Anal Bioanal Chem (2006) 384: 343–353
DOI 10.1007/s00216-005-3390-2
R EV IE W
Jeffrey T. Mabeck Æ George G. Malliaras
Chemical and biological sensors based on organic thin-film transistors
Received: 15 April 2005 / Revised: 7 June 2005 / Accepted: 13 June 2005 / Published online: 4 August 2005

Springer-Verlag 2005
Abstract The application of organic thin-film transistors
(OTFTs) to chemical and biological sensing is reviewed.
This review covers transistors that are based on the
modulation of current through thin organic semicon-
ducting films, and includes both field-effect and elec-
trochemical transistors. The advantages of using OTFTs
as sensors (including high sensitivity and selectivity) are
described, and results are presented for sensing analytes
in both gaseous and aqueous environments. The primary
emphasis is on the major developments in the field of
OTFT sensing over the last 5–10 years, but some earlier
work is discussed briefly to provide a foundation.
Keywords Gas sensors Æ Biosensors Æ Organic
field-effect transistors Æ Microelectrochemical enzyme
transistors
Introduction
Organic thin-film transistors (OTFTs) offer a great deal
of promise for applications in chemical and biological
sensing. For a broad range of sensing applications (e.g.,
medical diagnostics, food monitoring, detection of
chemical, biological warfare agents, etc.), there is a de-
mand for small, portable, and inexpensive sensors.
OTFTs have many advantages over other types of sen-
sors that may allow them to meet this need. Organic
semiconductors can be deposited using low-temperature
processes on a variety of substrates, including mechan-
ically flexible ones. As a result, low-cost fabrication
techniques can be used to produce OTFTs. Miniaturi-
zation of these devices is straightforward, so portability,
small sample volumes, and arrays with many elements
are achievable. In addition, they provide a response
J. T. Mabeck Æ G. G. Malliaras (&)
Department of Materials Science and Engineering,
Cornell University, Ithaca, New York, 14853-1501, USA
E-mail: ggm1@cornell.edu
(current change) that is easy to measure with simple
instrumentation. With these advantages, it is feasible
that single-use, disposable sensors could be realized
using OTFTs.
Of course, it is also important in many applications
for sensors to be able to detect low concentrations of
specific analytes with high sensitivity and high selectiv-
ity. Here, too, OTFTs offer distinct advantages. Because
OTFTs are based on organic semiconductors, precise
organic synthesis can be used to fine-tune their chemical
and physical properties. Both molecular structure and
morphology can be adjusted to enhance sensitivity and
selectivity. Furthermore, it is possible to covalently
integrate recognition elements directly to the organic
semiconductor to provide highly specific interactions
with chosen analytes. Detection limits and sensitivity
also benefit from the signal amplification that is inherent
in transistor devices, allowing transistor-based sensors
to outperform chemiresistors as well as amperometric
and potentiometric sensors.
In general, OTFTs utilize a thin film of organic
semiconducting material as the active layer of the tran-
sistor. Two electrodes (‘‘source’’ and ‘‘drain’’) in contact
with the organic semiconductor are used to apply a
source–drain voltage and measure the source–drain
current that flows through the organic semiconductor,
while a third electrode (‘‘gate’’) is used to modulate the
magnitude of the source–drain current. The gate can be
used to switch the transistor ‘‘on’’ (high source–drain
current) and ‘‘off’’ (negligible source–drain current).
Depending on the organic semiconducting material used
as the active layer, the mobile charge carriers can either
be electrons (n-type material) or holes (p-type material).
OTFTs can be roughly classified into two primary
categories: organic field-effect transistors (OFETs) and
organic electrochemical transistors (OECTs). In OFETs
(Fig. 1a, b), the source–drain current is modulated by
field-effect doping, where the charge carrier density in
the organic semiconductor is controlled by the gate
electrode via an electric field applied across an insulating
layer (gate dielectric). In OECTs (Fig. 1c) the source–
344
Fig. 1 a Schematic cross section of an organic field-effect transistor
(OFET). b Schematic cross section of an ion-sensitive organic field-
effect transistor (ISOFET). c Schematic cross section of an organic
electrochemical transistor (OECT). In each schematic, the analyte
of interest is represented by solid red circles. The applied source–
drain voltage Vd and gate voltage Vg are also shown
drain current is modulated by electrochemical doping or
de-doping, where the change in conductivity of the or-
ganic semiconductor is mediated by ions from an adja-
cent electrolyte. OECTs exhibit much lower operating
voltages than OFETs, but due to the movement of ions
involved in OECTs, their switching times are consider-
ably slower (on the scale of seconds or longer) than
those for OFETs (on the scale of milliseconds or
shorter).
OTFTs have been used in a variety of configurations
for the detection of chemical and biological analytes.
Three simplified schematics that illustrate these different
approaches are shown in Fig. 1. Figure 1a shows an
OFET in which the active semiconductor layer is ex-
posed to the analyte on one side, and the gate electrode
is separated from the active layer by an insulator on the
other side. This is simply a conventional OFET with
a back gate, where the active layer is exposed to
either gases or liquids containing an analyte of interest.
Figure 1b shows an ion-sensitive OFET (ISOFET) in
which the insulator is exposed to an electrolyte con-
taining the analyte, and the gate electrode is separated
from the insulator by the electrolyte. For ISOFETs, the
source–drain current is modulated by field-effect doping
just as in conventional OFETs, but the electric field
across the insulating gate dielectric is controlled by ions
at the electrolyte/insulator interface. Figure 1c shows an
OECT in which the active semiconductor layer is ex-
posed to an electrolyte containing the analyte, and the
gate electrode is separated from the active layer by the
electrolyte. The essential difference between an OFET
and an OECT is that the insulating gate dielectric used
in OFETs is replaced with an electrolyte in OECTs.
Since the active layer can be directly exposed to the
analyte for both OFETs and OECTs, it is important to
note that the analyte may induce changes in charge
carrier density, charge carrier mobility, trap density,
charge injection, and other parameters, all of which will
alter the measured source–drain current and affect the
sensor response.
In this paper, we review the work that has been done
to develop chemical and biological sensors based on
OTFTs (see Table 1). We cover only devices operated as
transistors with source, drain, and gate electrodes, where
the active layer of the transistor is a thin film of organic
semiconducting material. Therefore, neither inorganic
ion-sensitive field-effect transistors (ISFETs) with or-
ganic semiconductor gate electrodes nor conducting
polymer electrodes for amperometric/potentiometric
sensors are covered. We also do not cover transistors
based on diamond films and carbon nanotubes. We di-
vide the field of OTFT sensors into OFET sensors and
OECT sensors, first focusing on OFETs for gas sensing
and then discussing OFETs (including ISOFETs) for ion
sensing and biosensing. We then focus on OECTs as
chemical sensors and finally review the incorporation of
biological recognition elements into OECTs for biosen-
sing applications. We follow a roughly historical line in
each section, though occasionally deviate in order to
group similar work together for clarity. Other reviews
that may be of interest to the reader have been published
by Torsi [1], Bartlett and Astier [2], Katz [3], and Potje-
Kamloth et al. [4].
Organic field-effect transistors (OFETs)
Gas sensing
Not long after the first OFETs were reported in the mid-
1980s [5–8], several groups observed that the source–
drain current could be sensitive to the presence of spe-
cific gases. Laurs and Heiland [9] fabricated transistors
based on various phthalocyanines and observed that the
source–drain currents increased by orders of magnitude
in the presence of oxygen, iodine, and bromine. Assadi
et al. [10] reported that the source–drain currents of
poly(3-hexylthiophene) transistors decreased upon
 345

Table 1 Summary of reviewed OTFT sensors

Active layer Recognition element Analytesa

OFETs
Phthalocyanines Oxygen [9], iodine [9], bromine [9], NO2 [12],
ozone [13, 14], alcohols [20], ketones [20], thiols [20],
nitriles [20], esters [20], ring compounds [20],
lactic acid [28],pyruvic acid [28]
Naphthalene tetracarboxylic Nitrogen [15], oxygen [15], water vapor [15, 16],
derivatives alcohols [20], ketones [20], thiols [20], nitriles [20],
esters [20], ring compounds [20]
Pentacene Water vapor [17], 1-pentanol [27], aqueous analytes
[28] (and J.T. Mabeck et al. (2004) unpublished results)
Oligothiophenes Alcohols [2–23], ketones[20], thiols [20], nitriles [20],
esters [20], ring compounds [20], lactic acid [28],
glucose [28]
Polythiophenes Alkyl or alkoxy side Ammonia [10], water vapor [11], chloroform [11],
chains [24, 25] alcohols [20, 24, 25], ketones [20, 24, 25], thiols [20],
nitriles [20], esters[20],
ring compounds [20], alkanes [24, 25]
Poly(phenylene ethynylene) Enantioselective pendant Volatile chiral molecules [26]
groups [26]
ISOFETs
Pentacene H+ [31]
Poly(3-hexylthiophene) Proton-sensitive dielectric H+ [29, 30], glucose [30]
layer [29, 30],
glucose oxidase [30]
OECTs
Polypyrrole Diaphorase [41], penicillinase NADH [41], penicillin [42], H+ [42]
membrane [42]
Poly(3-methylthiophene) Platinum particles [35] H+ [34, 35], IrCl26 [34], O2 [35], H2 [35]
Polyaniline Moisture-sensitive solid-state H+ [33, 43], Ru(NH3)3+/2+
6 [33], Fe(CN)36 /4
[33],
electrolyte [36, 40], crown ether [38], water vapor [36], SO2 [37], K+ [38],
glucose oxidase [43–45, 50–52], glucose [43–45, 50–52],
horseradish peroxidase [47], hydrogen peroxide [47], urea [50, 51],
urease [50, 51], lipase [50, 51] triglycerides [50, 51]
Polyaniline composites Glucose oxidase [48] Glucose [48], NADH [49]
Modified polyaniline Horseradish peroxidase [52] Hydrogen peroxide [52]
Polycarbazole Cu(II) ions [39]
PEDOT IgG antibodies [56], DNA [57] IgG antibodies [56], DNA [57]
PEDOT/PSS Glucose oxidase [58] Water vapor [40], glucose [58]
a
Gaseous analytes are shown in italics

exposure to ammonia. Ohmori et al. [11] also demon-
strated that water vapor and chloroform gas enhanced
the source–drain currents of poly(3-butylthiophene)
transistors. In each of these early reports, the changes in
source–drain currents were observed to be reversible,
and the application of OFETs to gas sensing was sug-
gested.
Since the year 2000, interest in this area has greatly
intensified. Further development of phthalocyanine
transistors for gas sensing has been accomplished by Hu
et al. [12] who showed that transistors based on Lang-
muir–Blodgett films of an asymmetrical phthalocyanine
could be used to measure the concentration of NO2. At
concentrations below 70 ppm, the source–drain current
increased linearly with NO2 concentration, but at higher
NO2 concentrations, the source–drain current began to
saturate. The increase in source–drain current was
attributed to the chemical adsorption of NO2 to the
phthalocyanine surface, where NO2 further doped the
phthalocyanine by accepting electrons and increasing
the hole concentration. As the adsorbed gas molecules
saturated the surface at higher concentrations, the in-
crease in current also saturated.
Bouvet et al. [13, 14] have shown that phthalocyanine
transistors can also be used as sensitive and stable ozone
sensors in which the sensing mechanism for O3 is similar
to that for NO2, since both gases act as electron accep-
tors. They demonstrated that using a field-effect tran-
sistor rather than a conventional chemiresistor offers
several advantages. Whereas, the initial current of
phthalocyanine chemiresistors is dominated by the
presence of impurities, the initial current of phthalocy-
anine transistors can be precisely controlled by appli-
cation of a gate voltage. In addition, they provided
evidence that their OFET sensor performed better than
a similar resistor-type sensor in terms of drift, sensitivity,
signal-to-noise ratio, response time, lifetime, and oper-
ating temperature.
Another advantage of using transistors rather than
chemiresistors was demonstrated by Torsi et al. [15]. In
addition to measuring the bulk conductivity of the or-
ganic semiconductor upon exposure to chemical species,
346
they showed that transistors can be used to easily mea-
sure the 2D field-induced conductivity, threshold volt-
age, and field-effect mobility. They fabricated n-type
OFETs based on 1,4,5,8-naphthalene-tetracarboxylic-
dianhydride (NTCDA), and exposed them to controlled
atmospheres of nitrogen, oxygen, and water vapor.
Measurement of the four parameters mentioned above
provided a ‘‘fingerprint’’ of each gas. This multi-
parameter sensing makes it possible for transistors to be
more selective than conventional chemiresistors.
Torsi et al. [16] also demonstrated that transistors can
be superior to simple resistors for the detection of a
single analyte. Using an NTCDA transistor as a
humidity sensor, they compared the response of the on-
current (when Vg=60 V) to the response of the off-
current (when Vg=0 V and the device is essentially just a
chemiresitor). The on-current not only exhibited higher
values, as expected due to the amplification inherent to
transistors, but it also showed a larger dynamic range
and superior reversibility. The improved reversibility
was attributed to electrically induced water desorption
that resulted from the applied gate voltage.
Further work on humidity sensors using OFETs has
been conducted by Zhu et al. [17] A p-type pentacene
transistor was used to monitor relative humidity (RH)
and it was found that the saturation current decreased
by as much as 80% when RH changed from 0 to 30%.
The sensitivity was shown to depend on the pentacene
Fig. 2 Map illustrating the effect of 16 analytes on 11 sensor
materials. Black indicates that data are not available and white
indicates negligible response. Increases in sensor current are shown
in shades of blue while decreases are shown in shades of red.
Reprinted with permission from Crone et al. [20] Copyright 2001,
American Institute of Physics
film thickness, and the sensing mechanism was explained
in terms of a decrease in the pentacene hole mobility in
the presence of water vapor. Qiu et al. [18] and Li et al.
[19] have conducted studies on how humidity decreases
the conductivity of pentacene and other p-type OFETs.
Their work confirmed that the presence of polar water
molecules can reduce the hole mobility by trapping
charge at grain boundaries and thereby reduce the
source–drain current.
The wide variety of organic semiconducting materials
that can be used in OFETs offers advantages for fabri-
cating selective arrays of gas sensors, as has been shown
by Crone et al. [20]. OFETs based on a range of different
oligothiophenes, phthalocyanines, and other organic
semiconductors were fabricated and exposed to a variety
of gaseous analytes, including alcohols, ketones, thiols,
nitriles, esters, and ring compounds. By measuring the
source–drain current the authors were able to observe
patterns associated with each analyte, as shown in
Fig. 2, due to the variety of different response mecha-
nisms associated with different semiconductor–analyte
pairs. It is important to note that this selectivity can be
further tuned by modifying both the morphology and
molecular structure of the active organic materials.
Crone et al. [21] have also pointed out that OTFT
sensors are superior to chemiresistor sensors owing to
the fact that they can more easily be incorporated into
sensing circuits with enhanced performance over discrete
sensors. They have demonstrated an organic compli-
mentary ring oscillator based on chemically sensitive
didodecyl a-sexithiophene (DDa6T) transistors that
showed a sensing response to octanol vapor of >40%
(change in ring oscillator frequency), compared to a
sensing response of 15% (change in source–drain
current) for a discrete DDa6T transistor. The ring
oscillator sensor also displayed a faster recovery time
than the discrete sensor. In addition, they demonstrated
organic high gain differential amplifiers with adaptive
feedback that allowed enhanced detection of low analyte
concentrations due to voltage gains of 20 as well as
improved background elimination compared to discrete
sensors.
The mechanism of vapor sensing by OFETs has been
further explored by Torsi et al. [22] and Someya et al.
[23]. They fabricated oligothiophene transistors with a
range of different oligothiophene film morphologies and
studied their responses to alcohol vapors. Devices with
larger numbers of grain boundaries showed larger re-
sponses when exposed to 1-pentanol, whereas devices
without grain boundaries showed almost no response.
They also observed that there was no swelling of the
oligothiophene films upon exposure to the alcohol va-
pors, which suggests that the sensor response is due to
surface interactions rather than bulk interactions. In
addition to depositing organic films with a range of
different grain sizes, they also varied the source–drain
channel length in order to control the number of grain
boundaries per device systematically. Their results indi-
cate that the sensing of alcohol vapors with oligothi-

ophene transistors is primarily due to semiconductor–
analyte interactions at grain boundaries. They have
proposed that vapor molecules adsorb more readily at
grain boundaries, where they are closer to the conduct-
ing channel at the interface with the dielectric and can
more strongly affect the electrical response.
In addition to studying the effects of the morphology
of the active organic semiconductor, Torsi et al. [24, 25]
investigated the effects of modifying the molecular
structure of the active material. Polymer transistors were
fabricated using two different types of active layers
based on the same polythiophene backbone: one with
alkyl side chains and the other with alkoxy side chains.
These two chemically different transistors were exposed
to a range of organic vapors, including alcohols, alk-
anes, and ketones. Polythiophene transistors with alkyl
side chains showed responses that were correlated with
the alkyl chain length of the analyte, whereas the tran-
sistors with alkoxy side chains showed responses that
were correlated with the dipole moment of the analyte.
These results demonstrate the enhancement in selectivity
that can be achieved with OFET sensors by tuning the
active organic semiconductor via chemical synthesis. As
an example of pushing this idea further, Tanese et al.
Fig. 3 a Schematic cross section of a pentacene transistor with
integrated microfluidics. The microfluidic channel was formed by
molding poly(dimethylsiloxane) (PDMS) and then laminating it to
the pentacene transistor. b Optical micrograph showing top view of
the device with the microfluidic channel aligned between Au source
and Au drain
347
[26] proposed OFETs based on active polymeric layers
bearing enantioselective pendant groups for the detec-
tion of volatile chiral molecules.
In an effort to lower the limit of detection for OFET
sensors, Wang et al. [27] have explored the gas-sensing
responses of nanoscale organic transistors, since the
incremental change in signal for each analyte molecule
should increase as the active area of the device decreases.
They fabricated pentacene transistors with channel
lengths ranging from 36 lm down to 20 nm and mea-
sured their responses to the airborne analyte 1-pentanol.
The source–drain current was found to decrease upon
analyte exposure for the larger-scale devices; however,
surprisingly, they observed that the source–drain current
increased upon analyte exposure for the smaller-scale
devices. In addition, they found that the channel length
corresponding to the crossover of response behavior
depended on the pentacene grain size. These results were
explained in terms of two competing mechanisms: a
reduction in mobility due to charge carrier trapping at
the grain boundaries and an increase in charge density
due to (not yet fully understood) interactions between
the analyte molecules and the pentacene grains.
Ion sensing and biosensing
There are many applications for which the analyte of
interest must be detected in an aqueous medium rather
than in the vapor phase as discussed above for gas
sensors. For example, biological analytes and biologi-
cally derived recognition elements are only active in
aqueous media. Therefore, it is necessary to explore the
operation of OFETs in aqueous media in order to ex-
tend their applicability to a broader range of sensing
needs.
Someya et al. [28] have established that OFETs based
on a range of different organic semiconductors can be
operated with the active semiconducting material in di-
rect contact with both stationary and flowing water.
They coated the source and drain electrodes with a
fluorinated polymer to confine the water to the active
region of the transistor and prevent a parallel ionic
current from overwhelming the electronic current in the
active layer. They also utilized an adhesion promotion
layer designed to make the semiconductor film as resis-
tant as possible to water-induced delamination from the
substrate. With this setup they were able to test several
combinations of semiconductors and dissolved hydroxy
and carboxy compounds (at concentrations down to
1 ppm) and observe significant signal responses that
showed some solute specificity.
J.T. Mabeck et al. (2004, unpublished results) have
further pursued the integration of OFETs with micro-
fluidic channels. Standard molding techniques were used
to fabricate microfluidic channels with dimensions of
50-lm wide · 50-lm high from the silicone elastomer
poly(dimethylsiloxane) (PDMS). These channels were
then aligned between the source and drain electrodes
348
and laminated to pentacene transistors to confine the
aqueous solution over the active region of the device and
protect the electrodes from contact with the solution, as
shown in Fig. 3. A hydrophobic coating of polycar-
bonate was used to prevent water-induced delamination
of the pentacene. The current-voltage characteristics
remained stable under flowing water, but the mobility
decreased by 30% compared to its value when dry.
A pH sensor using an OFET in which the active or-
ganic semiconductor does not actually come into contact
with the aqueous solution has been demonstrated by
Bartic et al. [29]. They fabricated a poly(3-hexylthioph-
ene) (P3HT) transistor with a proton-sensitive silicon
nitride dielectric layer. Instead of using a metallic gate
electrode on the dielectric layer as is usually done for
OFETs (see Fig. 1a), they exposed the dielectric layer to
an aqueous solution and used a Ag/AgCl electrode as
the gate. This setup (see Fig. 1b) is similar to conven-
tional silicon-based ion-sensitive field-effect transistors
(ISFETs), but the use of organic semiconductors for
ISOFETs offers advantages in terms of fabrication cost
and compatibility with plastic substrates. By applying a
gate voltage to the Ag/AgCl electrode and monitoring
the source–drain current, they were able to achieve a
stable and reproducible pH-dependent response over the
pH range 2–10. They attributed this response to changes
in the field-induced conductivity of the P3HT which
occurred due to proton-induced changes in the potential
drop at the solution/Si3N4 interface.
Bartic et al. [30] have also taken this idea a step
further and shown that a selective biosensor can be
realized by adding a specific biorecognition layer to the
ISOFET. For this work they have again used P3HT as
the active semiconducting layer, but they have used
Ta2O5 as the dielectric layer owing to its larger number
of proton-sensitive surface sites (which improves the pH
sensitivity) and its higher dielectric constant (which re-
duces the operating voltages). An enzymatic layer of
Fig. 4 Effect of the biocatalytic reaction of glucose with glucose
oxidase on the current–voltage characteristics of a P3HT ISOFET,
shown at two different gate voltages. Reprinted with permission
from Bartic et al. [30] Copyright 2003, American Institute of
Physics
glucose oxidase was immobilized on the Ta2O5 surface,
and the device was exposed to glucose solutions with
different concentrations (10 5–10 2 M). The transistor
yielded a linear response with a slope of 0.3 lA/dec-
ade. Figure 4 shows the current–voltage characteristics
of their device at two different gate voltages and the
changes in source–drain current that result from the
presence of glucose. The transistor response was
understood in terms of the pH change that takes place
when the immobilized glucose oxidase converts glucose
to gluconic acid and thereby increases the proton con-
centration near the Ta2O5 surface.
Loi et al. [31] have recently developed an ISOFET
that takes advantage of the mechanical flexibility of
organic semiconductor devices. They evaporated Au
source and drain contacts along with pentacene on one
side of a 900-nm-thick Mylar sheet that acted as both a
flexible substrate and the gate dielectric. The other side
of the Mylar sheet was exposed to an aqueous solution
along with a Ag/AgCl electrode as the gate. The device
was shown to be responsive to changes in pH, and the
authors suggest that with the addition of selective rec-
ognition elements to the Mylar sheet, this type of device
could be used to produce flexible smart electronic films
for a range of innovative applications such as smart food
packaging.
Organic electrochemical transistors (OECTs)
The first OECT was reported in 1984 by White et al.
[32]. They fabricated three Au microelectrodes covered
with polypyrrole and demonstrated that the device
functioned as a transistor when immersed in an elec-
trolyte solution of 0.1 M [n-Bu4N]ClO4 in acetonitrile
(see Fig. 5). The middle Au microelectrode was used as
the gate, while the two outer electrodes were used as
source and drain. When the gate was held at a negative
potential where the polypyrrole was expected to be in
its insulating state, the transistor was off and the
source–drain current was very small. When the gate
potential was increased to be more positive than the
oxidation potential of polypyrrole ( 0.2 V versus
SCE), the device turned on and significant source–drain
current flowed through the oxidized (conducting)
polypyyrole, as shown in Fig. 5. The authors com-
mented that their device had ‘‘no immediate practical
application’’ but noted the growing interest in devel-
oping chemical and biological sensors based on
microelectronic devices. As we will see, this type of
device shows a great deal of promise for precisely this
application.
We should note some of the differences between the
device shown in Fig. 5 and the simple schematic of an
OECT shown in Fig. 1c. First, the gate voltage here is
carefully controlled by a potentiostat, which ensures that
it remains stable relative to the reference electrode. It is
also important to note that the middle Au gate micro-
electrode used here is not required, since the gate voltage
 349

Fig. 5 Current–voltage
characteristics for a polypyrrole
OECT. Each curve corresponds
to a different value of the gate
voltage, Egate. The inset shows a
schematic of the device. From
Bartlett and Astier
[2]—reproduced with
permission of The Royal
Society of Chemistry (an
adaptation with permission
from White et al. [32] Copyright
1984, American Chemical
Society)

could alternatively be applied relative to the source

electrode, as shown in Fig. 1c. In fact, devices based on
only two microelectrodes covered with an organic semi-
conductor can show faster response times and greater
sensitivity, since the source and drain can be closer to-
gether and a smaller amount of the active material must
be oxidized and reduced to switch the device on and off.

Chemical sensing

The first examples of chemical sensing with OECTs were

Fig. 6 Sensor response of a polyaniline/18-crown-6 transistor
upon exposure to various concentrations of alkali metal ions.
The sensor response is represented by Dg/g0, where g0 is the
conductance of the sensor in the absence of analyte, and Dg=g
g0, where g is the conductance of the sensor in the presence of the
analyte. a Set of curves recorded at three gate voltages in the
presence of various concentrations of K+ ions. b Set of curves at
the same gate voltages in the presence of various concentrations
of Na+ ions. The counterion in both cases is Cl . Reprinted with
permission from Dabke et al. [38] Copyright 1997, American
Chemical Society
reported by Wrighton and co-workers [33–35]. They
demonstrated a polyaniline transistor that operated in
an aqueous electrolyte solution and was responsive to
small changes in pH as well as to redox reagents such as
Ru(NH3)3+/2+
6 and Fe(CN)36 /4 [33]. Using poly(3-
methylthiophene) (P3MT) as the active layer, they were
able to produce OECTs that were stable in aqueous
electrolytes over a wide range of pH and were capable of
responding to very small amounts (<10 15 mol) of a
chemical oxidant (IrCl26 ) [34]. In addition, they dem-
onstrated that P3MT films impregnated with platinum
particles could be used to make OECTs that functioned
as room-temperature sensors for O2 and H2 in aqueous
solution and that reproducibly responded to pH changes
in the pH range 0–12 [35]. The platinum particles were
incorporated in an amount that effectively catalyzed the
reactions of H2 and O2 without significantly altering the
transistor properties of the P3MT.
350
Fig. 7 Left Solid-state OECT humidity sensor printed on polyethylene-coated paper. Right The sensor was capable of operating when
bent at a radius of curvature of approximately 5 cm. Reprinted from Nilsson et al. [40] Copyright 2002 with permission from Elsevier
Not all early work was confined to sensing analytes in
liquid electrolytes. Chao and Wrighton [36] demon-
strated a humidity sensor based on a solid-state OECT.
Polyaniline was used as the active semiconductor layer,
which was overcoated with the solid-state electrolyte
poly(vinyl alcohol)/phosphoric acid. A silver electrode in
contact with the electrolyte was used as the gate. The
authors found that significant ionic conductivity in the
electrolyte required moisture in the surrounding atmo-
sphere and that the device could be used as a stable and
reversible humidity sensor. The reversibility of the sen-
sor was attributed to a combination of both the moisture
dependence of the ionic conductivity in the electrolyte,
which turned the device on in the presence of moisture,
and the gate ‘‘leakage’’ current, which caused the device
to turn off again in the absence of moisture.
Polyaniline OECTs in acidic aqueous solutions have
been explored further for applications in chemical
sensing by other groups as well. Gaponik et al. [37]
exploited the fact that polyaniline is an effective catalyst
for SO2 oxidation and demonstrated detection of dis-
solved SO2 by monitoring the source–drain current at a
gate voltage sufficient to convert the polyaniline into its
conducting form. Dabke et al. [38] showed that incor-
poration of 18-crown-6 ethers into the polyaniline film
made it possible to detect very low concentrations
(10 8 M) of K+ ions. It was also possible to distin-
guish K+ ions from other ions owing to the specificity of
the interaction between 18-crown-6 and K+ (see Fig. 6).
The transistor response was attributed to conforma-
tional changes of the polyaniline induced by the high
local electrostatic field of the bound metal ion in the
crown cavity.
Saxena et al. [39] have made use of the fact that
polymers can have specific interactions with certain
analytes without the need for additional recognition
elements. They developed a Cu(II) ion-selective OECT
based on polycarbazole, in which the polycarbazole film
served not only as the active layer of the transistor but
also as the ion-selective layer. The device was very sen-
sitive to Cu(II) ions (over a short concentration range
from 2.5 to 100 lM), whereas it showed no significant
response to a variety of other cations. The selectivity and
sensing mechanism were attributed to incorporation of
Cu(II) ions into cavities in the polycarbazole film that
resulted in conformational changes of the polymer and
therefore changes in the source–drain current.
Nilsson et al. [40] demonstrated the potential for
OECT sensors to be manufactured inexpensively using
printing techniques for mechanically flexible single-use
tags. They fabricated humidity sensors on thin polyester
foils and on paper (see Fig. 7) using the commercially
available conducting polymer poly(3,4-ethylenedioxy-
thiophene):poly(styrene sulfonate) (PEDOT:PSS) and
Nafion, a humidity-sensitive solid-state electrolyte. A
lateral geometry was used for ease of processing, with
one layer of patterned PEDOT:PSS acting as the source,
drain, active transistor channel, and gate. The Nafion
was deposited as a second layer to connect the gate
electrode with the active region of the PEDOT:PSS.
Upon application of a positive gate voltage, the PE-
DOT:PSS in the active region was reduced, and the
PEDOT:PSS of the gate was oxidized. The extent of the
oxidation and reduction in the active region was deter-
mined by the humidity-dependent ionic conductivity of
the Nafion. Since PEDOT:PSS is more conductive in its
oxidized state, the source–drain current could be used to
monitor the humidity level. After each measurement, a
bias applied to the gate electrode was used to revert the
transistor to its original state.
Biosensing
Matsue et al. [41] were the first to incorporate a bio-
recognition element into an OECT and thereby achieve a

chemically selective biosensor with an organic transistor
as the transducer (often called a microelectrochemical
enzyme transistor or enzyme switch, whenever the bio-
recognition element is an enzyme). The authors chose a
polypyrrole derivative as the active semiconducting
layer, since it could be deposited from a neutral aqueous
solution and used to entrap enzymes. Their initial de-
vices employed the flavin enzyme diaphorase for the
specific detection of NADH, a critical energy storage
molecule for many biochemical reactions. A free-dif-
fusing redox mediator was also used to couple the en-
zyme-catalyzed reaction to the active polymer. Upon
addition of NADH, the diaphorase enzyme catalyzed
the reduction of the active polymer (via the redox
mediator) from its conducting (oxidized) state to its
insulating state, causing the OECT to switch from on to
off in 15–20 min. As we have seen previously, the gate
voltage could then be used to reset the transistor in
preparation for the next measurement.
Nishizawa et al. [42] found that the conductivity of a
polypyrrole film was sensitive to pH and used this
finding to design an OECT biosensor sensitive to en-
zyme-catalyzed pH changes without the addition of a
redox mediator. They coated the polypyrrole film with a
penicillinase membrane, and monitored the source–
drain current as the device was exposed to various
concentrations of penicillin. The penicillinase catalyzed
the hydrolysis of penicillin, which reduced the local pH
and increased the source–drain current. This pH-
dependent response was attributed to the reversible
protonation–deprotonation reaction at the nitrogen
atom in polypyrrole. It is important to note that this pH
response was reversible and did not require the appli-
cation of a specific gate voltage to reset the transistor.
A similar pH response was used by Hoa et al. [43] to
detect glucose using a polyaniline OECT. The polyani-
line was used as both the active layer of the transistor
and the immobilization layer for the enzyme glucose
oxidase. The decrease in local pH upon generation of
gluconic acid by the glucose–enzyme interaction was
observed to cause an increase in the source–drain cur-
rent. It should be noted that this pH behavior is similar
to that observed for polypyrrole as described above;
however, glucose oxidase could not be used with poly-
pyrrole because its conductivity is irreversibly destroyed
upon exposure to hydrogen peroxide, which is also
generated upon the interaction of glucose with glucose
oxidase. Fortunately, polyaniline does not react with
hydrogen peroxide under these conditions, and the work
of Hoa et al. [43] demonstrates that polyaniline tran-
sistors can successfully be used to detect biomolecules
using H2O2-producing enzymes.
Polyaniline is also more stable and can be deposited
more reproducibly by electrochemical methods than
polypyrrole, and OECTs based on polyaniline for bio-
sensing applications have been explored extensively by
Bartlett and colleagues [2, 44–49]. They demonstrated
glucose-sensitive devices by immobilizing glucose oxi-
dase on the polyaniline film in a layer of 1,2-diamino-
351
benzene, which acted as both an immobilization layer
and a permselective insulator that provided selectivity
against interference from solution species [44, 45]. A
free-diffusing redox mediator was used to couple the
enzyme-catalyzed reaction to the polyaniline so that it
switched from its insulating (fully oxidized) pernigrani-
line form to its conducting (partially oxidized) emeral-
dine form upon addition of glucose. In this case, the
device was switched from off to on in 10 s by the
analyte. By optimizing the deposition and fabrication
conditions of their OECT, the authors were able to
achieve reproducible measurements of glucose concen-
trations down to 2 lM, a detection limit that was 40
times lower than the detection limit for the same device
operated as an amperometric sensor [46]. The team was
also able to demonstrate a hydrogen peroxide sensor
based on the enzyme horseradish peroxidase that did not
require the use of a redox mediator [47]. The polyaniline
film was switched from on to off in 100 s upon addi-
tion of hydrogen peroxide due to direct electrochemical
communication with the enzyme that chemically oxi-
dized the polyaniline.
All of the work by Bartlett and colleagues on poly-
aniline-based biosensors described above was carried
out at pH 5, since polyaniline typically loses its con-
ductivity at higher pH. However, they were able to show
that composite films of polyaniline and a high molecular
weight counterion such as poly(vinyl suflonate) (PVS) or
poly(stryene sulfonate) (PSS) remained conductive at
neutral pH. Using these composite films, they were able
to demonstrate OECTs responsive to glucose [48] and
NADH [49] at pH 7. In addition, the NADH sensor did
not require an enzyme (in contrast to the polypyrrole-
based NADH sensor reported by Matsue et al. [41]),
since polyaniline acted as an efficient catalytic surface
for the oxidation of NADH.
Sangodkar et al. [50] have succeeded in developing a
biosensor array based on polyaniline OECTs. They
immobilized three different enzymes on three closely
spaced devices and used the gate potential to direct
immobilization to the desired device while preventing it
on the neighboring devices also in contact with the
electrolyte solution. Using the enzymes glucose oxidase,
urease, and lipase, the authors were able to analyze
samples containing mixtures of glucose, urea, and tri-
glycerides in a single measurement due to local changes
in pH. Sukeerthi and Contractor [51] have been able to
improve the response of this type of array by a factor of
103. Rather than using a flat substrate, they fabricated
their devices on microporous membranes to produce
disordered polyaniline microtubules that showed much
larger changes in conductivity upon exposure to ana-
lytes.
Battaglini et al. [52] have shown that glucose-
responsive OECTs based on the electrochemical reduc-
tion of polyaniline can be made that do not require the
addition of an external redox mediator. They accom-
plished this through covalent attachment of an osmium
complex mediator directly to the glucose oxidase en-
352
Fig. 8 Source–drain current Id versus time for a PEDOT:PSS
OECT in PBS buffer solution, in which first glucose oxidase (GOx),
and then glucose were added. The gate voltage Vg was pulsed from
0 to 0.6 V for 1-min intervals, while the source–drain voltage Vd
was held at 0.2 V. Inset shows the relative change of Id (sensor
response) as a function of Vg for solutions with and without
glucose. From Zhu et al. [58] and reproduced with permission of
The Royal Society of Chemistry
zyme. Battaglini and co-workers [53] have also demon-
strated an improved technique for fabricating polyani-
line OECTs that operate at pH 7. Rather than using
composite films of polyaniline and a polymer counterion
(as was done by Bartlett and colleagues [48, 49]), they
partially modified the polyaniline structure itself with
propane sultone. This partially sultonated polyaniline
showed a dramatic improvement in conductivity at pH 7
and was successfully used to make a hydrogen peroxide
sensitive OECT based on horseradish peroxidase that
performed well at neutral pH. Astier and Bartlett [54, 55]
also recently demonstrated that polyaniline transistors
operating in acidic solutions can be used to detect very
low analyte concentrations (0–5 nM) in short times
(1 min) at any pH by using a novel two-compartment
cell that separates the OECT from the analyte solution.
Another solution to the pH constraints of polyaniline
is simply to use a semiconducting polymer that is
inherently stable and conducting in neutral solutions.
PEDOT has been shown to meet these criteria, and
Kanungo et al. [56] have developed a reagentless OECT
immunosensor using electrochemically polymerized
PEDOT as both the active layer of the transistor and the
immobilization layer. They immobilized goat antirabbit
IgG antibodies in PEDOT microtubules during poly-
merization on a microporous membrane and exposed
their devices to solutions containing different amounts
of the antigen rabbit IgG at different gate potentials.
The source–drain current increased upon addition of the
antigen with a response time of 3 min. Krishnamoor-
thy et al. [57] used the same basic device to develop a
label-free DNA sensor. Single-stranded probe DNA was
entrapped in the PEDOT during electrochemical poly-
merization, and the devices were exposed to single-
stranded complementary target DNA. The source–drain
current of the devices decreased upon exposure to the
target DNA, and this decrease was attributed to con-
formational changes of the PEDOT upon DNA duplex
formation.
Using a soluble and commercially available form of
PEDOT complexed with poly(styrene sulfonate) (PE-
DOT:PSS), Zhu et al. [58] have demonstrated an
OECT capable of detecting glucose at neutral pH. In
contrast to previous OECT glucose sensors, no micro-
electrodes were required, and the PEDOT:PSS active
layer was deposited by spin-coating. A platinum wire
was used to apply the gate voltage, and it was observed
that the gate-induced modulation of the source–drain
current increased dramatically in the presence of both
glucose oxidase and glucose (see Fig. 8). The response
was found to result from the generation of hydrogen
peroxide by the enzyme and not from local changes in
pH.
Mabeck et al. [59] recently demonstrated a ‘‘micro-
fluidic gating’’ technique that showed how OECTs could
be used as transducers in microfluidic-based sensors.
Instead of using a conventional passive microfluidic
channel capable only of controlling fluid flow over the
substrate, a gate electrode was integrated into the
‘‘ceiling’’ of the channel so that the channel itself became
an electrically active component of the device. Gold was
used as the microfluidic gate electrode owing to its
electrochemical inertness and because it can act as a
convenient platform for immobilizing a wide array of
specific biorecognition elements (e.g., DNA, antibodies,
viruses, etc.) within the device using well-known thiol
chemistries.
Conclusion and future outlook
OTFTs have been demonstrated as effective sensors in
both gaseous and aqueous environments. They can be
used as either field-effect transistors or electrochemical
transistors, and they show superior performance com-
pared to resistor-type, amperometric, and potentiomet-
ric sensors. The amplification inherent to transistors
enhances their sensitivity, and they offer several oppor-
tunities for achieving selectivity, including multi-
parameter measurements and direct integration with
specific recognition elements.
In fact, the ability to covalently integrate recognition
elements directly with the active layer of the device is one
of the most promising features of OTFT sensors, and
one that still needs to be investigated more fully. An-
other promising area of development for OTFT sensors
is the fabrication of arrays and circuits to realize elec-
tronic noses (for gaseous analytes) and tongues (for li-
quid analytes) that are capable of analyzing and
classifying complex samples. Furthermore, important
contributions to current sensor research in the area of

lab-on-a-chip micro total analysis systems can be made
by integrating OTFT sensors with microfluidic systems.
Many of the applications for OTFT sensors will likely
involve disposable devices where long-term stability is
not critical; however, more studies are needed to
understand device degradation mechanisms and im-
prove sensor lifetimes.
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