JOURNAL OF CHEMISTRY AND CHEMICAL SCIENCES
An International Open Free Access, Peer Reviewed Research Journal
www.chemistry-journal.org
ISSN 2229-760X (Print)
ISSN 2319-7625 (Online)
Abbr: J. Chem. & Cheml. Sci.
2014, Vol.4 (3): Pg.150-155
Synthesis and Characterization of Polypyrrole (PPY) Thin
Film by Spin Coating Technique
S. Sakthivel and A. Boopathi
Thin film Physics and Nano Science Laboratory,
PG and Research Department of Physics
Rajah Serfoji Govt. College,
Thanjavur, Tamilnadu, INDIA.
(Received on: July 9, 2014)
ABSTRACT
Polypyrrole (PPy) was synthesized by chemical oxidative
polymerization technique using monomer Pyrrole and ammonium
per sulphate as an oxidant in a ratio of 1:1. Thin films of
polypyrrole were prepared by dissolving polypyrrole in m-cresol
and cast using spin coating technique on glass substrates. Thin
films of polypyrrole were characterized by X ray diffraction
(XRD), Scanning electron microscopy (SEM), Fourier transform
infra red spectroscopy (FTIR), UV visible spectroscopy, Raman
spectroscopy and electrical resistivity measurements by four probe
method.
Keywords: Polypyrrole, Chemical Polymerization, FTIR, SEM,
XRD, Raman Spectrum.
1. INTRODUCTION
Conducting
Polymers
with
conjugated double bonds have been attracted
much attention as advanced materials.
Polypyrrole (PPy) has received widespread
interest due to its good Environmental
stability, facile synthesis, and higher
conductivity than many other conducting
polymers1,2. It could be always used in Drug
delivery systems, Rechargeable batteries,
Super capacitors, Sensors, and Microwave
shielding3-6.
Polypyrrole (PPy) based
polymer blends can protect the corrosion of
metals7, Because of the strong adhesion of
PPy to iron or steel treated with nitric acid,
PPy polymers can be used as good
adhesives8. Polypyrrole as a neural switch
may be used to control and modulate the
communication between different artificial
Journal of Chemistry and Chemical Sciences Vol. 4, Issue 3, 31 July, 2014 Pages (118-155)
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S. Sakthivel, et al., J. Chem. & Cheml. Sci. Vol.4 (3), 150-155 (2014)
neurons9.
Electrochemical
process
parameters affecting the properties of the
PPy coatings are also investigated10. PPy can
be easily prepared by either a chemical
oxidatively or electrochemical polymerization of Pyrrole monomer. However
synthetically conductive PPy is insoluble
and infusible which restricts in its processing
and applications of other fields. The problem
has been extensively investigated and new
application fields have also been explored in
the past several years. For example, PPybased polymers can be used to load and
release drugs and bio molecules11. PPybased polymer blends can protect the
corrosion of metals12. In the present
investigations attempts were made to report
on our observation of structure morphology,
optical and electrical properties of
polypyrrole thin films using the spin coating
technique.
2. EXPERIMENTAL
2.1 Materials
Polypyrrole (PPy) was synthesized
by chemical oxidative polymerization
technique using monomer Pyrrole were
purchased from Sigma-Aldrich (C4H5N,
M.W. 67.09) reagent grade was distilled
prior to use. Analytical grade ammonium
per-sulphate APS ((NH4)2S2O8 M=228.20g/
mol) Merck Specialities Mumbai was used
as oxidizing agent. All reactions were
conducted at room temperature. The solution
of the oxidizing agent, APS was prepared
using distilled water and used in the ratio of
1:1(monomer: oxidant). The Solvent mcresols
(C7H8O,
M.W.108.14)
were
purchased from Sisco Research Laboratories
Mumbai.
2.2 Preparation of Polypyrrole Thin Film
The Polypyrrole was prepared by
Chemical polymerization method. 1M
Pyrrole solution was prepared using distilled
water and then mixed with an oxidizing
agents in the ratio of 1:1, slowly under
constant stirring for 30 minutes. Then the
polymerization was conducted for 5 hours
under constant stirring. This preparation was
kept unagitated for 24 hours so polypyrrole
powder settled down. Then the PPy powder
was filtered out and washed with distilled
water in several times to remove any
impurities and reacting monomers. The
Polypyrrole was dried for two days at room
temperature.
The Thin film of polypyrrole was
deposited using spin coating method on pre
cleaned glass substrate. The polypyrrole
powder was dissolved in m- cresol to
prepare the concentrated solution. The
solution preparation required 4-5 days of
stirring make the solution homogenous. A
thin film of Polypyrrole was deposited on
glass substrates using spin coating technique
at a speed of 3000 rpm. The thin film was
dried in air at 60min.
2.3 Testing and Characterizations
FTIR and XRD analysis were used
to confirm the formation of PPy powder
sample. The chemical bonding was analyzed
by using FTIR Perkin Elmer make-model
Spectrum RXI spectroscopy. UV-Visible
measurements were carried out on Perkin
Elmer make-Lambada 35 model and
absorption spectra were obtained by
depositing the film PPy on glass substrate.
X-ray diffraction (XRD) studies were
Journal of Chemistry and Chemical Sciences Vol. 4, Issue 3, 31 July, 2014 Pages (118-155)
S. Sakthivel, et al., J. Chem. & Cheml. Sci. Vol.4 (3), 150-155 (2014)
carried
out
using
Rigaku
X-ray
Diffractometer.
Raman
spectroscopic
studied by Raman Systems RSIQ model.
And Scanning Electron Microscope (SEM)
studied by SEM TESCAN Vega-3 SBU
model using acceleration voltage of 5.0 kV.
The thin film resistance was measured by
using four-point probe method.
3. RESULTS AND DISCUSSION
3.1. FTIR Spectroscopy Analysis
152
The FTIR spectra of PPY powder
are represented in Figure 1. The stretching
peaks of C-N were detected at 1473 cm-1.
The absorption peak at 1046 cm-1 is
corresponded to C-H and N-H deformations.
The occurrence of small peaks at all these
peaks is the main characteristic of PPy13-15.
The peak 916.59 cm-1 is out of plane
deformation and the small peak 792 cm-1 is
out of plane ring deformation another one
small peak of 678 cm-1 is C-C out of plane
ring deformation or C-H rocking16.
Figure1. FT-IR Spectrum of PPy Powder
3.2. X-Ray Diffraction Analysis
The X-ray diffraction (XRD) studies
of the samples were done on Rigaku X-ray
Diffractometer with Cu K radiation
operating at 40kV and 15 mA. Scanning was
carried out in the 2 range from 10 to 900 at
a scan speed of 100 per minute. The XRD
patterns of the PPy powder are shown in
Figure 2. The peak in PPy powder sample is
mostly amorphous in nature. Broad peak
was observed at about 2 = 250. The board
peak is characteristic of amorphous and
indicates short range arrangement chains of
PPy [17]. The crystallite size from a sharp
peak at 250 for PPy is estimated by using
scherrers formula leads to the crystallite
size high intensity sharp peak of about
77.412nm for PPy powder. The value of dspacing for PPy powder 3.5569.
Journal of Chemistry and Chemical Sciences Vol. 4, Issue 3, 31 July, 2014 Pages (118-155)
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S. Sakthivel, et al., J. Chem. & Cheml. Sci. Vol.4 (3), 150-155 (2014)
feature of this filling level, which may have
an adverse effect on the electrical
conductivity.
3.4. Raman spectral Analysis
Figure 2. XRD Pattern of PPy powder
Raman spectroscopic study is one of
the important tools to obtain structural
information on polymers. In most cases,
Raman scattering is sensitive to the degree
of crystallinity in a sample. Typically, a
crystalline material yields a spectrum with
very sharp and intense Raman peaks, while
an amorphous material shows broader and
less intense Raman peaks.
The Raman spectra of PPy thin film
shows Figure 4, The most important peak at
about 1589 cm-1 which can be attributed to
the C=C backbone stretching of PPy. The
peak at about 1052 cm-1 is assigned to the CH in plane deformation. Another peak at
1393 cm-1 is attributed to the ring-stretching
mode of PPy. The band located at about 925
and 988 cm-1 are assigned to the ring
deformation associated with dication
(bipolaron) and radical cation (polaron),
respectively18-20.
Figure 3 Scanning Electron Microscope image of
PPy Thin film.
3.3 Scanning Electron Microscopy
Analysis
The SEM study of PPy films shows
Figure 3 demonstrated that the surface was
covered with grains. The scanning electron
microscopy shows the non uniform
distribution of PPy particles over the surface
of substrate. The rod and spherical shape
particle formation and much weaker interparticle bonding appear to be a prominent
Figure 4 Raman scattering spectra of PPy Thin
film
Journal of Chemistry and Chemical Sciences Vol. 4, Issue 3, 31 July, 2014 Pages (118-155)
S. Sakthivel, et al., J. Chem. & Cheml. Sci. Vol.4 (3), 150-155 (2014)
154
3.5. UV Vis Spectroscopy Analysis
3.6. Conductivity study
The UV- Vis spectroscopy of
polypyrrole thin film is shown in the Figure
5. These absorption spectra have been
recorded over wavelength range 300 to 1100
nm using a Lambda 35 UV-Vis spectroscopy
model at room temperature two main
absorption bands are present in this region
for 469 and 590 nm. The film displayed
strong absorption peak at 469nm, assigned
as transitions from the PPy valance band to
an anti-bipolarons band. This broad
absorption is attributed to electron transition
from the polypyrrole valence band to a
second bipolarans band in the band gap21, 22.
Thin films of PPy sample were
measured for resistance using four-point
probe technique show in Figure 6.
The four probe technique is a very
efficient method for measuring the sheet
resistance23,24. It measures the sample
resistance by current that flows for a given
applied voltage. The outer two pins force a
current through the sample and the inner two
pins measure the voltage drop. The
resistance of the pure PPy Spin Coated Thin
film variation of electrical resistance as a
function of temperature25. In this case it was
observed that as temperature increases the
electrical resistance decreases and hence
conductivity increases so in this film
suggests that the thermally activated
behaviour of conductivity has been
confirmed.
4. CONCLUSIONS
Figure 5 UV-Vis absorbance spectrum of PPy
Thin film
The Polypyrrole synthesized using
chemical polymerization process and thin
film coated with Spin coating technique. The
film non uniform distribution of particles
morphology and structure of PPy confirmed
by FTIR, XRD and Raman Spectroscopy
techniques. UV-Vis studies showed that the
PPy films exhibit absorption peak at 469 nm.
The pure PPy thin film shows a thermally
activated of conductivity.
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Figure
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