OPEN Redox-active charge carriers of

SUBJECT AREAS:
conducting polymers as a tuner of
SENSORS
POLYMER CHARACTERIZATION
conductivity and its potential window
CHEMICAL PHYSICS
Han-Saem Park, Seo-Jin Ko, Jeong-Seok Park, Jin Young Kim & Hyun-Kon Song
POLYMERS

i-School of Green Energy, UNIST, Ulsan 689-798, Korea.

Received
20 June 2013
Electric conductivity of conducting polymers has been steadily enhanced towards a level worthy of being
Accepted called its alias, ‘‘synthetic metal’’. PEDOT:PSS (poly(3,4-ethylenedioxythiophene) doped with poly(styrene
30 July 2013 sulfonate)), as a representative conducting polymer, recently reached around 3,000 S cm21, the value to open
the possibility to replace transparent conductive oxides. The leading strategy to drive the conductivity
Published increase is solvent annealing in which aqueous solution of PEDOT:PSS is treated with an assistant solvent
16 August 2013 such as DMSO (dimethyl sulfoxide). In addition to the conductivity enhancement, we found that the
potential range in which PEDOT:PSS is conductive is tuned wider into a negative potential direction by the
DMSO-annealing. Also, the increase in a redox-active fraction of charge carriers is proposed to be
responsible for the enhancement of conductivity in the solvent annealing process.
Correspondence and
requests for materials

P
should be addressed to EDOT:PSS is one of the most well-known conducting polymers due to its high conductivity, high optical
J.Y.K. ([email protected]. transparency, high thermal stability, high mechanical flexibility and high water solubility. The characteristic
kr) or H.-K.S.
properties enabled the conducting polymer as transparent electrodes or current collectors of various
optoelectronic devices such as solar cells, light-emitting diodes, liquid crystal displays and touch panel displays1,2.
(philiphobi@hotmail.
The conductivity of PEDOT:PSS have increased steadily, recently reaching 3,065 S cm21 3 which is the value to
com) enable PEDOT:PSS to replace widely used transparent conductive oxides such as indium tin oxide or fluorine-
doped tin oxide. The primary method to increase conductivity is the solvent annealing in which a solvent molecule
such as DMSO is introduced into an aqueous solution of PEDOT:PSS and then the mixture is processed into the
form of interest like films. Various organic compounds were used as the assistant solvent such as DMSO, alcohols,
ionic liquids and anionic surfactant4–9. The driving force to enhance conductivity has been proposed as (1) charge
screening of the interaction between PEDOT and its dopant (PSS) by the organic compounds4, (2) enhanced
interchain interaction between PEDOT chains due to their conformational transformation from benzoid-favor-
ing coil structure to quinoid-favoring linear or extended coil structure caused by incorporation of organic
molecules interacted with PEDOT as well as PSS5,10 and (3) development of 3D conducting network associated
with exclusion or reduction of excess PSS from conductive PEDOT:PSS domains6,11,12. With additional post-
treatment of solvent-annealed PEDOT:PSS, highly conductive film (1,418 S cm21) was obtained13. The film made
from ethylene glycol-containing PEDOT:PSS aqueous solution was thermally annealed and then immediately
immersed in a solution of the same organic compound. The highest value (3,065 S cm21) was obtained by post-
treating as-prepared PEDOT:PSS film with H2SO4 at 160uC3. The anionic HSO42 functioned as the secondary
dopant for PEDOT like tosylate9, showing the effects similar to those of organic compounds used in solvent
annealing.
The research focus of the solvent annealing of PEDOT:PSS has been made on how to improve electric
conductivity and how the organic molecules or additives work. Rather than the electric properties, in this work,
we investigated on the change of electrochemical properties induced by solvent annealing. That is to say, we
moved focus from the level of electric conductivity (ordinate view) to the range of potential in which the electric
conductivity maintains (abscissa view).

Results
Widening conductive potential window. Conducting polymers including polypyrroles, polyanilines and
polythiophenes (e.g., PEDOT) are prepared by oxidizing corresponding monomers. They have positive
charges every three to five monomeric units along polymeric backbone. The positively charged ensembles
work as a charge carrier for conduction. During synthesis, counter-anions called dopants are introduced into

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the conducting polymers to neutralize the positive charges of to 1.3 V for its dimer to 1.0 V for its trimer to 0.7 V for its polymer18.
backbones. PSS functions as a polyanionic dopant in PEDOT:PSS. Structural modification of monomeric unit would be the first choice
The conducting polymers intrinsically in a doped or oxidized state to control the E0. The reduction potential of conducting polymers
turn electrically insulating when being reduced by applying negative was controlled by substituents attached to the 3 and 4 positions of
potentials. During reduction, the cationic charge carriers of thiophene: from more positive than 10.5 V with polythiophene
conducting polymers are lost. Simultaneously, small-sized dopant to 10.3 V with poly(3,4-dimethoxythiophene) or 20.2 V with
molecules are effluxed from the films while foreign cations are PEDOT:tosylate in 0.1 M tetrabutylammonium perchlorate in acet-
influxed from electrolyte to the films in presence of large-sized onitrile19. The negative shift of E0 is caused by electron-donating
dopants such as PSS: properties of the alkoxy moieties. The choice of solvent also affects
the values of E0. 11.24 V and 10.84 V were measured as anodic
EDOTz : { { z 0 : {: z
n SS ze zC ?EDOTn SS C peak potential of poly(3-methyl thiophene) with 0.1 M LiClO4 in
ðdoped or oxidized stateÞ ðdedoped or reduced stateÞ ð1Þ glycol and acetonitrile, respectively.
Even without any modification of monomeric units as well as any
Conductive Insulating control of molecular weight in an identical electrolyte, cyclic voltam-
mograms of bare and solvent-annealed PEDOT:PSS (2DMSO and
where EDOT 5 the monomeric unit of PEDOT, n 5 number of 1DMSO) showed that the extension of conductive window of
EDOT, SS2 5 styrenesulfonate of PSS, e2 5 electron and C1 5 PEDOT:PSS can be achieved by solvent annealing as a simple and
cation in electrolyte. versatile strategy to control E0 (Fig. 1). Three different PEDOT:PSS
Therefore, shifting the reduction potential (E0, estimated by E1/2 5 films were tested, which are prepared from commercially available
(Epa 1 Epc)/2 with Epa and Epc as anodic and cathodic peak potentials aqueous solution of PEDOT:PSS: AI4083, PH and PH1000. 5% (or
in cyclic voltammograms, respectively) of PEDOT to a more negative 50%) of DMSO were added to the aqueous solution, followed by drop
value extends the conductive potential window by keeping PEDOT casting on carbon electrodes. Almost identical electrochemical prop-
in its oxidized state. The wider conductive range is beneficial when erties were obtained with both 5% and 50% DMSO. Without solvent
the conductive polymer is used as electrodes of electric double layer annealing (2DMSO), the electric conductivity was estimated by four
capacitors (EDLCs)14, electrolytic capacitors15, sensors16 and other point probe measurement at 6.3 3 1024 (0.05) S cm21 for AI4083, 3.8
electrochemical applications17. Various factors determine the value 3 1023 (1.1) S cm21 for PH and 0.24 (0.25) S cm21 for PH1000 (the
of E0. Higher degree of polymerization or molecular weight leads to values before and in parentheses are the conductivities of the films
more negative E0: e.g., the values of E0 decreased from 2.0 V (all dried at room temperature and 140uC, respectively). After solvent
potentials are reported versus Ag/AgCl) for thiophene as a monomer annealing (1DMSO), the conductivities were markedly enhanced to

Figure 1 | Conductive potential widow widening of PEDOT:PSS induced by DMSO-annealing. Cyclic voltammograms (a) to (c), (e) to (g), (i) to (k)
and scan-rate (v) dependency of peak currents (ip) (d), (h), (l) of three different PEDOT:PSS. The first, second and third rows correspond to AI4083, PH
and PH1000, respectively. The first and second columns are for bare (2DMSO) and solvent-annealed (1DMSO) PEDOT:PSS, respectively. The cyclic
voltammograms at 100 mV sec21 are compared between –DMSO and 1DMSO of the same PEDOT:PSS in the third column. The values of anodic peak
current were used for d to l because cathodic peak current showed similar behaviors in terms of v-dependency. The lines in figures of the fourth column
show the linear relationship with a unity slope indicating that faradaic processes responsible for currents are surface-confined with facile kinetics.

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Figure 2 | Increase of the amount of redox-active charge carriers of PEDOT:PSS induced by DMSO-annealing. (a) and (b), X-ray photoelectron spectra
(XPS) of PH1000 (2DMSO and 1DMSO) potentiostatically conditioned at 10.5 V, 20.5 V and 20.8 V. Intensity was normalized by the maximum
value of T peak. The peak locations of doublets for T, S1 and S2 were indicated on the abscissa. (c), Spectral change of potentiostatically controlled
samples from their fully oxidized states at 10.5 V. Squared brackets indicate the spectrum of PH1000 potentiostatically controlled at the potential
indicated within it. (d), 2DMSO/1DMSO ratio of the redox-active fraction of total charge carriers estimated spectroscopically from XPS and
electrochemically from cyclic voltammograms (CV) in Fig. 1.

15 (870) S cm21 for PH and 250 (1,300) S cm21 for PH1000 (The increasing the number of charge carriers. However, the solvent
conductivity of AI4083 after solvent annealing was difficult to mea- annealing was known not to increase number of charge carriers or
sure because a film was poorly and heterogeneously formed). doping level but to enhance mobility or hopping rate of the fixed
PH1000, as a representative example, experienced the E0 shift from number of carriers existing along polymer backbones (due to
10.15 V to 20.62 V at 100 mV sec21, being conductive in an addi- conformational change or enhanced 3D conducting network)10.
tional potential range of , 0.8 V (Fig. 1k). Also, carrier densities of all PEDOT:PSS films were estimated
The scan-rate dependency of peak currents responsible for oxida- around 2.2 3 1020 cm23 independent of solvent annealing (Fig. S1
tion of PEDOT:PSS (Fig. 1d, h, l) showed that solvent-annealed films and Table. S1 in Supporting Information). As an alternative
(1DMSO) follow faithfully the behavior of surface-confined electro- hypothesis, the DMSO-annealing leads to additional energetics or
chemical processes indicated by a unity slope (slope 5 1) in log-log redox stages of the identical number of oxidized states. The second
plots (that is to say, ip / v1 with ip 5 peak current and v 5 scan rate). interpretation could be supported by the fact that similar values of
However, the bare films (2DMSO) exhibited a deviation from the currents are obtained at the different potentials and also the peaks are
ideal behavior especially at high scan rates. Due to their low electric merged together without any increase of current in some cases.
conductivity, AI4083 and PH1000 films delivered peak currents However, it is still difficult to imagine multiple oxidation states of
lower than the values expected from the surface-confined oxidation a fixed redox-active site are possible.
from 100 mV sec21 and 500 mV sec21, respectively. PH film, the To investigate why those multi-stage redox behavior is found after
conductivity of which is in the level of 100 S cm21, ideally behaved solvent-annealing, the binding energy of sulfur 2 p orbitals (S2p)
in terms of scan-rate dependency. were traced along reducing passage. Even if many literatures focus
simply on the relative ratio of PEDOT to PSS, the S2p peaks can be
Redox-active charge carriers. With a closer look, the voltammetric deconvoluted to three different doublet peaks for EDOT (T at
curve of solvent-annealed PH1000 (1DMSO) consists of three 163.4 eV and 164.4 eV), EDOT1?SS2 (S1 at 166.8 eV and
different redox stages (Fig. 1k): Epa/Epc 5 125 mV/280 mV for 1, 167.8 eV) and H1?SS2 (S2 at 168 eV and 169 eV)20. Via reducing
2230 mV/2420 mV for 2 and 2550 mV/2680 mV for 3. The the fully oxidized PEDOT:PSS (PH1000 as a representative), signifi-
redox stage 1 is found at the potential roughly identical (or slightly cantly different spectral changes of X-ray photoelectron spectra
more negative) to the redox of –DMSO (at 1150 mV/130 mV) (XPS) were observed between –DMSO and 1DMSO (Fig. 2).
with the similar current values. Some of peaks are merged in 1DMSO was fully reduced at a more negative potential (20.8 V)
AI4083 and PH prepared in presence of DMSO. As a first guess, while the reduced state of –DMSO was prepared at 20.5 V as men-
therefore, we could hypothesis that DMSO-annealing would tioned above (Fig. 1). The decrease of S1 peak responsible for doping
generate additional doping sites of different redox potential with contents was experienced by –DMSO during the reduction. On the

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other hand, the increase of S2 peak was found after full reduction of
1DMSO at 20.8 V. At a middle potential (20.5 V) for 1DMSO,
there was no significant spectral difference from the fully oxidized
sample at 10.5 V, differently from the case of 2DMSO. During
reduction, positive charge carrier sites of the polymer backbone are
lost so that the electrostatic interaction between EDOT1 and SS2
becomes weak with the formation of H1?SS2. As shown clearly in
the intensity subtraction plot (Fig. 2c), therefore, the decrease in S1
peak for –DMSO (DS1, negative peaks, black) as well as the increase
in S2 for 1DMSO (DS2, positive peaks, blue) can be interpreted as
dedoping. The dedoping fraction or redox-active portion of dopants
during reduction can be quantified by the ratio of peak areas of DS1
or DS2 to T (RS1/T or RS2/T): RS1/T 5 1.1373/2.8279 5 40% or RS2/T
5 2.6705/2.6783 5 100%. Charge carriers of 1DMSO were comple-
tely (,100%) reduced while only 40% of the charge carries were
electroactive in –DMSO. The ratio of RS1/T of 2DMSO to RS2/T of
1DMSO consists with the ratio of charges stored in –DMSO to
1DMSO (Q–/Q1) as shown in cyclic voltammograms (Fig. 1k):
Q–/Q1 5 22.4 C g21/58.2 C g21 5 38.4% for the cathodic process
(Fig. 2d). That is to say, the amount of redox-active charge carriers of
1DMSO would be 2.5 times larger than that of –DMSO, even if there
were no difference of doping level between –DMSO and 1DMSO in
a fully oxidized state. Therefore, we could conclude that all redox
stages including 1, 2 and 3 work electrochemically in the conforma-
tion induced by solvent-annealing (linear or extended coil config-
uration) while only redox stage 1 is electrochemically active in the
bare PEDOT:PSS. DMSO or equivalent assistant solvent molecules
function as a potion to revive dead charge carriers in terms of elec-
trochemical activity. Charge screening of the interaction between
PEDOT and its dopant (PSS) by the organic compounds4 could make
Figure 3 | Electrochemical impedance spectra of PEDOT:PSS. (a) and
dedoping process thermodynamically more comfortable. Also, the
(b), AI4083. (c) and (d), PH. (e) and (f), PH1000. The left and right
enhanced connectivity of conductive pathways6,11,12 would enable
columns are for PEDOT:PSS prepared in absence and presence of DMSO
electron to reach all of the potentially redox-active sites.
(2DMSO and 1DMSO), respectively. Impedance was measured at
The conductivity enhancement by solvent-annealing also can be 10.5 V and 20.5 V as biased potentials every sample from 100 kHz to
interpreted in terms of the redox-active doping level or the number of 0.5 Hz.
redox-active charge carriers. From the discussion above, the solvent-
annealing increases the number of redox-active charge carriers from
40% utility to , 100% utility of total number of intrinsic charge showed higher values of capacitance as expected from their superior
carriers. There is every possibility that only the redox-active charge conductivities. At 20.5 V where 1DMSO is conductive but –DMSO
carriers are responsible efficiently for electric conductivity, consider- is insulating, clearly different impedance behaviors were obtained.
ing that the positive charge carriers of EDOTn1 accept electrons Charge transfer processes caused by reduction of oxidized states and
during conduction like transient reduction. Conductivities (s) come vice versa were observed with 1DMSO. On the contrary, diffusion
from the product of mobility (m) and carrier density (n). Due to a limited processes recognized by Warburg-type impedance were
disorder broadening of energy levels of charge carriers, m is the func- found because the PEDOT:PSS layer works as a porous insulating
tion of n with an approximate linearity in log-log scale of a specific film.
range of n21,22:
s!nm!nnb ~nbz1 ~nb ð2Þ Detection of electroactive species. To clarify the difference between
–DMSO and 1DMSO as well as to emphasize why the extension of
When the number of redox-active charge carriers is used for n conductive potential window of conducting polymers is useful, we
instead of total number of charge carriers detected by non-electro- measured the electrochemical signals of three different electroactive
chemical method (reflectance spectra), the empirical relationship species on electrodes of –DMSO and 1DMSO (Fig. 4). K3Fe(CN)6
approximated the conductivity enhancement ratio of PEDOT:PSS (FeCN, 1 mM) shows one electron reversible charge transfer
with b 5 7 , 8 with poly(3-hexylthiophene) from the literatures21,22. electrochemistry based on Fe31/21: [Fe(CN)6]32 1 e2 R
For example, the increase of redox-active carrier density estimated at [Fe(CN)6]42. Its standard reduction potential (Eo) is 10.27 V at
2.5 times (100% utility of 1DMSO versus 40% of –DMSO for which both 2DMSO and 1DMSO are conductive. Even if
PH1000) leads to the conductivity enhancement of (2.5)8 , 9 5 electrochemical signals of FeCN are expected to be successfully
, 103 order of magnitude. The enhancement factor is consistent measured with –DMSO and 1DMSO, the peaks responsible for
with the value obtained by conductivity measurement: 0.24 S cm21 the faradaic reaction were observed clearer on 1DMSO than
for –DMSO versus 250 S cm21 for 1DMSO of PH1000. –DMSO due to higher conductivity of 1DMSO (Fig. 4a). Indigo
–DMSO and 1DMSO were compared in terms of equivalent cir- carmine (IC, 0.25 mM) is electroactive with a proton-involved
cuit parameters by electrochemical impedance spectroscopy (Fig. 3 electrochemical reaction: IC 1 2H1 1 2e2 R ICH2. Therefore, we
and Table S2 in Supporting information). At 10.5 V where both of controlled pH to adjust its reduction potential (E) to the value at
PEDOT: PSS is conductive, both –DMSO and 1DMSO showed the which –DMSO is insulating while 1DMSO is conductive. At pH3.5,
qualitatively same capacitive behaviors normally obtained from con- E1/2 was estimated at 20.086 V on a glassy carbon disk electrode. As
ductive porous structures with 45u-inclined line at higher frequencies expected, the electrochemical signal of IC is detected only on
and near-but-not-90u line at lower frequencies23–25 1DMSO samples 1DMSO (Fig. 4b). The same signals were not found clearly on the

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Conductivity measurement. Electric conductivities were measured by using a four-

point-probe technique (CMT-SR1000N, Advanced Instrument Technology). 1 mL
of aqueous solutions of PEDOT:PSS with or without 5 vol.% DMSO were coated on
glass substrates (1.5 cm by 1.5 cm) at 1,500 to 2,000 rpm for 60 s and then dried at
room temperature for 1 day or 140uC for 10 min.

Electrochemical measurement. Cyclic voltammograms and impedance spectra were

measured by using a potentiostat (VMP3, Bio-Logic). Electrochemical measurements
were configured with three electrode systems: screen-printed carbon electrodes as
working electrodes, Pt flag as a counter electrode and Ag/AgCl (0.197 V vs. NHE) as a
reference. 0.1 M H2SO4 (aq) was used as electrolyte for measuring redox activity of
PEDOT:PSS. Three different electroactive species were used to confirm the
conductive windows of –DMSO and 1DMSO: 1 mM K3Fe(CN)6 in 0.2 M NaCl (aq);
0.25 mM indigo carmine in 0.2 M NaCl (aq) at pH 3.5 adjusted by 0.15 mM H2SO4;
and 1 mM flavin adenine dinucleotide in phosphate buffer solution at pH 6.0.

X-ray photoelectron spectroscopy (XPS). Prior to XPS measurements (K-alpha,

Thermo Fisher), PEDOT:PSS films were conditioned potentiostatically at 10.5 V,
20.5 V and 20.8 V.

1. Na, S.-I., Kim, S.-S., Jo, J. & Kim, D.-Y. Efficient and Flexible ITO-Free Organic
Solar Cells Using Highly Conductive Polymer Anodes. Adv. Mater. 20, 4061–
Figure 4 | Electrochemically detected signals of three different 4067 (2008).
electroactive species (A) on PH1000-filmed electrodes (2DMSO and 2. Hu, Z., Zhang, J., Hao, Z. & Zhao, Y. Influence of doped PEDOT:PSS on the
1DMSO). The net currents were calculated by subtracting the current performance of polymer solar cells. Sol. Energy Mater. Sol. Cells 95, 2763–2767
obtained in A-absent electrolyte (-A) from the current obtained in A- (2011).
3. Xia, Y. J., Sun, K. & Ouyang, J. Y. Solution-Processed Metallic Conducting
present electrolyte (1A). K3Fe(CN)6 (FeCN, 1 mM, (a)), indigo carmine
Polymer Films as Transparent Electrode of Optoelectronic Devices. Adv. Mater.
(IC, 0.25 mM, (b)) and flavin adenine dinucleotide (FAD, 1 mM, (c)) 24, 2436–2440 (2012).
were selected as A. To identify the species responsible for peaks, the cyclic 4. Kim, J. Y., Jung, J. H., Lee, D. E. & Joo, J. Enhancement of electrical conductivity of
voltammograms obtained on glassy carbon disk electrodes (GC, area 5 poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) by a change of
3.14 mm2) were also shown with indicated magnifications of current. The solvents. Synth. Met. 126, 311–316 (2002).
5. Ouyang, J. et al. On the mechanism of conductivity enhancement in poly (3,4-
raw cyclic voltammograms were provided in Fig. S2 of Supporting ethylenedioxythiophene): poly(styrene sulfonate) film through solvent treatment.
Information. Polymer 45, 8443–8450 (2004).
6. Crispin, X. et al. The origin of the high conductivity of poly(3,4-
ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT- PSS) plastic
electrodes of –DMSO because the PEDOT:PSS film is at least electrodes. Chem. Mater. 18, 4354–4360 (2006).
partially insulating so that there are less chances of collision 7. Nardes, A. M., Janssen, R. A. J. & Kemerink, M. A Morphological Model for the
between conductive electrode and the electroactive species. As the Solvent-Enhanced Conductivity of PEDOT:PSS Thin Films. Adv. Funct. Mater.
last electroactive species, a bimolecule was selected, which is used as 18, 865–871 (2008).
8. Dobbelin, M. et al. Influence of ionic liquids on the electrical conductivity and
an electron transfer mediator in enzymes or various biosystems. The morphology of PEDOT: PSS films. Chem. Mater. 19, 2147–2149 (2007).
electrochemistry of flavin adenine dinucleotide (FAD, 1 mM) also 9. Fan, B. H., Mei, X. G. & Ouyang, J. Y. Significant conductivity enhancement of
involved proton like IC: FAD 1 H1 1 e2 R FADH with E 5 conductive poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate) films by
20.36 V at pH6.0. Not on the insulating electrode (2DMSO) but adding anionic surfactants into polymer solution. Macromolecules 41, 5971–5973
(2008).
on the conductive electrode (1DMSO), FAD was clearly detected
10. Ouyang, J. et al. High-Conductivity Poly(3,4-ethylenedioxythiophene):
(Fig. 4c). Poly(styrene sulfonate) Film and Its Application in Polymer Optoelectronic
Devices. Adv. Funct. Mater. 15, 203–208 (2005).
11. Jonsson, S. K. M. et al. The effects of solvents on the morphology and sheet
Discussion resistance in poly (3,4-ethylenedioxythiophene)-polystyrenesulfonic acid
In this work, we reported that the solvent anealing not only increases (PEDOT-PSS) films. Synth. Met. 139, 1–10 (2003).
electric conductivity of PEDOT:PSS but also widens conductive 12. Lee, H. J., Lee, J. & Park, S. M. Electrochemistry of Conductive Polymers. 45.
potential window of the conducting polymer. Also, evidences were Nanoscale Conductivity of PEDOT and PEDOT:PSS Composite Films Studied by
Current-Sensing AFM. J. Phys. Chem. B 114, 2660–2666 (2010).
provided, which support the hypothesis that electroactive portion of
13. Kim, Y. H. et al. Highly Conductive PEDOT:PSS Electrode with Optimized
charge carriers could determine the conductivity of conducting poly- Solvent and Thermal Post-Treatment for ITO-Free Organic Solar Cells. Adv.
mers. Even if total number of charge carriers or doping level were Funct. Mater. 21, 1076–1081 (2011).
unchanged, the solvent annealing would induce the increase of the 14. Ghosh, S. & Inganäs, O. Conducting Polymer Hydrogels as 3D Electrodes:
electroactive carriers. The widened conductive potential window of Applications for Supercapacitors. Adv. Mater. 11, 1214–1218 (1999).
15. Kudoh, Y., Akami, K. & Matsuya, Y. Solid electrolytic capacitor with highly stable
conducting polymers was shown to be utilized as electrodes of chem- conducting polymer as a counter electrode. Synth. Met. 102, 973–974 (1999).
ical sensors. 16. Pan, L. et al. Hierarchical nanostructured conducting polymer hydrogel with high
electrochemical activity. Proc. Natl. Acad. Sci. U. S. A. 109, 9287–9292 (2012).
17. Groenendaal, L. et al. Poly(3,4-ethylenedioxythiophene) and Its Derivatives: Past,
Methods Present, and Future. Adv. Mater. 12, 481–494 (2000).
Materials. Three different PEDOT:PSS solutions (1.0 , 1.7 wt.%) were purchased 18. Diaz, A. F. et al. Electrooxidation of aromatic oligomers and conducting polymers.
from Heraeous: AI4083, PH and PH1000. The other reagents were purchased from J. Electroanal. Chem. 121, 355–361 (1981).
Sigma-Aldrich. 19. Zotti, G., Zecchin, S., Schiavon, G. & Groenendaal, L. B. Conductive and Magnetic
Properties of 3,4-Dimethoxy- and 3,4-Ethylenedioxy-Capped Polypyrrole and
Solvent annealing. 50 mL dimethyl sulfoxide (DMSO) were added to 1 mL of Polythiophene. Chem. Mater. 12, 2996–3005 (2000).
PEDOT:PSS solution, followed by stirring over 2 h. 20. Crispin, X. et al. Conductivity, morphology, interfacial chemistry, and stability of
poly(3,4-ethylene dioxythiophene)–poly(styrene sulfonate): A photoelectron
Film formation. The bare or DMSO-containing polymer solutions were casted as a spectroscopy study. J. Polym. Sci., Part B: Polym. Phys. 41, 2561–2583 (2003).
form of film on substrates. They were drop-casted on screen printed carbon 21. Arkhipov, V. I. et al. Charge carrier mobility in doped semiconducting polymers.
electrodes (Zensor R&D, Area 5 19.6 mm2) for electrochemistry or spin-coated on Appl. Phys. Lett. 82, 3245–3247 (2003).
glass substrates for conductivity measurement. The same amount of PEDOT were 22. Jiang, X. et al. Doping-induced change of carrier mobilities in poly(3-
loaded on the electrodes independent of its kind. The thicknesses of the films were hexylthiophene) films with different stacking structures. Chem. Phys. Lett. 364,
around 3.5 um with less than 0.5 um deviation. 616–620 (2002).

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23. Song, H. K., Hwang, H. Y., Lee, K. H. & Dao, L. H. The effect of pore size Author contributions
distribution on the frequency dispersion of porous electrodes. Electrochim. Acta H.-S.P., J.-S.P.: material preparation and electrochemical characterization and analysis.
45, 2241–2257 (2000). S.-J.K., J.Y.K.: charge transport characterization. H.-K.S.: data analysis, writing and project
24. Song, H. K., Jung, Y. H., Lee, K. H. & Dao, L. H. Electrochemical impedance planning.
spectroscopy of porous electrodes: the effect of pore size distribution. Electrochim.
Acta 44, 3513–3519 (1999).
25. Song, H. K. et al. Electrochemical porosimetry. J. Electrochem. Soc. 151, Additional information
E102–E109 (2004). Supplementary information accompanies this paper at http://www.nature.com/
scientificreports
Competing financial interests: The authors declare no competing financial interests.
How to cite this article: Park, H., Ko, S., Park, J., Kim, J.Y. & Song, H. Redox-active charge
Acknowledgments carriers of conducting polymers as a tuner of conductivity and its potential window. Sci.
This work was supported by MOTIE (Green:10042948(KEIT), Inter-ER:R0000491) and Rep. 3, 2454; DOI:10.1038/srep02454 (2013).
MSIP (CRC: 2013K000210), Korea.
This work is licensed under a Creative Commons Attribution-
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SCIENTIFIC REPORTS | 3 : 2454 | DOI: 10.1038/srep02454 6