Japanese Journal of Applied Physics REGULAR PAPER

Gold Nanoparticle Synthesis Using Three-Dimensionally Integrated

Micro-Solution Plasmas

Tatsuru Shirafuji1 ∗ , Jun Ueda1 , Akihiro Nakamura1 , Sung-Pyo Cho2 , Nagahiro Saito2 ,
and Osamu Takai3

1
Department of Physical Electronics and Informatics, Osaka City University, Osaka 558-8585, Japan
2
Department of Materials, Physics and Energy Engineering, Nagoya University, Nagoya 464-8603, Japan
3
Materials and Surface Engineering Research Institute, Kanto Gakuin University, Yokohama 236-0004,
Japan

Three-dimensionally integrated micro-solution plasmas (3D IMSPs), in which microplasmas are generated
in gas bubbles in an aqueous solution held in a porous dielectric material, have been applied to gold
nanoparticle synthesis. Conventional solution plasma processes require additional chemicals to increase
the electrical conductivity of the aqueous solution for generating plasmas. In contrast to this, 3D IMSPs have
been found to generate plasmas without such a procedure when the aqueous solution has a low electrical
conductivity as in the case of HAuCl4 for gold nanoparticle synthesis. The gold nanoparticle synthesis has
been confirmed through the observation of optical absorption due to the plasmon resonance at 550 nm,
and also through the characterization of their size, crystallinity, and composition by transmission electron
microscopy and energy dispersive X-ray spectroscopy.

1. Introduction
Plasmas in and in contact with liquid have attracted much attention because of their possible
applications to nanomaterial synthesis, surface modification, water treatment, sterilization,
recycling of rare materials, and decomposition of toxic compounds.1–3) Among them, various
types of plasma are used for these purposes.1–15)
In their previous works, Takai and Saito et al.2, 16) have successfully obtained glow dis-
charges in an aqueous solution, which have been named “solution plasmas” (SPs). They ap-
plied this technique to nanoparticle synthesis and the modification of the surface of nanoma-
terials.2, 16–18)
The original solution plasma, however, is ignited in a small volume between two stylus
electrodes. The actual treatment area or volume should be enlarged for practical industrial ap-
plications. In the case of gas phase processes, large-area processing is realized by producing

∗
E-mail: sirafuji@elec.eng.osaka-cu.ac.jp

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large-area plasmas. In the case of solution plasma processing, however, large-volume plasmas
in liquid are meaningless, because the most important region for solution plasma processing
is the gas-liquid or plasma-liquid interface. Thus, the preparation of a large number of tiny
plasmas (microplasmas19) ), which may be called “integrated micro-solution plasmas” (IM-
SPs), is rather important in the case of solution plasma processing, because we can expect a
much larger area of the interface between the gas (or plasma) and the liquid medium.
This kind of approach has been reported by Sakai et al., in which they have used small
bubbles formed on a novel fabric-type electrode through the electrolysis of an electrolyte so-
lution,7) which can be called two-dimensional (2D) IMSPs in contrast to the zero-dimensional
(0D) SP generated between two stylus electrodes. They have demonstrated that their tech-
nique can be applied to CO2 reduction.8) We have also generated a kind of 2D IMSP between
a glass plate and a porous dielectric material, and demonstrated the possible decomposition
of methylene blue molecules in an aqueous solution.20)
To treat a large-volume liquid medium with higher efficiency, we proposed a reactor that
can generate three-dimensional (3D) IMSPs. We previously confirmed the feasibility of 3D
IMSPs by numerical simulations21) and experiments.22) We have also investigated the capa-
bility of decomposing an organic substance, i.e., methylene blue, in an aqueous solution, and
revealed that the decomposition can be performed with higher energy efficiency than in the
case of conventional 0D SP.23)
In addition, since 0D SP employs Joule heating by ion conduction current for bubble
formation in which plasma is generated, the electrical conductivity should be high enough to
induce electrical current for Joule heating. In previous reports on gold nanoparticle synthesis,
the electrical conductivity of HAuCl4 aqueous solution was adjusted to 500 µS/cm or higher
by adding KCl.2, 16)
In contrast, 3D IMSPs are predicted to be not effective for the treatment of an aqueous
solution with a high electrical conductivity,21) but effective for that of an aqueous solution
with a low electrical conductivity. This means that 3D IMSPs may be used to synthesize gold
nanoparticles or other nanoparticles without the need for additional chemicals for adjusting
the electrical conductivity of aqueous solutions.
Thus, in the first part of this paper, we report our experimental confirmation of the liquid-
electrical-conductivity dependence of 3D IMSPs, which has been numerically predicted.
Then, we report that gold nanoparticles can be synthesized using 3D IMSPs and HAuCl4
aqueous solution without additional chemicals for adjusting the electrical conductivity of
aqueous solutions.

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Side cross Front cross
sectional view sectional view
š30 mm

Insulator

electrode
HV metal
Glass Liquid

Metal mesh

Metal mesh
Grounded
Grounded
Plasma

Plasma

Main Sub small

porous porous
dielectric dielectric
material
Gas

Fig. 1. (Color online) Schematic illustration of the reactor for obtaining 3D IMSPs.

2. Experimental Procedure
Figure 1 shows a schematic illustration of the reactor for generating 3D IMSPs, which is
almost the same as that in our previous reports,22, 23) but there is a slight difference in the
gas feed system. The main porous material is a rod-shaped silica pumice (20 mm diameter),
which is inserted into a glass tube. The average diameter of the pores is approx. 0.5 mm.
The pores are not isolated but partially connected. Thus, we can supply liquid and gas in the
main porous material. A metal electrode, to which a high-voltage pulse is applied, is inserted
at the center axis of the pumice rod. The voltage is supplied from a bipolar high-voltage
power source (Haiden SBP-5K-HF2). The voltage waveform is a square-wave pulse with an
amplitude of 5 kV, a frequency of 20 kHz, and a pulse width of 9.4 µs. The grounded electrode
(metal mesh) is attached to the outer surface of the glass components. The temperature of the
aqueous solution in the reactor was kept at 30 ◦ C by circulating the aqueous solution through
a cooling bath.
In the first part of our experiments, we experimentally confirmed the liquid electrical
conductivity dependence of 3D IMSPs, which was predicted through numerical simulation.21)
The aqueous solutions used for this experiment had electrical conductivities of 1, 200, and
500 µS/cm, which were prepared by mixing KCl with deionized water.
In the second part of our experiemnts, we performed gold nanoparticle synthesis. The
source material for this experiment was 0.15 mM HAuCl4 aqueous solution. 2 mL of 10
wt% gelatin aqueous solution was added to 100 mL of 0.15 mM HAuCl4 aqueous solution
to prevent the coagulation of nanoparticles, because gelatin has hydrophobic and hydrophilic
amino acid sections on its side chains24) and works as a surfactant to inhibit the coagulation
of nanoparticles.25–29) The electrical conductivity of this aqueous solution is 150 µS/cm. The
gas supplied with the aqueous solution is Ar at 2 L/min.
The synthesized gold nanoparticles were characterized by optical absorption spectroscopy
using UV-1800 (Shimadzu) to confirm plasmon resonance absorption by gold nanoparti-

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1 uS/cm

3 cm

200 uS/cm

3 cm

500 uS/cm

3 cm

Fig. 2. (Color online) Photographs of the 3D-IMSP reactor being operated with aqueous solutions with
electrical conductivities of 1, 200, and 500 µS/cm.

cles. Furthermore, they were sampled on a holey microgrid (copper, 200 mesh) and char-
acterized by scanning transmission electron microscopy (STEM), energy-dispersive X-ray
spectroscopy (EDS), and high-resolution transmission electron microscopy (HRTEM) for the
analyses of their size, composition, and crystal structure, respectively, using JEM-2500SE
(JEOL).

3. Results and Discussion

3.1 Dependence on electrical conductivity of properties of aqueous solution in 3D
IMSPs
Figure 2 shows photographs of the actual 3D-IMSP reactor during operation using aqueous
solution with electrical conductivities of 1, 200, and 500 µS/cm. In the case of the low electri-
cal conductivity of 1 µS/cm, we can confirm the generation of plasmas in the porous dielec-
tric material inserted in the cross-shaped glass tube. With increasing electrical conductivity
of the aqueous solution, optical emission from plasmas in the porous dielectric material is
suppressed. Instead, parasitic electrical discharges appear between the grounded metal mesh

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AuHCl4 0.15 mM

0 10 20 30 40 50 60

Time (min)

Fig. 3. (Color online) Photographs of the aqueous solution after the 3D IMSP treatments for 0 to 60 min.

electrode and the glass-tube surface, as can be seen in the results for 200 µS/cm. They become
significant in the case of the higher electrical conductivity of 500 µS/cm.
The above phenomenon is due to the fact that the applied voltage is concentrated in the
area with a higher electrical resistivity. If the medium in the glass tube has a high electri-
cal conductivity, namely, a low resistivity, the voltage is concentrated in the areas between
the inner surface of the glass-tube wall and the outer surface of the metal-mesh electrode.
Since air gaps exist between the glass-tube surface and the metal mesh, there can be atmo-
spheric pressure plasmas between them if the gap voltage becomes high enough to ignite
electrical discharges between them. From these results together with our previous numerical
prediction,21) we can conclude that 3D IMSPs are not effective for the treatment of aqueous
solutions with a high electrical conductivity. However, we can also consider these results as
an advantage of 3D IMSPs. Conventional 0D SP requires additional chemicals to increase
the electrical conductivity of aqueous solutions to an appropriate level for igniting electrical
discharges when we need to treat aqueous solutions with a low electrical conductivity.2, 16) In
the case of 3D IMSPs, in contrast, we can treat aqueous solutions as they are without raising
the electrical conductivity of aqueous solutions by mixing additional chemicals, which may
be accompanied by unfavorable and/or unintentional reactions.

3.2 Confirmation of plasmon resonance absorption of gold nanoparticles

Figure 3 shows the aqueous solution after the 3D IMSP treatments for 0 to 60 min, where
we can confirm that the aqueous solution changes from colorless to wine red. This suggests
that gold nanoparticles are formed in the aqueous solution.30, 31) In order to further confirm
the gold nanoparticle synthesis, we measured the optical absorption spectra of the aqueous
solution before and after the treatments, expecting the plasmon resonance absorption of gold
nanoparticles at 550 nm.30, 31)
Figure 4 shows optical absorption spectra of the aqueous solution after the 3D IMSP

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1.0

0.15 mM

Absorption coefficient (cm )

-1
0.8

60 min
0.6
50 min
40 min
0.4 30 min
20 min
0.2 10 min

0.0
300 400 500 600 700 800

Wavelength (nm)

Fig. 4. (Color online) Absorbance spectra of the aqueous solution treated with 3D IMSPs for 0 to 60 min.

treatments for 0 to 60 min. We can see a broad absorption peak at approximately 530 nm
corresponding to the plasmon resonance absorption by gold nanoparticles. The intensity of
the peak at 530 nm increases monotonically with increasing treatment time while maintaining
the same peak wavelength. According to the Mie theory, if the scattering by the nanoparticles
is neglected, the absorption coefficient increases with increasing size and concentration of
the nanoparticles. If the size exceeds 50 nm in radius, the peak wavelength is known to shift
toward longer wavelengths.31) Such peak shift is not observed in our results, which means
that the synthesized gold nanoparticles have a radius of less than 50 nm. The size and shape
of the synthesized gold nanoparticles are discussed on the basis of the results of the TEM and
HRTEM observation of the nanoparticles.

3.3 Size, composition, and crystal structure of the gold nanoparticles

Figure 5(a) shows a bright-field STEM (BF-STEM) image of the sample prepared after the
3D IMSP treatment for 60 min. We can confirm that nanoscale particles, which are black
dots in the figure, are synthesized, but their sizes are not the same. The size distribution of
the nanoparticles is shown in Fig. 6, which has been obtained by counting the number of
particles in each size range in several STEM images in different areas. The average size of
the nanoparticles is 6.4 ± 3.5 nm.
Figure 5(b) shows an EDS map for gold (characteristic X-ray Au-M line) corresponding
to the area shown in Fig. 5(a). Since the positions of the nanoparticles in Fig. 5(a) correspond
to those of gold in the EDS image shown in Fig. 5(b), we can definitely conclude that the
synthesized nanoparticles are made of gold.
The possibility of contamination has also been investigated with the EDS in the same
area. Figures 5(c) and 5(d) show EDS images of carbon and oxygen (characteristic X-ray C-

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(a) BF-STEM Image (b) Au-M

(c) C-K (d) O-K

Fig. 5. (Color online) (a) BF-STEM image and EDS maps of major elements of (b) Au, (c) C, and (d) O.
Relative frequency (%)

30

20

10

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Diameter (nm)

Fig. 6. (Color online) Size distribution of gold nanoparticles synthesized using 3D IMSPs.

K and O-K lines, respectively). As can be understood from these figures, we cannot observe
carbon or oxygen at the position where gold nanoparticles are observed. To investigate pos-
sible contamination by other elements, we have measured the EDS profiles in several view
fields. Figure 7 shows a typical EDS profile of the same sample, in which the major peaks
except those of gold are carbon, oxygen, and copper, which belong to the microgrid used for
STEM. This can also be confirmed in Figs. 5(c) and 5(d), in which carbon and oxygen are
detected only in the area where the edge of the microgrid exists. They are considered to be the
elements of a polymer film prepared on a holey TEM grid to sustain the sample nanoparticles.
To investigate the shape and crystal structure of the synthesized gold nanoparticles, we
took HRTEM images of the nanoparticles. Figures 8(a)–8(c) show HRTEM images of the
typical gold nanoparticles observed in the sample prepared after the 3D IMSP treatment for

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Counts (arb. unit)

O
Cu
Au

0 1 2 3 4 5 6 7 8 9 10
Energy (keV)

Fig. 7. (Color online) Typical EDS profile of the samples prepared with 3D IMSPs.

2 nm 2 nm

(a) Icosahedron (b) Icosahedron

}
{1
1
11
{11

{111}
nm
5
23
0.

2 nm 2 nm

(c) Icosahedron (d) Single crystal

Fig. 8. HRTEM images of the gold nanoparticles synthesized using 3D IMSPs.

60 min. The particles have an icosahedron structure composed of distorted fcc tetrahedra,
which is typical of gold particles with 3–5 nm diameter.32–35) Single-crystal gold nanoparti-
cles, shown in Fig. 8(d), are also observed. However, their concentration is low, because they
form an energetically unfavorable structure at the diameter mentioned.34)
Looking at the structure of the gold nanoparticles synthesized with 3D IMSPs, the fea-
tures of the gold nanoparticles are the same as those of the same nanoparticles synthesized
with conventional 0D SP.2, 16) Although 3D IMSPs are generated in Ar gas bubbles, while
0D SP is generated in bubbles filled with H2 O vapor, the basic mechanisms of creating gold
nanoparticles using both SPs are considered to be the same. Namely, the solid-phase gold
is produced from AuCl−4 ions through reduction reactions with hydrogen radicals and/or hy-

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drated electrons, which can be supplied by plasma in gas bubbles containing H2 O vapor.

4. Conclusions
Gold nanoparticles have been synthesized using novel 3D IMSPs, in which microplasmas are
generated in Ar gas bubbles in AuHCl4 aqueous solution held in a porous dielectric material
without additional chemicals to increase the electrical conductivity of the aqueous solution
as in the case of conventional 0D SP. The gold nanoparticle synthesis has been confirmed
through the observation of the optical absorption due to the plasmon resonance at 530 nm,
and also through the characterization of the size, crystallinity, and composition of synthesized
nanoparticles by TEM and EDS. HRTEM has revealed that the synthesized gold nanoparticles
mostly have an icosahedron structure, as in conventional 0D SP.

Acknowledgments
This work has been partly supported by a Grant-in-Aid for Scientific Research on Innova-
tive Areas “Frontier Science of Interactions between Plasmas and Nano-Interfaces” (No.
21110003) from the Ministry of Education, Culture, Sports, Science and Technology, Japan,
and a Grant-in-Aid for Scientific Research (C) (No. 24540540) from the Japan Society for the
Promotion of Science. This work has also been partly supported by CREST/JST, the Knowl-
edge Cluster Initiative Tokai Region Nanotechnology Manufacturing Cluster.

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