PCCP
Paper
sealed with a hot-melt gasket with 25 mm thickness made of the potentiostat with a Zview software, at open circuit, both in the
ionomer Surlyn 1702 (Dupont). The redox electrolyte was driven dark and under illumination. Spectra were analyzed with a Zview
into the cells through two holes previously drilled in the counter- equivalent circuit modeling software, including the distributed
electrode. The iodine-based type of electrolyte used for rhenium- element DX11 (transmission line model). All the measurements
based dyes consists of 0.7 M LiI, 0.025 M I and 0.2 M TBP in ACN. were performed one day after cell preparation.
2
The cobalt-based type of electrolyte contained instead 1 M LiTFSI,
0
3 4 2 3 4 3
.33 M [Co(bpy) (B(CN) ) ], 0.06 M [Co(bpy) (B(CN) ) ] and 0.2 M
Conflicts of interest
TBP in ACN. Finally, the hole was sealed using Surlyn and a cover
glass (0.1 mm thickness). Solid state devices (SSDs) were
prepared following a similar procedure. An FTO glass plate
with 1.4 ꢁ 2.3 cm was laser etched to create a non-conductive
There are no conflicts to declare.
zone for the separation of the contacts, then it was cleaned Acknowledgements
and UV/O treated before undergoing flame spray pyrolysis. A
3
The use of instrumentation purchased through the Regione
Lombardia – Fondazione Cariplo joint SmartMatLab Project
2013-1766) is gratefully acknowledged.
solution containing 0.6 mL of titanium isopropoxide acetylace-
tonate [Ti(OiPr) (acac) ], 0.4 mL of acetylacetone and 9 mL of
ethanol was then sprayed (gas carrier: O , 0.8 bar) on the glass
plates at 450 1C, creating a non-porous transparent TiO layer.
2
2
(
2
2
The transparent mesoporous layer, in this case made of 30 nm
sized TiO2 particles (Dyesol DSL30NR-D), was printed with a
different mesh on the FTO conducting glass, followed by a no
scattering layer. Sintering was carried out as described above.
The titania films were then dipped into 0.3 mM toluene solution
of the dyes overnight at room temperature, then dried, and
transferred into a glove box. A solution of the hole transporting
material (HTM), Spiro-OMeTAD, was spin coated onto the
adsorbed dye. The final thickness of the whole cell was mea-
sured to be around 2 mm. The counter-electrode, metallic gold,
was deposed via physical vapor deposition, without sealing the
cell before measurements.
Notes and references
1 B. O’Regan and M. Gr ¨a tzel, Nature, 1991, 353, 737.
2 T. M. Brown, F. De Rossi, F. Di Giacomo, G. Mincuzzi, V. Zardetto,
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4 M. Nazeeruddin, F. De Angelis, S. Fantacci, A. Selloni,
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6 S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. E.
Curchod, N. Ashari-Astani, I. Tavernelli, U. Rothlisberger,
Md. K. Nazeeruddin and M. Gratzel, Nat. Chem., 2014, 6,
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7 (a) M. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker,
E. M u¨ ller, P. Liska, N. Vlachopoulos and M. Gr ¨a tzel, J. Am.
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DSSC and SSD characterization. All measurements were
carried out in air directly after the fabrication of the cells. A
black shadow mask with a fixed aperture was used on DSSCs
2
and SSDs, so that the active area was set to be 0.16 cm . The
current–voltage characteristics were recorded by applying an
external potential bias to the cell while recording the generated
photocurrent using a digital source meter (Keithley model
2400) connected to a pc. The light source was a 450 W xenon
lamp (Oriel) equipped with a Schott K113 Tempax sunlight
filter (Pr ¨a zisions Glas & Optik GmbH) to match the emission
spectrum of the lamp with the AM 1.5 G standard. Before each
measurement, the exact light intensity was determined using a
calibrated Si reference diode equipped with an infrared cutoff
filter (Schott KG-3). The incident photon to collected electron
conversion efficiency (IPCE) measurement was plotted as a 10 (a) T. Bessho, E. C. Constable, M. Gr ¨a tzel, A. H. Redondo,
function of wavelength by using light from a 300 W xenon lamp
ILC Technology), which was focused through a Gemini-180
double monochromator (Jobin Yvon) onto the photovoltaic cell
under test. A computer-controlled monochromator equipped
with automatic grating and wavelength selection and operating
C. E. Housecroft, W. Kylberg, M. K. Nazeeruddin, M. Neuburger
and S. Schaffner, Chem. Commun., 2008, 3717–3719; (b) C. L.
Linfoot, P. Richardson, T. E. Hewat, O. Moudam, M. M. Forde,
A. Collins, F. White and N. Robertson, Dalton Trans., 2010, 39,
8945–8956.
(
in the spectral range (300–800 nm) generates a photocurrent 11 (a) W. Wu, X. Xu, H. Yang, J. Hua, X. Zhang, L. Zhang,
action spectrum with a sampling interval of 10 nm and a current
sampling time of 4 s to reduce scattered light from the edge of
the glass electrodes of the dyed TiO2 layer. Electrochemical
Y. Longa and H. Tian, J. Mater. Chem., 2011, 21,
10666–10671; (b) E. A. M. Geary, L. J. Yellowlees, L. A.
Jack, I. D. H. Oswald, S. Parsons, N. Hirata, J. R. Durrant
and N. Robertson, Inorg. Chem., 2005, 44, 242–250.
ꢀ
1
ꢀ6
impedance spectroscopy (10 mV steps in the 10 –10
Hz
range) was carried out only on the transparent layer-only version 12 B. Bozic-Weber, E. C. Constable and C. E. Housecroft,
of the already assembled DSSC cells, using a BioLogic SP-300
Coord. Chem. Rev., 2013, 257, 3089–3106.
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