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PEDOT/PSS nanoparticles: synthesis and properties

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Cite this: RSC Adv., 2016, 6, 87147

Koji Muro,b Mitsuru Watanabe,*a Toshiyuki Tamai,a Kenji Yazawab
and Kimihiro Matsukawaac

Conductive polymer consisting of poly(3,4-ethylenedioxythiophene)/cross-linked poly(p-styrenesulfonate)

(PEDOT/CL-PSS) particles was synthesized, and its dispersion and film properties were evaluated. CL-PSS
was synthesized by sulfonation of poly(styrene-co-divinylbenzene) prepared by emulsion polymerization,
and PEDOT/CL-PSS was synthesized by oxidative polymerization of EDOT in the presence of CL-PSS
particles. The dispersion of PEDOT/CL-PSS exhibited lower viscosity than that of the usual PEDOT/PSS,
Received 30th June 2016
Accepted 30th August 2016
enabling the highly concentrated dispersion of the conductive polymer in water. The electrostabilities of
the PEDOT/CL-PSS film against heat and humidity were significantly improved by the cross-linkage,
DOI: 10.1039/c6ra16829a
although the conductivity decreased with the increase of crosslink density. PEDOT/CL-PSS was miscible
www.rsc.org/advances with PEDOT/PSS and could be used as a surface roughness-controlling agent for PEDOT/PSS film.

region, tough mechanical exibility, decent thermal stability7–11

Introductions and high hole-transporting property.20,21 PEDOT/PSS is gener-
Transparent conductive materials (TCMs) play an important ally synthesized by oxidative polymerization of 3,4-ethyl-
role in their application as the transparent electrodes of a wide enedioxythiophene (EDOT) monomer in water with linear PSS
range of electronic devices. Liquid crystal display, light-emitting as a stabilizer and a dopant for PEDOT polymer.9 Oxidative
diodes, touch screen panels,1 e-paper2–4 and photo voltaic cells5,6 polymerization of EDOT generates the cationic charged PEDOT,
are obvious examples of the use of TCMs as transparent elec- which strongly interacts with the sulfonate ion of PSS to form
trodes. There are many research studies concerning TCMs, a stable PEDOT/PSS complex. Although PSS is an indispensable
including both inorganic materials and organic materials. The component of PEDOT/PSS, the linear PSS is so hygroscopic that
most widely used inorganic and organic TCMs are tin-doped the water-resistant property and environmental reliability of
indium oxide (ITO)7–11 and poly(3,4-ethylenedioxythiophene)/ PEDOT/PSS lm is poor, and its conductivity easily changes
poly(p-styrenesulfonate) (PEDOT/PSS),12–16 respectively. ITO has depending on the temperature and humidity condition.22–24
advantageous properties such as higher conductivity and higher Nevertheless, there is an application of PEDOT/PSS utilizing its
transparency17 than PEDOT/PSS. However, the formation of ITO high sensitivity to humidity,25 although it is usually recognized
lm always suffers from its relatively low production efficiency as an unfavorable feature of PEDOT/PSS. In order to improve
and high production cost because the lm has to be formed by the environmental reliability of the material, we investigated
sputtering method, which must be carried out under vacuum using a cross-linked PSS (CL-PSS) particle instead of linear PSS
condition. Although it is not difficult to deposit ITO on exible as a stabilizer and dopant for PEDOT. It is expected that the
substrates, the conductivity of the lm easily decreases with water resistivity of PEDOT/CL-PSS will be superior to that of
mechanical deformation, whereas exible transparent conduc- PEDOT/PSS because CL-PSS is less hygroscopic owing to its
tive lms are highly required components in industry nowa- cross-linkage.
days.18,19 Therefore, it is expected that solution-processible The shape of the complex of PEDOT and CL-PSS will be rigid
organic TCM would be a promising material that is exible particles, unlike that of linear PEDOT/PSS, because CL-PSS
and can be processed under ambient condition, leading to particles will serve as seed particles (Fig. 1). The formation of
higher production efficiency and lower production cost. Among particles rather than linear polymer is expected to have some
those solution-processible organic TCMs, PEDOT/PSS is widely advantages. The dispersion of PEDOT/CL-PSS particles will
used because it exhibits sufficient transparency at the visible exhibit lower viscosity compared to a PEDOT/PSS dispersion,
enabling the dispersion of higher concentrations.
Examples of PEDOT adsorbed on particles have already been
a
Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto-ku, Osaka reported by a few groups.28,29 In the reports, PEDOT was
536-8553, Japan. E-mail: [email protected]
b
synthesized on silica core particles and attempted in various
OIKE & Co., Ltd., Frontier Center R & D, 65 Daimotsu-cho, Kamitoba, Minami-ku,
applications including as a photonics catalyst, biocatalyst and
Kyoto 601-8121, Japan
c
Kyoto Institute of Technology, Hashigami-cho, Matsugasaki, Sakyo-ku, Kyoto 606-
drug delivery system. However, there is no report that utilizes
8585, Japan PEDOT particles as TCMs. This is because PEDOT directly

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g, 31.7 mmol) was added. The mixture was stirred for 5 h at 50

C. Aer the reaction, a brown-colored deposit was obtained.
The deposit was rinsed three times with 1,2-dichloroethane and
dried in a vacuum oven at 120
C for 1 h; a gum-like solid of CL-
PSS polymer was obtained. The solid (3.61 g) was redispersed in
100 ml water, and the dispersion was directly used in the next
reaction. The diameter of CL-PSS in the dispersion was also
evaluated by DLS.
Ratio of carbon, sulfur and hydrogen in CL-PSS was evalu-
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ated by chemical elemental analysis (CE Instruments, EA1110),

and sulfonation ratios for each CL-PSS were calculated.

Fig. 1 Schematic image of a liner PEDOT/PSS polymer and a PEDOT/

Synthesis of PEDOT/CL-PSS
CL-PSS particle.
EDOT (0.24 g, 1.69 mmol) and 3.61 wt% CL-PSS dispersion in
water (21.5 g) was placed into a ask. The mixture was purged
deposited on a silica particle would not exhibit high conduc- with nitrogen gas and kept at 18
C. An aqueous solution of 1
tivity without dopants. The combination of PEDOT and CL-PSS wt% aq. iron(III) sulfate (1.38 g) and 11 wt% sodium persulfate
will not only provide PEDOT particle with, but also improve, solution (3.45 g) were added to the mixture. The mixture was
conductivity because CL-PSS contains a lot of dopant units, i.e. stirred for 23 h at 18
C. Aer stirring, cationic ion exchange
sulfonate groups. We also expect that the PEDOT particle is resin (Mitsubishi, SK-1BH, 20 g) and anionic ion exchange resin
applicable as a roughness-controlling agent for the hole- (Mitsubishi, SA-10AOH, 25 g) were added to absorb free ions.
transporting layer of organic photovoltaic (OPV) cells. A hole- Aer ltration of the resin, dispersion of PEDOT/CL-PSS was
transporting layer is placed between the electrode and the obtained. Solid content of PEDOT/CL-PSS dispersion was 0.98
organic active layer of OPV cells, and its surface roughness wt% by gravimetric measurement. PEDOT/PSS was also
inuences the strength of adhesion between the hole- synthesized for comparison. Viscosities of dispersions were
transporting layer and active layer, light absorption ratio, and evaluated by an E-type viscometer (Thermo Scientic).
charge collection ratio.26,27 The addition of the highly conduc-
tive PEDOT particle to the PEDOT/PSS layer will improve the Ink formulation and coating procedure
surface roughness without reducing electronic properties.
In this article, synthetic procedures for CL-PSS and PEDOT/ Coating inks of PEDOT/CL-PSS and PEDOT/PSS were prepared
CL-PSS are shown, and properties of the PEDOT/CL-PSS by adding 50 wt% of 2-propanol and 5 wt% of dimethylsulfoxide
dispersion in water and its lms were evaluated. Also, the (DMSO). Solid content of the ink was 0.44 wt%. 2-Propanol was
effect of the addition of PEDOT/CL-PSS particles on the surface added to decrease the surface tension of the dispersion to
roughness of PEDOT/PSS layer was examined. improve wettability, and DMSO was added to enhance
conductivity as a secondary dopant. The lm formation was
carried out by bar coating in this article. We have also
Experimental conrmed the availability of other methods such as spray
Synthesis of CL-PS coating, gravure coating, slot die coating and so on. Coating ink
was coated on polyethylene terephthalate (PET) lm substrates
Cross-linked polystyrene particles (CL-PS) were prepared by by bar (#9) to an estimated 20 mm wet-coating thickness. Coated
emulsion co-polymerization of styrene and divinylbenzene lm was obtained aer the evaporation of water and solvent at
(DVB). As a typical procedure, styrene (5.0 g, 48 mmol), DVB 120
C in a drying oven. Thickness of the lms was measured
(0.11 g, 0.48 mmol) and sodium dodecylsulfate (SDS, 0.35 g, 1.2 with surface stylus proling (Tencor P-6) and estimated to be
mmol) were placed into a four-necked round-bottom ask, and approximately 100 nm for each sample. For the evaluation of
100 g of water was added. The mixture was purged with nitrogen PEDOT/CL-PSS as a surface roughness-controlling agent,
gas for 15 min and then heated to 80
C. An aqueous solution PEDOT/CL-PSS ink and PEDOT/PSS ink were combined and
(2.0 ml) of potassium persulfate (0.1 g, 0.37 mmol) was added to stirred with a magnetic stirrer for 5 min prior to coating.
the ask, and the mixture was kept at 80
C for 2 h with vigorous
stirring. Evaluation of PEDOT/CL-PSS lms
The diameter of CL-PS was evaluated by dynamic light scat-
tering (DLS, Otsuka Electronics, FPAR-1000). Morphology of the lms was observed by eld emission scan-
ning electron microscope (FE-SEM, Hitachi, FE-4700)
measurement. Surface roughness of the lms was evaluated
Synthesis of CL-PSS by atomic force microscopy (AFM, Shimadzu, SPM-9600).
The dispersion of CL-PS was dried by a rotary vacuum evapo- Conductivity was calculated from lm thickness and sheet
rator to obtain its powder. CL-PS powder (1.0 g, 9.57 mmol) was resistance (4-point probe method, Mitsubishi, MCP-T610).
dissolved in anhydrous 1,2-dichloroethane (20 ml). Acetic Environmental reliabilities, i.e. heat resistivity and humidity
anhydride (3.0 g, 28.7 mmol) and concentrated sulfuric acid (3.2 resistivity, of the lms were measured by R/R0, with storage

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under 90
C for 250 h or 60
C and 95% relative humidity for 250 Table 1 Diameters of CL-PS, CL-PSS and PEDOT/CL-PSS particlesa
h, respectively, where R stands for the resistivity aer the test
Content of CL-PS CL-PSS PEDOT/CL-PSS
and R0 stands for the initial resistivity.
DVB (%) (nm) (nm) (nm)

0.5 45 304 1100

Results and discussion 1 44 230 984
3 40 100 886
Synthesis of PEDOT/CL-PSS and properties of the dispersion 5 40 95 762
As a component of PEDOT/CL-PSS, the ratio of PEDOT to CL- 10 39 45 406
PSS, the size, crosslinking ratio, and the concentration of a
Determined by DLS measurement.
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sulfonic acid group of CL-PSS are expected to be important

factors for the overall property. Since there would be a lot of
choices for the synthetic method of CL-PSS, we synthesized CL-
PS particles by emulsion polymerization and conducted the Table 2 shows the results of chemical elemental analyses of
sulfonation reaction to obtain CL-PSS. Emulsion polymeriza- CL-PSS with different DVB contents and calculated sulfonated
tion provides relatively small (<0.1 mm) particles, which would ratio versus monomer unit. The sulfonation ratio obtained from
be suitable for use as a TCM that requires low haze and suffi- the sample without DVB was 73%. In the case of PSS containing
cient smoothness of the lm. 3% DVB, the sulfonation ratio slightly decreased from 73% to
Scheme 1 shows the synthetic procedure for CL-PS, CL-PSS 69%. PSS containing 10% DVB showed further decrease to 58%.
and PEDOT/CL-PSS. CL-PS was synthesized by emulsion co- These results suggested that co-polymerization of DVB would
polymerization of styrene and DVB. Sulfonation of CL-PS was increase steric hindrance and decrease the sulfonation ratio.
carried out by the Friedel–Cras type reaction with sulfuric acid The relatively low sulfonation ratio of highly cross-linked CL-
and acetic anhydride to obtain CL-PSS. And nally, EDOT was PSS would also be responsible for the smaller swelling ratio in
polymerized in the presence of CL-PSS with sodium persulfate water. Nevertheless, CL-PSS with 10% DVB was moderately
and iron(III) sulfate as oxidant to give PEDOT/CL-PSS. sulfonated even with the high crosslink density, and it was ex-
As shown in Table 1, the diameters of CL-PS were around 40 pected to possess sufficient sulfonic acid groups to work as
nm irrespective of the crosslinking ratio. Aer the sulfonation, a dopant of PEDOT.
CL-PSS with low DVB content showed a signicantly large The ratios of PEDOT to CL-PSS were not precisely constant
diameter compared to that of CL-PS, suggesting that the particle for each sample because the sulfonation ratio varied. According
easily absorbed water and swelled. The swelling ratio of CL-PSS to the reaction condition, the feed ratio of EDOT to sulfonic acid
was highly dependent on the DVB content, indicating that the group was calculated to be between 1 : 1.8 and 2.1. We consider
degree of crosslinking increases with the increased content of that a ratio variation of this range will not make a serious
DVB and that the cross-linkage on the PS main chain did not difference in the electronic properties of each sample.
suffer from the sulfonation reaction. Since the swelling of CL- PEDOT/CL-PSS with varied contents of DVB were casted on
PSS containing 10% DVB was prevented by the cross-linkage, glass plates, and their morphologies were observed by FE-SEM.
the change of diameter was almost ignorable. Aer the poly- As shown in Fig. 2, PEDOT/CL-PSS containing more than 3%
merization of EDOT, the diameters of PEDOT/CL-PSS were far DVB was clearly observed to be a coagulum of particles, whereas
larger than that of CL-PSS. This result suggested the formation PEDOT/PSS without crosslinkage showed no specic
of aggregated particles of PEDOT/CL-PSS, which is probably due morphology and PEDOT/CL-PSS with 1% DVB was composed of
to the hydrophobic interaction of PEDOT-rich domains on the fused particles. As the crosslinking ratio of CL-PSS increases,
surface of PEDOT/CL-PSS particles. the uniformity of the lm decreases, and voids and particle
boundary remain inside the lms. The average diameter of the
primary particles was observed to be around 40 nm from each
SEM image and was almost identical to that of CL-PS as shown
in Table 1. This result indicated that the sulfonation reaction
and subsequent complexation with PEDOT did not affect the
crosslinking and did not give rise to change of primary particle

Table 2 Carbon, sulfur content and calculated sulfonation ratio of CL-

PSS

Content of DVB Carbon content Sulfur content Sulfonation ratio

(%) (%) (%) (%)

0 25.1 5.06 73
3 31.1 5.76 69
10 35.4 5.16 58
Scheme 1 Synthesis of CL-PS, CL-PSS, and PEDOT/CL-PSS.

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Fig. 4 Relationship between content of DVB and the conductivity of

PEDOT/CL-PSS films.

Fig. 2 SEM images of (a) PEDOT/PSS film, (b) PEDOT/CL-PSS (1% DVB)
film, (c) PEDOT/CL-PSS (3% DVB) film, and (d) PEDOT/CL-PSS (10%
DVB) film. crosslinked PEDOT/CL-PSS contains a lot of voids and micro-
cracks as shown in the SEM pictures (Fig. 2c and d), which
would be another reason for the low conductivity. Nevertheless,
size. Also, the result agreed with the assumption that PEDOT/ the result clearly showed the difficulty of forming uniform lms
CL-PSS particles formed aggregated secondary particles. with high conductivity by cross-linked PEDOT/CL-PSS.
It is well known that conventional PEDOT/PSS suffers high Environmental reliability of the lms was tested by storing
viscosity when it is slightly concentrated. Too-high viscosity of them at high temperature (90
C) and high humidity (60
C,
the dispersion is a serious defect in its use as a coating solution. 95% RH) conditions for 250 h, and the effects on resistivity were
As shown in Fig. 3, the viscosity of the dispersions of PEDOT/CL- measured. The relationship between the content of DVB and
PSS decreased when the content of DVB increased. This result relative resistivity is shown in Fig. 5. PEDOT/PSS without DVB
would be responsible for the decrease of intermolecular poly- was easily affected by both humidity and heat. Under the heat
mer chain entanglement because all PSS chains were cross- storage test, it was found that the value of R/R0 decreased as the
linked to form particles. In the case of PEDOT/CL-PSS with 10% crosslink density increased. In the humidity storage test, it is
DVB, the increase in viscosity was so small that it was easy to well known that dedoping of PEDOT/PSS occurs due to the
obtain a highly concentrated dispersion of up to 3.5% under 10 hygroscopicity of PSS.30 However, R/R0 became stable by adding
mPa s1. The availability of high-concentration PEDOT disper- only 0.5% DVB. These results indicated that the dedoping of
sion is one of the most advantageous features of the present PEDOT/PSS was prevented by the steric hindrance and less
research. hygroscopic nature of the crosslinked PSS. Thus, it can be
concluded that introduction of cross-linking signicantly
improved the environmental reliability of PEDOT/CL-PSS lms.
Film formation of PEDOT/CL-PSS and conductivity of the The results showed that PEDOT/CL-PSS is a more stable and
lms reliable material than PEDOT/PSS. Whereas the cross-linkage
Coating ink was prepared by adding additives (2-propanol and also caused the decrease of conductivity, and the sample with
DMSO) to PEDOT/CL-PSS dispersions, which were then coated 1% DVB exhibited sufficient conductivity, signicantly
on a PET substrate by wire bar. As shown in Fig. 4, the decreased viscosity, and improved environmental reliability at
conductivity of PEDOT/CL-PSS lms decreased with the cross- the same time. High environmental reliability is expected to
link density increased. The lower density of sulfonic acid group enrich various device applications in extreme environmental
in the highly cross-linked CL-PSS particle would affect the
conductivity of PEDOT/CL-PSS lms. Also, the lms of highly

Fig. 3 Relationship between solid concentration of PEDOT/CL-PSS Fig. 5 Relationship between the content of DVB and relative resistivity
dispersions and their viscosities. (R/R0) of the films.

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conditions such as a touchscreen panel application in auto- transporting layer itself. Higher roughness of the lm is ex-
motive and OPVs for outdoor use. pected to enhance the adhesion between the PEDOT/PSS lm
and the next layer fabricated onto the lm, i.e. active layer.
Surface roughness and conductivity of PEDOT/PSS + PEDOT/ Thus, this novel method will be readily applicable to improving
CL-PSS composite lms the reliability and durability of organic electronic devices that
One of the well-known applications of PEDOT/PSS is as a hole- contain the PEDOT/PSS layer, such as OPV cells.
transporting layer for OPVs. Although PEDOT/PSS usually has
very smooth surface as shown in Fig. 6a, increasing the surface
roughness of PEDOT/PSS as a hole-transporting layer is ex- Conclusions
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pected to improve OPV efficiency due to increasing surface area, CL-PSS was synthesized by the emulsion co-polymerization of
higher light-scattering property, and improved adhesion toward styrene and DVB and the subsequent sulfonation of thus ob-
the active layer.26,27 The lm of conventional PEDOT/PSS has tained CL-PS. Then, PEDOT/CL-PSS was synthesized by oxida-
smooth surface with Ra of 0.88 nm (Table 3). On the other hand, tive polymerization of EDOT with the existence of CL-PSS in
the mixture of 1% PEDOT/CL-PSS (DVB 10%) + 99% PEDOT/PSS water. The viscosity of the dispersions decreased with increased
gave rise to increased surface roughness with Ra of 1.15 nm. The crosslink density. It was revealed that the shape of the PEDOT/
more PEDOT/CL-PSS particles were added, the rougher the CL-PSS complex was an aggregated dispersion of stable primary
surface that was obtained. The composite lm with 90% particles unlike that of linear PEDOT/PSS. The low viscosity of
PEDOT/PSS + 10% PEDOT/CL-PSS exhibited higher Ra up to 6.29 the PEDOT/CL-PSS dispersion enabled the preparation of
nm. From Fig. 6b, it can be seen that PEDOT/CL-PSS particles a high-concentration dispersion, up to 3.5%, which could not
were well dispersed in PEDOT/PSS lm without aggregation, be achieved by conventional PEDOT/PSS. Although the lm of
probably because they have same functional groups and there- highly cross-linked PEDOT/CL-PSS exhibited relatively low
fore they are miscible with each other. Moreover, the conduc- conductivity, the conductivity was stable against high temper-
tivities of 100% PEDOT/PSS lm and composite lm of 90% ature and humidity, indicating the improvement of environ-
PEDOT/PSS + 10% PEDOT/CL-PSS were 200 S cm1 and 198 S mental reliability by the introduction of cross-linkage on the
cm1, respectively, indicating that the addition of PEDOT/CL- PSS chain. The PEDOT/CL-PSS particles were easily mixed with
PSS particles did not reduce the conductivity of PEDOT/PSS PEDOT/PSS, and the composite lm with rough surface was
lms at all. The conductivity of the composite lms was obtained without decrease of conductivity.
retained because PEDOT/CL-PSS uniformly dispersed in Those interesting properties of this material will lead to
PEDOT/PSS lm and electricity was mainly conducted through various applications. For example, the PEDOT/PSS + PEDOT/CL-
the PEDOT/PSS region. PSS composite with increased surface roughness will readily be
The results demonstrated that PEDOT/CL-PSS particles can applicable as a hole-transporting layer of OPV, with improved
be used as a surface roughness-controlling additive of PEDOT/ reliability and durability as well as increased surface area,
PSS lm without affecting conductivity of the hole- higher light-scattering property, and improved adhesion toward
the active layer. Also, it is expected to be used in applications
such as conductive additives for conductive dispersant,
conductive ller and coloring ller.

Acknowledgements
This research was partly supported by Japan Science and
Technology Agency (JST), A-Step program AS2524023M.
Fig. 6 AFM images of (a) PEDOT/PSS surface and (b) of PEDOT/
PSS:PEDOT/CL-PSS surface (DVB 10%) ¼ 90 : 10.
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