1 3
Microsyst Technol
DOI 10.1007/s00542-017-3389-6
TECHNICAL PAPER
ZnO/TiO
2
core–shell photoelectrodes for dye-sensitized solar cells
by screen printing and room temperature ALD
He Sun
1
· Hayato Kurotaki
1
· Kensaku Kanomata
2
· Fumihiko Hirose
2
·
Matthew Schuette White
3
· Tsukasa Yoshida
1
Received: 9 March 2017 / Accepted: 24 March 2017
© Springer-Verlag Berlin Heidelberg 2017
TiO
2
is amorphous and can only be converted to crystal-
line anatase TiO
2
by annealing at 450 °C. The crystalliza-
tion recovered current but lost the advantage of the voltage
increase. EIS has indicated a high trap density introduced
by the amorphous ALD TiO
2
, which could be reduced by
crystallization, but accompanied with an increased rate of
recombination.
1 Introduction
Dye-sensitized solar cells (DSSCs) employing zinc oxide
(ZnO) as the photoelectrode material could offer poten-
tial advantages to the traditionally used titanium dioxide
(TiO
2
), in that high temperature sintering process might be
avoided to permit use of flexible plastic substrates. Strongly
adhering porous ZnO layers can be fabricated by low tem-
perature methods such as electrodeposition (Goux et al.
2006) and screen printing of nano-particles with subse-
quent warm water treatment (Yane and Yoshida 2012). This
is a welcome feature not only for cost and weight reduction
of the device, but also for versatility in its use, especially
as indoor energy harvesting devices to substitute batteries
which are seen as one of the most promising applications
of organic solar cells (Lungenschmieda et al. 2007).
While high efficiencies above 10% have been reported
with TiO
2
, efficiency of DSSCs with ZnO remained low,
up to about 6% (Saito and Fujihara 2008). One of the
reasons is the lack of a broad absorbing dye matched to
ZnO. Broadly absorbing Ru(II) polypyridine dyes are well
suited to TiO
2
and achieve a short circuit current (J
SC
) over
20 mA cm
-2
for the best examples (Chen et al. 2009).
On the other hand, that of ZnO sensitized with a narrow
absorbing organic dye is somewhere around 13 mA cm
-2
,
despite the high incident photon to current efficiency
Abstract Mesoporous photoelectrodes for dye-sensitized
solar cells (DSSCs) in a ZnO/TiO
2
core–shell structure
have been fabricated at low temperature by combination of
screen printing of ZnO nanoparticles and room tempera-
ture atomic layer deposition (ALD) of TiO
2
. ALD nicely
achieved a uniform coating of the individual ZnO particles
with a thin skin of TiO
2
of uniform thickness. The overall
mesoporous structure was unchanged, so that a high sur-
face area for dye adsorption and pores for penetration of
the electrolyte solution were preserved. DSSCs employ-
ing the core–shell electrode sensitized with D149 indoline
dye achieved a higher open circuit voltage (V
OC
) than that
with ZnO, but accompanied with a decrease of short circuit
photocurrent density (J
SC
) due to decreased efficiency of
electron injection. Increase of the recombination resistance
to extend the electron lifetime by the TiO
2
shell has been
confirmed by electrochemical impedance spectroscopy
(EIS). X-ray diffraction analysis has revealed that the ALD
Electronic supplementary material The online version of this
article (doi:10.1007/s00542-017-3389-6) contains supplementary
material, which is available to authorized users.
* Tsukasa Yoshida
yoshidat@yz.yamagata-u.ac.jp
He Sun
sunhepeter@hotmail.com
1
Department of Chemistry and Chemical Engineering,
Faculty of Engineering, Yamagata University, Jonan 4-3-16,
Yonezawa, Yamagata 992-8510, Japan
2
Department of Electrical Engineering, Faculty
of Engineering, Yamagata University, Jonan 4-3-16,
Yonezawa, Yamagata 992-8510, Japan
3
Department of Physics, Materials Science Program,
University of Vermont, Burlington, VT 05405, USA