3596 Chem. Mater.

2006, 18, 3596-3598

Layer-by-Layer Assembled TiO2 Nanoparticle/ for their synthesis and characterization. Among them, poly-
PEDOT-PSS Composite Films for Switching of (3,4-ethylenedioxythiophene) doped by poly(4-styrene-
Electric Conductivity in Response to Ultraviolet and sulfonate) (PEDOT-PSS) is one of the most promising
Visible Light conducting polymers and has been intensively studied
Nobuyuki Sakai, Gangavarapu K. Prasad, Yasuo Ebina, because of its good film-forming properties, high conductiv-
Kazunori Takada, and Takayoshi Sasaki* ity, high visible light transmissivity, and excellent stability.11
Nanoscale Materials Center, National Institute for Materials The fields of application have extended to include optoelec-
Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan tronic devices such as light-emitting diodes, solar cells, and
ReceiVed March 23, 2006 thin-film transistors, as well as other devices, including
ReVised Manuscript ReceiVed May 31, 2006 sensors, smart windows, lithium batteries, and capacitors.12
The tuning of electric conductivity is one of the important
The sequential layer-by-layer adsorption of oppositely
keys in the field of organic-based optoelectronics.13 Although
charged polyelectrolytes is one of the most promising ways
the chemical and electrochemical tunings of the electric con-
of fabricating multilayer thin films with precisely controlled
ductivity of PEDOT have been reported by several groups,14
composition, thickness, and architecture on a nanometer
there have been no reports on conductivity tuning by light
scale.1 The components for the multilayer assemblies using
irradiation at different wavelengths. In the present paper, we
this method range from polyelectrolytes to inorganic nano-
show the layer-by-layer assembly of PEDOT-PSS/TiO2
scale materials.2-7 The integration of organic and inorganic
nanoparticle composite films and how their electric conduc-
materials with different functions is also interesting from both
tivity can be tuned by the excitation light of each component.
fundamental and practical points of view. The present paper
The charge of TiO2 is dependent on the pH of the sus-
describes the layer-by-layer assembly of two different
pension because of its amphoteric nature.15 Because TiO2
components, an n-type inorganic semiconductor (TiO2 nano-
nanoparticles are positively charged at pH 1.5, negatively
particles) and a p-type semiconducting polymer (PEDOT-
charged PEDOT-PSS can be employed as a counterpart for
PSS), and how their electric conductivity responds to the
layer-by-layer assembly. The film assembly on a quartz
excitation light of each component.
substrate could be followed by UV-vis absorption spectra.
Since the Honda-Fujishima effect on the photolysis of
Figure 1 shows the UV-vis absorption spectra as a function
water at TiO2 semiconductor electrodes was reported in
of the number of TiO2 nanoparticle/PEDOT-PSS bilayers
1972,8 semiconductor photocatalysts have been extensively
deposited on a quartz glass substrate. The absorption at λ <
investigated. Electronic excitation of TiO2 or related materials
350 nm is characteristic of TiO2 nanoparticles. Its band-gap
produces photoexcited electrons and holes, causing reduction
and oxidation reactions, respectively. These materials have
(9) (a) Fujishima, A.; Rao, T. N.; Tryk, D. A. J. Photochem. Photobiol.,
drawn much attention because of their potential applications, C 2000, 1, 1. (b) Hashimoto, K.; Irie, H.; Fujishima, A. Jpn. J. Appl.
such as environmental cleaning and solar-to-chemical energy Phys. 2005, 44, 8269. (c) Kudo, A.; Kato, H.; Tsuji, I. Chem. Lett.
2004, 33, 1534.
conversion.9 (10) (a) Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G.; Chiang, C. K.;
Since the discovery of polymeric organic conductors in Heeger, A. J. J. Chem. Soc., Chem. Commun. 1977, 578. (b) Chiang,
1977,10 on the other hand, extensive efforts have been made C. K.; Fincher, C. R., Jr.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.;
Louis, E. J.; Gau, S. C.; MacDiarmid, A. G. Phys. ReV. Lett. 1977,
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* To whom correspondence should be addressed. Fax: 81-29-854-9061. (11) (a) Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes, J. H.;
E-mail: [Link]@[Link]. Marks, R. N.; Taliani, C.; Bradley, D. D. C.; Dos Santos, D. A.;
(1) Decher, G. Science 1997, 277, 1232. Brédas, J. L.; Lögdlund, M.; Salaneck, W. R. Nature 1999, 397, 121.
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1999, 15, 6460. (b) Xie, A. F.; Granick, S. J. Am. Chem. Soc. 2001, J. R. AdV. Mater. 2000, 12, 481. (c) Kirchmeyer, S.; Reuter, K. J.
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(3) (a) Caruso, F.; Möhwald, H. J. Am. Chem. Soc. 1999, 121, 6039. (b) (12) (a) Xu, Y.; Peng, J.; Mo, Y.; Hou, Q.; Cao, Y. Appl. Phys. Lett. 2005,
Schneider, T.; Lavrentovich, O. D. Langmuir 2000, 16, 5227. (c) 86, 163502. (b) Ravirajan, P.; Bradley, D. D. C.; Nelson, J.; Haque,
Krasteva, N.; Besnard, I.; Guse, B.; Bauer, R. E.; Müllen, K.; Yasuda, S. A.; Durrant, J. R.; Smit, H. J. P.; Kroon, J. M. Appl. Phys. Lett.
A.; Vossmeyer, T. Nano Lett. 2002, 2, 551. (d) Zhang, J.; Chua, L. 2005, 86, 143101. (c) Sirringhaus, H.; Tessler, N.; Friend, R. H.
S.; Lynn, D. M. Langmuir 2004, 20, 8015. Science 1998, 280, 1741. (d) Jang, J.; Chang, M.; Yoon, H. AdV. Mater.
(4) (a) Fang, M.-M.; Kaschak, D. M.; Sutorik, A. C.; Mallouk, T. E. J. 2005, 17, 1616. (e) DeLongchamp, D. M.; Kastantin, M.; Hammond,
Am. Chem. Soc. 1997, 119, 12184. (b) Tang, Z.; Kotov, N. A.; P. T. Chem. Mater. 2003, 15, 1575. (f) Chang, C.-C.; Her, L.-J.; Hong,
Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413. J.-L. Electrochim. Acta 2005, 50, 4461. (g) Joo, J.; Park, S.-K.; Seo,
(5) (a) Fendler, J. H. Chem. Mater. 1996, 8, 1616. (b) Lvov, Y.; Munge, D.-S.; Lee, S.-J.; Kim, H.-S.; Ryu, K.-S.; Lee, T.-J.; Seo, S.-H.; Lee,
B.; Giraldo, O.; Ichinose, I.; Suib, S. L.; Rusling, J. F. Langmuir 2000, C.-J. AdV. Funct. Mater. 2005, 15, 1465.
16, 8850. (c) Caruso, F.; Lichtenfeld, H.; Giersig, M.; Möhwald, H. (13) Crispin, X.; Marciniak, S.; Osikowicz, W.; Zotti, G.; Denier van der
J. Am. Chem. Soc. 1998, 120, 8523. (d) Crisp, M. T.; Kotov, N. A. Gon, A. W.; Louwet, F.; Fahlman, M.; Groenendaal, L.; de Schryver,
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T.; Muramatsu, M.; Ebina, Y.; Tanaka, T.; Wang, L. Z.; Watanabe, Shashidhar, R. Synth. Met. 2004, 144, 101. (b) Johansson, T.;
M. Chem. Mater. 2003, 15, 807. (c) Wang, L. Z.; Omomo, Y.; Sakai, Pettersson, L. A. A.; Inganäs, O. Synth. Met. 2002, 129, 269. (c)
N.; Fukuda, K.; Nakai, I.; Ebina, Y.; Takada, K.; Watanabe, M.; Sasaki, Morvant, M. C.; Reynolds, J. R. Synth. Met. 1998, 92, 57. (d)
T. Chem. Mater. 2003, 15, 2873. Lapkowski, M.; Pron, A. Synth. Met. 2000, 110, 79.
(7) (a) Ma, R.; Sasaki, T.; Bando, Y. J. Am. Chem. Soc. 2004, 126, 10382. (15) The isoelectric point is 6.2. Ring, T. A. Fundamentals of Ceramic
(b) Tokudome, H.; Miyauchi, M. Chem. Commun. 2004, 958. Powder Processing and Synthesis; Academic Press: San Diego, CA,
(8) Fujishima, A.; Honda, K. Nature 1972, 238, 37. 1996.

10.1021/cm060696g CCC: $33.50 © 2006 American Chemical Society

Published on Web 07/04/2006
Communications Chem. Mater., Vol. 18, No. 16, 2006 3597

Figure 1. UV-vis absorption spectra for multilayer films of (TiO2/PEDOT-

PSS)n on a quartz glass substrate. Inset shows the dependence of the
observed absorbance at 228 nm on the number of deposition cycles.

energy, which seems wider than that of bulk anatase, may

not be attributable to the size-quantization effect of nano-
particles.16 The concentration of embedded TiO2 nanopar-
ticles may be too low to yield the absorption signal in this
wavelength range. In practice, the original colloidal solution
showed the spectrum comparable to that for bulk anatase.
The progressive enhancement in absorbance with an increas- Figure 2. (a) Change in current under UV light irradiation and subsequent
ing number of layer pairs supports the successful multilayer storage in the dark. The current was measured at a constant voltage of 1.0
mV. The light intensity was 6.7 mW cm-2. (b) Reversible change in current
buildup, as shown in the inset of Figure 1. The absorbance upon UV light irradiation and dark storage.
enhancement rate is very similar to our previous results on
the multilayer assembly of TiO2 nanoparticles/PSS films.6c
The optical absorption of PEDOT-PSS lies in the visible light
region but is very weak and invisible in this scale.
We measured the electric conductivity of the films
fabricated on an interdigitated Pt electrode printed on a quartz
glass substrate. The width of the electrode and the gaps
between electrodes are 10 and 5 µm, respectively. Because
the height of the electrode is 120 nm, the layer-by-layer
assembled films may be formed inside the space surrounded
by the quartz glass substrate and two electrodes. A constant Figure 3. Reversible change in current under alternate irradiation of UV
current was flowed under a biased voltage of 1 mV. UV and visible light. The current was measured at a constant voltage of 1.0
light (λ ) 300-400 nm) irradiation for 30 s decreased the mV. The intensities were 6.7 and 130 mW cm-2 for UV and visible light,
respectively.
current to approximately one-tenth of its original value
(Figure 2a). The current gradually reverted to its original to their original conductivity upon exposure to visible light
value when the UV light was switched off, although it took for 60 s, which is much faster than the time taken for
much longer (∼1000 s) than the time taken for the conductivity to increase for those stored in the dark, as shown
conductivity to decrease by UV light irradiation. Because in Figure 2b. Thus the conductivity of the films could be
the action spectrum, which is plotted between the decrease controlled by light irradiation with different wavelengths.
rate of the current and the incident wavelength of mono-
chromatized light, was closely overlapped with the absorption Next, the mechanism of the conductivity change under UV
spectral profile of TiO2 nanoparticles, the excitation of TiO2 and visible light irradiation and in the dark is discussed.
nanoparticle plays an important role in the conductivity Because the previously reported films of TiO2 nanoparticle/
decrease. The alternate procedure of UV light irradiation (30 PSS6c did not show such a conductivity change under UV
s) and subsequent storage in the dark (30 min) showed a and visible light irradiation, the conductivity of the present
quasireversible switching of the conductivity, although the composite films is derived from the carriers of PEDOT,
maximum current gradually decreased (Figure 2b). which are holes, because PEDOT is a p-type semiconductor.
The excitation of a TiO2 nanoparticle by UV light irradiation
We also examined the effect of visible light (λ ) 400-
produces excited holes and electrons, causing oxidation and
700 nm) irradiation on the conductivity change. Alternate
reduction reactions, respectively. The phenomena observed
irradiation of UV (30 s) and visible (60 s) light decreased
suggest that the electrons are injected into the valence band
and increased the current, respectively (Figure 3). The low-
of PEDOT-PSS, which decreases the carrier number of the
conductivity films induced by UV light irradiation returned
PEDOT-PSS and, consequently, lowers the conductivity of
the composite films. On the other hand, the holes may oxidize
(16) (a) Kamat, P. V. Chem. ReV. 1993, 93, 267. (b) Hoffmann, M. R.;
Martin, S. T.; Choi, W.; Bahnemann, D. W. Chem. ReV. 1995, 95, the adsorbed water or PEDOT-PSS. In the dark, the injected
69. electrons are possibly trapped by electron acceptors such as
3598 Chem. Mater., Vol. 18, No. 16, 2006 Communications

change, however, is very small compared to the conductivity

decrease under UV light irradiation; most of the PEDOT-
PSS is not decomposed in this short period of UV light
irradiation. Because a number of stabilized states can exist
in the oxidized PEDOT because of its π-conjugation in a
long range, the PEDOT may be slightly oxidized by the
photogenerated holes of TiO2. Accordingly, the holes
preferentially oxidize water molecules and/or hydrocarbons
adsorbed on the films.
Recently, Hiroi and co-workers reported the tuning of the
Figure 4. FT-IR difference spectra for (TiO2/PEDOT-PSS)10 on a Si wafer
conductivity of PEDOT-PSS films deposited on a Nb-doped
chip (a) under in situ UV light irradiation, and subsequent storage in the strontium titanate perovskite.20 The excitation of SrTiO3 via
dark for (b) 0, (c) 5, (d) 10, and (e) 20 min. The baseline was obtained UV light irradiation or the excitation of PEDOT via visible
with the films before UV light irradiation. The acquisition of spectra a was
started after preirradiation of UV light for 30 s. The values on the vertical
light irradiation enhances the conductivity of PEDOT-PSS
axis are the absolute ones without offsets.19 films. The effect of UV light irradiation on the conductivity
change is contrary to the present work. The energy levels of
oxygen in the air, and the carrier density of the PEDOT- the conduction and the valence band for TiO2 and SrTiO3
PSS increases, which results in the enhancement of conduc- are similar to each other. It is possible that the photoexcited
tivity. Because the band-gap energy of the p-type semicon- electrons and holes are injected into the conduction and
ducting polymer, PEDOT-PSS, is 1.6 eV,17 the PEDOT-PSS valence bands of PEDOT unless the bands of both semi-
can be excited by visible light. The visible light irradiation conductors are bending, because the conduction and valence
excites the electrons in the valence band of PEDOT-PSS into band edges of PEDOT are lower and higher than those of
the conduction band, producing the holes as a carrier. The TiO2 or SrTiO3, respectively (see Supporting Information,
excited electrons may be transferred to electron acceptors, Scheme S1). In the case of SrTiO3/PEDOT-PSS films, it is
e.g., oxygen molecules in the air. considered that the increase in conductivity is derived from
The FT-IR study provides insight into the aforementioned the hole injection from the valence band of SrTiO3 into
mechanism of conductivity change under UV light irradiation PEDOT, which results in the increase in carrier number.
and in the dark. Difference FT-IR spectra of the layer-by- Because SrTiO3 and PEDOT-PSS in this case have dimen-
layer assembled TiO2 nanoparticle/PEDOT-PSS films on a sions in the bulk regime, the excited electrons in the
Si wafer chip were acquired using the data before UV light conduction band of SrTiO3 cannot be injected into PEDOT,
irradiation as a baseline. As shown in Figure 4a, absorption because of the Schottky barrier formed at the interface
peaks at 800-1400 cm-1 were found to decrease under in between SrTiO3 and PEDOT. In contrast, TiO2 nanoparticles
situ UV light irradiation. The IR bands at 1303, 1187, 1085, and PEDOT-PSS in the present case are several nanometers
978, and 834 cm-1 are derived from the PEDOT.18 The IR in size, and thus, the band bending should be small. Although
bands at 1142 and 1034 cm-1 are assigned to SO3- of the both of the photoexcited carriers generated in TiO2 are able
PSS.6b The peak at 1008 cm-1 is attributable to a bending to be injected into PEDOT, the electrons may be preferably
mode of C-H on aromatic rings of the PSS.6b Spectra b-e captured by PEDOT in the present case.
were acquired at 0, 5, 10, and 20 min, respectively, after the In conclusion, we have achieved the photoinduced tuning
UV light was switched off.19 The decreased absorbance of electric conductivity of PEDOT-PSS/TiO2 nanoparticle
gradually increased in the dark and recovered to its original composite films via the layer-by-layer assembly fabrication
state within 20 min. The behavior with this time scale is in of these components in a nanometer scale. We have shown
good accord with that of the conductivity change under UV a new method for the conductivity tuning of PEDOT other
light irradiation and subsequent storage in the dark, as shown than the chemical and electrochemical methods.14 FT-IR
in Figure 2b. It is reported that the electrochemical oxidation spectra of the films suggested that the reduction of PEDOT
of PEDOT enhances the absorbance in the IR region.18 In by photogenerated electrons of TiO2 induces the conductivity
the present case, therefore, the decrease in absorbance under decrease under UV irradiation and the reoxidation of PEDOT
UV light irradiation suggests the reduction of PEDOT by recovers the conductivity in the dark. Visible light irradiation
the electron injection via the excitation of TiO2. The increase promotes the oxidation of PEDOT. These materials should
in absorbance in the dark corresponds to the oxidation of contribute to the development of organic-based optoelec-
reduced PEDOT. tronics.
The slight decrease in the maximum current (Figure 2b)
is probably due to photocatalytic decomposition of PEDOT- Acknowledgment. This work was supported by CREST of
PSS by the photogenerated holes of TiO2 nanoparticles. This Japan Science and Technology Agency (JST).
Supporting Information Available: Experimental details and
(17) Cao, Y.; Yu, G.; Zhang, C.; Menon, R.; Heeger, A. J. Synth. Met.
1997, 87, 171.
possible energy diagram for TiO2 and PEDOT (PDF). This material
(18) Kvarnström, C.; Neugebauer, H.; Blomquist, S.; Ahonen, H. J.; is available free of charge via the Internet at [Link]
Kankare, J.; Ivaska, A.; Sariciftci, N. S. Synth. Met. 1999, 101, 66.
(19) Because the acquisition time for the IR spectra is 80 s, there are CM060696G
differences between the samples for in situ UV irradiation (a) and 0
min after switching off the UV light (b). The data for (b) is given as (20) Yamaura, J.; Muraoka, Y.; Yamauchi, T.; Muramatsu, T.; Hiroi, Z.
an average during the acquisition time. Appl. Phys. Lett. 2003, 83, 2097.