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11735

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Post modication of perovskite sensitized solar cells by

aluminum oxide for enhanced performance
Wenzhe Li,a Jiaoli Li,b Liduo Wang,*a Guangda Niu,a Rui Gaoa and Yong Qiua
The method of post-modication by aluminum oxide was successfully introduced into perovskite sensitized
solar cells with a liquid electrolyte. Post-modication by Al2O3 could both protect the perovskite sensitizer
from corrosion by electrolyte and eectively suppressed electron recombination. The UV-vis spectra
revealed an enhanced absorption especially in the long wavelength range after modication. The XRD
results showed a disappeared peak of PbI2, demonstrating that the modication could eectively
protect the perovskite from dissolution in the electrolyte. Stability test showed that the remaining JSC
improved from 10% to 50% at a given period of time. The EIS results and dark current curves illustrated

Received 10th June 2013

Accepted 25th July 2013

that this modication increased the interface resistance in dark, conrming that the electron
recombination process was eectively restrained. Finally, the corresponding eciency was largely
increased from 3.56 to 6.00% by 68%. The strategy using aluminium oxide to post-modify a perovskite

DOI: 10.1039/c3ta12240a

sensitized solar cell was therefore proved to be a useful tool for the optimization of perovskite

www.rsc.org/MaterialsA

sensitized solar cells.

Introduction

The CH3NH3PbI3 perovskite and its derivative nanocrystals are

used as light harvesters for solar cells.19 These compounds have
some physical properties such as 20 multiple roles of lightabsorption, electroluminescence, organic-like mobility,
magnetic properties, charge separation, transport of both holes
and electrons in single material.7,1012 In addition, the sensitized
solar cells based on this kind of materials with the advantages
of low-cost and high eciency have the potential to be the ideal
photoelectric conversion device.1,13
The CH3NH3PbI3 perovskite solar cells were divided into two
categories: all-solid-state solar cells and liquid state solar cells.
It was reported that in the all-solid-state sub-micron thin lm
mesoscopic solar cells, the spiro-MeOTAD (2,20 ,7,70 -tetrakis(N,N-di-p-methoxyphenylamine)-9,90 -spiro-biuorene) was used
as the hole transport material (HTM), and achieved a very high
PCE of 12%.3 Aer the iodine in CH3NH3PbI3 was practically
changed by chlorine, the device stability and incident-photonto-carrier conversion-eciency (IPCE) increased, the PCE
improved to 12.3%.5,7 On the other hand Kojima2 used
CH3NH3PbI3 perovskite as a sensitizer and the iodine redox as
electrolytes fabricated liquid state perovskite sensitized solar
cells, and the power conversion eciency (PCE) was 3.81%.
Then Im6 optimized the precursor concentration of
a

Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education,

Department of Chemistry, Tsinghua University, Beijing 100084, China. E-mail:
chldwang@mail.tsinghua.edu.cn; Fax: +86 10 62795137; Tel: +86 10 62788802

State Key Lab of Polymer Physics and Chemistry, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, 100190, P.R. China

This journal is The Royal Society of Chemistry 2013

CH3NH3PbI3 perovskite, the nal PCE was boosted to 6.5%. The

CH3NH3PbI3 perovskite nanoparticles are unstable in an iodidecontained liquid electrolyte due to rapid dissolution, the fast
degradation of performance was oen witnessed.6 The perovskite sensitizer was therefore hardly applied to the most ecient liquid-cell-structure.
post-modication focused on a sensitized TiO2/electrolytes
interface was proposed by Gr
atzel14 in dye sensitized solar cells
(DSCs). The 4-tert-butylpyridine (TBP) was used as the modication agent so that the electron recombination from a
conductive band of TiO2 to an electrolyte was retarded. The PCE
improved from 3.7 to 8.5%. Due to the problem of organic
modication agents that includes a low boiling point and
solubility in electrolytes, the inorganic materials with a wide
bandgap such as Al2O31519 could also suppress electron
recombination. In quantum dots sensitized solar cells (QDSCs)
post-modication materials, for instance ZnS,20,21 tetrabutylammonium iodide (TBAI),22 halogen ions23 were also used to
improve the photoelectric conversion eciency and device
stability. However, the post-modication in CH3NH3PbI3
perovskite solar cells has never been reported. Compared with
all-solid-state solar cells, the liquid state solar cells were more
sensitive to photovoltage performance through post-modication by Al2O3.
Here we report a useful strategy to stabilize perovskite in a
liquid cell by the method of post-modication. It was found in
our former work that the Al2O3 overlayer could act as an insulator barrier to retard recombination between the TiO2 and the
dye/quasi-solid state electrolyte interface.15,24 A similar eect
was observed in the perovskite sensitized liquid cell where the

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Al2O3 overlayer eectively improved the eciency 1.71 times,

and at the same time the stability from 10% remaining JSC to
50% at a given period of time. The paper systematically discussed the CH3NH3PbI3 post-modication and passivation,
which potentially revealed a normally applied method for
interface modication in all-solid-state perovskite solar cells.

Experimental

2.1

Materials synthesis

CH3NH3I was synthesized and puried based on the method

proposed by J. H. Im.6 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 with
the hydrothermal method which was well documented in a
previous report.25
2.2

Solar cell fabrication

The cleaned FTO glasses were coated with 0.15 M titaniumdiisopropoxide bis(acetylacetonate) (75% Aldrich) in 1-butanol
(Aldrich) solution by the spin-coating method with 3000 rpm and
30 s, which was heated at 125  C for 5 min, and then raised to
500  C for 30 min. The nanocrystalline TiO2 paste was deposited
on the pre-treated FTO substrate, which was followed by heating
at 500  C for 1 h. The thickness of the annealed TiO2 lms was 5.4
mm, determined by SEM (JEOL JSM-7401F). The perovskite
coating solution was spread on the annealed TiO2 lm and spun
for 60 s at a speed of 2000 rpm in air atmosphere. Then the lms
were heated at 100  C for 15 min. The room temperature lms
were immersed into a 45 mM aluminium triethyl (Alfa, Al(C2H5)3
25% w/w in hexane) hexane solution for 30 s. The hydrolysis rate
was very fast in the air. Aluminium triethyl is ammable, therefore it was reasonable to keep it in a glovebox. The redox electrolyte was prepared by dissolving 0.9 M LiI (Alfa), 0.45 M I2 (Alfa),
0.5 M N-methylbenzimidazole (Aldrich, NMBI), 0.05 M urea
(Aldrich) in ethyl acetate (Alfa). Here the NMBI was used as
electrolyte additives, considering the lower boiling point of the
normally used 4-tert-butylpyridine (TBP).26 Chemically platinized
conductive glass was used as the counter electrode. When
assembling the DSCs, the sensitized TiO2 electrode and a counter
electrode were sandwiched using an adhesive tape with a thickness of 15 mm. Last, the electrolyte was introduced into the space
of the sealed electrodes prior to measurement.
2.3

Characterization

The UV-vis absorption spectra were used for testing the

absorption of the perovskite sensitized TiO2 lm with a Hitachi
U-3010 spectroscope. X-Ray diraction (XRD) patterns were

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

X-Ray photoelectron spectroscopy (XPS) was measured with a
PHI 5300ESCA instrument. Photocurrentvoltage (JV), incident
photon-to-electron conversion eciency (IPCE) and electrochemical impedance spectros (EIS, ranged from 0.1 Hz to 105
Hz) were measured by a ZAHNER CIMPS electrochemical
workstation, Germany.

11736 | J. Mater. Chem. A, 2013, 1, 1173511740

Paper

Results and discussion

3.1 Characterization of the sensitized lms with Al2O3 postmodication

To investigate the generated material aer Al(C2H5)3 treatment,
XPS was used to analyze the TiO2/CH3NH3PbI3 lm before and
aer surface modication. All of the peaks were calibrated
using C1s (284.8 eV) as the reference. The elements of the
composite lms could be identied in the XPS wide-scan survey
spectrum, as shown in Fig. 1a. A detailed analysis of the XPS
spectra presented a clear evidence that the lms were chemically modied and conrmed by high resolution spectra of O 1s
and Al 2p based on a Gaussian spectral deconvolution. Fig. 1b
showed that aer the modication the peak of Al was located at
74.5 eV. As shown in Fig. 1c, the O 1s spectrum for TiO2/
CH3NH3PbI3 in line (A) could be partitioned to two peaks of
TiO2. The large peak at 530.0 eV was assigned to lattice oxygen
in anatase TiO2, whereas the other peak located at 531.5 eV
could be attributed to the hydroxyl O atoms.27 Aer the modication, a new peak appeared at 531.9 eV shown in line (B),
which was the binding energy of Al2O3.28,29 It was therefore
proved that the Al2O3 layer was generated aer the Al(C2H5)3
modication.

3.2 Photovoltage performance of perovskite solar cells by

Al2O3 post-modication
The liquid state perovskite solar cells were fabricated using
CH3NH3PbI3 sensitized TiO2 lms as a photoanode and the JV
curves were shown in Fig. 2a. For electrode without postmodication by Al2O3, the open circuit voltage (VOC) increased
from 0.56 to 0.68 V. A similar phenomenon was observed in our
former results about Al2O3 post-modication of a quasi-solid
state solar cell, where a 0.13 V increase was acquired.15 The ll
factor was relatively high, 0.68 in comparison with 0.53 before
modication. The Al2O3 coating between the sensitized TiO2
lm and the electrolyte served as an insulating barrier layer. The
Al2O3 coating depressed the recombination between the injected electrons and the electrolytes. As a result, the overall eciency of 6% was doubled for the device modied with Al2O3
layer. The post-modication thus proved to be an ecient
method to improve the eciency of the perovskite sensitized
liquid perovskite solar cells.
The photocurrent response in monochromatic was also
investigated by IPCE, and the results were shown in Fig. 2b. The
narrow IPCE curve revealed a maximum eciency of 58% at 500
nm, while having an eciency above 50% in the range of 440
580 nm. Aer modication with Al2O3, the range was broadened
from 140 to 210 nm, which was 530740 nm in detail. This
might be due to a more ecient incident photon absorption in
the long wavelength range. However the photo-electron current
response of TiO2/CH3NH3PbI3/Al2O3 perovskite solar cells was
10% lower than that of the device before modication. In the
testing process, TiO2/CH3NH3PbI3 perovskite solar cells with
lower stability would generate more PbI2 than the devices aer
modication, leading the higher photocurrent response at
500 nm wavelength which was attributed to absorption from

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Fig. 1

Journal of Materials Chemistry A

XPS wide-scan survey (a), O 1s and (Al) 2p patterns (b), (c) of the (A) TiO2/CH3NH3PbI3 and (B) TiO2/CH3NH3PbI3/Al2O3 lms.

PbI2. Even though the IPCE was lower in the range from 400 to
550 nm, the enhanced eect of Al2O3 layer in the range from 550
to 760 nm played a dominant role. The corresponding short
circuit current exhibited an increase of 12% aer modication
under illumination of 1 sun, as shown in Fig. 2a.
The decay of the device performance was recorded by
continually testing under 1 sun without the device packaged.
The JSC decreased with time, as shown in Fig. 2c. The aging of
the liquid cell happened very quickly, less than 10% values was
remained aer 15 min of illumination. In comparison, the
modied cell maintained more than 50% values. The Al2O3
layer could perfectly protect the perovskite sensitizer from
dissolution by the electrolyte and erosion by the moisture in air.
Although the overall stability was not so far ideal as solid state
perovskite solar cells, this work inspired a possible method for
the development of liquid cells by using perovskite as a sensitizer and provided a feasible method to further improve the PCE
of the solid state.
3.3 Eect on suppressing the corrosion process by Al2O3
post-modication

Fig. 2 (a) JV curves of TiO2/CH3NH3PbI3 and TiO2/CH3NH3PbI3/Al2O3 perovskite solar cells; (b) IPCE; (c) device stability.

This journal is The Royal Society of Chemistry 2013

The CH3NH3PbI3 perovskite sensitized TiO2 lm had a broad

UV-vis spectrum until 775 nm, as shown in Fig. 3. This is
comparable to the traditional successful black dye. However for
a liquid cell, the electrolyte decomposed the perovskite easily,
which made the cell unstable. It was clearly seen that aer
contact with the electrolyte, the spectrum of the sensitized TiO2
lm without Al2O3 layers was strongly narrowed to 520 nm.
Fortunately, the electrolyte decay could be eectively restrained
by post-modication of the sensitized photoanode with Al2O3.
The Al2O3 is traditionally formed by hydrolysis of aluminium
isopropoxide. However in our experiment one of the hydrolysis
products isopropanol also aected the stability of CH3NH3PbI3
perovskite. Here the Al(C2H5)3 was used as a modication agent
whose hydrolysis products do not decompose the CH3NH3PbI3.
The absorption spectrum of the corresponding lm showed a
slight blue shi, while retaining the enhanced absorption until
789 nm as before the erosion. This was probably because the
Al2O3 overlayer blocked the water in air, so the erosion of the
perovskite was eectively retarded. The Al2O3 overlayer could
suppress both electrolytes and vapour in the air corrosion
process. A similar phenomenon was observed in Luo's work, the

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3.4 Eect on retarding the recombination by Al2O3 postmodication

The chemical corrosion retarded by Al2O3 was revealed while
the physical performance was also needed to be investigated. In
order to reveal the role of Al2O3 for the improvement of the
device, the EIS spectra were measured. Under full illumination,
the Nyquist plot (Fig. 5a) showed typical semicircles in the
measured frequency range of 0.1 Hz to 100 kHz. As reported in
such perovskite solar cells, the resistance at the TiO2/sensitizer/
electrolyte interface (the R2 in the equivalent circuit represented
in Fig. 5a) can be determined by the middle frequency (10100
Hz) semicircle in the Nyquist plots.31 The values of R2 are 192 U,
and 225 U for TiO2/CH3NH3PbI3 and TiO2/CH3NH3PbI3/Al2O3

Fig. 3

UV-vis spectra of the sensitized TiO2 lm.

cell with an insulating coating showed better stability under

both low and high illumination.15
The crystal structure changes in the corrosion process were
further veried by a XRD experiment. Fig. 4 shows the crystal
information existing in the photoanode. The peaks at 28.30 and
31.71 in curve B, corresponding to the (220) and (310) planes,
conrmed the formation of a tetragonal perovskite structure
and c 12.677 A,

with lattice parameters of a b 8.883 A

which was well consistent with previous reports.3,4,13 Only the
sensitized lm without modication showed a typical 002 and
102 crystal face of PbI2 located in 25.8 and 34.2 , respectively,
which was produced by the erosion procedure. The bandgap of
bulk PbI2 is 2.57 eV30 with absorption at 482 nm wavelength
which is similar to the TiO2/CH3NH3PbI3 aer the erosion
curve in Fig. 3. That meant the CH3NH3PbI3 was dissolved and
decomposed to PbI2 and CH3NH3I in electrolyte conditions. In
comparison, the sensitized TiO2 lm aer modication maintained a similar spectrum both before and aer erosion. This
therefore proved the idea that the Al2O3 overlayer could eectively protect the perovskite sensitizer to obtain improved
stability.

Fig. 4

XRD spectra of the sensitized TiO2 lms.

11738 | J. Mater. Chem. A, 2013, 1, 1173511740

Fig. 5 Impedance spectra of the studied device under illumination of AM 1.5G

(a) and in the dark (b), and dark JV curve of the investigated device (c).

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device, respectively. The interface resistance slightly increased
by 17%, reecting that the forward electron transmission was
impeded. In theory, the JSC would be decreased, which was
contradicted with the increased JSC in the JV curve (Fig. 2b).
However, the Al2O3 in the devices protected CH3NH3PbI3 from
corrosion by the electrolyte. The relatively stable CH3NH3PbI3
contributed the higher JSC in modied cells which had been
illustrated above. The Nyquist plot of impedance spectra in the
dark under 0.8 V bias voltage revealed an increased interface
resistance at sensitized TiO2/electrolyte interface (Fig. 5b). The
values changed from 50 U before modication to 125 U aer
modication 150% times. The interface resistance was reected
in the obstruction of electron transmission from TiO2 conductive band (CB) to electrolytes. Normally an increased resistance
in the dark indicated restrained electron recombination.32 As
shown in Scheme 1 the electron recombining process from TiO2
CB to the electrolyte was suppressed by the Al2O3 insulating
layer. Considering both the interface resistance changes in the
illustrated and dark conditions, the recombination resistance
increased much more substantially than the resistance of the
forward electron transport. Therefore the current density was
enhances, also reected in the JV curves. In our case, this
was veried by dark current measurements. The JV curve was
recorded using the fabricated device measured in the dark. As
shown in Fig. 5c, 2.8 times dark current was found for the
unmodied device in comparison with the modied one, for
example at VOC 0.6 V. The recombination of the separated
excitons was thus eectively restrained. VOC could be determined using the formula below:33,34
 


mRT
ISC
ln
VOC
1
(1)
F
I0
where ISC is the short-circuit photocurrent, I0 is the dark
current, m is the ideality factor, whose value is between 1 and 2
for perovskite solar cells,35 and R and F are the ideal gas and
Faraday constants, respectively. The formula proved that VOC
increased with decreasing I0. An increased photovoltage
performance and decreased dark current suggested that the
dark reaction at the interface of the sensitized-TiO2 electrode/
electrolyte in perovskite solar cells was reduced aer the
modication of Al2O3 and that electron transfer from the
conduction band of the TiO2 lm to the triiodide ions was
suppressed.

Scheme 1 Illustration of the interfacial charge transfer processes occurring at

the sensitized TiO2/electrolyte interface. Also shown is the Al2O3 overlayer as
developed in this study.

This journal is The Royal Society of Chemistry 2013

Journal of Materials Chemistry A

Conclusions

An ecient method both improved the photovoltaic performance of perovskite sensitized solar cells and developed the
device stability. The Al2O3 overlayer could act as an insulator
barrier to protect the easily dissolved perovskite sensitizer and
retard the recombination between the sensitized TiO2/liquid
state electrolyte interface. The corresponding eciency was
improved by 68%, and an overall eciency of 6.00% was
obtained. Moreover, the remaining JSC improved from 10% to
50% at a given period of time. At least two factors resulted in the
improvement: one was the enhanced absorption in the long
wavelength range, coming from the protected perovskite
sensitizer. This was evidenced by the XRD, where a disappeared
peak of PbI2 indicated that the modication could eectively
protect the perovskite from dissolution in the electrolyte;
another was the increased interface resistance in the dark,
which aorded restrained electron recombination. This work
thus supplied a normally applicable strategy for interface
modication in liquid state perovskite solar cells, which could
also be applied in solid state perovskite sensitized solar cells.
This part of the work was underway in our lab.

Acknowledgements
This work was supported by the National Natural Science
Foundation of China under Grant no. 51273104, the National
Key Basic Research and Development Program of China under
Grant no. 2009CB930602, and the Ministry of Science and
Technology of China (no. 2012CB933200).

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