Abstract:
This work mainly concerns with the preparation, characterization and studies
of some nanostructured composites and blends of Intrinsic Conducting Polymers (ICPs)
with special reference to their charge transport mechanisms and device applications.
These nanostructured composites consisted of two phases; a conducting phase and an
insulating phase. Different series of nanocomposites with ICPs; Polypyrrole (PPy),
Polyaniline (PANI) and Poly (p-phenylene vinylene) (PPV) as conducting phase and
MMT clays and other lamellar structured materials such as CdPS 3 as an insulating phase
were prepared and studied.
A series of Polyaniline / Montmorillonite clay (PANI.MMT) composites was
synthesized by in situ polymerization of aniline in the presence of varying amount of
MMT clays in acidic medium. DC electrical conductivity was studied as a function of
MMT loading and temperature to understand the charge transport mechanism in these
composites. The conductivity followed quite well the temperature-dependence
relationship σ(T) = σ 0. exp[-T o /T) 1/2 ], characteristic of one-dimensional variable-range
hopping (1-D VRH). Frequency dependant AC conductivity followed the universal
power law; this work is described in chapter 3.
Another series of nanocomposites; PPy intercalated in the interlamellar region of
Aluminum Pillared Montmorillonite (Al PMMT) clay with varying amounts of Al
PMMT were prepared and studied. The Pyrrole was polymerized into the layers of Al
PMMT replacing the Aluminum pillars and forming regular aligned chains of PPy, which
not only enhanced AC and DC conductivities, but also affected the mechanism of
conduction to switched from 3-D VRH in case of pristine PPy to 1-D VRH in all PPy Al
PMMT nanocomposites. Maxwell Wagner effect was observed in dielectric
spectroscopy. TGA curves of both the series of clay based ICP nonocomposites showed
that the thermal stability is enhanced by insertion of ICPs in MMT clays.
Blends of Polypyrrole and Polyaniline with poly (methyl methacrylate)
(PMMA) in the presence of Hydroquinone were also prepared and studied. The
percolation threshold in PANI.DBSA PMMA with 1% hydroquinone blends was
observed as low as 3% which is very low as compared to that of theoretical value of 16%.
iiThe percolation threshold in PPy.DBSA PMMA was recorded as 7% which shows that
PPy.DBSA has less interaction with PMMA as compared to that of PANI.DBSA. These
results were further confirmed by FT-IR, Raman spectroscopy and dielectric
spectroscopy.
Single crystal Cadmium hexathiohypodiphosphates Cd(PS 3 ) 2 generally
written as CdPS 3 and Poly (p-phenylene vinylene) (PPV) were successfully synthesized.
PPV was synthesized by chemical polymerization method. Intercalation of K + , Eu + and
then PPV into the layers of CdPS 3 was confirmed by XRD. PPV intercalated in layers of
CdPS 3 and heated at 120°C (CPPV120) show enhanced conductivity and luminescence
properties.
Electrical Properties of polypyrrole (PPy) doped with dodecylbenzene
sulfonic acid (DBSA) were studied with and without a plasticizing agent hydroquinone.
Hydroquinone was used as a compatibilizer to maximize solubility of PPy.DBSA in
organic solvents which facilitated easy processing of flexible and mechanically strong
PPy films for device applications. In order to assess the effect of hydroquinone on the
electrical properties of PPy.DBSA /Aluminum (Al) Schottky junction, capacitance-
voltage (C-V) and current density-voltage (J-V) characteristics were measured in Indium
Tin Oxide (ITO)/PPy.DBSA /Al and ITO/PPy.DBSA .hydroquinone/Al structures. The
observed J-V and C-V characteristics can be satisfactorily fitted to the modified Schottky
equations. The junction parameters were found to be strongly influenced by
hydroquinone. From C-V characteristics, the built-in voltage and charge concentration
were also found to be influenced by the presence of hydroquinone. These results indicate
that addition of hydroquinone to PPy.DBSA imparts better diode quality to the doped
polymer/metal Schottky junction.