1

CHARACTERIZATION AND THERMAL CONDUCTIVITY

OF Poly(3,4-ethylenedioxythiophene) (PEDOT) and

DOPED SAMPLE

A PROJECT REPORT

Submitted by

NINAD RAMESH TAJANPURE

In partial fulfilment for the award of the degree

Of

BACHELOR OF SCIENCE

In

PHYSICS

H.P.T. ARTS & R.Y.K. SCIENCE COLLEGE, NASHIK.

SAVITRIBAI PHULE PUNE UNIVERSITY, PUNE 411 007.

MARCH-2020
 2

Examination Seat No.:-

SAVITRIBAI PHULE PUNE UNIVERSITY, PUNE- 411007

BONAFIDE CERTIFICATE

Certified that this project report “CHARACTERIZATION AND

THERMAL CONDUCTIVITY OF Poly(3,4-ethylenedioxythiophene)
(PEDOT) and DOPED SAMPLEs” is the Bonafide work of “NINAD
RAMESH TAJANPURE” of T. Y. B.Sc. (physics) during the academic
year 2019-20 who carried out the project work under my supervision.

Dr. M. D. DESHPANDE Dr. M.D. DESHPANDE

PROJECT GUIDE H.O.D. of
DEPARTMENT OF PHYSICS, DEPARTMENT OF PHYSICS,
HPT ARTS & RYK SCIENCE HPT ARTS & RYK SCIENCE
COLLEGE, NASHIK-422005 COLLEGE, NASHIK-422005

Internal Examiner External Examiner

Date: /03/2020
 3

ACKNOWLEDGEMENT

I wish to thank the Principal V. N. SURYAVANSHI of my

college for permitting me to use all the facilities available in the
institution for my project work. I would also like to thank the Head
of the Physics Department Dr. M. D. DESHPANDE, the teaching
faculty and all the non-teaching staff of my college for their
support in completing the work successfully.
I am grateful to my Guide Dr. M. D. DESHPANDE and Dr. A. B.
CHOURASIA for there encouragement, guidance and supervision
of my project work during the year. My classmates have been of
great help to me during the project work. My ideas were shaped
and refined progressively through my discussion with them from
time to time. I cannot miss to thank them all.

Date: NINAD RAMESH TAJANPURE

T. Y. B.Sc (Physics)
Year: 2019-20
 4

INDEX
Sr Topic Page no
no.
1 Chapter 1 (Introduction) 5
-Introduction
-General information
-Properties
-Derivatives of polythiophene
-Derivatives of PEDOT
-Application of PEDOT
2 Chapter 2 (sample Preparation and characterization 9
techniques)
-Sample preaparation
-characterization techniques
3 Chapter 3 (Result and Analysis) 15
-Sample Preparation
-Analysis
-References
 5

CHAPTER 1
INTRODUCTION
In the project “Characterization and Thermal analysis of undoped and doped
poly((3,4-ethylenedioxythiophene) (PEDOT) our aim is to find the thermal and electrical
conductivity of polymer based nano particle. There are many applications od polymers
like organic polymers in water purifications, to construct electronic components like
capacitors, PCB (Printed Circuit Board), in optoelectronics.
Our interest is to understand the effect of dopand in PEDOT nano partiicles. The
examples of polymers are nucleic acids, proteins, nylon, polyethylene, polyester, Teflon,
epoxy, Poly(3,4-ethylenedioxythiophene) (PEDOT).
The survey of literature of polythiophene showed that many researchers have used
LiBF4, NaAsF6, NaPF6, Bu4NCIO4, Et4NBF4, Et4NPF6, and Iodine as a dopant. However,
polythiophene doped using FeCl3, is not much reported. Hence in the present work FeCl3
is selected as a dopant and it was decided to carry out doping of polythiophene by FeCl3.
The FeCl3 doping in polythiophene chains may causes changes in the structural as well as
in the electrical properties. From the literature survey, as mentioned earlier, derivatives of
polythiophene are more intensively studied. It is therefore thought to carry out study of
more recent and less studied derivative, namely poly(3,4-ethelynedioxythiophene)
(PEDOT). Another reason to study properties of PEDOT is that from literature survey of
derivative of polythiophene, it was found that PEDOT is more suitable for electronic
applications, as it has inherent high conductivity, than any other derivative of
polythiophene. PEDOT will be chemically synthesized and doped with FeCl3, as well as
by camphor sulfonic acid (CSA). Before discussing the project here we are explaning the
some of the major information about the polymers.
Properties of Polymers: -
 High strength
 Light weight
 Toughness
 Low cost
 Lack of conductivity
Our interest is to understand the conductivity od polymer depending upon the dopants.
 6

GENERAL INFORMATION
A polymer may be defining as a large molecule consisting of repeating structural
units joined by covalent bonds. In fact, the name polymer is derived from the Greek
‘polys’ meaning many and ‘meros’ meaning ‘part’. In this context, a large molecule is
commonly arbitrarily regarded either as one having a molecular weight of at least 1000 or
as one containing 100 structural units or more. By a structural unit is meant a relatively
simple group of atoms joined by covalent bonds in a specific spatial arrangement. Since
covalent bonds also connect the structural units to one another, polymers are
distinguished from those solid and liquid where the repeating units (ions, atoms or
molecules) are held together by ionic, metallic bonds, hydrogen bonds, Dipole interaction
or van der forces.

TYPES OF POLYMERS
1. Natural Polymers
2. synthetic Polymers
1. Natural Polymers: - Natural Polymers are those substances which are obtained
naturally. These polymers are formed either by the process of addition
polymerization or condensation polymerization. Polymers are extensively found
in nature. Our body is made up of many natural polymers like nucleic acids,
proteins, etc.
2. Synthetic polymers: -Synthetic polymers are human-made polymers derived from
petroleum oil. From the utility point of view, they can be classified into three main
categories: thermoplastics, elastomers and synthetic fibres. The examples of
synthetic polymers are nylon, polyethylene, polyester, Teflon, epoxy, Poly(3,4-
ethylenedioxythiophene) (PEDOT).

Some Properties of the Polymers

1. ELECTRICAL PROPERTIES OF POLYMERS
For polymers to conduct electricity, the existence of conjugation i.e. the presence
of alternate single and double bonds in these linear chains is usually a necessary but not
the sufficient condition for the conduction process in these polymers. Most of the
conjugated polymers without doping are electrically insulators or low conductivity and
has a high band gap, semiconductors in their pristine form. However, these materials can
be converted into highly conductive and low-band semiconductor or metal-like
conductors by proper choice of dopants and their concentrations. Conjugation gives the
pathway for the movement of electrons/charge carriers in the polymer called as polarons,
bipolarons or solitons. Following section take a review of attempts made by different
workers/researchers to improve the electrical conductivity of pure polythiophene using
different dopants and /or techniques.
 7

2. THERMAL PROPERTIES OF POLYMERS

Thermal analysis embraces all methods in which measurements are made of physical
property that changes as temperature is varied. Thermal analysis of polymers is important
as it provides enthalpy or entropy changes that occur when transformation such as crystal
melting occurs. Thermal analysis also used to study a wide variety of response of the
system to temperature including polymerization, degradation or other chemical changes .

DERIVATIVE OF POLYTHIOPHENE
PEDOT Among the numerous derivatives of polythiophene such as
poly(methylthiophene), poly(butylthiophene), poly(hexylthiophene),
poly(octylthiophene), poly(decylthiophene), poly(dodecylthiophene),
poly(alkylthiophene) etc. which are most studied and best documented; a recently
developed and less studied derivative namely poly(3,4- ethylenedioxythiophene) also
known as PEDT or PEDOT has been selected for present investigation. PEDOT is one of
the most successful material from both a fundamental and practical perspective [46]. It
possesses several advantageous properties as compared to other polythiophene
derivatives; it combines a low oxidation potential and moderate band gap with good
stability in the oxidized state. PEDOT is found to be highly transparent in thin, oxidized
films [46,49]. As a result, PEDOT and its derivatives are now utilized in several industrial
applications including anti-static coatings for photographic films, electrode material in
solid-state capacitors, substrates for electrode less metal deposition in printed circuit
boards, hole conducting material in organic/polymer based light-emitting diodes
(OLEDS/ PLEDS) and electroluminescent lamps [46,49].
PEDOT was developed by the scientists at the Bayer A G research laboratories in
Germany during late 1980s. The structure of PEDOT is as shown in figure (2a). It can be
synthesized using standard oxidative chemical or electro chemical method. PEDOT was
initially developed to give a soluble conducting polymer, but was found to be insoluble
yet exhibited some very interesting properties. In the present investigation PEDOT has
been chemically synthesized, as reported by A. B. Chourasia but with slight
modifications. The synthesized polymer was undoped by treatment with hydrazine.
Undoped PEDOT was then re-doped by FeCl 3 as well as CSA. All the Polymer samples
have been analysed using FT-IR analysis, U-V visible analysis and X-ray Diffraction
analysis. conductivity measurements of undoped, FeCl 3, and CSA doped PEDOT have
also been carried out in this project.

PROPERTIES OF PEDOT
Some properties of the PEDOT as compared to other conducting polymers are
electrochemically synthesized films of PEDOT have a low redox potential and excellent
stability in their doped state [6]. Some other properties of PEDOT are light weight,
reversible doping state, excellent environmental stability, low band gap and high
conductivity, high strength [1]. This made it an excellent candidate for several electronic
 8

applications like capacitor [1], electroluminescent lamps [2], electronic devices [3],
sensors [4], photovoltaic cell [1] and OLED [1].

APPLICATIONS OF PEDOT
F. Jonas et al reported that PEDOT is superior to polypyrrol in an application as
antistatic packaging material. They also report that PEDOT/ PSS solution mixed with
binders such as polyvinyl acetate or polyvinyl alcohol with the aid of suitable organic
solvent, are suitable for the transparent, antistatic finishing of plastics and glass. They
also reported the method to construct/fabricate a capacitor using PEDOT whose
capacitance is comparable to that of similar liquid electrolyte capacitors and high
frequency properties of this capacitor (fabricated using PEDOT) are considerably better.
A recently developed derivative of polythiophene namely poly(3,4
ethylenedioxythiophene) (PEDOT) is selected for the investigation in the present work
rather than other already studied derivatives. PEDOT has inherently high conductivity
compared other derivatives and the electrical properties of polymers are essential for their
successful application in the electronic industry. PEDOT and its derivatives are now
therefore more utilized in electronic applications.
The following chapters (1&2) will explain the methodology to prepare sample and
result analysis.

CHAPTER 2
 9

SYNTHESIS AND CHARACTERIZATION TECHNIQUES

SAMPLE PREPARTAION
PEDOT was chemically synthesized as reported by Ashish chourasia [5]. For
synthesis 1.42gm (0.01 mol) of monomer-EDOT was carried in 140ml of distilled water.
The reaction was stirred for 15 min. to this mixture 4.05gm (0.025 mol) of anhydrous
FeCl3 was added. The above mixture was the stirred for 24 hours with constant magnetic
stirring at 348 K in oil bath. Precipitate obtained was filtered using glass crucible. It was
then washed with methanol and distilled water alternately till the filtrate became
colourless. It was dried under the lamp of 60W till it got completely dried.
The above synthesized and dried powder was undoped by immersing 1 gm of
polymer in a mixture of 65 ml of hydrazine and 35 ml of distilled water. The above
mixture was stirred for 5.5 hr with constant magnetic stirring. The undoped PEDOT was
re-doped using 5%(wt/volume) aqueous FeCl3. In a mixture of 100ml distilled water and
5gm of anhydrous FeCl3 powder, 1 gm of undoped polythiophene was immerged for 5
hours with constant magnetic starring to obtain uniform doping. The powder was then
filtered and washed with water to remove excess, unreacted FeCl 3. The prepared sample
dried in natural atmosphere and used for different analysis.
The synthesized sample is characterized with various techniques like FT-IR, XRD, U-V
VISIBLE. Here we are explanining the techniques:-

1. FT-IR ANALYSIS
Infrared Spectroscopy The word 'infra-red' defines a specific region (1μm to 50
um) of electromagnetic spectrum. Infrared spectroscopy is one of the most powerful
analytical techniques which provide information on transitions between vibrational and
rotational energy levels in molecules. Every type of bond has a different natural
frequency of vibration and since two bonds of some type in different compounds are in
two slightly different environments, no two molecules of different structure have exactly
same infrared absorption pattern or infrared spectrum. Thus the use of the infrared
spectrum is to determine structural information about molecule. The instrument that
determines the absorption spectrum for a compound is called an infrared spectrometer or
more precisely spectrophotometer. It is devised to measure the relative energy that is
transmitted or absorbed in the infrared region as a function of wavelength or
wavenumber. Two types of infrared spectrometers are in common use: dispersive and
Fourier Transform (FT) instruments. Both these types of instruments provide spectra of
compounds in the common range of 4000 cm to 400 cm. Although the two provide nearly
identical spectra for a given compound, FT infrared spectrometers provide the infrared
spectrum much more rapidly than the dispersive instruments. In the present investigation
FTIR spectra of all polythiophene as well as PEDOT samples recorded using were
Shimadzu FTIR-8400S spectrophotometer, operating with normal slit in the 10-minute
scan mode in the spectral range 400 cm to 4000 cm. A pellet of all samples, prepared in
KBr, was kept in the sample holder and it was directly introduced in the path of infra-red
beam.
 10

2. U-V VISIBLE SPECTROSCOPY

Absorption spectrophotometry in the ultraviolet and visible region is oldest

physical method used for quantitative analysis and structural elucidations. Infrared and
NMR techniques are mainly used for structural elucidation and qualitative analysis
whereas UV-visible spectrophotometry is mainly used for quantitative analysis and serves
as a useful auxiliary tool for structural elucidation. The wavelength region for UV
radiation is from 4000 A° to 2000 A° whereas for visible radiation it is 8000 A° to 4000
A°. Spectroscopically, visible light acts in the same way as UV light.
The typical UV-Visible spectrophotometer consists of a light source, a
monochromator (which allows a band of wavelengths usually much more than a narrow
 11

filter) and a detector. The light source is usually a deuterium lamp, which emits
electromagnetic radiation in the ultraviolet region of the spectrum. A second light source,
a tungsten lamp, is used for wavelengths in visible region of the spectrum. The
monochromator is a diffraction grating its role is to spread the beam of light into its
component wavelengths. A system of slits focuses the desired wavelength on the sample
cell. The light that passes through the sample cell reaches the detector, which records the
intensity of the transmitted light. The detector is generally a photomultiplier tube,
although in modern instruments photodiodes are also used. In a typical double beam
instrument, the light emanating from the light source is split into two beams, the sample
beam & the reference beam. When there is no sample cell in the reference beam, the
detected light is taken to be equal to the intensity of light entering the sample.

3. X- RAY DIFFRACTION
In recent years’ x-ray diffractometers are used to record XRD patterns due to certain
typical advantages over the photographic techniques. The recent x-ray diffractometer is based
mainly on the original x-ray spectrometer design developed by Friedman around the year 1943.
An x-ray spectrometer can measure x-ray spectra by means of crystal of known structure.
However, using x-ray diffractometer, the diffraction patterns are obtained using x-rays of known
wavelength for crystalline as well as for non- crystalline materials.

Calculation of Crystallinity Index, Crystallite Size and particle size

From the radial scans of intensity versus 2ϴ, the lateral order or crystallinity index was
determined using Manjunath's formula [6].

The crystallite size was determined using Scherrer’s formula (7] given by,

Kλ
D (h k l) ¿
βCOSϴ
 12

where D (h k l) = crystallite size in a direction perpendicular to the plane (h,k,l) corresponding to

the measured reflection.

λ = Wavelength of radiation used (1.542 A ̊)

K = Constant (0.9 for polymer)

Β = Half-maximum width in radians

ϴ = Bragg’s angle

Scherrer's equation of the form given of very tiny crystals by measurement of diffraction can be
used to calculate the particle size, t [5], of very tiny crystals by measurement of diffraction line
broadening ‘β’.

4. ELECTRICAL CONDUCTIVITY MEASUREMENT: -

The properties of the bulk material used for the fabrication of semiconductor devices are
essential in determining the characteristics of the (completed) devices. The resistivity and hence
the conductivity, in particular, must be measured accurately since its value is critical in many
devices.

DC. electrical conductivity of semiconductors and metals can be measured using two
different techniques

a) Two probe method: To obtain the information about the bulk conducting properties
of the sample.

b) Four probe method: To study the conductivity of the sample.

1. Two probe conductivity measurements: -

Two probe apparatus used for the conductivity measurement was fabricated in the
laboratory. The assembly used for measuring I-V characteristics consists of sample holder and a
temperature measuring device too. The sample holder is in the central part of the instrument.
The unit consists of six terminals; two for heater, two for temperature sensor and two for
measuring current flowing through the sample. Figure show electrical circuitry used for I-V
measurements. The Keithley electrometer (model no. 6514) capable of measuring current in the
range 10-12 to 10 ampere was used to measure the current. Heating rate of the heating coil was
controlled using dimmerstat. The heated coil in tern heats the upper plate of the sample and
thereby gets heated. For controlling as well as for measuring a temperature Sonit relay (SE-2120-
RTD) along with temperature sensor PT 100 was used. The regulated power supply (Testronix-
32) was used to vary DC voltage from 0 V to 100 V. In order to have good electrical contacts, the
sample was Sandwiched between small copper plates (1 x1 cm 2) and was then mounted on the
sample holder. After keeping the sample in the sample older properly, the measurements were
carried out.
 13

2. Four probe conductivity measurement: -

Many conventional methods for measuring resistivity are unsatisfactory for
semiconductors because of metal-semiconductor contacts usually rectifying in nature. Also there
is generally minority injection by one of the current carrying contacts. An excess concentration
of minority carriers will affect the potential of other contacts and modulate the resistance of the
material.

The four probe method overcomes the difficulties mentioned above. Injection of
minority carriers can be prevented by mechanically lapping the surface on which the probes rest.
This also ensures a good contact of sample surface and four probes.

Four probe conductivity measurements were carried out using digital four probe set-up
(model DFP-02#1054) as shown in figure ( ). The apparatus consists of: -

1. Constant current generator (Maximum current 20 mA).

 14

2. Millivolt meter for measuring voltage across the sample.

3. Power unit to supply power to oven (of maximum temperature 200 °C).

The apparatus provides digital display for measuring current and voltage to avoid
parallax error. The heater (oven) unit consists of a cylindrical hollow furnace in which the sample
holder can be inserted. A thermometer is provided for reading the temperature. The sample in
the form of pellet was placed on a thin mica sheet. Four linearly oriented spring loaded probes
were used to make contact on the pellet. A constant current (up to 20 mA) was passed through
the outer two probes and potential difference between the inner two probes was measured at
different temperature ( ). The space between two consecutive probes was 2 mm. The
conductivity was calculated using the relation,

σ=I/(2∏S)V………(S/cm)

Where, V= voltage

I= Current through the probes

S = distance between the probes.

Using this data log10σ versus 1/T graph was plotted. The slope of this graph was used to
calculate the band gap Ea , expressed in eV.
 15

CHAPTER 3
RESULT AND DISCUSSION
SAMPLE PREPARTAION
PEDOT was chemically synthesized as reported by Ashish chourasia [5]. For
synthesis 1.42gm (0.01 mol) of monomer-EDOT was carried in 140ml of distilled water.
The reaction was stirred for 15 min. to this mixture 4.05gm (0.025 mol) of anhydrous
FeCl3 was added. The above mixture was the stirred for 24 hours with constant magnetic
stirring at 348 K in oil bath. Precipitate obtained was filtered using glass crucible. It was
then washed with methanol and distilled water alternately till the filtrate became
colourless. It was dried under the lamp of 60W till it got completely dried.
The above synthesized and dried powder was undoped by immersing 1 gm of
polymer in a mixture of 65 ml of hydrazine and 35 ml of distilled water. The above
mixture was stirred for 5.5 hr with constant magnetic stirring. The undoped PEDOT was
re-doped using 5%(wt/volume) aqueous FeCl3. In a mixture of 100ml distilled water and
5gm of anhydrous FeCl3 powder, 1 gm of undoped polythiophene was immerged for 5
hours with constant magnetic starring to obtain uniform doping. The powder was then
filtered and washed with water to remove excess, unreacted FeCl 3. The prepared sample
dried in natural atmosphere and used for different analysis.
We have characterized it by,
 16

1. FT-IR ANALYSIS 1]

2]

3]
 17

FT-IR Spectra of 1] Undoped PEDOT 2] FeCl3 Doped PEDOT 3] CSA Doped PEDOT
 18

Fig. 1 shows FT-IR spectra of undoped and FeCl 3 doped PEDOT. The synthesized
polymer after treatment with hydrazine gives rise to the IR spectrum as depicted in Fig.
1A. The band appearing at 840.99 cm -1 could be ascribed to vibration mode of C–S bond
in thiophene ring. The band at 890 cm-1 associated to the bending mode of C–H bond in
EDOT monomer disappears after polymerization indicating that formation of PEDOT
molecular chains with α-α’ coupling [6]. The presence of band at 918.15 cm -1 is due to
ethylenedioxy ring deformation mode. A very strong band at 1060.88 cm -1 and 1193.98
cm-1 is characteristic band of C–O [7]. The band at 1141.90 cm -1 is assigned to stretching
mode of ethylenedioxy group. Also a very strong band observed at 1340.57 cm -1
is C=C characteristic band [7]. A band observed at 1500.67 cm -1 is due to ring vibration
mode of thiophene ring [8]. Furthermore, a weak characteristic CH 2 stretching of the
dioxyethylene bridge (2850–3000 cm-1) confirms that the synthesized polymer is PEDOT
and is coupled at α-α’ position.
After doping PEDOT by FeCl3 for 5 h, a new band appears at 570.93 cm -1. This
band is not observed in undoped PEDOT. It has been reported by D. Pavia et al. [9] that
the bands within 550–780 cm-1 are associated to C–Cl. Thus it appears that due to doping
by FeCl3, C–Cl bonding must take place. A band appearing at 918.15 cm -1 in undoped
PEDOT shifts to 920.05 cm-1 in FeCl3 doped PEDOT, indicating that ethylenedioxy ring
deforms after doping. This might be due to the fact that Cl from FeCl 3 forms a bond with
C of ethylenedioxy ring resulting in C–Cl band, which appears in IR-spectra at 570.93
cm-1. It is also observed that after doping PEDOT by FeCl 3, a band at 840.99 cm-1
associated to vibration mode of C–S bond in thiophene ring shifts to 835.18 cm -1. It can
be therefore concluded that Fe of FeCl 3 might be getting attached to (and/or replacing) S
of thiophene ring causing thiophene ring to deform and results in shift of band. Moreover,
a shift in characteristic band of C–O appearing at 1060.88 cm -1 and 1193.98 cm-1 in
undoped PEDOT to 1053.13 cm-1 and 1207.44 cm-1, respectively, after doping it by FeCl3
indicates that Fe must bond with O of ethylenedioxy ring. Furthermore, a shift in band
from 1500.67 cm-1 appearing in undoped PEDOT to 1514.12 cm -1 in FeCl3 doped PEDOT
associated to ring vibration modes of thiophene ring (1350–1500 cm -1) indicates a change
in structure of substituted thiophene. It appears from this shift/change that the double
bond of thiophene ring changes its position and a double bond appears between b-b’
position of thiophene rings. The possible change in structure of PEDOT after doping it by
FeCl3 is shown in Figs. 2a and 2b.
Thus appearance of new band and shifting of some of the bands indicates FeCl 3 is
getting doped in PEDOT and forms a complex with PEDOT chain where Cl - gets attached
with C of thiophene ring at b position and Fe gets attached with S of thiophene and/or O
of ethylenedioxy ring.
After doping undoped PEDOT by CSA for 5 h new bands appear at 1091.71,
1382.96cm-1 associated to S-Aryl, asymmetric deformation of CH3–S band respectively.
These bands are not observed in undoped PEDOT. A shift in characteristic band of C–O
appearing at 1143.79 cm-1 after doping by CSA indicates that SO3H group, probably
after getting detached from CSA, forms a band or interaction with O of ethylenedioxy
 19

ring or CSA molecule after detaching SO3H group gets attached to O of ethylenedioxy
ring and deforms it. A shift in band from 1500.67 cm-1 appearing in undoped PEDOT to
1517.98 cm-1 in CSA doped sample associated to ring vibration modes of thiophene ring
(1350–1500 cm-1) indicates that one of the CH3 group of CSA moiety either forms bond
or interacts with S of thiophene ring, giving a new band at 1382.96 cm-1. Furthermore
appearance of strong and medium bands at 2922.16 and 2850.79 cm-1, respectively,
indicates presence of alkane group in CSA doped PEDOT. Thus shifting of some of the
bands and appearance of new bands indicates that CSA is getting doped in PEDOT chains
and attached to S of thiophene and/or SO3H group or CSA molecule after detaching
SO3H group gets attached to O of ethylenedioxy ring. The change in structure of PEDOT
after doping it by CSA is shown in Fig 2c.
2a] Structure of UNDOPED PEDOT

2b] FeCl3 doped PEDOT

2c] CSA Doped PEDOT

 20

2. U-V VISIBLE ANALYSIS

U-V Analysis of Hydrazine Undoped PEDOT :-

UV- visible of Hydrazine Undoped PEDOT

4
3.5
3
Absorption

2.5
2
1.5
1
0.5
0
290 340 390 440 490 540 590 640 690 740

Wavelengh in nm

 UV-Visible spectrum of Poly (3,4-ethylenedoixythiophene) shows peak

wavelength at 299nm.
 At this wavelength Poly (3,4-ethylenedoixythiophene) absorbs maximum energy.
And thus by using this value of wavelength we calculate the optical band gap
energy of Poly (3,4-ethylenedoixythiophene).

E=hc/λ, h=plank’s constant=6.6×10-34 Js

c=velocity of light=3×108 m/s
E=4.15eV
 Optical band gap energy of Poly (3,4-ethylenedoixythiophene) =4.15eV
 21

U-V Analysis of FeCl3 DOPED PEDOT:-

 U-V Visible spectrum of FeCl3 doped PEDOT shows peak wavelength at 304nm.
 At this wavelength FeCl3 doped PEDOT absorbs maximum energy. And thus by
using this value of wavelength we calculate the optical band gap energy of FeCl 3
doped PEDOT.

E=hc/λ, h=plank’s constant=6.6×10-34 Js

c=velocity of light=3×108 m/s
E=4.08eV
 Optical band gap energy of FeCl3 doped PEDOT is =4.08eV

U-V Analysis of CSA Doped PEDOT:-

U-V Analysis of CAS Doped PEDOT

4.5

4
Absorption

3.5

2.5

2
300 350 400 450 500 550 600 650 700 750
Wavelenth in nm
 22

 U-V Visible spectrum of CSA doped PEDOT shows peak wavelength at 306nm.
 At this wavelength CSA doped PEDOT absorbs maximum energy. And thus by
using this value of wavelength we calculate the optical band gap energy of CSA
doped PEDOT.

E=hc/λ, h=plank’s constant=6.6×10-34 Js

c=velocity of light=3×108 m/s
E=4.055eV
 Optical band gap energy of CSA doped PEDOT is =4.055eV.

3. XRD ANALYSIS: -
Figures show XRD scans of undoped and FeCl3, as well as CSA doped PEDOT
samples. Peaks around 26 and 11 which are common in all cases are due to the distance
between the dopant and the S atom of thiophene ring. The peaks are found to be shifted
after doping, indicating that the crystal structure has been modified after doping PEDOT
by FeCl3, as well as by CSA.
In the present work manjenath et al [] analysis is used to calculate the crystallinity of
the undoped and doped PEDOT samples. It is observed that, after doping PEDOT by
FeCl3 and CSA crystallinity decreases. It is also observed that as crystallinity decreases
the band gap also decreases.
Samples Peak position at Crystallinity Band Gap
2ϴ
Undoped PEDOT 26.8 48.13% 4.15eV
FeCl3 doped PEDOT 26.1 39.60% 4.08eV
CSA Doped PEDOT 26.1 21% 4.055eV

4. Electrical Analysis: -
Conductivity measurements of undoped and all doped PEDOT samples were
carried out using four probe technique in the temperature range from 302 K to 400 K
in a step of 5 K. It is evident that conductivity increases by two orders of magnitude
after doping.
Due to doping more number of +ve and -ve ions gets-attached to the polymer
chain. When electric field is applied the attached charge carriers give away extra
electrons. These electrons then get carried over polymeric chains and conductivity
increases. The conductivity of undoped PEDOT is very less. From the graph it is
observed that the conductivity increases after doping by FeCl3 and CSA.the
conductivity for FeCl3 doped PEDOT is more than the CSA doped sample.
 23

The electrical band gap od undoped PEDOT is less than the FeCl3 and
CSA doped PEDOT.

0.6

0.5

0.4
Fecl3 doped PEDOT
0.3 Undoped PEDOT
CSA doped PEDOT
0.2

0.1

0
275 295 315 335 355 375 395 415 435

The graph of temperature vs conductivity.

Samples Electrical Conductivity

Undoped PEDOT 0.1146eV
FeCl3 doped PEDOT 0.2346eV
CSA Doped PEDOT 0.1328eV

5. Thermal conductivity
Thermal conductivity of measurements of undoped and doped samples were carried
out using four probe instrument. The conductivity of undoped sample at room
temperature (330 K) is 0.07385. and it is nearly equal to the conductivity value measured
by the standard instrument FOX 50 heat flow meter which is 0.07047. We also have
calculated the conductivity at different temperatures. From the readings it is observed that
the thermal conductivity of doped samples were less than that of undoped sample.
Thermal conductivity depends in general on number of free electrons and
phonons. In undoped PEDOT sample motion of phonons must have been responsible for
carrying heat from one point to another point at room temperature. The number of
phonons and/or their orientation/alignment must have been changed in such a way that as
the temperature of undoped PEDOT sample increases thermal conductivity of it also
increases. Thermal conductivity is a resultant of heat carried by phonons and free
electrons. In the present case, though after doping PEDOT by FeCl3 and CSA electrical
conductivity values increases due to increase in number of electrons and their mobility at
higher temperature; the thermal conductivity values after doping were almost same at
higher temperatures. have stopped assisting thermal conductivity and must not be
allowing electrons also to carry heat from one point to another point. Hence thermal
conductivity was reduced after doping. thermal conductivity, of both doped samples, due
to increase in temperature.
 24

References