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Extracting Time-Resolved Information from Time-Integrated Laser-Induced

Breakdown Spectra

Article in Journal of Spectroscopy · December 2014

DOI: 10.1155/2014/849310

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Hindawi Publishing Corporation
Journal of Spectroscopy
Volume 2014, Article ID 849310, 5 pages
http://dx.doi.org/10.1155/2014/849310

Research Article
Extracting Time-Resolved Information from
Time-Integrated Laser-Induced Breakdown Spectra

Emanuela Grifoni,1 Stefano Legnaioli,1 Marco Lezzerini,2 Giulia Lorenzetti,1

Stefano Pagnotta,1 and Vincenzo Palleschi1,3
1
Applied and Laser Spectroscopy Laboratory, ICCOM-CNR, Research Area of Pisa, Via G. Moruzzi 1, 56124 Pisa, Italy
2
Department of Earth Sciences, University of Pisa, Via S. Maria 53, 56126 Pisa, Italy
3
Department of Civilizations and Forms of Knowledge, University of Pisa, Via L. Galvani 1, 56126 Pisa, Italy

Correspondence should be addressed to Vincenzo Palleschi; vincenzo.palleschi@cnr.it

Received 29 October 2014; Revised 6 December 2014; Accepted 9 December 2014; Published 29 December 2014

Academic Editor: Violeta Lazic

Copyright © 2014 Emanuela Grifoni et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

Laser-induced breakdown spectroscopy (LIBS) data are characterized by a strong dependence on the acquisition time after the
onset of the laser plasma. However, time-resolved broadband spectrometers are expensive and often not suitable for being used in
portable LIBS instruments. In this paper we will show how the analysis of a series of LIBS spectra, taken at different delays after
the laser pulse, allows the recovery of time-resolved spectral information. The comparison of such spectra is presented for the
analysis of an aluminium alloy. The plasma parameters (electron temperature and number density) are evaluated, starting from the
time-integrated and time-resolved spectra, respectively. The results are compared and discussed.

1. Introduction
The importance of performing time-resolved measurements
in LIBS was stressed many years ago by Cadwell et al. [1],
who introduced the acronym TRELIBS (time-resolved LIBS)
to identify this kind of analysis. The plasma parameters, in
LIBS, vary in space and time; the very concept of plasma
temperature and electron density makes sense only in the
framework of a Local Thermal Equilibrium approximation
[2], which may hold in a limited temporal window, but is
surely not fulfilled in the first moments of plasma creation
and expansion (the plasma expansion characteristic times
being larger than the collisional equilibrium time) and in the
last part of the plasma lifetime, when the plasma cools down
and the electron number density drops below the limit value
given by the McWhirter criterion [3]. Therefore, any kind of
LIBS analysis which relies on the calculation of one of the
parameters above should be, in principle, performed using a
time- (and space-) resolved spectrometer.
However, time-resolved broadband spectrometers, as the
one used in LIBS applications, are in general expensive and
they are often not suitable, because of their dimensions, com-
plexity, and sensitivity to external variables such as ambient
temperature, for any use outside of the laboratory. Cheap
broadband spectrometers, on the other hand, are robust and
reliable for the use in mobile and portable LIBS instruments,
providing a more than acceptable spectral resolution, but
their spectral acquisition can only be delayed with respect
to the laser pulse, being the integration time typically much
longer than the plasma lifetime.
One can thus wonder whether the plasma parameters
that can be calculated from such time-integrated spectra,
at a given delay from the laser pulse, would be actually
representative of the “true” values of plasma temperature and
electron number density at that moment. From an intuitive
point of view, since the LIBS spectral intensity is an exponen-
tially decreasing function of the acquisition delay time, it is
reasonable to hypothesize that the main contribution to the
time-integrated spectrum would come from a very limited
temporal window, of the order of the decay time of the signal,
thus mimicking the effect of a time-resolved measurement
(see Figure 1).
2 Journal of Spectroscopy

Table 1: Acquisition delays used in this work. An additional internal delay of 260 ns must be added to the set delay for obtaining the actual
delay from the second laser pulse.

Set delay (ns) Actual delay (ns) (Δ𝑡𝑖 + Δ𝑡𝑖+1 )/2 (ns) Δ𝑡𝑖+1 − Δ𝑡𝑖 (ns)
Δ𝑡1 0 260 301 83
Δ𝑡2 83 343 405 125
Δ𝑡3 208 468 614 292
Δ𝑡4 500 760 1010 500
Δ𝑡5 1000 1260 1760 1000
Δ𝑡6 2000 2260 3760 3000
Δ𝑡7 5000 5260 7760 5000
Δ𝑡8 10000 10260 — —

Equivalent gate time Pulse 1 Pulse 2

1.0

0.8
LIBS spectral intensity (a.u.)

I0
0.6

0.4
I0 /e

t
0.2 1 𝜇s Δt 2.48 ms

Figure 2: Scheme of the acquisition delay and gate.

Delay
0.0
0 5 10 15 20 25 30 35
Time (a.u.) 18000

16000
Figure 1: Equivalent gate time in time-integrated LIBS analysis.
14000

12000
LIBS signal (a.u.)

The purpose of this work is the analysis of the temporal

dependence of time-integrated LIBS spectra, acquired at 10000
different delay times in single and double pulse configuration 8000
on an aluminium sample, with the aim of reconstructing
6000
time-resolved spectra and comparing the plasma parameters
estimated from these spectra with the ones obtained using a 4000
time-integrated approach.
2000

0
2. Experimental Procedure
200 300 400 500 600 700 800 900
With the purpose of obtaining time-resolved information Wavelength (nm)
from the time-integrated spectra, we acquired a set of LIBS 260 ns
spectra of a target, an aluminium sample of known compo- 468 ns
sition, using the Modı̀ Instrument [4], which is based on a 1260 ns
double-pulse [5] Nd:YAG laser, operating at the wavelength
Figure 3: Time-integrated spectra.
of 1064 nm. In the present experiment, the two laser pulses
were delayed of 1 𝜇s; each pulse had energy of 60 mJ in
10 ns. The laser pulses were focused on the target, using a
100 mm focal length lens. The LIBS signal was collected with to 10260 ns (see Figure 2 and Table 1). The integration time of
an optical fiber and sent to a AvaSpec Dual-channel Fiber the spectrometer was 2.48 ms.
Optic Spectrometer from Avantes; the acquisition time was 100 spectra were independently acquired and then aver-
delayed with respect to the first laser pulse in such a way aged, to obtain a better signal/noise ratio.
to have an effective acquisition delay from the second pulse In Figure 3 are shown three time-integrated spectra,
ranging from 260 ns (internal delay of the spectrometer) up acquired at the delays of 240, 468, and 1260 ns (see Table 1).
Journal of Spectroscopy 3

2000 1800
Al III
1600

1500 1400

LIBS intensity (a.u.)

1200
LIBS signal (a.u.)

1000
1000
800 Al II
600
500
400

200
0 0
200 300 400 500 600 700 800 900 440 445 450 455 460 465 470
Wavelength (nm) Wavelength (Å)
301 ns 301 ns 614 ns
405 ns 405 ns 1010 ns
1010 ns
(a)
Figure 4: Time-resolved spectra. 7000
Time-integrated LIBS intensity (a.u.)
6000
3. Time-Resolved Spectra Al II
5000
The intensity of the time-integrated spectra can be expressed
as 4000
∞
Al III
𝐼 (𝑡0 ) = ∫ 𝐼 (𝑡) 𝑑𝑡, (1) 3000
𝑡0
2000
where 𝐼(𝑡) represents the LIBS spectral intensity (time-
depending) at a given wavelength, 𝑡0 is the acquisition delay 1000
time with respect to the laser beam, and the upper limit of
the integral is approximated to infinity (much larger than the 0
lifetime of the plasma). 440 445 450 455 460 465 470
𝐼(𝑡) can be obtained by differentiating (1) in the form Wavelength (nm)
260 ns 468 ns
𝑑𝐼 (𝑡0 ) 343 ns 760 ns
𝐼 (𝑡) = . (2)
𝑑𝑡0 (b)

Since 𝐼(𝑡0 ) is known only at the discrete intervals reported Figure 5: Al III and Al II emission, evaluated from time-resolved
in Table 1, the differentiation must be done numerically, (a) and time-integrated (b) spectra.
according to the formula

Δ𝑡𝑖 + Δ𝑡𝑖+1 𝐼 (Δ𝑡𝑖+1 ) − 𝐼 (Δ𝑡𝑖 )
𝐼( )=
2 Δ𝑡𝑖+1 − Δ𝑡𝑖
Note that the numerical evaluation of the derivative is cal-
culated at the time (Δ𝑡𝑖 + Δ𝑡𝑖+1 )/2, although no actual mea-
surement is done at that delay time.
In Figure 4 are shown three time-resolved spectra calcu-
lated at 301, 405, and 1010 ns (see Table 1).
The time-resolved LIBS spectra make the sharp decrease
in spectral intensity evident with the increase of the time
delay. Their analysis also reveals the presence of intense
emission lines from higher ionization stages of aluminium,
such as Al III, whose presence dominates the time-resolved
spectra at early delays in a way that is not so evident in the
original time-integrated spectra.
Figure 5 shows the three main Al III emission lines in the
. (3) region around 450 nm, in comparison with the Al II line at
466.3 nm; in the time-resolved spectra the Al III emission is
stronger than the Al II one at delays shorter than 500 ns. On
the other hand, in the time-integrated spectra the three Al III
lines always appear less intense than the Al II emission.
Another interesting comparison between time-integrated
and time-resolved spectra is the one involving the intensity
of the LIBS spectra, integrated over the whole spectral range
(200–900 nm) (Figure 6).
As expected, the total LIBS intensity decays exponentially
with the acquisition delay. However, while in time-integrated
measurements the decay constants are of the order of 600 ns,
the time-resolved analysis reveals that the actual decay time
is a factor of three shorter (200 ns).
4 Journal of Spectroscopy

1400
300
1200

Time-resolved LIBS intensity (a.u.)

250
Total LIBS intensity (a.u.)

1000
200
800
150
𝜏 = 580 ns 600
𝜏 = 740 ns
100
400

50
𝜏 = 210 ns 200 𝜏 = 810 ns

0 0
0 2000 4000 6000 8000 10000 0 1000 2000 3000 4000 5000 6000 7000 8000
Δt (ns) Δt (ns)
Time-integrated Al II 358.7 nm
Time-resolved Al I 281.6 nm

Figure 6: Dependence of the total LIBS intensity on the acquisition Figure 7: Dependence of the LIBS signal on the acquisition
delay. The dotted curves are the best fit with an exponential function. delay. The dashed curves represent the best fit of the data with
Red circles: time-integrated spectra; black squares: time-resolved an exponential function. Red circles: Al I line at 281.6 nm; black
spectra. squares: Al II line at 358.6 nm.

The decay time of the total LIBS emission is essentially 1.2

dominated by the decay of the continuum radiation. The
Electron temperature (eV)

decay time of the emission lines is longer and varies from line 1.1
to line, since the line intensity depends exponentially on the
ratio between the energy of the upper level of the transition 1.0
(𝐸𝑘 ) and the plasma electron temperature (𝑘𝐵 𝑇), where 𝑘𝐵 is
the Boltzmann constant: 0.9

𝐼 (𝑡) ∝ 𝑒−𝐸𝑘 /𝑘𝐵 𝑇(𝑡) . (4) 0.8

A further dependence on the plasma parameters is given 0.7

by the Saha-Boltzmann equilibrium between neutrals and
ionized species, with the ionized lines decaying faster than the 0.6
neutral ones because of the decrease of plasma temperature 0 1000 2000 3000 4000 5000 6000 7000 8000
and electron density with the delay time. Δt (ns)
This effect is clearly visible in the time-resolved spectra, Time-integrated
as evidenced in Figure 7. Time-resolved

Figure 8: Comparison of plasma electron temperature evaluated

4. Determination of the Plasma Parameters
In the hypothesis of Local Thermal Equilibrium conditions
[2] the electron temperature can be estimated from the
calculation of the intensity ratio of two lines emitted by the
same species:
𝑔𝑙 𝐴 𝑙𝑚 𝐼𝑘𝑖
log ( 𝑙𝑚
)=− 𝑘
𝑔𝑘 𝐴 𝑘𝑖 𝐼
where 𝐴 𝑘𝑖 and 𝐴 𝑙𝑚 are the transition probabilities of the two
lines, 𝑔𝑘 and 𝑔𝑖 are the degeneracies of the upper level, and 𝐸𝑘
and 𝐸𝑙 are the energies of the upper levels of the transition.
In Figure 8 the time evolution of the electron temperature
is reported, calculated from the ratio of the two Al II lines at
281.6 nm (𝐸𝑘 = 9.5 × 104 cm−1 ) and 358.6 nm (𝐸𝑘 = 1.23 ×
105 cm−1 ).
from time-integrated and time-resolved spectra. The dotted line
represents the best exponential fit of the data.
Figure 8 confirms the idea that the time-integrated spec-
tra are essentially equivalent, for what is concerned with the
(𝐸 − 𝐸𝑙 ) evaluation of the plasma parameters, to the time-resolved
, (5) spectra, with an “equivalent gate time” roughly corresponding
𝑘𝐵 𝑇
to the decay constant of the LIBS lines’ intensity, which in our
case is of the order 800 ns (see Figure 7).
The same conclusion can be achieved for the calculation
of the electron number density (see Figure 9), which can be
estimated by measuring the Stark linewidth of the Balmer
alpha hydrogen line at 656.3 nm [6].
In spite of the relatively large experimental errors, the
electron number density obtained from the time-resolved
Journal of Spectroscopy 5

4.5 [3] R. W. P. McWhirter, R. H. Huddlestone, and S. L. Leonard, Eds.,

Plasma Diagnostic Techniques, chapter 5, Academic Press, New
Electron number density (cm−3 ×1017 )

4.0
York, NY, USA, 1965.
3.5 [4] A. Bertolini, G. Carelli, F. Francesconi et al., “Modı̀: a new
mobile instrument for in situ double-pulse LIBS analysis,”
3.0
Analytical and Bioanalytical Chemistry, vol. 385, no. 2, pp. 240–
2.5 247, 2006.
[5] F. Colao, V. Lazic, R. Fantoni, and S. Pershin, “A comparison of
2.0
single and double pulse laser-induced breakdown spectroscopy
1.5 of aluminum samples,” Spectrochimica Acta Part B: Atomic
Spectroscopy, vol. 57, no. 7, pp. 1167–1179, 2002.
1.0
[6] A. M. El Sherbini, H. Hegazy, and T. M. El Sherbini, “Mea-
0.5 surement of electron density utilizing the H𝛼-line from laser
produced plasma in air,” Spectrochimica Acta Part B: Atomic
0.0
Spectroscopy, vol. 61, no. 5, pp. 532–539, 2006.
0 2000 4000 6000 8000 10000
Δt (ns)
Time-integrated
Time-resolved

Figure 9: Comparison of plasma electron number density, evalu-

ated from time-integrated and time-resolved spectra. The dotted line
represents the best exponential fit of the data.

spectra is in good agreement with the values derived from

the time-integrated ones.

5. Conclusion
The simple method illustrated in this paper allows recovery of
time-resolved spectra using time-integrated spectrometers.
The technique is applicable whenever the spectral acqui-
sition system has the capability of starting the acquisition
at a programmable delay after the laser pulse. The results
presented also support the idea that the time-integrated
spectra give information about the plasma parameters which
is substantially equivalent to the information that could be
obtained using a time-resolved spectrometer, with a gate time
comparable with the decay time of the LIBS spectral intensity,
which is, in the typical LIBS conditions, of the order of a few
hundreds of nanoseconds.

Conflict of Interests
The authors declare that there is no conflict of interests
regarding the publication of this paper.

References
[1] L. Cadwell, J. Belliveau, L. Huwell, and H. Griffin, “LIBS vs
TRELIBS—the relative merits of laser-induced breakdown
spectroscopy versus time resolved laser-induced breakdown
spectroscopy,” in Remote Sensing, vol. 644 of Proceedings of
SPIE, pp. 16–18, 1986.
[2] G. Cristoforetti, A. De Giacomo, M. Dell’Aglio et al., “Local
thermodynamic equilibrium in laser-induced breakdown spec-
troscopy: beyond the McWhirter criterion,” Spectrochimica Acta
Part B, vol. 65, no. 1, pp. 86–95, 2010.

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