Materials Letters 63 (2009) 2236–2238

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Synthesis of uniform silver nanoparticles with a controllable size

Tali Dadosh ⁎
Department of Condensed Matter Physics, Weizmann Institute of Science, Rehovot 76100, Israel
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel

a r t i c l e i n f o a b s t r a c t

Article history: A new method for the synthesis of uniform silver nanoparticles using a single silver reduction step is
Received 25 June 2009 presented. Fine control over the nanoparticle's size is achieved by varying the concentration of tannic acid,
Accepted 21 July 2009 one of the reducing agents, resulting in uniform nanoparticles in the range of 18 nm to 30 nm in diameter
Available online 28 July 2009
with a standard deviation of less than 15%. Changes in the optical properties of the nanoparticles are
correlated with their diameter. As the diameter increases the absorption peak is red-shifted. Specifically, for
Keywords:
Electron microscopy
six different sizes of nanoparticles, ranging from 18 nm to 30 nm in diameter, a red-shift from 401 nm to
Raman spectroscopy 410 nm in the absorption peaks is measured. In addition, the extinction coefficient increases as the third
Optical absorption power of the nanoparticle radius. Rhodamine 123 adsorbed to 30 nm silver nanoparticles exhibits
Nanomaterials characteristic Raman spectrum suggesting that these nanoparticles are efficient substrate for surface-
Silver colloids enhanced Raman spectroscopy.
Nanoparticles © 2009 Elsevier B.V. All rights reserved.

1. Introduction distribution and different morphologies [12]. These nanoparticles give

high SERS signal, but the surface shape is not well defined. Only a
Silver nanoparticles have unique electronic and optical properties. limited number of methods are available to synthesize uniform silver
Hence, they have been used in a broad range of fields, including particles. A two-step method involving a gold core coated with a silver
catalysis, biological labeling, photonics, and surface-enhanced Raman shell has been shown to provide a narrower size distribution [6,15,16].
scattering (SERS) [1–6]. As the field of SERS has been greatly extended Though the two-step method provides acceptable particles for SERS,
in the past years, silver has been found to provide the highest SERS the synthesis is still complex. Here a one-step method for synthesizing
signal enhancement with respect to other metals. The absorption monodisperse silver nanoparticles with a controllable size is described.
spectrum of silver nanoparticles is sharp and strong, a feature which is
ascribed to the excitation of collective electron oscillations (so called
2. Materials and methods
surface plasmons), in response to an electro magnetic field [7]. Previous
studies have shown that surface plasmons of aggregates of nanoparticles
The synthesis of silver nanoparticles was carried out as follows:
interact, and a high near-field is formed at the contact points of the
20 mL of 6.8 mM aqueous solution of tri-sodium citrate, containing
nanoparticles. It is agreed that most of the SERS enhancement is caused
increasing amounts of tannic acid (1.8–23.5 μM), was heated to 60 °C
by this mechanism [4,6,8].
and added with vigorous stirring to 80 mL of 0.74 mM AgNO3 pre-
The optical properties of silver nanoparticles are dictated by the
heated to 60 °C. The mixture was kept at 60 °C for 3 min, or until its
geometrical parameters such as shape and size [9], hence it is crucial
color turned yellow, boiled for 20 min, cooled down to room
to be able to control these parameters. Many strategies have been
temperature and stored in a dark bottle at 4 °C.
developed for the preparation of silver nanoparticles, including micro-
Sample praparation for SERS measurements of Rhodamine 123
emulsion techniques [10], organic-water two phase synthesis [11], and
(Rh123): Rh123 was dissolved in ethanol at approximately 10−5 M
aqueous solution reduction [12–14]. However, synthesizing uniform
(determined by its absorption at 510 nm, using an extinction
and stable silver nanoparticles with a controllable size is difficult. The
coefficient of 85,000 M− 1 cm− 1), diluted in double distilled water
commonly used citrate reduction method for SERS experiments
(DDW) to 1 nM and 100 μL were mixed with 900 μL of the Ag colloid
according to Lee and Meisel, results in nanoparticles of broad-size
solution made up by mixing 390 μL of DDW, 10 μL of 100 mM NaCl and
500 μL of 30 nm silver nanoparticles. The reaction mixture was
⁎ Present address: Department of Physics and Astronomy, University of Pennsylvania,
incubated at 4 °C for 24 h, and then adsorbed for 15 min on a glass
Philadelphia, PA, 19104, USA. Tel.: +1 215 573 3096; fax: +1 215 898 2010. substrate covered with polylysine (1 mg/mL). The samples were
E-mail address: dadosh@sas.upenn.edu. mounted on an inverted microscope and excited using a frequency-

0167-577X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2009.07.042
 T. Dadosh / Materials Letters 63 (2009) 2236–2238 2237

Fig. 1. TEM images of silver nanoparticles synthesized using different molar concentration of tannic acid (a) 2.9 µM of tannic acid, average particle size 19.5 ± 3 nm, (b) 5.9 µM of
tannic acid, average particle size 25.4 ± 2.8 nm, (c) 23.5 µM of tannic acid, average particle size 29.7 ± 4.3 nm.

doubled Nd2+-YVO4 laser at 532 nm. The typical excitation intensity 410 for the 18- and 30-nm nanoparticle, respectively. Such a red-shift
for Rh123 was 30 W/cm2. An area of 15 µm in diameter of the sample is a characteristic of an increased nanoparticle size [18,19]. The spectra
was epi-illuminated by focusing the laser beam at the back focal plane were stable over a period of months, indicating colloid stability over
of a 100× NA = 1.3 oil immersion objective. The back-scattered light that period of time. The extinction coefficient (maximum absorption)
was collected by the same objective and a long-pass filter was used to at the plasmon peak is also expected to be size dependent. The inset of
discard the Rayleigh scattered light. The light was then focused on the Fig. 3b shows that for a given nanoparticles' concentration it increases
entrance slit of the spectrograph attached to a side port of the as the nanoparticle gets larger. Moreover, a linear dependence is
microscope. A resolution of 10 cm− 1 was achieved using a diffraction observed as a function of the third power of the radius. This result is
grating of 600 grooves/mm. The spectra were registered on a with agreement with Mie theory [7].
thermoelectrically-cooled CCD camera. To demonstrate the potential use of the silver nanoparticles
described here, we measured the SERS of Rhodamine 123 (Rh123).
Fig. 4 shows the SERS spectrum of Rh123, which is in agreement with
3. Results previously published SERS spectra of this molecule [6,20,21]. The use
of the uniform silver nanoparticles described in this paper results in
Fig. 1 shows typical TEM images of silver nanoparticles synthesized similar SERS spectrum of Rh123 compare to nonuniform nanoparticles
with various molar concentrations of tannic acid. It can be seen that produced by known methods [12,21]; however, the uniform nano-
the average size of the nanoparticles increased with increasing tannic particles used in this experiment have additional benefits of being
acid concentration. The diameter of the nanoparticles obtained ranged well characterized and enable to modeling more easily.
between 18 and 30 nm (as determined by TEM), with standard
deviations of less than 15%, and depended linearly on the log of the 4. Conclusions
tannic acid concentration (Fig. 2, and insert). As the small nanopar-
ticles are spherical, the bigger nanoparticles are slightly ellipsoidal. In summary, a simple one-step synthesis method for the prepara-
Interestingly, though this method is similar to the method of Slot and tion of uniform and stable silver nanoparticles was presented. The
Geuze for the synthesis of monodisperse gold nanoparticles [17], the optical properties and the size of the NPs were shown to be easily
tannic acid concentration has the opposite effect (for gold nanopar-
ticles, increased tannic acid concentration resulted in smaller
nanoparticles). When a higher concentration of silver nitrate was
used, the resulting nanoparticles population was not uniform and
various shapes and sizes appeared. In some cases two populations of
uniform-size particles were observed.
The evolution of the UV–visible spectra for growing silver
nanoparticles is shown in Fig. 3a for nanoparticles made with tannic
acid at 11.8 μM. Early in the reaction, the absorption plasmon spec-
trum was broad, with a major peak at 425 nm. As the reaction pro-
ceeded, the major plasmon peak shifted to the blue and reached a final
wavelength value of 408 nm after approximately 15 min. This behav-
ior was consistently observed in all syntheses that were carried out.
The shift of the maximum wavelength of the absorption spectrum
during the reaction is similar to earlier reports [2]. The absorption of
the nanoparticles solution increased faster when the tannic acid con-
centration in the reaction was larger, indicating a faster formation of
nanoparticles.
Characterization of the optical properties of silver nanoparticles is
shown in Fig. 3b. It can be seen that the maximum wavelength of the
absorption is changing with the amount of tannic acid in the reaction
due to a change in the nanoparticles' size. As the diameter increases Fig. 2. The diameter of silver nanoparticles as a function of the concentration of tannic
the maximal plasmon absorption peak is red-shifted: from 401 nm to acid in the reaction.
2238 T. Dadosh / Materials Letters 63 (2009) 2236–2238
Fig. 3. (a) Evolution of the absorption spectra during the formation of nanoparticles, for tannic acid concentration of 11.8 μM. As the reaction proceeded, the absorption peak is shifted to a
shorter wavelength until it reached its final value of 408 nm. (b) Absorption spectra of silver nanoparticles of different sizes normalized to a concentration of 0.16 nM. Inset: extinction
coefficient versus cubic radius of the nanoparticles. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
tuned in the range of 18 to 30 nm by the concentration of tannic acid
in the reaction. As the tannic acid concentration was increased, the
diameter of the nanoparticle grew up. The plasmon resonance of the
resulting nanoparticles was shifted to blue during the reaction, and
the final values of the resonance were red-shifted with increased
nanoparticle diameter. A SERS experiment was conducted for Rh123
in the presence of 30 nm silver nanoparticles, and a clear spectrum of
Rh123 was recorded.
Acknowledgements
I wish to thank Professors Joseph Sperling and Israel Bar-Joseph for
useful suggestions and encouragement. I also acknowledge Prof. Gilad
Haran for using his SERS setup. The electron microscopy studies were
conducted at the Irving and Cherna Moskowitz Center for Nano and
Bio-Nano Imaging at the Weizmann Institute of Science. This work
was supported by the Eshkol fellowship by the Israel Ministry of
Science and Technology, and by a grant from the Israel Ministry of
Science and Technology.
Fig. 4. SERS spectrum of Rh123 adsorbed on 30 nm silver nanoparticles. The excitation
wavelength is 532 nm; collection time is 2 s. Inset: schematic drawing of Rh123.
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