ELSEVIER Sensors and Actuators B 28 (1995) 173-179

Polyaniline thin films for gas sensing

N.E. Agbor a*b,M.C. Petty a, A.P. Monkman b
’ School of Engineering and Centre for Molecular ElectroGcs, Universityof Durham, Lkham DHl 3LE, UK
bPhpics Department and Centre for Molecular Elecbunics, Universl?, of Dwfwn, Durham DHl 3LE, UK

Received 13 May 1994; in revised form 22 December 1994, accepted 9 January 1995

Abstract

Thin films of polyaniline have been deposited by spinning, evaporation and by the Langmuir-Blodgett technique. The Nms
are shown to possess slightly different in-plane electrical mnductivities, reflecting differences in their chemical structure and
layer morphology. The conductivity is found to depend on the gas ambient. All types of polyaniline films are sensitive to H2S
and NO, at concentrations down to 4 ppm. However, only spun and evaporated films are responsive to SOz.

Key~or& Gas sensors; Polyaniline; Thin films

1. Introduction

The importance of environmental gas monitoring is

well understood and much research has focused on the
development of suitable gas-sensitive materials. Re-
cently, there has been considerable interest in exploiting
organic substances such as porphyrins [l], phthalocy-
anines [2,3] and doped conductive polymers [4]. For
maximum gas sensitivity, these compounds are usually
studied as thin fihns.
Among the doped conductive polymers that have
been investigated are polypyrrole [5] and polythiophene
[6]. Unfortunately, these materials are not readily pro-
cessible. In contrast, polyaniline (PANi) is soluble in
organic solvents [7] from which free-standing films can
be cast [8]. In this work, polyaniline was processed
into thin-film form using three different methods: spin-
ning, vacuum ‘sublimation and the Langmuir-Blodgett
(LB) technique. The gas sensitivities of the different
films are compared.
2. Experimental
2.1. Substrate
Fig. 1 shows a schematic diagram of the interdigitated
electrode structure used in this work. It consists of
gold electrodes patterned onto the surface of a quartz
substrate; the overlap electrode length was 15 mm and
the electrode gap was 0.38 mm. Chemiresistors were
Fig. 1. An interdigitated electrode structure on a quartz substrate:
l-15 mm, d=O.38 mm and h=75 mm.
fabricated by coating these electrodes with the poly-
aniline films.
2.2. spun films
Polyaniline powder (synthes&d in-house) [8] in the
emeraldine base form was dissolved in N-methylpyr-
rolidinone (NMP), in a polymer:solvent weight ratio
of l:lOO,and sonicated for 30 min. The starting material
had a purity of 99.8%, as determined by NMR spec-
troscopy [9]. The resulting solution appeared blue in
reflected light. This was spun onto the interdigitated
electrode structure shown in Fig. 1. Spinning was un-
dertaken using a Dynapert PRS 14E model spinner,
at a fixed speed of 3000 rpm for 30 s. The spun !ihns
were transferred to a vacuum oven and heated to a
temperature of 120 “C, at lo-” mbar for 10 min. A
typical film-thickness value, obtained from an Alpha
Tenco surface profiling Talystep, was 2.0f 0.1 pm. Full

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174 N.E. A&w e: a!. I Sensors and Actuators B 28 (1995) 173-179

details of the sample preparation have been published steady reading had been obtained, the next highest
elsewhere [lo]. concentration of the active gas was admitted to the
chamber and the entire measurement procedure re-
2.3. Thermal evaporation peated. Using this procedure, the gas responses reported
in #is paper were repeatable to 10% with the same
An Edwards 6E4 vacuum-deposition system was used sample. The uncoated electrode (i.e., no polymer)
to evaporate polyaniline. The equipment possessed an showed no response to any of the gases at the maximum
evaporation chamber of 30 cm diameter and used a concentrations used.
water-cooled diffusion pump. The base vacuum level
was 10e3 mbar. The source temperature was maintained
by means of a Radio Spares temperature controller. 3. Results and discussion
40 mg of emeraldine base polyaniline was weighted
into a source boat, placed into the system and pumped 3.1. Chemical stnrcture
down. When the pressure in the chamber was E=10e3
mbar and stable, the temperature of the boat was Polyaniline is known to possess a number of reversible
increased to 400 “C. Once equilibrium had been oxidation states, each with a distinct backbone structure
achieved, the shutter was opened and film deposition composed of different ratios of quinoid to benzoid rings.
carried out for a tixed length of time. After evaporation, These are shown in Fig. 2. For example, emeraldine
the system was allowed to cool down to room tem- base polyaniline (Fig. 2(a)) possesses one quinoid ring
perature ( =5 h). It was then opened to air and the for every three benzoid rings. Other states include
substrates were removed. A typical film thickness from leucoemeraldine base (Fig. 2(b)), in which there are
the Talystep was 210& 10 nm for a 60 min evaporation. no quinoid units, and pernigraniline (Fig. 2(c)), in which
there are equal numbers of quinoid and benzoid rings.
2.4. Langmuir-Blodgettfilms
3.2. Film characterisation
A floating layer on a water subphase was formed by
spreading a solution made from polyaniline mixed with
Both the spun and LB polyaniline films on glass
acetic acid and dissolved in a chloroform/NMP mixture.
appeared blue. This colour is indicative of the emer-
The deposition of LB films was undertaken using troughs
aldine base form of the polymer [12]. In contrast, the
designed and built in Durham and housed in a micro-
evaporated films initially appeared colourless on glass
electronics clean room. Full details have been described
microscopy slides, suggesting that the film was in a
previously Ill]. The film thickness was measured to be
state close to leucoemeraldine base [13,14]. However,
approximately 6.0*0.1 nm per layer.
upon prolonged exposure to air/moisture (at least two
weeks), the colour of the evaporated film changed to
2.5. Gas measurements
purple and eventually to blue, similar to that of the
The room-temperature current versus voltage char- spun and LB layers. This effect was almost certainly
acteristics of the uncoated and coated interdigitated due to the oxidation of the film in the atmosphere, as
electrode structures were measured using a Time Elec- reported elsewhere [14].
tronics d.c. voltage calibrator and a Keithley 410A
picoammeter. The samples were placed in a chamber
through which a gas could be passed. The gas con-
centration was varied using a Signal Instrument Series
850 gas blender. The gases used (NO,, HzS, SO,, CO
and CH,) were all diluted with nitrogen. These were
obtained from Air Products Limited and had purity
levels of 99.99%. The procedure for measuring the
electrical conductivity in the presence of a gas was as
follows. With a fixed voltage applied to the thin-film
structure, pure nitrogen was passed through the sample
chamber until a steady current reading had been ob-
tained. The active gas was then admitted in its lowest
concentration and the current recorded after a fixed
period. This isochronal approach was used because
Fig. 2. The chemical structures of polyaniline: (a) emerald& base;
current saturation was not obtained in some of the (b) leucnemeraldine base; (c) pemigraniline base; (d) a generic
samples studied. The active gas was then turned off formula for polyaniline where n is a positive integer, x= l/2 for
and the sample left to recover in nitrogen. When a emeraldine base,1 = 0 for Ieucoemeraldine and x = 1 for pemigraniline.
 N.E. A&r et al. I Sensors and Actuators B 28 (1995) 173-179 175

The current versus voltage characteristics of spin-
coated emeraldine base polyaniline are shown in Fig.
3. The measurements were undertaken in an atmosphere
of nitrogen, at room temperature and after the current
had stabilized (see next section). Data for the uncoated
electrode (under nitrogen a current of 1.2f 0.2x lo-l2
A was measured with 10 V applied) confirmed that
the current was flowing through the polyaniline film
rather than through the substrate. The change in re-
sistance for different film thicknesses (1.0, 2.0, 4.0 pm)
indicates that Ohmic contacts have been established
between the gold electrodes and the polymer. Using
the thickness values from the surface profiler, the
average room-temperature in-plane d.c. conductivity
was 4.4~hO.9XlO-‘~S cm-‘, which is comparable to
the literature value of 1.0X 10-l’ S cm-’ for the base
form of emeraldine 171.The current versus voltage
characteristics for both the evaporated and LB films
of polyaniline were qualitatively similar to those of
shown in Fig. 3 (including the linearity with film thick-
ness).
The average room-temperature d.c. conductivity of
freshly evaporated polyaniline film, in nitrogen, was
1.0*0.2x lo-” S cm-‘. This compares with a value
of 2.0~10~~ S cm-’ reported in the literature for
similar material [15].The conductivity is slightly higher
than that of our spin-coated films (4.4&0.9x lo-” S
cm-‘). This can be explained by the absence of quinoid
rings to disrupt rr-r mixing between adjacent benzoid
different oxidation states and (b) external influences
(impurities) may result in doping of the material.
3.3. Gas sensitivity
3.3-l. Nitrogen
Fig. 4(a) shows the effect of dry N2 on the d.c.
conductivity of a spun polyaniline chemiresistor. The
conductivity decreased very rapidly upon the intro-
duction of N2 and became stable after approximately
60 min. This can be associated with the removal of
surface/bulk trapped water molecules. A similar re-
sponse was also obtained for polyaniline in LB film
form. Fig. 4(b) shows the effect of dry nitrogen on the
d.c. conductivity of an evaporated polyaniline layer. In
this case, the shorter time to achieve a stable conductivity
value can be attributed to the lower level of water and
the evaporated film. The effects of water on the con-
ductivity of polyaniline are well documented [17,18].
No evidence for oxidation (see previous section) was
noted for the evaporated film in the nitrogen envi-
ronment.
N2m
1.0
09
0.8

rings in the polymer chain [16]. 0.7

Electrical measurements on polyaniline LB filmshave 0.6
been reported previously [ll]. The film has a room- g 05
temperature conductivity in nitrogen of 10W8S cm-‘. 0.4
This is significantly higher than that of the emeraldine
03
base form of polyaniline, suggesting that a degree of
protonation, possibly by the acetic acid, had occurred. 0.2

In general, the agreement between the conductivity 01

0 4 12 20 28 30 44 52 60 Zdnys 3days &days
values reported here and those in the literature is not
Tinehitlsl
unreasonable considering that (a) polyaniline exists in

0.8 -
I I I
-500 500 1500
0 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’
Supply voltage [mVl 0 12 26 36 48 60 72 SL 96 106 120
Fig. 3. The room-temperature current vs. voltage characteristics for Tine Imins~
spun emeraldine base polyaniline on gold-plated interdigitated copper Fig. 4. ‘l%e effect of dry nitrogen on the d.c. conductivity of: (a)
electrodes for different film thicknesses: (a) 1.0 pm; (b) 2.0 pm: (c) 1.0 Frn thick spun PANi; (b) 210 MI thick evaporated PANi films
4.0 p.m. at room temperature.
176 N.E. Agbor et al. / Sensors and Achtators B 28 (1995) 173479

3.3.2. Nitrogen dioxide

Fig. 5 shows the effect of 10 ppm NO, on the spun
polyaniline. It can be seen that exposure to the gas
produced an increase in conductivity, which continued
to rise until the gas was turned off. The original
conductivity was restored approximately 90 min after
the NO, had been turned off, in an atmosphere of
nitrogen.
Fig. 6(a) shows how the conductivity change, after
NO, mnc. [vpml
a fixed exposure time, varies with NO, concentration.
T
The threshold (limited by the measuring equipment)
concentration level is about 4 ppm. The interaction
between NO, and the spun polyaniline can be explained
as follows. NO, is a well-known oxidizing gas which,
on contact with the T-electron network of polyaniline
(or any other system with electron lone pairs), is likely
to result in the transfer of an electron from the polymer
to the gas. When this occurs, the polymer becomes
positively charged. The charge carriers thus created NOx cone. [vpml

give rise to the increased conductivity of the film. This ?

is analogous to the well-known increase in conductivity
upon protonation for emeraldine.
The effect of NO, on a 210 nm thick freshly evaporated
polyaniline chemiresistor in a nitrogen atmosphere at
room temperature was similar to that observed for spin-
coated polyaniline, i.e., an increase in conductivity with
increasing gas concentration. However, at high gas
concentration (> 40 ppm), the response was found to
be only partially reversible. The response to different
NO, gas concentrations is shown in Fig. 6(b).
NO, also produced an increase in conductivity for
18 LB layers of polyaniline (approximately 110 nm in
thickness) at room temperature. However, the effect
was not reversible when .the gas was turned off. Fur-
thermore, the calibration graph (Fig. 6(c)) exhibits a
detection threshold of approximately 30 ppm, compared
to 4 ppm for both the evaporated and spin-coated
material. The lack of reversibility and reduced sensitivity
Fig. 6. The response of PANi films to different NO, concentrations:
(a) 1.0 w spun film: (b) 210 nm evaporated film; (c) 100 nm LB
film (2 V supply and temperature 203~2 “C).
of the LB film could be due to the fact that acetic
acid molecules have occupied and chemically blocked
sites responsive to NO,.
It is difficult to make direct comparisons between
the results presented in Fig. 6 for the three different
films, as these are in different chemical and physical
forms. For example, the higher sensitivity and faster
response time for the (thinner) evaporated film (Fig.
6(b)) over the (thicker) spun layer (Fig. 6(a)) may be
the result of the gas reaction taking place throughout
the bulk of the polymer layer. The data may also be
an indication of a reaction occurring at the polymer/
substrate interface. However, these effects may also
result from differences in the sensing materials: the
spun layers are in the emeraldine base state while the
evaporated film is in a form close to leucoemeraldine.

3.3.3. Hydrogensulfide
rw IlnSl
H,S was found to produce an increase in the con-
Fig. 5. The effect of 10 ppm NOz on a spun polyaniline chemiresistor ductivity of the spun polyaniline chemiresistor. No
at room temperature (2 V supply, film thickness 1.0 pm and tem- significant difference in response was observed between
perature 20f2 “C). a film previously exposed to NO, and a fresh sample
 N.E. Agbor et ai. f Sen.wn and Acmatm B 28 (1995) 173-179 I77

of the same thickness. Complete recovery for 10 ppm

of the gas was achieved after a period of about 60
min. A similar effect was observed with an 18 LB layer
polyaniline chemiresistor. The change in conductivity,
after a fixed exposure time, for both spun and LB
polyaniline chemiresistors is shown in Fig. 7. The thresh-
old for detection is about 4 ppm H,S for both films,
H++HS-
H2S is a known reducing gas. Thus, we would expect aqueousphase
I
to observe a decrease in the conductivity of the poly Fig. 8. An illustration of the state of HsS in different environments
aniline chemiresistors. The observed increase in con- [21]. In this work, the vapour phase is equivalent to H&surface
ductivity indicates that either more than one type of bound water molecules and the aqueous phase is equivalent to HsS/
reaction site is available or that a number of different water molecules trapped in the bulk of the film.

reactions are possible. At room temperature and pres-

sure, H,S dissociates in water into H+ and HS- [19-221 nine[ruins]
0 4 8 12 16 20 24 28 32 36 40 44 48
as illustrated in Fig. 8.
The H’ ion may subsequently protonate the polymer,
i.e.,
FANi]+[H]* c== [PANiH]+ (0
where the equ~jb~um is shifted to the right during
exposure and to the left after exposure. The protonation
again produces charge carriers (semiquinone radicals)
resulting in an increase in the d.c. conductivity. This Gas off
reaction is likely to involve different sites in the polymer
than for the NO, response. As a result, the sensit~ities
of the LB and spun films are similar (compare the
poor sensitivity of the LB film to NO, in Fig. 6).
Fig. 9(a) shows the effect of 10 ppm H2S on a 210
nm freshly evaporated polyaniline chemiresistor. This
reveals an irreversible decrease in conductivity at room

Fig. 9. (a) The effect of 10 ppm HaS on an evaporated polyaniline

chemiresistor at room temperature. (b)The msponse of an evaporated
polyaniline chemiresistor to different concentrations of H&3 at room
temperature (2 V supply, film thickness 210 nm and temperature
205~2 “C in both cases).

oL-----J
0 4 8 12
temperature. The device response to different H,S gas
H2S cone. [vpml concentrations is shown in Fig. 9(b). A threshold de-
tection value of 10 ppm is evident. Note that spun and
LB films are likely to possess more H,O than the
evaporated material (Fig. 4), thus increasing the like-
lihood of the reaction given by Eq. (1).

3.3.4. suZfir dioxide

SO2 produced an increase in conductivity of spun
polyaniline as well as complete reversibility at room
temperature. The effect of different SO, gas concen-
trations is shown in Fig. 10(a), revealing that the device
v
E$ cone. @ml is capable of measuring changes down to 2 ppm.
Fig. 7. The response of PANi films to different HsS concentrations:
Fig. 10(b) shows the response of an evaporated
(a) 1.0 pm spun film; (b) 110 nm LB film (2 V supply and temperature polyaniline chemiresistor to different concentrations of
20f2 “c). SOz. Here, the detection threshold is about 10 ppm,
178 N.E. Agbor et al. I Sensors and Achutors B 28 (1995) 173-l 79
Dr Alex Milton and Dr Phil Adams for the synthesis
of the polyaniline.
References
100
60 80
1 so cont. [vpm]
” 2
Fig. 10. The response of (a) a 1.0 pm spun film; (b) a 210 nm
evaporated film to different concentrations of SO? (2 V supply and
temperature 20*2 “C).
compared to 2 ppm for NO,. However, freshly evap-
orated polyaniline films showed a much higher sensi-
tivity, down to 0.5 ppm. This increased to 10 ppm as
the film was cycled continuously between air and ni-
trogen. This result suggests that the conversion of phenyl
rings into the quinoid structures on exposure to air
(film oxidation) is equivalent to blocking the SO, reactive
sites. SO, had no effect on LB polyaniline films. Again
a possible explanation is that the acetic acid, used for
the LB film formation, could have blocked the chemically
sensitive sites.
No effect was observed using CO and CH, gases on
spun, evaporated or LB polyaniline films.
4. Conclusions
Thin films of polyaniline have been deposited by
evaporation, spinning and the Langmuir-Blodgett tech-
nique. The as-deposited films on interdigitated elec-
trodes have been shown to possess different electrical
conductivities in different gaseous environments. It may
well be possible to exploit the different sensor sensi-
tivities to make a highly specific gas-sensor array [23].
Acknowledgements
This work was sponsored by British Gas plc and the
Cameroon government. We would also like to thank
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Biographies
NE. Agbor was awarded a B.Sc. from Keele Univer-
sity in 1988 and obtained an M.Sc. from the University
119
of Manchester in 1990. He subsequently received his
Ph.D. from the University of Durham for work on gas
sensing using organic films.
Andy Monkman obtained his BSc. and Ph.D. degrees
from Queen Mary College, University of London. Cur-
rently he heads the Organic Electroactive Materials
Group in the Department of Physics, University of
Durham. His research activities include the charac-
terization and applications of conductive polymers, es-
pecially polyaniline, and laser spectroscopy, including
femtosecond time-resolved measurements.
Michael Petty is a professor of electronics in the
School of Engineering at the University of Durham.
He is also co-director of the Durham Centre for Mo-
lecular Electronics. He gained his B.Sc. and D.Sc. from
the University of Sussex and his Ph.D. from Imperial
College, London. His research interests include the
development of organic materials, particularly Lang-
muir-Blodgett films, and their incorporation in novel
electronic and optoelectronic devices.