Spectrochimica Acta Part B 59 (2004) 271289

Review

Laser-induced plasma expansion: theoretical and experimental aspects

M. Capitellia,b,*, A. Casavolaa, G. Colonnab, A. De Giacomoa
a

Chemistry Department, University of Bari, 70126 Bari, Italy

CNR-IMIP (National Research Council-Institute of Inorganic Methodologies and of Plasmas), Chemistry Department, University of Bari,
70126 Bari, Italy

Received 28 July 2003; accepted 19 December 2003

Abstract
Theoretical and experimental efforts to describe the expansion of laser-induced plasma plume are reviewed. Particular attention
has been devoted to a comparison between experimental and theoretical time of flight (TOF) profiles. The theoretical results
obtained by inserting plasma kinetics in one-dimensional fluid-dynamic code show that chemical processes strongly influence the
fluid dynamic expansion. Moreover fluid-dynamics codes based on both NavierStokes and DSMC models, which in addition
include the possibility of different temperatures for electrons and heavy particles, are discussed.
2004 Elsevier B.V. All rights reserved.
Keywords: Laser-induced plasma; Fluid-dynamics; Time of flight; LIBS

1. Introduction
Laser induced plasma, LIP, is a topic of growing
interest in different fields such as material processing,
diagnostic techniques and space applications. Pulsed
laser deposition (PLD) has been successfully employed
for the deposition of thin films of classical and novel
materials w1,2x. The possibility of producing species in
LIP with electronic states far from chemical equilibrium
enlarges the potential of making novel materials that
would be unattainable under thermal conditions. An
excellent example is the production of single carbon
nanotubes (SCN) by laser-oven method proposed by
Smalley w3x. However, a great effort has been done in
developing handable sensors based on laser induced
plasma spectroscopy (LIPS) for elemental chemical
analysis in a wide range of applications: heavy metal
detection in soils w4x, bio-molecules detection w5x, online control over different laser processes w6x etc. Finally,
the development of compact laser source is leading the
LIP based techniques in space applications as chemical
*Corresponding author.
E-mail address: cscpac62@area.ba.cnr.it (M. Capitelli).

sensor for Mars exploration w7x or micro-propulsion

technique for the exact positioning of satellites w8x.
LIP technological applications require a parallel investigation of the formed plasma from a more fundamental
point of view. Indeed, while the generation of LIP
requires an easy experimental set-up, the LIP phenomena
need a lot of theoretical and experimental work to be
understood.
By the interaction of high power laser with matter,
the vaporization of surface layers leads to the formation
of an expanding atomic plasma. During nanosecond
laser ablation, this high-density plasma (1017 1019
cmy3) is heated to high temperatures (600020 000 K)
and is ionized by the inverse Bremsstrahlung and the
photoionization processes, expanding rapidly (approx.
106 cmys) perpendicularly to the surface. During the
expansion, the main mechanism of transition of bound
electrons from the lower level to the upper level and
vice versa is driven by inelastic collisions of electrons
with heavy particles, while the concentration of charged
particles is controlled by the electron impact ionization
and the three-body recombination of electrons with ions.
Radiative processes as reabsorption, spontaneous and
stimulated emission are also important in determining

0584-8547/04/$ - see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2003.12.017

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M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

the concentration of emitting levels w9x. The evolution

of the hierarchy of the basic processes occurring during
the expansion makes the analysis of the plume really
complex and theoretical studies are needed for the
interpretation of the experimental data.
The traditional set of methods for measuring the
parameters of the LIP includes the optical emission
spectroscopy (OES) w10x, the laser-induced fluorescence
(LIF) w11x, laser absorption, probing w12x, mass spectrometry w13x and beam deflection w14x. Charged particle
detection and laser excitation techniques give the best
results in what concerns the investigation of LIP far
from the targets whereas the OES is the simplest way
to investigate the brightness zone of LIP (010 mm).
OES is based on the intrinsic light emission of the LIP
and does not need any other excitation source or
intrusive systems. This peculiarity makes the OES experimental set-up very simple and adaptable to automation
and remote sensing w7,15,16x. The classical approach of
this technique is based on some assumptions, most
importantly those of the existence of local thermodynamic equilibrium (LTE) conditions and of optically
thin plasma w17x. Unfortunately, as a consequence of
the fast expansion, the plasma parameters can change in
times shorter than those necessary for the establishment
of elementary process balances w18x, thus leading to
non-equilibrium excitation and chemical processes. The
knowledge of the deviations from the LTE is really
important to understand the limits of theory to be taken
into account for practical applications w18,19x.
The growing interest on laser-induced plasma has
generated numerous theoretical models in order to
improve the basic knowledge and determine the best
experimental conditions of LIP processes. The main
difficulty in modeling LIP is that both the dynamics of
plume and plasma chemical reactions occurring in it
should be investigated. To reproduce the temporal and
spatial evolution of the plasma a lot of theoretical
investigations have been devoted to the simulation of
the plume expansion w20x. In this frame different
approaches have been proposed: an analytical approach
w21,22x, a fluid dynamic model w2325x and Monte
Carlo methods w26,27x. Moreover the role of plasma
chemical processes and the possibility of deviations
from equilibrium conditions have been taken into
account.
The aim of this review is to report recent theoretical
and experimental efforts made to describe the expansion
of plasma plume. In this sense, this paper complements
the recent theoretical work w18x on analyzing microscopic aspects of LIP.
A complete discussion on laser-induced plasma is a
too vast argument to be reported in a single paper so
that we will focus our attention on the luminous plasma
produced by nanosecond laser ablation. The laser solid
interaction as well as the dependence of ablation pro-

cesses on laser parameters has been considered beyond

the aim of the present work.
2. Laser-induced plasma spectroscopy
2.1. Optical emission spectra
The experimental set-up for laser induced plasma
spectroscopy (LIPS) basically consists of a laser source
for the vaporization of the target and for plasma formation, a high-resolution monochromator and a time
resolved detector. In this review paper, the attention is
focused on fluid dynamic aspects of the plume and
plume monitoring by spectroscopic diagnostics.
To show the typical behavior of a laser-induced
plasma we report the results of a simple experiment of
KrF laser ablation on metallic titanium (wavelength 248
nm, laser fluence 5 J cmy2, pulse duration 30 ns).
The threshold energy to produce a luminous plume
depends on the target material, its morphology as well
as the laser pulse wavelength and duration w28x. The
temporization of the spectroscopic system is extremely
important because of the rapid expansion of the plume.
The main trigger is obtained by the signal of a fast
photodiode detecting a portion of the laser beam. The
pulse generator, then, controls the detector acquisition
times including the delay between the laser pulse and
the gate width. The delay time and the gate width should
be optimized with respect to the experiments to obtain
clear and readable spectra.
The spatial resolution is obtained by focusing the
plume image in a plane where the optical fiber entrance
is placed. The magnitude of the plume image and the
size of the optical fiber aperture determine the spatial
resolution generally within a few hundreds of microns.
The dynamic aspect of the LIP is a complex question
for diagnostics since plasma parameters change quickly
in time and in space. It means that it is necessary to
find the experimental condition to approximate the LIP
to an uniform plasma. Hermann et al. studying the line
shape of Tiq 348.38 nm found out that the plasma is
rather symmetric during the early stage (delay time
lower than 150 ns) and close to the target surface. The
authors proposed two successive steps in LIP evolution
with different expansion modes. Initially, for a time
where the distance of the LIP front from the target
surface is smaller than the laser spot dimension, the
propagation of plasma can be considered one-dimensional and strictly directed perpendicularly to the target
surface. At later times a non-uniform distribution with
cylindrical symmetry takes place and Abel inversion is
required for the LIP diagnostics w9x.
A typical temporal evolution of a fragment of Ti-LIP
emission spectrum at a fixed distance (0.5 mm, gate
width 40 ns) is shown in Fig. 1. Inspection of the figure
shows the initial spectral continuum contribution, essen-

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

273

the spectral line intensity corresponding to a transition

from an upper excited level u to a lower excited level l
is given by:
IulsGulNuhnulAulPnuln.

Fig. 1. Typical temporal distribution of a fragment of LIP spectra at

the distance of 0.5 mm in vacuum. For figure clarity are reported only
the spectra with an increasing temporal step of 50 ns. Experimental
conditions: metallic titanium target, laser fluence 5 J cmy2, pulse
duration 30 ns.

where N u is the population density of the upper level u,

Aul is the transition probability from level u to l, nul is
the frequency, h is the Planck constant and Gul is an
experimental factor which depends on the analyzed
plasma volume, the solid angle of observation and the
spectral response of the optical system. The function
P(nul,n) is the normalized line profile of the spectral
line.
If the plasma is optically thick, it is necessary to add
to the Eq. (1) the terms taking into account selfabsorption and-induced emission. Generally in LIP emission spectra the contribution on spectral lines due to the
induced emission can be neglected as exp(hvykT)41
w31,32x. Many methods have been developed to take
into account self-absorption in LIP spectral lines (see
for example Refs. w9,3136x). At high background
pressure this effect can play an important role as a
consequence of the confinement of LIP in smaller
volume.
The spectral line intensity, including the self-absorption and considering the plasma as an homogeneous
medium in LTE (local thermodynamic equilibrium), is
expressed as w31,37x:
Iuls

tially due to mechanisms involving free electrons

(inverse Bremsstrahlung, radiative recombination)
w29,30x. At this stage it is not possible to retrieve
information about atoms and ions. Some tens of nanoseconds after the laser pulse is over, atomic and especially ionic lines rise up from the spectral continuum.
The emission lines become progressively narrower during the expansion as a consequence of the electron
number density evolution (Fig. 2). As has been extensively reported in literature the fast decrease of the
electron number density is caused by plasma expansion
and three body recombination w9,10x. As a consequence
the excitation temperatures must decrease during the
time evolution. The maximum intensity of the spectral
lines is reached after a characteristic time, depending on
the observation distance, and it represents the most
populated section of the LIP. Because of the high
ionization degree, for the most part of spectra the ionic
lines are more intense than those of atoms, while on the
tails of the temporal distribution of the LIP line intensities, which correspond to the cold part of the plasma,
one can observe the disappearance of ionic lines.
Under the assumption of an optically thin plasma, i.e.
all the emitted photons escape from the plasma w31x,

(1)

Ithin
ul
1yexpytl..
tl

(2)

where Ithin
is the intensity as described in Eq. (1) and
ul
tl is the dimensionless optical thickness at wavelength
l defined by tlsalR with l, the absorption coefficient
in cmy1 and R path length in centimeters.

Fig. 2. Electron number density temporal evolution (Ne) at different

background pressures. Experimental conditions: metallic titanium target, laser fluence 5 J cmy2, pulse duration 30 ns.

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M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Fig. 3. Experimental Boltzmann plots after 150 ns from the laser pulse, at distance from the target of 1 mm and in vacuum (a) for Ti and (b)
for Tiq. Experimental conditions: metallic titanium target, laser fluence 5 J cmy2, pulse duration 30 ns.

Optical thick plasma inhomogeneity is reflected on

the spatial gradient of the temperature and of the atom,
ion and electron concentrations. This leads to the formation of strongly asymmetric self reversed emission
lines within asymmetric absorption lines having a valley
in the middle and line wings asymmetric respect to the
frequency at which the intensity of self reversal is
minimal. In this case, only by theoretical modeling it is
possible to retrieve information from the experimental
spectra w38,39x.
Due to the difficulty in determining the optical thickness without assuming strong approximations (plasma
homogeneity, LTE etc.), when it is possible, transitions
involving high energy levels should be selected for the
spectral analysis in order to minimize the self-absorption
problem and considering the LIP as a thin medium.
The gate width of the detector should be adapted to
the spontaneous emission time of the selected spectral
lines so that high transition probability allows higher
time resolution of the detection system.
The spectral line profile is mainly a convolution of
the Lorentz function due to the Stark effect. In addition,
a Gauss function due to the Doppler effect (generally
negligible, -10% w33,34x) and the apparatus function
of the entire spectroscopic system also contribute to the
profile. However, because other effects are less pronounced, the study of line broadening allows in determining the electron number density by Stark effect
without assuming LTE condition (see Fig. 2) w31x.
2.2. Investigation of atomic and ionic state distribution
function by LIPS
The relative line intensities of atomic and ionic lines
can be used to determine the characteristic temperature
of each species when the mechanisms of excitation and
de-excitation of atoms and ions involve mainly electron
impact. In this case, the excited state population of the
considered species follows the Boltzmann distribution,

and the following equation for homogeneous plasma

(GsGul) can be employed:
B

E
Iul
FsmAEuqqA
D gunulAul G

lnC

mAsy

B N
E
1
A
; qAslnC
GF
D ZATA. G
kTA

(3)

(4)

where k is the Boltzmanns constant, Eu and gu are,

respectively, the energy and the statistical weight of the
upper excited energy level, ZA is the partition function
of the chemical species A calculated at the temperature
TA, NA is the concentration of the chemical species A in
the ground state. It is important to note that if LTE
conditions are established and if the target evaporation
is assumed congruent, the Boltzmann plot analysis
would lead to the free-calibration method proposed in
Ref. w40x. In this paper, the authors determine the
temperature by the Boltzmann distribution of different
excited electronic state of the same element by Eq. (1)
and then, in order to remove the unknown experimental
factor G from the intercept qA, they use the normalization relation SiNis1. The method, indeed, it is not
always reliable because the accuracy is strictly dependent on the assumption of LTE condition. In any case,
care should be taken when calculating the internal
partition function especially at high temperature w18x.
As a typical example Fig. 3 shows the Boltzmann
plot of atoms and ions during the laser ablation of the
metallic titanium target at 10y5 Torr. Table 1 reports the
temperature at different delay times recovered by the
slope of the Boltmann plot.
To improve the accuracy of the temperature determined by Boltzmann plot analysis Yalcin et al. apply
the Saha equation to enlarge the energy axis by using
the transitions from different ionization stages w17x in
the same plot. Unfortunately, this methodology, as previously established by Van der Mullen w41x, works only

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Table 1
Results of Boltzmann plot analysis at different delay times from the
laser pulse and pressures (distance from the target 1 mm): internal
temperature T (K) for Ti and Tiq species, intercept of Boltzmann
plots, q(NTi) and qNTiq..
Delay (ns) Ti

Tiq

T"800 (K) q(NTi)"0.5 T"800 (K) qNTiq."0.5

Vacuum (10y5 Torr)
50
11 800
100
8700
150
8800
200
9600

y30.2
y28.6
y28.6
y29.0

11 200
8850
8600
8950

y25.4
y23.3
y23.2
y23.9

3.4=10y2 Torr
50
10 900
100
10 100
150
8900
200
8600

y29.3
y28.9
y28.2
y28.1

10 700
9800
8700
8300

y24.6
y23.5
y23.2
y23.7

in LTE conditions and so cannot be proposed as a

general method in LIP diagnostics.
If the high ionization degree suggests a Maxwell
distribution for the electron energy distribution function
and Boltzmann distribution for the excited states, the
natural conclusion of the LTE conditions should be
taken with caution. The system indeed may become
much more ionized than that obtained by applying the
Saha equation at the temperature obtained by the Boltzmann plot and at the electron number density as recovered by the Stark effect as has been observed in Ref.
w42x.
2.3. Temporal evolution of LIP
If the ground state of all atomic and ionic species is
in the Boltzmann equilibrium with the excited state
population of the species, then Eq. (1), neglecting the
shape function and assuming the homogeneity of the
sampled portion of the plasma, can be written as:
Iulf

Iul
NA
s
expyEuykTexc.
GhnulAulgu ZATexc.

275

This equation allows determining the ratio between

the ion and the atom concentrations (generally in the
range of 1015 1018 cmy3) from the selected spectral
lines of ionic and atomic species. In fact, the assumption
of the Boltzmann equilibrium between ground and
excited states densities may lead to underestimation of
the ground state population if the spontaneous emission
decay process dominates over collisional de-excitation
mechanisms, as suggested in Ref. w43x.
Fig. 4 shows the ratio between ion and atom concentrations of Ti-LIP obtained by the method described
above at 2 and 3 mm from the target as function of
time. In the figure, the ratio decreases by two orders of
magnitude in few hundreds of nanoseconds, as a consequence of the recombination processes and of the
physical expansion.
The evolution of LIP species by temporally and
spatially resolved OES at different distances from the
target can be used to determine the expansion rate close
to the target w40,44x. The determination of the mean
expansion velocity can be achieved by measuring the
ionic emission temporal profiles, suitably corrected by
tabulated spectroscopic data (the so called time of flight
(TOF) profiles). Actually this procedure for the determination of plasma velocity should be used with care
due to the superposition of both expansion and forward
movement of the plasma plume. Moreover the procedure
does not take into account the different populations and
the different origins of the same species. Ionic lines
have been preferred with respect to the atomic ones
because, as will be explained later, the Ti TOF can
present an additional delay due to the three-body recombination mechanism. Fig. 5a,b show normalized TOF of
Tiq species in vacuum (10y5 Torr) and at 3.4=10y2
Torr. From the time shift of the TOF peaks for each
distance it is possible to obtain the mean velocities of

(5)

where Texc is the (internal) temperature of electronic

levels of the species A, which can be different from TA.
In this hypothesis, the ratio of the ground state
densities of two different species (e.g. A and B) can be
expressed as a function of the ratio of excited state
densities of those two species, which is the ratio of a
line intensity of A to a line intensity of B,
B
B
NB Iu9l9 ZBTexc.
Eu9yEu E
F
s A
expCy
D
NA Iul ZATexc.
kTexc G

(6)

where u9l9 indicate the upper and lower level of species

B.

Fig. 4. Ionization degree as function of time during laser ablation of

metallic titanium target at 10y5 Torr at 2 and 3 mm from the target.
Experimental conditions: metallic titanium target, laser fluence 5 J
cmy2, pulse duration 30 ns.

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

276

Fig. 5. TOF profiles of Tiq species at 0.5, 1 and 2 mm from the target (a) in vacuum, (b) at 3.4=10y2 Torr. Experimental conditions: metallic
titanium target, laser fluence 5 J cmy2, pulse duration 30 ns.

LIP along the propagation axis. The velocities can be

determined, as suggested in Ref. w10x, by the ratio dyt
(peak), where d represents the difference in the observation distance and t (peak) the corresponding time
difference calculated at the peak of TOF for each
selected distance. Calculated velocities have been reported in Table 2 and are in good agreement with the values
present in literature (see for example Refs.
w10,11,13,19x). Inspection of Table 2 shows that the
background pressure modifies the expansion dynamics.
In the range of distances investigated in this experiment
under vacuum condition the velocity of LIP increases
and probably will reach a maximum not so far from the
last observed distance (2 mm). This trend of the LIP
velocity is due to the initial acceleration of the ablated
particles from the initial velocity V0s0, before the laser
pulse energy reaches the ablation threshold, to a maximum of velocity, Vmax. Then the velocity decreases since
part of the energy is expended in intra-plume collisions,
in heating and moving the ambient gas. At 3.4=10y2
Torr, the velocity immediately decreases with the distance, denoting that the deceleration of LIP due to the
collisions of the background gas particles with the front
head of LIP occurs at shorter distance.
As already underlined, the LIP is a dynamic system.
To investigate the same section of the plasma, the spectra
corresponding to the maximum of the temporal evolution
of the Tiq TOF collected at different distance has been
analyzed and plotted in Fig. 6. In this way for each

distance there is a time delay when the temporal evolution of Tiq line emission reaches its maximum. As
can be seen from Fig. 6, the characteristics of the spectra
are similar to those described previously for the temporal
evolution (Fig. 1) at a fixed distance. The electron
number density, Ne of the same section of plasma
corresponding to the maximum of Tiq TOF curves,
obtained by Stark effect, has been reported in Fig. 7.
The decrease of Ne is mainly governed by the recombination between electrons and ions, plasma expansion
playing a minor role. The electron number density
evolution reported in Fig. 7 can be expressed by the

Table 2
Peaks velocity (cm sy1) at different distances from the target at
3.4=10y2 and 1=10y5 Torr
Distance"0.1 (mm)

0.50
1.00
2.00

Peaks velocity"5=104 (cm sy1)

Ps3.4=10y2 Torr

Ps1=10y5 Torr

1.25=106
1.11=106
9.09=105

8.33=105
1.25=106
1.54=106

Fig. 6. Set of spectral fragments corresponding to the maximum of

Tiq TOF signal at different distances at 3.4=10y2 Torr. Experimental
conditions: metallic titanium target, laser fluence 5 J cmy2, pulse
duration 30 ns.

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277

To this end the theoretical study of different aspects of

the LIP can be a powerful tool to verify the validity of
the assumptions.
To improve the basic knowledge as well as to foresee
the LIP phenomena, a large effort in modeling LIP
systems has been done in the last decades. Two main
peculiarities of the LIP should be investigated to model
such kind of systems: the dynamics and the kinetics. In
this section the main progress and the basic principles
of LIP theoretical aspects and modeling will be
discussed.
Fig. 7. Time evolution of electron number density corresponding to
the maximum Tiq TOF signal in vacuum and at 3.4=10y2 Torr.
Experimental conditions: metallic titanium target, laser fluence 5 J
cmy2, pulse duration 30 ns.

following kinetic expression:

dNe
skionNeNTiIykrecNe3
dt

(7)

where N indicates the concentration (cmy3) of the

particle denoted by the subscripts; kion (cm3 sy1) and
krec (cm6 sy1) are the rate constants of ionization and
three-body recombination, respectively.
If dNe ydts0 equilibrium conditions can be established. If dNe ydt/0, then ionization (dNe ydt)0) or
recombination (dNe ydt-0) prevails and the departure
from the equilibrium occurs w18x. So, as it is observable
from Fig. 7, in the examined case the three body
recombination process prevails over the ionization one
and LTE assumption cannot hold during the expansion.
This effect is visible when comparing the TOF of atoms
and ions (Fig. 8). The apparent delay between Ti and
Tiq TOF maxima is the effect of the additional amount
of atoms produced by the recombination of ions with
electrons. In fact considering the velocity of expansion
in the range of 106 cm sy1, as has been determined
experimentally, and a mean laser spot size of 1 mm, we
can estimate an expansion time of 10y7 s. The recombination time can be estimated by the values of the rate
constant of the recombination process reported in previous works w23,42,44x as trecs(N2e krec)y1;10y6 s.
So the characteristic time of expansion is less than that
corresponding one for the establishment of Saha balance
and the plume expands in quasi-equilibrium state and
the deviation from equilibrium has a recombination
character w18,42x. In these cases, suitable theoretical
models including both the dynamic and the kinetic
aspects are necessary for the interpretation of experimental data.
3. Theoretical aspects of LIP expansion
As has been shown in previous sections, the interpretation of experimental data needs some approximations.

3.1. Laser-induced plasma expansion

The expansion of ablated particles, starting when the
laser pulse is on and continuing after the end of the
laser pulse, can be simulated by means of essentially
three different theoretical approaches: (i) analytical
w21,22,4548x, (ii) fluid dynamic w2325,44,4954x
and (iii) Monte Carlo w26,27,5559x.
A commonly accepted idea on laser-induced plasma
expansion is that photons strike a solid surface and that
particles are therefore emitted during the laser pulse.
When the density is small enough (-0.5 monolayer in
few nanoseconds) a collision-less vapor is produced
w28,45x. At higher vapor densities, many collisions occur
near the surface: in this case a so-called Knudsen layer
is formed above the target surface, which transforms the
half-Maxwellian velocity distribution function of the
nascent atoms into a full-range Maxwellian with a center
of mass velocity uCM in the direction perpendicular to
the target surface w13,28,46,47x.
Therefore, it is possible to distinguish two kinds of
gas-dynamic behavior: particles pass directly into
unsteady adiabatic expansion (UAE), a problem for
which an analytical solution already exists w13,48x;

Fig. 8. Comparison of normalized TOF curves of Ti and Tiq at different distance from the titanium target at 3=10y2 Torr. Experimental
conditions: metallic titanium target, laser fluence 5 J cmy2, pulse
duration 30 ns.

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

278

particles first form a Knudsen layer (KL), then pass

into UAE.
An analytical approach to solve the problem concerning the UAE plus the KL has been widely discussed by
Kools et al. and by Kelly w13,48x. They solve the
hydrodynamic equations for an unsteady adiabatic
expansion with the correct boundary conditions. This
approach is justified in all cases where the gas density
is so large that the number of collisions between particles
is sufficient for thermodynamics or hydrodynamics
description. Since the necessary number of collisions is
very low w27x, it is appropriate to follow this approach
for cases when more than one monolayer desorbs on a
time scale of tens of nanoseconds. Moreover the use of
flow equations, which assume local thermodynamic
equilibrium, for an expansion, which takes place into
vacuum, could appear questionable. The usual way to
overcome this contradiction is to assume that the flow
equations remain valid until the density falls into a
critical value and the particles go abruptly into free
flight w48x.
Detailed analytical descriptions of the adiabatic plasma expansion have been discussed by several authors
w21,22x. For example, Anisimov et al. w21x have calculated the profile of a film produced by pulsed-laser
deposition from a solid target. A simple analytical
solution has been obtained for the range of parameters
typically employed in PLD, by solving the gas-dynamical equations under the assumption of an adiabatic
expansion of the plume into vacuum.
Let us consider now numerical fluid dynamic models,
which allow calculating spatial and temporal evolution
of several macroscopic quantities, such as density, temperature and velocity, which can be directly compared
with experimental results.
The most rigorous fluid-dynamic approach to describe
the plasma expansion is the solution of the threedimensional axisymmetric compressible NavierStokes
equations for a multispecies gas, including the effects
of mass and forced diffusion and thermal conduction
and viscosity w24x:
ri
w
.zsv
qdivyrinqn
di ~
i
t

(8)

rn

qdivrnnyPIqt
.s0
t

(9)

w
Ea
yP Iqt.nqq
zsS
qdivyEany
a
~
a
t

(10)

w
Ee
.z|sS qF
qdivxyEeqPe.nqn
die ~
e
e
t

(11)

In these equations ri,

ndi and vi are the density, the

forced diffusion due to the presence of an electric field,

and mass source term of species i, respectively.
n is the
velocity, r is the density of the mixture, Pa and Pe are
the atomion and electron pressure, respectively, P is
the overall pressure and t is the viscous shear stress
tensor. Ea and Ee are the atomion and electron energies,
and Sa and Se are the atomion and electron energy
source terms.
Le et al. also assume an ideal-gas equation of state
for each species (heavy particle, electron) w24x. The
overall pressure is given by:
RT
RTe
PsPaqPes8ri qre
Mi
Me
i/e

(12)

i is the molecular weight of species i,

where M
Me is
the molecular weight of the electron and R denotes the
universal gas constant. The plasma is assumed to be
quasi-neutral and two-temperature modeling (T, Te) is
used to describe the ionization non-equilibrium condition. The electron temperature Te deviates from the
heavy-particle temperature T because of the slow rate
of energy transfer between electrons and heavy particles
caused by the large difference in the mass of electrons
and heavy particles.
At the beginning of the plasma expansion and close
to the surface (initial conditions), the temperatures of
electrons and atoms are assumed to be equal as a
consequence of local thermodynamic equilibrium during
the laser pulse. However, a two-temperature modeling
is used due to the non-equilibrium ionization hypothesis.
In Fig. 9a,b the temporal evolution of the electron and
heavy particles temperatures is plotted at different distances z from the target. It can be observed that at a
distance of 1 mm from the target the electron temperature is lower than that of the heavy particles in the
shock front. Between 3 and 5 mm the electron and
heavy particle temperature become almost equal. At a
distance of 7 mm from the target, Te is globally higher
than T. This is probably due to the slower cooling
mechanism of electrons, with respect to that of heavy
particles w24x.
Le et al. w24x have also considered the ambipolar
diffusion due to the presence of an electric field.
Electrons have higher mobility and diffuse faster than
ions, leaving behind them an excess of positive charge.
The electric field produced by this initial charge separation tends toward a slowing down of the electrons and
an acceleration of the ions. Thus the electric field affects
the diffusion process of electrons and ions. The rigorous
treatment of the problem of forced diffusion by an
electric field requires a complex system of equations, as
shown by Lee w60x. A simplified method has been used
by the same authors, who consider this effect by introducing the ambipolar diffusion concept, occurring when

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

279

have been reported in Fig. 10ab at different times. It

can be observed that in the early stage of expansion
(ts0.12 ms) the density profiles provided by the two
models are similar, while at longer times (ts1.1 ms)
and at shorter distances (z-0.4 cm) the Si density is
higher in the NavierStokes model w24x. This behavior
is strictly linked to inserting (NavierStokes) or neglecting (Euler) the diffusion processes behind the expanding
front operated by the two models.
Euler equations can be used to simulate the process
in the early stage of the evolution. The simple Euler
approach allows inserting detailed kinetic schemes.

Fig. 9. Results of two-dimensional NavierStokes gas dynamic calculation with a laser fluence of 1.5 Jycm2 and 400 mTorr of Ar. Time
evolution of electron and heavy-particle temperatures at different z
positions, 1 and 3 mm (a) and 5 and 7 mm (b). (Taken from Ref.
w24x with permission from the authors and the American Physical
Society).

an electron pressure gradient exists in an ionized gas, in

the presence of small charge separation.
The same authors have shown that a more rigorous
approach w24x, i.e. the solution of NavierStokes equations, is necessary only for expansions in a background
gas at not negligible pressures ()0.4 mTorr) or for
expansion to longer times (1 ms). To understand this
point, density profiles of Si neutral atoms calculated by
Le et al. by using NavierStokes and Euler equations

Fig. 10. Comparison of two-dimensional results from Euler and

NavierStokes gas dynamics calculations, with a laser fluence of 1.5
Jycm2 and 400 mTorr of Ar. Profiles of Si density as a function of Z
position and at times ts0.12 ms (a) and ts1.1 ms (b). (Taken from
Ref. w24x with permission from the authors and the American Physical
Society).

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M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Euler equations have been extensively used in Refs.

w23,25,4954x. For instance, Aden et al. have described
the plume expansion through the compressible and nondissipative conservation equations for mass-, momentum- and energydensity. Since, in the gas-dynamical
description, the time-averaged electric field of the laser
radiation is zero, electrons and heavy particles move
with the same velocity w50x. Moreover, Aden introduces
the energy equation for electrons, because the electron
component of the plasmayplasma gains energy from the
laser field, so that the electron temperature may be
different from the atomic one.
A simplification of the three-dimensional Euler equation could be obtained supposing that after the pulse
termination the cloud starts expanding spherically w53x.
For moderate background pressures, the hypothesis of a
spherical expansion appears to be reasonable for the
description of near-axis plume behavior w50x, but in high
vacuum the plume is essentially forward directed and,
therefore a one-dimensional code can describe the system w23,25,44,54,61,62x.
Taking into account all these information, we have
investigated the expansion of a laser-ablation plume by
means of a one-dimensional fluid dynamic model
w23,25,44,54x. This model considers only the stage of
expansion during and after the laser pulse without
detailing the evaporation process. At the end of the laser
pulse, a plume is assumed to be formed in the direction
perpendicular to the target, in the same position of the
irradiated spot center. The laser energy is spent on
melting, vaporization and heating of the target material,
and on heating and ionization of the vaporized particles.
Before the expansion, the plasma can be considered in
thermal equilibrium. After pulse termination, the cloud
begins to expand perpendicularly to the target into an
ambient gas at pressure Pb w53x. The plasma has been
treated as a single fluid characterized by one velocity u
and one temperature T. This fluid dynamic approach
disregards the effects of space charge separation, as the
time-averaged electric field of the laser radiation is zero.
The validity of the one-dimensional approximation is
largely demonstrated in literature. In fact, numerous
studies have shown that the angular distribution of the
laser-generated flux is often much more strongly forward
peaked than the flux obtainable from small-area effusive
sources operating under collision-less conditions. This
forward peaking phenomenon for deposition in vacuum
is now generally accepted as arising from collisions of
the plume species among themselves. In the presence of
a background gas, additional scattering effects must be
considered w28x, as well as the possibility of plume
confinement w28x.
Quite different approaches to simulate the laserinduced plasma expansion have been proposed by Wood
et al. w6368x and Nemirovsky w69x. The Woods model
is based on a combination of multiple scattering and

hydrodynamic approaches. The plume is allowed to be

broken into components, or scattering orders, whose
particles can undergo many collisions with the background. Particles can only be transferred from one order
to the next higher order by collisions. The densities in
the individual orders propagate according to the usual
conservation equations to give the overall plume expansion. Nemirovsky et al. w69x, starting from the Boltzmann equation, have derived the hydrodynamic
equations of motion for partially ionized plasma when
the charged component and the neutral component have
different flow velocities and different temperatures. They
have developed a general approach for the hydrodynamics of a gas in a binary mixture, when the interaction
between particles of the same species is much stronger
than that between particles of different species. The
following processes of interactions were studied: selfcollisions, interspecies collisions, ionization, recombination and charge exchange.
All gas-dynamical models, however, which have been
so far discussed, are invalid when the velocity distribution of the ablated particles deviates from the Maxwellian distribution. As a result, they cannot correctly be
applied for the regions of strong density gradients.
Moreover diffusive processes are not well described by
the continuous gas-dynamics and the mixing of the
ablated species with the background gas cannot be
rigorously studied with these models. This mixing occurs
at the later stage of the plume expansion, so that it can
be neglected if only the early stage of plasma evolution
is considered. It is necessary to investigate the effective
mixing between the ablated and the buffer particles in
the reactive laser ablation, because it provides the
condition required for the formation of the reactive
products.
To overcome the limits of the gas-dynamic approach,
many authors have investigated the plume expansion
and the effects of collisions amongst particles desorbed
from solid surfaces by means of Direct Monte Carlo
simulation w26,27,70,71x.
Urbassek et al. in Ref. w70x obtained preliminary
information about sputtering yield by developing a
simple model, based on the assumption of a collisionfree molecular flow. Then Urbassek et al. w71x developed
a Monte Carlo simulation to investigate the plasma
expansion, also taking into account collisions between
particles, assuming that particles desorb during a time
interval t from a circular area (radius r0) of a plane
surface into vacuum. The desorption mechanism is
supposed thermal, so that all species can be described
by a MaxwellBoltzmann distribution at the same temperature. Above the surface, particles may collide with
each other. The code is based on Birds direct simulation
Monte Carlo algorithm w72x. In Fig. 11, the time
evolution of the density of the desorbed gas cloud is
shown. At the end of the desorption period t the gas

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Fig. 11. Contour plot of the density of the axisymmetric gas cloud at
three different times after desorption. z denotes distance from surface;
r the radial distance from the center of the laser spot. Black shading
indicates particle density. Upper part: light species; lower part: heavy
species. (Taken from Ref. w70x with permission from the authors and
the American Physical Society).

cloud is very oblate, corresponding to the large desorption area chosen for this case study. It becomes more
and more spherical at 2t, assuming a prolate form at
4t. In fact, as a result of the steep pressure gradient
initially present in the direction normal to the target, the
expansion occurs preferentially in this direction. Moreover Fig. 11 displays an interesting spatial segregation
effect of light and heavy particles; in particular, due to
the different velocity of desorbed heavy and light particles, in the back part of the cloud both species appear
to be well mixed while in the front part of the cloud
consists mainly of light species w71x.
More recently, a three-dimensional Monte Carlo simulation of the laser-induced plasma plume expansion
under a non-reactive atmosphere has been developed
w26x. Itina et al. used a three-dimensional algorithm that
combines both the direct Monte Carlo (DSMC) technique w27,71x, to simulate the desorption and the initial
cloud expansion, and the Monte Carlo simulation of the
random trajectories (MCRT) of the ablated particles in
the ambient gas w55x. This kind of approach allows
considering both the interactions between ablated particles and ablated particle-background gas atom collisions.
The latter were found to decrease the kinetic energy of
particles. Moreover at higher background pressures, the
particles are thermalized and randomly scattered from
their initial trajectories, producing a more uniform flow.
This thermalization occurs at different pressures for light
and heavy particles. This behavior can be observed in
Fig. 12, where the distribution of mean kinetic energy
E(x) of particles deposited at the plane substrate as a
function of the radial distance from the center of the

281

substrate is plotted. At low pressure (Ps0.01 mTorr)

heavy particles are more energetic than light particles
and their distribution of mean energy is more focused
toward the center. As the background pressure increases,
the mean energies of both species diminish and the
distributions become less focused toward the center.
This effect is more evident for light particles than for
heavy particles. The decrease of the kinetic energy of
the plume particles is due to the collisions with the
background gas, which thermalize the particles. The
decline of energy is more pronounced for light species,
because they lose energy more efficiently in a collision.
Therefore a smaller background pressure is required for
thermalization of light components. At high pressures
(Ps100 mTorr) most of the particles are thermalized
and energy distributions become broadened along the
normal of the surface w26x.
Therefore the difficulties of the gas-dynamic description of the diffusive processes are avoided in direct

Fig. 12. Mean energy E(x) of light (a) and heavy (b) particles deposited at a plane substrate as a function of radial distance from the center
of the substrate. The distribution were normalized by E0s2kT0, where
T0 is the temperature of the surface. (Taken from Ref. w26x with permission from the authors and the American Institute of Physics.)

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M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Fig. 13. Contour maps of the calculated spatial distribution of the plume number density as a function of time obtained in calculation with oxygen
pressure. (Taken from Ref. w56x with permission from the authors and the American Physical Society.) (1a): Pb s0.7 Pa, ts0.6 ms, (1b): Pbs
0.7 Pa, ts1.5 ms, (1c): Pb s0.7 Pa, ts2.7 ms; (2a): Pb s13 Pa, ts0.6 ms, (2b): Pb s13 Pa, ts1.5 ms, (2c): Pb s13 Pa, ts2.7 ms; (3a): Pbs
70 Pa, ts0.6 ms, (3b): Pbs70 Pa, ts1.5 ms, (3c): Pbs70 Pa, ts2.7 ms, (3d): Pbs70 Pa, ts6.3 ms.

simulation Monte Carlo (DSMC). However, other limitations arise in this kind of method. When the DSMC
is used to simulate the plume expansion process, most
of the computer resources are used to calculate only the
initial stage of the expansion. In the presence of a
background gas, additional collisions between the plume
and the buffer molecules should be considered. As a
result, the DSMC becomes computationally expensive
in terms of computer memory and calculation time, in
the case of a high rate laser ablation and in the presence
of a background gas with pressure more than ;10 Pa
w56x.
To solve the limits of both the continuous and microscopic approach, recently Itina et al. have proposed a
new hybrid method w57x. The three-dimensional model
with axial symmetry combines the continuum gasdynamic approach for the first stage of the plume
expansion with the direct Monte Carlo simulation of the
ablated flux into a background gas at the later stage. In
particular, at the first stage the plasma plume is considered as a non-viscous and non-heat conductive plasma
containing atoms, ions and electrons. The electron temperature deviates from the atom and ion temperature,
due to the slow rate of energy transfer between electrons
and heavy particles. Based on these considerations, a
one-fluid two-temperature gas dynamics is used to
describe the plume movement. The continuum gas-

dynamic calculations are performed until a certain time

t0; then the motion of the ablated and background
particles is followed by using a microscopic Monte
Carlo method. The switch time t0 should be long enough
for the plume density to diminish by several orders of
magnitude with respect to the initial values. Moreover,
t0 should be short enough so that the mass diffusion and
the heat exchange between the plume and the background gas are insignificant during t0. This approach
allows determining the background pressure needed for
the beginning of the snowplough effect, from the plume
and gas density profiles obtained at different pressures.
In particular, the combined method has been used to
study the laser ablation of aluminium in the presence of
an oxygen background gas. Fig. 13 shows the dynamics
of the plume expansion at three different pressures,
respectively, Ps0.7 Pa, 13 Pa and 70 Pa. At low
pressure (Fig. 13-1a1c) a strong expansion of the
plume is observed and no compressed layer is formed,
neither in the plume, nor in the background gas. The
leading edge of the plume moves away with a practically
constant velocity, while the center has a velocity one
order of magnitude smaller (see Fig. 14). At intermediate pressure (Fig. 13-2a2c) the plume expansion is
similar to that in the first case at the beginning and then
the plume starts being decelerated. The plume edge
decelerates and stops at approximately t;2.5 ms (see

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

283

snow-plough effect: the ablated material pushes the

ambient gas away from the target as long as the plume
pressure overcomes that one of the background gas. As
a result, both the ablated material and the ambient gas
are compressed. The plume compression and deceleration can be observed also at ts0.6 ms. At t;2.5 ms the
plume pressure becomes equal to the background pressure, the plume stops and its energy is dissipated by the
interaction of the compressed plume zone with the
compressed background gas. As a result, the plume goes
backward and equilibrates. The plume center goes back,
thus preventing the gas background filling up the region
initially occupied by the plume. Only after the equilibration and if there is still enough energy the plume
will move outward w57x.
The limit of this work is that, to reduce the computational time, it did not include any chemical reactions,
although in previous works, with a simpler fluid dynamic approach, also chemical non-equilibrium were taken
into account w58x.
3.2. Chemical models: a macroscopic and a microscopic
approach

Fig. 14. (a)(c) Time evolution of the z-position of the plume center
(h), of the plume edge (s), of the gas edge (m) and of the gas peak
(%). (a) Pbs0.7 Pa, (b) Pbs13 Pa, (c) Pbs70 Pa. (d) Time evolution of the gas peak number density at two different oxygen pressures. (Taken from Ref. w56x with permission from the authors and
the American Physical Society.)

Fig. 14b). The gas density peak rises at the first stages
of the expansion and then it decreases (see Fig. 14d)
When pressure is further increased (Fig. 13-3a3d) the
plumebackground interaction leads to the so-called

The large effort dedicated to the plume expansion

dynamics is generally not accompanied by a similar
effort in the understanding of the plume chemical
reactivity. Generally, infinitely slow chemical process
rates are supposed, which generate an expansion with
frozen plasma chemical reactivity w48x. To simulate the
real system under study, it is necessary to include
chemical models into the fluid dynamic code.
As a first attempt to simulate a reactive fluid dynamic,
a TiO plasma in local thermodynamic equilibrium (LTE)
was studied w25x. In the LTE approximation, the plasma
thermodynamics is completely defined by two independent parameters, such as pressure and temperature, or
enthalpy and pressure. A strong non-linear coupling
occurs between the chemical kinetics and the fluid
dynamics. Implicitly in the LTE approach one supposes
that the rate coefficients of chemical processes are
infinite.
This approximation, assumed by different authors
w25,73x for the interpretation of experiments as well as
for the development of theoretical codes, is still an open
problem w18,74x. Therefore the development of a new
model, which allows us to include the effect of nonequilibrium chemical processes during the plume expansion is essential.
Le et al. w24x observe a pronounced difference
between heavy-particle and electron temperatures: this
clearly demonstrates a persistent lack of equilibrium
between the electron and the heavy particle in the plasma
plume expansion. To take into account this effect, Le et
al. couples the fluid dynamic method with a kinetic
approach. The source terms in Eqs. (8)(11) depend

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

284

on ionization and recombination rate constants, which

are given by Zeldovich and Raizer w75x. The processes
included in the Le et al.s model are the ionization of
the ground state and the three-body recombination into
the ground state and the photo-recombination into the
ground state.
In addition, other authors w50x take into account the
absorption of laser radiation in the plasma and the
dynamics of its ionization state. To investigate the effects
of finite rate coefficients on the plume expansion, a
fluid dynamic model including the following processes
for a titanium plasma was developed w23,44,54x:
a
b

ionization by electron impact (direct process)

three-body recombination (inverse process)
Tikqey.mTiqq2ey

f. v.sRR,k.d

(18)

where f() is the electron energy distribution function,

approximated with a Maxwellian distribution (eVy1),
v() is the electron velocity. To obtain the total radiative
recombination rate we have summed over all the atomic
levels k:
(19)

KRRs8KRR,K
k

Aek

(14)

The ionization cross sections sion,k() were calculated

using the classical Grizinskii approach from each internal level and for a wide range of the electron energy
w76x. The ionization rate coefficients Kion,k from a given
level k have been calculated by integrating the relevant
cross sections sion,k() w76x over a Maxwellian electron
energy distribution function f w77x:

KRR,ks

(13)

radiative recombination

Tiqqey.Tikqhn

where a0 is the Bohr radius, Z is the ion charge, Ry is

the Rydberg constant, n is the principal quantum number,
Fk is the photon energy and is the electron energy.
The radiative recombination rate on level k is calculated by integrating the cross section (Eq. (17)) over
the electron energy distribution f():

The radiative recombination converts electron translational energy in electromagnetic energy (continuous
emission light). The energy emission rate for ions
recombining on atomic level k is given by:

RRR,ks

f. v.sRR,k.Fk.d

(20)

and the total irradiated energy per time unit and volume
unit (J my3 sy1) is given by:

Kion,ks

f. v.sion,k.d

(15)

nlevels

QesNeyNTiq 8 RRR,k

The total ionization rate coefficients Kion have been

calculated by summing the state selected rate coefficients over a Boltzmann distribution nk at the same
temperature as the free electrons.
(16)

Kions8Kion,k nk

(21)

ks1

where Neyand NTiq are the electron and titanium ion

number densities. To take into account the loss of energy
due to the radiative recombination, the energy continuity
equation has been modified as:

The three-body recombination process, which can be

seen as the inverse of the electron impact ionization,
involves two electrons and one ion. One of the electrons
recombines with the ion, forming an atom in state k.
The excess energy released in this process is transferred
to the other electron. The global three-body recombination rate is the sum over all the levels k. The ionization
and recombination rates are related through the principle
of detailed balance.
The radiative recombination cross sections sRR,k.
have been calculated in the hydrogen-like approximation, by means of Kramers formulas w23,44,54,78x:
sRR,k.spa20

32Z4Ry2
3y3137.3Fk.n3

(17)

rE ruE
u
q
qP syQe
t
x
x

(22)

where r is the density, E is the energy per mass unit, u

is the flow speed and P is the pressure. In this model
the inverse Bremsstrahlung absorption w12x, extremely
effective during the laser pulse, has been not considered
as we focus on the temporal evolution of the LIP species
after the laser pulse.
The role of plasma chemical processes in affecting
the macroscopic physical quantities, such as temperature,
density, pressure, and composition profiles was investigated w25,44x. It was found that the kinetic processes
strongly affect the time of flight (TOF) plots, which
can be simply obtained from the spatial profiles of each
quantity.

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Fig. 15. TOF plot of Ti and Tiq molar fractions at ds0.5 mm from
the target. T0s30000 K, v0s7000 mys, zds107 Kg my3 sy1, as1
(ionization degree).

Fig. 16. TOF plot of normalized concentrations at ds2 mm from the

target for T0s50 000 K. v0s7000 mys, zds107 Kg my3 sy1, as1.

The plasma initially produced by the lasermatter

interaction was supposed to be completely ionized. In
the free flow case, when no plasma chemical reactions
are included, the time of flight plots of the titanium

285

molar fractions show a null value everywhere. When

kinetics is included, the TOF plots of Ti become
significant, due to recombination processes.
As an example, the time evolution of the atom and
ion molar fractions at a distance of 0.5 mm from the
target is represented in Fig. 15. At the first instant, the
plume arriving in that point is essentially composed of
ions, as the kinetic effect is still negligible. As time
increases, recombination takes place, and consequently,
the Ti molar fraction grows up, while the ion molar
fraction decreases and becomes less than 0.5.
The developed kinetic model shows the fundamental
role of kinetics during the plume expansion. TOF plot
analysis highlights an apparent separation between atom
and ion concentrations (see Fig. 16) as has been
observed experimentally w44x, when kinetics is introduced in the numerical modeling.
Model results strongly depend on the initial conditions, which in the case of a continuous evaporation
approximation with a fluence of approximately 5 Jy
cm2 are temperature, rate of evaporation, initial velocity
and plume composition. The difficulties to find initial
adjustable parameters for our model from experiments
have been overcome by using the Simplex method,
i.e. by minimizing the differences between theoretical
and experimental molar fractions at a distance of 0.5
mm from the target w23x. The initial parameter values,
such as temperature, rate production of matter, velocity
and ionization degree are the following: T0s25410.4 K,
v0s8012.34 mys, zds3.06493=106 Kg my3 sy1, as
0.972948 (xTis0.0270521, xTiqsxeys0.486474).
These are reasonable if we consider that the rate of
expansion, as experimentally determined at the closest
distance (0.5 mm) from the target, is approximately
103 mys and the temperature, as obtained by the experimental Boltzmann plot, is 11 000 K (at 0.5 mm after
100 ns from the laser pulse) w42x.

Fig. 17. (a) Comparison between theoretical (i) and experimental (ii) temporal profile of Ti (continuous line and circle) molar fractions at xs
0.5 mm from the target. The estimated experimental error is ;10%. (b) Comparison between theoretical (i) and experimental (ii) temporal profile
of Tiq (dashed line and triangles) molar fractions at xs0.5 mm from the target. The estimated experimental error is ;10%.

286

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

Fig. 18. (a) Comparison between theoretical (i) and experimental (ii) temporal profile of Ti (continuous line and circle) molar fractions at xs1
mm from the target. The estimated experimental error is ;10%. (b) Comparison between theoretical (i) and experimental (ii) temporal profile
of Tiq (dashed line and triangles) molar fractions at xs1 mm from the target. The estimated experimental error is ;10%.

To validate the calculated initial parameters, we can

compare experimental and theoretical molar fractions at
different distances from the target, where no optimization has been performed. In particular, in Fig. 17a,b, the
Ti and Tiq molar fractions are reported as a function of
time, at the distance of 0.5 mm from the target, where
the optimization between theoretical and experimental
results has been performed. Then in Fig. 18a,bFig. 19a,b
a comparison between calculated and measured molar
fractions is reported, respectively, at 1 mm and 2 mm
from the target for both the atom and the ion molar
fractions.
From all these figures, we can note that the agreement
between theoretical and experimental results is good,
taking into account all the approximations that have
been used in the theoretical approach. In particular, we
can observe that our theoretical approach seems to
overestimate the atom molar fraction with respect to the
experimental values. Probably, this is due to the fact
that we have neglected the re-absorption effect of laser

pulse and that we did not include the photo-ionization

process.
From a more microscopic point of view, non-equilibrium conditions can also arise during the plume expansion in the electron energy distribution functions and in
the atomic level distributions.
In previous works w74x we investigated conditions
typically met under laser induced breakdown spectroscopy (LIBS) and characterized by large ionization
degrees. To verify the existence of LTE conditions, one
should solve a collisional-radiative model for the population densities of excited states coupled to an adequate
Boltzmann equation for the electron energy distribution
function (eedf). Both kinetics should be then inserted
in a fluid-dynamic code describing the plasma expansion. In Ref. w74x, we focus attention on a single point
of this procedure, i.e. on the possibility of deviation of
the eedf from Maxwell distribution. These deviations
can be caused by an unbalance between inelastic and
superelastic electronatom collisions caused by a differ-

Fig. 19. (a) Comparison between theoretical (i) and experimental (ii) temporal profile of Ti (continuous line and circle) molar fractions at xs2
mm from the target. The estimated experimental error is ;10%. (b) Comparison between theoretical (i) and experimental (ii) temporal profile
of Tiq (dashed line and triangles) molar fractions at xs2 mm from the target. The estimated experimental error is ;10%.

M. Capitelli et al. / Spectrochimica Acta Part B 59 (2004) 271289

287

the collisional-radiative state-to-state kinetics of relaxation of the ionization degree and excited atoms population distribution w79x.
4. Conclusions

Fig. 20. Evolution of electron energy distribution function. Te relaxes

from 5000 to 10 000 K.

ence between the temperature of electrons and that of

excited atoms. Since the first stage of the LIPS plasma
evolution is the lowering in plasma density and temperature, while the ionization degree and excited state
population distribution are changed slower, the plasma
during its evolution can be considered in an over-cooled
non-equilibrium state. The main source of deviation
from the Maxwellian form in the overcooled LIBS
plasma is superelastic collisions of electrons with excited
atoms. Inelastic collisions as well as electronelectron
and electronion collisions tend to Maxwellize eedf.
As an example, in Fig. 20 it is reported the case
referring to the heating of electron temperature from
5000 to 10 000 K, with an ionization degree and a
population density of excited states obeying Saha and
Boltzmann equilibrium at 10 000 K. As it is seen, the
eedf deviates from its Maxwellian form at practically
all the times during its evolution. In particular, the
formation of a hump at 11 eV is the result of superelastic
processes. Electronelectron Coulomb collisions are
able at times larger than 10y8 s to establish a Maxwell
distribution function.
It should be noted that in a real simulation the
relaxation of eedf through the inelastic and superelastic
collisions is accompanied by the alteration in the ionization degree and excited atom population distribution.
Both these groups of processes promote the relaxation.
Thus, for a more accurate conclusion the task related to
evolution of eedf should be solved simultaneously with

In the present study we have reported recent efforts

both experimental and theoretical for characterizing the
plume expansion in laser-induced plasmas, restricting
our analysis to nanosecond regime.
From the experimental point of view, spectroscopic
methods used to investigate the time evolution of the
plume have been discussed, with particular attention to
the characterization of TOF profiles. The fundamental
assumptions for OES experiments have been considered
in order to point out the limits and the constraints of
experimental techniques and to underline the necessity
of theoretical modeling.
Several fluid-dynamic models including Navier
Stokes and DSMC to characterize the plume expansion
have been discussed. Three-dimensional axisymmetric
compressible NavierStokes equations for a multispecies gas w24x, including two-temperature modeling (T,
Te) and the ambipolar diffusion are presented. The
deviation of velocity distribution of the ablated particles
from the Maxwellian one and the difficulty of investigating diffusive processes have been considered in the
frame of direct Monte Carlo simulation w26,27,70,71x
and of a new hybrid method w57x.
An Euler code including non-equilibrium plasma
kinetics has been used to understand the role of chemistry in affecting the fluid-dynamics w23,25,44,54x.
Moreover, the same approach has been validated by
comparing theoretical and experimental TOF profiles.
Finally, the development of microscopic models which
take into account collisional-radiative models as well as
non-Maxwell velocity distribution functions of free electrons seems to be a promising tool to completely shed
light on the complex LIP phenomenology.
Acknowledgments
This work has been partially supported by MIUR
(PON TECSIS and contract 2001031223-009).
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