Materials Science in Semiconductor Processing 22 (2014) 2836

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Materials Science in Semiconductor Processing

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

Biosynthesis of large area (30
30 cm2) silver thin films

N.M. Shinde a, A.C. Lokhande b, J.S. Bagi b, C.D. Lokhande a,n
a
Thin Film Physics Laboratory, Department of Physics, Shivaji University, Kolhapur-416 004, Maharashtra, India
b
Production Engineering Department, KIT0 s College of Engineering, Kolhapur-416 234, Maharashtra, India

a r t i c l e in f o abstract

Available online 19 February 2014 For the first time, biosynthesis of large area (30
30 cm2) silver thin films onto glass
Keywords: substrates using chemical successive ionic layer adsorption and reaction (SILAR) method is
SILAR reported. The SILAR deposition method is relatively inexpensive and convenient for large
Silver area deposition of metal thin films. Silver nanostructurals are deposited using AgNO3
Thin films solution and guava leaves extract. The characteristics of silver thin films are studied using
Biosynthesis UVvisible spectrophotometer, scanning electron microscopy (SEM), X-ray diffraction
Guava extract (XRD), atomic force microscopy (AFM), contact angle and photoluminescence (PL)
techniques. The UVvisible spectrophotometer confirmed the formation of silver thin
film. Also, the absorbance spectra confirmed that the silver thin films exhibit absorption
maximum at 435 nm, which is a characteristic feature of surface plasmon resonance (SPR)
peak for silver nanoparticles. The scanning electron microscopy (SEM) images showed the
formation of aggregated silver nanoparticle with increasing thicknesses. The AFM study
showed that the silver nanoparticles are nonuniform on the substrate surface. The XRD
analyses confirmed the nanocrystalline phase of silver thin film with face center cubic
(FCC) crystal structure. Contact angle measurement suggested that the film is hydrophilic
in nature. The silver thin films are found to be photoluminescent with a characteristic
peak at 479 nm. The present study demonstrates an easy method for biosynthesis of large
area silver thin films using green and ecofriendly SILAR method. Finally, as an application
these films are used effectively in antibacterial activity study.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction synthesis of silver nanoparticles, chemical and physical

For utilization of chemical or physical properties of
nanosized metal particles effectively, many research groups
have focused on to control the size and shape with their
tuning with physical, chemical and optical properties [1].
Depending upon the properties, metal nanoparticles com-
pounds have found applications in various fields including
electronic devices [2], chemical/biological sensing [3], cata-
lysis [4], surface enhanced Raman spectroscopy [5] etc.
Silver nanoparticles are intensely studied due to their
unique optical, electrical and catalytic properties [6]. For
n
Corresponding author. Tel.: 91 231 2609223; fax: 91 231 2691533.
E-mail address: l_chandrakant@yahoo.com (C.D. Lokhande).
methods used are radiation chemical reduction [7], elec-
trochemical reduction [8], photochemical reduction [9],
thermal evaporation [10], sonochemical [11] and micro-
wave assisted method [12]. In synthesis process, passivator
reagents like thiophenol, thiourea and marcaptoacetate
are needed to prevent nanoparticles from aggregation.
These passivators are toxic, if these nanoparticles are used
in medical applications and are also responsible to pollute
the environment if large scale nanoparticles are produced.
To overcome this problem, an alternative inexpensive,
reliable, safe and ecofriendly green synthesis route is
preferred. Such green synthesis route includes use of
different methods like polyoxometallates, polysaccharide,
tollens, irradiation and biological [13]. Out of these, biolo-
gical method using plant leaves extract has shown a great

1369-8001/$ - see front matter & 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mssp.2014.01.011
 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836 29

potential in silver nanoparticle synthesis in comparison
with other chemical and physical routes. Green synthesis
route has advantages such as low cost, environment
friendly and easy for large scale synthesis. Alongwith no
need to use high pressure, energy, temperature and toxic
chemicals [14].
Recently, several groups have a success in the green
synthesis of silver nanoparticles using leaves extract
obtained from various plants, e.g. neem [15], anacardium
occidentale [16], curry [17], hibiscus [18], lemon [19],
guava [20] etc. Out of which, guava leaves extract is a
potential candidate for the synthesis of silver nanoparti-
cles. The presence of high quantity terpenoids, flavonoids,
polysaccharides, proteins and alkaloids in guava leaves
extract are responsible for formation of silver nanoparti-
cles. On the other hand, other parts of the guava tree
including the fruit, stem and root extracts are not useful
for reduction of AgNO3 solution to silver nanoparticle
because of chloride content in it which suddenly forms
AgCl resulting white precipitation. Therefore leaf is the
only part to be used in reduction of Ag ions to silver (Ag)
nanoparticles [20].
This way is complex one as in the colloidal solutions,
nanoparticle size is uncontrolled and large amount of
material wastage takes place. Heat is needed as it takes
long time for the formation of nanoparticles and purity of
nanoparticle is also not reliable. Further, one cannot use it
directly for any large area applications.
For large area application, there is a necessity to design
a method to synthesis silver nanoparticles in the form of
thin film layer. Thin film is nothing but when any solid or
liquid system possesses two dimensional order of periodi-
city, it is called as thin film. Thin films can be designed
using physical and chemical methods [21]. Out of these,
chemical methods of thin film formation are easy to
synthesis, inexpensive and low cost. Pawar et al. discussed
the chemical synthesis of metal oxide and chalcogenide
materials thin film forms and their applications in super-
capacitor, solar cell and gas sensor devices [22], where
large area surface is desired.
Chemical methods can control size of nanoparticles and
open a new way for materials production in life sciences.
Outstanding reliable reproducibility of nanoparticles by
this way has a great advantage in comparison with micro-
bial synthesis. Silver thin films have been synthesized by
different chemical methods using various solvents or
reducing agents. Deposition of silver thin film has been
carried out using formaldehyde as a reducing agent
[23,24]. Lee synthesized silver thin films by spin coating
method in which gel was prepared using isopropyl alcohol
[25]. Photochemical method is reported for the laser
directed deposition of silver thin films [26]. Also the silver
nanoparticles are loaded on the surface of the titanium
thin film by dip coating method using methanol as a
solvent [27]. Khan et al. synthesized silver thin films
by dip coating method [28]. To avoid silver nanoparticles
from agglomeration, many chemicals such as glucose,
polyvinyl pyrrolidone and sodium hydroxide have been
used.
In the present work, biosynthesis of silver thin film is
carried out using simple chemical method. The silver thin
films with different thicknesses are deposited on large

Fig. 1. (a) The schematic diagram of SILAR method for the deposition of silver thin films. Beaker 1st contains cationic precursors of AgNO3, beaker 2nd and
4th contain double distilled water (DDW) and beaker 3rd contains anionic precursor of guava leaves extract as a reducing agent, (b) photograph of computer
based SILAR unit and (c) photographs of silver thin films deposited over glass substrate at different thicknesses as (a) 475, (b) 1080, (c) 1780, (d) 2480 and
(e) 2860 nm.
30 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836
area (30
30 cm2) glass substrates. The effect of film
thickness on structural, morphological, optical properties
etc is investigated. As an application, the antibacterial
activity of silver thin films are studied on E. coli bacteria.
2. Experimental details
2.1. Materials
The fresh guava leaves were collected from the garden
of Department of Physics, Shivaji University Kolhapur.
To prepare guava leaves extract, fresh guava leaves were
thoroughly rinsed with deionized water. After carefully
removing midribs of guava leaves, 5 g guava leaves were
chopped into small pieces. The chopped leaves were boiled
in 100 ml of deionized water for 10 min. The leaves extract
was then cooled and filtered through filter paper (Whit-
man No. 1). AgNO3 solution procured from S. D. Fine
Chemical Ltd is used as a silver ion (Ag+) source.
2.2. Preparation of silver thin films
For preparation of silver thin film, a chemical method
known as successive ionic layer adsorption and reaction
(SILAR) is used. Fig. 1(a) shows the experimental setup for
the deposition of silver thin films on to glass substrate. First
beaker contains the cationic precursor of 50 ml of 1 mM silver
nitrate (AgNO3) solution. Third beaker contains anionic solu-
tion of 50 ml of (5 g) guava leaves extract as a reducing agent.
The pH values of cationic and anionic precursor solutions are
370.1 and 570.1, respectively. The two beakers (2 and 4)
containing double distilled water are placed after cationic and
anionic beakers. The photograph of the SILAR unit used for
silver thin films deposition is shown in Fig. 1(b). The visual
basic (VB) language based software is used to interface SILAR
unit with computer, which has ability of controlling each
station of the unit independently, with respect to dipping
time, rinsing time and temperature of the bath. The prepara-
tive parameters such as adsorption time in cationic solution
and reaction time in anionic solution and rising time in double
distilled water are optimized as 10, 15 and 30 s, respectively.
Biosynthesized silver thin films were obtained by
immersing glass substrate into separately placed cationic
precursor silver nitrate (AgNO3) and anionic precursor
guava plant leaves extract along with rinsing between
Fig. 2. Reaction mechanism for silver reduction.
every immersion with ion exchanged double distilled
water. The growth kinetics of a thin film deposition
process involves ion-by-ion deposition at nucleation sites
on the immersed surfaces. According to Lundin and Kitaev
[29], nucleation takes place by adsorption of the ions and
growth takes place as a result of surface coagulation of
these ions, giving thin and adherent film.
The well-cleaned glass substrates were dipped in first
beaker containing cationic precursor i.e. AgNO3 solution
for 10 s in which Ag+ ions are adsorbed on to the glass
surface. After immersion of the glass substrate into first
beaker precursor, the substrate was rinsed with double
distilled water for 30 s to remove loosely bonded Ag 1
ions. The substrate is then immersed in the guava leaves
extract for 15 s, where silver ion reduction occurred on
glass substrate and dark brown silver thin film is formed.
The substrate was again rinsed in distilled water for 30 s to
remove unreacted guava leaves extract solution, silver ions
and loosely bonded powdery silver particles. This com-
pletes one cycle for the deposition of silver thin film. By
repeating such cycles, silver thin films with different
thicknesses were obtained.
Fig. 1(c) shows photograph of silver thin films with
different thicknesses such as 475, 1080, 1780, 2480 and
2860 nm deposited on glass substrate obtained by repeat-
ing 5, 10, 20, 50 and 100 deposition cycles, respectively. A
glass substrate is kept aside for reference to differentiate
colour of silver thin films with thickness. The visual colour
change of silver thin films from yellowish to brownish
with thickness is attributed to the quantum size effect.
Similar observations in case colloidal synthesis of silver
nanoparticles have been cited by many workers [1520].
We used different concentrations of cationic and anionic
precursors. Among different concentrations, films obtained
with above concentrations are uniform and well adherent to
the glass substrate. The higher concentration of precursor
solutions resulted in to a higher growth rate but the quality of
the film was poor due to powdery deposit.
In colloidal silver nanoparticle, formation of a bulk
phase silver nanoparticle occurs upon the transformation
of a supersaturated solution to the saturated state. Two
distinct steps, nucleation and subsequent particle growth,
are involved in this process. During nucleation, clusters of
Ag 1 metal precursor likely undergo rapid decomposition
by adsorbed flavanones on its surface. Earlier study has
confirmed that flavanones is only responsible for reduction
 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836
of silver nanoparticle in case of guava plant leaves extract
[20]. When guava plant extract is mixed to AgNO3 solution,
flavanones can be adsorbed on the surface of silver
metallic nanoparticles through the interaction with their
carbonyl groups or -electrons. The internal mechanism
of converting ketone group to carboxylic acid in flavonoids
recommended to drive an important role in the bioreduc-
tion of Ag 1 in to Ag0 nanoparticle is represented in Fig. 2.
In Fig. 2, luteolin is a common flavanones found in the
guava plant leaves which liberates reactive hydrogen
responsible for the conversion of enol form of luteolin to
its keto form [20].
In order to demonstrate the feasibility of SILAR method
for deposition of silver thin film over large area surface,
glass substrate of dimensions (30
30 cm2) was deposited
using above optimized conditions.
2.3. Growth mechanism of silver thin film formation
There are three steps taken into account during bio-
synthesis of silver thin film. Fig. 3(a) represents nucleation
in which silver ions come closer to each other resulting
into cationic nuclei on the substrate surface called as
aggregation. In successive steps, substrate is dipped in to
anionic precursor bath containing guava plant leaves
extract. This extract solution contains large quantities of
bioreducing groups such as terpenoids, flavonoids, poly-
saccharides, proteins and alkaloids which are generally
potential candidates for reduction of silver metal ion. This
all reduction species act as reduction machinery of silver
nanoparticles [30]. All above mentioned bioreduction
group, flavonoids are mainly involved in reduction of silver
metal ions after expose to guava leaves extract [15]. This
process is called as aggregation. In the second step, many
such silver nanoparticles molecules are merged with each
Fig. 3. Schematic representation of growth process of silver thin film (a) aggregation (b) coalescence and (c) crystal growth. [Inset shows enlarged SEM
image of deposited silver thin film].
31
other, leading to coalescence stage as shown in Fig. 3(b).
Finally, crystal growth process in third step results in to
formation of irregular and aggregated nanoparticles on
substrate surface as shown in Fig. 3(c). Inset shows
enlarged SEM image of deposited aggregated silver nano-
particles thin film. Similar type of growth mechanism of
CdS thin film formation is explained by Hodes et al. [29].
Also Lokhande et al. described similar type of mechanism
in case of SILAR deposited CZTS thin film [31]. In colloidal
synthesis method, Ramanathan et al. demonstrated sys-
tematic growth mechanism of silver nanoparticles using
morganella psychrotolerans leaves extract [30].
2.4. Characterization techniques
The crystal structure of the silver thin films was
identified by X-ray diffraction analysis using D2 PHASER
model purchased from bruker AXS Analytical Instruments
Pvt Ltd with Cu (1.5404 ) target. The surface morphol-
ogy was visualized using a Model JEOL-6360 scanning
electron microscope. The Raman spectrum of the films was
recorded in the spectral range of 5001500 cm  1 using
Raman spectrometer (Bruker MultiRAM, Germany Make).
The optical absorption study was carried out within a
wavelength range of 350850 nm using a UV-1800
Shimadzu spectrophotometer, with glass substrate as a
reference. The wettability of the film was studied out
by Ramehart USA equipment with CCD camera. The
room temperature photoluminescence was investigated
using Perkin Elmer LS-55 using Xenon excitation source.
The topographic images of the assemblies on the glass
were recorded with a multimode atomic force micro-
scope (Innova 1B3BE) operating in the contact mode.
The thickness of film was computed by using fully
32 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836
Fig. 4. (a) Schematic representation of thickness measurement and (b) variation of silver thin film thickness with number of deposition cycles.
Fig. 5. (a) The variation of absorption (t) with wavelength () of silver
thin films on glass substrate at different thicknesses as (a) 475, (b) 1080,
(c) 1780, (d) 2480 and (e) 2860 nm. (b) The absorbance at max as a
function of different film thicknesses of silver films as (a) 475, (b) 1080,
(c) 1780, (d) 2480 and (e) 2860 nm.
Computerized AMBIOS Make XP-1 surface profiler with
1 vertical resolution.
3. Results and discussion
3.1. Thickness measurment study
Thickness is the most significant factor which alters the
properties of thin film material due to surface phenomena.
In order to obtain the terminal film thickness of the silver
thin films, number of deposition cycles were repeated
several times. For measurement of thickness of thin film.
As the stylus is moved over the substrate surface from
position 1 to 2 as shown in Fig. 4(a). Position 1 corre-
sponds to glass substrate and Position 2 where material
deposition starts. Stylus measures the difference in thick-
ness with respect to positions 1 and 2. Fig. 4(b) shows the
variation of silver film thickness with number of SILAR
cycles. In SILAR method, one can easily control the film
thickness with number of SILAR cycles. The maximum
thickness of silver thin film obtained is 2860 nm. Fig. 4(b)
shows silver film thickness variation with number of
deposition cycles. The rate of increase in the film thickness
is nonlinear, which has been attributed to the growth by
nucleation and coalescence process. More nucleation sites
contribute to coagulation during the growing procedure.
Furthermore, slight decrease in film thickness observed
after 100 cycles which may be attributed to the formation
of outer porous layer and/or silver film, which may develop
stress to cause delamination, resulting in peeling off the film
after the film reaches at maximum thickness [32].
3.2. Optical studies
The colour appearance of silver thin film from yellow-
ish to brownish is due to the surface plasmon resonance
(SPR) of the silver nanoparticles, which is considered to be
the primary symptoms of nanoparticle formation [33].
UVvisible absorption spectrum confirmed the formation
 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836
Fig. 6. (a) Transmittance and (b) reflectance spectra of silver thin films on glass substrate at different thicknesses as (a) 475, (b) 1080, (c) 1780, (d) 2480
and (e) 2860 nm.
Fig. 7. Contact angle measurement of silver thin films at different
thicknesses (a) 475, (b) 1080, (c) 1780, (d) 2480 and (e) 2860 nm.
of nanostructured silver thin film. Fig. 5(a) shows the UV
visible absorbance of silver thin films at different thick-
nesses Fig. 5(a)(e). The peak at 435 nm (max) corre-
sponds to the absorbance of silver nanoparticles [15]. The
intensity of the peak at 435 nm is increased with film
thickness. From Fig. 5(a), it is seen that as the film
thickness is increased, the surface plasmon resonance
(SPR) band becomes broader and shifts to higher wave-
length side signifying an increase in particle size of silver
thin film. Fig. 5(b) shows the absorbance at max as a
function of film thicknesses Fig. 5(a)(e). It shows that the
formation of silver thin film slows down after 2860 nm
thickness.
Fig. 6(a) and (b) shows transmittance and reflectance
spectra of silver thin films with different thicknesses such
as 475, 1080, 1780, 2480 and 2860 nm. From Fig. 6(a)
transmittance decreases with increase in film thickness.
The transmittance spectrum characterized by a deep
minimum near 450 nm confirmed the formation of silver
thin film. Also reflectance spectrum (Fig. 6(b)) shows
similar variation with film thickness as that of transmit-
tance. The reflectance spectrum confirmed that the depos-
ited film is useful as the light absorbing coatings [34].
33
Fig. 8. The X-ray diffraction patterns of silver thin films on glass substrate
at different thicknesses as (a) 1780, (b) 2480 and (c) 2860 nm.
3.3. Contact angle study
The surface morphological results also support to con-
trolling and/or modifying the surface of silver thin film
with respect to film thickness. If the wettability is high,
contact angle () is small and the surface is hydrophilic.
Quite the opposite, if the wettability is low, contact angle
is large and the surface is hydrophobic. Fig. 7 shows the
variation of water contact angle with silver film thickness.
The silver thin film surface is hydrophilic in nature as
water contact angle is less than 901 for all the film
thicknesses. It is seen from Fig. 7 that contact angle
increases from 29 to 731 as film thicknesses increased
from 475 to 2860 nm. A liquid in contact with solid
exhibits a contact angle which depends upon the surface
tension of the liquid and the solid as well as the interfacial
tension between them. The silver thin film become hydro-
philic with increasing film thickness which may be due to
different microstructure or modification of surface due to
adsorption of flavanones on surface of silver thin films
with increasing film thickness.
34 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836

Fig. 9. The SEM images of silver thin films deposited at different thicknesses (a) 1779, (b) 2480, (c) 2859 nm at
2000 magnification and (d) 3D-AFM
image of silver thin film on glass substrate.

3.4. Structural studies

The XRD patterns of biosynthesized silver thin films of

three different thicknesses (1780, 2480 and 2860 nm) are
shown in Fig. 8(a)(c). The only one peak is indexed as
(111) plane which corresponds to FCC structure of silver by
comparing with JCPDS data [04-0783]. The grain size of
crystallites was calculated using Scherer0 s relation
0:9
D 1
cos

where is the broadening of diffraction line measured at

half maximum intensity (radians) and 1.5404 , the
wavelength of the CuK X-ray. The crystallites size was
found to be 53 nm for (1 1 1) plane at 2860 nm thickness.
The XRD pattern thus clearly illustrate that the silver thin
films synthesized by the SILAR method are nanocrystalline
[15].
Fig. 10. P L spectra of silver thin films at different thicknesses (a) 1780,
(b) 2480 and (c) 2860 nm.
3.5. Surface morphology
Fig. 9(d) shows AFM image of film deposited on glass
Fig. 9(a)(c) shows the SEM images of silver thin films substrate with thickness of 2860 nm. A topographic AFM
deposited at different thicknesses 1780, 2480 and 2860 nm image (Fig. 9(d)) demonstrates continuous growth of silver
at
2000 magnification. The total glass substrate surface thin film on the glass surface with randomly distributed
is covered uniformly with granular and aggregated silver different sized particles in the order of 100 nm width and
nanoparticles with increase in film thickness. 27 nm height over the surface roughness 48.5 nm. Similar
 N.M. Shinde et al. / Materials Science in Semiconductor Processing 22 (2014) 2836
Fig. 11. Antibacterial activity carried out of silver thin film using
Escherichia coli bacteria, growth of bacteria is seen on the part where
silver film is not deposited.
type of result was obtained for silver thin film deposited
by spin-coating method [35].
3.6. Photoluminescence (PL) spectrum study
The synthesized colloidal silver nanoparticles are found
to be photoluminescent [36]. Photoluminescence (PL)
spectra obtained for silver thin films at room temperature
are shown in Fig. 10(a)(c). It is seen that for all different
thicknesses of silver thin films, the PL peak appeared at
479 nm. The PL emission peak and UVvisible peak
appeared in the wavelength range of 400 to 600 nm. The
visible luminescence from silver nanoparticles has been
reported earlier and attributed to the excitation of elec-
trons from occupied d bands into states above the Fermi
level [37]. Subsequent electronphonon and holephonon
scattering process lead to an energy loss and finally
photoluminescent radiative recombination of an electron
from an occupied sp band with the hole [38]. Fig. 10(a)(c)
shows that there is no change in position of SPR
(max 479 nm) for different thicknesses (1780, 2480 and
2860 nm) of silver films, confirming stable formation of
silver thin film.
3.7. Antibacterial activity study
Antibacterial activity of the synthesized silver thin films
was studied using Ager diffusion method [39]. In this
method, nutrient agar was poured in the petri dish where
the silver thin film was previously placed. Nutrient agar
covers the whole surface of the silver thin film. Then
Escherichia coli bacteria culture was spread in the Agar
plate. Agar plate is then incubated for 24 h at 310 K and
inhibition zone was monitored above and around the
deposited area of silver thin film as shown in Fig. 11. It is
found that, there was growth of bacteria in the area where
there was no coating of silver thin film on the glass surface
and around it. Similar type of colloidal silver nanoparticle
antibacterial activity is tested in E. coli [40]. Hence from
antibacterial study, it was confirmed that the silver thin
film shows antibacterial activity towards to the E. coli
bacteria.
35
3.8. Conclusions
The biosynthesis of large area (30
30 cm2) silver thin
films has been carried out using chemical (SILAR) method.
The synthesis of silver carried out using guava leaves
extract is rapid and produces uniform thin film. The XRD
study showed formation of the face centered cubic lattice
of silver nanoparticle thin film. The significant silver
nanoparticle reduction in reaction with guava leaves
extract and formation of thin film are the important
results and enables synthesis of large area silver in thin
film form rather than colloidal form. These films showed
antibacterial activity toward E. coli bacteria.
Acknowledgment
Authors are grateful to DSA-I (UGC) New Delhi, PURSE
and FIST programs of Department of Science and Technol-
ogy (DST), New Delhi for the financial supports through
scheme no. 03(1165)/10/EMR-II. One of the author NMS is
very much thankful to the Departmental of physics, Shivaji
University, Kolhapur for the award of DST-PURSE Fellow-
ship. Authors are very thankful to Mr. S. B. Talekar,
Department of Biotechnology, KIT0 s college of Engineering,
for experimental help.
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