Synthetic Metals 125 (2002) 313±317

Effect of regioregularity on the photoresponse of Schottky-type

junctions based on poly(3-alkylthiophenes)
N. Camaionia,*, M. Catellanib, S. Luzzatib, A. Martellia, A. Miglioric
a
Istituto CNR-FRAE, via P. Gobetti 101, I-40129 Bologna, Italy
b
Istituto CNR-ICM, via Bassini 15, I-20133 Milano, Italy
c
Istituto CNR-LAMEL, via P. Gobetti 101, I-40129 Bologna, Italy
Received 15 December 2000; received in revised form 16 May 2001; accepted 25 May 2001

Abstract

The electrical and photoelectrical characteristics of sandwich-type devices based on regioregular head-to-tail (HT) poly(3-
alkylthiophenes) (PATs) have been investigated and compared with those obtained with regiorandom polymers. Better performances
have been achieved in sandwich-type devices made with regioregular polymers having a short alkyl substituent. A spectroscopic and
morphological investigation of the materials have been also done. # 2001 Elsevier Science B.V. All rights reserved.

Keywords: Poly(3-alkylthiophenes); Regioregularity; Solar cells

1. Introduction
Poly(3-alkylthiophenes) (PATs) are among the most pro-
mising conjugated polymers. They are relatively easy to
synthesize, possess excellent processability and environ-
mental stability. These advantages combined with their
interesting optical and electrical characteristics make these
materials good candidates for a cheap opto-electronic tech-
nology on plastic substrates.
The most common and easy way to prepare PATs is an
oxidative coupling via chemical or electrochemical synth-
esis. The drawback of the oxidative polymerization consists
in the formation of conjugated backbone with irregular
enchaimnet of the thiophene units due to the asymmetry
of the 3-alkylthiophene monomer. These polymers contain
usually 70% of regular 2,5 head-to-tail (HT) coupling, and
regioirregular head-to-head (HH) and tail-to-tail (TT)
enchaiments that increase both the steric hindrance and
the torsion angle between consecutive rings. The distortion
of the conjugated backbone due to the steric interaction
between adjacent monomers produces a decrease of the p-
orbital overlap and consequently a shortening of the effec-
tive mean conjugation length of the backbone. The decreas-
ing of the conjugation in¯uences the electrical properties
*
Corresponding author. Tel.: ‡39-51-639-9784; fax: ‡39-51-639-9844.
E-mail address: camaioni@frae.bo.cnr.it (N. Camaioni).
of the materials and the optical properties such as a blue shift
of the electronic absorption spectra. Moreover, the organi-
zation of regioirregualr PATs in the solid state is dif®cult
to control and, therefore, synthetic strategies have been
developed to prepare regioregular polythiophenes. The ®rst
synthesis of regioregular PATs via a metal catalyzed cross-
coupling reaction has been reported by McCullough and
Lowe [1] in 1992. Regioregular polymers are usually char-
acterized by enhanced electrical and optical properties with
respect to the regiorandom ones (see, e.g. [2,3]).
The effect of regioregularity on the photoluminescence
[4] and on the thermochromic properties of PATs have been
investigated [5]. Schottky-diodes [6], light-emitting diodes
[7±10] and ®eld-effect transistors [11,12] have been fabri-
cated by using regioregular PATs. Better electrolumines-
cence properties and higher ®eld-effect mobilities have been
reported for devices based on regioregular polymers over the
ones based on random materials.
In this paper, the photoresponse of sandwich-type devices
based on both regioregular and regiorandom PATs is
compared. The polymer used for this study are a poly-
(3-butylthiophene) (PBT) containing a short alkyl-chain,
and a poly(3-octylthiophene) (POT) with a longer substi-
tuent of thiophene rings. The random PATs were prepared
via oxidative coupling with FeCl3 and the regioregular
polymers were synthesized via cross-coupling polymeriza-
tion with the McCullough route. The as prepared materials
were characterized by absorption and emission spectroscopy

0379-6779/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 ( 0 1 ) 0 0 4 0 0 - 3
314 N. Camaioni et al. / Synthetic Metals 125 (2002) 313±317

and the morphology of thin ®lms were studied by transmis- line was used as excitation. The spectra were corrected for
sion electron microscopy (TEM). the instrumental spectral response.

2. Experimental 3. Results and discussion

Two regioregular PBT and POT (PBT-R and POT-R) have In Fig. 1, the electronic spectra of both random and
been prepared (yield 78%) using the synthetic route giving regioregular PAT samples used for the fabrication of the
absolute regiocontrol at each coupling step in the polymer- Schottky-type junctions are reported, the ®lms were spin
ization reaction [13]. By 1 H NMR analysis the polymers coated on ITO glass. The regular enchainment of the back-
show more than 99% HT couplings. The molecular weight bone produces a red shift of the absorption maxima and the
(Mw) distribution obtained by size exclusion chromatogra- appearance of a structure in the spectra. The red shift can be
phy (SEC) in tetrahydrofuran using polystyrene as standards interpreted as an increase of the mean conjugation length
were M w ˆ 29 500 for PBT-R and M w ˆ 40 000 for POT-R. passing from the random to regioregular polymers. The
We have also synthesized the same PATs, PBT and POT, presence of the ®ne structure evidences an increased order
via oxidative reaction with FeCl3 obtaining a lower HT of the regioregular polymer ®lm. This feature can be inter-
regularity [14]. The as prepared polymers (95% yield) were preted either by the coexistence of phases with different
extracted in Soxhlet apparatus with methanol in order to interchain coupling (phases with different three-dimensional
remove the residual oxidant. The polymers were dissolved in order) or as a vibronic structure due to the coupling of the
chloroform and insoluble products were removed by ®ltra- C=C stretching mode of the conjugated backbone to the
tion. Then they were precipitated from a solution of hydra- p±p transition [15,16].
zine in methanol to eliminate traces of the catalyst. The The absorption and the emission optical properties of both
polymer was extracted in a Kumakawa apparatus with random and regioregular PBT samples are reported in Fig. 2.
hexane to remove the low Mw. The HT regioregularity for The photoluminescence spectra of PBT-R shows a red shift
both samples was found to be around 70% by 1 H NMR of the maxima respect to that of PBT sample and two
spectroscopy. The average Mw by SEC chromatography separated emission bands. This behavior is probably due
were M w ˆ 99 600 for PBT and M w ˆ 116 600 for POT. to the presence of two phases with a different three-dimen-
The polymer ®lms (with thickness ranging between 120 sional order degree in the regioregular polymer. In PATs the
and 160 nm) were processed by spin coating technique
(at 2000 rpm) onto indium-tin-oxide (ITO) substrates
(Balzers, 23 O/&). The polymers were dissolved in chloro-
form (concentration: 20 mg/cm3) and the solutions were
®ltered with a PTFE ®lter.
The top electrode was realized by vacuum evaporating a
semitransparent aluminum layer (11 nm thick) onto the
polymer ®lms. The electrical characterization was done with
a Keithley 2400 source meter. The junctions were illumi-
nated through the aluminum side with a 300 W Xe arc lamp.
The incident photon to current ef®ciency (IPCE) was deter-
mined for a wavelength of 500 nm, by using an interference
®lter. The variation of the incident light intensity was Fig. 1. Electronic absorption spectra of random and regioregular poly-
achieved by using neutral density ®lters. The optical bench (3-alkylthiophenes).
was equipped with a water ®lter to cut-off IR. The incident
light intensity was measured with an Oriel thermopile and
corrected for the Al layer absorption. No correction was
made for light re¯ection. The electrical characterization was
done under vacuum.
The TEM observations were performed using a Philips
CM30 microscope operating at 300 keV. The polymer sam-
ples for TEM characterization were prepared by spin coating
(at 2000 rpm) from a chloroform solution (5 mg/cm3) onto
carbon ®lms supported by a copper grid.
The UV±VIS spectra were performed with a Varian Cary
2400 instrument. The photoluminescence spectra were
detected at 80 K by means of a ¯at ®eld monochromator Fig. 2. Absorption and emission spectra of random (full line) PBT and
and a nitrogen cooled CCD detector. The 2.41 eV Ar‡ laser regioregular PBT-R (dashed line) films.
 N. Camaioni et al. / Synthetic Metals 125 (2002) 313±317
Fig. 3. Bright-field transmission electron micrograph of a random POT film spin coated on a carbon films supported by a copper grid.
luminescence is believed to be the result of radiative decay
of singlet excitons, and the degree of structural order/dis-
order of conjugated chain has a strong in¯uence on the
emission of the materials. It has been also observed that the
chain stiffness, varied through the number of HT enchain-
ment, is affecting the emission ef®ciency [4,17].
A morphological analysis was done in the case of POT by
using TEM. Both random and regioregular ®lms showed a
dense and smooth morphology but characterized by micro-
scopic holes (Fig. 3). We hypothesize that the solvent
evaporation could give rise to these pin-holes, very danger-
ous for the device realization. The morphology is a very
important factor affecting the device parameters in the
dark and, as a consequence, the photovoltaic performance.
Pin-hole formation has been already observed in the
case of regular poly(3-dodecylthiophene) ®lms cast from
chloroform [18].
The dark current±voltage (I±V) characteristics of the
junctions based on the regioregular polymers have a recti-
®cation ratio (at 2 V) of an order of magnitude higher than
that of the junctions based on random PBT and POT, as a
consequence of very higher forward currents in the former
case. A recti®cation ratio of 6  104 has been obtained in the
case of PBT-R. Furthermore, PBT-based junctions exhibit
higher forward currents with respect to the ones based on the
polymer with the longer alkyl-chain, both in the case of
315
regioregular and regiorandom polymers. As expected, in all
cases the I±V characteristics are far from ideality. However,
lower values of the ideality factor (n) have been found to
correspond to better transport properties of the investigated
junctions. In the case of PBT-R a value of 2.7 has been found
for n. Higher values have been obtained in the regiorandom
case and with POT-based systems. Large values of n are
usually attributed to the presence of thick interfacial layers
or to recombination in the depletion region of the junction
[19]. As it is not easy to understand why the effect of the
presence, very probable, of interfacial layers should depend
on regioregularity and on the length of the side-chain of the
polymer, we assume that recombination current is the main
cause of departure from ideality. It is known that this
phenomenon should be important in materials of low life-
time. It is plausible to hypothesize that the polymer orga-
nization and the encumbrance of the side-chains could affect
the nature and the energy of the localized states through
which the recombination normally takes place.
By illuminating the junctions with white light through the
semitransparent aluminum electrode, a photovoltaic effect
was observed. These junctions exhibited a large open-circuit
photovoltage (ca. 0.6 V) and the short-circuit photocurrent
(jsc) was found to vary as a power law with the incident
irradiation power (Pin), with a power factor of ca. 0.8±0.9.
The sublinear relationship between jsc and Pin, very common
316 N. Camaioni et al. / Synthetic Metals 125 (2002) 313±317
Fig. 4. Plots of the photovoltaic conversion efficiency as a function of the
incident irradiation power for the systems: ITO/PBT-R/Al (squares), ITO/
PBT/Al (circles).
in imperfect materials, is a sign of trapping effects [20]. The
®ll factor was found to be low in all cases, ranging between
0.23 (for PBT-based junctions) and 0.18 (POT-based junc-
tions) for low incident irradiation power, and little decreas-
ing with the incident irradiation power. The photovoltaic
conversion ef®ciency (Z) of junctions based on both regiore-
gular PBT-R and regiorandom PBT is compared in Fig. 4. As
expected for devices based on pure conjugated polymers, Z
is too low for practical applications, but the main value of
this investigation is in the advancement of the understanding
of the basic science. The better performance of the junctions
based on the regioregular polymer should be ascribed to the
enhanced transport properties of the latter polymer. X-ray
studies on regioregular PATs have shown that regularity
induces a higher structural order (see, e.g. [18] and refer-
ences therein) over the regiorandom polymers and the
structural organization is of utmost importance for obtaining
better transport properties. Also in the case of POT-based
junctions a signi®cant improvement of the photoresponse
was obtained with the regular polymer (Fig. 5), though Z was
found to be lower, both for POT and POT-R polymer, with
respect to the PBT-based junctions. The operation of a
photodetector is basically controlled by two phenomena:
photogeneration and transport. Higher conversion ef®cien-
cies, in the present case mainly due to higher photocurrents,
could be ascribed to better transport properties of the
Fig. 5. Plots of the photovoltaic conversion efficiency as a function of the
incident irradiation power for the systems: ITO/POT-R/Al (squares), ITO/
POT/Al (circles).
Fig. 6. Plots of the incident photon to current efficiency as a function of
the reverse bias applied to the junctions: ITO/PBT-R/Al (squares), ITO/
PBT/Al (circles). The intensity of the incident light (of wavelength of
500 nm) was about 1 mW/cm2.
materials. It could be hypothesized that the encumbrance
of the alkyl-chains in¯uences the carrier mobility, in parti-
cular the inter-chain carrier mobility. X-ray diffraction
studies on polyalkylthiophenes have shown that the inter-
layer spacing is an increasing function of the alkyl-chain
length (see, e.g. [21] and references therein) and the inter-
layer spacing could likely affect the carrier interchain
mobility. A decreasing conversion ef®ciency with the length
of the alkyl-chain in Schottky-type junctions based on PATs
has already been observed [22] and an increasing distance
for interchain hopping was hypothesized in that case. In all
cases, the photovoltaic ef®ciency is a decreasing function of
the incident irradiation power, due to the sublinear relation-
ship between jsc and Pin. Fig. 6 compares the IPCE, obtained
by illuminating with monochromatic light of wavelength of
500 nm, of both regioregular and regiorandom PBT-based
junctions. The conversion ef®ciency is bias dependent and
follows a superlinear behavior with the reverse bias applied
to the junctions. As previously demonstrated [23], conju-
gated polymers should be very attractive candidates for
photodiode applications, with sensitivities comparable with
that of photodiodes made with inorganic semiconductors,
even at relatively low reverse voltage of operation.
4. Conclusion
The morphological analysis by TEM of polymeric ®lms
showed a dense and smooth morphology with microscopic
holes. The optical spectra reveal an increased order degree
and mean conjugation length in the case of the regioregular
polymers. Better transport properties in the dark and higher
performance under illumination were obtained with the
junctions based on regioregular polymers. In particular,
higher recti®cation ratios of the dark I±V characteristics,
due to higher forward currents, were obtained for PBT-R and
POT-R with respect to the random polymers. Furthermore,
the departure from ideality of the I±V curves was mainly
attributed to the recombination in the depletion region of the
junctions and it was hypothesized that this process should be
much more important in the systems with higher values of
 N. Camaioni et al. / Synthetic Metals 125 (2002) 313±317
the ideality factor, that is in the ones based on the random
polymers. As far as the photoelectric performances, the
photovoltaic conversion ef®ciency was found to be about
twice, in the considered range of the incident irradiation
power, in PBT-R and POT-R based systems with respect
to that of those based on random polymers. Finally, both
for random and regioregular polymers, better performances
were obtained with PBT. An enhanced hopping mobility was
hypothesized for the polymer with the shortest alkyl-chain.
Acknowledgements
This work was supported by the National Research
Council of Italy in the framework of the Progetto Finalizzato
`Materiali Speciali per Tecnologie Avanzate II'.
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