Send Orders of Reprints at reprints@benthamscience.

net
192

Current Nanoscience, 2013, 9, 192-196

Fabrication and Optical Absorption Properties of Gold - Silver and Gold-Platinum

Alloy Nanoparticles Formed by Laser Ablation
Souad A. El-Feky1,2,* and El-Sayed A. Al-Sherbini1
1

National Institute of Laser Enhanced Science (NILES), Department of Laser applications in Metrology, Photochemistry and Agriculture, Cairo University, Cairo, Egypt, P.O. Box 12613; 2Department of Chemistry, University of Bath, Claverton down, BA2 7AY,
United Kingdom
Abstract: Gold, silver and platinum nanoparticles were fabricated by a laser-induced breakdown technique of Au, Ag and Pt metal
plates. On the other hand, bimetallic nanoalloys consisting of AuAg and AuPt have been synthesized by irradiation of the prepared
nanoparticles under UV light, which leads to an alloy type of structure. The optical characterization and particle sizes were determined by
using absorption spectroscopy and transmission electron microscopy.

Keywords: Nanoparticles, laser-induced breakdown, alloy, bimetal, TEM.

1. INTRODUCTION
Nanoparticles (NPs) of Ag and Au less than 5 nm in diameter
are particularly interesting as they may exhibit both classical and
quantum size effects in their absorbance spectra [1-3]. Nanoalloys
of gold and silver, metals that have essentially identical lattice constants and are completely miscible, present new opportunities to
investigate the effect of nanostructure on optical properties [4]. In
the case of both gold and silver, with large diameter, D > 5 nm,
nanoalloys charge stabilizes in water [5, 6]. Many studies reported
the synthesis of various nanoalloys by chemical methods [7-11].
Interest in research on the synthesis of metallic nanoparticles
has been evolving due to their amazing properties in catalysis, optics, and electronics [12]. It is known that with the decrease of particle size, particularly to the point where the critical dimensions are
in the nanometer regime, many properties can be significantly different from those of their bulk counterparts, especially the catalytic
properties [13].
The primary routes to prepare metal nanoparticles include reduction, which is carried out by employing a powerful reducing
agent, such as sodium borohydride (NaBH4), in the presence of a
stabilizer [14]. The excess use of NaBH4 may result in the adsorption of unused BH4 ions onto the nanoparticle surface resulting in
the contamination of borides on the nanoparticle surface. Furthermore, as the phase transfer agent and the stabilizer are sometimes
chemically different, a long postsynthesis purification procedure is
still an issue in this technique. At this point, irradiation-based synthesis becomes a good choice due to the advantage of being free
from preadded reducing agents.
Reduction of metal ions is facilitated by an abundance of highenergy electrons and radicals created in situ through the ionization
and excitation of solvent molecules by radiation. Nanoparticle synthesis using an intense
ray [15] has been explored as a key method
in irradiation-based techniques for the past two decades, while synchrotron X-ray [16, 17] and femtosecond laser [18-26] techniques
have recently attracted much attention due to the identical process
underlying the reduction process of metal precursors to zero valence nanoparticles. In particular, water molecules have been reported to be decayed by femtosecond laser techniques via
*Address correspondence to this author at the National Institute of Laser
Enhanced Science (NILES), Department of Laser Applications in Metrology, Photochemistry and Agriculture, Cairo University, Cairo, Egypt, P.O.
Box 12613; Tel:/Fax: 001123931944;
E-mail: dr_souad_elfeky@niles.edu.eg
1875-6786/13 $58.00+.00

two-photon absorption, generating solvated electrons and hydrogen

and hydroxyl radicals along with dissociation products such as hydronium ions and H3O+, at decimolar concentrations [27]. Furthermore, exposing the system to different additives such as dispersants
and ion scavengers will generate a series of reducing radicals with
different reduction potentials, which can reduce metal precursors
selectively. Even though
-ray and synchrotron X-ray irradiation
sources are very efficient, these methods have some drawbacks,
such as radioactivity and poor accessibility. From this viewpoint, a
laser-induced breakdown irradiation method seems to be more
promising due to its simple, safe and green properties. Using a
100 mJ/pulse, we report the formation of Au, Ag and Pt nanoparticles in distilled water. Gold is very useful as an alloying metal in
conjunction with other metals, and the structure of bimetallic combinations depends mainly on the preparation conditions and the
miscibility of the two components [28]. Combinations such as Au
Pd and AuPt have been reported to exhibit a core-shell structure
while AuAg forms either a core shell or an alloy [29]. Cheng et al.
(2011) have also investigated an AuPt system in which they found
that the fabricated particles were alloys but possessed a broad size
distribution with an average of about 15 nm. They suggested that
this might be because of the midlevel laser pulse energy used in this
work or because of the miscibility gap of Au and Pt systems for
making a solid solution [30].
In the present study, we fabricated gold nanoalloys with silver
or platinum in an effort to combine the optical properties of the
noble metal alloys. These nanoalloys can be conjugated with functional groups and applied in biosensing as extremely pure and efficient sensors. We report the fabrication of gold nanoparticles by
laser ablation of a gold metal plate in different solvents of different
physical properties. In addition, we have investigated the formation
of AuAg, AuPt and AgPt alloy nanoparticles.
2. EXPERIMENTAL SECTION
2.1. Materials and Methods
Gold, silver and platinum (>99.9%, Fluka) nanoparticles were
prepared by laser ablation of the corresponding metal plates. The
ablation in the case of gold was carried out in different solvents
(purse, Fluka). Double distilled water was used. As shown in Fig.
(1), the metal plate was placed on the wall of a quartz cuvette filled
with 3 mL of solvent. Laser pulses (
= 8 ns at 10 Hz) from a NdYAG laser (continuum SLI-10) at  = 1064 nm were focused onto
the surface of the metal plate using a fused silica cylindrical lens (p
= 100 nm).
2013 Bentham Science Publishers

Current Nanoscience, 2013, Vol. 9, No. 2

Fabrication and Optical Absorption Properties

Lens F =150mm

B.S.

Nd-YAG

Metal Plate

Power Meter

Fig. (1). Schematic diagram of the experimental setup.

The focused region on the gold plate had a rectangular shape of

6 nm long and 0.5 nm wide. The samples were placed 5 cm below
the laser source and were exposed for the required irradiation time.
Particles sizes were determined by transmission electron microscopy (TEM). The energy of the Nd-YAG laser was 100 mJ/pulse,
measured using a power energy meter (molectron-EPM 2000:Tar5).
The colloidal solution of the fabricated nanoparticles was measured
using a Perkin Elmer Lambda-40 spectrophotometer. Then, the
prepared samples were mixed and irradiated using a UV light
source (Analamp mod. 81-105-7-01, 230 nm, USA). To fabricate
the nanoalloy, 3 ml of a colloidal solution of the nanoparticles was
exposed at a distance of 5 cm from the light source for the required
irradiation time.
3. RESULTS AND DISCUSSION
3.1. Fabrication of Au Nanoparticles in Different Solvents
Fig. (2) shows the absorption spectra of the spherical gold
nanoparticles prepared by the chemical method in distilled water
[19].
The spectra illustrated a plasmon absorption band at
max. = 522
nm. Fig. (3) shows the absorption spectra of gold nanoparticles
prepared by laser ablation in different solvents.

gradual variation in the gold SPR peak. The spectra are characterized by different positions of the maximum absorption bands depending on the solvent polarity as shown in the figure. Fig. (3) also
shows that the absorption band for Au NPs in water is similar to
that shown by Turkevich [31] (Fig. (2)). It is well known that the
plasmon absorption position of the gold nanoparticles is dependent
on the polarity of the surrounding solvents [32]. The greater the
value of the solvent polarity, the greater the interaction between the
nanoparticles and the solvents, which results in high dispersion of
the particles. This might be due to the fact that the interaction between the nanoparticles and the polar solvent is more favorable than
particle-particle interactions. The results showed red shifts by ~ 69
nm after decreasing the solvent polarity from water (
max = 522 nm,
polarity=9) to THF (
max = 591 nm, polarity=4) (polarity order H2O
> CTAB > EtOH > THF [33]). In other words the higher the dipole
moment (H2O=1.85 Debye), the higher the particles dispersion and
the lower the dipole moment (THF=1.65 Debye) [34] the lower the
particle dispersion. As shown in Fig. (3), the absorption spectra of
nanoparticles in THF were broad and extended. The broadening of
the spectra may be due to the particle-particle interaction since in
less polar (small dipole moment) solvents the ability of nanoparticles to aggregate is higher than the interaction between the solvent
molecules and the nanoparticles [22]. In the case of the chemical
method, the capping materials might be preventing the nanoparticles from aggregating, unlike those prepared by laser ablation.
Water

(CTAB)

Ethanol

THF

0.2
H2O
Ethanol

Optical Density (O.D)

3 mL Solvent

193

CTAB

THF

0.1

0.0
400

500

600

700

800

900

Wavelength (nm)

Fig. (3). UV-vis absorption spectra of the nanoparticles prepared by laser

ablation in different solvents.

OPTICAL DENSITY (O.D)

0.4

0.2

0.0
400

600

800

WAVELENGTH(nm)

Fig. (2). UV-vis absorption spectra of spherical nanoparticles prepared by

sodium citrate method.

Additionally, the photographs of the irradiated solutions are

presented in the inset of Fig. (3), where the colors clearly indicate a

3.2. Fabrication of AuAg Nanoalloys

Fig. (4) shows the absorption spectra of gold and silver
nanoparticle mixtures (Fig. (4a)) and nanoalloys (Fig. (4b)). The
spectra in Fig. (4a) represent a physical mixture of the individual
Ag and Au particles. It shows two plasmon peaks corresponding to
the monometallic counterparts, the first one at
max = 403 nm for
silver and the second at
max = 522 nm for gold. After irradiation of
the bimetals mixture for 1 hour, the UV-visible spectroscopy study
was carried out (Fig. (4b)), and the optical absorption spectra show
only one plasmon peak for the bimetals located at
max = 508 nm,
confirming the formation of bimetallic AuAg alloy nanoparticles.
It is known from the literature that alloy NPs of two metals
show an absorbance peak between those of the two individual
nanoparticles [24]. Thus, the obvious red shift of the silver nanoparticle peak provides strong evidence of the formation of a AuAg
nanoalloy. The shape and size of the resultant nanoparticles are
elaborated with TEM. The TEM images and the particle size distribution of AuAg alloy nanoparticles are presented in Fig. (5a and
5b). The particles are nearly spherical with high uniformity in size

194 Current Nanoscience, 2013, Vol. 9, No. 2

El-Feky and Al-Sherbini

0.9
0.8
Optical Density (O.D)

Optical Density (O.D)

0.2

0.1

0.7
0.6
0.5
0.4
0.3
0.2

0.0
300

400

500

600

700

800

900

400

Wavelength (nm)

500

600

700

800

900

Wavelength (nm)

Fig. (4). UV-vis absorption spectra showing (a) a mixture of gold and silver nanoparticles before irradiation and (b) a mixture of gold and silver nanoparticles
after irradiation with a Nd-YAG laser at
= 1064 nm.

Fig. (5) TEM images of (a) bimetallic AuAg nanoparticles in water after 1 hr irradiation by Nd-YAG laser at
= 1064 nm (b) At high magnification (inset
shows their electron diffraction pattern) The white arrows refers to the same nanoalloy particles before and after magnification.

Optical Density (O.D)

0.8

0.6

0.4

(a)
Au
AuPt
(b)

0.2
Pt
(c)

400

500

600

700

800

900

Wavelength (nm)

Fig. (6). UV-vis absorption spectra of AuPt nanoparticles prepared by (a), (b) laser ablation and (c) after irradiation.

and are well separated. The mean diameter of AuAg alloy

nanoparticles was about 10 nm.
These results are in strong agreement with the UVvis spectroscopic data discussed previously and the reported data [35].
The Laser radiation has identical process underlying the reduction process of metal precursors to zero valence nanoparticles. Particularly, water molecules have been reported to be decomposed
using lasers, generating solvated electrons, hydrogen and hydroxyl

radicals, along with dissociation products such as hydronium ions

and H3O+ that can reduce metal precursors selectively [16].
3.3. Fabrication of Au-Pt Nanoalloys
In the case of AuPt nanoalloys, the optical spectra of the gold
nanoparticles along with the spectrum of Pt nanoparticles alone
produced under similar conditions to those of the AuAg NPs are
shown in Fig. (6).

Current Nanoscience, 2013, Vol. 9, No. 2

Fabrication and Optical Absorption Properties

195

Fig. (7). TEM images of (a) AuPt nanoalloys after 1 hr irradiation by Nd-YAG laser at
= 1064 nm. (inset shows their electron diffraction pattern) (b)
HRTEM.

The Au nanoparticles alone display a peak at
max = 522 nm

while platinum particles show only a monotonous increase in absorbance as the wavelength decreases [36]. For AuPt alloy NPs, a
peak at 518 nm is observed with small blue shift, and the decrease
in the optical density peak compared to the gold NPs suggests the
formation of alloy NPs by the optical characterization. For further
confirmation of alloy formation, the alloy NPs were subjected to
TEM characterization. Fig. (7) indicates that the NPs are mostly
polydisperse in nature with an average size of ~ 510 nm 0.5, and
some alloy particles tend to form aggregates due to the absence of a
capping material [37].
When the particles become several nanometers in size, most of
the atoms generated by the laser irradiation are expended so that
particle growth may be terminated [18].
4. CONCLUSIONS
We prepared Au, Ag, and their bimetallic nanoparticles using
Nd-YAG laser irradiation of metal plates in distilled water. Metal
nanoparticles with variable size can be achieved. Not only Au and
Ag but also the AuAg and AuPt bimetallic particles are very fine
with particle sizes of 510 nm, well separated from each other, and
essentially near monodispersed. The AuAg bimetallic system was
confirmed by the appearance of single plasmon bands that were
between those for monometallic nanoparticles. The mechanism of
nanoparticle formation was also proposed. The advantages of the
presented NPs synthesis method in comparison to the classical,
colloid chemistry, employing chemical reagents are the ease of the
creation procedures without using chemical reagents. Thus, this
method produces clean nanoparticles that can be used safely in
biological applications.
CONFLICT OF INTEREST
The authors confirm that this article content has no conflicts of
interest.
ACKNOWLEDGEMENTS
Declared none.
REFERENCES
[1]
[2]

Kreibig, U.; Vollmer, M. Optical Properties of Metal Clusters; SpringerVerlag, Berlin., 1995.
Wilcoxon, J.; Williamson, R.; Baughman, R. Nanocrystal systems, including
semiconductor quantum dots. J. Chem. Phys., 1993, 8, 9933-9950.

[3]

[4]
[5]
[6]

[7]

[8]

[9]

[10]

[11]

[12]
[13]

[14]
[15]

[16]

[17]

[18]
[19]

[20]

Wilcoxon, J.; Martin, J.; Provencio, P. Optical properties of gold and silver
nanoclusters investigated by liquid chromatography. J. Chem. Phys., 2001,
115, 998-1008.
Jess, W. Optical absorption properties of dispersed gold and silver alloy
nanoparticles. J. Phys. Chem. B, 2009, 113, 2647-2656.
Mallin, M.; Murphy, C. Solution phase synthesis of sub10 nm AuAg alloy
nanoparticles. Nano. Lett., 2002, 2, 1235-1237.
Lu, L.; Wang, H.; Zhou, Y.; Xi, S.; Zhang, H.; Hu, J.; Zhao, B. Seedmediated growth of large, monodisperse coreshell goldsilver nanoparticles
with Ag-like optical properties. Chem. Commun., 2002, 2, 144-145.
Liang, W.; Yusuke, Y. Controlled aqueous solution synthesis of platinum
palladium alloy nanodendrites with various compositions using amphiphilic
triblock Copolymers. Chem. Asian J., 2010, 5, 2493-2498.
Hamed, A.; Yoshihiro, N.; Masataka, I.; Yusuke, Y. Facile synthesis of
nanoporous PtRu alloy spheres with various compositions toward highly active electrocatalysts. Chem. Asian J, 2012, 7, 876-880.
Liang, W.; Yusuke, Y. Strategic synthesis of trimetallic Au@Pd@Pt
core_shell nanoparticles from poly(vinylpyrrolidone)-based aqueous solution
toward highly active electro catalysts. Chem. Mater, 2011, 23, 2457-2465.
Liang, W.; Yusuke, Y. Autoprogrammed synthesis of triple-layered
Au@Pd@Pt core-shell nanoparticles consisting of a Au@Pd bimetallic core
and nanoporous Pt shell. J. Am. Chem. Soc., 2010, 132, 13636-13638.
Liang, W.; Yoshihiro, N.; Yusuke, Y. Direct synthesis of spatially-controlled
Pt-on-Pd bimetallic nanodendrites with superior electrocatalytic activity. J.
Am. Chem. Soc., 2011, 133, 9674-9677.
Haruta, M. Advances in the catalysis of Au nanoparticles. Appl. Catal. A:
Gen., 2001, 222, 427-437.
Beatriz, R. Synthesis and catalytic properties of metal nanoparticles: Size,
shape, support, composition, and oxidation state effects. Thin Solid Films,
2010, 518 (12), 3127-3150.
Goulet, P.; Lennox, R. New insights into Brust_Schiffrin metal nanoparticle
synthesis. J. Am. Chem. Soc., 2010, 132, 9582-9584.
Belloni, J. Nucleation, growth and properties of nanoclusters studied by
radiation chemistry: Application to catalysis. Catal. Today, 2006, 113, 141156.
Wang, C.; Hsao, B.; Lai, S.; Chen, W.; Chen, H.; Chen, Y.; Chien, C.; Cai,
X.; Kempson, I.; Hwu, Y.; Margaritondo, G. One pot synthesis of AuPt
alloyed nanoparticles by intense X-ray irradiation. Nanotechnology, 2011,
22, 065605(1).
Cai, X.; Wang, C.; Chen, H.; Chien, C.; Lai, S.; Chen, Y.; Hua, T.;
Kempson, I.; Hwu, Y.; Yang, C.; Margaritondo, G. Tailored Au nanorods:
optimizing functionality, controlling the aspect ratio and increasing biocompatibility. Nanotechnology, 2010, 21, 335604(1).
Zhao, C.; Qu, S.; Qui, J.; Zhu, C. Photoinduced formation of colloidal Au by
a near infrared femtosecond laser. J. Mater. Res., 2003, 18, 1710-1714.
Abid, J.; Wark, A.; Brevet, P.; Girault, H. Preparation of silver nanoparticles
in solution from a silver salt by laser irradiation. Chem. Commun., 2002,
792-793.
Fan, G.; Qu, S.; Wang, Q.; Zhao, C.; Zhang, L.; Li, Z. Pd nanoparticles
formation by femtosecond laser irradiation and the nonlinear optical proper-

196 Current Nanoscience, 2013, Vol. 9, No. 2

[21]

[22]

[23]

[24]

[25]

[26]

[27]

[28]

El-Feky and Al-Sherbini

ties at 532 nm using nanosecond laser pulses. J. Appl. Phys., 2011, 109,
023102 (1).
Zeng, H.; Zhao, C.; Qiu, J.; Yang, Y.; Chen, G. Preparation and optical
properties of silver nanoparticles induced by a femtosecond laser irradiation.
J. Cryst. Growth, 2007, 300, 519-522.
Nakamura, T.; Mochidzuki, Y.; Sato, S. Fabrication of gold nanoparticles in
intense optical field by femtosecond laser irradiation of aqueous solution. J.
Mater. Res., 2008, 23, 968-974.
Nakamura, T.; Takasaki, K.; Sato, S. Fabrication of platinum particles by
intense, femtosecond laser pulse irradiation of aqueous solution. Appl. Surf.
Sci., 2009, 255, 9630-9633.
Nakamura, T.; Magara, H.; Herbani, Y.; Sato, S. Fabrication of silver
nanoparticles by highly intense laser irradiation of aqueous solution. Appl.
Phys, A: Mater. Sci. Process, 2011, 104, 1021-1024.
Herbani, Y.; Nakamura, T.; Sato, S. Femtosecond laser-induced formation of
Au-rich nanoalloys from the aqueous mixture of Au_Ag ions. J. Nanomater.,
2010, 154210 (1).
Chau, J.; Chen, C.; Yang, M.; Lin, K.; Sato, S.; Nakamura, T.; Yang, C.;
Cheng, C. Femtosecond laser synthesis of bimetallic Pt_Au nanoparticles.
Mater. Lett., 2011, 65, 804-807.
Pommeret, S.; Gobert, F.; Mostafavi, M.; Lampre, I.; Mialocq, J. Femtochemistry of the hydrated electron at decimolar concentration. J. Phys.
Chem. A, 2001, 105, 11400-11406.
Abdelsayed, V.; Glaspell, G.; Nguyen, M.; Howe, J.; El-Shall, S. Laser
synthesis of bimetallic nanoalloys in the vapor and liquid phases and the

Received: October 22, 2012

Revised: December 5, 2012

Accepted: December 21, 2012

[29]

[30]

[31]
[32]

[33]

[34]
[35]

[36]
[37]

magnetic properties of PdM and PtM nanoparticles (M = Fe, Co and Ni).

Faraday Discuss, 2008, 138, 163-80.
Yuliati, H.; Takahiro, N.; Shunichi, S. Synthesis of near-monodispersed
Au_Ag nanoalloys by high intensity laser irradiation of metal ions in hexane.
J. Phys. Chem. C, 2011, 115, 21592-21598.
Chau, J.; Chen, C.; Yang, M.; Lin, K.; Sato, S.; Nakamura, T.; Yang, C.;
Cheng, C. Femtosecond laser synthesis of bimetallic Pt_Au nanoparticles.
Mater. Lett., 2011, 65, 804-807.
Turkevich, J. Colloidal Gold Part I: Historical and preparative aspects, morphology and structure. Gold Bull, 1985, 18, 86-91.
Thomas, K.; Zajicek, J.; Kamat, P. Surface binding properties of tetraoctylammonium bromide-capped gold nanoparticles. Langmuir., 2002, 18(9),
3722-3727.
Dina, P.; Maria, R.; Jose, M.; Caterina, M.; Ana, G.; Eduard, V. Polarity
index of pharmacological agents used for maintenance treatment of bipolar
disorder. Eur. Neuropsychopharm., 2012, 22(5), 339-346.
George Wypych. Handbook of Solvents, Chem. Tec., 2001.
Prashant, K.; Kyeong, S.; Ivan, H.; Mostafa, A. Calculated absorption and
scattering properties of gold nanoparticles of different size, shape, and composition: Applications in biological imaging and biomedicine. J. Phys. Chem.
B, 2006, 110, 7238-7248.
Creighton, J.; Eadon, D. Ultravioletvisible absorption spectra of the colloidal metallic elements. J. Chem. Soc, Faraday Trans., 1991, 87, 3881-3891.
Lou, L.; Yu, K.; Wang, Y.; Zhu, Z. Color-tunable magnetic and luminescent
hybrid nanoparticles: Synthesis, optical and magnetic properties. Appl. Surf.
Sci., 2012, 258(8), 3744-3749.