Synthetic Metals 143 (2004) 283287

Construction of a photovoltaic device by deposition of thin lms

of the conducting polymer polythiocyanogen
V.P.S. Perera
a
, P.V.V. Jayaweera
a
, P.K.D.D.P. Pitigala
a
, P.K.M. Bandaranayake
a
,
G. Hastings
b
, A.G.U. Perera
b
, K. Tennakone
a,
a
Institute of Fundamental Studies, Hantana Road, Kandy, Sri Lanka
b
Department of Physics and Astronomy, Georgia State University, Atlanta, GA 30303, USA
Received 9 June 2003; received in revised form 18 December 2003; accepted 18 December 2003
Abstract
A method is developed for electro-deposition of thin lms of the conducting polymer polythiocyanogen on conducting tin oxide glass
or other conducting substrate by anodic discharge of SCN

ions form a solution KSCN in propylene carbonate. Films are found to be

highly stable and resistant to heat and chemical action. SEM pictures indicate that the lms are uniform and free of pin hole. Band gap and
band positions are determined from optical absorption spectra and MottSchottky plots, respectively. A photovoltaic cell is constructed by
depositing polythiocyanogen on nanocrystalline lms of n-TiO
2
followed by p-CuI to form a heterojunction. Photocurrent action spectra
shows that light absorption by polythiocyanogen generates the photovoltaic response. Results suggest that polythiocyanogen could nd
applications in optoelectronic devices.
2004 Elsevier B.V. All rights reserved.
Keywords: Polythiocyanogen; Conducting polymer; Photovoltaic cell
1. Introduction
Conducting polymers are extensively studied as potential
materials for application in optoelectronic devices [111].
Their low cost and easy control of properties leave more
exibility in fabrication procedures compared to the conven-
tional single crystal or polycrystalline inorganic semicon-
ductors. An area where the conducting polymers could make
signicant practical impact is photovoltaics [18]. Here the
low temperature deposition techniques without the involve-
ment of vacuum technology become a great advantage.
Many attempts have been made to construct photovoltaic
cells with conducting polymers as the light harvesting ma-
terial, which generate the carriers. Basically these systems
have a heterojunction conguration with a thin lm of the
polymer interposed between two electrodes of which at least
one needs to be optically transparent. Polythiophene, poly-
acetylene, polyphenylene vinylene derivatives, polyaniline
and many other conducting polymers with complex organic
molecules as the monomer have been tested for photovoltaic
effects in sandwich conguration or blended with other
materials to form composite lms. A simple molecule that

Corresponding author. Tel.: +94-8-232002; fax: +94-8-232131.

E-mail address: tenna@ifs.ac.lk (K. Tennakone).
readily undergoes polymerization is thiocyanogen (SCN)
2
.
Cataldo [1214] have conducted extensive investigations
to elucidate the structure of polythiocyanogen. Polythio-
cyanogen of general composition [S
y
(CN)
2
]
x
was shown to
be constituted of long polyazomethine chains analogous to
that of polycyanogen or paracyanogen [15] but crosslinked
with sulfur bridges of different length depending on the
sulfur chain length in the original monomer. Although the
electronic conductivity [16] and photosensitivity [17,18] of
polythiocyanogen ([SCN]
n
) was noted earlier, there are no
records describing the use of this material in an optoelec-
tronic device. We have developed methods for deposition of
polythiocyanogen on conducting glass or other conducting
substrate and also fabricated a photovoltaic cell by coat-
ing polythiocyanogen on a nanocrystalline lm of TiO
2
.
This paper describes preparation of thin lms of poly-
thiocyanogen, their characterization and construction of a
photovoltaic cell.
2. Experimental
Conducting tin oxide (CTO) glass plates (0.25 cm2 cm,
sheet resistance 15 /sq) are cleaned by warming in a solu-
tion of KOH in propan-2-ol, rinsed with water followed by
0379-6779/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2003.12.018
284 V.P.S. Perera et al. / Synthetic Metals 143 (2004) 283287
propan-2-ol and dried avoiding contamination with grease.
Polythiocyanogen was deposited on CTO surfaces as fol-
lows: KSCN dried at 105

C for several hours is dissolved

in moisture free propylene carbonate (0.15 M solution). The
solution was heated to 90

C and electrolyzed under gal-

vanostatic conditions (2 mAcm
2
) with the CTO glass plate
as the anode and a platinum foil as the counter electrode.
Discharged SCN

ions undergo polymerization at the CTO

surface depositing a orangeyellow lm on the CTO surface.
If the solution is not warmed polymerization becomes slow
and polymeric particles of (SCN)
2
formed near the anode
tend to break away from the electrode surface and leach into
the solution. Polythiocyanogen in the powder form was pre-
pared by rapid electrolysis of a solution of KSCN in propy-
lene carbonate. Ultrasonic agitation of the solution prevented
adherence of polythiocyanogen to the anode. A compressed
pellet of the powder was used to measure the density as well
as the conductivity. Thickness of the lm is deduced from
the charge that has passed through the electrolyte. To mea-
sure the resistivity of the lm, the thiocyanogen coated plate
and platinum foil are immersed in a sodium sulfate solution
(0.1 M) and resistance is measured using an impedance me-
ter (Hewlett Packard 4276A LCZ Meter). The resistivity of
the lm is calculated by comparing with the resistance of a
cell of same geometry when the thiocyanogen coated plate
is replaced with a CTO glass plate. The same set up is used
measure the capacitance (C) and plot the MottSchottky di-
agram (i.e. the plot of 1/C
2
versus applied voltage V). The
photoresponse of the lms were examined in a three elec-
trode conguration under potentiostatic conditions in a elec-
trolytic medium (0.1 M Na
2
SO
4
).
Nanocrystalline lms of TiO
2
were prepared as described
[19]. Briey, the procedure involves spreading of a col-
loidal solution of titanium dioxide (prepared by hydrolysis
of titanium isopropoxide) on CTO glass plates heated to
150

C and sintered at 450

C for 30 min. After cooling,

the loose crust on the surface is wiped off with cotton wool
and the process is repeated until a lm thickness reaches
10 m. Surface area of the lm was estimated by deposi-
tion of a dye of known surface coverage, extraction of the
dye and spectrophotometric estimation. Polythiocyanogen
was coated to the nanocrystalline TiO
2
surface by the same
method as for CTO plates. Polythiocyanogen lms coated
on CTO and nanocrystalline TiO
2
surfaces and for com-
parison the bare CTO and TiO
2
surfaces were examined
by SEM. FT-IR spectrum of lms deposited on the above
substrates could not be obtained due to strong IR absorp-
tion by the CTO surface. However, to conrm that the
material deposited is polythiocyanogen, the FT-IR spec-
trum was obtained by scraping off the lm from the CTO
surface. The photovoltaic cell was formed by deposition of
a layer of p-CuI over the polythiocyanogen deposited on
TiO
2
. CuI was deposited by drop coating from a solution
of CuI in acetonitrile (6.3 10
3
M). A gold plated CTO
glass plate pressed onto the CuI surface served as the back
contact (construction of the cell is shown in Fig. 1). IV
Fig. 1. Construction of the photovoltaic cell.
characteristics of the cell at 1000 Wm
2
, 1.5 AM illumina-
tion were ascertained using a source meter (Keithley 2420).
3. Results and discussion
Fig. 2 shows the FT-IR spectrum of a sample of poly-
mer scraped from the CTO surface. The spectrum has the
same general characteristics of polythiocyanogen prepared
by other methods [13]. Films deposited on CTO glass (or on
TiO
2
) were found to be highly stable and rmly adhered to
the substrate. They are resistant to concentrated nitric and
sulfuric acids but attacked by strong alkalis. The lm softens
and peels off when immersed in a strong solution of sodium
sulde. On heating no sign of chemical decomposition or
lm breakdown was detected up to 300

C. An 100 nm
thick lm deposited on TiO
2
substrate has a conductivity
9 10
8
Scm
1
. Compressed pellets had a higher conduc-
tivity of 4 10
6
Scm
1
. Presumably rapid electrolysis in-
troduces some dopant. In photoresponse measurements of
Fig. 2. FT-IR spectrum of the polythiocyanogen scraped off from a lm
deposited on conducting tin oxide glass (T = transmittance).
V.P.S. Perera et al. / Synthetic Metals 143 (2004) 283287 285
Fig. 3. MottSchottky plot for a lm of polythiocyanogen deposited on
conducting glass. Measurement frequency: (a) 1.5 kHz; (b) 1 kHz.
the lms an anodic signal was observed, suggesting n-type
behavior. Iodine doping increases the conductivity and the
sign of the photocurrent indicating p-type behavior. Exper-
iments with compressed pellets of polythiocyanogen have
also demonstrated an increase in conductivity of polythio-
cyanogen on doping with iodine and bromine [13]. Fig. 3
shows MottSchottky plots at 1.5 and 1 kHz for a lm of
polythiocyanogen deposited onto conducting glass. From
Fig. 3 the conduction band edge is positioned at 0.46 Vver-
sus standard calomel electrode (SCE). The positive slope of
the plots conrms n-type conductivity. Fig. 4 shows the opti-
cal absorption spectrum of the polythiocyanogen lm. From
Fig. 4 the band edge is found at 550 nm, corresponding to a
band gap of 2.25 eV. Fig. 5 compares the SEM pictures of
polythiocyanogen deposited onto a CTO surface and a bare
CTO surface. Structures other than the granulites in the CTO
surface are absent in the former indicating that the polymer
Fig. 5. SEM picture of (a) polythiocyanogen deposited on conducting tin oxide glass surface and (b) bare conducting tin oxide glass surface.
Fig. 4. Absorption spectrum of a lm of polythiocyanogen and photocur-
rent action spectrum of the cell n-TiO
2
/[SCN]
n
/p-CuI.
deposits as an uniform interconnected matrix free of pin
holes and large irregularities in thickness. Fig. 6 compares
SEM images of TiO
2
coated onto CTO glass with SEM im-
ages of polythiocyanogen deposited onto TiO
2
coated CTO
glass. It is obvious from Fig. 6 that the polymer lm fully
covers the rough surface of the nanocrystalline TiO
2
surface.
Comparison of the photocurrent action spectrum (plot
of IPCE = incident photon to photocurrent conversion
efciency versus wavelength) and the optical absorption
of the lm shows that the photocurrent originates from
the light absorbed by the lm. Fig. 7 shows the IV char-
acteristics of the photovoltaic cell n-TiO
2
/[SCN]
n
/p-CuI
at 1000 Wm
2
, 1.5 AM illumination. The short-circuit
photocurrent, open-circuit voltage and efciency being
2 mAcm
2
, 325 mV and 0.3%, respectively. Fig. 8 shows
a schematic diagram illustrating the positions of the con-
duction and valence bands of TiO
2
, [SCN]
n
and CuI. The
mechanism of the photovoltaic effect can be explained as
follows: photons absorbed by [SCN]
n
generate excitons
286 V.P.S. Perera et al. / Synthetic Metals 143 (2004) 283287
Fig. 6. SEM picture of (a) polythiocyanogen deposited on a nanocrystalline lm of TiO
2
and (b) bare nanocrystalline TiO
2
lm.
Fig. 7. IV characteristics of the cell n-TiO
2
/[SCN]
n
/p-CuI measured at
1000 Wm
2
, 1.5 AM illumination.
Fig. 8. Schematic energy level diagram showing band positions of TiO
2
,
[SCN]
n
and CuI.
which decomposes to electrons and holes at the interfaces
[SCN]
n
/TiO
2
and [SCN]
n
/CuI as the diffusion length of ex-
citons in a polymer is expected to be of the order of 10 nm,
it is unlikely that diffusion of excitons generated in the bulk
of the 100 nm lm of [SCN]
n
contribute signicantly to
the photocurrent. However, when the excitons are decom-
posed at the TiO
2
/[SCN]
n
, the position of the conduction
band of TiO
2
allows electron injection to n-TiO
2
. The hole
remaining in [SCN]
n
could diffuse to the [SCN]
n
/TiO
2
interface and pass onto CuI. Similarly, when excitons are
decomposed at the [SCN]
n
/CuI interface a hole is injected
to p-CuI and the electron remaining in [SCN]
n
diffuses
to the [SCN]
n
/TiO
2
interfaces and passes onto TiO
2
. The
rates of the above processes depend on the mobilities of
electrons and holes in [SCN]
n
. We have not succeeded in
measuring the mobilities of electrons and holes in [SCN]
n
.
The dark IV curve for the cell in the forward and re-
verse bias is presented in Fig. 9, rectication characteristics
needed for functioning as a photovoltaic device is evident.
On prolonged illumination, both short-circuit photocur-
rent and open-circuit voltage undergo a slow decay as is
found in other photovoltaic devices based on CuI [20]. On
Fig. 9. Dark rectication curve for the cell n-TiO
2
/[SCN]
n
/p-CuI.
V.P.S. Perera et al. / Synthetic Metals 143 (2004) 283287 287
replenishing the CuI overlayer (i.e. dissolution of original
layer in acetonitrile and deposition of new CuI layer), the
same photovoltaic response reappears indicating that there
is no hysteresis in the polymer lm. Decay of photocurrent
and open-circuit voltage, originate almost entirely from the
deterioration of CuI.
4. Conclusion
We have devised a method for deposition of thin lms
of the conducting polymer [SCN]
n
on conducting tin ox-
ide glass or other conducting substrate. Films are found be
highly resistant to chemical action and temperature. Again
the lms deposited by this method are uniform and largely
free of irregularities or pin holes. Films of [SCN]
n
were
also deposited on nanocrystalline TiO
2
lms and the hetero-
junction n-TiO
2
/[SCN]
n
/p-CuI demonstrated good photo-
voltaic response. We believe that further characterization and
other studies on thin lms of [SCN]
n
could lead to practical
applications.
References
[1] L.A.A. Pettersson, L.S. Roman, O. Inganas, J. Appl. Phys. 86 (1999)
487.
[2] T. Yohannes, T. Solomon, O. Inganas, Synth. Met. 82 (1996) 215.
[3] R. Valaski, A.F. Bozza, L. Micaroni, I.A. Hummlelgen, J. Solid State
Electrochem. 4 (2000) 390.
[4] C.M. Ramsdale, J.A. Barker, A.C. Arias, J.D. MacKenzie, R.H.
Friend, N.C. Greenham, J. Appl. Phys. 92 (2002) 4266.
[5] M.P.T. Christiaans, M.M. Weink, P.A. van Hal, J.M. Kroon, R.A.J.
Janssen, Synth. Met. 101 (1999) 265.
[6] N.A. Anderson, E. Hao, X. Ai, G. Hastings, T. Lian, Chem. Phys.
Lett. 347 (2001) 304.
[7] G. Yu, J. Gao, J.C. Hummelen, F. Wudl, A.J. Heeger, Science 270
(1995) 1789.
[8] C.O. Too, G.G. Wallace, A.K. Burrell, G.E. Collis, D.L. Ofcer,
E.W. Boge, S.G. Brodie, E.J. Evans, Synth. Met. 123 (2001)
53.
[9] G. Wang, X. Hu, T.K.S. Wong, J. Solid State Electrochem. 5 (2001)
150.
[10] R.F. Service, Science 279 (1998) 1135.
[11] S. Chao, M.S. Wrighton, J. Am. Chem. Soc. 109 (1987) 2197.
[12] F. Cataldo, J. Inorg. Organomet. Polym. 7 (1997) 35.
[13] F. Cataldo, Polyhedron 19 (2000) 681.
[14] F. Cataldo, Polyhedron 21 (2002) 1825.
[15] F. Cataldo, Eur. Polym. J. 35 (1999) 571.
[16] F. Cataldo, P. Fiordiponti, Polyhedron 12 (1993) 279.
[17] M. Bragadin, G. Capodaglio, P. Cescon, G. Scarponi, F. Pucciarelli,
J. Electroanal. Chem. 122 (1981) 393.
[18] M. Bragadin, G. Scarponi, G. Capodaglio, F. Ossola, V. Bartocci, F.
Pucciarelli, Mol. Liq. Cryst. 121 (1985) 345.
[19] K. Tennakone, G.R.R.A. Kumara, A.R. Kumarasinghe, K.G.U. Wi-
jayantha, P.M. Sirimanne, Semicond. Sci. Technol. 10 (1995) 1689.
[20] G.R.A. Kumara, A. Konno, K. Shiratsuchi, J. Tsukahara, K. Ten-
nakone, Chem. Mater. 14 (2002) 954.