Journal of Alloys and Compounds 494 (2010) 8487

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

Silver nanoparticles prepared by chemical reduction-protection method, and

their application in electrically conductive silver nanopaste
Jianguo Liu , Xiangyou Li, Xiaoyan Zeng
Wuhan National Laboratory for Optoelectronics, College of Optoelectronics Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China

a r t i c l e

i n f o

Article history:
Received 19 November 2009
Received in revised form 10 January 2010
Accepted 17 January 2010
Available online 28 January 2010
Keywords:
Ag nanoparticles
Chemical reduction-protection method
Electrically conductive Ag nanopaste

a b s t r a c t
Ag nanoparticles were prepared in a water-phase system with a mixture of silverammonia complex, sodium borohydride, and lauric acid according to molar feed ratio of approximately 6:3:1. The
mechanism of preparation and separation by chemical reduction-protection method was explored. The
as-synthesized Ag nanoparticles were characterized by transmission electron microscopy (TEM), X-ray
diffraction (XRD) and UVvis spectroscopy, respectively. It was found that the size of high purity Ag particles was ranging from 30 to 50 nm with slight agglomeration. In addition, the as-synthesized wet Ag
nanoparticles were dispersed stably in organic vehicle to formulate electrically conductive nanopaste.
Upon direct-written and sintered, the array pattern of the nanopaste with the resolution of about 30 m
was achieved with the electrical resistivity in the order of magnitude of 105  cm.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Compared with the bulk material, silver (Ag) nanoparticles
exhibit the unique thermal, optical, electrical and catalyzing properties due to their small-sized effect, surface effect and quantum
size effect. Therefore, they have attracted great research interest
and been widely applied in the elds of biomedicine, electronics,
microelectronics, optics and optoelectronics [1].
In the elds of electronics and microelectronics, the silver
nanoparticles are mainly used as the conductively functional phase
to formulate electronic nanopastes. The nanopastes have some
advantages over conventional micropastes. For example, they can
save the content of precious metal Ag, miniaturize the feature size
of the electronic devices, decrease the temperature of heat treatment, and realize low-temperature sintering (the melting point of
bulk silver metal is 960.3 C, whereas the silver nanoparticles with
510 nm diameter can be melted at only 150 C) [24]. Particularly, they are suitable for exible fabrication of electronic devices,
and have a potential to replace the conventional SnPb solders in
printed circuit board (PCB), integrated circuit (IC) and chip packaging for environmental reasons [512].
The preparation of Ag nanoparticles usually involves such
methods as vacuum evaporation, electrical arc discharge, microemulsion, phase transfer, and chemical reduction-protection
[1318]. Among them, chemical reduction-protection method is
preferable because it has many merits (mild reaction condition,

Corresponding author. Tel.: +86 27 87792404; fax: +86 27 87541423.

E-mail address: ljg712@yahoo.com.cn (J. Liu).
0925-8388/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2010.01.079

high yield, low energy consumption, and simple separating procedure). During the preparation, the surfactant in the reaction system
plays a crucial role. It also acts as adsorbant and dispersant. Many
polymers and compounds, such as polyvinylpyrrolidone (PVP) [12],
alkanethiolate [15], alkaneamine, sodium dodecyl sulfate [19] and
sodium linoleate [20], have been sampled as the surfactants.
In this paper, Ag nanoparticles with a particle size ranging from
30 to 50 nm were synthesized by chemical reduction-protection
method, and in a water-phase system, lauric acid as the surfactant
was employed in the preparing system for the rst time. Also, the
as-synthesized wet Ag nanoparticles were testied the application
in the electrically conductive nanopaste.
2. Experimental
2.1. Materials
AR grade chemicals including silver nitrate (AgNO3 ), ammonia (NH3 H2 O,
25%), lauric acid (CH3 (CH2 )10 COOH), ethanol (EtOH), orthophosphoric acid (H3 PO4 ),
sodium borohydride (NaBH4 ), ethyl cellulose, terpilenol, Span-85 and tributyl citrate were obtained from Sinopharm Chemical Reagent, and used as received without
further purication. Al2 O3 Ceramic board substrates (0.5 mm thickness) were purchased from Suzhou Ruibang Advanced Ceramics Co., Ltd. (China).
2.2. Preparation and separation of Ag nanoparticles
A 1-L three-mouth round-bottomed ask equipped with dropping funnel and
Teon stirrer was charged with 60 mL of distilled water and 12.2 g (0.072 mol) of
AgNO3 . After the AgNO3 was dissolved completely, 12 mL of ammonia was added,
and then was a solution of 2.4 g (0.012 mol) of lauric acid and 30 mL of ammonia
in 400 mL-distilled water. Under violent stirring, a solution of 1.4 g (0.036 mol) of
NaBH4 in 100 mL water was dropped slowly (one drop per s) into the system. After
the solution was dropped over, the reaction was kept for another 30 min to produce
a silver colloidal system. Then stopped stirring and placed still for 1 h.

J. Liu et al. / Journal of Alloys and Compounds 494 (2010) 8487

85

3. Results and discussion

3.1. Preparation and separation of Ag nanoparticles

Fig. 1. Schematic diagram of micro-pen direct-writing setup.

The above colloidal system was ltrated through moderate lter paper. Under
stirring, the ltrate was adjusted pH value to 46 by 1:4 (v/v) H3 PO4 . Then it was
placed still for 3 h, ltrated under vacuum, and washed with water. Dark slurry was
obtained. The slurry was washed with EtOH to remove a majority of lauric acid, and
to generate wet Ag nanoparticles. After the nanoparticles were dried at 45 C under
vacuum, 7.5 g of dry Ag nanoparticles were obtained (97% yield).

2.3. Preparation and micro-pen direct-writing of conductive nanopaste

Under mechanical stirring, the above wet Ag nanoparticles (7.5 g) were mixed
thoroughly with 8.0 g of organic vehicle (mainly containing ethyl cellulose, terpilenol, Span-85 and tributyl citrate). Then they were dispersed by supersonic
vibration for 30 min, and the electrically conductive nanopaste was acquired. The
paste was direct-written on the ceramic substrate with micro-pen fabrication setup
(Fig. 1). The direct-writing array patterns were dried at 120 C for 20 min to evaporate solvent, and sintered at temperatures ranging from 200 to 250 C for 15 min,
respectively.

2.4. Characterization and measurements

The structure of the as-synthesized nanoparticles was characterized by XPert
PRO X-ray powder diffractometer. Transmission electron microscopy (TEM) images
were performed on Tecnai G2 20 transmission electron microscope. TEM samples
were prepared by placing a drop of the as-synthesized Ag colloid dispersing in water
onto an amorphous carbon-coated copper grid and then drying under an IR lamp.
UVvis spectroscopy (UV-2550) was used to characterize the optical absorbance
of the Ag colloid. Scanning electron microscopy (SEM) images were obtained from
JSM5510LV scanning electron microscope. SEM sample was 5 mm 5 mm 0.5 mm
ceramic board with direct-writing array pattern, on whose tested surface, an ultrathin gold (Au) conductive coating was deposited by high vacuum evaporation.
After the direct-writing array patterns were sintered, the electrical resistance of
the conductive line in the array pattern was measured by the standard four-probe
resistance measuring method, and the electrical resistivity (,  cm) was calculated
using following Eq. (1):
=

RhD
L

(1)

where h (cm), D (cm), L (cm), and R () were the thickness, width, length, and measured electrical resistance of the line, respectively. The prole (width and thickness)
of the conductive line was tested on a surface probe prolometer (KLA-Tencor P16+).

Ag nanoparticles could be prepared conveniently by chemical

reduction-protection method [11,12,19]. During the preparation,
reductant directly reduced Ag+ or its complex ions to generate
metallic Ag atoms. In the same time, the surfactant was needed
to adsorb on the surface of the Ag atoms, and to well disperse in
the system. The newly born Ag atoms acted as the embryos of the
nanoparticles. With the further reduction, the resultant Ag atoms
continuously deposited on the surface of the embryos. In the other
hand, the adsorption and encapsulation of the surfactant were able
to prevent the nanoparticles from agglomeration and growth without limit. Therefore, the nanoparticles with certain size and size
distribution could be achieved by altering the species and concentration of the reductant and surfactant, respectively.
In this work, AgNO3 was main salt, but its oxidative tendency
was strong. So the reaction of AgNO3 and ammonia produced
silverammonia complex as oxidant for further oxidation (Eq. (2)):
AgNO3 + 2NH3 H2 O = Ag(NH3 )2 + + 2H2 O + NO3

(2)

The reductant was NaBH4 , which had strong reducibility in

the strongly alkaline solution (pH 13). It was able to rapidly
reduce silverammonia complex into metallic Ag atom (Eq. (3)).
Other reductants, for example, formaldehyde, vitamin C, hydrazine
hydrate and glucose, had been also tested, but the results were
unsatisfactory. This was probably due to their different reducibility:
4Ag(NH3 )2 + + 4OH + BH4 = 4Ag + BH2 (OH)2
+ 2NH3 H2 O + 6NH3

(3)

Lauric acid was a long-chain fatty acid, whose solubility was able
to vary with the pH value in the aqueous system. To our knowledge,
it had not been documented that it was sampled as the surfactant
to prepare Ag nanoparticles in a water-phase system.
Before the above reduction reaction was initiated, the
silverammonia complex, reductant and surfactant were in a
homogeneous aqueous solution. When the reaction began and
the embryos came into being, they would be adsorbed and
encapsulated by the surfactant. When the reaction was over, the
homogeneous system transferred into a stable colloid. The whole
process was illustrated in Fig. 2.
In order to separate out the Ag nanoparticles, the rst was to
remove impurity and huge particles by ltering the colloid through
the moderate lter paper. The next was to destroy the colloid. This
could be achieved by decreasing the solubility of the lauric acid in
the system. When the pH value in the system was 46, the lauric
acid became less soluble, and it was able to sediment out. Consequently, its encapsulation and adsorption on the surface of the Ag
nanoparticles were released, and the nanoparticles were precipitated out.

Fig. 2. Schematic diagram of preparation process of nanometer Ag colloid.

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J. Liu et al. / Journal of Alloys and Compounds 494 (2010) 8487

Fig. 3. TEM images (a1, b1 and c1) and size distribution histograms (a2, b2 and c2) of the as-synthesized Ag nanoparticles with different feed (silverammonia complex:
sodium borohydride:lauric acid) ratios ((a1 and a2) 6:3:1; (b1 and b2) 3:3:1; (c1 and c2) 12:3:1).

3.2. Characterization of Ag nanoparticles

Experiments showed that the Ag nanoparticles had very narrow
size distribution when they were prepared in a water-phase system
with a mixture of silverammonia complex, sodium borohydride,
and lauric acid according to molar feed ratio of approximately 6:3:1.
This could be testied by their TEM image (Fig. 3a1) and particle
size distribution histogram (Fig. 3a2), where it was observed that
the nanoparticles had a particle size ranging from 30 to 50 nm. This
was benecial to the next formulation of the electrically conductive paste. If the molar feed ratio was changed, for example, into
3:3:1 or 12:3:1, the particle size distribution would become wider
(i.e., 545 nm in Fig. 3b1 and b2; 1090 nm in Fig. 3c1 and c2). Also,
slight agglomeration had been found in the nanoparticles. One possible explanation was that different feed ratios were able to affect

Fig. 4. UVvis spectra of the as-synthesized nanometer Ag colloid after different

storage periods ((a) 1 day; (b) 1 month; (c) 3 months).

Fig. 5. XRD pattern of the as-synthesized Ag nanoparticles.

J. Liu et al. / Journal of Alloys and Compounds 494 (2010) 8487

87

Fig. 6. Direct-writing array pattern (a) and its SEM photograph (b).

signicantly the generation rate of the Ag embryos, growing rate

of the Ag nanoparticles, and adsorbing and encapsulating degree of
the surfactant.
After the as-synthesized nanometer Ag colloids underwent different storage periods, their UVvis spectra were displayed in
Fig. 4(a) 1 day, (b) 1 month and (c) 3 months. It was found that they
all had very similar UVvis absorption curves, in which, there were
maximal absorbing peaks, and these peaks were very symmetric in
shape, and high in absorbance. According to the Mie Theory [1,2],
these peaks should be corresponding to the surface plasma resonance absorption of the Ag nanoparticles, and their symmetric
shape and high absorbance were attributed to the narrow distribution of the particle diameters. On the other hand, compared Fig. 4b
and c with a, their peak width at half-height became broader, and
peak position shifted from 397 to 398 nm. But the changes were
very small. So it could be inferred that the colloidal system was
considerably stable. The changes of the peak shape and position
might be due to the further agglomeration of the nanoparticles [2].
Additionally, in the curves, the absorption around 600 nm was possibly resulted from a very small quantity of the surfactant lauric acid
in the colloid.
It was found that all the diffraction peaks in Fig. 5 were corresponding to those of metallic silver. Therefore, the as-synthesized
Ag nanoparticles had very high purity, and neither silver compound
nor impurity was intermixed in.
3.3. Preparation and direct-writing of conductive Ag nanopaste
During the formulating of the electrically conductive Ag
nanopaste, it was very important for the Ag nanoparticles to disperse thoroughly and stably in the organic vehicle. For this reason,
the wet Ag nanoparticles other than the dry were employed as
the dispersing phase, and the mechanical stirring plus supersonic
vibration as the dispersing drive. The prepared conductive Ag
nanopaste was a dark and viscous uid. After it was direct-written
with 20 m inner-diameter nozzle (the setup in Fig. 1), and next
sintered, an array pattern was achieved (Fig. 6a). It showed that its
resolution (line and space) was about 30 m. Its SEM photograph
(Fig. 6b) displayed perfect conductive network. It had been measured that the electrical resistivity of the line in the array pattern
was about in the order of magnitude of 105  cm. The nanopaste
also had low sintering temperature (250 C).
4. Conclusions
Ag nanoparticles were prepared in a water-phase system of
silverammonia complex as oxidant, sodium borohydride as reduc-

tant, and lauric acid as surfactant/dispersant, and conveniently

separated out by adjusting the pH value of the system. TEM, UVvis
and XRD analyses showed that they had a particle size ranging
from 30 to 50 nm, and their size distribution was very narrow, and
they had very high purity and slight agglomeration when the molar
feed ratio was approximately 6:3:1. The electrically conductive Ag
nanopaste was formulated by dispersing thoroughly and stably the
as-synthesized wet Ag nanoparticles in the organic vehicle. After
the paste was direct-written and sintered, the array pattern with
the resolution of 30 m was achieved, and it had been measured
that the electrical resistivity of the line in the array pattern was
about in the order of magnitude of 105  cm.
Acknowledgements
This project is supported by the National Natural Science Foundation of China (Grant No. 60806035). We thank the Analytical and
Testing Center of Huazhong University of Science and Technology
for the test of TEM, SEM and XRD.
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