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Fabrication of silver nanoparticles by highly intense laser irradiation of

aqueous solution

Article in Applied Physics A · September 2011

DOI: 10.1007/s00339-011-6499-5

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Fabrication of silver nanoparticles by
highly intense laser irradiation of aqueous
solution

Takahiro Nakamura, Hideyuki Magara,

Yuliati Herbani & Shunichi Sato

Applied Physics A
Materials Science & Processing

ISSN 0947-8396
Volume 104
Number 4

Appl. Phys. A (2011) 104:1021-1024

DOI 10.1007/s00339-011-6499-5

1 23
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 Author's personal copy
Appl Phys A (2011) 104:1021–1024
DOI 10.1007/s00339-011-6499-5

Fabrication of silver nanoparticles by highly intense laser

irradiation of aqueous solution
Takahiro Nakamura · Hideyuki Magara ·
Yuliati Herbani · Shunichi Sato

Received: 9 February 2011 / Accepted: 23 May 2011 / Published online: 30 June 2011
© Springer-Verlag 2011

Abstract Silver (Ag) nanoparticles were fabricated by The main method for preparing Ag nanoparticles is a re-
highly intense femtosecond laser irradiation of aqueous so- duction process using reducing agents such as hydrazine
lutions of silver nitrate (AgNO3 ) with various concentra- (H2 NNH2 ), sodium borohydride (NaBH4 ), and dimethyl
tions. After irradiation, a broad absorption peak at around formamide ((CH3 )2 NCHO, DMF). These chemicals are
420 nm originating from surface plasmon resonance of highly reactive and hence give rise to environmental and
Ag nanoparticles was observed in 30 and 300 mM solu- biological problems [6–9]. In recent years, a more environ-
tions. Transmission electron microscopy revealed that Ag mentally friendly process has been developed that involves
nanoparticles produced in 300 mM AgNO3 solution had a laser ablation of a solid metal target immersed in a solu-
typical size in the range of 2 to 20 nm and a mean size of tion [10–15]. This method has been used to fabricate Ag
4 nm. The addition of 1.0 × 10−2 wt% polyvinylpyrroli- nanoparticles in solution with no chemicals except for a dis-
done as a dispersant to the 300 mM solution caused a nar- persant [15]. However, it produces large particles (known
rower particle size distribution as well as a narrower absorp- as debris) with a broad size distribution. Although a melt-
tion peak width after the laser irradiation. As a result, Ag ing and fragmentation process applying additional laser ir-
nanoparticles with a mean particle size of about 2 nm were radiation was effective to reshape and resize the debris, this
fabricated. process was essentially a two-step synthesis.
As an alternative approach, we have reported a method
for preparing stable gold [16] and platinum [17] nanoparti-
cles with no reducing agent by highly intense laser irradia-
1 Introduction
tion of metal salt solutions containing a suitable dispersant.
This method enables us to produce metal nanoparticles with
Noble metal nanoparticles have been intensively studied
both narrow size distribution and particle size down to 2 nm.
due to their unique optical, electrical, and catalytic prop- While oxidation of metals is generally a problem in material
erties. Among them, silver (Ag) nanoparticles are one of processing in water, silver (like gold and platinum) is not ox-
the most popular catalysts for oxidation of ethylene [1] and idized in water since it has a higher free energy than water
have higher electrical and thermal conductivities than other in the Ellingham diagram.
nanoparticles. Moreover, silver has strong inhibitory and In this study, we fabricate Ag nanoparticles by highly in-
bactericidal effects, and a broad spectrum of antimicrobial tense laser irradiation of aqueous solutions of silver nitrate.
activities; these properties have been exploited for a long The effects of the silver nitrate concentration and the ad-
time to prevent and treat a wide variety of diseases [2–5]. dition of a dispersant on the production efficiency and Ag
nanoparticle size are investigated.

T. Nakamura () · H. Magara · Y. Herbani · S. Sato

Institute of Multidisciplinary Research for Advanced Materials, 2 Experimental
Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577,
Japan
e-mail: [email protected]
Silver aqueous solutions with concentrations of 0.3, 3, 30,
Fax: +81-22-2175145 and 300 mM were prepared by dissolving silver nitrate
 Author's personal copy
1022 T. Nakamura et al.

(AgNO3 , Wako Pure Chemical Industries, Ltd., >99.9%) chirped-pulse amplified Ti:sapphire laser. The laser beam
in ultra-pure water. All the solutions were transparent. Fig- was introduced normal to an aspherical lens (focal length:
ure 1 shows UV-visible absorption spectra of these silver 8 mm; numerical aperture: 0.5), which is set just before the
nitrate solutions obtained using a UV-visible spectropho- cuvette, and tightly focused inside the solution. The spot di-
tometer (Jasco Co., V630 iRM). The absorption peaks at ameter was estimated to be 175 μm. The laser intensity was
around 310 nm are due to nitrate ions in the solution. Fig- theoretically estimated to be 2.1 × 1014 W/cm2 . The irradia-
ure 2 shows a schematic representation of the experimental tion time was 45 min in all experiments. The optical charac-
setup. A 10 × 10 × 45 mm3 quartz glass cuvette, which was teristics of the solutions after irradiation were evaluated us-
optically transparent at the laser wavelength, was filled with ing the UV-visible spectrometer. Transmission electron mi-
3 ml of the aqueous solutions. Highly intense femtosecond croscopy (TEM; JEOL, JEM2000EXII) micrographs of the
laser pulses (wavelength: 800 nm; pulse energy: 6 mJ; pulse products were obtained after laser irradiation. TEM samples
width: 100 fs; repetition rate: 10 Hz) were generated by a were prepared by dropping the solution on a carbon-coated
copper grid (Okenshoji Co., Ltd., microgrid B) immediately
after irradiation and then drying them in air. The particle size
and size distribution were obtained by measuring the parti-
cle diameter in the TEM micrographs.

3 Results and discussion

When the solutions were irradiated by femtosecond laser

pulses, a tiny plasma flash was observed and fine bubbles
were generated near the focus. The bubbles were identified
as hydrogen and oxygen by chromatographic analysis (Shi-
Fig. 1 UV-visible absorbance spectra of aqueous solutions of silver madzu Co., GC-8A), indicating the decomposition of water
nitrate with concentrations of 0.3, 3.0, 30, and 300 mM
molecules by the highly intense laser field [18]. No visible
changes were observed during the irradiation except for the
Fig. 2 Schematic 300 mM solution, which turned light gray after irradiation.
representation of the
In the 300 mM solution, a black precipitate appeared on the
experimental setup
bottom of the cuvette one day after the laser irradiation. This
precipitate seemed to be formed by the agglutination of sil-
ver particles fabricated by the laser irradiation.
Figure 3 shows the UV-visible absorption spectra of the
AgNO3 aqueous solutions before (dotted lines) and after

Fig. 3 UV-visible absorbance

spectra of aqueous solutions of
silver nitrate salt with
concentrations of (a) 0.3,
(b) 3.0, (c) 30, and 300 mM
after laser irradiation (solid
curves). Spectra of the solutions
before irradiation (dotted
curves) are also indicated in
each figure for comparison
 Author's personal copy
Fabrication of silver nanoparticles by highly intense laser irradiation of aqueous solution 1023

(solid lines) irradiation for 45 min. The spectra of the 0.3 after irradiation, while the broken curve shows the spec-
and 3.0 mM AgNO3 solutions are the same before and af- trum of the AgNO3 solution without PVP after irradiation.
ter irradiation. In contrast, a weak but broad absorption peak The absorption peak at around 420 nm due to the SPR
near 420 nm is visible in the spectra of the 30 and 300 mM of Ag nanoparticles [19, 20] became sharp and the tail in
solutions. This peak wavelength indicates the surface plas- the longer-wavelength region was suppressed. This result
mon resonance (SPR) of Ag nanoparticles and its broadness strongly indicates that the addition of PVP reduces the par-
implies that the scattering is caused by a small number of ticle size and makes the size distribution narrower.
large particles simultaneously formed in the solution (see Figure 5 shows TEM micrographs and corresponding
discussion below). particle size distributions obtained by estimating the parti-
To ensure that the silver particles remain dispersed, cle diameters from the TEM images. It also shows the mean
0.01 wt% polyvinylpyrrolidone (PVP, Merck), which is a sizes and standard deviations of the particles. These mi-
commonly used dispersant for metal colloids, was added to crographs and profiles were obtained for AgNO3 solutions
the 300 mM AgNO3 aqueous solution. This PVP concen-
without PVP (Fig. 5a) and with 0.01 wt% PVP (Fig. 5b).
tration was found to give good dispersibility for both gold
Selected-area electron diffraction (not shown) revealed that
and platinum nanoparticles in our previous studies [16, 17].
the particles in the bright-field images are silver. The sil-
After a certain irradiation time, the AgNO3 solution con-
ver particles formed in the solution without PVP (Fig. 5a)
taining PVP changed from transparent to yellow. The solid
had a relatively broad size distribution. The particles may
curve in Fig. 4 shows the UV-visible absorption spectrum
agglomerate during and/or after irradiation. In contrast, the
of the 300 mM AgNO3 solution containing 0.01 wt% PVP
mean particle size was small and the size distribution of the
particles was narrow in the solution with 0.01 wt% PVP
(Fig. 5b). This result is consistent with the UV-visible spec-
tra of the solutions shown in Fig. 4. Namely, the increase
in the number of small silver particles is attributed to the
sharp peak of SPR. Moreover, the spectral broadening due
to scattering by large particles is diminished. Silver nanopar-
ticles stabilized with PVP have an average particle size of
nearly 2 nm, which is similar to those of gold and platinum
nanoparticles [16, 17].
The formation of Ag nanoparticles in the absence of
Fig. 4 UV-visible absorption spectrum of aqueous solution of 300 mM any reducing agent can be attributed to the strong reduc-
silver nitrate with 0.01 wt% PVP after irradiation (with PVP, solid
curve). The absorption spectrum of the solution without PVP after ir- ing species (i.e. solvated electrons and free radicals) gen-
radiation (no additives, broken curve) is also shown for comparison erated by highly intense laser irradiation of the solution,

Fig. 5 TEM images obtained

from samples prepared by a
drop of a solution (a) without
PVP and (b) with 0.01 wt%
PVP (upside), and the
corresponding size distribution
profiles of particles obtained by
measuring the diameter of
particles in the micrographs
(downside)
 Author's personal copy
1024 T. Nakamura et al.

as proposed for radiolytic reduction [21, 22] and the so- Acknowledgements This work was partially supported by a Grant-
lution plasma method [23]. Solvated electrons (eaq− ) and in-Aid for Young Scientists (B) (No. 21760575) from the Japan Society
hydrogen radicals (H˙), which are strong reducing agents for the Promotion of Science, the Nippon Sheet Glass Foundation for
− ) = −2.87 V and E o (H+ /H) = −2.87 V), are Materials Science and Engineering, and the Hattori-Hokokai Founda-
(E o (H2 O/eaq tion.
produced from water molecules:
− , H˙, OH˙, etc.
H2 O → eaq (1) References

The strong absorption at around 300 nm in Fig. 2 is caused

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