Journal of ELECTRONIC MATERIALS, Vol. 42, No.

12, 2013

DOI: 10.1007/s11664-013-2816-4
 2013 TMS

Modification of Novel Conductive PEDOT:Sulfonated Polyimide

Nano-Thin Films by Anionic Surfactant and Poly(vinyl alcohol)
for Electronic Applications
NATHAVAT ROMYEN,1 SUPAKANOK THONGYAI,1,3
PIYASAN PRASERTHDAM,1 and GREGORY A. SOTZING2
1.Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of
Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330,
Thailand. 2.Department of Chemistry and the Polymer Program, University of Connecticut, 97
North Eagleville Road U-3136, Storrs, CT 06269-3136, USA. 3.e-mail: tsupakan@chula.ac.th

Conductive poly(3,4-ethylenedioxythiophene):sulfonated polyimide (PEDOT:

SPI) nanoscale thin films were successfully developed by addition of anionic
surfactant and poly(vinyl alcohol) (PVA) for potential application in electronic
devices. In this work, sodium dodecyl sulfate (SDS) surfactant was introduced
into PEDOT:SPI aqueous suspensions to improve the dispersion stability of
the particles in water, leading to high transparency and low contact angle of
PEDOT:SPI thin films. All of the conducting polymer thin films showed high
transparency of more than 85% transmission. Conductivity enhancement and
good film-formation properties of PEDOT:SPI were achieved by adding various amounts of PVA to each polymer aqueous suspension because of the
resulting conformational changes. The highest conductivity of 0.134 S/cm was
achieved at 0.08 wt.% PVA in PEDOT:SPI2/SDS/PVA film, increased by a
factor of 3.5 compared with the original material. In addition, PVA also
improved the thermal stability of the conductive films, as verified by thermogravimetric analysis (TGA). The interactions between conducting polymers, PVA, and SDS surfactant affecting nano-thin film properties were
revealed and investigated. Moreover, the interactions between SDS and SPI
were proven to be different from those between SDS and poly(styrenesulfonate) (PSS) in conventional PEDOT:PSS solutions.
Key words: Conductive materials, polymer, thin films, anionic surfactant,
poly(vinyl alcohol)

INTRODUCTION
After the discovery of electrically conducting
polymers (CPs) in 1977, they have become an
interesting area in which huge efforts have been
invested to develop commercial products for various
applications, such as organic light-emitting diodes
(OLEDs),1 organic photovoltaic devices (OPVs),2
capacitors,3 and sensors4 due to their light weight,5
high conductivity, and electrochromic properties.6
One of the most successful CPs commercialized
(Received February 9, 2013; accepted September 23, 2013;
published online October 19, 2013)

worldwide is poly(3,4-ethylenedioxythiophene):poly
(styrenesulfonate) (PEDOT:PSS) due to its many
advantages, such as high conductivity,7 high stability in the p-doped form,8 good film-forming properties,9 easy processing,10 and excellent transparency
in the visible range.11 PEDOT:PSS is a polyelectrolyte complex formed during a polymerization reaction as a gel particle dispersed in water, consisting of
conductive PEDOT (polycation) and insulating PSS
(polyanion). The PEDOT joins the repeating units of
the PSS via ionic interaction, and cannot be separated by electrophoresis.12 The PSS segment in
PEDOT:PSS does not contribute to charge transport
directly but acts as a template to keep PEDOT in the
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3472

dispersed state; that is, the dissociated sulfonate

groups of PSS balance the charges of the cationic
PEDOT by forming a stable salt.13,14 However, integration of PSS into PEDOT represents a main factor
diminishing its conductivity due to distortion of the
PEDOT chain in PEDOT:PSS.15 In the polymerization step, excess PSS is nonstoichiometrically added
to stabilize soluble particles in solution and provides
film-forming properties. However, oxidizing agents
used for polymerization of EDOT in water such as
iron(III) nitrate and iron(III) chloride lead to precipitation of the PEDOT:PSS complex in the latest
stages of the reaction.16 This is due to the fact that
multivalent cations such as Fe(III) form a complex
with PSS and reduce the stability of the PEDOT:PSS
complex. Sulfonic acid groups of PSS can cause
swelling of films after the baking process because of
water absorption in air, resulting in change in film
thickness and mechanical properties.17 Furthermore, the strong acidity of PSS will oxidize the metal
to form a thin, poorly defined, insulating AlOx layer
when vacuum-deposited Al contacts are used on
PEDOT:PSS film.18,19 However, the strong acidity in
solution acts as an effective catalyst for EDOT polymerization, and it was also found that the highest
conductivity occurred at pH value between 0 and 3.20
In the absence of acid, oxidation of EDOT can result
in keto-functionalized side-products.21 PEDOT:PSS
is thermally stable up to 200C;22 however, annealing
beyond this temperature leads to an obvious decrease
in its conductivity.23 To maintain the quality of
PEDOT:PSS film, exposure to ultraviolet (UV) light
in ambient air under high relative humidity must be
avoided. Radiation at wavelengths below 320 nm,24
elevated temperature above 70C, as well as high
relative humidity in air will dramatically degrade the
film conductivity due to oxidation of PEDOT.25,26
Encapsulation of conducting film or addition of stabilizing agents will reduce the increase of resistivity
over time.24 Due to several problems with
PEDOT:PSS, including high acidity, easy water
uptake, UV-light-induced degradation, and varying
morphology, mainly resulting from the PSS segment,
there have been several studies focused on other
materials to replace it.27,28
Sulfonated polyimides (SPIs) are well known as
high-performance polymers, because of their excellent properties such as thermal stability surpassing
400C, mechanical properties, solution processability, and superior chemical resistance;29 therefore,
integration of sulfonated polyimide into PEDOT
(PEDOT:SPI) instead of the conventional PSS template (PEDOT:PSS) has been considered in order
to effectively solve some of the drawbacks of
PEDOT:PSS, especially to maintain the conductivity value at high annealing temperature.30 This
conductive polymer has the ability to extend use
into the area of high-temperature processing and
applications in the electronics industry. For wide
applications, use of an aqueous dispersion of conductive polymer that can be formed into nanoscale

Romyen, Thongyai, Praserthdam, and Sotzing

thin films with good conductivity, high transparency,

and excellent environmental stability is required.
Again, however, the lack of good dispersion of
PEDOT:SPI in aqueous solution because of the strong
interaction between PEDOT:SPI particles is the main
issue hindering nanoscale thin-film formation. In
addition, other important properties of PEDOT:SPI
film such as good thermal, mechanical, and morphologic properties are also needed for use in demanding
conditions. To achieve these crucial properties, the
concept of polymer blending to combine the desirable
properties of each pure component in the final product
has been considered. However, to date, PEDOT:SPI
has not been mixed with other polymers, in particular
poly(vinyl alcohol) (PVA), which is a polymer offering
many advantages such as wide commercial availability, excellent solubility in water with high transparency, good film formation, and good flexibility.31 Thus,
PVA becomes a suitable polymer to modify PEDOT:
SPI to achieve desirable properties.
Therefore, this research aims to investigate the
formation of PEDOT:SPI nanoscale thin films synthesized with the aid of an anionic surfactant and
the conventional spin-coating process, and also to
study the effects of PVA in the PVA/PEDOT:SPI
blend on the enhancement of various properties of
PEDOT:SPI for application as a conductive material
for electronic device applications. In addition, the
effects of different polyimide structures in
PEDOT:SPI on the thin-film properties have also
been investigated.
EXPERIMENTAL PROCEDURES
Materials
4,4-Oxydiphthalic anhydride (O-DPDA), triethylamine (Et3N), m-cresol, iron(III) p-toluenesulfonate
hexahydrate, 3,4-ethylenedioxythiophene (EDOT),
poly(vinyl alcohol) (PVA) (MW = 146,000 to 186,000),
and sodium dodecyl sulfate (SDS) were purchased
from Sigma-Aldrich. EDOT was distilled before
use. 4,4-Hexafluoroisopropylideneoxydiphthalic anhydride (6FDA) was purchased from TCI America. Concentrated sulfuric acid (95%), sodium hydroxide
(NaOH), and hydrochloric acid (HCl) were purchased
from Fisher Scientific and were used as received.
Surfynol 2502 surfactant was purchased from Air
Products, Inc. Ion-exchange resin DOWEX 50WX8
50100 mesh was purchased from Acros Organics.
Dialysis tubes [molecular weight cutoff (MWCO) =
3.5 kDa to 5 kDa] were purchased from Spectrum
Laboratories Inc. Sodium poly(styrenesulfonate) and
glass beads (50 lm to 100 lm) were purchased from
Polysciences, Inc.
Preparation of PEDOT:SPI Aqueous
Suspensions
Preparation of Sulfonated Polyimide (SPI) Films
To a 100-mL three-necked flask with a nitrogen
inlet and outlet were added 3.5 g (9.71 mmol) of

Modification of Novel Conductive PEDOT:Sulfonated Polyimide Nano-Thin Films by Anionic Surfactant

and Poly(vinyl alcohol) for Electronic Applications

4,4-diaminodiphenyl ether-2,2-disulfonic acid (4,4

ODADS) prepared according to the previously published procedure,16 50 mL of m-cresol, and 1.96 g
(19.42 mmol) of triethylamine. After the 4,4-ODADS
was completely dissolved, 3.01 g (9.71 mmol) of
O-DPDA (for PSI1) or 4.32 g (9.71 mmol) of 6FDA (for
SPI2) was added and the solution was stirred under
nitrogen atmosphere at room temperature for 72 h.
When the reactions were completed, the poly(amic
acid) solution was cast onto glass dishes and thermally treated at 70C and 150C for 1 h each, and at
250C for another 30 min in a temperature-controlled oven. After thermal curing, the SPI film in salt
form was obtained.
Ion Exchange of Sulfonated Polyimide Films
SPI film in salt form dissolved in deionized (DI)
water was changed to SPI in acid form by reaction
with an ion-exchange resin of strong acid type
(DOWEX 50WX8, cation exchange). The SPI in salt
form was stirred in DI water with the ion-exchange
resin for 3 h to convert it to the free acid form (H+). It
was then centrifuged to separate the ion-exchange
resin from the polyimide solution and evaporated at
100C to obtain the polyimide acid form as a template for conducting polymer polymerization.
Polymerization of PEDOT:SPI
The typical procedures for preparing PEDOT:SPI
dispersion are described as follows. First, 3.015 g of
SPI1 or 3.458 g of SPI2 was dissolved in 300 mL of
DI water, and then 0.3195 g (2.25 mmol) of EDOT
was added. The suspensions were continuously
stirred for 2 h, and then 1.626 g (2.4 mmol) of
iron(III) p-toluenesulfonate hexahydrate was added
for polymerization. The reaction mixtures were
stirred vigorously for 5 days at room temperature,
leading to a dark-blue dispersion of PEDOT:SPI.

3473

of spin-coating at fixed spin speed of 4000 rpm for

60 s, resulting in film thicknesses ranging from
80 nm to 340 nm. Glass slides were sonicated in
soap water, DI water, acetone, and isopropyl alcohol
(IPA) for 15 min in each solvent sequentially before
use as substrates. The thin films were thermally
treated on a hotplate at 70C for 1 h and then kept
in a dark desiccator for future characterization.
Characterizations
Thermogravimetric analysis (TGA) was performed
using a PerkinElmer TGA 7 series analysis system at
a heating rate of 20C/min under air at a flow rate of
60 mL/min. Conductivities were measured using a
four-line collinear array utilizing a Keithley Instruments 224 constant current source and a 2700 multimeter. The CPs coated on glass substrates were
placed on the device which has four gold-coated leads
on the surface across the entire width of the polymer,
located 0.25 cm apart. The current was applied
across the outer leads, and the voltage was measured
across the inner leads. Transmittance values at
550 nm were measured using a Varian Cary 5000
UVVis-near infrared (NIR) spectrophotometer.
Polymer film images were obtained using a Nikon
Metaphot metallurgical microscope at magnification
in the range from 259 to 10009. The contact angle of
conducting films was measured by a rame-hart
model 100 goniometer by measuring the static contact angle of a liquid droplet on a solid surface (with 0
being defined as absolute wetting and 180 as completely nonwetting). PEDOT:SPI particles were imaged using JEOL 2010 Fas and Philips EM420
transmission electron microscopes. Atomic force
microscopy (AFM) images of conductive films were
obtained using a scanning probe microscope (Veeco
model MMAFMLN, 1959EX, operated in tapping
mode).
RESULTS AND DISCUSSION

Fabrication of PEDOT:SPI Nanoscale Thin

Films on Glass Substrates
The dark-blue PEDOT:SPI dispersed in aqueous
solution was centrifuged at 500 rpm for 3 min to
separate agglomerated particles from the suspension. After that, SDS surfactant was added to the
residual suspension with ratio of PEDOT:SPI to
surfactant of 1:2 by weight, and subsequently sonicated for 3 h and then transferred into a rotary
evaporator at 40C for partial water evaporation to
obtain a high concentration and good dispersion of
PEDOT:SPI in aqueous solution. Surfynol was
added to the highly concentrated PEDOT:SPI
aqueous suspensions at a ratio of PEDOT:SPI to
Surfynol of 5 mL:1 lL to reduce its surface tension. Various amounts of PVA were then added to
the PEDOT:SPI aqueous suspensions to obtain
0.05 wt.% to 1.0 wt.% of PVA. PVA/PEDOT:SPI
films with different PVA weight fractions were
deposited on dried, clean glass substrates by means

The main issue of this research is to address the

precipitation of PEDOT:SPI particles in aqueous
solution, which prevents the formation of a conductive thin film. SDS surfactant was mainly used
to stabilize the conductive particles and to enhance
the film wettability. It also had a side benefit of
providing better film conductivity compared with
other surfactants;15,32 however, its amount was
fixed at the ratio of PEDOT:SPI to SDS of 1:2 by
weight, which is the initial point for complete stabilization of the PEDOT:SPI particles without precipitating to the bottom of the vial. If the amount of
SDS exceeds this point, residual surfactant can not
only lead to rough conductive film but also diminishes the film conductivity because it penetrates
between the PEDOT:SPI particles, obstructing
charge transfer. Moreover, Surfynol offered the
benefit of reducing the formation of bubbles in
PEDOT:SPI during preparation and making a
smoother film than when using SDS alone as well;

3474

Romyen, Thongyai, Praserthdam, and Sotzing

however, the small amount used does not have a

significant effect on the film conductivity. Both the
SDS and Surfynol additives remain totally in the
fully processed thin film because the thin film was
thermally cured at low temperature. In addition,
PVA was used with the aim of forming nanoconductive thin films and to improve various conductive
properties of the PEDOT:SPI film for electronic
applications.
Dispersion State of PEDOT:SPI
In this work, the role of the SDS surfactant is to
improve the dispersion stability of the PEDOT:SPI
particles after completing the polymerization step.
Otherwise, they have a tendency to agglomerate into
large particles in a short time, finally leading to an
inability to form a conductive film on the glass substrate during spin-coating. This effect is due to the
weak electrostatic repulsion between the sulfonated
polyimide molecules. The chemical structure of
both PEDOT:SPI materials is shown in Fig. 1. The
transmission electron microscopy (TEM) images in
Fig. 2 show the individual particles of each PEDOT:
SPI material to be about 70 nm in size. Without the
SDS surfactant, however, their dispersion in water
was observed to be unstable. It was found that a
suitable ratio of PEDOT:SPI to SDS surfactant to
prevent PEDOT:SPI precipitation was 1:2 by
weight. Good dispersion stability of PEDOT:SPI in
water with SDS surfactant was retained even after
2 months, as shown in Fig. 3. This phenomenon
is totally different from the addition of SDS to
PEDOT:PSS as reported in Ref. 15, in which a less
stable solution was found, lasting for just 1 week
after addition of SDS surfactant to PEDOT:PSS
aqueous solution. This evidence clearly indicates
that the mechanism of interaction between SDS
surfactant and PEDOT:PSS is completely different
from that of PEDOT:SPI. In the case of PEDOT:
PSS, the SDS surfactant supplied counteranions to
PEDOT, resulting in conformational changes and
eventually to precipitation of the PEDOT:PSS particles. In the case of PEDOT:SPI, the stability might
be due to electrostatic repulsion between the
PEDOT:SPI particles stemming from enclosure of
PEDOT:SPI by the SDS surfactant.
Film Conductivities
The results presented in Fig. 4 show that, in the
case of PEDOT:SPI2, the conductivity gradually
increased from the starting material (0.038 S/cm) to
reach a highest value of 0.134 S/cm at 0.08 wt.%
PVA, because of the rearrangement of the morphology with PVA. When PVA was added to PEDOT:SPI,
the OH groups of PVA might bond by strong covalent
bonding to the SO3 of SPI.33 This might lead to
interactions among the PEDOT:SPI chains in which
PVA could act as a connector linking the PEDOT:SPI
chains together to improve the connection network
between the polymer chains. This phenomenon

Fig. 1. Molecular structures of PEDOT:SPI1 and PEDOT:SPI2.

could reduce the distance (gap) between the PEDOT:

SPI chains, causing the PEDOT chains to approach
one another. Therefore, charge transport from one
PEDOT chain to another was improved, which
eventually contributed to the increase in the conductivity of the film. The change in the film morphology with PVA is also seen in the AFM images in
Fig. 5. The PEDOT:SPI (without PVA) clusters were
separately dispersed throughout the film, as shown
in Fig. 5a, whereas connection of the PEDOT:SPI
particles to form conductive bridges after addition of
PVA can be observed in Fig. 5b. This change in the
morphology may imply a role of PVA in the conductivity enhancement, regardless of difference domain
in micron scale found in microscope picture. After
the concentration of PVA exceeded this optimum
point, the conductivity continuously decreased
because the insulative behavior of PVA had a greater
influence as more PVA was added to the polymer
suspension. Furthermore, since the OH group of
PVA can bond by strong covalent bonding to SO3
groups of SPI, which reduces some of the negative
charge of the CPs, higher PVA concentration in the

Modification of Novel Conductive PEDOT:Sulfonated Polyimide Nano-Thin Films by Anionic Surfactant

and Poly(vinyl alcohol) for Electronic Applications

3475

Fig. 2. TEM images of (a) PEDOT:SPI1 and (b) PEDOT:SPI2 particles.

Fig. 3. Dispersion of PEDOT:SPI in aqueous solution (a) without

SDS and (b) with SDS, after 2 months.

due to the decrease in the number of conductive SO3

groups.33 In contrast, the conductivity of PEDOT:
SPI1 monotonically decreased with increasing PVA
concentration up to 0.3 wt.%, then increased again.
This difference from PEDOT:SPI2 is due to the difference in the polyimide molecules. Based on comparison between PEDOT:SPI1 and PEDOT:SPI2 in
previous work,34 it was claimed that, after heat
treatment, the chain alignment in the conductive
film will change due to the different rigidity of the
polyimide, leading to modified morphologies, which
causes the observed conductivity enhancement;
That is, the rigid stricture can retain the straightness of its polymer main chain, which finally promotes easier electron transfer along the straight
chain than the distorted one. For this reason, the
conductivities of the PEDOT:SPI2 films were better
than those of PEDOT:SPI1 because of their more
rigid molecular structure. In all the experiments, the
interaction between SPI and PVA, naturally insulated due to the properties of the PVA additive, and
the rigidity of the polymer backbone, were the main
influences on the conductivity of the conductive
PEDOT:SPI films.
Transparency Properties

Fig. 4. Variation of conductivity of PEDOT:SPI1 and PEDOT:SPI2

with PVA weight fraction.

mixture means that more SO3 groups of SPI would

be bonded with OH groups of PVA, which ultimately
degrades the conductivity of the blended polymer

Transparency throughout the visible spectrum is

one of the properties required for application as a
transparent conductive film. From Fig. 6, it is clearly
seen that PEDOT:SPI in pure form and with various
weight fractions of PVA provided high transmittance
values across the whole visible spectrum. In addition,
the cutoff wavelength for all samples was about
280 nm, indicating that they were transparent films.
Although all the PVA/PEDOT:SPI2 spectra were
close to each other, a significant difference in the
transmittance values was found upon magnification.
Figure 7 shows the transmission of visible light
at 550 nm by PEDOT:SPI thin films with various amounts of PVA. The transmittance values

3476

Romyen, Thongyai, Praserthdam, and Sotzing

Fig. 5. AFM images of (a) SDS/PEDOT:SPI2 and (b) 0.3 wt.% PVA/SDS/PEDOT:SPI2 film; the unit of the scale bar (xy axis) is microns (lm).
The height (z axis) is in nanometers (nm).

Fig. 6. UVVis spectra of pure PVA and PVA/PEDOT:SPI2 thin

films with various weight fractions of PVA. The inset shows a magnification of the range from 500 nm to 700 nm which does not include
pure PVA (red line).

decreased with increasing PVA weight fraction

because, when the amount of PVA in the polymer
suspension was increased, the polymer viscosity also
increased, leading to thicker films produced by spincoating at a fixed spin rate, as shown in Fig. 8. These
thicker polymer films caused the decreased transmittance values. The PEDOT:SPI2 film was somewhat thicker than that of PEDOT:SPI1, but its
transmittance values still remained higher than
those of PEDOT:SPI1, as shown in Fig. 6, demonstrating that the transparency of the PEDOT:SPI2
films was better than that of PEDOT:SPI1, as the CF3
groups in the polyimide molecules of PEDOT:SPI2
gave higher intrinsic transparency than the ether
groups present in PEDOT:SPI1. The bulky CF3 group
in polyimide was effective in decreasing charge
transfer complex (CTC) formation between polymer

Fig. 7. Transmittance at 550 nm of PEDOT:SPI1 and PEDOT:SPI2

thin films with various weight fractions of PVA.

chains through steric hindrance.35 This reduction of

CTC formation eventually led to the improvement in
the transparency of the polyimide. Since CF3 is
bulkier than ether, PEDOT:SPI2 provided more
transparent conductive films than PEDOT:SPI1
because of less charge transfer. However, all specimens still showed fairly high transparency values
above 85%, due to the good dispersion of the small
PEDOT:SPI particles in aqueous solution with the
aid of the SDS surfactant. For comparison, the film
thickness and transmittance values for each pure
specimen are presented in Table I.
Contact Angle of PEDOT:SPI Thin Films
The hydrophilicity, adhesiveness, and wettability
of PEDOT:SPI films are some of the important

Modification of Novel Conductive PEDOT:Sulfonated Polyimide Nano-Thin Films by Anionic Surfactant

and Poly(vinyl alcohol) for Electronic Applications

Fig. 8. Film thickness of PEDOT:SPI thin films with various weight

fractions of PVA.

Table I. Film thickness and transmittance values

of each pure specimen
Sample
Pure PVA
Neat PEDOT:SPI1
Neat PEDOT:SPI2

Film Thickness
(nm)

Transmittance
at 550 nm (%)

91.2
84.6
89.8

93.37
90.55
90.63

properties that must be studied through the investigation of contact angle. Figure 9 shows the effects
of various amounts of PVA on the contact angle of
the conducting polymer films. We found that the
contact angle values gradually decreased with
increasing PVA weight fraction from the original
material to 1.0 wt.% PVA content. The very low
contact angle values for each original film material
are due to the influence of the anionic SDS surfactant remaining in the film. This may imply that the
PEDOT:SPI/SDS film surface has exceptional wettability properties in contact with other materials.
With increasing addition of PVA, lower contact
angle values were obtained. To understand this
phenomenon, it should be considered together with
the optical microscopy images shown in Fig. 10.
The film roughness and PEDOT:SPI agglomeration
decreased with increasing PVA weight fraction,
thus leading to lower contact angle values and
smoother films. Note that these optical microscopy
results do not conflict with the AFM imaging,
because the AFM analysis captures effects on the
molecular scale, which cannot be observed by optical
microscopy, which instead shows overall images of
the film on the micron scale. Since the OH groups of
PVA could interact with salt complexes formed upon
polymerization, a decrease in salt complexes was
obtained with increasing PVA amount. This
decrease in salt complexes not only resulted in more

3477

Fig. 9. Contact angle of PEDOT:SPI1 and PEDOT:SPI2 thin films

with various weight fractions of PVA.

stable PEDOT:SPI particles in aqueous solution,

but also boosted the electrostatic repulsion between
PEDOT:SPI particles, thus leading to a reduction of
particle agglomeration during film formation. In
addition, the hydrophilicity of the conductive films
would increase with the amount of PVA due to its
OH groups. Therefore, the addition of the hydrophilic PVA was the main driving force changing the
hydrophilicity of the conductive films and also
resolved the problem of particle agglomeration,
resulting in more transparent PEDOT:SPI films
with increasing amount of PVA. More conductive
films with lower surface energy and lower contact
angle values were obtained with PEDOT:SPI2 due to
the higher polarity of the polyimide molecule of
PEDOT:SPI2 compared with PEDOT:SPI1; That is,
the polarity of the CF3 groups in SPI2 is greater than
that of the ether groups in SPI1. Although the SPI
materials were combined with PEDOT to make the
conductive films, the PEDOT:SPI2 films still exhibited greater hydrophilicity than the PEDOT:SPI1
films. Therefore, the wettability of PEDOT:SPI2 is
better.
Thermal Stability of PEDOT:SPI Thin Films
The effect of PVA on the thermal stability of CPs
is another interesting property that must be investigated further. This property is related to the
thermal degradation when the films are exposed to
severe conditions. High thermal stability of CPs is
required to extend the useful life of electronic
devices. The TGA results shown in Fig. 11 demonstrate that the thermal stability of PEDOT:SPI was
affected by the additives. The presence of the SDS
surfactant in the PEDOT:SPI films resulted in
weight loss at a temperature below 250C, while
pure PEDOT:SPI was quite stable in this temperature range. This weight loss was due to decomposition of SDS related to its thermal stability.

3478

Romyen, Thongyai, Praserthdam, and Sotzing

Fig. 10. Optical microscopy images of PEDOT:SPI2 thin films with various weight fractions of PVA. Dark spots are agglomerated PEDOT:SPI2.

Fig. 11. Thermal stability of pure PEDOT:SPI1 and pure PEDOT:

SPI2 with SDS and 0.3 wt.% PVA.

However, the presence of PVA in PEDOT:SPI/SDS/

PVA films could reasonably improve the thermal
stability because of the interactions between the OH
group of PVA and the SO3 groups of SPI. When PVA
was added to PEDOT:SPI, the OH group of PVA
could bond by strong covalent bonding to SO3
groups of SPI. Therefore, higher PVA concentration
in the mixture resulted in improved mechanical and

thermal properties of the film. It was noticed that,

after addition of PVA to the pure PEDOT:SPI
materials, the thermal stability of the PVA/PEDOT:
SPI materials was significantly better when compared with pure PEDOT:SPI, even though pure
PVA has worse thermal stability than that of pure
PEDOT:SPI. The Td 5% and Td 10% values of PVA
are 201C and 246C, respectively. In addition, the
thermal stability of PEDOT:SPI2 was slightly better than that of PEDOT:SPI1, as its molecular
structure exhibited greater rigidity; namely, the Td
5% and Td 10% values for PEDOT:SPI2 were
234.07C and 267.38C, whereas for PEDOT:SPI1
they were 215.47C and 261.19C, respectively. In
previous work,34 SPI1 and SPI2 were used as
templates for various CPs and their thermal stability was compared. It was claimed that use of the
more rigid initial template resulted in greater
thermal stability. For this reason, the results
showed that all the SPI2 CPs exhibited better
thermal stability than the SPI1 CPs. In the same
way, in this work, PEDOT:SPI2 had higher thermal stability than PEDOT:SPI1 because the CF3
groups in the polyimide molecules of PEDOT:SPI2
provided greater intrinsic rigidity than the ether
groups in PEDOT:SPI1. For comparison, the thermal decomposition (Td) temperatures for 5% and

Modification of Novel Conductive PEDOT:Sulfonated Polyimide Nano-Thin Films by Anionic Surfactant

and Poly(vinyl alcohol) for Electronic Applications

3479

Table II. Thermal decomposition (Td) temperatures for 5% and 10% weight loss of each specimen
SPI1 (C)

SPI2 (C)

Sample

Td 5%

Td 10%

Td 5%

Td 10%

Neat PEDOT:SPI
PEDOT:SPI + 0.3 wt.% PVA
PEDOT:SPI + SDS + 0.3 wt.% PVA
PEDOT:SPI + SDS

215.5
219.0
193.1
197.3

261.2
275.0
216.9
216.6

234.1
220.0
208.9
179.2

267.4
270.0
227.6
212.1

*Td 5% and Td 10% of pure PVA are 201C and 246C, respectively.

10% weight loss of each specimen are presented in

Table II.

CONCLUSIONS
We formed conducting PEDOT:SPI nanoscale
thin films with excellent properties by using PVA,
an anionic surfactant, and a conventional spincoating process. SDS surfactant was utilized to
improve the dispersion stability of PEDOT:SPI in
water due to the electrostatic repulsion between the
PEDOT:SPI particles, leading to highly transparent
PEDOT:SPI films. All of the obtained films showed
high transmission above 85% because of the good
dispersion of PEDOT:SPI particles in aqueous
solution aided by the SDS surfactant. The very low
contact angle values of the films (<10) were mainly
due to the hydrophilicity of the surfactant, and they
decreased with increasing PVA content. The highest conductivity of 0.134 S/cm was achieved for
0.08 wt.% PVA content in conductive PEDOT:SPI2/
SDS/PVA thin film due to the better connection
network of conducting polymer chains. In addition,
PVA also improved the thermal stability of the films
because of the interactions between the OH groups
of PVA and the SO3 groups of SPI, as verified by
TGA analysis. The differing film properties between
PEDOT:SPI1 and PEDOT:SPI2 depend on their
intrinsic molecular properties. Overall, combined
addition of SDS and PVA to PEDOT:SPI has the
potential to effectively modify conductive PEDOT:
SPI films to obtain various good properties to enable
their application as conductive materials in the
electronics field.
ACKNOWLEDGEMENTS
G.A.S. wishes to thank the Institute of Material
Sciences and the Polymer Program at the University of Connecticut. S.T. and N.R. wish to thank the
Royal Golden Jubilee Ph.D. Program. This work
was supported by the Higher Education Research
Promotion and National Research University Project of Thailand, Office of the Higher Education
Commission (EN283A) and Ratchadaphiseksomphot Endowment Fund (CU-CLUSTER-FUND).

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