Applied Surface Science 186 (2002) 546551

Nanoparticles produced by laser ablation of

solids in liquid environment
S.I. Dolgaeva, A.V. Simakina, V.V. Voronova, G.A. Shafeeva, F. Bozon-Verdurazb,*
a

General Physics Institute of the Russian Academy of Sciences, 38, Vavilov Street, 117942 Moscow, Russia
Laboratoire de Chimie des Materiaux Divises et Catalyse (LCMDC), Universite Paris 7 (Denis Diderot),
2, place Jussieu, 75251 Paris Cedex 05, France

Abstract
The formation of Ti, Si, Ag and Au nanoparticles under laser ablation of metal targets in liquid environment (H2O,
C2H5OH, C2H4Cl2) is reported. The use of a high-repetition-rate Cu vapor laser (wavelength 510.5 nm, pulse duration 20 ns,
repetition rate 15 kHz) allows high rate of nanoparticles formation as a sol. The nanoparticles are characterized by X-ray
diffraction (XRD), UVvisible transmission spectrometry, high resolution transmission electron microscopy (HRTEM) and
atomic force microscopy (AFM). The nanoparticle size dependence on both the laser uence and the nature of the liquid is
studied. In some cases, nanoparticles of compounds are formed via reaction of the metal with the liquid. # 2002 Elsevier
Science B.V. All rights reserved.
Keywords: Nanoparticles; Laser ablation; UVvisible; Ag; Au; Ti; Si

1. Introduction
Formation of nanoparticles under laser ablation of
solids either in gas or in vacuum has been extensively
explored during the last decade. Understanding the
mechanisms of cluster formations is needed to control
the process of pulsed laser deposition (PLD) now
widely used for the deposition of a large variety of
compounds. Formation of nanoclusters under laser
ablation in liquid environment has been much less
investigated. Formation of Ag [1,2], Au [1,2] and Cu
[3] nanoparticles by pulsed Nd:YAG laser ablation of
metals has been recently reported. Laser irradiation
has been also used to modify the size and the shape of
colloidal silver [4], gold [5,6], or goldsilver [7]
*

Corresponding author. Tel.: 33-144-27-5586;

fax: 33-144-27-6137.
E-mail address: bozonver@ccr.jussieu.fr (F. Bozon-Verduraz).

nanoparticles prepared by chemical or electrochemical methods. A large variety of chemical methods are
involved in the preparation of nanoparticles [8,9]. The
peculiarity of laser ablation of metals in liquid environment is to generate colloidal solutions without
counter-ions or surface active substances. The present
work deals with: (i) the genesis of Ti, Si, Ag and Au
nanoparticles under laser ablation of metal targets in
liquid environment; (ii) their characterization by various methods.
2. Experimental techniques
The formation of a sol of metal nanoclusters is
gained via irradiation of the corresponding metal plate
immersed into the liquid. A visible range Cu vapor
laser was used; the main wavelength emitted was
510.6 nm with some fraction at 578.2 nm depending

0169-4332/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 ( 0 1 ) 0 0 6 3 4 - 1

S.I. Dolgaev et al. / Applied Surface Science 186 (2002) 546551

on the pumping current. The pulse duration was 20 ns,

and the repetition rate 15 kHz. The laser beam was
focused (spot diameter about 50 mm) on the metal
surface through a liquid layer (thickness: several
mm). Typically, the energy density of laser radiation
on the solid surface was in the order of 12 J/cm2. The
irradiation of the metal surface results in fast removal of
the material conned to the laser spot; to avoid the
formation of deep holes, the metal plate was displaced
under the laser beam with the help of a computer-driven
XY stage. The scanning velocity was typically 1 mm/s.
The transmission spectra of the resulting liquid
were recorded on a Cary 5E spectrometer in the
200800 nm range. The X-ray diffractogram of the
particles were recorded after drying the suspension on
a glass plate. Identication of the crystallographic
phases of solid particles was performed using the
JCPDS-ICDD PDF (Joint Committee for Powder
Diffraction StandardsInternational Centre for Diffraction Data Powder Diffraction File) card. The
average particle size was calculated according to
the Scherrer relation.

547

3. Results
3.1. Laser ablation of Si in liquid environment
Fig. 1 shows the atomic force microscopy (AFM)
view of Si particles produced by ablation of a Si single
crystal in ethanol. The particle size is comprised
between 200 and 1000 nm with an average near
500 nm. These particles are polycrystalline as the
crystal size (deduced from X-ray line broadening) is
much lower; this is shown in Table 1, which presents
the inuence of different experimental parameters,
such as the laser uence, the nature of the liquid,
the type of surface active substance. In all the cases,
the Si crystal size ranges between 60 and 80 nm; the
nature of both the liquid and the surface active agents
do not seem to have a signicant inuence. In addition, the crystal size is almost independent on the laser
uence; however, the latter should be higher than the
Si melting threshold. This threshold uence is about
0.4 J/cm2 for a Cu vapor laser radiation [10]. No
changes in the optical transmission of the liquid is

Fig. 1. AFM image of Si clusters obtained by ablation of a Si single crystal in ethanol (in nm). The inset shows the size distribution centered
around 500 nm.

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S.I. Dolgaev et al. / Applied Surface Science 186 (2002) 546551

Table 1
Inuence of experimental conditions on the Si particle size

observed if the laser uence is below the melting

threshold.
It should be noted that Si is not the only material
dispersed in water upon laser ablation. Indeed, the
diffractogram of the solid phase obtained after evaporation of the aqueous sol shows the peaks of some
other compounds, not clearly identied through
JCPDS data les. These peaks might be ascribed to
a Si sub-oxide.

results in the formation of Ti nanocrystals (mean size

around 35 nm) having the cubic structure. It should be
reminded that the initial polycrystalline Ti plate has a
tetragonal structure. It is known that the cubic phase of
Ti is metastable and exists only at elevated temperature (>600 8C). At the same laser density of energy,
laser ablation of Ti immersed in dichloroethane leads
to the formation of nanoparticles of titanium carbide
TiC. The four most intense peaks of TiC can be
detected on the X-ray diffractogram of the evaporated
suspension. The size distribution is bimodal with
maxima near 150 and 25 nm. Finally, laser ablation
of Ti in water results in the formation of nanoparticles
having the composition of non-stoichiometric oxide
TiOx, where x 1:04. The peak width indicates that
the mean crystal size is about 35 nm. All diffractograms also contains unidentied peaks.
Formation of TiC via ablation of Ti in dichloroethane may be ascribed to the catalytic action of
Ti nanoparticles, since no carbon-containing particles
have been detected upon ablation of either Si or Au in
this liquid or otherwise under identical experimental
conditions. It is worthwhile to mention that the surface
of the Ti target after laser ablation in dichloroethane
does not contain any XRD detectable amount of TiC.

3.2. Laser ablation of a Ti in liquid environment

3.3. Laser ablation of Ag in liquid environment

The composition of nanoparticles produced by laser

ablation of Ti was found to depend on the nature of the
liquid (Fig. 2). Namely, laser ablation of Ti in ethanol

Ablation of Ag immersed into water results in the

yellowish coloration of the liquid. The optical spectrum (Fig. 3) shows a maximum at about 400 nm,

Liquid

Laser fluence
(J/cm2)

Si particle size
(nm)

Water

1.2
0.7

84 (no SASa), 80
(LSb), 74 (PVPc)
74 (no SASa)

Dichloroethane

1.5
0.7

66
60

Ethanol

1.2
0.7

78
76

Surface active substance.

Na laurylsulfate.
c
Polyvinylpyrrolidone, M 104 .
b

Fig. 2. Diffractograms of dried suspensions obtained by laser ablation of Ti in various liquids: (a) ethanol; (b) dichloroethane; (c) water. Laser
energy density is 4 J/cm2.

S.I. Dolgaev et al. / Applied Surface Science 186 (2002) 546551

549

Fig. 3. Absorption spectrum of a sol of Ag nanoparticles in water (path length 10 mm).

which is typical of plasmon absorption of Ag nanoparticles [11,12]. The intensity of the plasmon band
increases with irradiation time, whereas its position
does not vary signicantly.
Unlike Ag colloidal solutions prepared by chemical
ways [8,9], the colloid obtained by laser ablation of
metallic Ag in liquid environment contains only the
metal and the liquid, without any surface active agent
and remaining anions. Formation of Ag nanoparticles
in water allows to observe the surface enhanced
Raman scattering (SERS) of, e.g., acridine molecules
adsorbed on the nanoparticles (concentration as low as
10 5 mol/l) [13].
The high resolution transmission electron microscopy (HRTEM) view of Ag nanoparticles is shown in
Fig. 4. The average particle size is around 60 nm.
Moreover, they appear as at disks with thickness
much lower than their diameter. This is clearly seen in
the inset in Fig. 4, where the TEM image of the
intersection of two or more Ag particles is darker
than each separate particle. X-ray analysis of the dried
Ag suspension indicates that the size of coherent
scattering of nanoparticles (20 nm) is smaller than
the particle size measured by HRTEM (Fig. 4). This
suggests a complex structure of the Ag particles
obtained in these conditions.
A similar optical spectrum is observed after laser
ablation of bulk Ag in isobutanol. However, in other
liquids (ethanol, dichloroethane), the characteristic
plasmon peak is shifted towards the UV region. This

can be ascribed to a change in particle size and/or to

differences in the dielectric constant of the medium.
Experiments are in progress to elucidate this point.
3.4. Laser ablation of Au in liquid environment
The laser ablation of Au was carried out mostly in
aqueous environment. The optical spectra of the liquid
after laser exposure (Fig. 5) presents two well pronounced absorption bands at ca. 520 and 740 nm,
characteristic of the plasmon frequency of elongated

Fig. 4. HRTEM view of Ag nanoparticles obtained by ablation of

bulk Ag under water. Scale bar denotes 100 nm. Inset shows the
enlarged view of the intersection of individual particles. Scale bar
denotes 30 nm.

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S.I. Dolgaev et al. / Applied Surface Science 186 (2002) 546551

The coupling of laser radiation to the colloidal

solution can lead to the modication of the size
distribution and shape of Au nanoparticles. This is
conrmed by the TEM view of Au particles obtained
after the ablation of Au in water (Fig. 6a) and after
laser exposure of the colloidal solution itself, i.e. after
withdrawing the bulk metal target (Fig. 6b). The initial
particles are elongated (Fig. 6a), whereas further
exposition to laser radiation gives at disks as
observed in the case of Ag.
4. Discussion

Fig. 5. Absorption spectra of Au colloids obtained by laser

ablation of bulk Au in water with various laser uence. Irradiation
time being 2 h; path length is 10 mm, except for the lower spectrum
recorded with a 0.2 mm cell.

Au nanoparticles [14]. The Au colloids in water are

not very stable, and signicant coagulation of nanoparticles is observed within 30 days after preparation.
The plasmon band fades down, and the color of the
solution turns to gray-violet. However, since the colloidal solution absorbs at the wavelength of the Cu
vapor laser, its spectrum changes with irradiation time
and the spectrum of the initial Au colloid is almost
completely recovered after irradiation.

The formation of Ag clusters under laser irradiation

of metallic Ag is due to a strong interaction of the
evaporated metal with water vapor. Indeed, a thin layer
of Ag is heated above its melting temperature during
the laser pulse. The adjacent water layer is heated to
almost the same temperature owing to heat transfer
from the metal. Taking into account the heat diffusion
coefcient of liquid water a 10 3 cm2 =s and the
diffusion time equal to duration of the laser pulse
tp 20 ns, the thickness of the liquid layer h can
be estimated to atp 1=2 0:3 mm. This thin layer,
which reaches a much higher temperature than the
boiling point of the liquid at normal pressure, is in the
vapor phase. Its pressure may be roughly estimated as
the vapor pressure of the liquid at the temperature of the
substrate. This means that all liquids used in the present
study are in vapor phase at pressures in the order of tens
atmospheres. In these conditions, some liquids, like
dichloroethane, undergo chemical reactions, which

Fig. 6. TEM view of Au nanoparticles as obtained by ablation of bulk Au in water (a) and after 3 h of irradiation of the colloidal solution at
uence of 35 J/cm2 without the metal sample (b). Space bar denotes 100 nm.

S.I. Dolgaev et al. / Applied Surface Science 186 (2002) 546551

results in the synthesis of new materials in the vapor

layer, e.g., TiC. The characteristic scale of the clusters
formed is thus very small of the order of 50 nm. The
high vapor density induces a very high number of
molecular collisions per second. The interaction of
metal and solvent vapors leads to the fast agglomeration of the metal atoms to clusters. This is conrmed
by the fact that the Si clusters size is virtually independent of the nature of the surface active agent added
to the liquid, though its presence may alter the stability
of the suspension after its formation.
Melting of the solid is a necessary condition for the
formation of nanoparticles under ablation in liquid
environment. This is gained under sufciently high
laser uence depending on the absorptivity of the
material at the laser wavelength.
Coupling of laser radiation to the suspension of
nanoparticles through plasmon resonance may alter
the distribution of particle size as demonstrated in the
case of Au. Similar coupling to the radiation of a Cu
vapor laser is also gained for suspension of Cu nanoparticles whose plasmon frequency also lies in the
visible. This effect can be avoided by using a ow cell
with a typical liquid velocity of ca. 1 mm/s.
Acknowledgements
This work was partially supported by Russian
Foundation for Basic research, grants 01-02-17724

551

and 01-02-16495. We thank O. Gorbenko for AFM

imaging of DLF samples, R. Brayner for UVvisible
spectroscopy measurements and P. Beaunier for TEM
images of metal colloids.
References
[1] J. Nedersen, G. Chumanov, T.M. Cotton, Appl. Spectr. 47
(1993) 1959.
[2] M.S. Sibbald, G. Chumanov, T.M. Cotton, J. Phys. Chem.
100 (1996) 4672.
[3] M.-S. Yeh, Y.-S. Yang, Y.-P. Lee, H.-F. Lee, Y.-H. Yeh, C.-S.
Yeh, J. Phys. Chem. B 103 (1999) 6851.
[4] P.V. Kamat, M. Flumiani, G.V. Hartland, J. Phys. Chem. B
102 (1998) 3123.
[5] A. Takami, H. Kurita, S. Koda, J. Phys. Chem. B 103 (1999)
1226.
[6] S. Link, C. Burda, B. Nikoobakht, M.A. El-Sayed, J. Phys.
Chem. B 104 (2000) 6152.
[7] J.-P. Abid, H.H. Girault, P.F. Brevet, Chem. Commun. (2001)
829830.
[8] N. Toshima, T. Yonezawa, New J. Chem. 22 (1998) 1179.
[9] N. Toshima, in: T. Sugimoto (Ed.), Reactions in Homogeneous Solutions, Surfactant Science Series, Vol. 92, Marcel
Dekker, New York, 2000, p. 430.
[10] G.A. Shafeev, A.V. Simakin, Appl. Phys. A 54 (1992) 311.
[11] P. Mulvaney, Langmuir 12 (1996) 788800.
[12] J.A. Creighton, D.G. Eadon, J. Chem. Soc., Faraday Trans. 87
(1991) 3881.
[13] G. Levy, J. Aubard, G.A. Shafeev, F. Bozon-Verduraz, in
preparation.
[14] S. Link, M.A. El-Sayed, J. Phys. Chem. B 103 (1999)
8410.