Research Article

Received: 29 January 2013

Revised: 22 March 2013

Accepted: 25 March 2013

Published online in Wiley Online Library: 20 May 2013

(wileyonlinelibrary.com) DOI 10.1002/pi.4538

Synthesis of poly(3,4-ethylenedioxythiophene)
nanoparticles via chemical oxidation
polymerization
Nophawan Paradee and Anuvat Sirivat
Abstract
Poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles were synthesized via chemical oxidation polymerization using
3,4-ethylenedioxythiophene as the starting monomer and ammonium peroxydisulfate (APS) as the oxidant. The effects
of APS concentration, surfactant concentration and type of surfactant, namely dodecylbenzenesulfonic acid and sodium
dodecylsulfate, were investigated. Distinct particle shapes were obtained: irregular, raspberry agglomerate, coralliform,
orange-peel, globular and plum shapes. The particle sizes and the electrical conductivity are in the ranges 60 to 900 nm and <1
to 153 S cm1 , respectively, depending on the polymerization conditions. PEDOT synthesis in the absence of a surfactant yields
a smaller particle size because a larger amount of initiator induces lower molecular weights and smaller PEDOT particles. The
smaller PEDOT particles correspond to higher electrical conductivity because of the larger surface areas for electron transfer
and a smaller amount of obstructing surfactant aliphatic segments. Moreover, particle size and shape can be varied, depending
on surfactant type and concentration which dictate the micellar shapes in the polymerization reaction. This work is focused
on the tailor-made PEDOT shape and property relationship under synthesis conditions where several shapes have not been
previously seen.
c 2013 Society of Chemical Industry


Keywords: nanoparticle synthesis; poly(3,4-ethylenedioxythiophene); chemical oxidation polymerization; electrical conductivity

INTRODUCTION

106

A nanoparticle refers to a body in which at least one dimension

of its structure is below 100 nm; it is fabricated to improve
optical, electrical, mechanical and chemical properties.1 A wellcontrolled conducting polymer nanostructure is one of the targets
in nanotechnology towards many advanced applications. Poly(3,4ethylenedioxythiophene) (PEDOT), consisting of 3,4-disubstituted
thiophene rings, is one type of conducting polymer, previously
developed by Bayer AG in the 1980s.1 3 PEDOT has been widely
implemented in many applications: sensors,2,4 electrochromics,5,6
light-emitting diodes7 and solar cells.8 It has been widely used
because it shows promising electrical conductivity with a low band
gap, transparency, and thermal and environmental stability.3,9 11
Normally, PEDOT can be prepared by chemical oxidation polymerization or electrochemical polymerization. Electrochemical
polymerization is preferred for PEDOT in thin-film form; however, its yield is quite low. On the other hand, the synthesis of
PEDOT by chemical oxidation polymerization utilizes oxidizing
agents to produce a higher PEDOT yield.1,9,12
In general, several kinds of oxidants can be used in chemical
oxidation polymerization depending on the reaction conditions.
Corradi and Armes13 prepared PEDOT via a chemical synthesis
route. They used FeCl3 , Ce(SO4 )2 and (NH4 )Ce(NO3 )6 as the
oxidants. The electrical conductivity of PEDOT varied from
6.80 104 to 5.30 S cm1 , depending on the oxidant type, reaction temperature and reaction time. Choi et al.10 studied PEDOT
nanoparticle preparation by using a surfactant to produce emulsion polymerization. Dodecylbenzenesulfonic acid (DBSA) was
Polym Int 2014; 63: 106113

used to act as a surfactant to form micelles. FeCl3 and ammonium

peroxide were used as the oxidants. The PEDOT nanoparticles
obtained were spherical and their diameter varied from 35 to 120
nm and the electrical conductivity was between 1 and 50 S cm1 .
Huajing et al.2 prepared PEDOT nanoparticles by a reverse micelle
method. Sodium bis(2-ethylhexyl)sulfosuccinate mixed with FeCl3
was used to create an oxidant active point at the interface of the
reversed micelle. The PEDOT nanoparticles obtained possessed
particle sizes between 30 and 100 nm and electrical conductivity
between 16.7 and 33.7 S cm1 . However, the PEDOT particle
size also depends on other parameters in the synthesis: reaction
temperature, reaction time and oxidant concentration. The
PEDOT particle size obtained directly influences the electrical
conductivity.
In the work reported here, PEDOT nanoparticles were prepared
through chemical oxidation polymerization. Different particle
sizes, particle shapes and corresponding electrical conductivity
values of the obtained PEDOT are reported here under the effects
of oxidant concentration and type and concentration of surfactant.
PEDOT characterization was also carried out via Fourier transform
infrared (FTIR) spectroscopy and XRD to investigate the functional
groups and crystallography, respectively. In addition, TGA was

Correspondence to: Anuvat Sirivat, Conductive and Electroactive Polymer

ResearchUnit,PetroleumandPetrochemicalCollege,ChulalongkornUniversity,
Bangkok, 10330 Thailand. E-mail: anuvat.s@chula.ac.th
Conductive and Electroactive Polymer Research Unit, Petroleum and
Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand

www.soci.org

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Synthesis of PEDOT nanoparticles

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used to investigate the thermal properties and stability of PEDOT

as a function of aging time.

were converted to the electrical conductivity of PEDOT using the

following equation:
=

EXPERIMENTAL
Materials
3,4-Ethylenedioxythiophene (EDOT) was used as the monomer
and DBSA, a sodium salt, and sodium dodecylsulfate (SDS) as
the surfactants (purchased from Sigma-Aldrich). The oxidant,
ammonium peroxydisulfate (APS; AR grade), was purchased from
Qrec. Acetone and methanol were purchased from Labscan.
Distilled water was used as the solvent.
Synthesis of PEDOT nanoparticles
Nanoparticles of PEDOT were prepared by dropping 1.6 mL of EDOT
into 100 mL of APS solution, and the solution was stirred for 72 h.14
To study the effects of the type and concentration of surfactant, 100
mL of surfactant solution was prepared by stirring the surfactant
in distilled water for 2 h. Then 1.6 mL of EDOT was added dropwise
into the surfactant solution, and then the solution was stirred for
2 h before adding APS.3,10 The solution was then stirred for 72 h.
During this time, the mixture solution colour changed from yellow
to green and then blue to dark blue. The product in the solution was
centrifuged and washed with an acetone and methanol solution
(acetone/methanol = 3:20).14 Finally the polymer product was
dried in a vacuum oven at 60 C for 24 h.

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(1)

where is the specific conductivity (S cm1 ), is the specific resistivity ( cm), Rs is the sheet resistivity (), I is the
measured current (A), K is the geometric correction factor
(3.22 103 ), V is the applied voltage (V) and t is the pellet
thickness (cm).

RESULTS AND DISCUSSION

Structural characterization of PEDOT nanoparticles
FTIR analysis
The structures of PEDOT obtained using different synthesis
conditions were investigated using FTIR spectroscopy. The peaks
at 1520 and 1360 cm1 originate from the CC or C C stretching
of the quinoidal structure of the thiophene ring and the stretching
of the thiophene ring, respectively. The peaks at 1206, 1143 and
1099 cm1 correspond to the stretching vibration of the COC
bond in the ethylenedioxy group. The bands of the CS bond
in the thiophene ring are seen at 982, 845 and 693 cm1 . The
absorption peak at 1650 cm1 indicates the doping level of the
polymer; this peak shifts to a lower wavelength due to the overoxidant side reaction. The PEDOT particles, as obtained when using
a surfactant, show smaller peaks at 2800 to 3000 cm1 which can
be assigned to the aliphatic CH stretching mode depending on
the long alkyl tail of the surfactant.4,9,10
XRD patterns
XRD patterns of PEDOT particles obtained using various APS
concentrations with and without surfactant are shown in Figs 1(a)
and (b), respectively. PEDOT nanoparticle diffraction peaks appear
at 2 = 6.6 , 12.6 and 17.5 , which can be referred to a
structurally similar system where the interchain packing is along
a pseudo-orthorhombic a axis, while the diffraction peak at 2
= 25.7 can be referred to as the interchain planar ring-stacking
distance.15 Figure 1(a) shows that the intensity of the peaks
at 6.6 and 12.6 increases, and the peak at 25.7 shifts to
higher angle as the APS concentration changes from 0.15 to
0.30 mol L1 . This phenomenon suggests that increasing the
doping level with increasing APS concentration induces a higher
order in the PEDOT nanoparticle structure.2,10,11 When the APS
concentration is 0.45 mol L1 , it is in the over-oxidation state,
and the intensity of the peaks at 6.6 and 12.6 decreases.
Furthermore, the intensity of the diffraction peak at 17.5 increases
with increasing APS concentration; this can be ascribed to
the change in PEDOT particle shapes: irregular, raspberry and
coralliform.
Figure 1(b) shows the effect of DBSA and SDS surfactants
on the PEDOT structure. The intensity of the peaks at 6.6 and
12.6 decreases, and the peak at 25.7 shifts to a lower angle
with addition of surfactants. This indicates that the degree of
crystallinity decreases after adding the surfactants. The diffraction
peak of PEDOT synthesized using SDS is sharper than that of
PEDOT synthesized using DBSA. This is because the DBSA consists
of a bulky benzene ring structure leading to a more amorphous
structure for PEDOT.12,16,17

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107

Characterization of PEDOT nanoparticles

A FTIR spectrometer (Thermo Nicolet, Nexus670) was used to
identify the PEDOT nanoparticle functional groups. Samples were
prepared using the KBr pellet technique, with KBr as the background material. The spectrometer was operated in absorption
mode with spectra being obtained with 32 scans with a resolution
of 4 cm1 covering the wavenumber range 4004000 cm1 .
A wide-angle X-ray diffractometer (Bruker AXS, D8 Advance) was
used to determine the crystalline structure of the nanoparticles.
The Cu K radiation source was operated at 40 kV/30 mA. The
interference peak was eliminated by a K-beta filter. Divergence
slit and scattering slit of 0.5 together with a 0.3 mm receiving
slit were used. The nanoparticles were mounted on a sample
holder and a measurement was continuously run. The experiment
was run by monitoring the diffraction pattern appearing in the
2 range of 5 to 40 , with a scan speed of 1 min1 and a scan
step of 0.02 .
The thermal behaviour of the nanoparticles was investigated
using a thermogravimetric analyser (PerkinElmer, TGA7). Samples,
which weighed 5 to 10 mg, were loaded into an aluminium pan.
The mass change was scanned from 30 to 900 C at a heating rate
of 10 C min1 , under nitrogen flow.
The morphology of the nanoparticles was studied using SEM
(Hitachi, S4800). Samples were placed on the holder with adhesive
tape and coated with a thin layer of platinum. SEM images were
obtained using an acceleration voltage of 5 kV with magnification
in the range 25 to 200 000.
Electrical conductivity was measured using a two-point probe
(Keithley, model 8009). These probes were connected to a source
meter (Keithley, model 6517A) which provided the applied voltage
and the resultant current was recorded. The applied voltage was
plotted as a function of the current to determine the linear ohmic
regime for each sample based on the van der Pauw method. The
applied voltage and the current change in the linear ohmic regime

1
I
1
=
=

Rs t
K V t

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N Paradee, A Sirivat

Figure 1. XRD patterns of PEDOT nanoparticles: (a) various APS concentrations; (b) various types of surfactant.

Morphology
The SEM images in Figs 2, 3 and 4 show different PEDOT particle
sizes and shapes depending on the polymerization conditions.
Figure 2 shows the morphology of the PEDOT particles under
the effect of APS concentration without a surfactant. The particle
size varies from 70 to 212 nm and the shape changes from
irregular (Fig. 2(a)), to raspberry agglomerate (Fig. 2(b)), and to
coralliform (Fig. 2(c)). Thus, the particle size decreases and the
particle shape changes from irregular to coralliform with increasing
APS concentration. APS acts as oxidant and initiator, as shown in
Fig. 5, creating an EDOT cation radical in the first step. Then,
the PEDOT polymeric chain is generated from the EDOT cation
radicals to become a protonated dimer which subsequently gets
deprotonated. Finally, the PEDOT polymer is doped by sulfate ion
residues in which they can act as a counter ion.4,18,19 Because APS is
an initiator, the APS concentration affects the polymerization rate
and amount of PEDOT polymeric cation radicals in the first step.
A larger amount of PEDOT polymeric cation radicals can generate
a greater electro-repulsive force between the PEDOT polymeric
cation radicals during the polymerization in the second step. The
greater electro-repulsive force between PEDOT polymeric cation
radicals and the faster rate of polymerization lead to a smaller
particle size because there are more active sites of the EDOT cations.
On the other hand, a greater APS concentration can simultaneously
increase the amount of sulfate counter anions, which in turn
screens the electro-repulsive force between PEDOT polymeric
cations, the so-called screening effect of the electro-repulsive force.
This causes particle agglomeration resulting in a larger particle size.
At an APS concentration lower than 0.30 mol L1 , the largest PEDOT
particle size (ca 212 nm) is obtained with particles of irregular
shape (Fig. 2(a)). This is because a lower APS concentration creates

a smaller amount of PEDOT polymeric cation chains, a weaker

electro-repulsive force between the PEDOT polymeric cations and
a lower polymerization rate, thus leading to a larger PEDOT particle
size. At an APS concentration of 0.30 mol L1 , the PEDOT particle
size is the smallest (ca 70 nm), appearing as a raspberry shape,
as shown in Fig. 2(b). Thus, it appears that this amount of APS is
suitable for balancing the number of polymeric cation chains and
the electro-repulsive force to yield the smallest PEDOT particle
size. Nevertheless, the smallest PEDOT particles can easily become
agglomerated and create a larger particle size as in the raspberry
agglomerate. For higher APS concentrations (higher than 0.30
mol L1 ), the electro-repulsive force between PEDOT polymeric
cations is screened by sulfate anions as the counter ion, inducing
the fusion of the polymerizing PEDOT particles, and eventually
transforming them to the coralliform shape, as shown in Fig. 2(c).
The particle size under the effect of DBSA concentration varies
from 63 to 396 nm and the particle shape changes from the orangepeel shape (Fig. 3(a)), to the raspberry agglomerate (Fig. 3(b)) and
to the fused globular agglomerate (Fig. 3(c)) at 0.25 102 , 0.05
and 0.10 mol L1 DBSA concentration, respectively. At 0.25 102
mol L1 DBSA concentration, the particles are the largest (ca 396
nm) appearing as the orange-peel shape, as shown in Fig. 3(a). This
DBSA concentration is lower than the critical micelle concentration
(CMC, which is 0.29 102 mol L1 ), and there are no micelles
formed during polymerization. Above the CMC, the increase in
surfactant concentration produces more micelles.3,20,21 Figure 3(b)
shows the smallest particle size (ca 63 nm) as the raspberry agglomerate shape as obtained from 0.05 mol L1 DBSA concentration.
At a concentration greater than the CMC, polymerization occurs
within the micelle core, causing smaller PEDOT particles.22 On
the other hand, with a further increase in DBSA concentration to

108

Figure 2. Morphologies of PEDOT nanoparticles prepared using various APS concentrations: (a) 0.15 mol L1 ; (b) 0.30 mol L1 ; (c) 0.45 mol L1 .

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Figure 3. Morphologies of PEDOT nanoparticles prepared using various DBSA concentrations: (a) 0.25 102 mol L1 ; (b) 0.05 mol L1 ; (c) 0.10 mol L1 .

Figure 4. Morphologies of PEDOT nanoparticles prepared using various SDS concentrations: (a) 0.25 102 mol L1 ; (b) 0.25 101 mol L1 ; (c) 0.05
mol L1 ; (d) 0.10 mol L1 .

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these PEDOT plum particle sizes are approximately the same as

the SDS concentration increases from 0.25 101 to 0.10 mol L1 ,
because unilamellar vesicle micelle formation is limited at these
surfactant concentrations.
Electrical conductivity
The electrical conductivity increases and the particle size decreases
with increasing APS concentration up to 0.30 mol L1 , where the
smallest particle size and the highest electrical conductivity are
obtained (Fig. 6). The smallest particle size corresponds to the
highest surface area for electron transfer; this concentration also
corresponds to the optimized doping level along with the highest
electrical conductivity.4 At APS concentrations above 0.30 mol L1 ,
the electrical conductivity decreases and the particle size increases
with increasing APS concentration. There are two reasons for
the decrease in electrical conductivity: (i) aggregation of PEDOT
particles occurs, changing the particle shape into the coralliform,
which provides a lower surface area for electron transfer due to
greater free space, thus reducing electron mobility; and (ii) overoxidation occurs due to excessive APS concentrations, resulting in
lower electrical conductivity, as confirmed by the FTIR spectrum4,10
and the XRD pattern.10,11

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109

0.10 mol L1 , an agglomeration of PEDOT particles occurs as the

micelles undergo micelle fusion, resulting in larger PEDOT particle
sizes in the globular agglomerate shape,21 as shown in Fig. 3(c).
The particle size of the PEDOT particles under the effect of SDS
concentration varies between 147 and 938 nm and the particle
shape changes from a globular shape (Fig. 4(a)) to various plum
shapes (Figs 4(b)(d)) at 0.25 102 , 0.25 101 , 0.05 and 0.10
mol L1 SDS concentrations, respectively. Normally, the presence
of SDS can lead to micelles in a unilamellar vesicle form, consisting
of closed lamellar bilayers. The packing parameter, V H /lc a0 , is
close to 1 (V H is the volume occupied by the hydrophobic groups
in the micellar core, lc is the length of the hydrophobic groups
in the core and a0 is the cross-sectional area occupied by the
hydrophilic groups). There are critical geometric and flexibility
requirements for their formation.21 At 0.25 102 mol L1 SDS
concentration, it is not possible to create a unilamellar vesicle
micelle, even though the concentration is above the CMC. Due
to the lack of unilamellar vesicle micelles, the PEDOT particle size
is larger appearing in the globular form (Fig. 4(a)). With a further
increase in SDS concentration from 0.25 101 to 0.10 mol L1 ,
the PEDOT particles form a larger particle agglomerate (ca 896 to
938 nm) in the plum shape, as shown in Figs 4(b)(d). However,

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N Paradee, A Sirivat

Figure 5. Proposed polymerization mechanism of PEDOT: (1) EDOT as a monomer is oxidized by APS to a cation radical; (2) EDOT cation radicals form
dimers that subsequently get deprotonated; and (3) PEDOT polymer is doped and sulfate ion acts as counter ion.18

Figure 6. Electrical conductivity and particle size of PEDOT nanoparticles

as a function of APS concentration.

110

Table 1 compares the PEDOT particle sizes, particle shapes and

electrical conductivity with and without DBSA and SDS surfactants.
The results without the surfactants are shown in Fig. 6. PEDOT
was synthesized at various APS concentrations, APS acting as the
oxidant. The molar ratio between the monomer (EDOT) and oxidant (APS) without surfactant (1:1 to 1:4 molar ratio) was varied by
increasing the APS concentration. The particle size decreases with
increasing APS concentration (decreasing molar ratio) until the APS

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concentration reaches 0.30 mol L1 (1:2 molar ratio) resulting in

the smallest particle size of 70 nm. APS acts more as an initiator and
oxidant in the polymerization process.13,14 At an APS concentration
higher than 0.30 mol L1 , the particle size becomes larger in the
coralliform shape due to the screening effect from the counter ions
(sulfate anions). Electrical conductivity increases with increasing
APS concentration (0.15 to 0.30 mol L1 ) until it reaches the highest
value of 153 S cm1 at 0.30 mol L1 APS concentration. The smaller
particle size corresponds to the highest surface area for electrons
to transfer4 and the highest doping level due to the amount of APS
dopant used.14,23 As the APS concentration is increased to greater
than 0.30 mol L1 , the electrical conductivity decreases because
the PEDOT particle shape changes to a corralliform shape and overoxidation occurs for this greater APS concentration. The optimal
APS concentration is 0.30 mol L1 (1:2 molar ratio) and was further
investigated.
DBSA and SDS were used to study the effect of surfactant
concentration, reported in terms of molar ratio between the
monomer (EDOT) and surfactant, as shown in Table 1. The PEDOT
particle size at 0.25 102 mol L1 DBSA concentration is
the largest (ca 396 nm) in the orange-peel shape because this
DBSA concentration is lower than the CMC. Above the CMC, the
PEDOT particle size decreases with increasing DBSA concentration
(decreasing molar ratio) up to 0.05 mol L1 DBSA (3:1 molar ratio),
where the PEDOT particle size is the smallest. The smaller PEDOT
particles are polymerized within the micelle cores.22 When the

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Table 1. Comparison of particle size, particle shape and electrical conductivity of PEDOT obtained under various synthesis conditions
Synthesis method

Particle size (nm)

Chemical oxidation
polymerization

Emulsion polymerization
(DBSA as surfactant)

212 72
179 65
85 26
70 19
85 25
108 37
125 40
396 140

Irregular
Irregular agglomerate
Irregular
Raspberry agglomerate
Irregular
Coralliform
Coralliform
Orange-peel

7.65 1.00
21.16 4.57
51.53 7.59
153.72 6.52
25.44 2.03
11.49 5.75
0.29 0.67
3.96 104 0.03

Globular

3.73 102 0.08

63 14
90 25
118 37
146 50
147 37

Raspberry agglomerate
Semi-fused globular agglomerate
Fused globular agglomerate
Fused globular agglomerate
Globular

4.85 102 0.02

1.31 102 0.02
7.27 103 0.08
2.23 103 0.01
4.29 102 0.04

920 385

Plum

4.72 103 0.02

896 229
938 223

3560
60120
3040
5060
80100

Plum
Plum

Spherical
Spherical
Irregular
Irregular
Irregular

5.22 102 0.07

1.52 102 0.06
4.30
1.80
5.00 103
0.50
5.07 102
<1.00
50.00
33.70
28.30
16.70

96 26

Emulsion polymerization
(SDS as surfactant)

Chemical oxidation
polymerization13

Emulsion
polymerization3,10
Reverse micelle
polymerization2

Electrical conductivity (S cm1 )

Shape

Remarksa
EDOT:APS = 1:1 (0.15 mol L1 APS)
EDOT:APS = 1:1.5 (0.23 mol L1 APS)
EDOT:APS = 1:1.75 (0.26 mol L1 APS)
EDOT:APS = 1:2 (0.30 mol L1 APS)
EDOT:APS = 1:2.5 (0.38 mol L1 APS)
EDOT:APS = 1:3 (0.45 mol L1 APS)
EDOT:APS = 1:4 (0.60 mol L1 APS)
EDOT:DBSA = 3:0.05 (0.25 102 mol
L1 DBSA)
EDOT:DBSA = 3:0.50 (0.25 101 mol
L1 DBSA)
EDOT:DBSA = 3:1 (0.05 mol L1 DBSA)
EDOT:DBSA = 3:2 (0.10 mol L1 DBSA)
EDOT:DBSA = 3:3 (0.15 mol L1 DBSA)
EDOT:DBSA = 3:5 (0.25 mol L1 DBSA)
EDOT:SDS = 3:0.05 (0.25 102 mol
L1 SDS)
EDOT:SDS = 3:0.50 (0.25 101 mol
L1 SDS)
EDOT:SDS = 3:1 (0.05 mol L1 SDS)
EDOT:SDS = 3:2 (0.10 mol L1 SDS)
FeCl3 as oxidant, 25 C
FeCl3 as oxidant, 50 C
FeCl3 as oxidant, 95 C
Ce(SO4 )2 as oxidant, 25 C
(NH4 )2 Ce(NO3 )6 as oxidant, 25 C
DBSAAPS as surfactantoxidant
DBSAFeCl3 as surfactantoxidant
FeCl3 toluenesulfonic acid as oxidant
FeCl3 toluenesulfonic acid as oxidant
FeCl3 toluenesulfonic acid as oxidant

Ratios given are molar ratios.

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The PEDOT particle size when the reaction is carried out without
a surfactant is the smallest because surfactant molecules can form
micelles during polymerization allowing larger PEDOT particle
sizes and a more globular shape. However, the smaller PEDOT
particles obtained without a surfactant can still undergo particle
aggregation. Electrical conductivity of PEDOT particles formed
without a surfactant is highest because the structure of the
surfactant consists of an aliphatic chain, which cannot effectively
transfer electrons resulting in lower electrical conductivity.21 The
particle size when using SDS is larger than when using DBSA
because SDS can form unilamellar vesicles leading to a larger
particle size.21 Generally, the surfactant concentration significantly
affects the particle shape. The micellar shape changes from a
sphere to cylinder, to hexagonal, and to lamellar structures with
increasing surfactant concentration.24 Electrical conductivity, with
SDS as a surfactant, is higher than when using DBSA. The surfactant
leads to the incorporation of the dopant anion, which is the
dodecylbenzenesulfate anion of DBSA and the dodecylsulfate
anion of SDS, onto the PEDOT backbones. The DBSA dopant
consists of a bulky benzene ring which contributes to a steric
barrier for electron transfer in the PEDOT chain resulting in lower
electrical conductivity.25
Corradi and Armes13 synthesized PEDOT particles via chemical
oxidation polymerization. FeCl3 , Ce(SO4 )2 and (NH4 )2 Ce(NO3 )6
were used as oxidants and the effect of temperature was

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111

DBSA concentration is higher than 0.05 mol L1 (3:1 molar ratio),

the particle size increases with increasing DBSA concentration due
to micelle fusion and the permissible connection between the
PEDOT particles.21 When SDS acts as a surfactant, it can create
unilamellar vesicle micelles for the polymerization with the areas
of the tail groups facing each other, and eventually a plum shape
is created21 at SDS concentration higher than 0.25 101 mol L1
(3:0.05 molar ratio). At 0.25 102 mol L1 SDS concentration,
the smallest particle size results in a globular shape because the
SDS content is not sufficient to form unilamellar vesicle micelles.
Electrical conductivity increases with increasing surfactant
concentration until the electrical conductivity approaches the
highest value of 4.85 102 and 5.22 102 S cm1 at 0.05
mol L1 DBSA and SDS, respectively, due to the greater surface area
of the particles. In addition, both surfactants also act as dopants,
which can be correlated with the increase in the doping level
with increasing surfactant concentration.24,25 In contrast, electrical
conductivity decreases with increasing surfactant concentrations
higher than 0.05 mol L1 because of the lower surface area for
electrons to transfer due to larger particle sizes. One reason for
the decrease in electrical conductivity with increasing surfactant
content is the self-screening on polymerizing and the doping
process via excessive dodecylbenzenesulfate anions of DBSA and
dodecylsulfate anions of SDS.24,25

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investigated. At 25 C, using FeCl3 as an oxidant gave the
highest electrical conductivity compared to using Ce(SO4 )2 and
(NH4 )2 Ce(NO3 )6 . Thus the electrical conductivity significantly
depended on the type of anion in the oxidant structure acting as
a dopant. When using FeCl3 as an oxidant, electrical conductivity
decreased with increasing temperature because the increasing
polymerization rate led to more aggregation of the PEDOT
particles, resulting in decreased electrical conductivity. Oh and
Im3 and Choi et al.10 studied PEDOT synthesis using DBSA
as a surfactant, and APS and FeCl3 as oxidants. The PEDOT
particles showed a spherical shape with sizes of 3060 nm
and 6090 nm and electrical conductivity values <1.00 and
50.00 S cm1 for APS and FeCl3 , respectively. It was claimed
that, because different complexes of oxidantanionic surfactant
formed, electrical conductivity was strongly affected. The existence
of a complex between the oxidant and the anionic surfactant
(FeCl3 DBSA) in aqueous solution caused an insoluble complex
between the iron(III) species and dodecylbenzenesulfonate anion
which contributed to a greater attractive force and a higher doping
level on the PEDOT particles. Huajing et al.2 synthesized PEDOT
particles using various amounts of FeCl3 toluenesulfonic acid as
the oxidant. An irregular shape of PEDOT particles was obtained
and the particle size varied between 30 and 100 nm. Electrical
conductivity decreased with increasing PEDOT particle size. They
explained that the increase of toluenesulfonic acid concentration
could promote the ordering of the PEDOT particle monocubic
chain and hence lead to smaller particles.
We can observe from the results in Table 1 that electrical
conductivity increases with decreasing particle size. This
phenomenon can be explained by the quantum size effect.2
The particle size and shape of synthesized PEDOT significantly
depend on the synthesis conditions: oxidant type and
concentration, surfactant type and concentration, and synthesis
temperature.
Thermal stability of PEDOT nanoparticles
The thermal stability of the PEDOT particles was investigated
using TGA to give the onset decomposition temperature (T d,onset )
of PEDOT particles as shown in Fig. 7. The data indicate that
T d,onset decreases with decreasing particle size because a smaller
particle size has a higher surface area for heat transfer resulting in
more efficient material decomposition.26 T d,onset with a surfactant
is lower than without a surfactant because the decomposition
temperature of the surfactant is lower than that of the PEDOT
polymer.10,27 T d,onset with SDS as the surfactant is lower than that
with DBSA as the surfactant. This is because the amount of carbon
in the SDS structure is less than that in the DBSA structure, and
the decomposition temperature of SDS is lower than that of DBSA.
The char yield of the PEDOT particles is consistent with the T d,onset
data (Table 2). The char yield increases with decreasing T d,onset
because the lower T d,onset provides much more time for particle
decomposition and char formation.26 However, the char yield
when using SDS as the surfactant is lower than that when using
DBSA because of the lower T d,onset , and amount of carbon in the
SDS structure.

112

PEDOT stability (aging property)

PEDOT particles were studied for the effect of aging time reported
in terms of electrical conductivity. Figure 8 shows the electrical
conductivity of PEDOT particles synthesized using 0.30 mol L1
APS concentration without a surfactant. The electrical conductivity

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N Paradee, A Sirivat

Figure 7. Onset decomposition temperature of PEDOT nanoparticles as a

function of particle size.

Table 2. Char yield of PEDOT nanoparticles

PEDOT synthesis
conditionsa
No surfactant
EDOT:APS = 1:1
EDOT:APS = 1:1.5
EDOT:APS = 1:1.75
EDOT:APS = 1:2
EDOT:APS = 1:2.5
EDOT:APS = 1:3
EDOT:APS = 1:4
Surfactant addition
EDOT:DBSA = 3:0.05
EDOT:DBSA = 3:0.50
EDOT:DBSA = 3:1
EDOT:DBSA = 3:2
EDOT:DBSA = 3:3
EDOT:DBSA = 3:5
Surfactant addition
EDOT:SDS = 3:0.05
EDOT:SDS = 3:0.50
EDOT:SDS = 3:1
EDOT:SDS = 3:2
a

Particle
size (nm)

T d,onset ( C)

Char yield (%)

212 72
179 65
85 26
70 19
85 25
108 37
125 40

291.06 7.85
279.35 4.92
203.67 12.26
182.88 2.99
197.34 6.90
188.80 12.33
269.33 12.36

16.45 1.11
17.27 0.56
19.70 0.78
25.50 0.63
20.38 0.87
18.79 2.43
17.42 2.16

396 140
96 26
63 14
90 25
118 37
146 50

216.10 7.39
187.05 4.01
170.56 7.53
188.36 2.40
182.74 8.64
190.96 3.60

13.21 2.05
22.69 1.66
32.55 2.53
32.57 0.67
28.60 2.60
20.15 1.59

147 37
920 385
896 229
938 223

166.21 5.48
171.14 9.02
176.81 5.77
177.37 2.79

10.36 2.72
18.02 2.40
16.64 1.09
14.06 0.75

Ratios given are molar ratios.

increases to a maximum when PEDOT particles are kept at room

temperature for 14 days and at 50% relative humidity. The electrical
conductivity also remains approximately constant after 14 days.
This is because the PEDOT particles can absorb moisture from
the air creating a pathway for proton hopping through the
water channel. The phenomenon of moisture absorption by the
PEDOT particles can be confirmed using TGA, which shows the
decomposition of water at 80 to 100 C (Fig. 9). The weight (%) at
a temperature of ca 100 C decreases with increasing aging time.
This implies an increase in the water absorption of the PEDOT
particles with aging time.

CONCLUSIONS
This work focused on the tailor-made PEDOT shape and
property relationship under various synthesis conditions. PEDOT

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Polym Int 2014; 63: 106113

Synthesis of PEDOT nanoparticles

www.soci.org
the PEDOT polymerization reaction. Synthesis with SDS provides
a plum shape which is directly determined by the SDS micellar
shape. The plum-shape of the PEDOT particles is a porous-like
cage which can accommodate structural modifications for many
applications such as controlled drug release.

ACKNOWLEDGEMENTS
The authors are grateful for the financial support provided by
the Thailand Research Fund (TRF-RTA, RGJ PHD/0285/2551), the
Conductive and Electroactive Polymer Research Unit, the Royal
Thai Government and the Petroleum and Petrochemical College
of Chulalongkorn University.

REFERENCES
Figure 8. Electrical conductivity of PEDOT nanoparticles as a function of
aging time.

Figure 9. Weight loss of PEDOT nanoparticles over time.

nanoparticles were synthesized via the chemical oxidation

polymerization of EDOT using APS as the oxidant, with and without
a surfactant. DBSA and SDS were chosen as the surfactants at
various concentrations. The PEDOT particle size varies between
60 and 900 nm, the particles having various shapes: irregular,
raspberry agglomerate, coralliform, orange-peel, globular and
plum shapes. In addition, the electrical conductivity varies between
<1.00 and 153.72 S cm1 , depending on the polymerization
conditions. The PEDOT nanoparticles synthesized without a
surfactant show the smallest particle size and the highest electrical
conductivity. The presence of the surfactants was shown to affect
the particle shape because the surfactants can form different
micellar shapes depending on the type of surfactant: DBSA leads
to spherical micelles while SDS leads to unilamellar vesicles during

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