J. Phys. Chem.

C 2009, 113, 7411–7415 7411

Flexible Sandwich Photodetectors Based on Thick Polythiophene Films

Lei Tong, Chun Li, Feng’en Chen, Hua Bai, Lu Zhao, and Gaoquan Shi*
Department of Chemistry and Key Laboratory of Bio-organic Phosphorous Chemistry and Chemical Biology,
Tsinghua UniVersity, Beijing 100084, People’s Republic of China
ReceiVed: December 29, 2008

We report a flexible photodetector with a sandwich structure of Au/polythiophene (PTh)/Au, which consists
of two Au electrodes with a thickness of 30 nm each and a PTh layer with a thickness of 10-40 µm. The
devices showed strong and fast photoresponses under excitation through the gold electrodes using white light
or a 514 nm laser beam. Upon illumination with a 40 mW/cm2 514 nm laser beam and under a low bias
electric field of 0.2 V/µm, the device with a 20 µm thick PTh layer exhibited an external quantum efficiency
up to 136%. These devices are flexible and can be bent to large angles and fabricated into large sizes with
arbitrary shapes.

1. Introduction from Beijing Chang Yang Chemical Plant (Beijing, China). PTh
films were synthesized following a modified procedure reported
Conducting polymers have been widely applied in various
previously.7 Briefly, PTh films were deposited onto a stainless
electronic devices, such as sensors, light-emitting diodes, and
steel sheet (AISI 304) by electrolysis of freshly distilled BFEE
solar cells.1 Photoactive films of conducting polymer sandwiched
solution containing 30 mM thiophene at a constant applied
between two electrodes are usually used as photodetectors.2,3
potential of 1.3 V, using a CHI440 potentiostat (CH Instruments
The photoconductive properties of poly(p-phenylene vinylene)
Inc. USA). The counter and reference electrodes were a stainless
(PPV), polythiophene (PTh), and their derivatives have been
steel (AISI 304) sheet and an Ag/AgCl wire, respectively. To
studied extensively.4,5 Avalanche multiplication was observed
provide a more general reference, a correction of 0.069 V was
in these strongly disordered organic solids. For example, the
needed to bring the measured potentials in BFEE originally
electrodecollectionefficiencyofa255nmthickAu/arylamino-PPV/
versus Ag/AgCl to potentials versus the standard hydrogen
Al device was measured to be up to 2000% under a high bias
electrode.7 The electrolyte was deoxygenated by bubbling
field of -20 V/µm and illumination through its Al electrode
nitrogen gas, and a slight overpressure was maintained during
with 450 nm laser light.4 However, to date, almost all of the
electrosynthesis. The thickness of the PTh film was controlled
active layers of the photodetectors were based on films with
by the total charge passed through the electrochemical cell.
thicknesses thinner than 1 µm. Therefore, the films have to be
2.2. Fabrication of the Sandwich Photodetectors. The
deposited on a metallic sheet or a conductive plastic substrate.
configuration of the sandwich photodetector is illustrated in
The photoconductivities of free-standing thick conducting
Figure 1a. An as-grown PTh film was peeled off from the
polymer films have never been reported.
stainless steel working electrode and washed repeatedly with
On the other hand, conducting polymers are usually brittle
diethyl ether and deionized water. Then, it was dedoped with
and have low mechanical strengths. They cannot be fabricated
an aqueous solution of 1.0 M NaOH or 80% (by volume)
into desired structures by conventional polymer processing
hydrazine for 24 h. Successively, the film was washed thor-
techniques. Therefore, much effort has been devoted to fabricat-
oughly with deionized water and dried under vacuum. Finally,
ing flexible and low-cost electronic devices using ink jetting
both sides of the PTh film were coated with 30 nm Au layers,
and screen printing of soluble conjugated polymers.5,6 In this
each by sputtering. The resulting photodetector is flexible and
paper, we report flexible sandwich photodetectors based on thick
can be bent into large angles, as shown in Figure 1b.
high-strength PTh films formed by one-step electrochemical
2.3. Characterizations. UV-vis spectra were recorded by
polymerization of thiophene in freshly distilled boron trifluoride
using a U-3010 spectrophotometer (Hitachi, Japan). Electron
diethyl etherate (BFEE)7 and sputtering Au layers on both sides
spin resonance (ESR) spectra were recorded on a 200D SRC
of the PTh layer. The Au (30 nm)/PTh (20 µm)/Au (30 nm)
X-band spectrometer (Bruker, Germany). Microwave frequen-
device showed an external quantum efficiency (EQE) up to 95%
cies were measured with an SP3382A microwave counter. The
under a low positive bias field of 0.1 V/µm or 136% under 0.2V/
magnetic fields were calibrated by using an ER 035 M NMR
µm upon illumination through the bottom electrode (the side in
gaussmeter. The morphology of the films was examined by the
contact with the working electrode during film growth) with a
use of an FEI Sirion 200 scanning electron microscope (JEOL,
40 mW/cm2 514 nm laser beam.
Japan). J-V curves of the photodetector were taken out by using
a 2400 source meter (Keithley, USA) under AM1.5 simulated
2. Experimental Section sunlight irradiation or a 514 nm laser beam.
2.1. Electrochemical Deposition of PTh. Thiophene mono-
mer was purchased from Beijing Chemical Plant (Beijing, 3. Results and Discussion
China), and boron trifluoride diethyl etherate (BFEE) was bought
3.1. UV-vis Spectra. Figure 2 shows the absorption spectra
* To whom correspondence should be addressed. Phone: +86-10-6277- of a 200 nm PTh film dedoped with an aqueous solution of
3743. Fax: +86-10-6277-1149. E-mail: gshi@tsinghua.edu.cn. hydrazine (80%, by volume) and a glass sheet coated with a 30
10.1021/jp811458h CCC: $40.75  2009 American Chemical Society
Published on Web 04/06/2009
7412 J. Phys. Chem. C, Vol. 113, No. 17, 2009
Figure 1. (a) Configuration of the sandwich photodetector. (b) A
photograph of the flexible photodetector.
Figure 2. Absorption spectra of a 200 nm PTh film dedoped by
hydrazine and 30 nm Au layer coated on a glass sheet by sputtering.
nm Au layer. It is clear that the PTh film has a strong and broad
absorption band with a maximum around 500 nm. (This
spectrum is the same as that of the PTh film dedoped with 1.0
M NaOH.) The 30 nm gold layer shows strong absorptions at
wavelengths lower than 450 nm and higher than 550 nm and
exhibits a semitransparent optical window centered around 500
nm. The transmittance of a 514 nm laser light through a 30 nm
gold coating was determined to be about 25%. Accordingly,
the white light and 514 nm laser light can partly penetrate
through the 30 nm gold electrode and be absorbed by the PTh
layer to generate excitons.
3.2. Morphology. The scanning electron micrographs (SEMs)
of the top (in contact with the electrolyte) and bottom (in contact
with the electrode) surfaces of a 20 µm PTh film are shown in
Figure 3. It is clear that the surface of the bottom side in Figure
3a is more compact and smoother than that of the top side in
Figure 3b. After a 30 nm gold film was deposited on each
surface by sputtering, this morphology difference was kept, as
shown in Figure 3c,d, and gold nanoparticles on the PTh
surfaces formed continuous conductive layers. This morphology
implied that the top surface can scatter more light than the
bottom surface because of its higher roughness. Therefore, we
studied the photoresponses of the devices by illumination
through their bottom surfaces.
Tong et al.
Figure 3. SEM images of the bottom (a, c) and top (b, d) surfaces of
a 20 µm PTh film before (a, b) and after (c, d) sputtering 30 nm gold
layers. The inset of (b) shows a cross-sectional view of the film.
Figure 4. ESR spectra of 10 µm (O), 20 µm (4), and 40 µm (0) PTh
films dedoped in 1.0 M aqueous NaOH solution; 20 µm PTh film in
the doped state (top) and in hydrazine (bottom).
3.3. ESR Studies and Conductivity Measurements. The
doping states of the thick PTh films were studied by ESR
spectroscopy. It is widely accepted that the charge carriers of
conducting polymers are polarons and bipolarons, and both of
them can propagate the electrical current along the polymer
chains.8-10 In highly doped PTh, spinless bipolarons dominate,
and they cannot be quantitatively evaluated by ESR.10 Polarons
have magnetic moments and can be determined by using ESR
spectroscopy due to their paramagnetic character. Polarons
coexist with bipolarons in conducting polymers with high or
medium doping levels, and their ESR signals are sensitive to
the chemical environment. The ESR spectra shown in Figure 4
indicate that the polaron content of PTh films dedoped with
NaOH is much higher than that of as-grown and hydrazine-
dedoped PTh films. (All samples have the same weights.) The
ESR g-factors of as-grown, 1.0 M aqueous NaOH solution or
hydrazine-dedoped PTh films were calculated to be 2.0088,
2.0075 (40 µm in NaOH for 24 h), 2.0074 (20 µm in NaOH
for 24 h), 2.0071 (10 µm in NaOH for 24 h), and 2.0063 using
the following equation:
g ) hν/[µBBr]
where h is Planck’s constant, ν is the microwave frequency, µB
is the Bohr magneton, and Br is the resonance magnetic field.
A complex ESR line consists of Gauss and Lorentz components
related to two different groups of paramagnetic centers present
in polymers.11,12 The g-factors of the PTh films described above
are remarkably high (>2.0023, the free electron value) due to
Sandwich Photodetectors Based on Polythiophene Films J. Phys. Chem. C, Vol. 113, No. 17, 2009 7413

a strong spin-orbit coupling,13,14 and the Gauss component is

the principal factor. The g-factors of Lorentz lines are peculiarly
smaller than 2.0023 and less sensitive to doping levels than those
of the Gauss line.10 Upon the dedoping process, the g-factor
decreases gradually. On the basis of the results of ESR, one
can conclude that PTh dedoped by NaOH has a medium doping
level, and 1.0 M aqueous NaOH solution cannot dedope
micrometer thick PTh film extensively as hydrazine does.
Furthermore, the 20 µm PTh film has more polarons compared
with the 10 and 40 µm films. This is possibly due to the fact
that the 40 µm film still contains bipolarons, whereas the
polarons in the 10 µm film have been partially reduced, and its
reduced level is higher than that of the 20 µm film.
The dc conductivity measurements also confirmed the ESR
results described above. The conductivity of the as-grown PTh
films was measured to be about 10 S/cm by the conventional
four-probe technique. After the samples were dedoped with 1.0
M aqueous NaOH solution for 24 h, the conductivities of the
40 and 20 µm PTh films were decreased to around 10-2 S/cm,
whereas that of the 10 µm was about 10-3 S/cm. However, these
values are still much higher than that of the neutral PTh films
reported previously (10-5-10-10 S/cm).15 This is mainly due
to the fact that the PTh films dedoped with NaOH contain a
high content of conductive polarons, as observed from their ESR
spectra (Figure 4). Furthermore, the PTh film electrosynthesized
in the electrolyte of BFEE has a long chain length (about 80
units) with few chain defects.16,17 The high conductivities of
these PTh films are propitious to the charge generation and
transportation of the photodetectors. In comparison, the dc
conductivities of the PTh films dedoped with hydrazine solution
for 24 h were measured to be in the range of 10-7-10-8 S/cm.
This is mainly due to the fact that hydrazine has a much stronger
reduction activity than aqueous NaOH solution and reduces PTh
polarons more efficiently. Furthermore, because of diffusion
limitations, the doping level and conductivity of these three films
increased with their thickness.
3.4. Photovoltaic Tests. Photovoltaic properties were mea-
sured in a quartz cell filled with high-purity N2 for protection.
Figure 5 illustrates the current density-voltage (or field) J-V
Figure 5. J-V characteristics of a Au (30 nm)/PTh (20 µm)/Au (30
curves of the Au (30 nm)/PTh (20 µm)/Au (30 nm) photode- nm) device under dark and illumination conditions: (a) Illumination
tector in the dark and illuminated through the bottom Au from the bottom side using 100 mW/cm2 white light with an AM1.5
electrode with 100 mW/cm2 AM1.5 white light. The bias field filter. (b) The photocurrent density at various bias fields derived from
was defined as positive when the potential of the illuminated (a). (c) The photoresponses of the device illuminated with a 40 mW/
side is higher than that of the opposite side of the film. In Figure cm2 514 nm laser under 0.1 V/µm (black curve) and 0.2 V/µm (gray
curve). The time interval is 60 s.
5a, the J-V curve of the device under dark conditions is
asymmetrical because of the heterogeneity of the film in the
vertical direction formed by electrochemical deposition.18,19 electrons can easily move to the gold electrode; however, under
Under illumination, the current density of the device increased a negative bias field, electrons have to move into the polymer
dramatically even under a small bias field because of the matrix and are partly quenched by PTh polarons. The process
contribution of photocurrent (Jph). As can be seen from Figure of electron transfer shown with a band diagram of the Au/PTh/
5b, under a given positive bias field, the Jph recorded by Au device is given in Figure 6. The HOMO energy level of
illumination through the bottom electrode is higher than that PTh was measured to be -4.9 eV by cyclic voltammetry. The
under a negative bias field. These results can be explained as optical band gap (Eg) of PTh was calculated to be 1.9 eV,
follows. First, for the electrosynthesized conducting polymer according to the onset wavelengths (λonset) of the absorption
films, the polymer chains in contact with the electrolyte (the spectra of PTh (Eg ) 1240/λonset). Thus, the LUMO level was
top side) have more defects and a shorter conjugation length calculated to be around -3 eV. The energy level of the gold
than the chains in contact with the electrode (bottom side), where electrode is -5.1 eV.
more perfectly conjugated chain segments are probably found Upon illumination with a 40 mW/cm2 laser through the
in the inner layers close to the substrate. These could also be bottom electrode of the Au (30 nm)/PTh (20 µm)/Au (30 nm)
found in another conducting polymer electropolymerization photodetector, the device exhibited fast and stable photore-
process.19 Second, excitons are generated at the interface of the sponses, as shown in Figure 5c. The apparent external quantum
gold electrode and the PTh layer under illumination. With the efficiency of the device was calculated to be 23.8 (black curve)
help of an outside bias field, the excitons separated into charge and 34% (gray curve) under 0.1 and 0.2 V/µm, respectively,
carriers: electrons and holes. Under a positive bias field, using the equation: EQE (%) ) (100 × 1240)Jph/[λPi]; where
7414 J. Phys. Chem. C, Vol. 113, No. 17, 2009
Figure 6. Band diagram of the Au/PTh/Au device.
Figure 7. Photoresponse of the 40 µm (a) and 10 µm (b) devices whose
bottom sides were illuminated with a 40 mW/cm2 514 nm laser under
0.1 V/µm. The time interval is 60 s.
λ and Pi are the wavelength (nm) and intensity (mW/cm2) of
incident light, respectively, and Jph is the photocurrent density
(mA/cm2). The diameter of the laser beam is 3 mm. Taking
into account the transmittance of the electrode at 514 nm (25%),
we corrected the actual quantum efficiency of the device to be
95 (black curve) and 136% (gray curve). The high charge
efficiency can be explained by photocurrent multiplication at
the interface of the gold electrode and PTh layer.4
The performance of the photodetector depends strongly on
the conductivity or doping level of its PTh layer. As shown in
Figure 7a, under a 0.1 V/µm bias field, the photoresponse of
the device with a 40 µm PTh layer is much lower than that of
the device with a 20 µm PTh layer (Figure 5c). The apparent
and actual EQEs of the thicker device were measured to be about
8.5 and 34%, respectively, upon illumination with a 40 mW/
cm2 514 nm laser light (Figure 7a). As the thickness of the PTh
layer was reduced to 10 µm, the apparent and actual EQEs of
the device were measured to be only about 1.7 and 6.8%,
Tong et al.
Figure 8. Photocurrent densities of the Au (30 nm)/PTh (20 µm)/Au
(30 nm) devices dedoped with 1.0 M NaOH for 48 h (a) and 80% (by
volume) aqueous hydrazine solution for 24 h (b) under illumination
through the bottom Au electrode with AM1.5 100 mW/cm2 white light
and at various bias fields.
respectively, under the same excitation condition. These results
indicated that the device with a 20 µm film can exhibit the
strongest photoresponse because of its medium conductivity and
doping level.
If the as-grown 20 µm PTh films were dedoped with 1.0 M
aqueous NaOH solution for a longer time (e.g., 48 h) or with
hydrazine solution for 24 h, the resulting devices showed much
weaker photoresponses (Figure 8) than those shown in Figure
5d. This is mainly due to the fact that these films have much
lower conductivities than those of the films dedoped by 1.0 M
NaOH for 24 h, as described above. Interfacial excitions can
be generated only on neutral species of PTh; however, the
neutral PTh is an insulator. Therefore, a device with a highly
doped PTh cannot be photoexcited to generate a large amount
of excitons, whereas the device with a low doped PTh has a
large resistance, which limits charge separation and transporta-
tion. Thus, a PTh film with a medium doping level can provide
the device with a balance between excition generation and
resistance and exhibits a maximum photoresponse. This conclu-
sion was partly supported by a similar result observed in the
solar cells based on polyaniline films.20
4. Conclusions
In summary, PTh films synthesized by direct oxidation of
thiophene in BFEE and dedoped by 1.0 M aqueous NaOH
solution for 24 h contain a high content of polarons and have
much higher conductivities than those of neutral PTh films. The
Au/PTh/Au sandwich photodetectors based on these films with
thicknesses of 10, 20, and 40 µm are flexible and exhibit strong
Sandwich Photodetectors Based on Polythiophene Films
photoresponses. The avalanche multiplication of the photode-
tector with a 20 µm PTh layer under a low bias field of 0.2
V/µm was achieved, and its EQE was measured to be up to
136% upon illumination with 40 mW/cm2 514 nm laser light.
The conductivity or doping level of the PTh layer plays an
important role in controlling the performance of the device. This
work developed a simple route to fabricate flexible photode-
tectors based on conducting polymers without using supporting
substrates. The easy fabrication of the devices into large sizes
or desired shapes provides various potential applications.
Acknowledgment. This work was supported by the National
Natural Science Foundation of China (50533030, 20774056, and
20604013) and 863 project (2006AA03Z105).
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JP811458H