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Materials Chemistry A
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DOI: 10.1039/c4ta02711f
www.rsc.org/MaterialsA
Introduction
Recently, the methylammonium lead iodide perovskite has
been shown as an excellent absorber, hole and electron transporting material useful for semiconductor and thin lm
photovoltaic applications.1,2 The advantages of hybrid organic
inorganic methylammonium lead halide perovskites are large
absorption coecient, high charge carrier mobility and diusion lengths.310 Using methylammonium lead iodide perovskite as a light harvester, and 2,20 ,7,70 -tetrakis(N,N-di-pmethoxyphenylamine)-9,90 -spirobiuorene (spiro-MeOTAD) as
a hole transporting material, power conversion eciencies
(PCEs) of over 16% were obtained with both mesoporous metal
oxide scaolds and planar heterojunction architectures.1114 The
ease with which these organicinorganic hybrid perovskite
materials can be prepared and processed from solution313
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Table 1
cells
Cell type
Jsc
(mA cm2)
Voc (mV)
FF
h (%)
CH3NH3PbI3
CH3NH3PbI3 + 1 layer PbS QDs
CH3NH3PbI3 + 3 layer PbS QDs
CH3NH3PbI3 + 6 layer PbS QDs
3 layer PbS QDs
8.33
8.6
24.63
11
0.077
665.3
471
343.8
588.8
211
0.55
0.5
0.43
0.47
0.29
3.04
2.06
3.6
2.9
0.004
Fig. 2 (A) Absorption spectra on the TiO2 NP lm of the PbS QDs, lead iodide perovskite and lead iodide perovskite with 3 layers of PbS QDs. (B)
Emission spectra of the PbS QDs, lead iodide perovskite and lead iodide perovskite with 3 layers of PbS QDs.
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Fig. 3 (A) JV measurements of the lead iodide perovskite heterojunction solar cell and the hybrid PbS QD lead iodide perovskite heterojunction
solar cell. (B) The IPCE of the same heterojunction solar cells.
Conclusions
This work reports for the rst time on co-sensitization between
lead iodide perovskite and PbS QDs in a heterojunction solar
cell. As a result of this co-sensitization the photocurrent density
increased, achieving more than 24 mA cm2. The co-sensitization opens the possibility to achieve a high absorption of the
Experimental
Method and device fabrication
Colloidal PbS QDs capped with oleic acid were purchased from
Evident technologies and stored in a nitrogen-lled glove box.
CH3NH3I was synthesized by reacting 30 mL methylamine
(40% in methanol, TCI) and 32.3 mL of hydroiodic acid (57 wt%
in water, Aldrich) in a 250 mL round bottomed ask at 0 C for
2 h with stirring. The precipitate was recovered by putting the
solution on a rotavap and carefully removing the solvents at
50 C. The yellowish raw product of methylammonium iodide
(CH3NH3I) was washed with diethyl ether by stirring the solution for 30 min, a step which was repeated three times, and then
nally recrystallized from a mixed solvent of diethyl ether and
ethanol. Aer ltration, the solid was collected and dried at
60 C in a vacuum oven for 24 h.
Device fabrication thin dense TiO2 layers of 100 nm
thickness were deposited onto a SnO2:F conducting glass
substrate (15 U cm1, Pilkington) by the spray pyrolysis
method.34 The deposition temperature of the TiO2 compact
layer was 450 C. TiO2 nanoparticles lms of 0.5 mm thickness
were spin-coated onto this substrate. The TiO2 layer was
annealed at 500 C for 30 min in air. The substrate was
immersed in 40 mM TiCl4 aqueous solutions for 30 min at 70 C
and washed with distilled water and ethanol, followed by
annealing at 500 C for 30 min in air.
The synthesis of CH3NH3PbI3 on the TiO2 surface was
carried out by dropping a 40 wt% precursor solution of equimolar CH3NH3I and PbI2 in g-butyrolactone onto the TiO2 lm.
Film formation was induced by spin coating (2000 rpm, 30 s)
under glove box conditions. The lm coated on the TiO2 lm
changed color upon drying at room temperature, indicating the
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Photovoltaic characterization
Photovoltaic measurements employed an AM 1.5 solar simulator equipped with a 450 W xenon lamp (model no. 81172,
Oriel). Its power output was adjusted to match AM 1.5 global
sunlight (100 mW cm2) by using a reference Si photodiode
equipped with an IR-cuto lter (KG-3, Schott) in order to
reduce the mismatch between the simulated light and AM 1.5
(in the region of 350750 nm) to less than 2% with measurements veried at two PV calibration laboratories [ISE (Germany), NREL (USA)]. IV curves were obtained by applying an
external bias to the cell and measuring the generated photocurrent with a Keithley model 2400 digital source meter. The
voltage step and the delay time of the photocurrent were 10 mV
and 40 ms, respectively. A similar data acquisition system was
used to determine the monochromatic incident photon-toelectric current conversion eciency. Under full computer
control, light from a 300 W xenon lamp (ILC Technology, U.S.A.)
was focused through a Gemini-180 double monochromator
(Jobin Yvon Ltd, U.K.) onto the photovoltaic cell under test. The
monochromator was incremented through the visible spectrum
to generate the IPCE (l) as dened by IPCE (l) 12 400 (Jsc/l4),
where l is the wavelength, Jsc is the short-circuit photocurrent
density (mA cm2), and 4 is the incident radiative ux (mW
cm2). Photovoltaic performance was measured by using a
metal mask with an aperture area of 0.12 cm2. The measurements were preformed under bias light.
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This journal is The Royal Society of Chemistry 2014
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