Organic Electronics 15 (2014) 7181

Contents lists available at ScienceDirect

Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

H2S sensing using in situ photo-polymerized polyanilinesilver

nanocomposite lms on exible substrates
Ahmed Mekki a,c, Nirav Joshi b, Ajay Singh a,b,,1, Zakaria Salmi a, Purushottam Jha b,
Philippe Decorse a, Stphanie Lau-Truong a, Rachid Mahmoud c, Mohamed M. Chehimi a,,1,
Dinesh K. Aswal b,,1, Shiv K. Gupta b
a
b
c

Univ Paris Diderot, Sorbonne Paris Cit, ITODYS, UMR CNRS 7086, 15 rue J-A de Baf, 75013 Paris, France
Technical Physics Division, Bhabha Atomic Research Centre (BARC), Mumbai 400085, India
Ecole Militaire Polytechnique, BP 17, Bordj El Bahri 16111, Alger, Algeria

a r t i c l e

i n f o

Article history:
Received 8 July 2013
Received in revised form 12 October 2013
Accepted 13 October 2013
Available online 5 November 2013
Keywords:
Polymermetal nanocomposites lms
Photo-polymerization
Chemi-resistive gas sensor
XPS

a b s t r a c t
We demonstrate the preparation of exible polyanilinesilver (PANIAg) nanocomposite
lms via an in situ facile UV induced polymerization of aniline in presence of AgNO3.
The exible substrates used were (3-aminopropyl)trimethoxysilane (APTMS) modied
biaxially oriented polyethylene terephthalate (BOPET) substrates. The APTMS modication
of BOPET surface has two advantages: (i) improved adhesion of the lms, and (ii) directional growth of polymer perpendicular to the substrate plane, leading to nanobrush-like
morphology. The PANIAg lms have been characterized by various techniques, such as,
UV/Vis, FTIR, Raman, SEM and XPS. These lms were found to be highly selective and sensitive to the H2S i.e. chemiresistive response of 100% at 10 ppm with a reasonably fast
response time of 6 min. PANIAg lms prepared on pristine BOPET exhibits chemiresistive
response of 67% at 10 ppm of H2S exposure. In contrast pure PANI lms did not exhibit
any response on exposure to H2S. The plausible mechanism(s) of H2S sensing have been
discussed. This study highlights the importance of surface modication and the role of
Ag in PANI matrix for H2S sensing.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Conducting polymermetal nanocomposites are a new
class of materials, which provide device design possibility with new functionality, where best of both organic
and inorganic can be utilized [1]. Different approaches
have been used to prepare conducting polymer-metal
nanocomposites in the form of metal nanostructures covered with a polymer shell [2] or vice versa [3], or nano-

Corresponding authors. Address: Technical Physics Division, Bhabha

Atomic Research Centre (BARC), Mumbai 400085, India. Tel.: +91 22
25591664; fax: +91 22 25505296 (A. Singh).
E-mail addresses: asb_barc@yahoo.com (A. Singh), chehimi@
univ-paris-diderot.fr (M.M. Chehimi), dkaswal@yahoo.com (D.K. Aswal).
1
These authors contributed equally to this work.
1566-1199/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.orgel.2013.10.012

structures embedded in the polymer matrix [4]. Among

various conducting polymers, polyaniline (PANI) has attracted much attention due to ease of synthesis, excellent stability under environmental conditions, tunable
electrical conductivity, and biocompatibility [5]. Embedding metal nanoparticles (MNp) in PANI is one of the
attractive strategies to harness the sensing [6], electrochemical [7] and catalytic properties [8]. In the context
of chemiresistive gas sensor based on PANI, the incorporation of suitable metal in PANI matrix not only improves the sensitivity but also the selectivity towards a
particular gas [9]. In literature, nanocomposites of PANI
with different metals, such as, PANIAg [711], PANI
Au [12], PANIPt [13] and PANICu [14] etc. have been
reported. The synthesis of PANImetal nanocomposites
can be broadly classied into two categories: (i) post

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A. Mekki et al. / Organic Electronics 15 (2014) 7181

addition of MNp in the preformed polymer solution [7],

however the associated problem in this case is an
agglomeration of MNp in the polymer matrix; and (ii)
in situ addition of MNp via reduction of metal salt
during the polymerization process, and this approach
usually yields a homogenous distribution of MNp [11].
Among various nanocomposites, PANIAg is gaining considerable attention because it can be easily prepared by
in situ approach i.e. using direct oxidation of aniline by
Ag+ in the presence of UV irradiation [7], c irradiation
[15], ultrasonication in aqueous media [16] or chemical
polymerisation in ionic liquid media [17]. Most of the reported studies on the PANIAg nanocomposites are
mainly focussed on the preparation of this material in
the form of powder [11] or drop casted lms [7]. However, for many emerging exible devices, such as, displays, electronics, gas sensors and, it is essential that
the PANIAg lms are directly deposited onto the exible
substrates. In fact, conducting polymer (CP) thin lms on
exible substrates have been deposited by chemical,
electrochemical or photo-polymerization. Electrochemical
method has an inherent disadvantage as it requires
electrically conducting substrates. On the other hand,
chemical or photo-polymerization process allows in situ
polymerization providing thin CP layers on a wide range
of insulating substrates [1820]. Unfortunately, though
these methods are simple but have two major
limitations: (i) poor adhesion of CP layer to the
substrate; and (ii) non-uniform lm thickness and morphology over a large surface area. The commonly used
strategy to overcome these problems is the surface
modication of substrate using suitable coupling agents
[20].
In this paper, we report preparation of PANIAg nanocomposites lms on (3-aminopropyl)trimethoxysilane
(APTMS) modied bi-axially oriented polyethylene teraphthalate (BOPET) substrates by in situ photo-polymerization. We demonstrate that APTMS modied BOPET surface
not only improves the adhesion of the deposited PANIAg
lms but also provides a unique brush-like morphology.
These PANIAg nanocomposites lms exhibit superior response to H2S gas (at parts per million (ppm) level) as compared those prepared onto the unmodied BOPET. The
room temperature detection of H2S using PANIAg lms
is very important from application point of view. H2S is a
toxic, corrosive, and inammable gas produced in sewage,
coal mines, oil, and natural gas industries and utilized in
many chemical industries. It is important to detect H2S because it is colorless, ammable, heavier than air, and its
toxic limit is 10 ppm [21]. H2S can cause blood poisoning
and at high enough concentrations higher than 250 ppm
may lead to death. Therefore, H2S sensor that is sensitive
and rapid in its response at ppm level of H2S exposure is
needed. In this context, thick or thin lm sensors based
on semiconductor oxides such as tin oxide, tungsten oxide,
and have been widely reported [21a]. A major disadvantage of these sensors is their high operating temperatures
that make them highly power inefcient and reduce their
long term stability. More important, our PANIAg lms
exhibit reversible gas sensing characteristics and are

adherent, exible in nature, therefore may have longer

operating life.
2. Experimental
2.1. Materials
Aniline (SigmaAldrich, purity 98%) was refrigerated in
the dark prior to synthesis. Before using, it was passed
through a basic alumina powder (MERCK, size 63 lm)
lled column to remove the impurities. Silver nitrate (SigmaAldrich, purity 99.9%) was of analytical grade and
was used as received. The organic solvents used were of
analytical grade and deionized (DI) water was used for
washing and solution preparation. BOPET sheets of thickness 100 lm were procured from DuPont. These sheets
were cut into size of 25 mm  10 mm using steel scissor
for the experiments. (3-Aminopropyl)trimethoxysilane
(APTMS) (SigmaAldrich, purity 97%) used for surface
modication of BOPET. BOPET substrates were ultrasonically washed with chloroform, and ethanol for 30 min,
after that dried for 4 h at 70 C in an oven.
2.2. Surface modication of BOPET substrate by grafting of
APTMS
The surface modication of BOPET sheets were carried
out by the APTMS i.e. (3-aminopropyl)trimethoxysilane
layer. To graft APTMS on BOPET, rst the surface of BOPET
was hydroxylated by dipping it in the potassium hydroxide
(KOH) containing dimethyl sulphoxide (DMSO) solution
(4 mg of KOH dissolved in 30 ml of DMSO). The sheets
were left to react with KOH for 30 min, then thoroughly
washed in distilled water and dried. The hydroxylated
sheets were then dipped in an APTMS solution (115 mg
in 25 ml of ethanol and 1 ml of acetic acid) and left to react
for 72 h. After this the substrates were thoroughly cleaned
using ethanol and dried for 2 h at 70 C in an oven.
2.3. Preparation of PANIAg nanocomposite lms on APTMS
modied BOPET
The photo-polymerization of aniline on APTMS modied BOPET sheets was done in a glass bottle containing
xed amount of distilled aniline 931.3 mg (1 M) along with
2 M HNO3 in 10 ml of DI water. HNO3 is added to aniline
10 min prior to the photo-polymerization for the protonation of monomer. After protonation step of aniline,
849.4 mg (0.5 M) AgNO3 is added and nally after a uniform mixing, solutions were placed under a UV lamp
(Spectrolinker, XL-1500UV cross linker) set at wavelength
365 nm, UV source to sample distance 13 cm, intensity
5 mW/cm2 for 6 h. After UV exposure the samples were
thoroughly cleaned with deionized water and ethanol to
remove the unreacted species. This washing treatment
may partially de-dope the PANIAg lms and therefore
the lms were subsequently exposed to the HCl vapors
for about 2 min. Finally the samples were dried for 4 h at
70 C in an oven. In order to investigate the effect of Ag

A. Mekki et al. / Organic Electronics 15 (2014) 7181

on gas sensing characteristics of PANIAg lms, samples

with xed concentration of aniline (1 M) and varying concentration of AgNO3 (0.53 M) were also prepared under
identical experimental condition. Pure PANI lms were
prepared with chemical oxidation method using ammonium persulphate ((NH4)2S2O8) as oxidant.
2.4. Characterization
The prepared PANIAg lms were characterized by Fourier-transform infrared spectroscopy (Bruker 80 V), Raman
spectroscopy (Horiba Jobin Yvon). Surface morphology of
the lms was imaged using scanning electron microscopy
(SEM) (ZEISS SUPRA). X-ray diffraction analysis was carried
out on lms using XPert PRO (PANalytical) diffractometer
using Co Ka (1.789 ) radiation. In order to estimate the
crystallite size using Scherrer formula, the instrument contribution for broadening of the XRD peak was estimated by
using a polycrystalline Si (with large grains and no stress)
as a standard. A pure lorentzian t is done estimate the full
width at half maximum (FWHM) of each peak of the standard, and a caglioti function is obtained (FWHM2 =
f(tan h)). In this way we can estimate instruments contribution in FWHM at any angle, and this value is subtracted
to estimate correct value of the crystallite size.
X-ray photoelectron spectra (XPS) were obtained using
a Thermo VG ESCALAB 250 instrument tted with a monochromated Al K X-ray source. An electron ood gun was
used for charge compensation. The analyzer was operated
at 40 and 100 eV pass energy for the narrow regions and
survey spectra, respectively. Elemental atomic concentrations were calculated from the XPS peak areas and the corresponding Scoeld sensitivity factors corrected for the
analyzer transmission work function. Electrical conductivity of the samples was measured using conventional four
probe technique (with typical probe separation of 1 mm)
and Keithley 2400 source meter. For measurement 10 lA
current was passed through the outer probe in the sample
and voltage was measured at inner probe.
In order to perform the gas sensing measurement, few
pairs of Au electrodes (size: 3 mm  2 mm, thickness
1 lm) separated by 12 lm gap was rst thermally deposited onto the lms (shown in Fig. 6(b)). Gold was chosen as
the electrode materials due to following reasons: (i) it has a
very good work function (5.2 eV) matching with the
PANI, hence the lms electrode contact is ohmic and (ii)
being a noble metal gold does not react with most of the
test gases. The sensor lms with Au electrodes were
mounted in a leak tight stainless steel chamber having volume of 1000 cm3 and electrical wires were connected between gold electrodes and pins at electrical feed through
of the chamber. The pins at electrical feed through is already connected to and electrical property measurement
setup (Keithley 6487 voltage source/picoammeter). The response curves towards various test gases were measured
by applying a x bias of 1 V across the gold electrode and
the time dependence of the current passing between the
electrodes was recorded using computer based data acquisition system using Labview software. Gas sensing measurements were performed in a static environment
method. Required concentration of a test gas in the

73

chamber was attained by introducing a measured quantity

of desired gas using a syringe. All the test gases were commercially procured from M/s Chemtron Science Pvt. Ltd.
Mumbai, India. For these measurement Keithley 6487 voltage source/picoammeter was used. Once a steady state was
achieved, recovery of sensors was recorded by exposing
the sensors to air, which is achieved by opening the lid of
the chamber. The sensitivity (S) of the sensors was calculated from the response curves using the relation:

S%

jIg  Ia j
 100%
Ia

where Ig and Ia are the current values of the sensor lms in

test gas and fresh air, respectively. Response and recovery
times were dened as the times needed for 90% of total
change in conductance upon exposure to test gas and fresh
air, respectively.
Impedance spectroscopy measurement of the samples
was carried out using Wayne Kerr precision impedance
analyzer (model: 6500 B) in the frequency range
20 Hz10 MHz.
3. Results and discussion
3.1. Grafting of (3-aminopropyl)trimethoxysilane on BOPET
substrate
The surface modication of BOPET was carried out by
the APTMS (i.e. (3-aminopropyl)trimethoxysilane) layer.
The scheme for grafting of APTMS layer at hydroxylated
BOPET surface is shown in Fig. 1. In brief, the silanization
process in general takes place in following steps as [22]:
(i) hydrolyse of silane head-groups arriving close to the
substrate due to adsorbed water layer (inherently present)
on the surface, (ii) covalent bonds formation between
Si(OH)3 groups with the hydroxyl groups on BOPET.
The pristine, hydroxylated and APTMS modied BOPET substrates were further characterized by the XPS.
The XPS results shown in Fig. 2 suggest that pristine
and hydroxylated BOPET substrate shows the presence
of only C1s and O1s i.e. whereas the survey scan of the
APTMS modied BOPET shows the two additional peak,
i.e. N1s peak at 399.6 eV and Si2p peak at 102.1 eV;
which conrms the presence of APTMS layer at the surface of BOPET [23]. The elemental composition (in at%)
obtained from the high resolution XPS spectra for pure,
hydroxylated and APTMS treated BOPET are reported in
Table 1.
As seen from Table 1, for pristine BOPET the C/O ratio
was found to be very high (6.6), which does not match
with the chemical formula (C10H8O4)n for BOPET [24]. On
the hydroxylation of BOPET the C/O ratio was found to be
2.7, indicating that BOPET surface is regaining its intrinsic composition on hydroxylation. For APTMS modied BOPET the ratio of N/Si was found to be 1.8, which closely
matches with the reported value for other silanes grafted
on ITO surface [23,25]. The presence of Si 2p peak at
102.1 eV suggests the presence of SiO kind of layer as
shown in Fig. 1. It is interesting to note that for the APTMS
treated BOPET, the N1s spectra shows the presence of two

74

A. Mekki et al. / Organic Electronics 15 (2014) 7181

NH2
(CH2)3
Si
O

O
OH

NH2

NH
2

(CH2)3

OH OH OH OH
KOH+ DMSO

BOPET

BOPET

30 min

(CH2)3

Si

Si
O

H3CO
OCH3
OCH3

BOPET

CH3OH+ HOAc(72 h)

Fig. 1. Scheme showing the surface modication of BOPET substrate by APTMS.

I (arb. units)

(b)
APTMS modified
BOPET

100

200

400

600

Binding energy (eV)

800

102

104

106

Binding energy (eV)

Hydroxylated
BOPET

N1s

(c)
I (arb. units)

BOPET

Si2p

I (arb. units)

O1s

Si2p

N2p

C1s

(a)

396

398

400

402

Binding energy (eV)

Fig. 2. (a) XPS survey spectrums of the pristine, hydroxylated and APTMS modied BOPET substrates. (b) Si2p and (c) N1s spectra for APTMS modied
BOPET.

Table 1
Chemical composition of the pristine, hydroxylated, and APTMS modied
BOPET surface determined from the analysis of the XPS data.
Sample

C1s

N1s

Si2p

O1s

Comment

BOPET
Hydroxylated BOPET
APTMS modied BOPET

86.9
73.1
70.6

2.4

1.3

13.1
27.1
25.7

C/O  6.7
C/O  2.7
N/Si  1.8

peaks at binding energy values of 398.7 and 400.2 eV. The

low binding energy peak is associated with the nitrogen in
free NH2 group while the higher binding energy peak
400.2 eV is attributed to the slightly positively charged
nitrogen of the NH2. The presence of positively charged
nitrogen suggests the possibility of APTMS multilayers formation. Process of multilayers formation can be described
by the interaction of head group of the hydrolyzed APTMS
molecules (i.e. Si(OH)3 which is weak acid) in the presence
of adsorbed water layer with the surface NH2 groups (i.e.
basic in nature) of the monolayer through the dipoledipole interaction as shown in Fig. 1 [23].

3.2. Synthesis of PANIAg composite lms

In the present work, PANIAg nanocomposite lms
were prepared on the APTMS modied and pristine BOPET
substrates by the photo-polymerization approach. Briey
the process of photo-polymerization of aniline is given in
Fig. 3(a). On exposure to UV light, the preformed protonated aniline monomer gets excited and then electrons gets
transferred from the excited monomer to the Ag+ ions leaving aniline radical cation. This radical cation further reacts
with another radical cation and resulting in the polymerization of aniline. In this process, Ag+ ion after receive electrons from protonated aniline monomer reduced to the
metallic state [11].
When APTMS modied BOPET is placed in the mixed
solution of protonated aniline and AgNO3, the surface
NH2 group of APTMS layer are converted into radicals
(NH
2 ) on exposure to UV [20]. These amino radicals initiate the growth of PANI by photo-polymerization process
as shown in Fig. 3(b).

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A. Mekki et al. / Organic Electronics 15 (2014) 7181

NH3

Ag

hv

NH3

365 nm

Protonated
monomer

Ag

NH2

Radical
cation

Excited
monomer

(b)

NH2

NH

NH
(CH2)3
Si
O

OH

OH

NH
2

NH
2

(CH2)3

(CH2)3

NH2

Si
O

nAg

NH

Si

Polymerisedaniline

(CH2)3

Ag

Growth direction

(a)

Si
O

BOPET

+HNO3
AgNO3+UV(365 nm)

BOPET

Fig. 3. (a) Mechanism of photo-polymerization of aniline in presence of AgNO3 photo-initiators and UV light (365 nm). (b) Scheme showing the synthesis of
PANIAg nanocomposite lms on the APTMS modied BOPET substrate using photo-polymerization approach. In this scheme the N atoms denoted by red
color corresponds to the aniline while the one denoted by black correspond to the APTMS layer. (For interpretation of the references to colour in this gure
legend, the reader is referred to the web version of this article.)

3.3. Morphology and structural characterization

3.4. Spectroscopic characterization of PANIAg lms

Fig. 4(a) shows the low magnication SEM image of the

synthesized PANIAg lms (prepared with AgNO3
 0.5 M), which reveals the growth of nano-brush kind of
morphology. A more clear view of nano-brush type of morphology is clearly seen in Fig. 4(b), which reveals the nanobers with a typical average diameter <20 nm. It may be
noted that PANIAg lms prepared under identical condition on pristine BOPET substrate shows a smooth morphology (shown in inset of Fig. 4(a)). These results suggests, the
presence of APTMS layers at the BOPET surface controls the
photo-polymerization of aniline in the direction normal of
the substrate, as schematically shown in Fig. 3(b). Fig. 4(c)
shows the high magnication SEM image of the PANIAg
lms prepared with higher concentration of AgNO3
(3 M), it reveals the presence of Ag clusters in the PANI
matrix. The presence of these Ag clusters in the PANI
matrix could be due to the limited solubility of Ag in the
PANI matrix.
The XRD pattern recorded for PANIAg lms shown in
Fig. 4(d), which reveals the presence of Ag (1 1 1) diffraction peak at 44.6 degree along with the BOPET diffraction
peaks at 30 and 65 degrees due to the low thickness of
the lms [26]. From the full width half maximum (FWHM)
of the highest intensity (1 1 1) peak of Ag, the size of the Ag
crystallites was estimated by Scherrer formula as 70 nm.

PANIAg lms were characterized by UVvisible, FTIR,

Raman and XPS. The details such as assignment of the
peak and tting results are given in Ref. [37]. The UV
visible and FTIR spectra for PANIAg lms are shown
in Fig. 5(a) and (b) respectively. In the UVvisible spectra
three absorption peaks are observed at 340 nm, 692 nm
and 430 nm and which are respectively assigned to
pp transition, polaron band to p band and p band
to polaron band [11]. To clearly distinguish the IR peak
of PANIAg lms from the BOPET substrate, we have also
plotted the IR data for BOPET substrate in Fig. 5(b). The
appearances of the bands at 1568 cm1 and 1490 cm1
benzenoid suggest that both quinoid and benzenoid ring
structure are present in PANIAg lms. The ratio of peak
area gives the relative concentration of quinoid to the
benzenoid as 43% [27]. The band at 1235 cm1 is characteristics of the electrically conducting form of the PANI
[28].
A comparison of the Raman spectra of PANIAg lm and
BOPET (shown in Fig. 5(c)) suggest that BOPET has no contribution in the observed pattern for PANIAg lms. The
detailed peak assignment given in Ref. [37], suggest that
sample exhibit the characteristic of the protonated state
of PANI and correspond to the formation of delocalized
polaronic structures in the lms [7,28].

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A. Mekki et al. / Organic Electronics 15 (2014) 7181

(a)

(b)
(b)
1 m

1 m

100 nm

(c)

(d)
(111)

I (arb. units)

Ag clusters

PANI-Ag

BOPET

100 nm
0

20

40

60

80

2 (degree)

1568

1490

1444

1290

1178

Fig. 4. (a) SEM image PANIAg lms (prepared with AgNO3  0.5 M) grown on APTMS modied BOPET substrate at low magnication. Inset shows the
PANIAg lms grown on pristine BOPET (b) SEM image taken at 25tilt, (c) SEM image of the PANIAg lms (prepared with AgNO3  3 M) grown on APTMS
modied BOPET. (d) XRD data for pristine BOPET and PANIAg coated APTMS modied BOPET.

Absorbance

Absorbance

3231

692

340

3100

3200

3300

PANI-Ag

430

(a)
450

600

750

900

1200

1600

1800

C1s

1613

PANI-Ag

Cl2p

Ag3d
N1s

I (arb. units)

1500

1414

1463

1290
1310

1220

1164
1185

PANI-Ag

BOPET

(c)
1200

1400

Wavenumber (cm-1)

Wavelength (nm)

O1s

300

I (arb. units)

BOPET

(b)

(d)
1300

1400

1500

1600

Wavenumber (cm-1)

1700

200

400

600

800

Binding energy (eV)

Fig. 5. Characterization of PANIAg nanocomposite lms: (a) UVvis spectra. (b) FTIR spectra. Inset shows FTIR spectra in higher wave number region. (c)
Raman spectrum. (d) XPS survey scan.

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A. Mekki et al. / Organic Electronics 15 (2014) 7181

XPS spectra were recorded to obtain the information

about the various intrinsic/redox states of the PANIAg
lms. Survey XPS spectrum for PANIAg lms is shown
in Fig. 5(d); it shows the presence of nitrogen
(N1s  400 eV),
carbon
(C1s  285 eV),
chlorine
(Cl2p  199 eV) and Ag 3d doublet centered at 368.3
374.4 eV [29]. In order to obtain the information about
the doping level, high resolution C1s and N1s XPS spectra
were recorded and the quantitative information obtained
from the tting is given in Table 2 (details of the tting
is given in Ref. [37]). The ratio of positively charge nitrogen
(N+) with the neutral nitrogen corresponding to amine or
the ratio of counter ions (Cl and NO
3 ) to the total nitrogen
give a doping level of 36%.
In summary, the spectroscopic characterization of the
sample indicates that synthesized PANIAg lms are in
the doped emeraldine form.

of curvatures (r) at room temperature. A photograph showing the exible nature of PANIAg nanocomposite lms is
shown in Fig. 6(a).
In order to measure the electrical resistance (R) of the
samples, few pairs of gold electrodes were deposited on
the PANIAg lms (photograph shown in right side of
Fig. 6(b)). Left side of Fig. 6(b) shows the schematic of
our bending set up along with resistance measurement circuit. The variation of room temperature resistance of the
exible PANIAg lms as a function of r is plotted in
Fig. 6(c). It is seen that under at condition (without bending i.e. r ? /) the lms exhibit a resistance of 0.3 MX. On
increasing the lm bending, i.e. a decrease in r, results in a
very minor variation in the resistance. The stability of
resistance on bending is only possible if the lms are
adherent to the substrate and does not create any defect
state or cracks on bending. Thus, a highly stable resistance
with bending implies that these PANIAg lms are suitable
for the exible organic devices.
Qualitative adhesion test (90 peel test) was carried out
on PANIAg lms prepared under identical experimental
condition on pristine and APTMS modied BOPET. The results of adhesion test are shown in Fig. 6(d). The left side

3.5. Flexibility and adhesion

In order to demonstrate the mechanical exibility of the
PANIAg nanocomposites lms synthesized on APTMS
modied BOPET sheet, lms were bent to various radius
Table 2
Quantitative analysis (in at.%) of N1s and C1s XPS spectra.
ANH (399.1 eV)

AN@ (397.2 eV)

AN+ (400.4; 402.6 eV)

Doping level (N+/N; {Cl-+NO3-}/N)

60.99
CAC or CAH (284 eV)
37.58

2.41
CAN/C@N (284.9 eV)
23.42

36.59
CAN+/ C@N+/CACl (285.5 eV)
24.96

36.6, 36.04
C@O/CAO (286.7 eV)
14.04

(a)

(b)

Au electrodes (separated by 12 m)

PANI-Ag
film

Resistance (M)

(c) 0.35

(d)
90 peel test

0.30

0.25

Flat

Bend radius (mm)

Flat

PANI-Ag films on
(1) BOPET (2) APTMS modified BOPET

Fig. 6. (a) Digital photograph of PANIAg lms deposited on silanised APTMS modied BOPET substrate. (b) Left side shows the schematic of the bending
arrangement along with resistance measurement circuit. Right side shows the photograph of few pairs of gold electrodes (gap  12 lm) deposited on the
PPy-Ag lms. (c) Variation in resistance of PANIAg lms for different bend radius. (d) Left side photograph showing PANIAg lm prepared on pristine
BOPET (1) APTMS modied BOPET substrate (2). The lms are glued on adhesive tape under similar load. Right hand side photograph of the adhesive tape,
which shows the material detached from the lms by the adhesive tape after 90 peel test.

A. Mekki et al. / Organic Electronics 15 (2014) 7181

3.6. Electrical and chemiresistive gas sensing characteristics

Typical room temperature currentvoltage (IV) characteristics of the PANIAg lms (with AgNO3  0.5 M) in
the bias range of 1 V are shown in Fig. 7(a). IV curves
for these lms are linear indicating an ohmic contact between Au electrode and PANIAg lms. Similar linear IV
characteristics were observed for all other PANIAg lms
prepared with different AgNO3 concentration and the estimated conductivity (r) of the lms is plotted in the inset of
Fig. 7(a). It can be seen that r of the lms systematically
increases up to AgNO3 concentration 2 M and after that
it decreases at high concentrations 3 M. The decrease in
r at higher Ag concentration is quite surprising because

by increasing the Ag content in the PANI matrix should increase the r. As discussed earlier, PANIAg lms prepared
with AgNO3  3 M exhibit the presence of large number of
Ag clusters embedded in the PANI matrix. These big size Ag
clusters can form schottky barriers at the PANI/Ag interfaces impeding the easy ow of the charge carriers, and
therefore lowers r. Earlier we have observed similar
behavior for the polypyrrole-silver (PPy-Ag) nanocomposite lms, where r is low for the samples prepared at very
high AgNO3 concentration [26].
The chemiresistive gas sensing properties of PANIAg
lms was investigated by the exposure of 10 ppm of each
test gases such as NH3, H2S, Cl2, NO, NO2, CO, CH4, and
C2H5OH. Among all gases PANIAg lms showed the response for H2S only. The typical response curves recorded
of PANIAg lms (prepared with AgNO3  0.5 M) for different concentration of H2S exposure are shown in Fig. 7(b),
which reveals that there is an increase in current on exposure to H2S. Considering the electron donating nature of
H2S (reducing gas); the increase of current instead of expected decrease for PANIAg lms for H2S gas is quite
interesting.
Now we discuss the mechanism for response of PANI
lms towards H2S gas. H2S gas is a weak acid and PANI
gives a robust response to strong acids since they have
the ability to fully dope PANI (resulting a very large change
in conductivity). Weak acids only partially dope the PANI
and hence the response of PANI towards H2S is expected

18

-18
-24

-1.0

-0.5

0
0

0.5

Response (%)

10

1.0

100

Bias (V)

600

150

CO

Cl2

NH3

NO

40

C2H5OH

60

Test gases

PANI-Ag (2M)

10

15

20

60

25

200

300

400

500

80

Time (min)

500
400

(d)

450
375
300
225

2M
AgNO3 conc.(M)
1

1M

300

0.5 M

3M

200
100

PANI-Ag (0.5M)

0
40

Response (%)

80

20

Response (%)

10 ppm

H2S

Response (%)

300

20

H2S concentration (ppm)

Time (min)

100

450

700

(c)

NO2

Response (%)

600

75

AgNO3 conc.(M)
1
2
3

0.0

150

20

-3

-12

15

T
PE
BO
S/
ET
M
OP
T
P
g/B
g/ A
I-A
A
N
PA
NI
PA

225

15

-1

40

-1

-6

Current (A)

300

(b)

20

(x10 ) cm

Current (A)

PANI-Ag (0.5)

25 ppm

(a)

12

of Fig. 6(d) shows the photograph of the PANIAg lms (1

correspond to lms on pristine BOPET and 2 correspond to
lms on APTMS modied BOPET) glued with adhesive tap
after application of uniform weight (3 kg) for 10 min.
Right side photograph of Fig. 6(d) shows the material detached from the lms by the adhesive tape after 90 peel
test. It can be seen that adhesive tape removes more
amount of material from the lms grown on pristine BOPET surface, while for the lms prepared on APTMS modied BOPET negligible material gets detached from the
surface. These results qualitatively suggest that stronger
adhesion of PANIAg lm on APTMS modied BOPET
substrates.

10

78

100 120 140

10

15

20

25

H2S concentration (ppm)

Fig. 7. (a) Currentvoltage characteristics of PANIAg (0.5 M) lms. Inset shows the base resistance of the lms as a function of AgNO3 concentration. (b)
Response curve for PANIAg(0.5 M) lms at various H2S concentration. Comparative response (%) as a function of H2S concentration for PANIAg(0.5 M)
lms prepared on APTMS modied BOPET and pristine BOPET. (c) Comparative response curve for PANIAg (0.5 M) and PANIAg (2 M). Inset shows the
selectivity histogram of PANIAg(0.5 M) at 10 ppm concentration of different gases. (d) Response as a function of H2S concentration and AgNO3
concentration. Inset shows the response (%) of PANIAg lms prepared with different AgNO3 concentration at 25 ppm of H2S exposure.

79

A. Mekki et al. / Organic Electronics 15 (2014) 7181

to be minimal. Therefore in order to improve the response

of PANI for H2S, their composites have been used [12,30
33]. Although in literature various mechanism have been
proposed to explain the interaction of H2S with PANI based
composites but the most suitable explanation related to
our work can be described on the basis of dissociation
H2S on the metal surface under ambient condition because
it is a weak acid (acid dissociation constant pKa = 7.05)
[34]. The dissociation of H2S results into H+ and HS ions.
The resulting HS anion compensates for the positive N+
charges in the PANI chains but there is also proton liberation in the lms. Since the mobility of cation (H+) is much
larger than the anion (HS), therefore the overall effect is
the slight conductance rise on exposure to H2S [35]. This
mechanism is supported by the two facts: (i) with increasing the AgNO3 concentration the response of PANIAg
lms enhances (shown in Fig. 7(c) and (d)) due to availability of large numbers of Ag sites. (ii) In this work, we have
also prepared pure PANI lms on APTMS modied BOPET
using chemical oxidation, but these samples do not exhibit
any response to H2S, which suggest the importance of Ag
particles in the PANI matrix for H2S sensing [12a].
From Fig. 7(d), it can also be seen that PANIAg lms
prepared at very high concentration of AgNO3  3 M (>aniline concentration  1 M) exhibit less reponse due to the
fact that the effective area (which govern the conductivity
change on H2S exposure) of PANI matrix is reduced due to
larger size of embedded Ag clusters.
For comparison purpose, we have also investigated the
response of PANIAg lms (prepared with AgNO3  0.5)
prepared on pristine BOPET surface, these lms exhibit response 67% at 10 ppm of H2S exposure (inset of Fig. 7(b)).
The lower response of these lms might be mostly due to
the smooth surface exhibiting smaller surface area for

reaction. As discussed earlier in the APTMS modied BOPET, the PANIAg lms exhibit nano-brush type of morphology with large surface area, which not only offers
very large area for interaction with H2S but also provides
an easy access of the Ag interaction sites for fast response/recovery. The gas sensing results (such as lowest
detection limit of 1 ppm with a high response 100% and
fast response time 6 min at 10 ppm) obtained in present
work are better than earlier reported results on PANI-inorganic nanocomposites lms [12,3033]. The reliable detection of H2S gases in ppm level using exible PANIAg lms
makes them attractive candidates for gas sensing
application.

3.7. Impedance spectroscopy study

Detection of gases is generally carried out by measurement of dc resistance of lms. Sample resistance measured
using dc current has contributions from different regions of
the sample such as intra-grain, grain boundaries and electrodesample interface [36]. Impedance spectroscopy is an
important technique that has been widely used for distinguishing between different contributions to sensor response. In this technique, system is perturbed by a time
dependent potential of the form V = V0sin (xt) and the output signal is described by I = I0sin (xt + /), where / is the
phase angle. The ratio V/I is a complex number which
determines the impedance (Z) at the corresponding frequency. The real (Z0 ) and imaginary part (Z00 ) of the impedance and phase angle depends on the particular nature of
the dominant conductive behavior (such as resistive,
capacitive, or inductive) present in the system at a given
frequency range.

160

500

PANI-Ag (2M)

(a)

-Z" (k)

120

-Z" (k)

PANI

(b)

400

Fresh

80

Fresh

300
200

40

H2S exposed (50 ppm)

100
H2S exposed (50 ppm)

0
0

50

100

150

Z' (k)

(c)

200

250

200

400

600

800

Z' (k)

R1
R0

C1
Fig. 8. Impedance spectra of the fresh and H2S exposed (a) PANIAg (2 M) lms (b) PANI lms. Solid line represents the tting of the spectra using a single
resistancecapacitor (RC) network model shown in (c).

80

A. Mekki et al. / Organic Electronics 15 (2014) 7181

Table 3
Impedance parameters obtained for PANIAg (2 M) and PANI lms by
tting experimental data to the equivalent circuit.
Sample

R0 (X)

R1 (kX)

C1 (nF)

Fresh PANIAg (2 M)
H2S Exposed PANIAg (2 M)
Fresh PANI
H2S Exposed PANI

2
2
13
13

255
36.5
758
669

2.1
125
100
105

We have performed the impedance measurement on

the PANIAg (2 M) lms, which exhibits highest response
toward H2S gas among all synthesized samples. The
impedance measurements were carried out on fresh lm
(in air) and under exposure of 50 ppm of H2S gas, obtained
spectra is plotted in Fig. 8(a) in the form of Nyquist plot. It
can be seen that impedance spectra shows a perfect single
semicircle from low frequency to high frequency region,
and it can be tted into an equivalent circuit as shown in
Fig. 8(c), which consist of frequency independent resistance (R0) and a resistor (R1) and capacitor (C1) in parallel.
The corresponding mathematical equation for this equivalent circuit can be described as:
0

Z Z jZ

00

where Z 0 R0 1xRR1 C

1 1

xR21 C 1

and Z 00 1xR

1 C1

The physical signicance of this model can be described

as: R0 is the resistance between PANIAg lms and Au
electrodes, while R1 and C1 is the respective interfacial
resistance and capacitance between PANI nanobers. Here
x 2pf , and f is the frequency of A.C. Signal. From Fig. 8(a)
it can be seen that there is very good agreement between
the simulated (shown by solid lines) pattern and experimental data and the values of tted parameters are given
in Table 3. It is seen that on exposure with H2S gas, R1 falls
while C1 increases. This result is supported by the fact that
on interaction of H2S with PANIAg, large numbers of
charge carriers are generated at the surface of PANI
nano-bers, which will lowers the inter-ber resistance
and will also increase the inter-ber capacitance.
The impedance spectra for pure PANI lms under air and
under 50 ppm of H2S exposure are given in Fig. 8(b). A comparison of the impedance spectra for pure PANI and PANIAg
lms indicates that impedance spectra for pure PANI lms
exhibits a very small changes even on exposure of very high
H2S concentration of 50 ppm. For pure PANI lms impedance spectra also shows a perfect single semicircle from
low frequency to high frequency region, which can be tted
into an equivalent circuit as shown in Fig. 8(c). The obtained
parameters for pure PANI lm are shown in Table 3, it can be
seen that on exposure to H2S, parameter R1 decreases and C1
enhances marginally. This result is also supported by the fact
that on exposure to very high H2S concentration of 50 ppm,
pure PANI lms exhibit a response 15% while PANIAg
lms exhibit a very high response 550%.
4. Conclusions
In summary, we have modied the surface of BOPET substrates by APTMS for the covalent anchoring of PANIAg

nanocomposite lms synthesized via photo-polymerization

process. We demonstrated that PANIAg lms prepared on
APTMS modied BOPET substrate results in a nano-brush
kind of morphology with very high surface area. The PANI
Ag lms show high response with reversible conductivity
change on ppm level (125 ppm) exposure of H2S. These
sensors have fast response time  few min. Interestingly
higher response of the PANIAg lms prepared on APTMS
modied BOPET was noted compared to the lms prepared
on pristine BOPET, which highlights the paramount importance of surface modication of the substrate in tuning the
application potential of the deposited materials.
Acknowledgements
The authors would like to thank the Indo-French Centre
for the Promotion of Advanced Research (IFCPAR) for
nancial support through the Flexi-Sensors Project No.
4705-2. This work is also supported by DAE-SRC Outstanding Research Investigator Award (2008/21/05-BRNS)
granted to D.K.A.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.orgel.2013.10.012.
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