than in
the visible part of the spectrum, because of the
l3 dependence of IB on the laser wavelength).
More precisely, the efficiency of the laser heating
of the plasma by IB decreases with the square of
the laser wavelength when the degree of ionization
is low and as the cube of the wavelength when
the ionization is extensive w23,24x. The efficiency
of the IB photon absorption is such that the plasma
acts as a shield for the laser radiation, completely
preventing the last part of the beam pulse to reach
the target surface.
Shorter pulses (on the order of picoseconds) are
reported to produce higher mass ablation rates,
probably because they are not affected by the
plasma shielding, and also because the fraction of
the pulse energy loss by thermal diffusion in the
sample is much lower than in the case of nanosec-
ond pulses w25x.
Sdorra et al. w26x compared the characteristics
of plasmas induced by infrared and UV laser
wavelength (fundamental and fourth harmonic of
an Nd:YAG laser). Under the same pressure con-
ditions (buffer gas was argon), the UV wavelength
was much more effective in mass ablation. More-
over, using the fourth harmonic, the crater dimen-
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
sions and hence the amount of mass ablated were
almost independent on the kind of buffer gas and
on the pressure value (between 140 and 1000
mbar), indicating that radiation shielding is negli-
gible at this wavelength. As regards the investi-
gation of plasma temperature, the authors
measured in the center of the plasma the same
values either using the fundamental or the UV
wavelength, observed a more pronounced drop in
the lateral regions in the case of the UV-induced
plasma. In conclusion, the authors evaluated the
analytical results, and observed that the emission
signals obtained with UV radiation were not linear
with analyte concentration, even after comparing
the LIBS signal with reference lines. They sug-
gested that the poor analytical results obtained
with UV wavelength can be due to incomplete
atomization of the material ablated, and demon-
strated that linearity is obtained if the vapor ablated
is reheated by means of a second, independent IR
pulse.
However, different observations have been
reported by Berman and Wolf w27x, who compared
the analytical results obtained in the detection of
Ni in water by using alternatively the fundamental
Nd:YAG wavelength and the UV third harmonic.
They observed in the UV generated spectrum a
lower continuum intensity, leading to a better
signal-to-noise ratio; furthermore, after construct-
ing the calibration curves for the same spectral
lines, the one obtained with UV irradiation
revealed a higher slope and allowed a better limit
of detection (LOD) value. These results agree with
the results obtained on liquids by Ng et al. w28x,
who found that the main difference in the plasma
plume generated by visible or ultraviolet laser of
the same fluence is in the T value, which is quite
lower in the second case, while the Ne value is
approximately the same.
As an example of different laser–material cou-
pling at different wavelengths, Mao et al. w25,29x
reported the reflectivity coefficient R of metallic
Cu at three different typical wavelengths: R equals
0.976 at 1064 nm, 0.814 at 532 nm and 0.336 at
266 nm. The absorbed energy (a fraction 1yR of
the laser energy) in irradiating copper is thus much
higher in case of UV laser wavelength. The same
authors, in support of this observation, experimen-
1119
tally demonstrated that the transition between ther-
mal and explosive regimes in laser ablation occurs,
for the different wavelengths, at power density
values scaling inversely as the (1yR) factor.
In a recent work, Russo et al. analyzed the
influence of laser wavelength on the specific prob-
lem of fractionation in laser ablation w30x, com-
paring the effects of three different UV
wavelengths (Nd:YAG quadruplicated at 266 nm,
Nd:YAG quintuplicated at 213 nm and F2 at 157
nm). They demonstrated that depending on the
sample, fractionation can be present for each wave-
length used in ablation, but for each wavelength it
can be controlled (reduced or enhanced) by chang-
ing the power density. Moreover, they claim that
the shorter the wavelength, the more controlled or
reproducible is the ablation rate; also, the shorter
the wavelength, the lower is the fluence that is
required to initiate ablation.
However, Cabalin and Laserna w12x found that
the fluence threshold for plasma formation is
higher for shorter wavelengths. They measured the
emission intensity of the atomic lines characteristic
of some metals depending on laser fluence, for
different harmonics of a nanosecond Nd:YAG laser
(fundamental, second harmonic, fourth harmonic).
They found a general behavior for the three wave-
lengths and for the different metals: by increasing
the laser fluence values above the threshold, a
linear increase of the line intensity occurred, then
followed by a saturation regime. Both the thresh-
olds for plasma formation and the saturation regi-
me, however, were shifted towards lower fluences
for IR wavelength, while the energy threshold
values were higher for IR radiation. In the discus-
sion of the results, the authors stated that reflectiv-
ity does not seem to be a relevant parameter, at
high fluences (i.e. above the threshold), since the
plasma formation change substantially the proper-
ties of the target surface.
However, the choice of laser wavelength is, of
course, dependent on the analytical task. For
instance, Haisch et al. w31x preferred the second
harmonic of a Nd:YAG laser, instead of a higher
order one, for sampling the particles deposited on
a filter membrane used to select colloids from its
liquid solvent. In that case, indeed, the formation
of deep crater, which the fourth harmonic would
1120 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
have produced, was to be avoided in order not to
ablate a layer of the membrane together with the
filtered particles.
2.2. Interval of observation
Early stages of plasma evolution are character-
ized by the Bremsstrahlung continuum emission,
and only subsequent stages show the characteristic
line pattern, which allows for the LIBS composi-
tional analysis of the sample. It should be noted
that although the continuum emission may hinder
the line emission, it is not appropriate to consider
this background as noise, since it corresponds to a
physical process and it cannot be reduced through
averaging. Because of its characteristics, the back-
ground signal can be minimized only by activating
the spectra acquisition with a proper delay after
the laser pulse that produces the plasma. However,
at large delay times the absolute intensity of the
line emission can be too low for efficient detection.
The best compromise between high line intensity
and low background must be determined case by
case. Depending on the density of the ambient gas
and other factors, the plasma lifetime may range
from approximately 300 ns to more than 40 ms
w22x.
Ciucci et al. w32x compared the time evolution
of the plasma emission obtained by irradiating in
air the same sample with, respectively, the funda-
mental wavelength of an Nd:YAG laser and the
UV radiation of an excimer laser. They observed
that in the case of UV excitation the plasma
emission was initially dominated by the back-
ground up to approximately 400 ns, when the
atomic transitions started to appear against the
continuum. The emission generated by NIR exci-
tation showed characteristic longer times, on a
scale of several microseconds. The time scales of
the plasma induced by the two different sources
differ remarkably, suggesting a more rapid contin-
uum decay in the experiment performed with UV
excitation with respect to the one where NIR was
used.
In the framework of a study devoted to the
evaluation of the parameters affecting LIBS pre-
cision, Castle et al. w20x studied the reproducibility
of the LIBS spectra changing the delay of the
integration window with respect to the laser pulse.
In their experimental conditions (Nd:YAG laser at
the fundamental wavelength, power density of
approximately 2 GWycm2) the best compromise
between lower relative standard deviation (R.S.D.)
and higher signal-to-noise ratio was found at a
delay of approximately 6 ms. The integration time
was kept fixed at 15 ms.
Other researchers pursued the optimization of
delay and integration time in order to obtain the
higher signal-to-noise ratio. Wisbrun et al. w21x
reported a systematic bi-dimensional analysis for
two elements (Zn and Cd) in a sand sample. The
delay value resulted to be the most significant
parameter, and the optimal values for the elements
in study have been found to be a delay of approx-
imately 0.5 ms with an integration time of approx-
imately 1.5 ms.
Due to the time evolution of electron density
and temperature, also the ratio between the popu-
lation of neutral and ionized species changes with
time. Leis et al. w33x reported a study of the
evolution of the emission intensity of two iron
lines (Fe I 285.2 nm and Fe II 288.4 nm), in a
pure iron sample, recorded during the first 15 ms
of plasma lifetime. During the first 3 ms, the
intensity of the ionic line exceeded the neutral (at
its maximum, lying at 500 ns, the intensity ratio
was approximately 50); later, at a delay of approx-
imately 10 ms, the neutral line intensity (which
reached its maximum at 1.5 ms) was eight times
the other. The same authors evaluated the evolution
of the signal-to-noise ratio, for an Nd:YAG 5 mJ
pulse in 140 torr argon pressure, concluding that
good values can be obtained with delays greater
than 3 ms.
Aragon et al. w19x studied the evolution of line
intensity and of line-to-continuum ratios and found
a dependence on the specific line and on the pulse
energy. They concluded that line intensities and
line-to-continuum ratios cannot be simultaneously
maximized for all the elements investigated by
using a single detection time window. Their sug-
gestion was to use a large integration time (2–15
ms), which allows to collect most of the LIBS
signal for all the elements, while eliminating the
undesirable initial part of the emission.
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
Sabsabi and Cielo w18x chose for quantitative
analysis of aluminum alloys a delay time of 10 ms
and an integration time of 10 ms as well. The
same authors studied the temperature evolution in
a nanosecond Nd:YAG-induced plasma on alumi-
num and copper targets in air w34x. They obtained
in both cases a similar behavior of the temperature:
a quick decrease in the first few microseconds
(from approximately 1 eV to approximately 0.5
eV) and small changes at later times in the
microsecond scale. Analogous behavior with time
was reported by Leis et al. w33x, who determined
the time-resolved temperature for a series of binary
Fe–Cr alloys with iron content ranging from 10 to
100%. While the evolution in time of the temper-
ature was similar for all the samples, the absolute
value differed by approximately 50% among the
samples, with the pure iron showing the higher
temperature value.
2.3. Geometric set-up
The geometrical shape of the plasma and spatial
emission intensity profile are strongly dependent
on the laser power density and on other parameters,
therefore it is often necessary to optimize the
characteristics of the experimental apparatus as a
whole.
Eppler et al. w35x compared the precision of the
results obtained using a spherical and a cylindrical
lens to focus the laser pulse on the surface of a
soil sample. They found much more precise results
using the cylindrical lens, and explained the effect
by considering the larger area sampled in the latter
case, which allowed averaging of inhomogeneous
composition that is naturally associated with this
kind of sample.
Moreover, when the analytical collection system
is pointed on fixed spatial regions of the plasma,
changes in the plasma emission position might be
erroneously interpreted as a change in concentra-
tion of the element, unless the observation region
encompasses and spatially integrates the entire
geometrical extent of the plasma for all power
densities. This is sometimes obtained by directly
facing a fiber optic to the plume, at a distance of
some millimeters, in order to avoid damage by
excessive heating. The collection angle of the fiber
1121
end allows in fact gathering of light from a broad
plasma extension. On the other hand, the use of
optical fiber bundles has been proposed for the
simultaneous acquisition of spectral emission from
different regions inside the plasma plume w36x.
Due to the breakdown threshold of the optical
fiber material, optical fibers were initially used in
LIBS only to deliver the plasma emission to the
detection system w37–39x. The use of fiber-optic
was then proposed also for laser beam delivery, in
a configuration suitable for operating in hostile
environment, allowing to separate the focusing and
collecting head from the most delicate parts of the
instrumentation, i.e. laser source, spectrometer and
detector. Beside the flexibility, this configuration
also offers an obvious advantage in terms of safety
with respect to possible eye damage. On the other
hand, when the laser beam is coupled into a fiber,
a more restrictive limit is imposed on the maxi-
mum laser pulse energy, in order to avoid damage
to the fiber itself w40x. Various configurations have
been proposed, including the use of two optical
fibers w40–42x (one for delivering the laser beam
and one for collecting the plume emission) or one
single fiber for both the tasks w43,44x. A compar-
ison has been carried out between the perform-
ances of the fiber-coupled LIBS and lens-coupled
LIBS w44x: after optimization of different experi-
mental parameters the detection limits achieved
were found to be comparable, at least for some
elements.
The choice of on-axis plasma emission collec-
tion presents advantages in terms of simplicity and
reproducibility, and this configuration is often
adopted when aiming to perform on-line analysis
of some evolving process. It is well known that
the plasma plume expands in the direction perpen-
dicular to the sample surface w22,45x. The on-axis
detection, being performed along the direction
perpendicular to the surface, is less sensitive to
changes in the plasma-to-collecting-lens distance,
which occur when several shots are fired at the
same place on the sample surface and a crater is
formed. With on-axis collection, the plasma dis-
placement causes minimum perturbations on the
LIBS signal, because of the depth of focus of the
detection optics, which is typically longer than
crater depth w16x. In fact, lenses having focal
1122 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
length of a few centimeters are typically used for
LIBS measurements.
Moreover, there are certain types of changes
which will definitely occur in the plasma emission,
i.e. those produced by time evolution of the plasma
plume. The plume expansion is governed by the
strong explosion law. If we assume a one-dimen-
sional model, where the plasma expands along the
x-direction and the target surface is at xs0, the
distance x(t), reached at time t from the shock
wave front, can be expressed as
B
EI Emy2 m
xskC F t (2)
D r0 G
where EI is the energy deposited by the laser
during the ablation process and r0 is the ambient
gas density. The coefficient m depends on the
plasma expansion geometry and is equal to 2y3
for planar propagation and 2y5 for spherical sym-
metry w46,47x. It results from Eq. (2) that the
plasma is moving initially fast, while at later times
the plasma velocity is slower. The time gating and
the region of the plasma inspected must therefore
be matched in order to intercept the emission
signal w17x.
In laboratory LIBS analysis, however, the con-
figuration with collection axis perpendicular to the
laser beam direction is also common. Several
studies have investigated the dependence of the
emission intensity on the distance of the collection
axis from the target surface. Kim et al. w48x, for
instance, studied the spatial distribution of the
emission intensity by scanning the direction per-
pendicular to the target surface; the authors found
the highest intensity at a distance of 3 mm from
the target surface, at a delay of 30 ms, in air.
Regarding laser beam delivery, the most com-
mon choice for LIBS on solid targets seems to be
the direction perpendicular to the sample surface
(or very close to the perpendicular, see for example
Ref. w16x). After the focusing lens, the beam
fluence may reach along the path a value sufficient
to generate the breakdown in air even before the
focus position, especially when some air powder
particles are occasionally irradiated. To avoid these
fluctuations in the breakdown position, many
researchers used to set the distance between the
focusing lens and the target a little shorter than
the focal length. This configuration was found to
produce a stable breakdown, while maximizing the
interaction area w19,21x.
However, the perpendicular irradiation configu-
ration might induce some problems on liquid
samples, related to the splashing of liquid on the
lenses, which strongly reduces the reproducibility
of the measurements. Since droplets ejection is
mainly perpendicular to the liquid surface, Fichet
et al. w49x suggested a configuration with the laser
beam directed on the surface with a tilt angle of
158 (758 with respect to the perpendicular), thus
keeping the optics protected from splashing.
Typical LIBS measurements are performed by
integrating the emitted intensity over the line of
sight in the plasma. In this case, the inhomogeneity
of the plume should be always taken into account,
since the resultant information (unless it is spa-
tially resolved) includes contribution arising from
regions with different temperature and electronic
density. However, many authors intentionally
choose to collect as much as possible of the plasma
emission, for obtaining a better reproducibility. For
instance, Aragon et al. w19x used in the optical
collection path a demagnification factor of five, in
order to form on the entrance slit of the spectrom-
eter the image of the whole plume. Similarly,
´
Chaleard et al. w16x used for the collecting optics
a demagnification factor of 30, in order to image
the whole volume of the plasma on the 200-mm
entrance slit of the spectrometer. They stated that
this configuration could improve the reproducibil-
ity of the measurements, while the shot-to-shot
variations in the atomic densities and temperature
distribution inside the plasma affect the reproduc-
ibility of the measurement when only the central
part of the plasma is probed.
To clarify this latter issue, many researchers
have investigated the spatial distribution of the
emitters in the laser-induced plasma. Liu et al.
w50x studied in particular the early phase of the
plasma, and reported a double-peaked intensity
distribution along the normal to the irradiated
surface (similar results are reported in Ciucci et
al. w51x). For their LIBS analysis, they chose to
collect the signal from the region where the max-
imum intensity was recorded, avoiding at the same
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
time the region close to the target surface and at
the plasma–air interface, where self-absorption
was exhibited even from non-resonance lines.
Lee et al. w52x studied the spatial features of
laser-induced plasmas on different metallic target
by measuring the emission intensity along the axial
direction perpendicular to the target. The authors
used a non-time resolved apparatus, however, they
were able to measure for copper plasma a spatial
extension limited to approximately 2 mm in the
axial direction, with peak intensity lying at a
distance lower than 1 mm from the target surface;
while lead plasma extended for approximately 5
mm from the target, with peak intensity at approx-
imately 2 mm from it. Even if this different
behavior has not been completely explained, the
consequence seems to be that the spatial region
sampled in analytical measurements should be
optimized depending on the target material.
Other studies have been performed in order to
characterize the angular distribution of the LIBS
signal. According to the description given by Kim
w22x, Hansen et al. experimentally found that
ionized species are steeply localized along the axis
perpendicular to the irradiated surface, while neu-
tral species are smoothly distributed in the other
directions w53x.
2.4. Ambient gas
At elevated power density, the laser–material
coupling efficiency is reduced by the plasma
shielding effect. Plasma shielding importance is
governed, among other factors, by the nature of
the gas environment.
Grant and Paul w54x measured along the axial
direction the spatial-resolved emission intensity of
a laser-induced plasma produced with an excimer
XeCl laser on a steel target in different gas
atmospheres (air, helium and argon) and pressures
(0.5, 50 and 760 torr). With the limitation of a
non-time resolved apparatus, the evidence of lower
LIBS signals for any kind of ambient gas at 0.5
torr pressure was, however, observed. Furthermore,
it was clear that signal-to-noise ratios are reduced
in proximity of the target surface. The global
behavior of the emission intensity in dependence
of the three variables (gas, pressure, axial distance)
1123
was too complex for giving a unique interpretation.
However, the indication was provided of the con-
dition which yield the best signal-to-noise ratio,
i.e. argon atmosphere at 50 torr pressure, with the
LIBS signal sampled at approximately 6 mm from
the target surface. Leis et al. w33x instead suggested
an argon ambient pressure of 140 torr to yield the
higher intensity values (measured for the Si I
288.2 nm line in a steel sample, with a Nd:YAG
laser, 5 mJ pulse energy).
Sdorra and Niemax w55x compared the effect of
different ambient gases (argon, neon, helium,
nitrogen, air) in the production of plasma by means
of a nanosecond Nd:YAG on a copper target. For
fixed experimental conditions and in particular, at
pressure lower than atmospheric, argon was dem-
onstrated to produce the higher plasma tempera-
ture, the higher electron density and, despite the
lower mass ablation rate, the higher emission
intensity for the chosen monitored element. Fur-
thermore, the decay rate of the temperature during
the first 40 ms after the laser pulse was slower for
argon than for the other gases. The same behavior
was also found by Iida w56x. Helium, conversely,
produced the lower temperature, electron density
and emission intensity. In conclusion, argon was
found to be most efficiently heated by inverse
Bremsstrahlung, generating a buffer plasma which
optically shields the target surface, thus reducing
the amount of mass ablated. The shielding effect
also takes place in the presence of other gases, but
only for pulse energy values greater than 20 mJ,
whilst in argon there is a strong effect already at
laser energies of approximately 10 mJ. However,
argon is found to yield the highest analyte emission
intensity, except at high pressures, when neon
offers the best performance. Again, similar results
were shown by Iida w56x, who measured the higher
emission intensity with an argon atmosphere at
approximately 100 torr pressure.
Kim et al. w48x observed the same signal
increase and longer plasma lifetime in argon
atmosphere, as already described, and explained
this phenomenon with the smaller conductivity
(0.0387 calycm s deg in STP) and specific heat
(0.0763 calyg deg in STP) of argon gas with
respect to the corresponding air values. Such dif-
ferences in the thermal properties result not only
1124 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
in a higher temperature plasma leading to stronger
emission, but also in slower cooling of the plasma,
leading to a longer emission period. Another
important effect from the Ar environment is pro-
tection of the excited atoms from forming stable
compounds such as oxides, which might reduce
the LIBS emission from the analyte.
Also, Wisbrun et al. w21x found that the argon
atmosphere was most favorable both in terms of
higher analyte emission intensity (1.8 times the
intensity obtained in air for the Zn LIBS line at
481.1 nm) and better reproducibility (R.S.D.s
12% over 18 measurements, compared to 18% in
air). In the same work the authors observed that
as the atomic mass of the ambient gas increases,
the collisional translation energy transfer is less
effective and the plasma life is longer.
At low ambient pressure (-1 mbar), the ablated
vapor can expand almost freely, and the outer part
of the plasma becomes colder of the core, because
of the higher energy loss. When increasing the
pressure to approximately 1 mbar, the confining
effect of the vapor by the ambient causes a
reduction in energy loss and a more uniform
distribution. Hermann et al. w57x studied the time
and space evolution of the electron density and
temperature by changing the laser power density
value and the ambient pressure. In their experi-
mental conditions, the electron density was more
sensitive to power density changes than tempera-
ture. They also observed that plasma lifetime
(measured from line intensity as well as from Ne
and T decay rate) increased with power density.
This can be explained considering that the plasma
density increases with laser power density, and
self-absorption of the spectral lines becomes more
important. Thus, the radiation loss is reduced and
the plasma lifetime is increased. By increasing the
ambient pressure in the range from 0 to 1 mbar,
the electron temperature and density remained
unchanged at early times (t-200 ns from laser
pulse), while the decay rates for later times were
reduced, as a consequence of the confinement of
the vapor plasma by the ambient gas, which
prevents electrons or ion from rapidly escaping
from the observation point and facilitate the atom-
ization of droplets and particles. With respect to
the free expansion in vacuum, elastic and inelastic
collisions occur between target vapor and ambient
gas species. Thus, the plasma density decreases
slower and, as an effect of inelastic collision, the
kinetic energy is partially transformed in excitation
energy.
Thiem et al. w58x, after observing that analysis
at atmospheric pressure is hampered by the pres-
ence of a broadband background emission spec-
trum generated by atmospheric elements, preferred
the use of a vacuum chamber in order to obtain
better signal-to-noise ratios.
Certain arrangements must be envisaged, in
particular cases: for instance, if a UV spectrum
that ranges down to 180 nm is to be observed, the
experiment housing must be filled with nitrogen
or some other inert gas, in order to avoid the
absorption of the LIBS signal by oxygen
molecules.
2.5. Dual-pulse LIBS and selective excitation
It is generally agreed among the scientific com-
munity that poor detection limits are the most
important limitation of the LIBS technique, com-
pared to other consolidated analytical techniques.
Therefore, several research groups have investigat-
ed possible ways to improve the LIBS detection
limits. One of the most promising approaches to
this problem is the combined use of a pair of laser
pulses to ablate the material and further excite the
resulting plasma. The technique developed on this
basis is known as Dual-Pulse LIBS, or Repetitive
Spark Pair (RSP), or Double-Pulse Excitation.
In some cases the dual pulse is delivered by a
unique laser w59,60x, while other experiments make
use of two different lasers w61–63x. In the latter
case there is more flexibility in the arrangement
of the relative beams configuration, as for geom-
etry, energy and timing. On the other hand, the
use of a single laser keeps the system compact
and saves the problems of alignment between the
two pulses, ensuring better reproducibility.
In 1997 Pichahchy et al. w59x applied the RSP
technique to the analysis of metals under water.
While the single sparks produced weak spectra,
the use of two laser pulses separated in time by
tens of microseconds allowed to obtain hotter
plasmas (T;9000 K compared to 3000 K for a
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
single spark) and in consequence good detection
limits for the elements investigated. The explana-
tion proposed for the strong excitation produced
by the second pulse is the formation of a gas
bubble in the water environment at the solid
surface. The presence of a solid–gas interface
would allow the interaction of the second pulse
with the plasma in a way similar to the gaseous
environment.
In 1998 St-Onge et al. w64x published a study
of some parameters affecting the performance of
dual-pulse LIBS on metal samples in air. By means
of a series of time-resolved measurements, the
authors investigated the behavior of plasma tem-
perature and electron density in the case of a
double pulse compared to a single pulse. Accord-
ing to the authors, the resulting differences were
not sufficient to explain the observed signal
enhancement. The proposed interpretation calls for
a volume effect generated by the first plasma,
leading to a more uniform absorption of the second
pulse, whose energy is then distributed on a
broader volume.
While most papers dealing with dual-pulse LIBS
report the use of two pulses of similar wavelength,
namely the fundamental Nd:YAG emission at 1064
nm, St-Onge et al. w65x proposed the combined
use of a UV pulse to increase the ablation and of
an IR pulse to maximize heating efficiency. Also,
in this configuration significant signal enhance-
ment has been observed, the extent of which varies
depending on the ionization state and level energy
of the specific spectral line investigated. As in the
previous work, a correlation has been established
between the observed increase in intensity and the
theoretical increase expected as a result of the
higher plasma temperature generated by a combi-
nation of the UV-NIR pulses. However, the
enhancement of the signal is even greater than
predicted by the increased temperature, so that a
co-operative effect from a broader volume is still
supposed to act. The most promising result emerg-
ing from this paper is the possibility to also obtain
greater signal enhancement by simultaneously fir-
ing two pulses of different wavelengths. This
possibility allows the use of any kind of Nd:YAG
laser by just applying a harmonic-generator crystal
1125
to convert a fraction of the beam to the higher
frequency.
In contrast to the above-mentioned studies,
where the plasma obtained by the first ablating
pulse is reheated by a second pulse, Stratis et al.
w63x suggested firing a pre-pulse parallel to the
sample surface and focused to form an air plasma,
followed in a few microseconds by a second
orthogonal ablating pulse. The increase in intensity
of the spectral line emission was observed in
association with an increased mass ablation. The
same authors have obtained analogous results for
non-conducting materials like glasses w62x. In a
recent study the same authors investigated the
dependence of signal enhancement on the delay
between the pulses w61x. They measured simulta-
neously the time-resolved, spatially-integrated
emission intensity from two collection directions:
top view; and side view. The results were slightly
different, even if qualitatively consistent: on this
basis the authors made a very interesting point on
the importance of the collection geometry in the
LIBS measurements.
A different approach to improve detection limits
has been developed by applying to a laser induced
plasma the selective elemental excitation obtained
by a tunable diode laser. As an example of the
application of this technique, Smith et al. w66x
used atomic fluorescence to obtain selective iso-
tope detection of uranium containing samples. In
order to detect the fluorescence signal, two tech-
niques have been described: the fast wavelength
scanning of the diode laser during the lifetime of
the plasma produced by each shot of the ablating
laser and the time-integrated measurement with
the diode laser wavelength fixed at the isotope
line center. The optimal experimental conditions
were found by means of a systematic scanning of
the argon pressure in the experimental chamber, of
the distance from the sample surface and of the
ablating laser pulse energy. The limit of detection
in the optimal conditions was of the order of 0.6
ppm.
Many other combinations of LIBS and laser-
induced fluorescence (LIF) have been described
even in recent years w67–69x, giving a picture of
the achievements which can make LIBS a highly
performing technique. However, the high sophis-
1126 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
tication of these techniques makes a detailed
review of the specific experimental configurations
out of the scope of this paper.
2.6. Spectral detectors
In LIBS experiments, Czerny–Turner spectro-
graphs are usually employed, coupled to detectors
which offer the possibility of time resolved meas-
urements. These detection systems are intrinsically
limited in resolution andyor in spectral coverage.
This latter limitation is particularly disappointing
in view of the intrinsic multi-elemental detection
capability offered by the LIBS technique. There-
fore, when multi elemental analysis is required,
sequential measurements of the parts of the spec-
trum of interest must be performed, inspecting
each time a different sample of the material ablated
from the target surface. This procedure would in
principle limit LIBS application to homogeneous
samples. However, in practice most samples are
inhomogeneous and, as a consequence, the spectra
vary from shot to shot, both for changes in the
sample composition and for the stochastic fluctu-
ations in the plasma w70x. Therefore, the optimal
approach for all spectroscopic analytical tech-
niques is the simultaneous measurement of the
complete optical spectrum. Instruments which
allow simultaneous measurements are Paschen–
Runge spectrometers or the more compact echelle
spectrometers.
Echelle spectrographs offer excellent spectral
resolving power (lyDl up to 10.000 and more)
in combination with a spectral coverage of several
hundred nanometers. Matched to two-dimensional
multichannel detectors like intensified charge cou-
pled devices, echelle spectrometers represent a new
powerful tool for spectrochemical analysis w71x. In
the mentioned paper, Haisch et al. compared the
detection limits obtained for several elements with
an echelle system with those obtained with a
conventional Czerny–Turner system, showing the
substantial improvements achieved. A systematic
review of echelle vs. traditional spectrometer per-
formances was recently published by Detalle et al.
w72x.
The useful dynamic range of a common spectral
detector is approximately three orders of magni-
tude. In order to measure major and minor con-
stituents as well as trace elements in the lower
micrograms per gram range with single laser shots,
linearity over six or even more orders of magnitude
would be required. Despite the small dynamic
range of the detectors, such measurements can be
made if minor and major constituents of the sample
are measured by weak or very weak lines, respec-
tively, while resonance lines are selected for the
measurement of trace elements w70x.
2.7. Other parameters
When the analysis requires more than one laser
pulse, the effect of repetitive sampling on the same
spot has to be evaluated. Castle et al. w20x studied
the emission intensity during repetitive sampling
on a copper target. The greater reproducibility
(lowest R.S.D.) was obtained when each laser shot
was focused on a fresh surface of the sample. In
completely different samples (soils and sand) Wis-
brun et al. w21x observed the same behavior: higher
intensity and lower R.S.D. value were obtained
irradiating a fresh surface at each new laser pulse.
In the same paper by Castle et al., the precision
of the measurement depending on the number of
accumulated single-shot spectra was evaluated,
again for a pure copper target. Of course, the
R.S.D. improved during the accumulation of the
initial shots, due to the increase of the total counts
number, according to the Poisson statistic. How-
ever, after accumulating several shots (approx.
300), the R.S.D. increased again, revealing that a
different source of noise, not identified by the
authors, became dominant. Also, Dudragne et al.
w73x in a completely different situation (a gaseous
target), found that the maximum of the signal-to-
noise ratio was a function of the number of single
shot spectra accumulated, corresponding of
approximately 1000 shots. The same subject was
studied by Aragon et al. w19x, who demonstrated
that LIBS precision can be improved, achieving
R.S.D. values of 1%, if suitable reference line is
chosen. Wisbrun et al. w21x demonstrated how the
improvement in R.S.D. obtained through accumu-
lation of spectra depends on the signal-to-noise
ratio for the chosen line. In fact, for a weak
spectral line with a signal-to-noise ratio close to
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
1, the accumulation of 100 spectra kept the R.S.D.
unaltered and very high. A better performance was
obtained for a spectral line having a signal-to-
noise ratio of approximately 2, and even better
results were achieved with the accumulation of
spectra of a strong line having a signal-to-noise
ratio of 20.
Specific samples present particular characteris-
tics and problems. Dusty samples, for instance,
produce a persistent amount of aerosol above the
irradiated spot. At high laser repetition rates, the
aerosol production rate is high as well, and a
steady state aerosol concentration is produced
above the sample. Whilst a low concentration of
aerosol increases the signal, higher concentrations
reverse the effect and decrease the signal, mainly
because the laser light is absorbed along the
pathway. The result is that the maximum intensity
for soil samples has been observed at repetition
rates of 1 Hz, while for sand samples the optimal
repetition rate was 6 Hz (Wisbrun et al. w21x).
Similar considerations induced Arca et al. w74x to
use a slow repetition rate of 1 Hz during the
measurement of trace elements in water. In their
experimental apparatus, the laser beam was per-
pendicularly focused on the air-exposed surface of
the water sample through a 30-cm focal length
lens. The repetition rate (as well as the beam
energy) was then adjusted in order to obtain the
best LIBS signal reproducibility. It was found that
a repetition rate of 1 Hz allowed the surface waves
caused by the laser pulse to relax between two
consecutive shots, minimizing the surface
perturbation.
Wisbrun et al. also observed that the humidity
of the sample reduces the plasma emission inten-
sity w21x. This is because part of the pulse energy
is spent in evaporating the water content. The
practical consequence of this effect is that the
samples have to be dried in order to obtain
consistent results. Since the depth sampled by the
laser pulse is very limited, a ‘pulsed’ drying
procedure was suggested by the authors, through
the irradiation of the sample with a flash of a
halogen lamp.
One of the main criticisms addressed to LIBS
is the lack of reproducibility. Even for homogene-
ous samples, reproducibility in the amount of
1127
ablated mass can be poor with single pulsed
ablation (R.S.D. as high as 30–70% are reported),
due to variations of the surface chemical and
physical state, instability in the power and spatial
mode qualities of the laser, and instabilities of the
non-linear laser material interaction w14x. This kind
of instability is even more pronounced during
analysis of heterogeneous materials, such as soils.
The fraction of reflected light varies from pulse to
pulse due to various impact angles on a micro-
scopic level. The optical instabilities cause fluctu-
ations in the ablation process, in the plasma profile
and also in the inspected volume of the plasma
w21x.
Eppler et al. w35x tried to quantify this non-
reproducibility, at least in their experimental con-
ditions. Keeping fixed the same experimental
conditions for a series of 30 repeated measure-
ments, distributed over 3 days, they measured an
R.S.D. of approximately 4%, which was judged a
very satisfactory level of reproducibility.
3. Conclusions
The extreme versatility of the LIBS technique
suggests the use of different experimental config-
urations for different specific applications; it thus
seems evident that the ‘optimal’ LIBS configura-
tion is probably still far from being proposed.
However, the works that we have reported here,
have clarified that at least for broad categories of
materials (metallic alloys, liquids, soils, etc.) some
experimental configurations seem to be more suit-
able than others for obtaining quantitative LIBS
results. These general guidelines can be extremely
useful in designing new LIBS experiments, or for
the realization of commercial LIBS
instrumentation.
References
w1x L.J. Radziemski, D.A. Cremers, Laser-Induced Plasmas
and Applications, Marcel Dekker, Inc, New York, 1989.
w2x T.L. Thiem, Y.I. Lee, J. Sneddon, Lasers in atomic
spectroscopy: selected applications, Microchem. J. 45
(1992) 1–35.
w3x V. Majidi, M.R. Joseph, Spectroscopic applications of
laser-induced plasmas, Crit. Rev. Anal. Chem. 23 (1992)
143–162.
1128 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
w4x D.A. Rusak, B.C. Castle, B.W. Smith, J.D. Winefordner,
Fundamentals and applications of laser-induced break-
down spectroscopy, Crit. Rev. Anal. Chem. 27 (1997)
257–290.
w5x K. Song, Y.I. Lee, J. Sneddon, Applications of laser-
induced breakdown spectrometry, Appl. Spectrosc. Rev.
32 (1997) 183–235.
w6x R.J. Harrach, Theory of laser-induced breakdown over
a vaporizing target surface, Lawrence Livermore Lab-
oratory Report, 1977.
w7x C.R. Phipps, R.W. Dreyfus, Laser ablation and plasma
formation, in: A. Vertes, R. Gijbels, F. Adams (Eds.),
Laser Ionization Mass Analysis, Wiley and Sons, New
York, 1993.
w8x A.P. Thorne, Spectrophysics, Chapman and Hall, Lon-
don, 1974.
w9x A. Ciucci, M. Corsi, V. Palleschi, S. Rastelli, A. Salvetti,
E. Tognoni, New procedure for quantitative elemental
analysis by laser-induced plasma spectroscopy, Appl.
Spectrosc. 53 (1999) 960–964.
w10x M. Corsi, V. Palleschi, A. Salvetti, E. Tognoni, Making
LIBS quantitative: a critical review of the current
approaches to the problem, Res. Adv. Appl. Spectrosc.
1 (2000) 41–47.
w11x E. Tognoni, M. Corsi, G. Cristoforetti, V. Palleschi, N.
Omenetto, I. Gornushkin, B.W. Smith, J.D. Winefordner.
From sample to signal: a complex route to quantitative
analysis, in: A. Miziolek, V. Palleschi, I. Schechter
(Eds.), LIBS: Fundamentals and Applications, Cam-
bridge University Press, in press.
w12x L.M. Cabalin, J.J. Laserna, Experimental determination
of laser induced breakdown thresholds of metals under
nanosecond Q-switched laser operation, Spectrochim.
Acta Part B 53 (1998) 723–730.
w13x M. Milan, J.J. Laserna, Diagnostics of silicon plasmas
produced by visible nanosecond laser ablation, Spectro-
chim. Acta Part B 56 (2001) 275–288.
w14x R.E. Russo, Laser ablation, Appl. Spectrosc. 49 (1995)
14A–28A.
w15x W.T. Chan, R.E. Russo, Study of laser–material inter-
actions using inductively coupled plasma-atomic emis-
sion spectrometry, Spectrochim. Acta Part B 46 (1991)
1471–1486.
w16x C. Chaleard, P. Mauchien, N. Andre, J. Uebbing, J.L.
Lacour, C. Geertsen, Correction of matrix effects in
quantitative elemental analysis with laser ablation opti-
cal emission spectrometry, J. Anal. At. Spectrom. 12
(1997) 183–188.
w17x R.E. Russo, X.L. Mao, Chemical analysis by laser
ablation, in: M.C. Miller (Ed.), Laser Ablation and
Desorption, Academic Press, San Diego, 1998, pp.
375–412.
w18x M. Sabsabi, P. Cielo, Quantitative analysis of aluminum
alloys by laser-induced breakdown spectroscopy and
plasma characterization, Appl. Spectrosc. 49 (1995)
499–507.
w19x C. Aragon, J.A. Aguilera, F. Penalba, Improvements in
quantitative analysis of steel composition by laser-
induced breakdown spectroscopy at atmospheric pres-
sure using an infrared Nd: YAG laser, Appl. Spectrosc.
53 (1999) 1259–1267.
w20x B.C. Castle, K. Talabardon, B.W. Smith, J.D. Wineford-
ner, Variables influencing the precision of laser-induced
breakdown spectroscopy measurements, Appl. Spec-
trosc. 52 (1998) 649–657.
w21x R. Wisbrun, I. Schechter, R. Niessner, H. Schroder, K.
Kompa, Detector for trace elemental analysis of solid
environmental samples by laser plasma spectroscopy,
Anal. Chem. 66 (1994) 2964–2975.
w22x Y.W. Kim, Fundamentals of analysis of solids by laser-
produced plasmas, in: L.J. Radziemski, D.A. Cremers
(Eds.), Laser-Induced Plasmas and Applications, Marcel
Dekker, Inc, New York, 1989.
w23x S. Amoruso, M. Armenante, V. Berardi, R. Bruzzese,
N. Spinelli, Absorption and saturation mechanisms in
aluminium laser ablated plasmas, Appl. Phys. A 65
(1997) 265–271.
w24x G.M. Weyl, Physics of laser-induced breakdown: an
update, in: L.J. Radziemski, D.A. Cremers (Eds.), Laser-
Induced Plasmas and Applications, Marcel Dekker, New
York, 1989, pp. 1–67.
w25x X.L. Mao, A.C. Ciocan, O.V. Borisov, R.E. Russo, Laser
ablation processes investigated using inductively cou-
pled plasma-atomic emission spectroscopy (ICP-AES),
Appl. Surf. Sci. 127–129 (1998) 262–268.
w26x W. Sdorra, J. Brust, K. Niemax, Basic investigations for
laser microanalysis: IV. The dependence on the laser
wavelength in laser ablation, Mikrochim. Acta 108
(1992) 1–10.
w27x L.M. Berman, P.J. Wolf, Laser-induced breakdown spec-
troscopy of liquids: aqueous solutions of nickel and
chlorinated hydrocarbons, Appl. Spectrosc. 52 (1998)
438–443.
w28x C.W. Ng, W.F. Ho, N.H. Cheung, Spectrochemical anal-
ysis of liquids using laser-induced plasma emissions:
effects of laser wavelength on plasma properties, Appl.
Spectrosc. 51 (1997) 976–983.
w29x X.L. Mao, A.C. Ciocan, R.E. Russo, Preferential vapor-
ization during laser ablation inductively coupled plasma
atomic emission spectroscopy, Appl. Spectrosc. 52
(1998) 913–918.
w30x R.E. Russo, X.L. Mao, O.V. Borisov, H.C. Liu, Influence
of wavelength on fractionation in laser ablation ICP-
MS, J. Anal. At. Spectrom. 15 (2000) 1115–1120.
w31x C. Haisch, J. Liermann, U. Panne, R. Niessner, Char-
acterization of colloidal particles by laser-induced plas-
ma spectroscopy (LIPS), Anal. Chim. Acta 346 (1997)
23–35.
w32x A. Ciucci, V. Palleschi, S. Rastelli, R. Barbini, F. Colao,
R. Fantoni, A. Palucci, S. Ribezzo, H.J.L. van der Steen,
Trace pollutants analysis in soil by a time-resolved
laser-induced breakdown spectroscopy technique, Appl.
Phys. B 63 (1996) 185–190.
 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
w33x F. Leis, W. Sdorra, J.B. Ko, K. Niemax, Basic investi-
gations for laser microanalysis: I. Optical emission
spectrometry of laser-produced sample plumes, Mikro-
chim. Acta II (1989) 185–199.
w34x M. Sabsabi, P. Cielo, Quantitative analysis of copper
alloys by laser-produced plasma spectrometry, J. Anal.
At. Spectrom. 10 (1995) 643–647.
w35x A.S. Eppler, D.A. Cremers, D.D. Hickmott, M.J. Ferris,
A.C. Koskelo, Matrix effects in the detection of Pb and
Ba in soils using laser-induced breakdown spectroscopy,
Appl. Spectrosc. 50 (1996) 1175–1181.
w36x R. Krasniker, V. Bulatov, I. Schechter, Study of matrix
effects in laser plasma spectroscopy by shock wave
propagation, Spectrochim. Acta Part B 56 (2001)
609–618.
w37x K.Y. Yamamoto, D.A. Cremers, M.J. Ferris, L.E. Foster,
Detection of metals in the environment using a portable
laser-induced breakdown spectroscopy instrument, Appl.
Spectrosc. 50 (1996) 222–233.
w38x R. Barbini, F. Colao, R. Fantoni, A. Palucci, S. Ribezzo,
H.J.L. van der Steen, M. Angelone, Semi-quantitative
time resolved LIBS measurements, Appl. Phys. B 65
(1997) 101–107.
w39x H.S. Zhang, F.Y. Yueh, J.P. Singh, Laser-induced break-
down spectrometry as a multimetal continuous-emission
monitor, Appl. Opt. 38 (1999) 1459–1466.
w40x R.E. Neuhauser, U. Panne, R. Niessner, Laser-induced
plasma spectroscopy (LIPS): a versatile tool for moni-
toring heavy metal aerosols, Anal. Chim. Acta 392
(1999) 47–54.
w41x B.J. Marquardt, D.N. Stratis, D.A. Cremers, S.M. Angel,
Novel probe for laser-induced breakdown spectroscopy
and Raman measurements using an imaging optical
fiber, Appl. Spectrosc. 52 (1998) 1148–1153.
w42x R.E. Neuhauser, U. Panne, R. Niessner, Utilization of
fiber optics for remote sensing by laser-induced plasma
spectroscopy (LIPS), Appl. Spectrosc. 54 (2000)
923–927.
w43x A.I. Whitehouse, J. Young, I.M. Botheroyd, S. Lawson,
C.P. Evans, J. Wright, Remote material analysis of
nuclear power station steam generator tubes by laser-
induced breakdown spectroscopy, Spectrochim. Acta
Part B 56 (2001) 821–830.
w44x A.K. Rai, H.S. Zhang, F.Y. Yueh, J.P. Singh, A. Weis-
burg, Parametric study of a fiber-optic laser-induced
breakdown spectroscopy probe for analysis of aluminum
alloys, Spectrochim. Acta Part B 56 (2001) 2371–2383.
w45x R.A. Multari, L.E. Foster, D.A. Cremers, M.J. Ferris,
Effect of sampling geometry on elemental emissions in
laser-induced breakdown spectroscopy, Appl. Spectrosc.
50 (1996) 1483–1499.
w46x L.I. Sedov, Similarity and Dimensional Methods in
Mechanics, MIR Publishers, Moscow, 1981.
w47x M. Gatti, V. Palleschi, A. Salvetti, D.P. Singh, M.
Vaselli, Spherical shock waves in laser produced plas-
mas in gas, Opt. Commun. 69 (1988) 141–146.
1129
w48x D.E. Kim, K.J. Yoo, H.K. Park, K.J. Oh, D.W. Kim,
Quantitative analysis of aluminum impurities in zinc
alloy by laser-induced breakdown spectroscopy, Appl.
Spectrosc. 51 (1997) 22–29.
w49x P. Fichet, P. Mauchien, J.F. Wagner, C. Moulin, Quan-
titative elemental determination in water and oil by laser
induced breakdown spectroscopy, Anal. Chim. Acta 429
(2001) 269–278.
w50x H.C. Liu, X.L. Mao, J.H. Yoo, R.E. Russo, Early phase
laser induced plasma diagnostics and mass removal
during single-pulse laser ablation of silicon, Spectro-
chim. Acta Part B 54 (1999) 1607–1624.
w51x A. Ciucci, V. Palleschi, S. Rastelli, A. Salvetti, D.P.
Singh, E. Tognoni, Effect of imperfect focusing in laser-
induced plasma spectroscopy measurements, Nuovo-
Cimento-D 20D (1998) 1469–1478.
w52x Y.I. Lee, S.P. Sawan, T.L. Thiem, Y.Y. Teng, J. Sneddon,
Interaction of a laser beam with metals. II. Space-
resolved studies of laser-ablated plasma emission, Appl.
Spectrosc. 46 (1992) 436–441.
w53x T.N. Hansen, J. Schou, J.G. Lunney, Angular distribu-
tions of silver ions and neutrals emitted in vacuum by
laser ablation, Europhys. Lett. 40 (1997) 441–446.
w54x K.J. Grant, G.L. Paul, Electron temperature and density
profiles of excimer laser-induced plasmas, Appl. Spec-
trosc. 44 (1990) 1349–1354.
w55x W. Sdorra, K. Niemax, Basic investigations for laser
microanalysis: III. Application of different buffer gases
for laser-produced sample plumes, Mikrochim. Acta 107
(1992) 319–327.
w56x Y. IIda, Effects of atmosphere on laser vaporization and
excitation processes of solid samples, Spectrochim. Acta
Part B 45 (1990) 1353–1367.
w57x J. Hermann, C. Boulmer Leborgne, D. Hong, Diagnos-
tics of the early phase of an ultraviolet laser induced
plasma by spectral line analysis considering self-absorp-
tion, J. Appl. Phys. 83 (1998) 691–696.
w58x T.L. Thiem, R.H. Salter, J.A. Gardner, Y.I. Lee, J.
Sneddon, Quantitative simultaneous elemental determi-
nations in alloys using laser-induced breakdown spec-
troscopy (LIBS) in an ultra-high vacuum, Appl.
Spectrosc. 48 (1994) 58–64.
w59x A.E. Pichahchy, D.A. Cremers, M.J. Ferris, Elemental
analysis of metals under water using laser-induced
breakdown spectroscopy, Spectrochim. Acta Part B 52
(1997) 25–39.
w60x R. Sattmann, V. Sturm, R. Noll, Laser-induced break-
down spectroscopy of steel samples using multiple Q-
switch Nd:YAG laser pulses, J. Phys. D 28 (1995)
2181–2187.
w61x D.N. Stratis, K.L. Eland, S.M. Angel, Effect of pulse
delay time on a pre-ablation dual-pulse LIBS plasma,
Appl. Spectrosc. 55 (2001) 1297–1303.
w62x D.N. Stratis, K.L. Eland, S.M. Angel, Enhancement of
aluminum, titanium, and iron in glass using pre-ablation
spark dual-pulse LIBS, Appl. Spectrosc. 54 (2000)
1719–1726.
1130 E. Tognoni et al. / Spectrochimica Acta Part B 57 (2002) 1115–1130
w63x D.N. Stratis, K.L. Eland, S.M. Angel, Dual-pulse LIBS
using a pre-ablation spark for enhanced ablation and
emission, Appl. Spectrosc. 54 (2000) 1270–1274.
w64x L. St-Onge, M. Sabsabi, P. Cielo, Analysis of solids
using laser-induced plasma spectroscopy in double-pulse
mode, Spectrochim. Acta Part B 53 (1998) 407–415.
w65x L. St-Onge, V. Detalle, M. Sabsabi, Enhanced laser-
induced breakdown spectroscopy using the combination
of fourth-harmonic and fundamental Nd: YAG laser
pulses, Spectrochim. Acta Part B 57 (2002) 121–135.
w66x B.W. Smith, A. Quentmeier, M. Bolshov, K. Niemax,
Measurement of uranium isotope ratios in solid samples
using laser ablation and diode laser-excited atomic
fluorescence spectrometry, Spectrochim. Acta Part B 54
(1999) 943–958.
w67x I.B. Gornushkin, S.A. Baker, B.W. Smith, J.D. Wine-
fordner, Determination of lead in metallic reference
materials by laser ablation combined with laser excited
atomic fluorescence, Spectrochim. Acta Part B 52
(1997) 1653–1662.
w68x F. Hilbk Kortenbruck, R. Noll, P. Wintjens, H. Falk, C.
Becker, Analysis of heavy metals in soils using laser-
induced breakdown spectrometry combined with laser-
induced fluorescence, Spectrochim. Acta Part B 56
(2001) 933–945.
w69x H.H. Telle, D.C.S. Beddows, G.W. Morris, O. Samek,
Sensitive and selective spectrochemical analysis of
metallic samples: the combination of laser-induced
breakdown spectroscopy and laser-induced fluorescence
spectroscopy, Spectrochim. Acta Part B 56 (2001)
947–960.
w70x H.E. Bauer, F. Leis, K. Niemax, Laser induced break-
down spectrometry with an echelle spectrometer and
intensified charge coupled device detection, Spectro-
chim. Acta Part B 53 (1998) 1815–1825.
w71x C. Haisch, U. Panne, R. Niessner, Combination of an
intensified charge coupled device with an echelle spec-
trograph for analysis of colloidal material by laser-
induced plasma spectroscopy, Spectrochim. Acta Part B
53 (1998) 1657–1667.
w72x V. Detalle, R. Heon, M. Sabsabi, L. St Onge, An
evaluation of a commercial Echelle spectrometer with
intensified charge-coupled device detector for materials
analysis by laser-induced plasma spectroscopy, Spectro-
chim. Acta Part B 56 (2001) 1011–1025.
w73x L. Dudragne, P. Adam, J. Amouroux, Time-resolved
laser-induced breakdown spectroscopy: application for
qualitative and quantitative detection of fluorine, chlo-
rine, sulfur, and carbon in air, Appl. Spectrosc. 52
(1998) 1321–1327.
w74x G. Arca, A. Ciucci, V. Palleschi, S. Rastelli, E. Tognoni,
Trace element analysis in water by the laser-induced
breakdown spectroscopy technique, Appl. Spectrosc. 51
(1997) 1102–1105.