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Synthesis and Characterization of Sol–Gel Prepared Silver Nanoparticles

Article  in  International Journal of Nanoscience · April 2014

DOI: 10.1142/S0219581X14500045

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International Journal of Nanoscience
Vol. 13, No. 1 (2014) 1450004 (8 pages)
#.c World Scienti¯c Publishing Company
DOI: 10.1142/S0219581X14500045

Synthesis and Characterization

of Sol–Gel Prepared Silver Nanoparticles

Dharamvir Singh Ahlawat*, Rekha Kumari,

Rachna and Indu Yadav
Department of Physics
Chaudhary Devi Lal University
Sirsa-125055 (Haryana), India
*dahlawat66@[Link]

Received 4 March 2013

Accepted 6 February 2014
Published 10 March 2014

Silver nanoparticles (SNPs) have been successfully prepared using sol–gel method by annealing
the sample at 550
C for 30 min. The SNPs were not con¯rmed by X-ray di®raction (XRD)
analysis when the annealing temperature was considered at 450
C. They were also not con-
¯rmed without calcination of the sample. The physical mechanism of silver clusters formation in
the densi¯ed silica matrix with respect to thermal treatment has been understood. The presence
of silver metal in the silica matrix was con¯rmed by XRD analysis and TEM image of the
samples. The average size of nanoparticles dispersed in silica matrix was determined as 10.2 nm
by the XRD technique. The synthesized nanocomposites were also characterized by UV-Visible
spectroscopy with a peak in the absorption spectra at around 375 nm. The distribution of
particle size has been reported here in the range from 8 nm to 25 nm by TEM observations of the
sample prepared at 550
C. The spherically smaller size ( 10 nm) SNPs have reported the
surface plasmons resonance (SPR) peak less than or near to 400 nm due to blue-shifting and
e®ect of local refractive index. Without annealing the silica samples the absorption spectra does
not show any peak around 375 nm. The FTIR spectroscopy of the three types of samples
prepared at di®erent temperatures (room temperature, 450
C and 550
C) has also been
reported. This spectra have provided the identi¯cation of di®erent chemical groups in the
prepared samples. It has been predicted that the size of SNPs by XRD, UV-Visible and TEM
results have agreed well with each other. It may be concluded that formation of SNPs is a
function of annealing temperature.

Keywords: Silver nanoparticles; nanocomposites; XRD technique; FTIR spectroscopy;

UV-Visible spectra; TEM analysis.

1. Introduction in nanoscale materials stems from the fact that new

Fundamental understanding of the phenomenon properties are acquired at this length scale with
and materials at the nanoscale has become a subject their size or shape. Now a days serious e®orts are
of interest during the last one decade. The interest being made to use structures, devices and systems

1450004-1
D. S. Ahlawat et al.

that have novel properties and functions due to UV-Visible spectra and TEM observations of the
their small size, particularly under 100 nm.1 This prepared sample have also been studied.
development has been particularly pronounced in
the three areas where size e®ects are important;
viz., metals (Au, Ag, etc.), semiconductors (CdSe, 2. Experimental Details
Ag2S, etc.) and magnetic particles (Co, Ni, etc.).
2.1. Synthesis of silver–silica
Material properties and performance can be
improved and optimized by assembling such nano- nanocomposites
materials into 2D and 3D systems. Rustum Roy2 Sol–gel is a low-temperature method3 for the prep-
has introduced a new class of materials known as aration of metallic nanoparticles in temperature
nanocomposites. The preparation and processing of stable SiO2 oxide type matrices. Precursors used for
nanocompsites have earlier been studied by many silver and silica networks were silver nitrate (AgNO3)
researchers.3,4 The reason for the unique spectral and tetraethylorthosilicate (TEOS), respectively.
response of Ag and gold nanoparticles is that The SiO2 sols based on TEOS were prepared by hy-
speci¯c wavelengths of light can derive the con- drolysis of a water alcohol TEOS solution in the
duction electrons in the metal to collectively oscil- presence of nitric acid (HNO3). Aqueous solution of
late. This oscillation is known as surface plasmons silver nitrate was prepared by dissolving calculated
resonance (SPR). It causes the absorption and amount of AgNO3 in water by constant stirring
scattering intensities of such nanoparticles to be under gentle heating conditions in a conical °ask. For
much higher than identically sized nonplasmonic this a te°on coated stirrer bar was put into the con-
nanoparticles. Among the most promising nano- ical °ask. The °ask was placed at the heater plate
materials with antibacterial properties are metallic equipped with a temperature controller and a mag-
nanoparticles which exhibit increased chemical ac- netic controller. In another conical °ask 15.5 mL of
tivity due to their large surface to volume ratios and ethanol was stirred for 5 min. Then, 22.5 mL TEOS
crystallographic surface structure.5 This has pro- was taken in a conical °ask and stirring was done for
moted research in the well-known activity of silver 15 min. After this ethanol and TEOS were mixed and
ions, silver-based compounds and silver nano- constant stirring was applied to the solution for 25
particles (SNPs). Particularly silver nanocompo- min at room temperature (25
C). The pH value of
sites have potential applications in biotechnology the solution was measured by dipping a pH meter
and biomedical science.6 Silica nanoparticles are strip into the solution and the solution was found to
useful for cell imaging and intracellular sensing.7 be neutral. Now a few drops of HNO3 and 10.5 mL of
Thus, SNPs are used in biosensors. The SNPs water were taken in a burette and added to the
absorption and scattering properties can be tuned (TEOS þ Ethanol) solution at a very slow rate. After
by controlling the particle size, shape and local the addition of acid, a slight rise in temperature was
refractive index near the surface.8 observed. Water was added to the alcoholic solution
Sol–gel synthesis is a complex chemical reaction of TEOS to start hydrolysis and later on poly-
involving the presence of various intermediates condensation. The addition of HNO3 to the reaction
during the synthesis process. This can be used to mixture act as a catalyst to alter the rate of hydrolysis
generate nanoparticles by gelation, precipitation and condensation. After the complete addition of
and hydrothermal treatment. The sol–gel technique water and HNO3 the solution was constantly stirred
is a promising low-temperature route which provides for 35 min. The pH value equal to one of this solution
good homogeneity for the preparation of metallic was measured by the pH meter. Then to this reaction
nanoparticles in thin coatings in a thermally stable mixture aqueous solution of silver nitrate was poured
dielectric solid oxide matrix such as SiO2. In this and it was placed on the magnetic stirrer. The stir-
course of work, SNPs dispersed in silica matrix were ring was allowed to continue until the solution
prepared by sol–gel method with the use of SiO2 sols became viscous.
as precursors. X-Ray di®raction (XRD) setup was Now the prepared samples were put for two
used for investigating the e®ect of annealing tem- months in a desiccator to prevent them from
perature on the formation of SNPs. The FTIR moisture. These samples in conical °asks were cov-
spectroscopy has been carried out on the prepared ered with aluminum foil having few holes at the
samples which were annealed at di®erent tempera- center. During this time, gel is maintained in its
tures (room temperature, 450
C and 550
C). The pure liquid, its structure and properties continue to
1450004-2
 Synthesis and Characterization of Sol–Gel Prepared SNPs

change long after the gel point. This process is prepared silver silica samples on blank glass sub-
called \aging". Polycondensation of gel prepared is strate. A silica glass has been used as a reference
completed during this the period. After this, the sample. A monochromotor was used to select light
samples were dried in vacuum at 700 torr and at of di®erent wavelengths which fall on to the sample
600
C for 3 h. The dried samples were heated in an under study. The transmitted or re°ected intensity
oxidizing air environment at a heating rate of 50
C of light at di®erent wavelengths was detected by a
per minute at temperatures of 450
C and 550
C for photodetector.
half an hour. The heating rate and temperature
were kept constant for all the samples. 2.4. FTIR spectrometer
2.2. X-ray di®ractometer The FTIR technique is being used to identify
unknown materials present in a specimen.9,10 It is
The X-ray di®ractometers available for crystal based on the Michelson interferometer setup. In this
structure determination can be used for the analysis method, spectra are collected which are based on
of nanomaterials. The most commonly used dif- the measurements of temporal coherence of a
fractometer is a powder or Debye-Scherrer dif- radiative source using time domain measurements
fractometer. It comprises of a monochromatic source of infrared (IR) radiation. The Perkin-Elmer Spec-
of X-rays, sample holder, a di®ractometer assembly, trum BX FTIR spectrometer was used for the study
an X-ray detector and X-ray data analysis system. of SNPs. This was controlled by spectrum BX
The di®ractometer assembly controls the alignment software. Sample preparation is a di±cult task in IR
of the beam as well as the position and orientation of range as there is no IR transparent material for
both the specimen and X-ray detector. The Rigaku cuvettes. The sample was taken in powder form. It
Mini°ex-II di®ractometer was used for the charac- was mixed with KBr for the formation of pellets in
terization of SNPs. The X-rays are generated usually Hydraulic Pellet Press made by Kimaya Engineers.
from a copper target or anode giving CuK
–0.154 nm The concentration of sample was kept very low
after passing through nickel ¯lter which absorbs because thickness of the pellet was greater than a
strongly the -component of the K-radiation without liquid ¯lm used for the characterization of liquid
any appreciable reduction in the intensity of
-com- samples. The passage of IR radiations through the
ponent. Glass slide having a cavity of dimensions of sample was according to Beer's law. During FTIR
10  10  1 mm3 was used as a sample holder. SNPs analysis, an IR beam on the specimen was sub-
were ¯xed in this cavity with the help of a glass plate jected. The specimen's transmittance and re°ec-
and then the sample holder was placed in the dif- tance of IR rays at di®erent frequencies was
fractometer for scanning. The scan parameters were transformed into an IR absorption plot consisting of
set as, scan range 10
to 70
, step size 2
(2Þ, scan reverse peaks. The resulting FTIR spectral pattern
rate 2
per min. Cooling facility is also provided was than analyzed and matched with the fre-
within the system. Cooling water °ows at a rat of quencies of identi¯ed materials in FTIR library.
4–5 L per min. The di®racted rays make an angle of 2
at the detector with respect to the incident beam
2.5. TEM setup
direction. A scintillation counter was used as a
detector and it was mounted on a di®ractometer- Transmission electron microscope (TEM) Hitachi
goniometer stage. Power to the X-ray tube was make was used for obtaining TEM picture of the
switched on but voltage and current were increased sample annealed at 550
C. The TEM observations
slowly and then they were ¯xed at 30 kV and 15 mA, were made with accelerating voltage of 20–140 kV.
respectively. A shutter was also used with auto pro- The particle size of synthesized SNPs was analyzed
tection arrangement. through dynamic light scattering.

2.3. Absorption spectrometer

3. Results and Discussion
The optical absorption spectra were recorded in
the wavelength range of 200 nm to 600 nm at room 3.1. X-ray di®raction analysis
temperature using a Perkin-Elmer, dual beam spec- The XRD patterns of the prepared samples have been
trometer Varian Cary-5000 (Netherland CHRIST). shown in the Figs. 1(a)–1(c). The silver crystalline
The UV-Visible spectra were obtained for the peaks of the samples annealed at 550
C were

1450004-3
D. S. Ahlawat et al.

(a)

(b)

(c)

Fig. 1. (a) The XRD spectra of the 1.25 wt.% AgNO3 doped silica sample without calcination, (b) The XRD spectra of the sample
calcinated at 450
C for 30 min and (c) The XRD spectra of the 1.25 wt.% AgNO3 doped silica sample annealed at 550
C for 30 min.

1450004-4
 Synthesis and Characterization of Sol–Gel Prepared SNPs

Table 1. Annealing temperature, di®raction angle, FWHM,

size of 1.25 wt.% AgNO3 doped silica samples.

Annealing Di®raction angle FWHM Size

temp. [
C] [degrees 2] [radians] [nm]

Without — — Nanoparticles
annealing not observed
450
C — — Nanoparticles
not observed
550
C 38.1
0.014 10.6
44.3
0.017 8.9
64.5
0.015 11.1
77.4
0.018 10.0

(a)
observed at di®raction angles 38.1
, 44.3
, 64.5
and
77.4
. The di®raction peaks were found correspond-
ing to the formation of, SNPs in the amorphous silica
network.11 The average particle size of SNP was
found to be 10.2 nm. The XRD result shows that
nanoparticles formation take place with the increase
in annealing temperature.
Prior to peak width measurement, each di®rac-
tion peak was corrected for background scattering
and was stripped of the K
2 portion of the dif-
fracted intensity. The XRD peaks were analyzed to
determine intensity, position and width of di®rac-
tion peaks. The full width at half maximum was (b)
measured for each selected peak given in Table 1.
Fig. 2. (a) Absorption spectrum of AgNO3 doped silica
From this study, average particle size has been samples without annealing and (b) Absorption spectrum of
estimated by using Debye-Scherrer's formula for 1.41 wt.% AgNO3 doped silica samples annealed at 550
C for
peak broadening from size e®ects only 30 min.

D ¼ 0:9= cos ; ð1Þ

where  is the X-ray wavelength,  is the full width Figures 2(a) and 2(b) show the absorption spectra
at half maximum of a di®raction peak and  is the of the prepared 0.5 wt.% of AgNO3 without
di®raction angle. However, for extremely small annealing and 1.41 wt% of AgNO3 samples annealed
nanoparticles (< 2 nm) the broadening of X-ray at 550
C for 30 min, respectively. The strong in-
peaks arise from combination or evolution of grain teraction of metal–nanoparticles with incident light
size, microcrystalline strain and instrumental has its origin in resonance excitation of collective
broadening e®ects. It is necessary to correct the oscillation of conduction electrons called surface
instrumental broadening and to sort out the strain plasmon absorption band (SPAB). It may be ob-
components to determine the average grain size.9 served that signi¯cant SPAB peaks were present in
There is a broad peak for all the samples which is the prepared samples (1.41 wt.% of AgNO3) at the
due to amorphous silica matrix. For the original wavelength around 375 nm (3.1 eV), which has a
sample without annealing process and the sample resemblance to a well-known silver absorption peak
annealed at 450
C for 30 min, no di®raction peaks which is an evidence supporting for the formation of
were observed. SNPs.8 This absorption peak was of low intensity
and broader because it is believed that nano-
particles were smaller in average size and they have
3.2. UV-Visible spectra relatively wide size distribution. Average size of Ag
Optical properties of SNPs are supposed to be due nanoparticles in this nanocomposite was estimated
to interparticle network and substrate interactions. to be 12.4 nm. The resonance frequencies are
1450004-5
D. S. Ahlawat et al.

strongly dependent on the nanoparticles material

size, shape, neighboring particles, dielectric function
of the medium surrounding the nanoparticles and
the type of substrate.12,13 The absorption spectra of
isolated spherical silver particles have been charac-
terized by various research groups using Mie the-
ory.14 It was taken into account that silica network
was weakly interacting with SNPs and there were
no interface reactions resulting into charge transfer
between matrix and the particles.15 Absorption at
the shorter wavelength is due to interband tran-
sition of silver. The SPRB frequency of nano-
particles depends upon the valence electron density.
However, the SPR peak of SNPs are usually
observed at 420–450 nm. But smaller size particles (a)
around 10 nm have SPR peak slightly smaller than
or near to 400 nm as compared to the SPR peak of
larger size say 50, 60, 80, 90 and 100 nm.8,13 As the
diameter of SNPs increases, the peak plasmon res-
onance shifts to longer wavelengths and gets broa-
dened.16 Kelly et al.17 have also reported similar
results for the in°uence of size, shape and dielectric
environment on the optical properties of metal
nanoparticles. In support of our result for SPR at
shorter wavelength around 375 nm there is another
argument that the SPR peak location will shift to
shorter wavelength (blue-shift) if the particles are
transferred from water (refractive index ¼ 1:33) to
air (r:i: ¼ 1:00). On the other hand it shifts to
longer wavelength (red-shift) if the particles trans- (b)
ferred to oil (r:i: ¼ 1:5).13 In our case, the SNPs
were transferred from water to air. This is the e®ect
of local refractive index on optical properties. Fur-
thermore, the TEM image (Fig. 4) of the sample
clearly indicates that the SNPs are well separated
from each other rather than aggregation in the silica
matrix. The optical properties of SNPs change when
particles aggregate and the conduction electrons
near each particle surface become delocalized and
are shared amongst neighboring particles.17 When
this occurs, the SPR peak shifts to longer wave-
length (red-shift). This argument also supports
blue-shifting found in the present case as a result of
well-separated SNPs.
(c)
3.3. FTIR analysis
Fig. 3. (Color online) (a) FTIR spectra of the 1.25 wt.%
The FTIR spectra of the 1.25 wt.% AgNO3 doped
AgNO3 doped silica sample without calcination, (b) FTIR
silica samples were recorded in KBr powders. spectra of the sample calcined at 450
C for 30 min and
Figures 3(a)–3(c) show the FTIR spectra in the (c) FTIR spectra of the sample annealed at 550
C for
wavelength range 400–4400 cm 1 of the as-prepared 30 min.

1450004-6
 Synthesis and Characterization of Sol–Gel Prepared SNPs

sample without annealing, sample annealed at

450
C for 30 min and sample annealed at tem-
perature 550
C for 30 min respectively. In the FTIR
spectra of all the three samples the band centered
between 3450 cm 1 and 3500 cm 1 corresponds to
the fundamental stretching vibrations of di®erent
hydroxyl (–OH) groups. The broadening of this
band is due to overlapping of H–OH band with the
surface hydroxyl group vibrations and it decreases
as the samples were heat treated which has been
shown in the Figs. 3(a)–3(c). This decrease in
broadening of bands reveals that the Si(OH)4 is not
converted into SiO2 in the initial state of the
sample's preparation. The presence of adsorbed
water is indicated by the bands located at
1646.03 cm 1 , 1641.30 cm 1 and 1645.98 cm 1 for
Fig. 4. The TEM image of the sample annealed at 550
C.
the as-prepared sample without annealing, sample
annealed at 450
C for half an hour and sample
annealed at 550
C for 30 min, respectively. These di®erent chemical groups that were expected to be
bands are assigned to the bending vibrations of present in the silver silica matrix.
water molecules. These bands indicate hygroscopic
character of the samples. There is a noticeable 3.4. TEM analysis
decrease in the intensity ofthis band as annealing
temperature is increased due to decrease in the The TEM observations were made for the sample
amount of adsorbed water. The peak located at annealed at 550
C which is shown in Fig. 4. The
1384.66 cm 1 in Fig. 3(a) for the as-prepared TEM image clearly demonstrates that the SNPs
sample without annealing is assigned to the vi- were found dispersed in the silica matrix with
brations of ethoxy group which were very unstable spherical or nearly spherical in shape. Their size
and it disappeared very easily with the annealing distribution have been found in a wide range from
temperature. Its absence in the case of annealed about 8 nm to 25 nm. But, more particles size dis-
samples at di®erent temperatures may be due to tribution lies near 10 nm. While, larger spheres
completely hydrolyzed and no re-esteri¯cation of exhibit increased scattering and have SPR peaks
ethoxy groups occurs during the drying process. that broaden and shift toward longer wavelengths
The bands present around 1090 cm 1 and 970 cm 1 (red-shifting) which is not found in the present
are the characteristic bands of amorphous silica case.8,13 Thus, the obtained SPR peak [Fig. 2(b)]
(SiO2). Bands located near 1090 cm 1 are for of the same sample at shorter wavelength under
asymmetric stretching vibrations of Si–O–Si bond10 UV-Visible study is supported by the availability of
and their broadening decreases as annealing tem- smaller size particles ( 10 nm) con¯rmed by the
perature is increased. TEM study. Thus, there is a size e®ect on the optical
The bands at  800 cm 1 are associated with the properties for spherical morphology of SNPs.17 This
vibrational modes of ring structure of SiO2 tetra- is also nearly in agreement with the particle size
hedra. Bands that appeared between 800 cm 1 and obtained by XRD method. Moreover, the nano-
465 cm 1 is attributed to the terminal nonbridging particles are found well separated from each other in
Si–O groups arising from a Si–O–Ag network. These the silica matrix. It may be mentioned here that
bands are present for all the samples with decreas- when the sample was annealed at higher tempera-
ing intensity as the temperature is increased. The ture (550
C) the SPNs can be clearly seen and found
bands located near 470 cm 1 in all the spectra are embedded of smaller size in the SiO2 matrix.
related to the bending vibrations of Si–O–Si
bonds.10 These bands shift toward lower wave
number as the annealing temperature is increased. 4. Conclusion
Thus, the FTIR spectra have provided surface in- The SNPs in silica matrix were prepared success-
formation of the materials for identi¯cation of fully using the sol–gel technique by calcination of
1450004-7
 D. S. Ahlawat et al.

the sample at 550
C for 30 min. The synthesized References

SNPs of average size 10.2 nm dispersed in silica
1. B. L. Cushing, V. L. Kolesnichenko and C. J.
matrix have been observed by XRD technique. O' Connor, Am. Chem. Soc. 104, 3938 (2004).
However, the SNPs were observed at 550
C annealed 2. R. Roy, Solid State Inoics, 32–33, 3 (1989).
sample and not at 450
C annealing temperature. 3. G. Mitrikas et al., J. Sol-Gel Sci. Tech. 13, 503
Therefore, it concludes that distribution of nanoclus- (1998).
ters in the silica matrix is a function of annealing 4. H. J. Jeon, S. C. Yi and S. G. Oh, Biomaterials 24,
temperature. It indicates that temperature is an 4921 (2003).
important parameter for the formation of nano- 5. J. R. Morones et al., Nanotechnology 16, 2346 (2005).
particles. The FTIR spectroscopy results indicate 6. R. S. Patil et al., Adv. Nat. Sci. Nanosci. Nano-
that thermal treatment reveals almost complete technol. 3, 015013 (2012).
disappearance of the band typical to ethoxy group. 7. B. Korzeniowska et al., Nanotechnology 24, 442002
(2013).
It was also observed that intensity of the peak
8. www. [Link]/nanomaterials/silver-nano-
present near 1640 cm 1 decreases with annealing
materials.
temperature which indicates that number of water 9. K. Selvaraju, R. Valluvan and S. Kumararaman,
molecules adsorbed on the surface decreases with Mater. Lett. 60, 3130 (2006).
the increase in annealing temperature. The UV- 10. S. Mathur et al., J. Am. Ceram Soc. 89, 2027 (2006).
Visible spectra also con¯rm the formation of SNPs 11. H. Ono and T. Katsumata, Appl. Phys. Lett. 78,
in the silica matrix. The TEM observations con¯rm 1832 (2001).
the size distribution of SNPs in the range 8 nm to 12. X. C. Jiang et al., Nanoscale Res. Lett. 6, 32 (2011).
25 nm. Blue-shifting of the SPR peak from around 13. www. nano composix:silver nanoparticles: Optical
420 nm has been found and it is believed to be due properties.
to smaller sized SNPs ( 10 nm), spherical mor- 14. K. L. Kelly et al., J. Phys. Chem. B 107, 668 (2003).
phology and local refractive index. It may be con- 15. W. Cai et al., J. Nanopart. Res. 3, 443 (2001).
16. S. Link and M. A. El-Sayed, J. Phy. Chem. B 103,
cluded that the ¯ndings of XRD, UV-Visible and
8410 (1999).
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17. K. L. Kelly et al., J. Phys. Chem. B. 107, 668 (2003).
SNPs.

1450004-8

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