Thin Solid Films 583 (2015) 255–263

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Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Effect of anionic dopants on thickness, morphology and electrical

properties of polypyrrole ultra-thin films prepared by in situ
chemical polymerization
Mehrnoosh Mahmoodian a, Behzad Pourabbas a,⁎, Shams Mohajerzadeh b
a
Dep. of Polymer Engineering, Nanostructured Materials Research Center, Sahand University of Technology, Tabriz 51335-1996, Iran
b
Nano-Electronics and Thin Film Lab, School of Electrical and Computer Engineering, University of Tehran, P.O. Box 14395/515, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The effect of different dopant anions on deposition and characteristics of polypyrrole (PPy) thin film has
Received 30 July 2014 been studied in this work. Ultra-thin films of conducting PPy were deposited on insulating surfaces of
Received in revised form 30 January 2015 glass and oxidized silicon wafer by in situ chemical polymerization in the presence of different anionic
Accepted 17 March 2015
dopants including sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, α-naphthalene sulfonic
Available online 8 April 2015
acid, anthraquinone-2-sulfonic acid sodium salt monohydrate/5-sulfosalicylic acid dehydrate, and camphor
Keywords:
sulfonic acid. Hydrophilic/hydrophobic properties and morphology of the self-assembled monolayer of N-
Thin film (3-trimethoxysilylpropyl)pyrrole, the surface modifying agent in this work, and PPy thin films were
Deposition characterized before and after deposition by contact angle measurements, field emission scanning electron
Conducting polymers microscopy, and atomic force microscopy. Chemical structure, thickness, and conductivity of the thin films
Polypyrrole were also studied by attenuated total reflectance Fourier transform infrared spectrometer, ellipsometry,
Anionic dopants and four-point probe measurements. The results showed deposition of thin films of conducting PPy with
comparable thickness in the range of 6–31 nm and different morphologies, uniformity, and smoothness
with average roughness in the range of 0.3–6 nm and relatively high range of conductivity on the modified
surfaces.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Conducting electroactive polymers and their nanostructures have
unique electronic, magnetic, and optical properties similar to semi-
conductors or metals resulted from delocalized π-conjugated
structure and unusual doping concept, reversible doping/dedoping
process and electrical redox reversibility while retained their flexi-
bility, ease of processing and lightweight [1–3]. The mentioned out-
standing properties in addition to chemically tunable properties
have leaded conducting polymers to be applicable in the fields such
as in photovoltaic and electrochromic devices, electromechanical ac-
tuators, sensors and biosensors, transistors, batteries, capacitors,
printed circuit boards and anti-static coatings as well as in optoelec-
tronics nanodevices. [1,3–6].
Polypyrrole (PPy) is one of the most considerable conducting
polymers because of its high electrical conductivity upon doping,
ease of synthesis, thermal and environmental stability, biocompati-
bility and its film forming property [1,7]. Because PPys are insoluble
in most organic solvents except using some approaches such as
⁎ Corresponding author. Tel.: +98 41 3345 9083; fax: +98 41 344 4413, +98 41 3344
4313.
E-mail address: pourabas@sut.ac.ir (B. Pourabbas).
synthesizing with dopant counter ions, thin films of them are typi-
cally formed by electrochemical methods on conducting surfaces
such as metals or glass coated with indium tin oxide [4,8], or by in
situ chemical (oxidative) polymerization on insulating surfaces
such as glass or plastic [4,9], or frequently by plasma [10] or vapor
deposition techniques [11–13].
Conducting polymer nanostructures, especially one-dimensional
(1D) nanostructures including nanowires and nanotubes and two-
dimensional (2D) nanostructures as ultra-thin films with nanoscale
roughness or micro-nanoporosity deposited on the surface have
attracted great interest in nanoscience and nanotechnology for fabrica-
tion of nanodevices and chemical and biological sensors and so on [1–3,
6,14–16]. Because they have superior advantages over other nanostruc-
tured materials such as silicon nanowires (SiNWs) and carbon
nanotubes (CNTs) that have been applied in various types of devices
and sensors recently for instance, fabrication of nanostructures by
conducting polymer can easily be carried out using well established
electrochemical or chemical synthesis methods at ambient
conditions whereas both silicon nanowires (SiNWs) and carbon
nanotubes (CNTs) require rough conditions such as elevated
temperatures and expensive techniques such as vapor–liquid–solid
processes, chemical vapor deposition or laser ablation for their
fabrication [15,17–21].

http://dx.doi.org/10.1016/j.tsf.2015.03.043
0040-6090/© 2015 Elsevier B.V. All rights reserved.
256 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263
In this paper, ultra-thin films of conducting PPy were deposited on
insulating surfaces of glass and oxidized silicon wafer by in situ chemical
polymerization in the presence of different anionic dopants to investi-
gate their effects on thickness, morphology and conductivity of the
thin films of PPy in order to obtain uniform nano-thickness films
with relatively high conductivity. Chemical structure, thickness,
and conductivity properties of the thin films were studied by atten-
uated total reflectance Fourier transform infrared (ATR-FTIR) spec-
trometer, ellipsometry, and four-point probe measurements. The
surface properties including hydrophilicity/hydrophobicity and
the morphology were characterized before and after deposition
of PPy thin films on surfaces modified by monolayer of N-(3-
trimethoxysilylpropyl)pyrrole (Py-silane) using contact angle mea-
surements, field emission scanning electron microscopy (FE-SEM)
and atomic force microscopy (AFM).
The glass surfaces covered by ultra-thin films of conducting PPy can
be used in electrochromic devices [4] and ultra-thin films of conducting
PPy deposited or grown on the insulating SiO2 surface by adjusting
the doping degree can be used as a semiconducting layer in metal-
insulator semiconductor field effect transistor devices [22].
2. Experimental details
2.1. Materials and substrates
Py-silane (MW = 229.35) was obtained from Gelest Inc.
(Morrisville, PA), concentrated sulfuric acid (H2SO4, 95–98%), am-
monium hydroxide (NH4OH, 25%), hydrogen peroxide (H2O2, 30%),
pyrrole (+ 97%), extra pure ammonium peroxodisulfate (APS,
+ 98%), anthraquinone-2-sulfonic acid sodium salt monohydrate
(AQSANa, + 97%), 5-sulfosalicylic acid dihydrate (SSCA, + 99%),
sodium dodecyl sulfate (SDS, 90%), α-naphthalene sulfonic acid
(α-NSA, + 70%), acetonitrile (+ 99.9%), absolute ethanol, methanol,
2-propanol, diethyl ether and molecular sieve were purchased from
Merck. Sodium dodecylbenzenesulfonate (DBSNa, 80%) from Fluka
and camphor sulfonic acid (CSA, 98%) was prepared from Aldrich.
Pyrrole was redistilled in vacuum just before use and acetonitrile
(+99.9%) was dried prior to use first by clean and dry molecular sieve
for at least 3 days and then distillation. SDS was kept under diethyl
ether for 24 h and pure SDS was obtained after filtration and recrystal-
lization from water/ethanol mixture (50:50, v/v) [23]. Purification of
DBSNa was carried out first by keeping in a mixture of isopropyl
and methyl alcohol (50: 50, v/v) for 24 h and then filtration and recrys-
tallization from water [24]. The other chemicals were used without
further purification. Standard microscopy glass slides from Paul
Marienfeld GmbH & Co. KG (26 × 76 × 1 mm) were used as the glass
substrates and polished Si (100) wafers (100 mm diameter, n-doped,
0–100 ohm-cm, test grade) covered by native oxide from University
Wafer were used as the Si substrates.
2.2. Cleaning and silanization of slides
At first polished Si wafers were cleaned by RCA standard method
(NH4OH:H2O2 (30%):H2O 1:1:5), in which a solution of 25% ammonia
solution in water was heated to 70 °C and then H2O2 (30%) was
added. The silicon wafer was submerged in the solution and held at
70 °C for 15 min. The wafer was removed, washed several times with
deionized water, dried by nitrogen stream and used immediately.
Then, silicone oxide (100 nm) was grown on Si surface by dry thermal
oxidation method. Si/SiO2 surface preparation was carried out at
1050 °C and 15 sccm O2 flow for 2 h.
Prior to monolayer deposition, glass and Si/SiO2 substrates were
cleaned by Piranha solutions consisting of H2SO4/H2O2 (6:1, v/v) at
85–87 °C for glass slides and 12:1 (v/v) at 93–95 °C for Si/SiO2 slides
for 1 h followed by rinsing and sonicating with plenty of deionized
water. The cleaned substrates were used immediately after drying
with nitrogen. Moderately hydrophilic surfaces were obtained by this
procedure for silanization.
Surface modification was accomplished by liquid phase deposition
of Py-silane in an organic solvent on the hydrophilic surfaces. All
silanization steps were performed in a glove-box under ultra-pure
argon atmosphere to be protected from atmospheric water vapor. The
freshly cleaned substrates were immersed in a 3 mM solution of the
Py-silane in dry acetonitrile for 4 h. After the substrates had been
removed from the solution, they were rinsed first with acetonitrile
and then with ethanol to remove any physically adsorbed material.
Then they were dried and stored under argon for the next steps.
2.3. Polymerization and deposition of conducting PPy
As the general procedure, two solutions (one containing the mono-
mer and the other, oxidant and dopant) were prepared separately and
then mixed together to start polymerization. Polymerization time was
recorded when the two solutions became mixed together.
APS (0.05 M, oxidant/monomer molar ratio of 5:1) and dopant
(0.03 M, dopant/monomer molar ratio of 3:1) DBSNa, SDS, α-NSA,
AQSANa-SSCA (SSCA/AQSANa molar ratio of 7:1) mixture and CSA
was dissolved in 65 mL of deionized water at room temperature
to make “solution A”. Its temperature was lowered to 5 °C using
ice/water bath. The substrate slide (~ 1.5 × 2.5 cm2) modified with
Py-silane was then placed vertically in the solution A for 5 min.
Later, aqueous solution of pyrrole (0.01 M, 45 μL in 65 mL deionized
water), “solution B”, was added slowly to solution A with vehement
magnetic stirring at 5 °C.
After an elapsed time of polymerization, 10 min to 24 h for different
purposes, the substrates were taken out, washed and sonicated in
deionized water for at least 10 min to remove any physisorbed materials
and then dried by nitrogen. By this method, different conducting
PPy thin films were obtained by different dopants which are named
hereafter as PPy-DBSNa, PPy-SDS, PPy-α-NSA, PPy-(AQSANa-SSCA),
and PPy-CSA.
2.4. Instruments
Equilibrium contact angles were measured by sessile drop technique
using a TZM-2 microscope (BEL Company, Italy) under ambient labora-
tory conditions. A 2 μL drop of deionized water was placed on the
surface and the contact angle was measured after 15 s. ImageJ 1.43u
bundled with 32-bit Java 1.7.0 from Oracle Corporation was used for
contact angle measurements on the microscopy images of the drops.
The measurements were repeated on three samples and average value
was reported with standard deviation, for n = 5 measurements per
each slide. Angles below 8° were considered as zero for accuracy of
the measurements.
ATR-FTIR spectra of PPy thin films deposited on glass surfaces were
recorded on a Bruker Tensor 27 FT-IR spectrometer with OPUS data
collection program (version 1.1) using the standard pike ATR cell.
Surface morphology of PPy thin films on modified surfaces was studied
using FE-SEM (Hitachi, S-4160) with operating voltage 20 or 30 kV.
However, morphology of PPy nanoparticles in solution was observed
using transmission electron microscopy (TEM, Philips, CM30,
300 keV). Samples for TEM were prepared by drying a small drop of
dispersion solution of the particles in distilled water on 300 mesh
copper grid.
Ellipsometric measurements were carried out using an ESP300
Motion Controller/Driver ellipsometer with a 632.8 nm He/Ne laser
and with Si/SiO2 as the substrate. Electrical conductivity measurements
of PPy thin films deposited on modified Si/SiO2 were performed with
four-point probe method using a Keithley 224 high-current source
measure unit. Topology and surface roughness of Py-silane and PPy
thin films deposited on modified Si/SiO2 surface were investigated by
an AFM (model NT-MDT, Next Solver company).
 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263 257

Table 1
Chemical structure of anionic dopants.

Anionic dopants Abbreviation Structure

Sodium dodecylbenzenesulfonate DBSNa

Sodium dodecyl sulfate SDS

α-Naphthalene sulfonic acid α-NSA

Anthraquinone-2-sulfonic acid sodium salt monohydrate-5-sulfosalicylic AQSANa-SSCA

acid dihydrate

Camphor sulfonic acid CSA

3. Results and discussion
3.1. Mechanism of deposition of conducting PPy thin films
Thin films of conducting PPy were deposited on the modified glass
and Si/SiO2 surfaces by in situ chemical polymerization in the presence
of anionic surfactants and sulfonic acids as dopants as shown in Table 1.
It has been demonstrated that the presence of surfactants or sulfonic
acids in polymerization process promotes wettability of the substrate
surface to improve adhesion properties of the deposited films [1,14].
On the other hand, immobilization of PPy thin film can be improved
by modification of the substrate with a pyrrole bearing coupling agent
such as py-silane [14] as a self-assembled monolayer (SAM).
Firstly, by immersion of modified surfaces in solution A, the oxidant
APS, oxides and interacts with pyrrole rings of the SAM to convert it into
cation radicals. Then the organic anions in the solution A attach to
pyrrole cation radicals with electrostatic interactions. When solution B
containing pyrrole monomer is added to solution A, due to large

Fig. 1. Schematic diagram of deposition of conducting PPy thin films on modified surface.
258 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263
Table 2
Mean contact angle values for glass and Si/SiO2 surfaces.
Contact angle (°)
Substrate Before cleaning by After cleaning by After modification
Piranha solution Piranha solution by Py-silane
Glass 59.8 ± 7.0 ~0 61.0 ± 6.0
Si/SiO2 67.0 ± 3.3 ~0 68.0 ± 5.6
amounts of APS in the solution, pyrrole molecules become oxidized and
start to polymerize through the known mechanism via cation-radical
intermediates. In this way, one possibility is free PPy formation i.e. in
the solution and the next one is film formation on SAM layer. The latter
process is favored by amphiphilic organic anions which are aggregated
on the SAM layer as described above making a hydrophobic affinity
for pyrrole molecules or cation radicals from the aqueous solution, as
shown in Fig. 1. This leads to uniform thin films of PPy with nano-
scale thickness on glass or Si/SiO2 substrates which will be verified by
appropriate techniques later in the text. PPy thin films deposited on
the modified glass during 10 min of polymerization were transparent
for PPy-DBSNa, PPy-SDS, and PPy-(AQSANa-SSCA) but with little black
and blue hue for PPy-α-NSA and more for PPy-CSA.
3.2. Surface analysis, contact angle measurements, SEM and AFM
Water contact angle measurement is a rapid qualitative test for SAM
formation of silanes and thin films of deposited materials on the
surfaces [25,26]. In this work, the contact angles were measurements
Fig. 2. FE-SEM images of (a) Si/SiO2 and (b) glass surfaces modified by SAM of Py-silane, (c, d) PPy-DBSNa, (e, f) PPy-SDS, (g, h) PPy-α-NSA, (m, n) PPy-(AQSANa-SSCA), and (p, q) PPy-CSA
thin film deposited on modified Si/SiO2 and glass surfaces respectively.
immediately after rinsing with deionized water and drying with N2
which are reported in Table 2.
For glass slides before cleaning by Piranha solution, the mean contact
angle is 59.8 ± 7.0° that is consistent with the values reported in the
literature and is lower than the mean contact angle for Si/SiO2
(67.0 ± 3.3°). This may be due to the difference in surface nature be-
tween glass and thin film of SiO2 grown on the surface of silicon wafer
by thermal oxidation. Noticeably, RCA standard cleaning procedure
followed by thermal oxidation process for silicon wafer results in higher
roughness and therefore higher contact angle with respect to glass.
Considerable difference in contact angle value was observed for silicon
wafer carrying a native silicon oxide layer (43.6 ± 2.4°) compared to
Si/SiO2 (67.0 ± 3.3°) which can be attributed to metal particles and
other contaminations.
For making the covalent attachment of functional organo-silanes
such as Py-silane to glass, silica or Si/SiO2 and for uniform deposition
of SAM on the surface, surface treatments by Piranha solutions compos-
ing of different volume ratios of H2SO4 and H2O2 at different tempera-
tures were used at fixed treatment time (1 h). This resulted in
hydrophilic surfaces. In several trials, H2SO4:H2O2 (7:3 v/v) at 65 °C
for glass and H2SO4:H2O2 (8:1 v/v) at 85 °C for Si/SiO2 substrates were
examined however, the results were not satisfying in terms of the
obtained hydrophilic surfaces (mean contact angles were 17.7 ± 4.0°
for glass and 45.4 ± 6.6° for Si/SiO2). Therefore, H2SO4:H2O2 (6:1 v/v)
at 85 °C for glass and H2SO4:H2O2 (12:1 v/v) at 95 °C for Si/SiO2 were
used with almost zero contact angle for both substrates.
Then modification with Py-silane was performed on treated glass
and Si/SiO2 slides according to the procedure described in Section 2.2.
Py-silane layer formation on the surfaces is evident by contact angles
 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263
showing hydrophobic properties due to pyrrole rings on the modifying
agent which can be seen in Table 2. As can be seen in Table 2, the mean
contact angle for Py-silane modified glass is somewhat lower than that
of Si/SiO2 which can be due to the different surface topology of modified
glass and Si/SiO2 surfaces as can be seen in FE-SEM images (Fig. 2a and
b). On the other hand, this can also be due to the different effect of
Piranha solution on glass versus Si/SiO2 which is an effective factor on
final morphology of the deposited Py-silane on the surfaces leading to
different contact angles.
Also for further characterization of the SAM of Py-silane on
surfaces, topology and roughness of Si/SiO2 surface after Py-silane
deposition was studied by non-contact atomic force microscopy
(NC-AFM). Uniform smooth topology was observed for Py-silane
layer on Si/SiO2 surface (Fig. 3a) with root mean square roughness
of 0.411 nm and average roughness of 0.331 nm over sampling area
equal to 4.042 μm2. It is obvious to forecast almost same results for
smoothness of SAM of Py-silane on glass surface.
Fig. 3. Topography of (a) SAM of Py-silane on Si/SiO2 surface, (b) PPy-DBSNa, (c) PPy-SDS, (d) PPy-α-NSA, (e) PPy-(AQSANa-SSCA), and (f) PPy-CSA thin film deposited on modified Si/
SiO2 surface by NC-AFM.
259
3.3. Contact angle measurements of conducting PPy thin films
Contact angle measurements were carried out after PPy thin film
deposition on the surfaces in order to prove deposition. Data are collect-
ed in Table 3, the mean contact angle values for thin films of conducting
PPy synthesized in the presence of five different types of dopants
including anionic surfactants and sulfonic acids.
The obtained mean contact angles for PPy thin films on glass and
Si/SiO2 surfaces showed different values but in the same order of hy-
drophilicity ranging from 50 to 80° depending on the surface and the
surfactant used. The slight difference between the values observed
for glass and Si/SiO2 can be attributed to different morphologies
obtained after modification by Py-silane as discussed previously.
The mean contact angles for thin films of PPy-DBSNa, PPy-SDS,
and PPy-(AQSANa-SSCA) are higher than for both glass and Si/SiO2
compared to thin films of PPy-α-NSA and PPy-CSA. This can be
interpreted in terms of the chemical structure of the surfactants and
260 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263

Table 3
Mean contact angle values for PPy thin films deposited on modified glass and Si/SiO2
surfaces.

Contact angle (°)

Conductive polymer Glass Si/SiO2

PPy-DBSNa 71.6 ± 4.2 80.5 ± 6.6

PPy-SDS 78.0 ± 5.5 70.0 ± 7.5
PPy-α-NSA 56.0 ± 6.8 63.0 ± 6.2
PPy-(AQSANa-SSCA) 72.0 ± 3 76.0 ± 2.6
PPy-CSA 65.2 ± 7.6 57.4 ± 4.9

dopant ions (Table 1) which can penetrate through PPy film and be
absorbed to the positively charged surface of the film. For instance,
long alkyl chain in DBSNa and SDS and aromatic rings in AQSANa/
SSCA result in higher hydrophobicity of the films. From the other
hand, thin films of PPy-α-NSA and PPy-CSA with smaller nonpolar
portions in the dopant ions show lower contact angles.

Fig. 4. ATR-FTIR spectra of conducting PPy thin films deposited on modified glass surface,
3.4. SEM and AFM characterization of conducting PPy thin films (a) PPy-DBSNa, (b) PPy-SDS, (c) PPy-α-NSA, (d) PPy-(AQSANa-SSCA), and (e) PPy-CSA.

Morphology and surface roughness of PPy thin films deposited

on both modified glass and Si/SiO2 surfaces were studied by SEM
and AFM characterization. Fig. 2c and d shows FE-SEM images of PPy-
DBSNa thin film deposited on modified Si/SiO2 and glass surfaces. As
can be seen, similar smooth and uniform morphology is detectable for
both surfaces. Uniform and smooth surface with root mean square
roughness of 0.495 nm and average roughness of 0.363 nm was
observed by NC-AFM for PPy-DBSNa deposited on modified Si/SiO2
surface for sampling area equal to 8.997 μm2 as is shown in Fig. 3b.
The same situation was observed by FE-SEM for PPy-SDS thin film
deposited on modified Si/SiO2 and glass surfaces as can be seen in
Fig. 2e and f and by NC-AFM in Fig. 3c, with root mean square roughness
of 1.528 nm and average roughness of 1.078 nm deposited on modified
Si/SiO2 surface over sampling area equal to 2.234 μm2. However, non-
uniform morphology was observed for PPy-α-NSA with different sizes
of the nanoparticles being randomly spread on the surface as can be
seen in Fig. 2g and h. In this case, the morphologies are more or less
the same on both substrates. By NC-AFM, PPy-α-NSA showed an almost
uniform surface with root mean square roughness of 7.094 nm and
average roughness of 5.402 nm deposited on modified Si/SiO2 surface
over sampling area equal to 4.305 μm2 (Fig. 3d).
FE-SEM images for PPy-(AQSANa-SSCA) thin film deposited on
modified Si/SiO2 and glass surfaces are shown in Fig. 2m and n. The mor-
phology is uniform for both surfaces however, somewhat different from
each other. The comparatively uniform film of PPy-(AQSANa-SSCA)
deposited on modified Si/SiO2 showed root mean square roughness of
2.652 nm and average roughness of 1.890 nm over sampling area
equal to 8.130 μm2 (Fig. 3e) by NC-AFM. Finally, non-uniform and
rough morphology was observed in FE-SEM images for PPy-CSA thin
film deposited on modified Si/SiO2 and glass surfaces as are shown in
Fig. 2p and q. This is confirmed by NC-AFM so that PPy-CSA deposited
on modified Si/SiO2, showed a rough surface with root mean square
roughness of 8.392 nm and average roughness of 6.383 nm over
sampling area equal to 8.997 μm2 as can be seen in Fig. 3f.
The surface morphologies are comparable before and after deposi-
tion of PPy thin films with various counter ions for example, Fig. 2a
which is the modified Si/SiO2 before deposition is quite different from
Fig. 2c, e, g, m, and p (the same surface but after deposition). The
same situation is for glass surface so that modified glass surface in
Fig. 2b shows big differences with the glass surface after deposition
shown in Fig. 2d, f, h, n, and q.
In general, it was observed that dopant ions influence the PPy thin
film surface morphologies, as can be seen in different morphologies
in Fig. 2c, e, g, m, and p for Si/SiO2 surface and in Fig. 2d, f, h, n, and
q for glass surface. In general, results from NC-AFM and FE-SEM
show that the surface smoothness of the thin films increases as
PPy-DBSNa N PPy-SDS N PPy-(AQSANa-SSCA) N PPy-α-NSA N PPy-CSA.
Thickness measurements carried out by ellipsometry (Table 4,
Section 3.6) showed that the surface roughness of the films changes
with the thickness in a manner that roughness (root mean square
roughness and average roughness) increases with thickness.
3.5. ATR-FTIR analyses
Fig. 4 shows ATR-FTIR spectra of PPy-DBSNa, PPy-SDS, PPy-α-NSA,
PPy-(AQSANa-SSCA), and PPy-CSA thin films deposited on modified
glass substrates. Deposition (polymerization) time for PPy-DBSNa and
PPy-SDS samples was 24 h while for the others was 40 min. The results
obtained by ATR-FTIR are consistent with those of other researchers
reported for doped PPy [27–30].
Peaks at 760 cm−1 are due to out-of-plane bending vibration of C–H
bonds. However, the high intensity absorption band appeared at 870–
913 cm− 1 in all spectra is attributed to stretching vibrations of trans
double bonds of PPy conjugated system. This peak is stronger in PPy-
DBSNa (Fig. 4a), PPy-SDS (Fig. 4b), and PPy-α-NSA (Fig. 4c) relative to
PPy-(AQSANa-SSCA) (Fig. 4d) and PPy-CSA (Fig. 4e). Also the peak at

Table 4
Dummy.

Conductivity Conductance Sheet Resistivity Average Roughness Root Mean Square Thickness Conductive Polymer
(σ) (S/cm) (S) (kΩ)-1 (R) (kΩ/□) (nm) Roughness (nm) (t) (nm)

18.9 × 102 1.266 0.79 0.363 0.495 6.67 PPy-DBSNa

9.43 × 102 1.316 0.76 1.078 1.528 13.95 PPy-SDS
6.7 × 102 1.205 0.83 5.402 7.094 17.97 PPy-α-NSA
8.75 × 102 1.124 0.89 1.890 2.652 12.84 PPy-(AQSANa-SSCA)
3.8 × 102 1.176 0.85 6.383 8.392 30.89 PPy-CSA
 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263 261

871 cm−1 in PPy-CSA (Fig. 4e) can be attributed to stretching vibrations
of C–N bonds.
Peak appeared at 1518–1545 cm−1 is attributed to stretching vibra-
tions of C = C bonds in the pyrrole rings. The intensity of these peaks is
low for PPy-DBSNa (Fig. 4a) and PPy-SDS (Fig. 4b) and higher for PPy-
(AQSANa-SSCA) (Fig. 4d), PPy-α-NSA (Fig. 4c), and PPy-CSA (Fig. 4e)
respectively.
3.6. Ellipsometery and electrical properties of conducting PPy thin films
The thickness, sheet resistivity, conductance, and conductivity of
conducting PPy thin films deposited on modified Si/SiO2 are summa-
rized in Table 4. Refractive index for PPy thin films was considered to
be 1.817 for ellipsometry measurements [31].
As can be seen in Table 4, PPy thin films deposited for 10 min have
different and comparable thicknesses in the range of 6–31 nm showing
different electrical sheet resistivity or conductivity as well. It is notice-
able that different thickness of the films is related to different dopants
used because all the other conditions were the same in PPy thin film
deposition process. In Table 4, thin films of PPy-DBSNa and PPy-SDS in
which long flexible alkyl chains (Table 1) are in the chemical structure
of the dopant anion, have the lowest thickness among the other
samples. Also, PPy-(AQSANa-SSCA) with large aromatic groups in the
dopant molecule has lower thickness than PPy-α-NSA and PPy-CSA.
On the other hand, thin films of PPy-α-NSA and PPy-CSA with relatively
small molecules as the dopant have shown higher thicknesses.
Electrical conductivity of the samples shown in Table 4, are relatively
high and comparable. Conductivity is a function of few parameters
including:
– Doping level,
– Molecular structure of the dopant,

Fig. 5. TEM images of (a, b) PPy-SDS, (c, d) PPy-α-NSA, (e, f) PPy-(AQSANa-SSCA), and (g, h) PPy-CSA nanoparticles.
262 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263
– Polymerization conditions including relative concentration of mono-
mer, dopant, oxidant, polymerization temperature, and time.
Dopant structure and doping level are the key factors determining
the conductivity. Doping level is controlled by molar ratio of dopant
to monomer and concentration of the dopant in the polymerization
solution. In general, room temperature conductivity increases by
increasing the [dopant]/[monomer] ratios leading to enhanced dop-
ing level [1].
In this work, high doping level was obtained by using high molar
ratio of dopant to monomer (3:1) in relatively high concentration of
dopant (0.03 M), high molar ratio of oxidant to monomer (5:1) and
oxidant concentration of 0.05 M (APS) at low temperature of 5 °C
in order to obtain high conduction. Four-point probe conductivity
measurements are almost in the range of conduction levels which
have already been reported for PPy thin films [32,33].
As long as sheet resistivity is concerned, as shown in Table 4, DBSNa
and SDS surfactants with similar size and length of the alkyl chains in
dopant's structure have resulted in similar but low sheet resistivity
compared to other samples. On the other hand, PPy-(AQSANa-SSCA)
carrying a large aromatic groups in AQSANa has shown a higher sheet
resistivity than others. However, samples with α-NSA and CSA which
are relatively small sized molecules as dopants have shown moderate
sheet resistivity. These are consistent with the results obtained by
ATR-FTIR spectroscopy such that the higher intensity of absorption
bands can be observed for the samples with low sheet resistivity.
When the conductivity is of concern so that the thickness of the films
have to be incorporated in the calculations, PPy-DBSNa, the thinnest
layer, has shown the highest conductivity while PPy-CSA, the thickest
film, has shown the lowest conductivity. Therefore, it can be concluded
that all the effective factors in conductivity including molecular struc-
ture and the doping level of the conducting polymer, and in the case
of thin films, the thickness and density of the film, are changed by
chemical structure of the dopant ions. Dopants by moderately flexible
alkyl chains such as DBSNa, lead to lower sheet resistivity, thinner
films, and higher conductivity however, rigid groups in the dopant,
like NSA, increase the thickness and sheet resistivity but reduces the
conductivity. Small spherical groups when are incorporated in the
dopant ion, like in CSA, increase the thickness of the film significantly
with relatively high sheet resistivity resulting in low conductivity.
3.7. TEM characterization of PPy nanoparticles
In order to synthesize PPy nanoparticles, polymerization was contin-
ued for 24 h at 5 °C and then solutions were centrifuged at 14,000 rpm
for 15 min. All the samples of PPy nanoparticles were precipitated
except PPy-DBSNa so that PPy-DBSNa nanoparticles seem to be soluble
in the water.
PPy-SDS nanoparticles are shown in Fig. 5a and b, which are seen
as 100 nm dark particles surrounded by SDS molecules in the form of
light gray veil around the nanoparticle. PPy-α-NSA nanoparticles in
Fig. 5c and d are smaller with about 5 nm diameter however, PPy-
(AQSANa-SSCA) nanoparticles appeared in complex structures in
Fig. 5e and f with smaller particles being accumulated in bigger
structures of around 200 nm diameter. On the other hand, as can
be seen in Fig. 5g and h, nanoparticles of PPy-CSA are quiet big
with irregular shape of almost 500 nm.
Therefore, it can be concluded that dopant ions when act as a surfac-
tant as well, can alter the size and shape of PPy nanoparticles. It seems
that the main effect of the surfactant anion is in the size and shape
of the nanoparticle agglomeration which in turn can alternate the
dispersion stability of the nanoparticles in aqueous media. DBSNa was
found to be the most effective surfactant among the others to stabilize
nanoparticles so that no any precipitation was obtained by ultra-
centrifugation for this sample. This is one of the key factors to enhance
processability of the conducting polymers.
4. Conclusion
In conclusion, ultra-thin films as nano-structures of PPy conducting
polymer with different morphologies and thicknesses, uniformity and
smoothness and desired conductivity were deposited on modified
glass and Si/SiO2 by in situ chemical polymerization in the presence of
different anionic dopants. The major advantages of the method are
low cost, low toxicity, and ease of the in situ chemical polymerization
method for fabrication and patterning of uniform ultra-thin films of
conducting PPy with adjustable conductivity onto insulating substrates
for electronic applications, comparable to electrochemical methods
which are limited to conductive surfaces, rather small and carried out
usually in laborious procedures and complicated instruments.
It was shown that different dopant ions which can act as surfactants
in the same time have influences on the uniformity and smoothness of
the deposited film, thickness and conductivity, and on the size of the
nanoparticles and their agglomerations. Chemical structure of the
dopant ion that plays the most important role in the mentioned and
measured properties of the thin films was investigated. Moreover, the
dopant ion can facilitate the processes of the conducting polymers for
instance, deposition processes as thin films over solid substrates.
Acknowledgment
The authors wish to express their gratitude from the Iran Nano-
technology Initiative Council (grant number: 38119) for their partial
financial support of the present work. Also, the School of Electrical
and Computer Engineering, University of Tehran is appreciated for
their kind cooperation and the instruments with laboratory equip-
ment provided during the work.
References
[1] M. Wan, Conducting Polymers with Micro- or Nanometer Structure, Springer, 2008.
[2] A. Eftekhari, Nanostructured Conductive Polymers, John Wiley & Sons Ltd, 2010.
[3] Deepshikha, T. Basu, A review on synthesis and characterization of nanostructured
conducting polymers (NSCP) and application in biosensors, Anal. Lett. 44 (2011)
1126.
[4] G.G. Wallace, G.M. Spinks, L.A.P. Kane-Maguire, P.R. Teasdale, Conductive
Electroactive Polymers, Intelligent Polymer Systems, third ed. CRC Press, 2009.
[5] S. Kirchmeyer, K. Reuter, Scientific importance, properties and growing applications
of poly(3,4-ethylenedioxythiophene), J. Mater. Chem. 15 (2005) 2077.
[6] L. Xia, Z. Wei, M. Wan, Conducting polymer nanostructures and their application in
biosensors, J. Colloid Interface Sci. 341 (2010) 1.
[7] M. Omastova, M. Trchova, J. Kovarova, J. Stejskal, Synthesis and structural study of
polypyrroles prepared in the presence of surfactants, Synth. Met. 138 (2003) 447.
[8] S. Cosnier, Recent advances in biological sensors based on electrogenerated
polymers: a review, Anal. Lett. 40 (2007) 1260.
[9] A. Malinauskas, Chemical deposition of conducting polymers, Polymer 42 (2001)
3957.
[10] G.J. Cruz, J. Morales, R. Olayo, Films obtained by plasma polymerization of pyrrole,
Thin Solid Films 342 (1999) 119.
[11] A. Mohammadi, M.-A. Hasan, B. Liedberg, I. Lundstrom, W.R. Salaneck, Chemical
vapor deposition (CVD) of conducting polymers: polypyrrole, Synth. Met. 14
(1986) 189.
[12] A. Nannini, G. Serra, Growth of polypyrrole in a pattern: a technological approach to
conducting polymers, J. Mol. Electron. 6 (1990) 81.
[13] D.O. Kim, P.-C. Lee, S.-J. Kang, K. Jang, J.-H. Lee, M.H. Cho, J.-D. Nam, In-situ blends of
polypyrrole/poly(3,4-ethylenedioxythiopene) using vapor phase polymerization
technique, Thin Solid Films 517 (2009) 4156.
[14] B. Dong, M. Krutschke, X. Zhang, L. Chi, H. Fuchs, Fabrication of polypyrrole wires
between microelectrodes, Small 1 (2005) 520.
[15] M.A. Bangar, W. Chen, N.V. Myung, A. Mulchandani, Conducting polymer 1-
dimensional nanostructures for FET sensors, Thin Solid Films 519 (2010) 964.
[16] F.S. Kim, G. Ren, S.A. Jenekhe, One-dimensional nanostructures of π-conjugated
molecular systems: assembly, properties, and applications from photovoltaics,
sensors, and nanophotonics to nanoelectronics, Chem. Mater. 23 (2011) 682.
[17] H. Taghinejad, M. Taghinejad, M. Abdolahad, A. Saeidi, S. Mohajerzadeh, Fabrication
and modeling of high sensitivity humidity sensors based on doped silicon nano-
wires, Sens. Actuators B 176 (2013) 413.
[18] M. Abdolahad, M. Taghinejad, H. Taghinejad, M. Janmaleki, S. Mohajerzadeh, A
vertically aligned carbon nanotube-based impedance sensing biosensor for rapid
and high sensitive detection of cancer cells, Lab Chip 12 (2012) 1183.
[19] M. Abdolahad, M. Janmaleki, M. Taghinejad, H. Taghnejad, F. Salehi, S.
Mohajerzadeh, Single-cell resolution diagnosis of cancer cells by carbon nanotube
electrical spectroscopy, Nanoscale 5 (2013) 3421.
 M. Mahmoodian et al. / Thin Solid Films 583 (2015) 255–263
[20] M. Abdolahad, S. Mohajerzadeh, M. Janmaleki, H. Taghinejad, M. Taghinejad, Evalu-
ation of the shear force of single cancer cells by vertically aligned carbon nanotubes
suitable for metastasis diagnosis, Integr. Biol. 5 (2013) 535.
[21] M. Abdolahad, H. Taghinejad, A. Saeidi, M. Taghinejad, M. Janmaleki, S.
Mohajerzadeh, Cell membrane electrical charge investigations by silicon nanowires
incorporated field effect transistor (SiNWFET) suitable in cancer research, RSC Adv.
4 (2014) 7425.
[22] V. Saxena, B.D. Malhotra, Prospects of conducting polymers in molecular electronics,
Curr. Appl. Phys. 3 (2003) 293.
[23] I.M. Umlong, K. Ismail, Micellization behaviour of sodium dodecylsulfate and dioctyl
sulfosuccinate in the presence of sodium salicylate, J. Surf. Sci. Technol. 22 (2006)
101.
[24] D.C.H. Cheng, E. Gulari, Micellization and intermicellar interactions in aqueous
sodium dodecyl benzene sulfonate solutions, J. Colloid Interface Sci. 90 (1982) 410.
[25] J.J. Cras, C.A. Rowe-Taitt, D.A. Nivens, F.S. Ligler, Comparison of chemical cleaning
methods of glass in preparation for silanization, Biosens. Bioelectron. 14 (1999) 683.
[26] S. Flink, F.C.J.M. van Veggel, D.N. Reinhoudt, Functionalization of self-assembled
monolayers on glass and oxidized silicon wafers by surface reactions, J. Phys. Org.
Chem. 14 (2001) 407.
263
[27] B. Tian, G. Zerbi, Lattice dynamics and vibrational spectra of polypyrrole, J. Chem.
Phys. 92 (1990) 3886.
[28] M. Omastova, K. Mosnackova, M. Trchova, E.N. Konyushenko, J. Stejskal, P. Fedorko,
J. Prokes, Polypyrrole and polyaniline prepared with cerium (IV) sulfate oxidant,
Synth. Met. 160 (2010) 701.
[29] E. Håkansson, T. Lin, H. Wang, A. Kaynak, The effects of dye dopants on the conduc-
tivity and optical absorption properties of polypyrrole, Synth. Met. 156 (2006) 1194.
[30] L.D. Acqua, C. Tonin, R. Peila, F. Ferrero, M. Catellani, Performances and properties of
intrinsic conductive cellulose polypyrrole textiles, Synth. Met. 146 (2004) 213.
[31] M. El-Sherif, L. Bansal, J. Yuan, Fiber optic sensors for detection of toxic and biolog-
ical threats, Sensors 7 (2007) 3100.
[32] Z. Huang, P.-C. Wang, A.G. MacDiarmid, Y. Xia, G. Whitesides, Selective deposition of
conducting polymers on hydroxyl-terminated surfaces with printed monolayers of
alkylsiloxanes as templates, Langmuir 13 (1997) 6480.
[33] P.-C. Wang, J.-Y. Yu, Dopant-dependent variation in the distribution of polarons and
bipolarons as charge-carriers in polypyrrole thin films synthesized by oxidative
chemical polymerization, React. Funct. Polym. 72 (2012) 311.