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supramolecular complexes of conjugated

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Cite this: J. Mater. Chem. C, 2019,

7, 2987 polyelectrolyte PEDOTS†
Chiara Musumeci, *a Mikhail Vagin,b Erica Zeglio,a Liangqi Ouyang, a

Roger Gabrielssonb and Olle Inganäs*a

Counterion exchange strategies are used to modify the hydrophilic character of the self-doped
conjugated polyelectrolyte PEDOTS. The supramolecular complexes, soluble in organic solvents, are
suitable to fabricate finely performing thin active layers in organic electrochemical transistors (OECTs).
We demonstrate that ionic transport in these PEDOTS based complexes, thus their performance in
Received 16th November 2018, OECT devices, is governed by a delicate balance among degree of doping, wettability and porosity,
Accepted 7th February 2019 which can be controlled by a precise tuning of the polyelectrolyte/hydrophobic counterion ratio. We
DOI: 10.1039/c8tc05774e also show that the device operation can be modulated by varying the composition of the aqueous
electrolyte in a range compatible with biological processes, making these materials suitable candidates
rsc.li/materials-c to be interfaced with living cells.

Introduction conductivity, thus making it a suitable active material for the

fabrication of functional devices, such as organic electro-
Conjugated polyelectrolytes are a class of (semi)-conducting chemical transistors (OECTs).4–6 In a typical OECT, a gate voltage
polymers possessing charged groups covalently attached to the drives ions from an electrolyte into the bulk of the conjugated
conjugated backbone. By enabling both electronic and ionic polymer, thus modulating its redox state and conductivity. Low
transport, they bridge the gap between electronics and biology, voltage operation, high transconductance, and compatibility
allowing the development of intimate bioelectronics interfaces.1 with operation in aqueous environment (e.g. biological media)
The charged side groups, making these materials soluble in make OECTs ideal devices to be coupled and interfaced with
polar solvents, allow for the incorporation of water molecules living systems and to work as active amplifying ion-to-electron
and mobile ions into the polymer matrix, leading to improved transducers, ultimately increasing the signal-to-noise ratio with
ionic conductivity with respect to conjugated polymers having respect to traditional electrodes used for electrophysiology.7,8
hydrophobic side groups. Some conjugated polyelectrolytes are The manipulation of the hydrophobic/hydrophilic character of
self-doped, meaning that the charged side groups act as counter- these electrode materials may also have potential for the solid/
ions to balance the positive charges formed in the conjugated liquid/gas interfaces found in fuel cells driven with gases.
backbone upon oxidation.2 PEDOTS is a conjugated polyelec- The charged side chains of PEDOTS can also be exploited to
trolyte in which alkoxysulfonate side chains are covalently bound fabricate new materials by supramolecular interactions. The
to a poly(3,4-ethylenedioxythiophene) (PEDOT) backbone. The negative sulfonate groups can in fact interact electrostatically
negatively charged sulfonate groups render PEDOTS highly water with positively charged moieties, creating supramolecular
soluble and stabilize the positive charges on the polymer back- complexes with new functionalities. This strategy has been
bone in its pristine oxidized conductive state, thus making specifically used for the fabrication of conductive fibers from
PEDOTS a self-doped polymer with conductivity of tens of biotemplates such as protein fibers9–12 and DNA,13 for the
S cm1.3 Changes in the level of oxidation also change PEDOTS fabrication of multilayered electrochromic films14,15 and con-
ductive hybrid nanocomposites.16 By using counterion exchange
a
Biomolecular and Organic Electronics, Department of Physics Chemistry and strategies, i.e. by replacing small counterions with ions bearing
Biology, Linköping University, SE-58183 Linköping, Sweden. long hydrophobic chains, it is also possible to modify the
E-mail: chiara.musumeci@liu.se, olle.inganas@liu.se
b
hydrophilic character of PEDOTS, creating new materials which
Laboratory of Organic Electronics, Department of Science and Technology,
Linköping University, SE-60174 Norrköping, Sweden
are soluble in organic solvents and can form films that are stable
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ in aqueous electrolytes without the need of crosslinking.17 We
c8tc05774e have also shown that these materials can be used as active layers

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in OECTs,17 can be inserted into lipid membranes and used to interacting with the sulfonate side groups of PEDOTS during
modify biological functions in living cells.18 The OECTs based on the complex formation, and making them unavailable to
these hydrophobic complexes, however, required relatively con- stabilize the positive charges on the backbone. On the other
centrated aqueous electrolytes (e.g. 1 M KCl) to be operational. side, the PEDOTS : DOA 1 : 1 showed the lowest absorption at
We anticipate indeed that they show poor or null switching 560 nm, indicating a higher level of oxidation of the PEDOTS
ability at electrolyte concentrations around 0.1 M (or lower), backbone. PEDOTS : DOA 2 : 1 showed a similar spectrum to the
corresponding to physiological conditions where cells and bio- 1 : 1 sample, indicating similar doping level.
logical systems function. Here we investigate the parameters Electrochemical transistors having PEDOTS : DOA 1 : 10
affecting the operation of PEDOTS based hydrophobic complexes films as an active layer showed good switching properties when
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in OECTs, aiming to get guidelines for the design of these using electrolyte at high ionic strength, i.e. 1 M KCl, but scarce
Open Access Article. Published on 13 February 2019. Downloaded on 5/3/2019 10:58:06 PM.

materials and their use in biologically compatible environment. or null operation in 0.1 M KCl, as shown in Fig. 2a. Increasing
the PEDOTS to DOA ratio to 1 : 1 led to improved operation in
0.1 M KCl, suggesting that a higher content of hydrophobic
Results and discussion counterions in PEDOTS : DOA 1 : 10 may likely hinder both the
ionic and electronic transport. However, the use of the PEDOTS :
PEDOTS : DOA complexes having different compositions were DOA 2 : 1 did not seem to enable better device performance. On
obtained by mixing PEDOTS (from 1 mg mL1 solutions) with the contrary, these devices remained in the non-conductive state
dioctylammonium (DOA) at different molar ratios, namely in the voltage range investigated (Fig. 2b).
1 : 10, 1 : 1 and 2 : 1, with respect to the EDOTS monomer. The ionic permeability of the different films at different
Scheme and images relative to the different preparation steps ionic strengths was evaluated through cyclic voltammetry by
are shown in Fig. 1. In the three cases the formation of the using potassium ferricyanide as a redox probe (Fig. 3). The
complex resulted in a blue precipitate, insoluble in water blocking properties of the PEDOTS : DOA 1 : 10 at low ionic
(Fig. 1d), which could be readily dissolved in chloroform/ strength (0.1 M KCl) are demonstrated by the decreased current
methanol 1 : 1 v/v (Fig. 1e). At first glance, the three solutions with respect to the one observed on bare gold microelectrodes.
appeared slightly different in color. While the PEDOTS : DOA The increased currents in the PEDOTS : DOA 1 : 1 and 2 : 1 seem
1 : 10 solution showed a light purple color, the other two to indicate instead an improved ionic transport in these films.
appeared light blue. This color change, from purple to pale At higher ionic strengths, i.e. at electrolyte concentrations of
blue can be observed when PEDOTS is switched from the 0.5 M and 1 M (Fig. 3b and c), current increases for all film
neutral to the oxidized state, as a consequence of the decrease compositions. However, the cyclic voltammograms of Fig. 3
of absorption of the p–p* transition at around 600 nm.3,12 also show increased capacitive background contribution at
Accordingly, UV-Vis absorption spectra of the three complexes higher PEDOTS : DOA ratios, as well as electrolyte concentra-
(Fig. 1f) showed a higher level of dedoping for the 1 : 10 tions, which makes an accurate evaluation of the redox current
complex with respect to the other two complexes, demonstrated problematic.19 Peak currents, ip, increased linearly with the
by the increased absorption at around 560 nm. The increased square root of the scan rate (n1/2) as an indication of a diffusion-
dedoping is likely due to a larger amount of DOA cations limited process (Fig. S4, ESI†). By fitting the ip vs. n1/2 curves to

Fig. 1 Preparation of the PEDOTS:DOA complexes. (a) Scheme of the assembly of the complexes from the PEDOTS polyelectrolyte and dioctyl-
ammonium salt. (b) Solutions of PEDOTS after addition of the DOA at different PEDOTS/DOA ratios, namely 1 : 10, 1 : 1 and 2 : 1 with respect to the
monomer. (c) Precipitation of PEDOTS:DOA hydrophobic complexes from aqueous solutions obtained after vortexing the solutions in (b). (d) Dry
PEDOTS:DOA hydrophobic complexes. (e) PEDOTS:DOA solutions in chloroform/methanol. (f) UV-Vis absorbance spectra of PEDOTS:DOA complexes
in chloroform/methanol.

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level of compactness of the film, which may be the cause of the

hindered ionic transport into the bulk of the film during OECTs
operation. The highest roughness of PEDOTS : DOA 1 : 10
should instead favor ionic transport and enhance operation
in these films, since the capacitance of an electrode is generally
directly dependent on its surface area. However, capacitance
can also depend on other parameters such as pore size distribu-
tion and surface chemistry. For activated carbon materials, for
example, capacitance is higher for a sample with wider micro-
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pore size distribution than for a sample with higher surface area
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but too narrow micropore size distribution. In addition, a high

Fig. 2 Electrochemical transistors, OECTs. (a) Transfer characteristics amount of surface groups increase the capacitance of a porous
(solid line, left axis) and transconductance (dashed line, right axis) of
electrode, either by improving the wettability of the material or
PEDOTS : DOA 1 : 10 in 0.1 M and 1 M KCl. (b) Transfer characteristics of
PEDOTS : DOA 1 : 10, 1 : 1 and 2 : 1 in 0.1 M KCl. The scheme of the devices by pseudocapacitance effects.20 The poor performance of PED-
is shown in the inset in (b). Additional curves for these devices are shown in OTS : DOA 1 : 10 devices indicates that morphology and porosity
Fig. S1 and S2, ESI.† of the electrode is not the limiting parameter in this case.
Rather, its high hydrophobicity, being a consequence of a higher
amount of DOA counterions in the complex, may likely be the
the Randles–Sevcik equation we estimated the effective area in cause of a lower degree of swelling and ion uptake in the
the different electrolyte concentrations (Fig. S1, ESI†) and aqueous electrolyte.4,21
observed that while the PEDOTS : DOA 1 : 10 film showed only To assess the interplay between wettability and porosity of
a 19% area increase with respect to the bare Au electrode in the films with different PEDOTS : DOA ratios, we performed
0.1 M KCl, an increase of 72% was calculated for the 1 : 1 impedance spectroscopy in different background electrolytes,
sample. Moreover, higher electrolyte concentration resulted in i.e. 0.1 M KCl, 0.2 M KCl and 0.05 M KCl/0.05 M CaCl2 (hereby
a larger increase for both samples, up to 81% with respect to named KCl/CaCl2), having ionic strengths compatible with
the dilute solution for the PEDOTS : DOA 1 : 10 and 113% for biological activity, such as that found in cell culture media.
the PEDOTS : DOA 1 : 1 in 1 M KCl. These values suggest a Compared to the other two compositions, PEDOTS : DOA
different degree of swelling and ion uptake of the two samples. 1 : 1 revealed a minimized total impedance (Fig. 5a) probably
To get more insight on the changes in electrolyte-accessible due to a balance between wettability and porosity and a decrease
surface areas with varying the composition, we used a com- of total impedance with both ionic strength increase and calcium
bined characterization through atomic force microscopy (AFM) addition. The quantitative analysis of the impedance spectra of
and electrochemical impedance spectroscopy (EIS). AFM analysis the gold electrodes modified with thin films of the complexes was
showed a different morphology for the three films of comparable done with the unified equivalent circuit shown in Fig. 5a. The
thickness (Fig. 4). Although AFM only images the top surface of presence of two time-resolved processes could be modelled by two
the films, some information can be drawn when comparing the RC elements in the unified equivalent circuit developed for an
topography of the different samples. PEDOTS : DOA 1 : 10 shows a electrode covered with a porous coating.22,23 Due to the significant
high surface roughness approximately two times larger than the film conductivity at applied potentials higher than 0 V, the circuit
other two films, and a decreasing surface area from the 1 : 10 to has been reduced to a simple 4-element equivalent circuit. Since
the 1 : 1 and the 2 : 1, as shown in Table 1. The low value of surface the boundary between the layers is not ideally smooth, a quanti-
area difference, representing the ratio between the surface area tative analysis of the electrode impedance response requires a
and its projected area, in PEDOTS : DOA 2 : 1, indicate a higher more complicated, distributed circuit model featuring constant

Fig. 3 Cyclic voltammetry of 2 mM K3[Fe(CN)6] in 0.1 M (a), 0.5 M (b) and 1 M (c) KCl for bare gold IDME and PEDOTS : DOA films at different PEDOTS/
DOA ratios.

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Fig. 4 AFM topography images of dry PEDOTS : DOA 1 : 10 (a), 1 : 1 (b) and 2 : 1 (c) films.

Table 1 Morphology parameters of the PEDOTS:DOA films measured by providing the best fit consists of the solution resistance Rs and
AFM analysis
two parallel branches representing the diffusion through pores
PEDOTS : DOA 1 : 10 1:1 2:1 (pore resistance RP and pore capacitance (CPEP)) and the double
layer capacitance (CPEDL). A single set of parameters has been
Thickness 325 nm 385 nm 340 nm
Roughness RRMS 219 nm 119 nm 96 nm used to simultaneously fit the real and imaginary parts of the
Surface area 6693 mm2 6572 mm2 6484 mm2 impedance spectra over the frequency range from 0.1 Hz to 50 kHz
Surface area differencea 4.58% 2.68% 1.32% (Table 2 and Table S1, ESI†). A value of the fitting quality
a
The surface area difference represents the ratio between the surface area parameter w2 of r0.001 obtained for all spectra indicates a very
and the projected area (6400 mm2), relative to the images in Fig. 4a–c. good fit. Consistently with total impedance behavior, the PEDOTS :
DOA 1 : 1 showed higher capacitance with respect to the other thin
phase elements (CPE) rather than pure capacitors. The capaci- films, and up to 40 times decrease of pore resistance and slight
tance values have been calculated as:24 increase of both capacitances with both ionic strength increase
 1=f and calcium addition showing the ionic transport enhancement.
C ¼ PðRs Þð1fÞ (1) PEDOTS : DOA 1 : 1 revealed the lowest values of pore resistance
and highest capacitance in 0.2 M KCl and KCl/CaCl2.
where Rs is the solution resistance, P is a fitting parameter of the We note that the concept of pore in these soft materials may
CPE and f is the fitted exponent factor, which varies from 0 to 1. be problematic. The swelling of the more-or-less hydrophobic
When f is equal to 0, the CPE behaves as a pure resistor and when complex in electrolytes is a dynamic process and includes
f = 1 the CPE represents a pure capacitor. The equivalent circuit formation of ‘‘pores’’ where solvent may insert, thus changing

Fig. 5 (a) Impedance spectra acquired on different film-modified gold electrodes in 0.1 M KCl. (b) Impedance spectra of PEDOTS : DOA 1 : 1 in different
background electrolytes. The solid lines represent the results of the fittings with the equivalent circuit shown in the inset in (a). Bias 0.2 V, 10 mV
amplitude.

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Table 2 Solution resistance (Rs), pore resistance (RP), pore capacitance (CP) and double layer capacitance (CDL) of the different films in the different
background electrolytes, obtained from the fittings of the impedance spectra of Fig. 5, performed utilizing the unified equivalent circuit in Fig. 5a

PEDOTS : DOA Electrolyte Rs (W) Cp (mF) Rp (W) CDL (mF)

1 : 10 0.1 M KCl 135 0.14 3606 0.3
0.2 M KCl 76 0.3 606 1.9
0.05 M KCl, 0.05 M CaCl2 103 0.32 336 2.4

1:1 0.1 M KCl 121 0.24 7834 1.1

0.2 M KCl 81 0.89 165 5.5
0.05 M KCl, 0.05 M CaCl2 93 0.5 251 4.7
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2:1 0.1 M KCl 119 0.2 8274 0.12

0.2 M KCl 59 0.3 1821 0.62
0.05 M KCl, 0.05 M CaCl2 87 0.22 518 0.23

over time the distribution of pore size and tortuosity. We there- Another feature shown in Fig. 6 is a shift of the curves
fore treat these fitted parameters as very qualitative representa- towards more negative voltages when going from 0.1 M KCl to
tion of the steady state geometry of the swollen polymer film. 0.2 M KCl, and from 0.2 M KCl to KCl/CaCl2. Ion sensitive
To monitor the changes in conductance of the PEDOTS : DOA properties of OECTs have been observed in PEDOT:PSS based
1 : 1 active layer as a function of the applied voltage in the different devices, with the transfer curves shifting to lower gate voltages
electrolytes we then used a four-electrode electrochemical setup at increased cations concentrations. The relative change of the
comprising two working electrodes as source and drain contacts, gate voltage showed a logarithmic Nernstian dependence on
a reference electrode and a counter electrode (see inset in the concentration of the electrolyte, with larger shifts in
Fig. 6a).17,25–28 In the three electrolyte solutions, the film presence of multivalent cations, in accordance with the largest
showed a transition from a neutral, nonconducting form to shift observed for our sample in the presence of bivalent
an oxidized, highly conducting state, reaching channel resistances calcium ions.30 We cannot exclude also a stabilizing role of
2–3 orders of magnitude lower when changing the electrolyte the calcium ions when the devices are operated in KCl/CaCl2
from 0.1 M KCl to KCl/CaCl2 (Fig. 6a). As a result, the corres- (Fig. S3, ESI†). Crosslinking of PEDOTS with Ca2+ could indeed
ponding OECTs show greatly improved operation when KCl/CaCl2 cause the polymer precipitation from solutions at pH above 8,13
was used as electrolyte (Fig. 6b). Also, while the current increases and prevent detachment of thin films from solid substrates.31
with the scan rate in 0.1 M KCl, the channel resistance was found
to be completely independent on the scan rate in 0.2 M KCl or in
KCl/CaCl2 electrolyte, suggesting that ions encounter very low
Experimental
resistance to penetrate the bulk film in these conditions. Poly(4-(2,3-dihydrothieno-[3,4-b]-[1,4]dioxin-2-yl-methoxy)-1-
Improved switching ability of an OECT at increased electro- butanesulfonic acid, dowex-protonated) PEDOTS was synthe-
lyte ionic strength has been explained by both a faster ionic sized as previously reported.3 Dioctylammonium (DOA) chloride
motion and the reduction of the Debye length with the con- 2.5 mM stock solution was prepared by dissolving dioctylamine
comitant increase in the density of ions that accumulate at the (Sigma Aldrich) in 0.1 mM HCl and adjusting the pH to 4
active layer.29 (note that pH and concentration affect both DOA acid/base and

Fig. 6 Performance of PEDOTS : DOA 1 : 1. (a) Channel resistance as a function of the gate voltage and at different scan rates in a four-electrode setup.
The measurements were performed by varying the voltage at the CE (see scheme of the setup in panel (i)) while keeping 50 mV voltage difference
between WE1 and WE2. The three panels refer to different electrolytes, as indicated in the legend. (b) Transfer characteristics of OECTs in different
electrolytes.

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solubility equilibria and have a big impact on the assembly of IIIa system, by using commercial silicon cantilevers with a
the complexes, see also ref. 18). MilliQ water having a resistivity nominal spring constant of 40 N m1. Films thicknesses mea-
of 18.2 MO cm was used for preparation of the aqueous sured by AFM on representative devices were 325 nm for the 1 : 10,
solutions. Two-terminal gold interdigitated microelectrodes 385 nm for the 1 : 1 and 340 nm for the 2 : 1 PEDOTS : DOA films.
(IDME) on glass (MicruX Technologies) were used for electro-
chemical characterizations and device fabrication. All substrates
were washed in an ultrasonic bath in water, acetone and
Conclusions
isopropanol prior to film deposition. We have shown that ionic transport in PEDOTS based complexes
PEDOTS : DOA complexes having different compositions
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is governed by a delicate balance among degree of doping,

were obtained by mixing PEDOTS (from 1 mg mL1 solutions) wettability and porosity, and that these parameters can be
Open Access Article. Published on 13 February 2019. Downloaded on 5/3/2019 10:58:06 PM.

with DOA at different molar ratios with respect to the EDOTS controlled by engineering the supramolecular assembly through
repeat unit, namely 1 : 10, 1 : 1 and 2 : 1 (see Fig. 1b). Vortexing a precise tuning of the polyelectrolyte/hydrophobic counterion
for 5 min resulted in the formation of precipitates of hydro- ratio. We have also shown that is possible to improve OECT
phobic PEDOTS:DOA complexes (Fig. 1c), which could be operation by slightly increasing the ionic strength of the electro-
isolated by successive cycles of centrifugation (10 000 rpm, 10 min) lyte or by adding bivalent calcium ions, while maintaining it in a
and washing in 0.1 mM HCl to remove the excess of DOA or range compatible with biological operation. This material is
PEDOTS. Finally, the pellets were dried under nitrogen flux for therefore suitable to operate at cell interfaces.
60 minutes (Fig. 1d). PEDOTS:DOA complexes were dissolved in
methanol : chloroform 1 : 1, at a concentration of 1 mg mL1
with respect to PEDOTS. For UV-Vis absorbance spectra, all Conflicts of interest
solutions were diluted to 0.05 mg mL1.
There are no conflicts to declare.
Cyclic voltammetry of the PEDOTS:DOA films deposited
on IDME was performed on a Autolab/PGStat10 (Ecochemie,
The Netherlands), by using Ag/AgCl and a platinum wire as Acknowledgements
reference and counter electrodes, respectively. 2 mM K3Fe(CN)6
was used as redox probe, with KCl at different concentrations as This work was supported by the Knut and Alice Wallenberg
supporting electrolyte. foundation, through a Wallenberg Scholar grant to O. I., and
For the 4-electrode electrochemical measurements, PEDOTS: Advanced Functional Materials (AFM) at Linköping University –
DOA complexes were drop cast on the IDME on glass. Measure- a Swedish Government Strategic Research Area.
ments were performed on an Autolab type III bipotentiostat
(Metrohm Autolab, The Netherlands). In this setup, the two gold References
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