Sensors and Actuators B 145 (2010) 501–506

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

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

Molecular semiconductor-doped insulator (MSDI) heterojunctions:

Oligothiophene/bisphtalocyanine (LuPc2 ) and perylene/bisphthalocyanine as
new structures for gas sensing
Marcel Bouvet a,∗ , Hui Xiong b , Vicente Parra b,1
a
Institut de Chimie Moléculaire de l’Université de Bourgogne, CNRS UMR 5260, 9 Av. A. Savary, BP 47870, 21047 Dijon cedex, France
b
Laboratoire de Chimie Inorganique et Matériaux Moléculaires, CNRS UMR 7071, Université Pierre et Marie Curie-Paris 6, France

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

Article history: The combination of a sexithiophene and a perylene diimide derivatives, as p-type and n-type materials,
Received 26 August 2009 respectively, used as sub-layers, to an intrinsic semiconductor, namely the lutetium bisphthalocya-
Received in revised form nine, allows to obtain a new transducer for gas sensing. These transducers were called molecular
21 December 2009
semiconductor-doped insulator (MSDI) heterojunctions, were recently designed and reported, but with
Accepted 22 December 2009
only phthalocyanines as active materials. p-Type material leads to MSDIs that exhibit a positive response
Available online 4 January 2010
to ozone and a negative response to ammonia, whereas MSDIs prepared from n-type material exhibit a
positive response to ammonia and negative response to ozone. The remarkable point is that the only mate-
Keywords:
Molecular semiconductor
rial in contact with the analytes is the lutetium bisphthalocyanine. It means that the inverted responses
Heterojunction observed for both p-type and n-type MSDIs come from the modulation of the electronic properties of
Transducer LuPc2 by the p-type and n-type sub-layers. That study enlarges the potentialities of the MSDIs and opens
Ozone the way to their promising development in the field of chemical sensors.
Ammonia © 2010 Elsevier B.V. All rights reserved.

1. Introduction phthalocyanines behave either as semiconductor or as doped insu-

The development of researches on molecular materials are stim-
ulated by number of applications [1–6], among which solar cells
[7], electroluminescent diodes [8], field-effect transistors [9–11]
and sensors [12,13], all stimulated by the emergence of printed
and plastic electronics [14–16]. Beside inorganic semiconductors,
often used as active materials in conductimetric sensors, molecu-
lar materials offer the possibility to operate at room temperature,
instead of using high temperatures, which entails an advantage
for a number of applications. Among well-known small molecular
weight containing molecular materials adapted to applications in
the electronics field, we can cite oligothiophenes, arenes, fullerenes,
carbone nanotubes and phthalocyanines. Among them, the later
offer a large variation of molecular properties, due to the great num-
ber of possible peripheral substituents and coordinated metals.
That versatility appears particularly on the energy levels posi-
tion, their electrochemical properties and their intermolecular
interactions, for example with adsorbed gaseous molecules. Thus,
∗ Corresponding author. Tel.: +33 380396086; fax: +33 380396098.
E-mail address: marcel.bouvet@u-bourgogne.fr (M. Bouvet).
1
Current address: Pevafersa, Renewable Energies, Parque Tecnológico de Boecillo,
Av. Juan de Herrera 12-14, 47151 Boecillo,Valladolid, Spain.
lator (extrinsic semiconductors, of n- or p-type) [17], depending on
their chemical nature. Whereas non-radical monophthalocyanines
exhibits very low intrinsic conductivity, radical bisphthalocya-
nines, mainly sandwich complexes of rare earth elements (LnPc2 ,
Ln = Pr, Gd, Lu, and so on . . .), are intrinsic semiconductors. Thus,
the lutetium derivative (LuPc2 ) – the first intrinsic molecular semi-
conductor which was discovered [18,19] – owns an extraordinary
high density of free charge carriers (5 × 1016 cm−3 ), and an unusual
small energy gap (ca. 0.5 eV) leading to an high electronic conduc-
tivity at room temperature about 5 × 10−5 ( cm)−1 [18–22]. That
distinction between doped insulators and semiconductors is often
occulted, but is of the utmost importance when we are combining
both types of materials.
The mechanism of gas–molecular material interaction is usually
explained by the LuPc2 , due to its radical nature, can be easily oxi-
dized and reduced. Thus it has been used as sensing material for
the detection of different gases having a wide spectrum of electron
donating–accepting properties (oxidizing, reducing and even non-
redox active molecules as the volatile organic compounds, VOCs)
[23,24]. Elsewhere, we have used MPcs as sensitive element for
the development of sensor devices based on chemiresistors [25],
organic field-effect transistors [26–28] and, in recent times, even
p–n diodes [29,30]. In addition, high-quality performances as elec-
trochemical liquid sensors for electronic tongues have been also

0925-4005/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2009.12.064
502 M. Bouvet et al. / Sensors and Actuators B 145 (2010) 501–506
Fig. 1. Scheme of the MSDI heterostructure (bottom), and pictures of the MSDI heterojunctions studied therein.
reported [31,32]. In gas sensors, whereas p-type MPcs are well-
sensitive to acceptor gases [12,33–35], the detection of donor gases
is devoted to n-type MPcs [36]. These materials are rather insu-
lators – energy gap about 2.0 eV, density of charge carriers near
105 cm−3 , and thin film conductivities at room temperature lower
than 10−10 ( cm)−1 – but the doping effect of redox active gases
triggers off the creation of a noticeable percentage of extrinsic
charge carriers.
The mechanism of gas–phthalocyanine interactions is usually
explained by the occurrence of two connected processes: adsorp-
tion of the gas at the surface and its diffusion into the bulk [17]. In
parallel, a charge transfer can occur between the two phases lead-
ing to the injection of charge carriers in the molecular material.
Moreover, a modification of the charge carrier mobility can occur
that results from a variation of the dielectric constant of the mate-
rial. When redox active species are involved, the variation of the
density of free charge carriers plays the most important role, but
with non-redox active analytes, i.e. with most of volatile organic
compounds, the mobility variation has to be considered.
Beside classical resistors, few other conductimetric trans-
ducers using molecular materials were recently introduced,
namely transistors [26,28,37–39] and diodes [29]. As in the later
example, very recently, we designed and characterized a new
type of conductimetric transducer, called MSDI for molecular
semiconductor-doped insulator heterojunction and resulting from
the combination of two types of molecular materials [40]. That new
transducer has been patented [41]. It is a simple device formed by a
thin film-based heterostructure from unsubstituted or fluorinated
copper phthalocyanine Cu(Fn Pc) (n = 0, 8, 16), which is in contact
with two interdigitated electrodes, and LuPc2 as top layer, being
the only material available to interact with the outer atmosphere
(Fig. 1). Regarding the Cu(Fn Pc) materials, its n = 0 and its n = 16
derivatives are very functional materials used in organic electron-
ics purposes due to their efficient hole [42] and electron [43–45]
transport skills, respectively. In the MSDI heterojunctions, due to
its own electronic properties, LuPc2 behaves differently depend-
ing on the nature of the doped insulator used as sub-layer. Besides
the enhanced conductivity of the heterostructures in comparison
with the respective single-layer films, the gas sensitivity of LuPc2
was modulated, even inverted, depending on the degree of fluori-
nation (the electron affinity) of the underlying Cu(Fn Pc) sub-layer
[46]. Whereas a LuPc2 resistor exhibits a linear behavior of its I(V)
characteristics, the MSDIs show non-linear but symmetrical I(V)
curves.
The current of the MSDI LuPc2 /F0 prepared with CuPc as sub-
layer increases under O3 whereas, under NH3 , the same device
shows a current decrease. The electrical behavior is related to the
density of majority charge carriers, which increases under O3 and
decreases under NH3 . On the contrary, MSDI LuPc2 /F16, prepared
with Cu(F16 Pc) as sub-layer, yield a negative response to O3 and a
positive response to NH3 , as a result of an increase of the energy
barrier at the MSDI heterojunction. Due to the particular redox
properties of LuPc2 , the MSDIs are very sensitive, but without the
saturation effect observed in LuPc2 resistors. In the MSDI devices,
the semiconductor layer is the only organic film exposed to the
atmosphere, whereas the doped insulator one plays the role of
modulator of the effective charge carrier’s nature, by tuning the
electronic characteristics of the organic heterojunction.
Clearly the heterojunction between the MS and the DI plays a
key role in the MSDI behavior.
The MSDI-based transducer gives rise to a new generation
of gas sensors based on organic semiconductors, aiming to the
accomplishment of new sensing performances from advanced but
accessible functional materials, and then improving the up to now
best-known models, the classical and rather operation-limited
single-layer chemiresistors and without the complexity of the tran-
sistor technology.
In the present work, we show that MSDIs can be prepared
from other molecular materials than phthalocyanine deriva-
tives. We used as sub-layers the 5,5 -dihexyl-␣,␻-sexithiophene
(6T) and the N,N -dineopentyl-3,4,9,10-perylenetetracarboxylic-
diimide (PTCDI), in both case associated with LuPc2 (Scheme 1).
The first one is the favor molecule among the oligothiophenes fam-
ily, largely used as p-type active materials in organic field-effect
transistors [47–49], whereas the later is one of the few representa-
tives of n-type molecular materials [50,51]. In order to compare the
relative energy levels of these two molecular materials with those
of LuPc2 , we chose to indicate their redox potentials (Fig. 2). 6T
oxidized at 0.85 V vs the saturated calomel electrode (SCE) [52],
i.e. like CuPc, whereas PTCDI is reduced at −0.6 V vs SCE [53],
like the octafluorophthalocyanine [40,46]. The reduction and oxi-
dation potentials of LuPc2 appears at −0.29 and 0.19 V vs SCE,
respectively [20]. Clearly, the charge transfer that occurs at the het-
erojunction with LuPc2 will be different for the two materials. All
the devices were characterized by their optical absorption spec-
trum. Current–voltage characteristics were determined for all the
devices, which were then submitted to ozone or ammonia atmo-
spheres, at a given voltage.
 M. Bouvet et al. / Sensors and Actuators B 145 (2010) 501–506 503

Scheme 1.

2. Experimental Optical characterization. The UV–vis spectra of the ITO-deposited

samples were registered using a Shimadzu UV-2101 Spectrometer,
Molecular materials. 5,5 -Dihexyl-␣,␻-sexithiophene in the range 400–900 nm. A bare ITO/glass substrate was used as a
was purchased from Aldrich. N,N -Dineopentyl-3,4,9,10- reference.
perylenetetracarboxylic-diimide [54,55] and LuPc2 [56–58] Electrical measurements. The fundamental electrical and sensor
were synthesized according to previously reported methods. measurements were performed using a Keithley 6517 electrometer
Devices. The heterojunctions were built by successive depo- with an incorporated DC voltage supply, always at room tempera-
sition of the corresponding molecular materials onto ITO/glass ture. The electrometer is controlled by self-made software via the
(sheet resistance 10  cm−1 ) interdigitated electrodes separated by GP-IB board. Current–voltage (I–V) curves were registered in the
75 ␮m, by means of classical thermal evaporation (using a VEECO range (−10 and +10 V), starting and finishing at 0 V bias to avoid
770 system) from two Tantalum boats, at ca. 10−6 mbar, and 2 Å s−1
rate, without breaking the vacuum between each step. The thick-
ness (100 nm for each film) was controlled by two quartz crystal
microbalances placed independently in the vicinity of the respec-
tive boat. In the same evaporation process, ITO/glass substrates
without electrode were also used to prepare thin films for opti-
cal spectroscopy. MSDIs prepared with 6T and PTCDI combined to
LuPc2 are noted hereafter p-MSDI and n-MSDI, respectively.

Fig. 3. UV–vis absorption spectra of the PTCDI/LuPc2 heterostructure (top) com-

pared to that of a PTCDI film (bottom).

Fig. 2. Schematic view of the redox potentials measured by cyclic voltammetry (in
V vs SCE), corresponding to the energy levels (LUMO and HOMO or SOMO) involved
in the electrical properties of molecular materials studied here. Fig. 4. UV–vis absorption spectrum of the 6T/LuPc2 heterostructure.
504 M. Bouvet et al. / Sensors and Actuators B 145 (2010) 501–506

irreversible polarization effects. On the other hand, for gas sens-

ing experiments, the samples were constantly polarized at 5 V. The
experiments were performed in dark conditions to avoid photo-
electric effects.
Gas sources for sensing experiments. Ozone was generated by
an analyzer/generator (O3 41M Environment S.A.), which allows
a controlled supply of ozone in air at ppb level (total mass flow:
1.6 L min−1 ), besides a flow of clean air, used as purging gas. In
case of ammonia, a standardized bottle (1000 ppm in Ar, from
Air Liquide, France) was suitably diluted with dry Ar using mass
flow controllers (total mass flow: 0.5 L min−1 ), to attain controlled
ammonia concentrations.

3. Results and discussion

3.1. Optical spectroscopy

At a first glance, the two main absorption bands, at 666 and

464 nm, are common to both heterojunctions (Figs. 3 and 4). They
belong to LuPc2 , and correspond to the Q-band (666 nm) and to the
so-called “blue vibration band”, attributed to a transition from a Fig. 5. Response of p-MSDI to ozone (top) and ammonia (bottom), bias = 5 V.

deep orbital towards the semi-occupied molecular orbital (SOMO)

(464 nm), respectively [59,60]. The main differences appear in the
necessary to obtain a good reversibility, as seen above, when a ratio
range 480–600 nm. In Fig. 3, the two relative maxima at 544 and
of 3 or 4 between the rest period and the exposure period durations
577 nm correspond to absorption bands of PTCDI, as well as the
is applied [27].
shoulder at 492 nm. The more intense absorption band of PTCDI,
At first, let see the response of p-MSDIs to ozone and ammonia
at 468 nm, lies in the same region as the blue vibration band of
(Fig. 5). A dynamic methodology is used, which consists in alter-
LuPc2 . Finally, both spectra exhibit a shoulder near 605 nm, which
nating exposure-rest periods cycles [26,27]. For ozone, the rest
belongs to LuPc2 too. The spectrum of the 6T/LuPc2 bilayer is totally
periods are obtained only by stopping the ozone-containing air
superimposable to that of pure LuPc2 (Fig. 4). This is due to the
flow, whereas an argon flow is necessary to ensure the ammonia
fact that 6T absorption is center at 440 nm in solution, but which
removing. As expected, current increases under ozone, due to an
is highly broadened in thin film, with a strong dependence on its
increase of the density of free charge carriers in the LuPc2 layer.
structure [61–63]. So, no absorption band can be attributed to 6T
During the rest period, ozone self-decomposes, due to its short
in the bilayer.
life-time, and the current goes down to its origin value. On the con-
trary, under ammonia, current decreases. This can be attributed,
3.2. Electrical characterization
not only to the trapping of positive free charge carriers in LuPc2 ,
but further, to the presence of negative majority charge carriers,
In a MSDI device, the positive and negative polarization cor-
which implies the apparition of an energy barrier at the interface
respond to charge injection in the MPc sub-layer, in contrast to
between the p-type sub-layer and the become n-type LuPc2 upper-
the typical forward and reverse polarizations in diode-type het-
layer. Again, when ammonia is replaced by argon atmosphere takes,
erojunctions [40]. As a result, the current developed by the MSDIs
the current goes up its initial value. Thus, the oxidizing and donat-
remains perfectly symmetrical (Supplementary Information), dif-
ferent from the linear curve of LuPc2 resistor, in agreement with
the well-reported space-charge-limited conduction (SCLC) found
in phthalocyanine-based devices [64,65]. In any case, the cur-
rent developed by MSDI heterojunctions is markedly higher than
that exhibited by doped insulator single layer resistors (current
amplitude in the 10−11 A range), but slightly lower than that
developed by LuPc2 single layer (current amplitude in the 10−4 A
range). This indicates that the charge flow in the MSDI heterostruc-
tures is governed by the contribution of both the charge injection
into the sub-layer and the current flowing across the organic
heterointerface. Instead of the determined conductivity of single
semiconductor layer, the conductivity of the bilayer device is tuned
by changing the type of insulator sub-layer.

3.3. Gas sensing

Oxidizing gases are known to induce a current increase of p-

type materials, via a doping process, whereas donating species
diminish their conductivity, due to a trapping process. For n-type
device, alternative gas flow of ammonia and argon were applied,
the flowing argon might rush away ammonia associated to molec-
ular surface. For p-type device, after ozone exposure, there was no
gas flow, leaving ozone to decompose spontaneously. Nevertheless, Fig. 6. Response of an n-MSDI to ammonia (top) and its relative response I/I0 as a
the use of dynamic rest (inert gas flow), instead of static rest, is not function of the ammonia concentration (bottom), bias = 10 V.
 M. Bouvet et al. / Sensors and Actuators B 145 (2010) 501–506
ing species result in positive and negative responses, respectively;
both processes being reversible.
Contrarily, n-MSDIs exhibit higher conductivity after interaction
with ammonia (Fig. 6). As aforementioned, the majority charge car-
riers turn from positive to negative nature, leading to a decrease of
the heterojunction energy barrier. It confirms the ambipolar behav-
ior of LuPc2 , which can be easily oxidized and reduced, in relation
with its radical nature [10,17]. It appears clearly that a saturation
effect occurs during the 5-min long exposure periods. Thus, the
absolute response I defined as Ion − Ioff is almost the same after
only 2-min long exposure, 0.6 against 0.65 ␮A. It leads to a rela-
tive response defined as I/I0 of about 20% at 1000 ppb NH3 . The
response to ammonia is remarkably stable compared to that of
p-type MSDIs to ozone. A linear relative response was observed
in the range 1000–200 ppm NH3 (Fig. 6), and 200 ppm is not the
lower limit for such a device. In the case of ozone, a positive drift
of the Ioff current of p-MSDIs is observed, and a typical relative
response is about 10% at 400 ppb of ozone. The response is not
linear as a function of the ozone concentration, e.g. the measured
relative response was still 3% at 50 ppb. As already observed [26,27],
molecular materials-based sensors are adapted to low ozone con-
centration detection, in the ppb range. It is worth mentioning that in
order to compare the response of all the devices we used always the
same thicknesses, which could be diminished in order to reduce dif-
fusion processes, then to increase the response time and sensitivity
of the sensors.
4. Conclusion
That work show that the association of a doped insulator to
a more conductive material, in a MSDI heterojunction can be
applied to other materials than phthalocyanines. The performances
of the MSDIs here presented with 6T and PTCDI as sub-layers
were demonstrated with concentrations interesting for most of
the potential applications, typically in the ppb and ppm range for
ozone and ammonia, respectively. The use of thinner films, leading
to less crystalline films, should still allow improving the perfor-
mances of these new transducers, reducing diffusion phenomena
and the response time of sensors. Additionally, since the interface
plays a key role in the MSDI, thinner sensing layers should amplify
that phenomenon. MSDIs can be compared to organic field-effect
transistors introduced as chemical transducers about 10 years ago.
The new transducer opens the door to a promising development in
the field of chemical sensors.
Acknowledgements
The authors acknowledge the Agence Nationale de la Recherche
(A.N.R., France) for funding under POLL-CAP project Blan-06-
154000. Dr. M.L. Rodríguez-Méndez is also acknowledged for
supplying the electrode substrates. Dr. J. Brunet and Prof. A. Pauly
are thanked for thin films evaporation.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.snb.2009.12.064.
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Biographies
Marcel Bouvet obtained his Ph.D. from the University Pierre and Marie Curie
(UPMC), in 1992 on electrical properties of phthalocyanines. He has been working
mainly at the E.S.P.C.I. (Paris), as associate professor, but also at the UPMC (Paris),
and at the University of Conecticut (USA). He got a full professor position at the
Université de Bourgogne (Dijon), in 2008. Prof. Bouvet’s research interests are in the
field of molecular materials-based devices, among them sensors.
Hui Xiong was born in 1978. She obtained a bachelor of science from the University
of Fudan (China), then a master from the Erasmus Mundus Program “Molecular
Nano- and Bio-photonics for Telecommunications and Biotechnologies”, at the E.N.S.
Cachan (France). She is currently working in China.
Vicente Parra obtained his Ph.D. from the University of Valladolid (Spain) on elec-
tronic tongues for beverage and food analysis. Then he spend 2 years in France
as a post-doctoral fellow, at the UPMC, at the University Denis Diderot (Paris)
and at the University Blaise Pascal (Clermont-Ferrand). He is currently working on
renewable energies as the research manager of the Pevafersa Company (Valladolid,
Spain).