Preparation of Silver Nanoparticles and Their Characterization

Preparation of Silver Nanoparticles and Their Characterization

R. Das, S.S. Nath, D. Chakdar, G. Gope and R. Bhattacharjee
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DOI: 10.2240/azojono0129
Submitted: May 7th, 2009
Posted: June 17th, 2009

Topics Covered
Abstract
Introduction
Synthesis of Silver Nanoparticles
Experimental Result and Discussion
XRD Analysis
TEM Analysis
UV/ Vis Spectroscopy Analysis
Electroluminescence
Conclusion
Acknowledgements
References
Contact Details

Abstract
The preparation of stable, uniform silver nanoparticles by reduction of silver ions by ethanol is
reported in the present paper. It is a simple process of recent interest for obtaining silver
nanoparticles. The samples have been characterized by X-Ray diffraction (XRD) and
Transmission electron microscopy (TEM), which reveal of the nano nature of the particles.
These studies infer that the particles are mostly spherical in shape and have an average size of
16 nm. The UV/Vis spectra show that an absorption peak, occurring due to Surface Plasmon
Resonance (SPR), exists at 410 nm.
Keywords
Nanoparticle, Surface Plasmon Resonance (SPR), silver nanoparticles

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 R. Das, S. S. Nath, D. Chakdar, G. Gope and R. Bhattacharjee

Introduction
Nanoparticle synthesis and the study of their size and properties is of fundamental importance
in the advancement of recent research [1,2,3]. It is found that the optical, electronic,
magnetic, and catalytic properties of metal nano particles depend on their size, shape and
chemical surroundings [2,3].
In nanoparticle synthesis it is very important to control not only the particle size but also the
particle shape and morphology as well. In the present investigation the synthesis of silver
nanoparticles by chemical route [4,5] is discussed, which is an easy, simple and convenient
route for preparing metal particles in nanometer range. The prepared silver nano particles
have been dispersed in chloroform and then examined using X-ray diffraction (XRD),
Transmission Electron Microscope (TEM) and UV/Vis absorption spectroscopy. These studies
reveal that the prepared nanoprticles are of an average size of 16 nm, which indicates the
importance of the present work.
Perhaps the most important factor in this process is that the silver nano particles prepared by
this process are stable for months.
Synthesis of Silver Nanoparticles
Uniform silver nano particles can be obtained through the reduction of silver ions by ethanol at
a temperature of 80°C to 100°C under atmospheric conditions [4]. In this synthesis process,
20 ml of aqueous solution containing silver nitrate (0.5g of AgNO3), 1.5 g sodium linoleate
(C18H32ONa), 8 ml ethanol and 2 ml linoleic acid (C18H32O2) are added in a capped tube under
agitation. The system is sealed and treated at the temperatures between 80°C to 100°C for 6
hours.
In the aqueous solution of silver ions, sodium linoleate and the mixture of linoleic acid and
ethanol are added in order. A solid phase of sodium linoleate, a liquid phase of ethanol and
linoleic acid, and water ethanol solution phase containing silver ions formed in the system.
Ethanol in the liquid and solution phases reduced the silver ions into silver nanoparticles.
Along with the reduction process, linoleic acid is absorbed on the surface of the silver
nanoparticles with the alkyl chains on the outside which the produced silver nanoparticles of
near circular shape.
The product which collected at the bottom of vessel after cooling to room temperature, was
dispersed in chloroform to form a homogenous colloidal solution of silver nanoparticles. The
colour of the sample (colloidal solution of silver nanoparticle) becomes reddish brown. On
changing the concentration of electrolyte, it is found that the colour become reddish brown on
adding linoleic acid at the same proportions. This reddish brown colour of prepared
nanoparticles indicates nearly 100 % conversions of silver ions into nanoparticles. The
preparation of silver nanoparticles with different electrolyte concentrations has been tried, but
neither the samples with concentration other than the present one is found to be stable over 2
weeks nor of smaller size (more than 60 nm). Hence, we have recorded the data of the particle
of optimum size and of comparatively better stability (over 4 months).
Experimental Result and Discussion
XRD Analysis
The structure of prepared silver nanoparticles has been investigated by X-ray diffraction (XRD)
analysis. Typical XRD patterns of the sample, prepared by the present chemical method are
shown in the Fig.1.

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 Preparation of Silver Nanoparticles and Their Characterization

Figure 1. X-ray diffraction pattern of Ag nano particles.

The XRD study indicates the formation of silver (Ag) nano particles. Table 1 shows the
experimentally obtained X-ray diffraction angle and the standard diffraction angle [4] of Ag
specimen.
Table1. Experimental and standard diffraction angles of Ag specimen
Experimental diffraction angle [2θ in Standard diffraction angle [2θ in
degrees] degrees]
45 44.3
From this study, considering the peak at 45 degrees, average particle size has been estimated
by using Debye-Scherrer formula [6,7].
0 .9 λ
D =
WCos θ ........ (1)
Where ‘λ’ is wave length of X-Ray (0.1541 nm), ‘W’ is FWHM (full width at half mamimum), ‘θ’
is the diffraction angle and ‘D’ is particle diameter (size). The average particle size is
calculated to be around 14 nm. Table 2 gives the diffraction planes, d spacing, and average
size.
Table 2. Size, diffraction plane, d spacing of Ag sample

Diffraction FWHM d spacing Diffraction Size

angle plane
[radians] [nm] [nm]
[degree]
45 0.011 0.1788 200 14

TEM Analysis
A TEM image of the prepared silver nano particles is shown in the fig.2. The Ag nano particles
are spherical in shape with a smooth surface morphology. The diameter of the nano particles is
found to be approximately 16 nm. TEM image also shows that the produced nano particles are
more or less uniform in size and shape.

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 R. Das, S. S. Nath, D. Chakdar, G. Gope and R. Bhattacharjee

Figure 2. TEM image of Ag nano particles

UV/ Vis Spectroscopy Analysis
In metal nano particles such as in silver, the conduction band and valence band lie very close
to each other in which electrons move freely. These free electrons give rise to a surface
plasmon resonance (SPR) absorption band [8,9,10,11], occurring due to the collective
oscillation of electrons of silver nano particles in resonance with the light wave [6]. Classically,
the electric field of an incoming wave induces a polarization of the electrons with respect to
much heavier ionic core of silver nanoparticles. As a result a net charge difference occurs
which in turn acts as a restoring force. This creates a dipolar oscillation of all the electrons with
the same phase.
When the frequency of the electromagnetic field becomes resonant with the coherent electron
motion, a strong absorption takes place, which is the origin of the observed colour. Here the
colour of the prepared silver nanoparticles is dark reddish brown. This absorption strongly
depends on the particle size, dielectric medium and chemical surroundings [9,10]. Small
spherical nano particles (< 20nm) exhibit a single surface plasmon band [5]. The UV/Vis
absorption spectra of the silver nano particles dispersed in chloroform is shown in the fig. 3.
The absorption peak (SPR) is obtained in the visible range at 410 nm. With the above
mentioned concentration. The stability of silver nanoparticles is observed for 4 months and it
shows a SPR peak at the same wavelength.

Figure 3. The UV/Vis absorption spectra of Ag nano particles.

Electroluminescence
Fig. 4 displays the room temperature electroluminescence spectra of silver nanoparticles when
the silver nanoparticles (assembly of nanoparticle) are biased with ac supply voltage. This
experiment reveals that unlike fluorescence (FL), silver nanoparticles also exhibit
electroluminescence (EL).

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 Preparation of Silver Nanoparticles and Their Characterization

Radiative recombination of electron hole pairs between d-band and sp-conduction above the
Fermi level produces FL emission [12], which occurs practically at 480 nm when biased with ac
voltages. Also, the absorbed linoleic acid during the formation of silver nanoparticles further
enhances the intensity of emission [13, 14].
We believe that the reasons behind both the types of luminescence are same as EL and FL
peaks occur nearly in the same position which is around 480 nm. Fig 5 shows the variation of
luminescence intensity as a function of bias (applied voltage). It is observed that EL intensity
varies with bias almost in a linear fashion. This study indicates that silver nanoparticles
(assembly of silver nanoparticle) can act as “nano laser” when stimulated (excited) with
electrical energy (bias voltage).

Figure 4. Electroluminescence spectra of Silver nanoparticle

Figure 5. Variation of EL intensity with bias (AC Voltage)

Conclusion
Silver nanoparticles have been prepared through the reduction of silver ions by ethanol, which
is dispersed in chloroform. This is one of the simplest and cheapest processes for obtaining
silver nanoparticles. UV/Vis spectroscopy reveals the surface plasmon property, while XRD
analysis and TEM images reveal the nano nature of the prepared samples. Average size
estimated from above studies is 16 nm. Electroluminescence (with peak at around 480 nm)
shows the possibility of silver nanoparticles baing used as a “nano laser”.

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 R. Das, S. S. Nath, D. Chakdar, G. Gope and R. Bhattacharjee

Acknowledgements
Authors thank to Dr D. K. Avasthi (Scientist H) Material Science, IUAC, New Delhi, India, Dr B.
DKHR (S.O.) NEHU, Shillong, India and Dr. S. Sharma (S.O.), IIT,Guwahati, Assam, India for
their suggestions and assistance during the work.
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Contact Details
S. S. Nath, G. Gope and R. Bhattacharjee

Department of Physics
Assam University
Silchar, Assam, India

E-mail: nathss08@gmail.com

D. Chadkar

Department of Physics
NITS
Silchar, Assam, India

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