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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]
*
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
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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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Table 1
Inuence of experimental conditions on the Si particle size
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
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.
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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
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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.
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