Applied Surface Science 329 (2015) 47–57

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Size properties of colloidal nanoparticles produced by nanosecond

pulsed laser ablation and studying the effects of liquid medium and
laser fluence
Mohammad Hossein Mahdieh ∗ , Behzad Fattahi
Department of Physics, Iran University of Science and Technology, Narmak, Tehran 13114-16846, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, pulsed laser ablation method was used for synthesis of colloidal nanoparticles of aluminum
Received 27 September 2014 and titanium targets in distilled water, ethanol, and acetone as liquid environments. Ultraviolet–visible
Received in revised form 6 December 2014 (UV–vis) absorption spectrophotometer and scanning electron microscope (SEM) were used for charac-
Accepted 9 December 2014
terization of produced nanoparticles. Using image processing technique and analyzing the SEM images,
Available online 17 December 2014
nanoparticles’ mean size and size distribution were achieved. The results show that liquid medium has
strong effect on size properties of produced nanoparticles. From the results, it was found that ablation
Keywords:
of both metal targets in ethanol medium leads to formation of smaller size nanoparticles with narrower
Laser ablation
Colloidal nanoparticles
size distributions. The influence of laser fluence was also investigated. According to the results, higher
Particle size laser fluence produces larger mean size nanoparticles with broader size distribution.
Liquid type © 2014 Elsevier B.V. All rights reserved.
Laser fluence

1. Introduction with applications in biotechnology, luminescence, SERS (surface-

Nanoparticles play a major role in some applications such as
biology, medicine, energy conversion and storage, electronics, and
information storage [1–4]. Nanoparticles have large surface-to-
volume ratio. Such size-dependent characteristics provide unique
physical and chemical properties for nanoparticles. Metal nanopar-
ticles are an important class of nanomaterials with extraordinary
chemical, optical, magnetic, and electrical properties which have
offered new application possibilities [5–8].
Within the last two decades, several techniques have been
developed for producing nanoparticles with controlled sizes,
phases, shapes, and some other properties. These techniques
include chemical method, thermal evaporation and condensa-
tion, milling, and sputtering [9–13]. Unfortunately, these synthesis
methods are relatively expensive and often agglomerated particles
with sizes up to several micrometers are formed. In addition, in
some of these techniques, harmful and toxic materials are used.
Furthermore, they may also induce impurities to the nanoparticles
by some catalysts.
In recent years, pulsed laser ablation in liquids (PLAL) attracts
much attention as a new technique for nanoparticle synthesis
[14–16]. PLAL has been widely used for production of nanoparticles
∗ Corresponding author. Tel.: +98 21 73225877; fax: +98 21 77240497.
E-mail address: mahdm@iust.ac.ir (M.H. Mahdieh).
enhanced Raman scattering) detection, and nano-fertilizers for
seed development, and growth stimulation [17–20]. It has been
demonstrated that relatively more stable colloidal nanoparticles
can be produced by this method. Compared with other tech-
niques, PLAL is an effective, clean, and safe method for synthesis of
nanoparticles. In addition, this method is applicable for wide vari-
eties of materials, including metals and semiconductors [21,22].
For some applications (such as medical applications), size of
nanoparticles must be controlled [23–25]. Recent investigations
show that in PLAL method, size properties (mean size and size dis-
tribution) of produced nanoparticles significantly depend on laser
characteristics such as wavelength, fluence, and pulse duration.
It has been also shown that nanoparticle characteristics strongly
depend on both target material properties and liquid environment
in which ablation occurs [26–29]. Therefore, the mechanism of
laser ablation is closely dependent on both laser characteristics
and physical and chemical properties of target materials. In the
synthesis of nanoparticles by PLAL, during and after the target
irradiation, different dynamic processes may occur. In these pro-
cesses, the formation of plasma plume, creation of shock wave in
the liquid (generated by plume expansion), shock wave in the tar-
get (generated by plume recoil), cavitations (bubbles formation),
and the dynamic growth of nanoparticles are more important [30].
Although many scientific works have been performed to study the
above dynamic processes, the mechanism of nanoparticle growth
is not fully understood as nanoparticle generation is involved in

http://dx.doi.org/10.1016/j.apsusc.2014.12.069
0169-4332/© 2014 Elsevier B.V. All rights reserved.
48 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57
the above complex processes. In fact, generation of plasma, rapid
expansion of plasma plume, shock wave, and strong interaction of
plasma species (that are rapidly quenched in a highly confined liq-
uid environment) make a complex physics for this scenario [30].
Therefore, in PLAL, it would be very difficult to predict precisely
the size properties of produced nanoparticles. The full prediction
of size properties of the nanoparticles requires determination of
plasma and material density, pressure, temperature as well as full
particle–particle interaction during growth and collapse of cavi-
tation bubbles. Furthermore, liquid confinement may also occur
during and after interaction process which makes direct diagnostics
of the thermodynamic properties very challenging [31]. Neverthe-
less, the size of the produced nanoparticles can be tuned to some
extent by properly selecting laser and material parameters.
Within the last few years, many articles were published in the
field of nanoparticles synthesis by PLAL [32–39], but only a limited
number of them investigated size properties of the nanoparticles
produced by PLAL.
Among the conductor-based nanoparticles, aluminum- and
titanium-based nanoparticles have important applications. The
study of producing aluminum-based nanoparticles becomes
important due to their physical and chemical properties such as
high thermal conductivity, excellent corrosion resistance, and non-
magnetic and non-sparking characteristics. Due to such superior
properties, these nanomaterials can be used in various applica-
tions such as catalyst, coating material, thermal protections, and
microelectronics [40–44]. Titanium-based nanoparticles are also
considered as an important nanomaterial that has some useful
applicability. For example, titanium-based nanoparticles can be
used in photocatalytic activators, solar cells, and gas sensors. The
applicability of titanium-based materials is due to their interesting
properties such as high refractive index, high electrical conduc-
tivity, high melting point, and semiconducting behavior [45–48].
In spite of the fact that various metallic colloidal nanoparticles
have been synthesized by PLAL, only few syntheses of aluminum-
and titanium-based nanoparticles have been reported [49–51]. The
effects of liquid environment and laser fluence on size properties of
nanoparticles produced by PLAL have also been investigated only
by a few numbers of authors [26,27,29,52–54].
In PLAL processes, irradiation of active metal targets (such as
aluminum, titanium, and copper) in liquids usually leads to gen-
eration of metal compound nanoparticles through the chemical
reaction with the liquid. The type of compound nanoparticles
strongly depends on the interaction process and the liquid in which
the interaction takes place [53,55–58]. For example, PLAL of cop-
per in acetone produces copper nanoparticles, while the interaction
in ethanol results in the production of copper oxide nanoparticles
[55].
In this paper, we report the results of extensive investigations
in size characteristics of colloidal nanoparticles produced by abla-
tion of aluminum and titanium targets immersed in three different
liquids: distilled water, acetone, and ethanol. In addition, the effect
of laser fluence on size properties of colloidal nanoparticles pro-
duced in ambient distilled water was investigated. We will show
in the next sections that the effective parameters and mechanisms
related to production of nanoparticles with different size proper-
ties (mean size and size distribution) depend on liquid medium and
laser fluence.
2. The experiments and analyzing technique
2.1. The experiment
Fig. 1 shows a schematic diagram of the experiment. The abla-
tion was produced by a Q-switched Nd:YAG laser beam (with a
Fig. 1. Schematic experimental set up.
wavelength of 1064 nm and a pulse duration of 10 ns). Aluminum
(Aluminum 5052) and titanium metal plates (with dimensions
of 2.5 × 2.5 × 2.5 cm3 ) were used as targets in our experiments.
In order to remove thin-film oxide layer from the targets, their
surfaces were polished and cleaned by acetone just before the
experiment. The expanded Nd:YAG laser beam was focused on the
target by a doublet lens (with a focal length of 180 mm). In each
laser shot, a small fraction of the beam was sent to a pyroelectric
joule-meter for measuring the pulse energy. In these experiments,
the target was submerged in a liquid cell that was filled with
15 ml of liquid as ablation environments. In all the experiments,
the liquid level above the target surface was approximately 10 mm.
The beam spot diameter on the target surface (in all ambient liq-
uids) was measured ∼150 ␮m. It must be noted that the liquids in
these experiments have very close index of refraction; therefore,
similar measured spot for focused beam in three different liquids
is expected. Three different liquids (distilled water, acetone, and
ethanol) were used in these experiments. The liquid cell (with a
target inside) was placed on an x–y micro-positioner stage to move
the cell (together with the target) after each irradiation to a fresh
region.
We performed two separate experiments in order to investigate
the effect of different ambient liquids and different laser fluences
on size properties of the produced nanoparticles. In the first exper-
iment, aluminum and titanium targets in three different liquids
(distilled water, acetone, and ethanol) were irradiated by laser
beam with 12,000 pulses for a total time of 20 min. The laser flu-
ence in the first experiment was 46 J/cm2 . In the second experiment,
both aluminum and titanium targets in ambient water were irradi-
ated by laser with fluencies within a range of 46–140 J/cm2 (again
12,000 pulse for a total time of 20 min).
It must be noted that the color of colloidal samples (both
aluminum and titanium suspensions) varied continuously as con-
centration of nanoparticles were increasing during irradiation
time. The colors of aluminum- and titanium-based nanoparticles
(produced in different ambient liquids) were also unlike. Such
discrepancy in colors was apparently due to various chemical
and physical interactions of molten aluminum and titanium with
various liquid environments. In these experiments, the effect of
different environments appears on nuclei formation and nanopar-
ticles growing process over the formed nuclei. Thus, nanoparticles
with different size properties can be obtained when the interaction
takes place in different liquids. Furthermore, all the prepared col-
loids were stable against sedimentation for at least several months.
2.2. Analyzing technique
The size characteristics of produced colloidal nanoparticles were
analyzed by scanning electron microscope (SEM) (Model VEGA
TESCAN) and image processing techniques. The optical absorption
spectra of the different colloidal solutions were recorded in the
range of 200–900 nm with UV–Vis absorption spectrometer (Model
 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57
Rayleigh UV 2100). Using dip coating method, a thin film of each
produced colloidal particles was coated on the surface of a perfectly
cleaned glass plate and then dried. To ensure the uniformity of
nanoparticles dispersion, the colloids were vibrated with an ultra-
sonic vibrator for 15 min. The prepared samples were inspected by
SEM and image-processing techniques. The SEM images were ana-
lyzed by the image-processing technique. From the analyzed data,
the nanoparticle size characteristics, i.e. the effective mean size and
size distribution were extracted. Corresponding histograms of each
SEM image are shown in order to give the reader a better under-
standing of particle size characteristics. Although all histograms of
SEM images have information for particles sizes ranging from 5 to
300 nm, the data for particle sizes less than 10 nm may not be reli-
able. This is due to limitations in quality of SEM images and the
limitation in size resolution that can be achieved by this technique.
3. Results and discussion
It was explained that the characteristics of produced nanopar-
ticles by laser ablation are governed by a number of factors. We
have shown that in PLAL, both target material and liquid environ-
ment have crucial influence on the mean size and size distribution
of nanoparticles. Our experimental results show that the laser flu-
ence also has significant effect on characteristics of final generated
nanoparticles. The experimental results are given in the next sec-
tions and described in details.
3.1. Effect of target material and liquid environment
As already mentioned, composition of nanoparticles prepared
by PLAL strongly depends on the liquid medium. Ablation of
aluminum target in ethanol and acetone results in production
of aluminum nanoparticles, while oxide-based nanoparticles can
be formed if the ablation takes place in distilled water [59,60].
In the case of titanium, ablation in ethanol and distilled water
leads to production of a mixture of oxide-carbide-based nanopar-
ticles and oxide-based nanoparticles, respectively [61]. Ablation of
active metals such as copper and aluminum in acetone results in
production of metallic aluminum and copper nanoparticles, respec-
tively [55,59]. Figs. 2 and 3 show the SEM images and analyzed
data of aluminum- and titanium-based nanoparticles produced by
PLAL technique in three different ambient liquids: (a) acetone, (b)
ethanol, and (c) distilled water. The nanoparticles in these figures
were produced from the aluminum and titanium targets which
were irradiated by laser beam (fluence of 46 J/cm2 ) with 12,000
pulses for the total time of 20 min. The SEM images shown in
Figs. 2 and 3 indicated that the produced nanoparticles are almost
spherical or quasi-spherical.
As these figures show, the interaction in different ambient liq-
uids can lead to production of nanoparticles with different size
characteristics. The figures also show that the target material can
significantly affect the nanoparticle size characteristics. For exam-
ple, the interaction of laser beam with both aluminum and titanium
targets in ethanol and distilled water results in production of
extremely smaller nanoparticles in comparison to those in acetone
ambient. More details can be found in histogram diagrams. The data
from the histograms are summarized in Table 1.
The histograms in Fig. 2 show that in the case of ablation of
aluminum in acetone and distilled water environments, nanopar-
ticles with sizes larger than 100 nm are generated. The SEM images
and associated histograms in Fig. 3 also confirm the presence of a
great number of smaller size (in comparison to those of the other
conditions) spherical titanium-based nanoparticles in the liquids,
particularly in ethanol and distilled water environments. In fact,
ablation of titanium in both ethanol and distilled water resulted
49
Table 1
Average particle size (in nm) of prepared colloidal nanoparticles in three environ-
ment liquids: acetone, ethanol, and distilled water.
Target Medium
Acetone Ethanol Distilled water
Aluminum 58 22 35
Titanium 43 16 19
in rather narrow size distribution as the majority of nanoparticles
have sizes between 5 and 50 nm. In the case of ablation of titanium
in acetone medium, some larger particles are formed which have
regular spherical shape with diameter in submicron size range. The
mechanism of submicron particles formation is different from that
of the produced nanoparticles. The results show that the mean
size and size distribution of the aluminum- and titanium-based
nanoparticles (in a specific liquid environment) are different. Such
difference is mainly owing to optical characteristics of target mate-
rials such as refractive index and their physical properties, e.g.
thermal conductivity, melting and boiling points, electron–phonon
coupling constant, thermal conductivity, and surface energy. It has
been shown that these target properties can influence different
stages of nanoparticles evolution [30,62]. Some of these parameters
of aluminum and titanium are summarized in Table 2.
As explained, the interaction of laser beam with titanium in
ethanol and distilled water leads to formation of significantly
smaller size nanoparticles. The titanium-based nanoparticles are
also formed more uniformly than those of aluminum-based. How-
ever, acetone as an ambient influences the final interaction results
differently. In this specific liquid ambient, larger size nanoparti-
cles are produced for both aluminum and titanium targets. The
larger nanoparticles in some conditions (in Figs. 2 and 3) may not
necessarily be formed during the interaction but can be due to
agglomeration effect. This effect is more prominent in the abla-
tion of aluminum in acetone and distilled water media and also
in the ablation of titanium in acetone which results in genera-
tion of even some submicron particles. For further investigation
in this issue, we have measured the absorption spectra (within a
range of 200–900 nm) of the produced colloidal nanoparticles. Opti-
cal absorption spectra of aluminum- and titanium-based colloidal
nanoparticles by PLAL at different liquids are presented in Fig. 4a
and b, respectively.
As Fig. 4a and b shows, the formation efficiency of colloidal
nanoparticles in different liquids is dissimilar. The intensity of the
transmitted light through the suspension of nanoparticles varies
with wavelength due to the proper surface plasmon resonance,
which depends on the material, and the nanoparticle’s dimen-
sions and concentration. From the absorption spectra in Fig. 4, one
can conclude that both colloidal aluminum- and titanium-based
nanoparticles (prepared in ethanol and distilled water) have nar-
row size distribution. This implies that in the case of ablation of
aluminum and titanium in ethanol and distilled water, small size
Table 2
Some physical parameters of aluminum and titanium.
Physical parameter Target
Aluminum Titanium
Thermal conductivity at 2.37 0.219
27 ◦ C (W/cm K) [63]
Refractive index (At 1.37628 3.38789
1064 nm) [64]
Melting point (◦ C) [63] 660.32 1668
Boiling point (◦ C) [63] 2519 3287
Electron-phonon coupling 0.38 0.38
constant [65]
Surface energy (J/m2 ) [66] 1.160 2.10
50 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57

Fig. 2. SEM micrographs and corresponding histograms of colloidal nanoparticles prepared by nanosecond laser ablation of aluminum in (a) acetone, (b) ethanol, and (c)
distilled water.

nanoparticles with narrow distribution are formed. These results
are in good agreement with those of SEM micrographs. It must be
noted that the existence of peak absorbance around 350 nm for
both targets in acetone is most likely due to the presence of carbon
particles. Carbon atoms may be released from acetone molecule at
high temperature of plasma plume created by high laser fluences
[59,67,68]. In our research, we show that the colloidal products can
be a combination of nanoparticles including aluminum core (or tita-
nium core in the case of titanium target) coated by carbon shell and
carbon nanoparticles.
Therefore, not only the target material is important in PLAL pro-
cess, but also the liquid environment has major role in the size
properties of the prepared colloidal nanoparticles. For a given target
material and laser parameters, the rate of ablation and nanoparticle
 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57 51

Fig. 3. SEM micrographs and corresponding histograms of colloidal nanoparticles prepared by nanosecond laser ablation of titanium in (a) acetone, (b) ethanol, and (c)
distilled water.

generation depends on the transmission coefficient and refractive Table 3

Refractive index of three different liquid environments (at wavelength 1064 nm)
index of liquid medium at the laser wavelength [30]. The refractive
and optical transmittance (through 1 cm of the medium).
index and transmittance of three liquid environments at applied
laser wavelength (1064 nm) are shown in Table 3. Liquid Refractive index Transmittance
The laser beam has two reflection processes before reaching the Acetone [69] 1.36135 ≈1
target surface: (i) reflection from the air–liquid interface and (ii) Ethanol [69] 1.36371 ≈1
reflection from liquid–target surface interface. As Table 3 shows, Distilled water [70] 1.32604 0.54559
52 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57
Fig. 4. UV–vis absorption spectra of (a) aluminum-based and (b) titanium-based colloidal nanoparticles prepared by laser ablation (1064 nm) in three different liquids.
the refractive index of three liquids is almost the same. Therefore,
the energy portion of the reflected laser beam from air–liquid inter-
face in these three liquids would be similar. In laser ablation, the
laser beam reflectance (and absorbed energy) can be estimated
simply by using Fresnel relation (Eq. (1) for normal incidence)
which is related to the refractive indices of target and interaction
medium. An increase in absorption coefficient results in a decrease
in reflectance [30].
 n − n 2
T M
R= . (1)
nT + nM
In Eq. (1), R, nT , and nM are reflectance and the complex refractive
indices of target and ablation medium, respectively. For a spe-
cific target surface, the energy portions of the reflected laser beam
from liquid–target interface in these three liquids are also equal.
Table 4 shows the calculated reflectance of light (1064 nm) from
the interface of aluminum and titanium surfaces in three different
liquids.
In PLAL, if the light reflectance from a target interface in different
liquids is similar (ignoring the absorption of light inside the liquid),
one can expect to get similar ablation rates. However, since these
liquids have different transmission characteristics, the amount of
laser energy that reaches the target surface will be different if
the interaction environments are dissimilar. Therefore, the energy
portion that is absorbed at the target surface is different if the target
is irradiated in three different liquid environments. Detailed optical
characteristics of these three liquids show that acetone and ethanol
have similar (and almost perfect) transmissions (at 1064 nm) while
distilled water absorbs significantly the laser energy at this specific
wavelength. In such conditions in comparison to ethanol and ace-
tone as interaction environments, if the interaction is performed
in water, lower laser energy reaches the target surface. Therefore,
one expects to have higher rate ablation in ethanol and acetone.
Consequently, higher density nanoparticles are more likely to be
produced if the interaction occurs in acetone and ethanol liquids.
The other important issue in PLAL that may influence the
nanoparticles size characteristics is the processes in which the par-
ticles production is involved. Focusing of a high-intensity laser
beam on a solid target surface (through a transparent or semi-
transparent liquid) results in absorption of laser beam energy at
the target–liquid interface. If the laser energy is high enough, the
absorption of laser beam in target surface may lead to generation of
hot and high-pressure plasma plume, shock wave, and cavitations
bubble in interaction ambient.
There are three stages of plasma plume evolution in PLAL:
nucleation, phase transition, and growth of nanoparticles [71]. The
predominant mechanism of nanoparticles formation in PLAL is the
nucleation during the plasma plume cooling followed by nuclei
growth and coalescence [16]. Expansion of the plasma plume and
nucleation of clusters occurs inside the cavitations bubbles. It must
be noted that an expanding plasma plume with specific energy and
lifetime directly influences the size and lifetime of the cavitations
bubbles [30].
Plasma shielding effects in laser ablation processes at high inten-
sities are also an important issue [71,72]. At high laser intensities,
the density and temperature of laser-ablated plasma can be so high
that an efficient shielding of the target occurs during the laser pulse.
Thus, due to the shielding effect of the plasma, the amount of deliv-
ered energy to the target decreases. Such effect may change the rate
of ablation and consequently affects size properties of produced
nanoparticles.
It is believed that the growth of nanoparticle in the plasma
plume is related to condensation process which is involved in
plasma expansion and cooling. The colloidal nanoparticles can be
formed in two stages. In the first stage, nuclei is formed, and in
the second stage the nanoparticles grow over the formed nuclei
by a condensation mechanism. An important controlling param-
eter in the nanoparticle fabrication process is cooling speed of
plasma. The cooling speed influences the nanoparticle size distri-
bution. A faster cooling speed will result in production of higher
number of particles. In a colloid (produced by PLAL), the higher the
number of particles (which are resulting from condensation), the
smaller their mean size will be [71]. Thus, the cooling speed and the
consequent condensation influence the size characteristics of col-
loidal nanoparticles. The cooling speed and condensation depend
on plasma plume expansion and cavitations bubbles. On the other
hand, evolution, expansion, and collapse time of plasma plume and
the cavitation bubbles depend on laser, target material, and liquid
medium parameters.
It must be noted that some thermodynamic and optical prop-
erties of the liquid medium can greatly influence the evolution,
expansion, and collapse of plasma plume and cavitation bubbles
[30,71]. Therefore, the difference in mean size and size distribution
of produced nanoparticles in different liquid media may arise from
the difference in their thermodynamic and optical properties. Some
of the thermodynamic parameters for the interaction environment
liquids in our experiment are summarized in Table 5.
Practically, the number of nuclei per unit volume mostly
depends on pressure and temperature of the plasma plume, but
the number of condensed nuclei besides mentioned parameters
depends on the available material too. It must be noted that in
laser ablation in liquids, the nuclei formation and particles growth
are simultaneous and competing processes. Therefore, in order to
obtain small size nanoparticles, the process parameters that lead to
 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57 53

Table 4
Calculated reflectance of an incident light (at wavelength 1064 nm and normal incidence) from the interface of aluminum and titanium target surface in three different
liquids.

Aluminum in Aluminum in Aluminum in Titanium in Titanium in Titanium in

ethanol acetone distilled water ethanol acetone distilled water

93% 93% 94% 45% 45% 46%

nanoparticle formation must maximize the nuclei formation rate and thermal conductivity. High specific heat and high thermal con-
relative to the particle growth rate [71]. ductivity induce fast creation of plasma and cavitations bubbles.
In our experiment (as explained above), various interaction High surface tension generates strong confinement conditions that
media, i.e. ethanol, acetone, and distilled water, have different lead to a narrow size distribution for the produced nanoparticles.
transparency (which is related to different refractive index of these Furthermore, stronger dipole moment of surrounding
liquids). Therefore, such liquids as environments for interaction molecules of liquid medium results in stronger bonds between
may directly affect the pressure and the temperature of the plasma these molecules and surface of synthesized nanoparticles [74].
plume due to their influences on laser transmission. Different ther- So, it prevents the growth mechanism during ablation and causes
mal conductivity of the interaction liquids has also a consequence small mean size and size distribution.
on the decay process of the temperature and pressure of the plume.
Finally, the density and viscosity of the interaction liquids will 3.2. Effect of laser fluence
impact the expansion of the plasma plume [73]. All these issues
can be used as important parameters for controlling size char- The process of ablation of aluminum and titanium targets
acteristics of colloidal nanoparticles. The other important issue was performed at different laser fluences of 46–140 J/cm2 and
which may influence the nanoparticles size characteristics is the 46–109 J/cm2 , respectively. In Fig. 5, we have shown the SEM
electron–electron and electron–phonon interaction time scale. Par- images and corresponding histograms for nanoparticles produced
ticularly in the nanosecond regime, electron–electron interactions by ablation of aluminum in distilled water at fluences of 46, 78,
and electron–phonon coupling all occur within the lifetime of the 109, and 140 J/cm2 , respectively. Fig. 6 also illustrates the SEM
pulse. Electron–phonon coupling transfers the thermal energy to images and corresponding histograms for nanoparticles produced
the lattice within the time scale of the pulse and as a result, a by ablation of titanium in distilled water at 46, 78, 93, and 109 J/cm2
large volume of material is heated. The electron–phonon coupling fluences, respectively. If the laser intensity is high enough, optical
constant determines the efficiency by which the thermal energy is breakdown may occur in the focusing region which reduces the
transferred. In the interaction process, the electrons which absorb laser energy on the target surface. The threshold intensity for opti-
the incident laser photons, couple with the vibrational modes of cal breakdown is different for various liquids. Furthermore, the
the lattice, thus transferring thermal energy. This process to some interaction liquid initially is pure but ablated materials make it
extent determines the volume of material that is heated and also the impure when laser ablation takes place. Therefore, the liquid for
distribution of temperatures throughout that volume of material two different targets initially is pure and the optical breakdown
[62]. In the present research, titanium has higher electron–phonon intensity for two cases is similar. However, when the ablation takes
coupling constant with respect to that of aluminum, therefore the place, since the amount of the ablated materials are different for
heat-affected volume for the case of titanium is larger than that of two cases, the optical breakdown intensity for similar environ-
aluminum and as a result, nanoparticles with different size prop- ment liquids would be changed. In our experiment, when the laser
erties are produced. ablation process was performed in distilled water, optical break-
Thermal conductivity of materials also governs the time period down was occurred for titanium target at laser fluence of 140 J/cm2 .
during which the particles are in molten form and therefore the Therefore, in such case, the results of this laser fluence were not
period in which the nanoparticles have time to grow most effi- considered in our investigation.
ciently. Furthermore, surface energy of material governs the ten- The size of produced particles varies between few nanometers
dency of the particles to coagulate and thus results in a larger distri- to few hundreds of nanometers. Table 6 gives a summary of the
bution of sizes [62]. Thus, the smaller surface energy of aluminum average size of produced colloidal nanoparticles in various laser
with respect to that of titanium provides favorable condition for fluences for aluminum and titanium target materials.
synthesis of nanoparticle with small mean size and size distri- According to Fig. 6, in the case of ablation of titanium at laser flu-
bution. Compared to ethanol and acetone, distilled water has the ence of 46 J/cm2 , synthesized nanoparticles were mostly with sizes
highest dielectric constant, boiling point, surface tension, density, less than 100 nm, but at higher laser fluences for both aluminum
and titanium, the ablation of the targets results in production of
a large number of quasi-spherical nanoparticles. However, a few
Table 5
Some thermodynamic parameters of the interaction environment liquids. submicron particles can also be seen in this figure. As expected,
almost the mean diameter of nanoparticles is increased with laser
Parameter Ethanol Acetone Distilled water
fluencies in all cases.
Dielectric constant [63] 25.3 21.01 80.10 Laser fluence directly affects the thermodynamic properties of
Boiling point (◦ C) [63] 78.2 56 100 the cavitation bubbles and the produced plasma. This parameter
Density (g/mL) [63] 0.7893 0.7845 0.9970
Specific heat capacity 2.438 2.175 4.180
at 25 ◦ C (J/g K) [63] Table 6
Surface tension at 25 ◦ C 21.97 22.72 71.99 Mean particle size (in nm) of colloidal nanoparticles prepared by ablation of alu-
(mN/m) [63] minum and titanium targets in distilled water at different laser fluences.
Thermal conductivity 0.167 0.161 0.6062
at 25 ◦ C (W/m K) [63] Target Fluence (J/cm2 )
Dipole moment (Da) 1.69 2.88 1.8546
46 78 93 109 140
[63]
Viscosity (mPa s) at 1.074 0.306 0.890 Aluminum 35 41 – 42 43
25 ◦ C [63] Titanium 19 31 30 38 –
54 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57

Fig. 5. SEM micrographs and associated histograms of colloidal nanoparticles prepared by ablation of aluminum target in distilled water at four different fluences: (a)
46 J/cm2 , (b) 78 J/cm2 , (c) 109 J/cm2 , and (d) 140 J/cm2 .
 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57 55

Fig. 6. SEM micrographs and associated histograms of colloidal nanoparticles prepared by ablation of titanium target in distilled water at four different fluences: (a) 46 J/cm2 ,
(b) 78 J/cm2 , (c) 93 J/cm2 , and (d) 109 J/cm2 .
56 M.H. Mahdieh, B. Fattahi / Applied Surface Science 329 (2015) 47–57
also increases local concentration of ablated species due to the liq-
uid confinement. An increase in laser fluence allows the plasma
plume to reach a higher temperature and pressure, which results
in longer duration of the cavitation bubbles. This process would
promote the formation of larger size particles by coalescence [31].
Another important factor that influences the size properties of
nanoparticles is absorption of laser beam by produced nanopar-
ticles. The initial laser pulses can lead to formation of some
nanoparticles which may stay in the path of the following inci-
dent laser pulse. Such condition is due to the low mobility of
nanoparticles in liquid and limited volume of ablation cell. The
initially produced nanoparticles can absorb the energy of the fol-
lowing incident laser pulses. This effect is enhanced with increasing
laser fluence because of the increase in the amount of produced
nanoparticles. As a result of the laser beam absorption by colloidal
nanoparticles, the intensity of laser light that can reach the tar-
get is decreased. In addition, the size of nanoparticles that absorb
the incident laser is decreased because of the laser-induced frag-
mentation [75]. In summary, an increase in laser fluence not only
increases the nanoparticle production rate and its concentration
in liquid environment, but also allows the plasma plume to reach
higher temperature and pressure. Such condition results in a longer
life of cavitation bubbles (before its collapse) and consequently the
formation of larger nanoparticles.
4. Conclusion
Production of aluminum- and titanium-based nanoparticles by
pulsed laser ablation method in liquid environment was investi-
gated. According to the results, we concluded that in comparison
to distilled water and acetone, using ethanol as interaction liq-
uid media can result in production of smaller nanoparticles with
narrow size distributions. The results showed that increasing laser
fluence can lead to formation of nanoparticles with larger mean size
and broad size distribution. The results of these investigations were
explained by physics in detail and can be used for size controlling
of aluminum and titanium nanoparticles produced by PLAL.
Acknowledgements
The authors would like to thank Dr. R. Ejeyan and his group at
Thin Film Laboratory, Department of Physics, Iran University of Sci-
ence and Technology, for their supports in providing SEM images.
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