2010 International Conference on Nanotechnology and Biosensors

IPCBEE vol.2 (2011) (2011) IACSIT Press, Singapore

Preparation of Silver Nanoparticle with Different Particle Sizes for Low-

Temperature Sintering

Steve Lien-Chung Hsu, Rong-Tarng Wu

Department of Materials Science & Engineering, National Cheng-Kung University
Tainan, 701-01, Taiwan, R.O.C.
E-mail address: lchsu@mail.ncku.edu.tw

AbstractIn this study, silver nanoparticles were synthesized

by chemical reduction from silver nitrate using different II. EXPERIMENTAL
organic compounds as the protecting agent and organic bases
as the reaction promoter. The average sizes of the resulting A. Materials
silver nanoparticles were between 3 to 15 nm depending on the Silver nitrate (AgNO3) was obtained from Showa
type of the protecting agent, which allowed low-temperature Chemical Co. Triethylamine (TEA) were purchased from
sintering of the metal. These suspensions of silver Tedia Company Inc. Alpha-Terpineol was obtained from J. T.
nanoparticles prepared by this method are free from any metal
Baker. Formaldehyde (HCHO, 37 wt. % in water) was
ion contamination and are suitable for use in semiconductor
purchased from Tedia Company Inc. Thiosalicylic acid (TSA)
industry. The suspensions will be used to make micro-
interconnects in integrated circuits (IC) devices by inkjet was obtained from Acros Organic. Poly(N-vinyl-2-
printing. pyrrolidone (PVP) (molecular weight ~10,000) was obtained
frrom ICN Biomedical Inc.
Keywords-Silver; Nanoparticles; Suspensions B. Preparation of silver nanoparticles suspensions
The AgNO3 was dissolved in de-ionized water in a
I. INTRODUCTION beaker. To this solution, a protecting agent poly(N-vinyl-
In recent years, metallic nanoparticles have drawn a lot of 2-pyrrolidone or thiosalicylic acid or triethylamine was
attention due to their unusual physical and chemical added. After being stirred, HCHO solution was then added to
properties, which largely differ from their bulk properties [1, the solution. Subsequently, a promoter (triethylamine or
2]. They shows unique properties such as excellent pyridine) was added drop wise. The color of the solution
conductivity, chemical stability, and catalytic activity, etc. turned from clear to black. After being stirred for 200 min at
which are dependent on the particle size, size distribution room temperature, the precipitates were washed several
and shape [3-5]. Among all metals, silver has the highest times with ethanol, followed by centrifugation (6000 rpm, 10
electrical and thermal conductivity. Silver materials with min), to remove unbounded TEA. The particles were then
zero-, one-, or two-dimensional nanostructures such as dried at room temperature under vacuum for 24 h. The silver
nanoparticles, nanowires, and nanocubes are believed to nanoparticles suspensions were prepared from the dried
have great potential for applications in optics, catalysis, and silver nanoparticles by re-dispersing them into alpha-
other fields [6-9]. In the characteristic of silver material, the terpineol.
low sintering temperature of silver nanoparticles is important
in flexible electronic applications [10,11]. C. Characterization
In previous literature, to prepare silver nanoparticles The transmission electron microscopy (TEM) images of
suspensions by the chemical reduction method, a protecting silver nanoparticles were obtained with a JEOL JEM-
agent needs to be added, such as long-chain thiol, long-chain 1200EX transmission electron microscope operating at 120
amines, carboxylic compounds, poly(vinyl pyrrolidone) [12- KV with an Energy Dispersive Spectrometer (EDS). The X-
14], etc. In addition, reagents such as formaldehyde, glycol ray diffraction (XRD) experiment was conducted on a
ethylene, NaBH4 etc., are usually needed to be the reducing Rigaku D/MAX-IIIV X-ray Diffractometer using Ni-filtered
agent [15-17]. In this research, we use different organic Cu-K radiation with a scanning rate of 4 min1 at 30 kV
compounds as the protecting agent and organic bases as the and 20 mA. The weight loss of the silver films was analyzed
reaction promoter to prepare contamination-free suspensions using a TA Instrument Thermogravimetric Analyzer (TGA)
of silver nanoparticles with different particle sizes for ink jet 2050 at a heating rate of 10 oC/min under air. The UV-visible
printing application. spectra of the silver nanoparticle suspensions were obtained
on a Hitachi U-2001 UV-VIS spectrophotometer.

55
 III. RESULTS AND DISCUSSION shown in Figure 2(b) confirms that the particles are silver.
Figure 2(c) presents the particle size distribution of silver
A. Poly(N-vinyl-2-pyrrolidone) stabilized silver nanoparticles. The average size of the particles is 7.99 nm
nanoparticles with a standard deviation of 2.24 nm, which was calculated
According to literature, the reduction reaction of AgNO3 by Matrox Inspector 4.1 software from Figure 2 (a).
by formaldehyde is slow without the addition of basic
catalysts. A higher pH is favored for higher reducing power.
In order to avoid the use of inorganic bases as the reaction
promoter, which usually contains other unwanted metal ions,
we chose organic bases, triethylamine or pyridine as the
reaction promoter. These bases are easy to be washed out
after reaction and will not contaminate the resulting silver
nanoparticles. In our process, all reagents are organic
materials except the AgNO3 precursor. The final product is
only pure silver nanoparticles without other metal ion
impurities, so the silver nanoparticles product is suitable to
use in IC devices. As shown in Fig. 1(a) shows the silver
nanoparticles prepared from pyridine. The viscosity of the
dispersion was 1.25 cps and the particles sizes were around Figure 2. (a) TEM micrographs of silver nanoparticles prepared from
10-20 nm. Fig. 1(b) is the EDS pattern of the silver particles. TSA (b) EDS pattern (c) Particle size distribution of silver nanoparticles
Fig. 1(c) show the UV-Vis absorption spectra of silver
nanoparticles prepared from pyridine with different Fig. 3 shows the thermograms of pure TSA, TSA
concentrations of AgNO3. They have the characteristic protected silver nanoparticles and PVP protected silver
absorption bands with maxima at 420-430 nm. That could be nanoparticles. From the TGA thermogram, we can see the
due to the increase of polydispersity of particle sizes in decomposition temperature of pure TSA is at 150 oC. When
higher concentration of the reagents. The X-ray diffraction the TSA is bounded to silver nanoparticles, its
patterns of the silver nanoparticles, presented in Fig. 1(d), decomposition temperature increased to 280 oC. Although
show the peak characteristics of metallic silver. The its decomposition temperature increases, it is much lower
reflection peaks are indexed as the fcc (111), (200), (220), than PVP (at 450 oC), which was used in our previous
and (311) planes, indicating that the silver is well crystallized. experiment. We anticipated that TSA-protected silver
nanoparticles could be sintered at lower temperatures than
PVP-protected silver nanoparticles.

100 pure TSA

PVP-Ag
Weight ( % )

TSA-Ag
80

60

40

20

0
200 400 600 800
Figure 1. (a) TEM micrographs of silver nanoparticles prepared from PVP o
(b) EDS pattern (c) UV pattern (d) XRD pattern. Temperature ( C )

B. Thiosalicylic acid stabilized silver nanoparticles

Figure 3. TGA thermograms of pure TSA, silver nanoparticles prepared
The low molecular weight organic compound, from TSA , and silver nanoparticles prepared from PVP .
thiosalicylic acid (TSA), was also used as a protecting agent
to prepare the nanoparticles in order to reduce the sintering
temperature. As shown in Figure 2(a), when we used C. triethylamine stabilized silver nanoparticles
triethylamine as the reaction promoter and TSA as the During the preparation of Ag nanoparticle suspensions,
protecting agent, the silver nanoparticles were successfully the individual particles had a tendency to form large
reduced from the AgNO3 precursor. The EDS analysis agglomerates through the van der Waals force or Coulombs

56
force. In order to prevent the agglomeration of small
particles, we added TEA to the suspensions as the stabilizer.
The amine group can form a protective monolayer on the
particles surface through the Ag-N bonding. The TEA has a
dual function in the experiment. It can be served as a
protecting agent and also a reducing agent.When we used the
TEA as the reducing and protecting agent, the silver
nanoparticles were successfully reduced from the AgNO3
precursor. For TEA-protected silver nanoparticles, the
agglomeration of small particles increased with the
increasing TEA concentrations.
Fig. 4 shows a typical TEM image of the silver
nanoparticles, the histogram of diameters, and EDS. The
silver diffraction pattern is shown at right corner in Fig. 4(a).
The EDS analysis (in Fig. 4(c)) confirms that the
nanoparticles are silver. We were able to control the particle
size and the size distribution of silver nanoparticles from the
AgNO3/TEA molar ratio, and produce silver nanoparticles Figure 5. (a)UV-Vis absorption spectra of silver nanoparticles suspension
less than 5 nm in diameter. prepared from different AgNO3/TEA ratios (b) XRD (c) TGA

IV. CONCLUSIONS
Using PVP, TSA and TEA as the protecting agents, we
successfully prepared stable silver nanoparticles suspensions.
The average diameters of the nanoparticles were 15 nm, 7.99
nm, and 2.74 nm, when the protect agents were PVP, TSA
and TEA, respectively. The resulting silver nanoparticles
showed high crystallinity. The silver nanoparticle can be
used to fabricate flexible electronics by ink-jet printing,
because they have relatively low sintering temperatures.
ACKNOWLEDGMENT
Figure 4. (a) TEM micrographs of silver nanoparticles prepared from
TEA (b) Particle size distribution of silver nanoparticles (c) EDS pattern . The financial support provided by the National Science
Council (Taiwan, ROC) through project NSC-95-2120-M-
The UVVis absorption spectra of silver nanoparticles 006-003 .is greatly appreciated.
prepared from TEA with different molar ratios are shown in
Fig. 5. For Fig. 5(a), the absorption peak with the maxima at
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