Applications of Conducting Polymers

– For Sensing, LEDs & Actuation

Based on Guest lecture

held on 2nd April, 2018.

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 Introduction to Conducting Polymers

• Before proceeding with the applications, read

the introduction part to conducting polymers
which includes, synthesis and mechanism of
conduction of conducting polymers. [given by
your faculty]

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 Conduction Mechanism in CPs
• Chains of conducting polymers consist of alternative single
and double bonds, which leads to broad p-electron
conjugation.
• However, the conductivity of these pure conducting
polymers are rather low (<10-5 S cm-1). In order to achieve
highly conductive polymers, doping process is necessary.
• The concept of doping is the central theme which
distinguished conducting polymers from all other polymers
• Conducting polymers can be doped by redox reaction or
protonation, in which the latter is only applicable to PAni.

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 Conducting Polymers for Sensing
Applications

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 Conducting Polymers (CP)
• Conducting polymers, such as polypyrrole (PPy), polyaniline
(PANI), polythiophene (PTh) and their derivatives, have been
used as the active layers of gas sensors since early 1980s.
• In comparison with most of the commercially available
sensors, based usually on metal oxides and operated at high
temperatures, the sensors made of conducting polymers have
many improved characteristics.
• They have high sensitivities and short response time;
especially, these feathers are ensured at room temperature.
conducting polymers have good mechanical properties, which
allow a facile fabrication of sensors.

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 List of Conducting Polymers

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 Doping
• The conductivity of these pure conducting
polymers are rather low (<10-5 S cm-1). In
order to achieve highly conductive polymers,
doping process is necessary.
• The concept of doping is the concept which
distinguished conducting polymers from all other
polymers.
• Conducting polymers can be doped by redox
reaction or protonation.[protonation is only applicable to PANI].
06/01/2023 7
 Principle of Chemical Sensors
• There are many chemicals of concern that have to be sensed,
including toxic gases, volatile organic species, alcohol, and
humidity.
• Chemical sensors transform the concentration of analyte to other
detectable physical signals, such as currents, absorbance, mass or
acoustic variables.
• After exposing to the vapour of an analyte, the active
sensing material of the sensor interacts with the analyte, which
causes the changes in the physical property of the sensing material
• Most of the chemical sensors convert a chemical state into an
electric signal.

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 Principle of Gas Sensing using Conducting
Polymers

•In such sensors, a sensitive conducting

polymer layer is in chemical contact with the
analyte.
•Upon exposure to the vapours, the polymers
show conductivity changes that are
rapid and in general reversible at room
temperature.
• Sensing gases like NH3,CO,H2S, NO2 & I2 are
important in view of industrial safety.
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 Principle of Gas Sensing using Conducting Polymers
contd.,

• The physical properties of conducting

polymers strongly depend on their doping
levels.
• The doping levels of conducting polymers can
be easily changed by chemical reactions with
many analytes at room temperature, and this
provides a simple technique to detect the
analytes.

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 Principle of Gas Sensing using Conducting Polymers
contd.,

• Electron acceptors, such as NO2 and I2, can remove electrons

from the aromatic rings of conducting polymers.
• When this occurs at a p-type conducting polymer, the doping
level as well as the electric conductance of the conducting
polymer are enhanced.
• An opposite process will occur when detecting an electron
donating gas. Ammonia is an electron-donor; when
Ppy(Polypyrrole) reacts with ammonia, its electric resistance
goes down sharply.
• A resistance decrease of a PAni film was detected when it
exposed to CO gas (a poisonous gas).

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 Mechanism of CO sensing using PANI
The stable resonance structure of +C≡O− with the
positive charge at the carbon atom will withdraw a lone
pair electrons at the amine nitrogen: –NH–.
The positive charge at the carbon atom is transferred to
amine nitrogen, which results in a net increase of positive
charge carriers on the polymer backbones and therefore
an increase in conductivity.

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 pH sensing
• Polyaniline has also been found most suitable
organic material for pH sensing in aqueous
medium.
.
• Conductivity decreases rapidly with increase
in pH at a given potential. Similarly, at a given
pH, conductivity changes with respect to the
change in potential.

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 Volatile gas sensing
• Many important organic analytes, such as benzene, toluene
and some other volatile organic
compounds (VOCs) are not reactive at room temperature
and under mild conditions. Therefore, it is difficult to detect
them by their chemical reactions with conducting polymers.
• However, they may have weak physical interactions with the
sensing polymers, involving absorbing or swelling the
polymer matrixes, etc. These interactions do not change the
oxidation levels of conducting polymers, but can influence
the properties of the sensing materials and make these
gases detectable.

06/01/2023 14
 Volatile gas sensing contd.,
• Adsorption of the volatile gases can make
changes in the conductivity of these polymers.
• A basic model for polymer gas sensors which
consists of a thin uniform polymer film lying on
the top of a pair of coplanar electrodes
supported by an insulating substrate.

This is the
dimensionless
distance parameter
given by x/L
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 Biosensing- Electronic nose
• Early detection of microbial spoilage of milk-based
products can be studied using an electronic nose
system with conducting polymers.
• An array of conducting polymer sensors was used
to obtain the odour patterns of the headspace of
the meat samples.
• This electronic nose system was able to identify
meat samples contaminated with Salmonella
Typhimurium.
Salmonella typhimurium is a toxic pathogenic Gram-negative
06/01/2023 bacteria produced and found in spoilt meat samples. 16
 Conducting Polymers for LEDs

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 Polymer LED
What it is and How it works?
• A polymer Light-Emitting Diode (LED) is a thin light source in
which a polymer is used as the emissive material.
• The simplest polymer LED consists of a polymer layer, which is
sandwiched between two electrodes.
• The bottom electrode (anode) is a thin indium-tin oxide (ITO)
layer that is deposited onto a glass substrate. A vacuum-
deposited metal electrode serves as the top electrode
(cathode).
• The electrons and holes are injected from the electrodes and
confined in the emitting polymer layer for recombination, and
then light is emitted with different colours depending on the
energy gap of the chosen polymer. An electron transport can
also be inserted in between the emitting layer and cathode if
necessary.
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 Contd..,
• J. H. Burroughes had first fabricated the
PLED by using conjugated polymers in 1990. Possibility
of processing polymers to form robust and flexible
structure makes them suitable for display arrays.
• On electronic excitation, injection of electrons
and holes on the conjugated chain can lead to a
self localized excited state which can decay radiatively.
• Various conducting polymers are studied as the
emissive material.

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 poly-phenylene-vinylene (PPV)

• Poly (p-phenylene vinylene) (PPV) is used as

the active element in LEDs, with the device
configuration, ITO(anode)/PPV/Ca(cathode).
• But PPV is not processable as it is not flexible.

PPV
ITO: Indium-tin-oxide
-A transparent electrical conductor

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 PPV for LED
When a thin layer of ppv is sandwiched
between an anode and a cathode, as shown in
the diagram below, and a small positive
potential is applied the ppv glows.

By using this fact it is possible to adapt this

applications to larger light emitting displays,
and by using different derivatives of ppv
different colours can be obtained, making full
colour displays possible through mixing the
three primary colour (red, blue and green). 
Below are examples of the variety of colours
possible by using different derivatives of ppv.

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 Other PPV derivatives
• By changing the chemical structure of the PPV, the
solubility can be increased and also emission colour of the
device can be tuned from green to orange-red.
• Flexible PLED by spin coating a thin layer.
of poly aniline onto a sheet of poly ethylene terephthalate,
Poly (2-methoxy, 5-(2-ethylhexoxy)-1, 4- phenylene-
vinylene (MEH- PPV) used as emissive polymer, with
calcium cathode was devised.
• The robust and highly twistable device had shown a turn
on voltage at 1.8 V and orange yellow luminescence at 600
nm.

MEH- PPV
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 Polythiophenes
• Polythiophenes (PT) have been an active
candidate for the electroluminescent materials
in PLEDs
• Low PL quantum efficiency in the solid state
(typically 1-3 %]polythiophenes (PTs) have
limited their application as emissive materials in
PLEDs. Derivatives of PT like 3-hexyl
functionalized (P3HT) are also studied to
improve quantum efficiency.
• PT
P3HT
06/01/2023 23
 PEDOT:PSS

• This is actually a polymer mixture having poly(3,4-

ethylenedioxythiophene), PEDOT and polystyrene sulfonate,
PSS together.
• Sulphonyl groups are deprotonated and carry a negative
charge. The other component PEDOT is a conjugated polymer
and carries positive charges and is based on polythiophene.

PEDOT:PSS

06/01/2023 24
 PEDOT-PSS continuation….
• If organic compounds, including high boiling
solvents like methylpyrollidone,
dimethylsulfoxide, sorbitol, ionic liquids are
added conductivity increases by many orders
of magnitude.
• This makes it also suitable as a transparent
electrode, for example in touchscreens,
organic light emitting diodes, flexible organic
solar cells and electronic paper to replace ITO.
06/01/2023 25
 Different PLEDs and their light emission
property

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 Conducting polymers for Actuation

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 Polypyrrole (PPy)
* PPy Mainly used as actuator (artificial muscle- Robots)
* Insoluble, unmeltable - made as film
* Solvent and counterions randomly distributed
in between polypyrrole chains (act like a plasticizer)

Polypyrrole has disordered

rigid chains held together
by small, π-stacked bundles
Actuation occurs when polymer conducts charges/discharges and counterions
enter and leave the disordered regions between polypyrrole chains

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 Ppy Film –How it looks ?

As-deposited film is ≈ 40% polypyrrole,

30 % propylene carbonate and 30 % PF6 anion.

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 Mechanism of Actuation

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 Thank you

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