Optical diagnosis and theoretical simulation

of laser induced lead plasma spectrum

Cite as: Phys. Plasmas 19, 013302 (2012); https://doi.org/10.1063/1.3676633
Submitted: 20 September 2011 • Accepted: 05 December 2011 • Published Online: 20 January 2012

Hong Bo Fu, Chuan Song Chen, Bao Yuan Man, et al.

ARTICLES YOU MAY BE INTERESTED IN

The role of laser wavelength on plasma generation and expansion of ablation plumes in air
Journal of Applied Physics 113, 143305 (2013); https://doi.org/10.1063/1.4800925

Experimental and computational study of complex shockwave dynamics in laser ablation

plumes in argon atmosphere
Physics of Plasmas 19, 083504 (2012); https://doi.org/10.1063/1.4745867

Quantitative analysis of Al-Si alloy using calibration free laser induced breakdown
spectroscopy (CF-LIBS)
Physics of Plasmas 24, 063516 (2017); https://doi.org/10.1063/1.4985327

Phys. Plasmas 19, 013302 (2012); https://doi.org/10.1063/1.3676633 19, 013302

© 2012 American Institute of Physics.

 PHYSICS OF PLASMAS 19, 013302 (2012)

Optical diagnosis and theoretical simulation of laser induced

lead plasma spectrum
Hong Bo Fu, Chuan Song Chen, Bao Yuan Man,a) Xiao Song, and Dong Liu
College of Physics and Electronics, Shandong Normal University, Jinan 250014, People’s Republic of China
(Received 20 September 2011; accepted 5 December 2011; published online 20 January 2012)
Plasmas generated during incipient laser ablation of lead in air were studied using emission
spectroscopy and fast photography by an intensified charge coupled device (ICCD) camera. An
improved plasma emission model was introduced, invoking one-dimensional radiative transfer, to
describe the observed emission spectra, while taking into account Gaussian intensity distribution of
the laser used to form plasma. The effects of different parameters to the fitting results are discussed.
The plasma temperature got by Saha-Boltzmann plot method and the electron number density got
by line broadening method were compared with the fitting results. We also found that the distribu-
tion of plasma temperature is more uniform than that of the electron number density in the radial
C 2012 American Institute of Physics. [doi:10.1063/1.3676633]
direction. V

I. INTRODUCTION obtained by the simulation of the spectra with self-reversed

Laser-induced breakdown spectroscopy (LIBS) was first
recorded in 1963 by Maker et al.1 At present, LIBS have
achieved great interest as spectroscopic tool. The optical
emission spectroscopy (OES) of LIBS has become a very
useful tool for the fundamental researches of the interaction
of laser beams with materials, advanced micromachining,
thin-film deposition, and exploring the metal contents in
alloy and in soils.2–4 As an analytical technique, LIBS has
proved its unique versatility, permitting fast contact-less
analysis of almost any type of material, and the possibility to
adapt the technique to the special requirements of diverse
practical analytical problems.
The electron temperature and the electron number den-
sity are very important parameters for plasma. The problem
how to determine them has attracted the attention of numer-
ous researchers.5–8 Many scholars commonly use the line
broadening method and the Boltzmann plot method to deter-
mine the electron number density and the electron tempera-
ture.2,9 However, both the methods can be only used in the
case of the continuous spectrum is very weak relative to the
characteristic lines and the emission spectrum without
obvious self-absorption. Sakka et al.10 had described the
characteristics of plasma emission and absorption spectrum
theory based on the results of previous studies. Meanwhile,
they fitted the experimentally observed self-reversed emis-
sion profiles to the model which was based on the calculation
of one-dimensional radiative transfer. And they discussed
the impact of various parameters upon calculated results. A
plasma emission model was developed by Pakhal et al.,11
invoking one-dimensional radiative transfer, to describe the
observed emission spectra, meanwhile taking into account
the effect of continuum radiation. Less given parameters
were used in such model. The Al plasma temperature and
electron number density at different delay times were
a)
Author to whom correspondence should be addressed. Electronic addresses:
byman@sdnu.edu.cn and byman@yahoo.cn. Fax: þþ86-531-86180804.
structure.
In this work, the emission spectra and the images of lead
plasma were acquired at different delay times. The lead
plasma temperature and the electron number density were
got by the Saha-Boltzmann plot method and the line broad-
ening method, respectively. In theory, we used an improved
model based on the one given by Pakhal et al.11 to fit the
emission spectra. The effects of different parameters to fit-
ting results are discussed, respectively. The plasma tempera-
ture got by Saha-Boltzmann plot method and the electron
number density got by line broadening method were com-
pared with the fitting results. The improved model takes into
account the Gaussian distribution of the total particle
numbers in plasma interested.
II. THE EXPERIMENTAL EQUIPMENT
The experimental system had been illustrated in Refs.
12 and 13. The laser beam was produced by a Q-switched
Nd: YAG laser (Spectra Physics Quanta-RayDCR-3). The
laser has pulse duration of 10 ns, a repetition rate of 10 Hz,
and a wavelength of 1.064 lm. The laser energy is measured
by an energy meter (OPHIR DGX-30 A), and the maximum
laser energy is 1 J. The laser energy was kept at 35 mJ from
beginning to end in our experimental process. The laser
pulse is reflected by a right angle prism and then is focused
onto the polished Pb (with a nominal purity of 99.99%) sam-
ple surface by a quartz focus lens (with f ¼ 6.5 cm) in front
of the target. The sample was placed on a sample holder in a
chamber (in a vacuum or a gas atmosphere); in this work the
Pb sample was placed in atmospheric environment. The
chamber and lens were fixed on two dimensional (x-y direc-
tions) movable plates. The dispersed emission is subse-
quently detected by an ICCD camera (with a 5-ns gate
width), and output date is recorded on a computer. A time
resolved emission spectra are acquired using the apparatus
above from 0 ns to 300 ns, and the time interval is 10 ns. The
PI-MAX2 ICCD camera is set in camera mode to capture

1070-664X/2012/19(1)/013302/6/$30.00 19, 013302-1 C 2012 American Institute of Physics

V
013302-2 Fu, Chen, and Man Phys. Plasmas 19, 013302 (2012)

images of the plasma plume as a function of delay time. The

camera is placed normal to the laser beam. Images are cap-
tured every 10 ns from 0 to 300 ns.
In order to verify the accuracy of simulated results in
the following section, we use the Saha-Boltzmann plot
method and the line broadening method to determine the
plasma temperature and the electron number density. Many
scholars had used the Saha-Boltzmann plot method to deter-
mine the plasma temperature. In this work, Pb 266.3 nm,
280.21 nm, 357.28 nm, 368.35 nm, and 560.89 nm are used
to measure the plasma temperature. Table I gives the rele-
vant data, including the transitions, wavelengths ðkÞ, upper
energies ðEu Þ, and transition probabilities ðAul Þ. The line
broadening method for the electron number density determi-
nation has been used generally,2,9 so details are not given in
this article. The results of measurements by the Saha- FIG. 1. (Color online) Plasma average temperatures as a function of delay
time and xe .
Boltzmann plot method and the line broadening method will
be shown in Sec. IV.
1 mm, 5 mm, and r ¼ 10xe to simulate a group of experi-
III. THE THEORETICAL MODEL mental spectra at different delay times. Gaussian profiles for
plasma temperature and electron number density via the
A. The influence of xe plasma emission model are averaged in the radial direction.
In the present work, we compiled the theory developed The mean plasma temperature and electron number density
by Pakhal et al.11 into a program and used it to fit the laser are plotted as functions of delay times in Figs. 1 and 2. As
induced lead plasma experimental spectra lines. The proce- shown in Figs. 1 and 2, the plasma temperatures and electron
dure will output the plasma center temperature and electron number density basically remain unchanged at the same
number density when the fitting of experimental spectrum delay time for different values of xe . That is to say, the fitting
and calculation spectrum is best. There is an assumption that results are almost constant in the range of allowable error
the temperature and electron number density obey the Gaus- when 0:1mm  xe  1mm. So the small changes of xe have
sian distribution, because the energy of the laser we used has a little effect to the results of simulation. In experiment, it is
a Gaussian distribution, difficult to determine the exact size of the plasma. In our
work, we got the size of the plasma from the plasma visible
 2
x region. Fig. 3 shows temporal images of plasma plume pro-
Te ð xÞ ¼ Te0 exp  2 ; (1) duced by laser ablation of lead in air. In our study time frame
r
 2 (150 ns-300 ns), one can see that the radial size of plasma
x plume almost remain unchanged. So we took xe as
Ne ð xÞ ¼ Ne0 exp  2 ; (2)
r 0.5357 mm in our calculation process.

where Te0 ðK Þ and Ne0 ðm3 Þ are the plasma temperature and B. The influence of re and rt
the electron number density at the center of the plasma,
respectively, x is axis perpendicular to the plasma expanding According to the model given by Pakhal et al.,11
direction. The plasma plume exists from xe to xe . Te0 ðK Þ the spatial distribution of neutral lead atoms (n0 ), Pbþ
and Ne0 ðm3 Þ are the physical quantities which we need to
determine by simulating, so the factors which affect the mea-
surement are only xe and r.
First, we should consider the effect of xe to the results of
simulation. In order to determine the influence of xe , the line
of Pb I 368.31 nm is applied. Te0 ðK Þ and Ne0 ðm3 Þ can be
obtained by fitting the emission spectrum of lead plasma in
the range of 367–370 nm. We made xe ¼ 0.1 mm, 0.5 mm,

TABLE I. Parameters for the plasma temperature determination.

Number Transitions k ðnmÞ Eu ðcm1 Þ Aul ð106 s1 Þ

1 7s3 P2 ! 6p2 3 P2 266.32 48188.67 90.5 6 5.5

2 6d3 F3 ! 6p2 3 P2 280.21 46328.81 193.1 6 11.0
3 7s1 P1 ! 6p2 3 D2 357.28 49439.57 95.3 6 6.0
4 7s3 P0 ! 6p2 3 P1 368.35 34959.90 167.6 6 10.6
5 7p2 P3=2 ! 7s 2 S1=2 560.89 77272 84.8 6 8.5 FIG. 2. (Color online) Plasma average electron number density as a function
of delay time and xe .
013302-3 Optical diagnosis and theoretical simulation of laser induced lead plasma spectrum
FIG. 3. (Color online) Temporal images of plasma plume produced during laser ablation of lead in air for laser energy of 35 mJ. Each panel delineates a
15  15 mm2 region above the lead sample. All images were obtained using the same detector sensitivity.
(n1 ), Pb2þ (n2 ), Pb3þ (n3 ), Pb4þ (n4 ) and total particles
(N ¼ n0 þ n1 þ n2 þ n3 þ n4 ) are shown in Fig. 4 when
xe ¼ 0:5357 mm, r ¼ 1:5xe and the delay time is 300 ns.
As shown in Fig. 4, the concentration of neutral lead atoms
is higher in the edges as compared to the central region of
the plasma. This is because in the central region, most of
the lead atoms have undergone ionization. Pbþ has a distri-
bution with a maximum concentration somewhere in
between the plasma center and edges. The highest concen-
tration of bivalent lead ions is at the plasma center with its
number density dropping rapidly towards the plasma
edges. This behavior is also similar for Pb3þ and Pb4þ.
Fig. 4 also shows that the number density of Pb3þ and
Pb4þ are much less than that of other lower ionization
degree ions and neutral atoms. This trend is due to the very
high ionization potential of Pb3þ and Pb4þ. In summary,
the outer region of the plasma is predominantly composed
of neutral lead atoms and singly ionized lead ions, whereas
in the plasma core Pb2þ has the highest species concentra-
tion. However, the concentration of total particles
(N ¼ n0 þ n1 þn2 þ n3 þ n4 ) shows a monotonic increase
from the plasma center to the borders. We think it is not
reasonable and the distribution should be much less at the
edge of the plasma.
As we mentioned above, the energy of the laser we used
has a Gaussian distribution. We thought the place where the
laser energy is higher should have more particles. To date,
some scholars have studied the total particles number distri-
bution.14 As shown in Ref. 14, the highest concentration of
FIG. 4. (Color online) The distribution of particle including atoms and ions.
Phys. Plasmas 19, 013302 (2012)
the total particles is at the plasma center with its number
density dropping rapidly towards the plasma edges. So we
assumed the distribution of the total particles satisfies a Gaus-
sian distribution, and this distribution is the same as the elec-
tron number density distribution. Besides we thought that the
distribution parameters of plasma temperature and electron
number density should take different values as reported in
Ref. 15. We defined the distribution parameters for plasma
temperature and electron number density as rt and re , respec-
tively. Thus, the distribution equation of plasma temperature
and electron number density were changed into
 2
x
Te ðxÞ ¼ Te0 exp  2 ; (3)
rt
 2
x
Ne ðxÞ ¼ Ne0 exp  2 : (4)
re
Now the plasma temperature and electron number density at
different delay times can be obtained by fitting experimental
spectrum when rt and re have independent value, meanwhile
xe is 0.5357 mm.
We should discuss the influence of the two parameters
on the plasma temperature and the electron number density.
Te0 ðK Þ and Ne0 ðm3 Þ can be obtained by fitting the emission
spectrum of lead plasma in the range of 367–370 nm. The av-
erage values of plasma temperature and electron number
density at different delay times are shown in Figs. 5(a) and
5(b) for re remains unchanged, respectively. One can see
from Fig. 5(a), the plasma temperature remains basically
unchanged when rt > re , and from Fig. 5(b), the electron
number density decreased gradually with the increase of the
rt . The fall of electron number density is more and more not
obvious along with the increase of re . The average values of
plasma temperature and electron number density are shown
in Figs. 6(a) and 6(b) for rt remains unchanged, respectively.
As Fig. 6 shows, the plasma temperature and the electron
number density remain basically unchanged with the
increase of the re at the same delay time for rt > 3xe which
is in our considered range.
IV. RESULTS AND DISCUSSION
In order to verify the accuracy of simulated results, the
comparison of the simulated results with the results got by
the Saha-Boltzmann plot method and the line broadening
013302-4 Fu, Chen, and Man
FIG. 5. (Color online) The evolution of plasma temperature and electron number density with the change of the distribution parameters at different delay times
when re remain unchanged and rt increase gradually. (a) Plasma average temperature and (b) average electron number density.
method was executed. The spectral Pb line at 368.35 nm,
which was used for the line broadening measurements, was
chosen to measure the electron number density at different
delay times for the better comparison. The parameter of
w (the electron impact width parameter) is taken as
w  0:013ðnmÞ.16
By comparing the plasma temperature got by Saha-
Boltzmann plot method and the electron number density got
by line broadening method with the simulation results, we
found that the difference is smallest when rt ¼ 1:5xe and
re ¼ 1:25xe . The comparison of plasma temperatures
obtained by the Saha-Boltzmann plot method and the simula-
tion are shown in Fig. 7. One can see that the temperature
got by the Saha-Boltzmann plot method is lower than the
temperature got by simulating. On the one hand, the plasma
temperature got by Saha-Boltzmann plot method was the av-
erage temperature of the entire plasma, but the plasma tem-
perature got by simulation was the average value of the
plasma which only exists from xe to xe . The temperature
and the electron number density in the edge of plasma are
assumed too small to be considered, so the temperature got
by simulation is higher. The uncertainty of the Gaunt and
Biberman’s factors which were used in our procedure to
Phys. Plasmas 19, 013302 (2012)
calculate continuous spectrum may also influence the
simulation results. On the other hand, as mentioned in
Ref. 14 by Aguilera et al., the values obtained for the ioniza-
tion Saha–Boltzmann temperature are often higher than
those of the excitation Boltzmann temperature, especially at
initial interval of the plasma evolution. More lead atoms
have undergone ionization in the central region where the
temperature is relatively higher. At present, the four atomic
spectrum lines and one Pbþ spectrum line were used to
determine temperature. So actually the temperature we got
by Saha–Boltzmann method is mainly the excitation
temperature.
Fig. 8 shows the electron number density obtained
by the line broadening method and the simulation
(xe ¼ 0:5357 mm, rt ¼ 1:5xe , and re ¼ 1:25xe ), respec-
tively. The results by two methods are well agreement with
each other. The spatial characteristics of the plasma temper-
ature and electron number density are shown in Fig. 9 when
the delay time was 150 ns. The figure indicates that the
distribution of plasma temperature is more uniform than
the distribution of electron number density. Our results
show good accordance with the views expressed by Ferrero
et al.15
013302-5 Optical diagnosis and theoretical simulation of laser induced lead plasma spectrum Phys. Plasmas 19, 013302 (2012)

FIG. 6. (Color online) The evolution of plasma temperature and electron number density with the change of the distribution parameters at different delay times
when rt remain unchanged and re increase gradually. (a) Plasma average temperature and (b) average electron number density.

The spatial distribution of neutral lead atoms (n0 ), is 150 ns. Fig. 10 shows that the total particle number
Pbþ (n1 ), Pb2þ (n2 ), Pb3þ (n3 ), Pb4þ (n4 ) and total particles density (N) drops rapidly from the plasma center towards
(N ¼ n0 þ n1 þ n2 þ n3 þ n4 ) are shown in Fig. 10, when edges. We thought that this change is more reasonable
xe ¼ 0:5357 mm, rt ¼ 1:5xe , re ¼ 1:25xe and the delay time relative to Fig. 4.

FIG. 7. (Color online) The plasma temperatures obtained by the Saha- FIG. 8. (Color online) The electron number density obtained by the line
Boltzmann plot method and the simulation (xe ¼ 0:5357 mm, rt ¼ 1:5xe , broadening method and the simulation (xe ¼ 0:5357 mm, rt ¼ 1:5xe , and
and re ¼ 1:25xe ). re ¼ 1:25xe ).
013302-6 Fu, Chen, and Man Phys. Plasmas 19, 013302 (2012)

interested. We got the size of the plasma from the plasma

visible region. The plasma temperature got by Saha-
Boltzmann plot method and the electron number density got
by line broadening method were compared with the fitting
results. Furthermore, we found the plasma temperature and
the electron number density distribution function is not com-
pletely same. The distribution of plasma temperature is more
uniform than the distribution of electron number density.

ACKNOWLEDGMENTS
The authors are grateful for the financial support by the
National Natural Science Foundation of China (10874103)
(10874103, 11047161) and Specialized Research Fund for
the Doctoral Program of Higher Education (200804450002).
FIG. 9. (Color online) The spatial distribution of the plasma temperature and This work was also supported by the Open Fund of the State
electron number density for xe ¼ 0:5357 mm, rt ¼ 1:5xe , and re ¼ 1:25xe Key Laboratory of High Field Laser Physics (Shanghai Insti-
when the delay time was 150 ns.
tute of Optics and Fine Mechanics).
1
P. D. Maker, R. W. Terhune, and C. M. Savage, Quantitative Electronics,
edited by P. Grivet and N. Bloembergen, in Proceedings of the 3rd Inter-
national Conference, Paris, 1963 (Columbia University, New York,
1964), Vol. 2.
2
C. Aragón and J. A. Aguilera, Spectrochim. Acta, Part B 63, 893 (2008).
3
V. Burakov, N. Tarasenko, M. Nedelko, and S. Isakov, Spectrochim. Acta,
B 63, 19 (2008).
4
D. A. Cremers and L. J. Radziemski, Handbook of Laser-Induced Break-
down Spectroscopy (John Wiley & Sons Ltd., West Sussex, England,
2006).
5
H. L. Xu, J. Bernhardt, P. Mathieu, G. Roy, and S. L. Chin, J. Appl. Phys.
101, 033124 (2007).
6
A. Alonso-Medina, Phys. Scr. 55, 49 (1997).
7
Y.-I. Lee, S. P. Sawan, T. L. Thiem, and Y.-Y. Teng, Appl. Spectrosc. 46,
436 (1992).
8
Y.-I. Lee and J. Sneddon, Spectrosc. Lett. 29, 1157 (1996).
9
M. A. Hafez, M. A. Khedr, F. F. Elaksher1, and Y. E. Gamal, Plasma
Sources Sci. Technol. 12, 185 (2003).
10
T. Sakka, T. Nakajima, and Y. H. Ogata, J. Appl. Phys. 92, 2296 (2002).
FIG. 10. (Color online) The distribution of particle including atom and ions. 11
H. R. Pakhal, R. P. Lucht, and N. M. Laurendeau, Appl. Phys. B 90, 15
(2008).
12
B. Y. Man, Appl. Phys. B 67, 241 (1998).
13
V. CONCLUSION J. Guo, C. S. Chen, B. Y. Man, S. Y. Yang, X. M. Zhou, C. Wang, and
C. Y. Diao, Laser Phys. 19, 1832 (2009).
14
An improved plasma emission model was introduced, J. A. Aguilera and C. Aragón, Spectrochim. Acta, Part B 59, 1861 (2004).
15
F. S. Ferrero, J. Manrique, M. Zwegers, and J. Campos, J. Phys. B 30, 893
invoking one-dimensional radiative transfer, to describe the (1997).
observed emission spectra, while taking into account the 16
N. Konjevic, A. Lesage, J. R. Fuhr, and W. L. Wiese, J. Phys. Chem.
Gaussian distribution of the total particle numbers in plasma Ref. Data 31(3), 819 (2002).