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705

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Study on the stability of CH3NH3PbI3 lms and the

eect of post-modication by aluminum oxide in
all-solid-state hybrid solar cells
Guangda Niu, Wenzhe Li, Fanqi Meng, Liduo Wang,* Haopeng Dong and Yong Qiu
Degradation of perovskite has been a big problem in all-solid-state perovskite solar cells, although many
researchers mainly focus on the high eciency of these solar cells. This paper studies the stability of
CH3NH3PbI3 lms and nds that CH3NH3PbI3 is sensitive to moisture. The degradation reaction is
proposed according to UV-Vis spectra and XRD results. In order to improve the degradation of
CH3NH3PbI3, we introduce aluminum oxide as a post-modication material into all-solid-state
perovskite solar cells for the rst time. UV-Vis spectra show that Al2O3 modication could maintain the

Received 9th September 2013

Accepted 4th November 2013

absorption of CH3NH3PbI3 after degradation. XRD results reveal that Al2O3 could protect perovskite from
degradation. Moreover, the device post-modied by Al2O3 has shown more brilliant stability than that
without modication when exposed to moisture. EIS results and dark current illustrate that the

DOI: 10.1039/c3ta13606j

modication increased interface resistance in the dark, indicating the restrained electron recombination

www.rsc.org/MaterialsA

process.

Introduction

Inorganicorganic perovskite compounds (CH3NH3PbX3, X I,

Br and Cl) have attracted attention as light-harvesting materials
for solar cells.15 These compounds are advantageous for solar
cells because of their wide light-absorption and high extinction
coecients.69 Moreover, solar cells based on these compounds
could achieve high eciency and low-cost.2,10
Nowadays, there are two kinds of solar cells based on inorganicorganic perovskite compounds: liquid state solar cells
and all-solid-state solar cells. Liquid state solar cells based on
perovskite compounds were rst reported by Kojima and coworkers.11 They used CH3NH3PbI3 perovskite as a sensitizer and
iodine redox as an electrolyte in photovoltaic cells, and achieved
a power conversion eciency (PCE) of 3.81%. Then Nam-Gyu
Park fabricated CH3NH3PbI3 perovskite sensitized solar cells
with the nal PCE of 6.54% by optimizing the CH3NH3PbI3
solution concentration.12 However, due to rapid dissolution in
the I/I3 electrolyte, the stability of these cells was so poor that
perovskites can hardly be applied to the most ecient liquidcell-structure.13 In our former work, Al2O3 was used to protect
the perovskite sensitizer from corrosion by an electrolyte and
the eciency was increased from 3.56% to 6.12%.14 On the
other hand, the inorganicorganic hybrid lead halide perovskite

Key Lab of Organic Optoelectronics and Molecular Engineering of Ministry of

Education, Department of Chemistry, Tsinghua University, Beijing, P.R.China.
E-mail: chldwang@mail.tsinghua.edu.cn
Electronic supplementary information (ESI) available: Cross-sectional SEM
images and HRTEM images of perovskites. See DOI: 10.1039/c3ta13606j

This journal is The Royal Society of Chemistry 2014

compounds have been used in solid-state DSCs achieving high

performance and good stability.1,3,10,1517 All solid state perovskite solar cells with spiro-MeOTAD can be divided into two
categories. One is the pin junction solar cells which is
reported by Henry Snaith and his co-workers.6 They employed
Al2O3 as a scaold to support perovskites and spiro-MeOTAD,
perovskites and thin TiO2 formed the pin junction. Another
all solid state perovskite solar cells is sensitized solar cells
which is the same mechanism with dye sensitized solar cells.
All-solid-state perovskite CH3NH3PbI3 sensitized solar cells with
spiro-MeOTAD as hole transport materials have achieved a PCE
of up to 9.7%.3 Hui-Seon Kim used the TiO2 nanorod as a
photoanode and achieved a PCE of 9.4%.15 Jun Hong Noh
demonstrated highly ecient solar cells exhibiting 12.3% in
PCE
as
a
result
of
tunable
composition
for
CH3NH3Pb(I1xBrx)3.10 Recently, Gr
atzel and co-workers
described a sequential deposition method for the controlled
formation of CH3NH3PbI3 and achieved the highest PCE of
15.0% in perovskite-sensitized solar cells.18
Based on the present research in perovskite solar cells,
researchers mainly focus on the high performance by utilizing
dierent structures of photoanodes, fabrication methods and
dierent ratios of sensitizers and dierent kinds of hole
transport materials. However, the degradation of CH3NH3PbI3
and the sensitized lm is oen ignored, which hampers the
prospects for practical applications.
The perovskite CH3NH3PbI3 lms are extremely sensitive to
moisture in air. Gr
atzel and co-workers found that the device
fabrication should be carried out under controlled atmospheric
conditions and with a humidity of <1%.18 In our experiments,

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Journal of Materials Chemistry A

we also found a similar phenomenon that perovskite lms tend

to degrade in a high humidity environment. Hence, the stability
of perovskite under moisture urgently needs to be studied. This
paper systematically studies the corrosion of perovskite by
moisture and the mechanisms of corrosion are also revealed. In
order to improve the stability of CH3NH3PbI3 and the sensitized
lm, we introduce aluminum oxide as a post-modication
material to separate perovskites from moisture.
In this work, we employ Al2O3 as a post-modication material in CH3NH3PbI3 sensitized solar cells containing spiroMeOTAD as hole transport materials (HTMs). There are two
roles for Al2O3 in these cells. One is that Al2O3 protects
CH3NH3PbI3 and the sensitized lms from degradation by
moisture and sunlight. Another is that Al2O3 serves as an
insulation barrier between TiO2 and HTM to retard the electron
recombination process. Finally, the photo-conversion eciency
of the devices with post-modication by Al2O3 has shown more
stable performance in moisture. This article systematically
discussed the post-modication eect in all-solid-state DSCs for
the rst time and opens up a new pathway to improve the
performance of all-solid-state solar cells.

Paper

acetonitrile (170 mg mL1) and 17.5 mL 4-tert-butylpyridine

(TBP, 96%, Aldrich) in the solvent of 1 mL chlorobenzene
(99.8%, Aldrich). The CH3NH3PbI3-sensitized TiO2 lms were
coated with HTM solution using the spin-coating method at
3000 rpm for 30 s. For the counter electrode, a 50 nm thick Au
was deposited on the top of the HTM over layer by a thermal
evaporation. The active area was xed at 0.09 cm2.

2.3

Characterization

The UV-Vis absorption spectra were used for testing the

absorption of perovskite sensitized TiO2 lms with a Hitachi U3010 spectroscope. X-ray diraction (XRD) patterns were

obtained with a Smart LAB instrument Cu Ka beam (l 1.54 A).

X-ray photoelectron spectroscopy (XPS) was performed with a
PHI 5300ESCA instrument. Photocurrentvoltage ( JV), and
Electrochemical Impedance Spectra (EIS, ranged from 0.1 Hz to
105 Hz) were measured by using a ZAHNER CIMPS electrochemical workstation, Germany.

3 Results and discussion

2 Experimental section
2.1

Materials synthesis

CH3NH3I was synthesized and puried based on the method

proposed by Im J. H. To prepare perovskite CH3NH3PbI3, the
synthesized CH3NH3I (0.395 g) and PbI2 (1.157 g, Aldrich) were
mixed in g-butyrolactone (2 mL, TCI) at 60  C for 12 h with
stirring. The nanocrystalline TiO2 colloid was synthesized by a
hydrothermal method which has been well documented in a
previous report.19
2.2

Solar cell fabrication

The compact TiO2 layer precursor was prepared as follows:20

titanium(IV) isopropoxide (Ti[OCH(CH3)2]4, 1 mL) was mixed
with 2-methoxyethanol (CH3OCH2CH2OH, 5 mL) and ethanolamine (H2NCH2CH2OH, Aldrich, 99+%, 0.5 mL) and heated to
80  C for 2 h under magnetic stirring. Then the cleaned FTO
glasses were coated with the precursor by the spin-coating
method at 3000 rpm for 30 s in air. Then the substrate was
heated to 80  C for 10 min and 500  C for 30 min. Mesoporous
TiO2 lms with a thickness of 717 nm (determined by SEM
shown in Fig. S1) were deposited on the substrate by a spincoating TiO2 paste at 3000 rpm for 30 s, which was followed by
heating at 500  C for 1 h. The perovskite coating solution was
spread on the annealed TiO2 lm and spun at 2000 rpm for 60 s
followed by 3000 rpm for 60 s in air. Then the lms were heated
at 100  C for 10 min. The room temperature lms were
immersed into 30 mM triethylaluminum (Alfa, Al(C2H5)3 25%
w/w in hexane) hexane solution for 30 seconds which was conducted in a glove box.
The composition of the hole transport material (HTM) was
180 mg 2,29,7,79-tetrakis-(N,N-di-p-methoxyphenyl-amine)9,99-spirobiuorene (spiro-MeOTAD), 37.5 mL bis(triuoromethane)sulfonimide lithium salt (LiTFSI, 99.95%, Aldrich)/

706 | J. Mater. Chem. A, 2014, 2, 705710

3.1 Degradation of perovskites and the protecting eect of

Al2O3
Al2O3 is obtained by dip-coating into triethylaluminum in
hexane (see ESI for details). As shown in Fig. 1, aer dipcoating, a new peak located at 532.3 eV appeared in the O 1s
spectrum. O 1s in Al(OH)3 shows a binding energy of 531.68
eV.21 Then the new peak is the same with O 1s in Al2O3 rather
than Al(OH)3.22 This could verify that the dip-coating method
leads to the formation of an Al2O3 layer.
For degradation studies, sensitized lms were exposed to air
with a humidity of 60% at 35  C under sunlight for 18 h. Fig. 2(a)
shows UV-Vis spectra of the TiO2/CH3NH3PbI3 lm before and
aer degradation. Before degradation, the main absorption is
due to CH3NH3PbI3. However, aer degradation, the absorption
of the lm between 530 nm and 800 nm decreased sharply. The
residual absorption less than 520 nm is assigned to PbI2 (band
gap is 2.6 eV). This phenomenon veries that CH3NH3PbI3 is

XPS spectrum of the lms before and after post-modication by

Al2O3: (a) O 1s; (b) Al 2p.

Fig. 1

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In contrast, for the lm of TiO2/CH3NH3PbI3/Al2O3

(Fig. 3(b)), the peaks of CH3NH3PbI3 remain unchanged aer
degradation and no new peaks appears. This could be explained
by the fact that the Al2O3 layer could separate CH3NH3PbI3 from
moisture and the degradation is suppressed.
Considering UV-Vis spectra, XRD analysis and the circumstance of air and sunlight, the degradation process could be
explained as follows:
UV-Vis spectra of sensitized lms. (a) Film of TiO2/CH3NH3PbI3
before and after degradation. (b) Film of TiO2/CH3NH3PbI3/Al2O3
before and after degradation. The degradation time is 18 h.
Fig. 2

H2 O

CH3 NH3 PbI3 s )

* CH3 NH3 Iaq PbI2 s

CH3NH3I(aq) # CH3NH2(aq) + HI(aq)

very sensitive to moisture and the moisture could corrode
CH3NH3PbI3 into PbI2.
For the lm aer post-modied by Al2O3, the main absorption of CH3NH3PbI3 is maintained aer degradation. The
reason is that CH3NH3PbI3 is well protected and the absorption
of the lm decreases less than that without modication. The
Al2O3 layer separates CH3NH3PbI3 from air and prevents
degradation of the lm.
Then X-ray diraction (XRD) characterization (Fig. 3) is used
to study the degradation process and Al2O3 protecting eect.
XRD spectra of TiO2/CH3NH3PbI3 and TiO2/CH3NH3PbI3/Al2O3
before degradation are the same. The same XRD patterns before
and aer modication indicate the same crystalline structure
assignable to the perovskite system. The peaks at 31.86, 40.45
and 43.14 are attributed to the (310), (224) and (314) planes of
and c
the tetragonal perovskite structure with a 8.872 A
which is consistent with the previous reports.16 The
12.637 A,
other peaks are assigned to FTO. Post-modication by Al2O3
does not inuence the diraction peaks obviously.
XRD spectra of the TiO2/CH3NH3PbI3 lm before and aer
degradation are shown in Fig. 3(a). Aer degradation, the
original peaks of CH3NH3PbI3 all disappeared, indicating that
CH3NH3PbI3 has degraded into other chemicals. Moreover, new
peaks located at 34.3, 39.5 and 52.4 appeared, which can be
assigned to (102), (110) and (004) planes of hexagonal 2H polytype PbI2 (PDF#07-0235). Another new peak at 38.7 is assigned
to the (201) plane of orthorhombic I2 (PDF#05-0558). This could
be explained that when exposed to air, CH3NH3PbI3 will be
corroded by moisture and the nal products of the degradation
process contain PbI2 and I2.

XRD patterns of sensitized lms. (a) Film of TiO2/CH3NH3PbI3

before and after degradation. (b) Film of TiO2/CH3NH3PbI3/Al2O3
before and after degradation. The degradation time is 18 h.
Fig. 3

This journal is The Royal Society of Chemistry 2014

4HI(aq) + O2 # 2I2(s) + 2H2O

hn

2HIaq ) * H2 [ I2 s

(1)
(2)
(3-1)
(3-2)

In reaction (1), CH3NH3PbI3 will decompose into CH3NH3I

solution and PbI2 in the presence of H2O. In this process, the
equilibrium constant can be expressed as k(1) c(CH3NH3I)
and the Gibbs free energy is DG(1) RT ln k(1).
In reaction (2), CH3NH3I solution will decompose into
CH3NH2 solution and HI solution. Then the equilibrium
constant is k(2) c(CH3NH2)  c(HI)/c(CH3NH3I) and Gibbs
free energy is DG(2) RT ln k(1).
In reaction (3), there are two ways for HI to react. (3-1)
represents the redox reaction. The equilibrium constant is k(3 
1) 1/p(O2)  c(HI), and the standard Gibbs free energy can be
calculated as follows:
DG(3  1) 2DfGqm(I2) + 2DfGqm(H2O)  4DfGqm(HI)  DfGqm(O2)
0 + 2(237.129)  4  1.70  0
481.058 kJ mol1,
the negative standard Gibbs free energy indicates that reaction
(3-1) can move forward easily. (3-2) represents the photochemical reaction. HI can easily decompose into H2 and I2 under light
conditions.
According to Le Chateliers principle, the degradation
process is easy to move forward. Steps (3-1) and (3-2) are
important for the whole degradation process. In order to verify

Fig. 4 (1) CH3NH3I exposed to argon and without UV radiation. (2)

CH3NH3I exposed to argon and with UV radiation. (3) CH3NH3I
exposed to air and with UV radiation. (4) CH3NH3I exposed to air and
without UV radiation.

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Journal of Materials Chemistry A

that humidity is essential for the whole degradation process, we

conducted the experiments of degradation of CH3NH3I. Aer
exposure to air and UV radiation (Fig. 4), the white powder
turned brown, which is the color of I2. The same sample
exposed to an argon atmosphere or without UV radiation did
not turn brown. This phenomenon indicates during step (3), air
and sunlight are necessary for the degradation process. Then
CH3NH3PbI3 will degrade and the nal solid-state products
leaving the lms are PbI2 and I2, which is consistent with the
UV-Vis spectra and XRD results.

Paper
Table 1

Performance of solar cells before and after post-modication

by Al2O3

w/o modication
Post-modication

Voc/V

Jsc/mA cm2

FF

h%

0.71
0.86

13.66
11.11

0.48
0.46

4.69
4.60

3.2 Photovoltage performance of solar cells with Al2O3 postmodication

For solar cell fabrication, CH3NH3PbI3 sensitized TiO2 lms
were spin coated with a HTM layer (spiro-MeOTAD), followed by
thermal evaporation of a Au layer as the counter electrode.
Fig. S2(a) shows the cross-sectional SEM image of the photovoltaic device and Fig. S2(b) shows the schematic illustration
of devices with post-modication by Al2O3. The HTM layer of
spiro-MeOTAD works just like I3/I electrolytes in liquid dye
sensitized solar cells, which could reduce the oxidized state of
sensitizers.23 Aer device fabrication, the JV characterization
was conducted immediately to avoid the inuence of moisture
(Fig. 5 and Table 1). Aer modication, the short-circuit current
( Jsc) is decreased a little from 13.66 mA cm2 to 11.11 mA cm2,
the open-circuit voltage (Voc) is largely increased from 0.71 V to
0.86 V. The nal power conversion eciency (PCE) is similar,
from 4.69% to 4.60%. The increase in Voc is attributed to the
suppressed charge recombination between TiO2 and spiroMeOTAD, which is veried by the dark current test and electrochemical impedance spectra (EIS) under dark conditions.
The small decrease in Jsc is caused by the insulation eect of
Al2O3, which hampers the electron transfer at the
CH3NH3PbI3/spiro-MeOTAD interface.
However, when the lm was exposed to moisture, the protecting eect of Al2O3 makes the rst appearance. As shown in
Fig. 6, the eciency of the devices is decreased when exposed to
moisture. Aer 18 h of exposure to moisture, the device without
modication achieves only 0.942% power conversion eciency,
which is only 20% of the original PCE without degradation.

Fig. 5 The corresponding current densityvoltage (JV) characteristics before degradation under 100 mW cm2 AM 1.5 illumination.

708 | J. Mater. Chem. A, 2014, 2, 705710

Fig. 6 Degradation of eciency versus time exposed to air with a

humidity of 60% at 35  C under sunlight.

CH3NH3PbI3 undergoes a corrosion process and degrades into

PbI2 and I2 as veried by UV-Vis and XRD results. Aer 18 h of
exposure to moisture, the device with post-modication achieves 2.23%, which is 48% of the original PCE without degradation. The stability test shows that the Al2O3 layer is helpful for
the device performance. The reason is that post-modication by
Al2O3 could separate CH3NH3PbI3 from moisture physically and
the degradation is suppressed.

3.3 Suppressing recombination and improved electron

transfer by Al2O3
Another problem for all-solid-state perovskite solar cells is that
perovskite compounds could hardly cover the surface of the
TiO2 photoanode totally.12,15 We also found a similar phenomenon that there are uncovered sites on TiO2 (Fig. S1(e) and (f)).
The uncovered sites on TiO2 particles could be in contact with
hole transport materials directly, resulting in electron recombination from the conduction band (CB) of TiO2 to hole transport materials, which is similar to liquid dye sensitized solar
cells (DSCs). Post-modication at the TiO2/electrolyte interface
is a useful method to suppress charge recombination in liquid
DSCs and quasi-solid DSCs.2426 Gr
atzel used 4-tert-butylpyridine as the modication agent to suppress electron recombination in DSCs.24 Wide-gap inorganic materials such as Al2O3
(ref. 27 and 28), ZnS29,30 and TBAI31 have also proved to be
eective for retarding electron recombination. However, the
post-modication in all-solid-state perovskite solar cells has
never been reported.
The EIS under dark conditions is shown in Fig. 7(a). The
inset in Fig. 7(a) is the equivalent circuit employed to t the
spectra.15 Rs is related to the interface resistance of the FTO

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(a) Electrochemical impedance spectra (EIS) of the devices in

the dark. (b) Current densityvoltage curve characteristics in the dark.

Fig. 7

electrode, R1 is the interface resistance of the counter electrode,

and C1 is its capacitance. R2 and C2 are the interface resistance
and capacitance of the TiO2/sensitizer/HTM interface. In the
Nyquist plots, the main arc in Fig. 7(a) is caused by the
TiO2/CH3NH3PbI3/spiro-MeOTAD interface, which is a combination of the recombination resistance (R2) and the chemical
capacitance of the lm (C2). Aer post-modication, the
recombination resistance is increased from 187.0 ohm to
424.9 ohm. The increased interface resistance will retard back
reaction from the TiO2 conductive band to spiro-MeOTAD. The
dark current measurement is shown in Fig. 7(b). Aer modication by Al2O3, we nd that the dark current is greatly
decreased because of the insulting barriers for electron
recombination. Voc could be determined by the formula below:32
 


mRT
Isc
ln
Voc
1
F
I0
where Isc is the short-circuit current, I0 is the dark current, m is
the ideality factor, and R and F are the ideal gas and Faraday
constants, respectively. From the formula, Voc will increase with

Journal of Materials Chemistry A

decreasing I0, which is consistent with the JV curves under

light and dark current measurement.
The retarded back reaction is due to the whole cover of Al2O3
on TiO2 and CH3NH3PbI3. Then the direct contact between TiO2
and spiro-MeOTAD is successfully avoided. The wide-band
Al2O3 could prevent electrons in TiO2 from recombining with
spiro-MeOTAD, as shown in Scheme 1.
To enhance the stability, encapsulation of the device can also
work to protect the device in solar cells.33 However, post-modication by Al2O3 serves two roles in this kind of solar cells. One
is to protect perovskites from degradation and another is to
suppress the interface electron recombination, which has been
approved by EIS and dark current results.

4 Conclusion
In conclusion, post-modication has been introduced into allsolid-state hybrid solar cells for the rst time. The Al2O3 layer
could act as an insulator barrier to protect CH3NH3PbI3 from
degradation by moisture and suppress electron recombination
between TiO2 and spiro-MeOTAD. Finally, the device postmodied by Al2O3 has shown more brilliant stability than that
without modication when exposed to moisture. We found that
CH3NH3PbI3 could degrade in the presence of moisture and
sunlight and Al2O3 could successfully protect CH3NH3PbI3,
which is veried by UV-Vis spectra and XRD results. The
restrained electron recombination is caused by the coverage of
Al2O3 on TiO2 and CH3NH3PbI3, which is veried by the
decreased dark current and increased interface resistance in the
dark. This article systematically discusses the post-modication
eect in all-solid-state DSCs and opens up a new pathway to
improve the performance of all-solid-state solar cells.

Acknowledgements
This work was supported by the National Natural Science
Foundation of China under Grant no. 51273104 and the
National Key Basic Research and Development Program of
China under Grant no. 2009CB930602.

Notes and references

Scheme 1 Schematic energy level diagrams of the device with postmodication by Al2O3.

This journal is The Royal Society of Chemistry 2014

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