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Gold Nanoparticles Synthesized by Laser Ablation in Deionized Water

Article  in  Chinese Journal of Physics- Taipei- · August 2015

DOI: 10.6122/CJP.20150511B

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CHINESE JOURNAL OF PHYSICS VOL. 53, NO. 4 August 2015

Gold Nanoparticles Synthesized by Laser Ablation in Deionized Water

Mohammed A. Al-Azawi1 and Noriah Bidin2, ∗

1
Universiti Teknologi Malaysia, Faculty of Science,
Department of Physics, Johor Bahru, Johor, Malaysia, 81310
2
Universiti Teknologi Malaysia, Ibnu Sina Institute for Scientific and Industrial Research,
Laser Center, Johor Bahru, Johor Malaysia, 81310
(Received February 24, 2015; Revised May 3, 2015)
Gold nanoparticles were prepared by the pulsed laser ablation of high purity gold bulk im-
mersed in deionised water. Pulses of a Q-switched Nd:YAG laser (fundamental wavelength,
1064 nm; laser fluence, 15 J/cm2 ; pulse duration, 8 ns) were employed to irradiate the gold
surface during the ablation process. The effects of the thickness of the liquid layer and
the post-ablative modification processes on ablation efficiency, size, and aggregation of gold
nanoparticles were investigated. The experimental conditions that yielded the maximum ab-
lation efficiency were determined. The average size and redistribution of nanoparticles were
controlled by the subsequent treatment of the ablated colloid solution with a combination of
1064 and 532 nm pulses. The effects of post-ablation under laser-induced nanoparticles mod-
ification reduced the average particle size from 15.12 nm to 9.5 nm; the size distribution was
also narrowed with 532 nm pulses. The results of UV-Vis spectrophotometer and transmis-
sion electron microscopy were exploited to characterize the optical spectra of gold colloidal
solutions as well as to analyze the final shape and particle size distribution, respectively.

DOI: 10.6122/CJP.20150511B PACS numbers: 52.38.Mf, 78.67.Bf, 82.70.Dd

I. INTRODUCTION

The nanoparticles (NPs) of colloidal noble metals have been extensively studied in
nanoscience and nanotechnology because of their unique optical, electronic, and chemical
properties. Gold NPs (Au NPs) are promising materials for catalysis [1], electrochemical
sensors [2], clinical applications (e.g., drug and gene delivery systems) [3], highly sensitive
surface-enhanced Raman scattering [4], solar cells [5], photonic devices [6], and targeting
applications that involve systemic cancers [7]. The optical and electrical properties of NPs
strongly depend on their size and shape [8]. In view of the applications of NPs, these
particles should be stable, with well-defined sizes and narrow size distributions [9]. For
instance, Au NPs (size, < 30 nm) are chemically stable and strongly absorb light around
520 nm because of the presence of a surface plasmon resonant (SPR) [10]. Therefore,
the size, shape, and physicochemical properties of Au NPs are very important in future
applications and should be controlled during synthesis [11].
The chemical reduction method is often used to prepare Au NPs with dimensions
ranging from 5 nm to 100 nm [10]. However, colloidal Au NPs are generally contaminated

∗
Electronic address: noriah@utm.my

http://PSROC.phys.ntu.edu.tw/cjp 080803-1 ⃝
c 2015 THE PHYSICAL SOCIETY
OF THE REPUBLIC OF CHINA

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by residual ions and reducing agents [12]. Laser ablation in liquid (LAiL) is a widely
used method for synthesizing metal NPs; this method is based on pulse laser ablation
from bulk metals in a liquid environments (e.g., water). The laser ablation technique is
advantageous over traditional chemical methods because the LAiL can be conducted in
a clean environment and gives a unique opportunity to solve the toxicity problems [13].
Moreover, different morphological characters of the produced NPs can be controlled by
effects of post-ablation under laser-induced nanoparticle modification. Although LAiL is
highly advantageous, this technique suffers from the low formation efficiency of NPs, and
the prepared Au NPs exhibit a broader size distribution compared with those that are
chemically fabricated [9]. These disadvantages significantly reduce the applicability of LAiL
for particle production systems [14].
As reported in the previous reports [15–17], the ablation efficiency increases in the
presence of a liquid layer during the ablation process compared with that observed in the
gas system. Recent study has demonstrated the dependence of the ablation efficiency on
the thickness of the liquid layer using polymethyl-methacrylate samples in the presence
of a water layer [18]. In liquid-phase laser ablation, the surrounding liquid influences the
laser-induced breakdown at the solid–liquid interface and confines the generated plasma.
The generated plasma induces a much higher pressure. This induced pressure will lead to
a high temperature in the plasma, resulting in much ablation efficiency [19]. The physi-
cal properties for the liquid (e.g., polarity and temperature) determines the morphology,
stability, and growth of the synthesized NPs [20]. The liquid in laser ablation converts a
portion of the laser energy into mechanical impulse by vaporization and plasma generation,
and this impulse transfers the ablated species and induces shockwaves. In most cases, the
water-phase is favorable because it doesn’t absorb much light, is a cheap, safe medium, and
exhibits a high heat capacity [21].
Despite the size distributions of the NPs having been controlled and widely studied,
the attempts to optimize the ablation efficiency of nanoparticles generated by laser abla-
tion have not been deeply investigated. In this work, we endeavor to optimize the ablation
efficiency of Au NPs synthesized by laser ablation of a metal plate in pure deionised water
without adding any chemical material. This study was practically addressed by investi-
gating the effect of the thickness of the liquid layer and the post-ablation treatments on
the ablation efficiency, size, and aggregation of the gold nanoparticles. The effect of laser
ablation has been expressed as the ablation efficiency, which was quantified in terms of the
amount of ablated Au. At a sufficiently high laser fluence, we try to find the optimum con-
ditions of these parameters that play an important role in the formation of a large amount
of NPs. Meanwhile, the influences of post-ablative modification on the final particle size
under laser-induced modification were investigated.

II. EXPERIMENTAL SETUP

A highly pure Au plate (purity > 99.999%) with thickness of 2 mm and a diameter of
2 cm was employed in this research as a target material. Initially, this target was cleaned

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ultrasonically in ethanol and rinsed with deionized water to eliminate the contaminants.
The cleaned target was kept on the bottom of a pyrex vessel (volume, 15 mL) filled with
various thicknesses (6–16 mm) of an ultrapure 18.2 MΩ deionised water layer below the
liquid surface. A pulsed Nd:YAG laser (fundamental wavelength, 1064 nm; pulse duration,
8 ns; repetition rate, 1 Hz) was employed as irradiation source during ablation. Experiments
were conducted by adjusting the laser beam (fluence, 15 J/cm2 ) and focusing on the target
surface through a converging lens (focal length, 10 cm) for 4 min at room temperature.
During ablation, the Au colloidal solution was magnetically stirred to remove the Au NPs
from the laser path.
The optical spectra of these colloidal solutions were characterized with a UV-Vis
spectrophotometer (Perkin-Elmer, Lambda 25). A quartz cuvette (path length, 0.5 cm)
was used to measure the absorption. A transmission electron microscope (TEM; Philips
CM12; accelerating voltage, 120 kV) was used to obtain the micrographs of Au NPs. The
Au colloidal solution was placed in the ultrasonic bath for 20 min. Subsequently, a small
drop of the sample solution was placed on the carbon-coated copper grid and dried at room
temperature. The size and size distribution for each sample were obtained by counting at
least 250 particles in each TEM image.

III. RESULTS AND DISCUSSION

III-1. Effects of the thickness of liquid layer

The effects of the thickness of the water layer above the target surface on the ablation
efficiency were investigated. Fig. 1a shows a typical UV-Vis optical spectra of the colloidal
solution at various thicknesses of the deionised water layer from 6 mm to 16 mm; the solution
is produced by ablating the Au target. The absorbance of gold colloids demonstrated the
characteristic features of the surface plasmon resonance (SPR). The SPR peak around 525–
536 nm was attributed to the plasmon transition which depends on the size and shape of
the Au nanoparticles [22]. The prominent single peaks indicated that the obtained NPs
were nearly spherical in the colloidal solution. The morphologies of the Au NPs were also
verified by the TEM results, which are discussed below. The tail part of the absorption
band toward the UV range was ascribed to the interband transitions of Au NPs. The
final position of the SPR band toward the red-wavelength range was attributed to the
aggregation and cross-linking of the NPs.
The absorption caused by interband transitions is sensitive to the amount of particles
and does not appreciably shift with particle size. Thus, the absorption of the solution at
the wavelengths of the interband transitions determines the total amount of Au NPs in this
solution; these NPs could exhibit different sizes, clusters, and free gold atoms [9]. Therefore,
the ablation efficiency was estimated from the absorbance of the interband transition at
330 nm. This efficiency and the height of the SPR peaks were found to be dependent on
the thickness of the water layer. At the layer thickness of 6 mm, the ablation efficiency and
the height of the SPR peak were lower in comparison to the cases of the ablation obtained
at other layer thicknesses. The position of the SPR peak at a layer thickness of 12 mm was

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(a) (b)

FIG. 1: (a) Absorbance spectra of gold colloidal solution prepared at various thickness of water
layer, (b) the absorbance of the interband transitions as a function of the depth of water layer.

slightly shifted toward shorter wavelengths, indicating a certain decreasing of the particle
size [22].
Fig. 1b demonstrates the absorbance of the interband transitions of the Au colloidal
solution at 330 nm based on the small changes in the thickness of the water layer above
the target surface. The ablation efficiency linearly increased with increasing the thickness
of the water layer and reached its maximum at 12 mm; subsequently, this efficiency rapidly
decreased with increasing thickness (> 12 nm). This result was attributed to the increase in
the properties (e.g., temperature, pressure, and density) of the plasma after its confinement
by the water layer. The confined plasma plume adiabatically expanded within a certain
layer thickness. The energy concentrated in this plasma increased on the target surface,
resulting in more efficient ablation. However, the increased layer thickness enhanced the
water absorption of the laser energy. A small portion of the energy reached the target sur-
face, thereby decreasing the ablation efficiency. Thus, the plasma plume and the thickness
of the water layer should be equal to optimize the ablation efficiency. The results suggested
that the optimum layer thickness was 12 mm.

III-2. Size modification by laser irradiation

The concentration of ablated species increased, as shown by the UV-Vis optical spec-
tra of the gold colloidal solution (Figs. 1). After the laser stopped, the ablated species such
as atoms, clusters, and small fragments are aggregated and the size distributions of the
NPs tend to be broadened [9, 23]. To avoid this problem the final size of these particles
in the ablated colloidal solution was controlled by postablated laser-induced nanoparticles
modification.
The Au plate was removed from the ablated vessel. A two-step procedure was im-
mediately carried out by irradiating the colloidal solution. The first step was performed

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with unfocused laser pulses at 1064 nm (maximum fluence, 1.1 J/cm2 ) for 5 minutes. The
second step was performed by subsequent treatment with unfocused laser pulses at 532 nm
(maximum fluence, 0.7 J/cm2 ) for 5 minutes. The colloidal solution was slowly rotated
without ripples during laser irradiation. Fig. 2 shows the UV-Vis optical spectra of the Au
colloidal solution, which is inspected after the ablation and modification process by laser
irradiation. The Au plate was ablated by a 1064 nm laser under optimum conditions to
generate the colloid solution with optical spectral characteristics via the position of te SPR
peak at 521 nm. The absorbance considerably increased at the interband transition after
laser irradiation, indicating that the total concentration of the Au NPs and atoms increased
in the solution. Laser irradiation with the 1064 nm pulses on the colloidal solution enhanced
the ablation efficiency, whereas the position of the SPR peak remained nearly unchanged.
The subsequent irradiation with the 532 nm pulses caused a higher ablation efficiency than
that with the 1064 nm laser. In addition, the position of the SPR peak shifted to short
wavelengths from 521 nm to 518 nm, indicating that the particle size decreased.

FIG. 2: Absorbance spectra of the ablated gold colloidal solution at 12 mm thickness of water layer
before and after the laser irradiation process. Each first and second step of the laser irradiation
process were carried out for 5 min by 1064 nm laser pulses with laser fluence of 1.1 J/cm2 , and 532
nm pulses with laser fluence of 0.7 J/cm2 , respectively.

In this case, the photon energy was easily transformed to the internal modes of
the initial particles as heating, melting, and evaporation during the interactions between
the laser light and gold particles in the colloidal solution, resulting in laser-induced NP
modification [24]. The photon-particle interaction is a powerful influence and yields the
SPR excitation of the initial particles in the colloidal solution when the incident laser
wavelength falls within the SPR absorption band. Therefore, the irradiation by 532 nm
laser influenced the majority of the NPs at the SPR absorption band and yielded their size

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080803-6 GOLD NANOPARTICLES SYNTHESIZED BY LASER . . . VOL. 53

redistribution; in contrast, the irradiation by the 1064 nm laser influenced only the large
size NPs that exhibit a high near-infrared absorbance band.
Figs. 3 to 5 illustrate the TEM images of the Au NPs generated by the laser ablated
Au plate, as well as after the consecutive irradiation of the Au colloidal solution with
1064 and 532 nm pulses. Each TEM image was accompanied by the histograms of the
particle size distribution. The TEM images indicated that the majority of the NPs were
spherical. As shown in Fig. 3, the NPs synthesized by ablation of the Au target were
highly aggregated, and some chains of accreted particles were observed from the TEM
images. The particle size distribution was broadened with an average particle size of 15.12
nm based on the histograms. Figs. 4 and 5 suggest that the particle size distribution and
average particle size were modified after consecutive irradiations by the 1064 and 532 nm
lasers. The average particle size was 13.9 nm in the case of irradiation by the 1064 nm laser;
the NPs were aggregated, and the width of the size distribution slightly changed (Fig. 4).
In contrast, the average particle size was 9.5 nm for the subsequent irradiation with the
532 nm laser. Furthermore, the particles were diffused and not noticeably aggregated, and
the particle size distribution was narrow (Fig. 5). The results obtained by an analysis of
the particle size distribution for each histogram are summarized in Table I.

(a) (b)

FIG. 3: (a) TEM micrograph and (b) histogram of the gold nanoparticles produced by laser ablation
of the gold target in pure deionised water at (1064 nm, 15 J/cm2 ) for 4 min.

IV. CONCLUSION

The Au NPs were successfully synthesized by laser ablation of a Au target in pure

deionised water. The ablation efficiency is sensitive to the amount of particles at the inter-
band transition and depended on the thickness of the liquid layer. The ablation efficiency
linearly increased with increasing the thickness of the water layer and reached its maximum

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VOL. 53 MOHAMMED A. AL-AZAWI AND NORIAH BIDIN 080803-7

(a) (b)

FIG. 4: (a) TEM micrograph and (b) histogram of the gold nanoparticles produced after laser
irradiation of the ablated colloidal solution at (1064 nm, 1.1 J/cm2 ) for 5 min.

(a) (b)

FIG. 5: (a) TEM micrograph and (b) histogram of the gold nanoparticles produced after subsequent
laser irradiation of the ablated colloidal solution with (532 nm, 0.7 J/cm2 ) for 5 min.

TABLE I: The average particle size and the standard deviation of gold nanoparticles in the ablated
colloidal solution before laser irradiation and after the modification process.

Stage Average particle Standard deviation

size (nm) (nm)
Before laser irradiation 15.12 7.27
After laser irradiation with 1064 nm 13.9 6.78
After subsequent laser irradiation with 532 nm 9.50 3.12

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at 12 mm; subsequently, this efficiency rapidly decreased with increasing thickness (> 12
nm). The size redistribution and the reduction of aggregation were controlled by postab-
lated laser-induced nanoparticles modification with 1064 and 532 nm laser irradiation. The
effects of the postablation processes reduced the average particle size from 15.12 nm to 9.5
nm; the size distribution was also narrowed with 532 nm pulses without chemical additives.
The observations from TEM micrographs and UV-Vis spectrophotometer revealed that the
synthesized Au NPs were spherical.

Acknowledgement

We would like to express our thanks to the government of Malaysia through RUG-
Flagship vote 00G79 and UTM through RMC for the financial support of this project as
well as monitoring the progress of the work.

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