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Cite this: Nanoscale, 2013, 5, 3245

Received 12th January 2013

Accepted 1st March 2013

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All-solid-state hybrid solar cells based on a new

organometal halide perovskite sensitizer and
one-dimensional TiO2 nanowire arrays
Jianhang Qiu, Yongcai Qiu, Keyou Yan, Min Zhong, Cheng Mu, He Yan
and Shihe Yang*

DOI: 10.1039/c3nr00218g
www.rsc.org/nanoscale

A novel organometal halide perovskite (CH3NH3PbI2Br) is synthesized and used as a visible light absorber to sensitize one-dimensional (1D) TiO2 nanowire arrays (NWAs) for all-solid-state hybrid
solar cells. It achieved a power conversion eciency (PCE) of 4.87%
and an open circuit voltage (Voc) of 0.82 V, both higher than those of
its analogue CH3NH3PbI3.

All-solid-state hybrid photovoltaics based on mesoscopic inorganic semiconductor nanostructures and organic conducting
materials have been considered as promising next generation
solar cells, as they integrate the desirable advantages of nanofabrication and organic electronics.1,2 In this hybrid system,
extremely thin absorber (ETA) layers, such as molecular dyes1,3
or semiconductor quantum dots,47 are typically introduced to
the interface between the inorganic electron transport materials
(ETMs) and the organic hole transport materials (HTMs), to
enhance the light harvesting eciency. Upon light excitation,
the ETA injects electrons into the conduction band (CB) of the
semiconductor and holes into the HTMs, allowing the separation of photogenerated charges, which then diuse to the
corresponding electrodes. Such charge separation and transport occurring at the ETAETM and ETAHTM interfaces play a
crucial role to the device performance.2,3,8 In this vein, it is very
important to tune the optical and electronic properties of the
ETA layers by varying the band gaps of the semiconductor
quantum dots through quantum connement9,10 or by
employing organic dyes with dierent highest-occupied and
lowest-unoccupied molecular orbitals (HOMOLOMO)11,12 to
optimize the energy level alignment and light absorption in the
hybrid system. However, applying these ETA materials to the

Department of Chemistry, The Hong Kong University of Science and Technology, Clear
Water Bay, Kowloon, Hong Kong, China. E-mail: chsyang@ust.hk; Fax: +852-23581594; Tel: +852-2358-7362
Electronic supplementary information (ESI) available: Experimental procedures,
characterization details, including additional SEM, TEM, EDS, XRD and
photovoltaic characteristics of cells based on TiO2 NWAs with dierent lm
thickness. See DOI: 10.1039/c3nr00218g

This journal is The Royal Society of Chemistry 2013

conventional mesoscopic particulate lms could encounter

obstacles such as inecient electron transport in the nanocrystalline lms and incomplete lling of organic HTMs in the
mesopores of the lms.13,14 Our strategy in this work is to
develop a hybrid photovoltaic cell by fabricating ordered
nanostructures for ETMs, and meanwhile, establishing a simple
process to tune the optical and electronic properties of ETAs, so
as to tune the energy band alignment between ETAs and ETMs,
eventually improving the charge transfer and power conversion
eciency (PCE) of the device.
One-dimensional (1D) nanowire arrays (NWAs) provide a
direct path for the photogenerated electron transport.15,16 Of note
is that the straight channels among the nanowires could benet
the lling of the HTMs, thus enhancing the hole transport eciency.17,18 Between the 1D structure and the HTM lies an ETA
layer of organometal halide perovskite sensitizers. As an ETA,
perovskite sensitizers have demonstrated photovoltaic potential
in hybrid cells constructed with mesoporous lms,1921 but the
extension to 1D-based cells is yet to be studied. By a single
halogen substitution, we have synthesized a novel sensitizer
(CH3NH3PbI2Br) with higher absorption coecients and a
higher CB edge, which are auspicious for the 1D-based devices.
The resulting hybrid photovoltaic cells, fabricated by combining
TiO2 NWAs as the ETM, CH3NH3PbI2Br as the ETA and 2,20 ,7,70 tetrakis-(N,N-di-p-methoxyphenylamine)
9,90 -spirobiuorene
(spiro-MeOTAD) as the HTM, have achieved a 4.87% PCE with an
open circuit voltage (Voc) of 0.82 V, and both the PCE and Voc are
signicantly improved over those of CH3NH3PbI3.
The 1D TiO2 NWAs were grown on seeded uorine-doped tin
oxide (FTO) substrates via a hydrothermal process reported
previously with some modications (see ESI for details).22 The
morphologies of the TiO2 NWAs were examined by a eld
emission scanning electron microscope (FE-SEM). Fig. 1a shows
a typical cross-sectional SEM image of the as-synthesized TiO2
NWA lm. The NWAs lm is about 1.5 mm thick and most
nanowires grow approximately vertical to the FTO substrate.
Viewing from the top as in Fig. 1b, the diameters of most
nanowires are 50150 nm. According to the X-ray diraction

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Fig. 1 Cross-sectional (a) and top (b) view SEM images of TiO2 NWAs synthesized on FTO substrates. SEM images of CH3NH3PbI2Br (c) and CH3NH3PbI3 (d)
spin-coated on TiO2 NWAs. (e) Cross-sectional SEM image of the TiO2 NWAs/
perovskite sensitizer/spiro-MeOTAD hybrid photovoltaic cell. (f) Schematic illustration of the hybrid solar cell.

(XRD) pattern (Fig. S1, ESI), the nanowires take a tetragonal

rutile structure (JCPDS: 00-021-1276). Advanced microstructures
of the nanowires were determined by a transmission electron
microscope (TEM). The high resolution transmission electron
microscope (HRTEM) image (Fig. S2a, ESI) reveals a (110)
interplanar distance of 0.326 nm and a (001) interplanar
distance of 0.297 nm, both of which agree with the relevant
interplanar distances of rutile TiO2, suggesting the [001] growth
direction of the nanowires. The corresponding selected area
electron diraction (SAED) pattern (Fig. S2b, ESI) demonstrates that the nanowires have a single crystalline rutile
structure, in accordance with the XRD analysis above.
For solar cell studies, the as-synthesized TiO2 NWAs were
coated with the organometal halide perovskite sensitizers
(CH3NH3PbI3 and CH3NH3PbI2Br) (see ESI for details). From
the SEM images shown in Fig. 1c and d, it can be seen clearly
that a perovskite sensitizer layer composed of 1020 nm nanoparticles has been formed on the surface of the TiO2 NWAs.
These perovskite sensitized TiO2 NWAs were spin coated with a
HTM layer (spiro-MeOTAD), followed by thermal evaporation of
a Au layer as the counter electrode. The cross-sectional SEM
image of the photovoltaic cell, shown in Fig. 1e, portrays the
whole device structure, which conforms well to the layout of the
hybrid inorganicorganic FTO/TiO2 NWAs/perovskite sensitizer/spiro-MeOTAD/Au unit in Fig. 1f. The distribution of
perovskite sensitizers within the photoanodes was estimated by
energy dispersive X-ray spectroscopy (EDS) mapping analysis
(Fig. S3, ESI). The weight percentages of Br, I and Pb in the

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CH3NH3PbI2Br sensitized photoanode are 2.55%, 7.97% and
6.33%, respectively, translating to the expected 1 : 2 : 1 atomic
ratio (Fig. S4a, ESI), while those of I and Pb with CH3NH3PbI3
are 17.23% and 9.31%, respectively, resulting in a 3 : 1 atomic
ratio that correlates with the formula unit (Fig. S4b, ESI). The
formation of the perovskite ETA layers has been further
conrmed by XRD analysis. The XRD patterns for
CH3NH3PbI2Br and CH3NH3PbI3 coated on TiO2 NWAs (Fig. 2a)
and FTO (Fig. 2b) indicate that both materials have a similar
crystalline structure assignable to the perovskite system.23,24 The
CH3NH3PbI3 sensitized lm gives diraction peaks at 14.05,
28.45, 31.87, 40.45 and 43.13 , which can be assigned to the
(110), (220), (310), (224) and (314) planes of the tetragonal
and c 12.637 A,
while
perovskite structure with a 8.872 A
CH3NH3PbI2Br shows peaks at 14.40, 29.06 and 32.60 corresponding to the (110), (220) and (310) planes, respectively, of a
b 8.692 A
and
tetragonal perovskite structure with a 8.681 A,
Compared to CH3NH3PbI3, the diraction peaks of
c 12.268 A.
CH3NH3PbI2Br are shied uniformly to high angles, which can
be rationalized by the shrunken crystalline lattice wholly caused
by the single-atom replacement of I with Br. Those atomic to
structural changes in the ETA layer cast important variations in
its optical and electronic properties, thereby oering a handle
to modulate the photovoltaic operation of the hybrid devices.
Fig. 3a shows the diuse reectance spectra of the two
organometal halide perovskites spin-coated on TiO2 NWAs and
the corresponding absorption spectra (inset) converted
according to the KubelkaMunk relation (optical absorption
coecients f F(R) (1  R)2/2R). While CH3NH3PbI3 absorbs
light in a relatively longer wavelength region up to 800 nm, the
appreciable absorption of CH3NH3PbI2Br is mainly at <700 nm;
note that the absorption coecients of the latter at 400650 nm
are substantially higher than those of CH3NH3PbI3 (inset of
Fig. 3a). The dierent absorption ranges can be easily ascribed
to the variation of the energy band gaps (Eg) of those two
semiconductor sensitizers arising from the Br-replacement
induced structural modications. Eg for the perovskite sensitizers can be estimated using the conventional Tauc equation
[F(R)hn]n A(hn  Eg) (A is an empirical constant, n 2 for the
direct band gap semiconductor) by extrapolation of the linear
part of the [F(R)hn]n vs. hn plots (Fig. 3b). We found that the Eg

Fig. 2 XRD patterns of the perovskite sensitizers spin-coated on (a) TiO2 NWAs
and (b) FTO substrates.

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Fig. 3 (a) Diuse reectance spectra of the organometal halide perovskitecoated TiO2 NWAs and the corresponding absorption spectra obtained by the
KubelkaMunk method (inset). (b) Plots of [F(R)hn]2 vs. photon energy (hn). (c)(e)
UPS spectra of the perovskite-coated TiO2 NWAs.

value for CH3NH3PbI3 is 1.57 eV, which is in good agreement

with those reported elsewhere,20,23 while it is 1.78 eV for
CH3NH3PbI2Br, which is >0.2 eV larger, mainly caused by the
hybridization of the Br (4p) orbitals with the I (5p) and Pb (6s)
orbitals. Furthermore, such introduction of the Br (4p) orbitals
could give rise to the variation of the valence band (VB) edge of
the perovskite sensitizers. Ultraviolet photoelectron spectroscopy (UPS) was performed to investigate the VB edge positions
of these two sensitizers. Shown in Fig. 3ce are the corresponding UPS spectra with respect to the He I photon energy
(21.22 eV). The VB edge energy (EVB) values, with reference to the
vacuum level, are calculated to be 5.43 and 5.40 eV for
CH3NH3PbI3 and CH3NH3PbI2Br, respectively. The CB edge
energies (ECB) can then be determined from the Eg and EVB
values, yielding 3.62 eV for CH3NH3PbI2Br that is substantially
higher than that of CH3NH3PbI3 (3.86 eV). On the basis of the
results, Fig. 4 sketches the band alignment scheme for the

Fig. 4 Schematic energy level diagrams of the TiO2 NWAs, organometal halide
perovskite sensitizers CH3NH3PbI3 (a) and CH3NH3PbI2Br (b), and spiro-MeOTAD.

This journal is The Royal Society of Chemistry 2013

Nanoscale
hybrid photovoltaic cells. Apparently, the higher CB edge of
CH3NH3PbI2Br elicits a larger driving force for the photogenerated electrons to transfer from the sensitizer to the TiO2
NWAs, which could lead to an enhanced photogenerated electron injection eciency from the CH3NH3PbI2Br sensitizer to
the TiO2 NWAs,10,25 compared to the CH3NH3PbI3-based device.
Indeed, the CH3NH3PbI2Br-based photovoltaic cell gives higher
incident photon-to-current conversion eciency (IPCE) values
at 400650 nm than those of CH3NH3PbI3 as can be seen from
Fig. 5a, which, although mainly caused by the higher optical
absorption coecients at 400650 nm (inset of Fig. 3a), could
also benet from the enhanced electron injection from the
CH3NH3PbI2Br sensitizer to the TiO2 NWAs. The resulting
short-circuit current density (Jsc) of 10.12 mA cm2 (Fig. 5b and
Table 1) is comparable to that of the CH3NH3PbI3-based device
in spite of the much narrower absorption of CH3NH3PbI2Br
(Fig. 3a).
Contrasting the high IPCEs at 400650 nm, there is a smaller
dark current of the photovoltaic cell based on CH3NH3PbI2Br
compared to that of the CH3NH3PbI3-based device (Fig. 5b),
meaning that the solar cell featuring the TiO2 NWAs/
CH3NH3PbI2Br sensitizer/spiro-MeOTAD/Au junction can better
restrain the recombination of the photogenerated electrons
injected into the TiO2 NWAs and the holes extracted into spiroMeOTAD. Since the Voc and ll factor (FF) are closely related to
the recombination rate of the photogenerated charges, the
larger Voc (0.82 V) and FF (0.59) of the CH3NH3PbI2Br-based cell
are thus expected (Fig. 5b and Table 1). Altogether, it is because
of the improvements in IPCE (at 400650 nm), FF and Voc that
the CH3NH3PbI2Br cells could achieve an overall PCE of 4.87%,
almost 20% higher than that based on the CH3NH3PbI3 sensitizer (4.29%) (Table 1).
Of note is that the 1D TiO2 NWAs/CH3NH3PbI2Br/spiroMeOTAD device performs best when the length of the 1D NWAs,
or the lm thickness, is 1.5 mm (Fig. S5 and Table S1, ESI).
This is contrary to the hybrid perovskite photovoltaic cells based
on mesoporous lms, the thickness of which is restricted to the
submicron scale due partly to the limitations of electron
transport in nanocrystalline lms and the pore lling of polymer HTMs.19,20 This result indicates that the 1D NWAs-based
device oers the promise of employing thicker lms with larger

Fig. 5 (a) IPCE spectra of the TiO2 NWAs/perovskite sensitizer/spiro-MeOTAD

hybrid solar cells. (b) The corresponding current densityvoltage (JV) characteristics under 100 mW cm2 AM 1.5 illumination and in the dark.

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Table 1 Photovoltaic properties of the hybrid solar cells based on the organometal halide perovskite sensitizers and 1D TiO2 NWAsa

Perovskite sensitizer

Jsc
(mA cm2)

Voc (V)

FF

h (%)

CH3NH3PbI2Br
CH3NH3PbI3

10.12
10.67

0.82
0.74

0.59
0.54

4.87
4.29

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a
The estimated error is 5%. Preparation conditions of the TiO2 NWAs,
growth temperature: T 180  C, growth time: t 8 h.

surface areas without sacricing the charge transport eciency.

Besides the lm thickness, other morphology parameters of the
1D NWAs, such as the density and diameter, can also inuence
the device performance signicantly. As shown in Fig. 1a and b,
although the diameter of most nanowires is below 100 nm,
there are still lots of nanowires with a diameter larger than
150 nm grown on the substrate. Such thick nanowires thin
down the surface area of the 1D NWAs lm, resulting in a
decline of the device performance. Thus, synthesis of 1D NWAs
with a high density and a uniformly small diameter is a soughtaer goal for the development of hybrid solar cells. By precisely
controlling the lm morphology, such hybrid photovoltaics
with higher PCEs might be achieved.
In conclusion, a solution processed all-solid-state hybrid
solar cell based on a new organometal halide perovskite sensitizer and 1D TiO2 NWA with a PCE of 5% has been demonstrated. Our results show that higher Voc and PCE can be
achieved by Br-substitution in the perovskite sensitizer
CH3NH3PbI3. The signicantly improved Voc and eciency
achieved here highlight the superior electronic and optical
properties of the 1D TiO2 NWAs and CH3NH3PbI2Br sensitizer,
opening up new avenues for advancing the development of
hybrid photovoltaic cells.
This work was supported by the HK-RGC General Research
Funds (GRF no. HKUST 606511 and 605710). We thank Prof.
Jiannong Wang and Mr Shiguang Liu for providing access to the
metal evaporation facility.

Notes and references

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