Energy &

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Science

Volume 8 Number 3 March 2015 Pages 6771048

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ISSN 1754-5692

PAPER
Sangwook Lee, Hyun Suk Jung et al.
Highly efficient and bending durable perovskite solar cells: toward a
wearable power source

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Highly ecient and bending durable perovskite

solar cells: toward a wearable power source
Byeong Jo Kim,a Dong Hoe Kim,b Yoo-Yong Lee,b Hee-Won Shin,c Gill Sang Han,a
Jung Sug Hong,b Khalid Mahmood,a Tae Kyu Ahn,c Young-Chang Joo,b
Kug Sun Hong,b Nam-Gyu Park,cd Sangwook Lee*e and Hyun Suk Jung*a
Perovskite solar cells are promising candidates for realizing an ecient, exible, and lightweight energy
supply system for wearable electronic devices. For exible perovskite solar cells, achieving high power
conversion eciency (PCE) while using a low-temperature technology for the fabrication of a compact
charge collection layer is a critical issue. Herein, we report on a exible perovskite solar cell exhibiting
12.2% PCE as a result of the employment of an annealing-free, 20 nm thick, amorphous, compact TiOx
layer deposited by atomic layer deposition. The excellent performance of the cell was attributed to fast
electron transport, veried by time-resolved photoluminescence and impedance studies. The PCE
remained the same down to 0.4 sun illumination, as well as to a 45
tilt to incident light. Mechanical
bending of the devices worsened device performance by only 7% when a bending radius of 1 mm was
used. The devices maintained 95% of the initial PCE after 1000 bending cycles for a bending radius of 10

Received 1st August 2014

Accepted 3rd October 2014

mm. Degradation of the device performance by the bending was the result of crack formation from the
transparent conducting oxide layer, demonstrating the potential of the low-temperature-processed TiOx

DOI: 10.1039/c4ee02441a

layer to achieve more ecient and bendable perovskite solar cells, which becomes closer to a practical

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wearable power source.

Broader context
Perovskite solar cells, based on state-of-the-art inorganicorganic halide perovskite materials, are one of the most promising devices for realizing a wearable power
source, on account of their high energy conversion eciency, and economic fabrication processes such as roll-to-roll printing. Therefore, recently, the main concern of
research in this eld has moved to fabricating a highly exible device, while preserving the high eciency. The key process to achieve such a kind of highly ecient and
exible perovskite solar cells is the oxide lm deposition process to make compact-electron-collection layers at a low temperature. In this regard, we report on highly
ecient (12.2%) and bending durable perovskite solar cells on a cheap polyethylene naphthalate (PEN) substrate, with a TiOx compact-electron-collection layer that is
fabricated at below 80
C using the plasma enhanced atomic layer deposition method. We observed constant device performance up to 1000 bending cycles with 10
mm of bending radius. This study demonstrates that the exible perovskite solar cell is potentially used for a power solution of future wearable devices.

School of Advanced Materials Science & Engineering, Sungkyunkwan University,

Suwon 440-746, Korea. E-mail: hsjung1@skku.edu

1. Introduction

Flexible and lightweight thin lm solar cells have attracted

considerable attention for their potential applications, such as
portable electronic chargers, bendable display devices, and
nally wearable electronic textiles, on account of their convenience of integration and versatile functionality.1,2 The most
recently developed state-of-the-art solid-state solar cells based
on inorganicorganic light-absorbing halide perovskites are
highly promising candidates in this area due to their economically and practically viable fabrication processes which include
the use of low temperature and the roll-to-roll process for the
wearable/portable devices, as well as a high PCE of above 16%,
which was achieved within only a few years from the rst report
in 2009 of this type of system on a rigid substrate.37 Recently,
many groups have attempted to fabricate exible perovskite
solar cells with an all low-temperature (<130
C) process and

Department of Materials Science and Engineering, Seoul National University, Seoul

151-744, Korea

Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Korea

School of Chemical Engineering, Sungkyunkwan University, Suwon 440-746, Korea

Department of Materials Science and Engineering, University of California at Berkeley,

CA 94720, USA. E-mail: wook2@berkeley.edu

Electronic supplementary information (ESI) available: Grazing incidence XRD of

the Lt-ALD-TiOx compact electron-collection layer, XRD of the perovskite lms on
the each compact TiOx layer, histograms of the photovoltaic parameters of
Lt-ALD-TiOx based perovskite solar cells, IV hysteresis and static PCE of
representative device, FT-IR and XPS of various TiOx electron collection layers,
normalized device parameters of exible perovskite solar cells as a function of
bending cycles with diverse radii 400, 10, and 4 mm, schematic images for in
situ measurements of resistance and designed multilayered structures,
photovoltaic performance parameters and PL lifetime parameter of various TiOx
charge collection layers based exible perovskite solar cells. See DOI:
10.1039/c4ee02441a
These authors contributed equally to this work.

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have shown the possibility of higher eciency than that displayed by organic exible solar cells.8 The reported exible
perovskite solar cells have employed two types of light
absorbers, i.e. CH3NH3PbI3 and CH3NH3PbI3xClx.811 So far,
the best PCE of the exible perovskite solar cells has been
10.2%, obtained by using a 300 nm-thick CH3NH3PbI3 layer,9
however, this is still inferior to the rigid-type perovskite solar
cells. The main reasons for the relatively low performance are
the large series resistance and fast charge recombination, which
are expected to be improved by optimizing the TiO2 or ZnO
compact charge collection layer in the exible substrate.8,9
Usually, a few tens of nanometer-thick, solution-processed,
TiO2 thin lm as the compact layer can produce excellent
performance when it is baked at over 500
C.8,12,13 However, for
exible devices, the high temperature processes need to be
avoided. Therefore, it is extremely important to study the origin
of the inadequate properties of the low-temperature-processed
compact nanolayers, and to establish the optimal technology
for their development. Moreover, observation of the bending
fatigue of the exible perovskite solar cells, which has not been
reported to date, is also crucial for real-world application and
commercialization of the exible solar cells.
Here, we present highly bendable (up to 1 mm of bending
radius) and extremely ecient (PCE 12.2%) perovskite solar
cells based on tin-doped indium oxide (ITO) on PEN exible
substrates by forming an approximately 20 nm-thick TiOx
compact layer on the substrate at 80
C via plasma enhanced
atomic layer deposition (PEALD). Moreover, we investigate the
bending stability of the devices, with three eective bending
radii for the wearable devices: 400 mm (R400), 10 mm (R10), and
4 mm (R4) for human neck, wrist, and nger, respectively. The
device performance can withstand up to 1000 cycles of the
bending test for R400 and R10. However, in the case of R4, the
PCE signicantly deteriorates to 50% of the initial eciency
aer 1000 cycles. We demonstrate that the origin of degradation
is not the fracture in the perovskite layer but is rather due to the
fracture in the transparent conducting oxide layer (ITO in this
study) on the PEN substrate, by analysing the microstructure of
the damaged PEN/ITO/TiOx/perovskite multilayer aer the
bending test.

2.

Results and discussion

Fig. 1a and b present respectively a cross-sectional scanning

electron microscopy (SEM) image and schematic diagram of an
optimized exible device employing the planar heterojunction
structure. The TiOx layer, as the electron collection layer of
perovskite solar cells, was prepared by PEALD at 80
C (denoted
as Lt-ALD-TiOx) on the ITO/PEN electrode. Aer that, a layer of
light absorbing material, CH3NH3PbI(3x)Clx, was deposited on
the TiOx layer from a precursor solution containing CH3NH3I
and PbCl2 at a molar ratio of 3 : 1, as reported by Snaith et al.13
Details of the experimental are well given in the methods
section. Fig. 1c shows an image of an actual bent exible
perovskite solar cell, which is possible to patch onto sleeves,
thus providing a good energy source for future wearable devices.
The current densityvoltage (JV) characteristics of the

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(a) Cross-sectional SEM image of the inorganicorganic halide

perovskite planar heterojunction exible solar cell and schematic of
the exible device structure. Scale bar: 200 nm. (b) An actual bent
image of a exible perovskite solar cell. (c) JV characteristics
measured under the simulated solar light (100 mW cm2 AM 1.5G) for
the best performing PEN/ITO/TiOx/CH3NH3PbI(3x)Clx/spiro-MeOTAD/Ag exible device.
Fig. 1

optimized exible device are plotted in Fig. 1d. The optimized

exible device achieved 12.2% power conversion eciency
(PCE) at 21.4 mA cm2 short-circuit current density (Jsc), 0.95 V
open-circuit voltage (Voc), and 0.60 ll factor (FF). It is noteworthy that this exible perovskite solar cell exhibits similar
photovoltaic performance to typical glass substrate-based
perovskite solar cells.810 This exible device demonstrates a
high photocurrent density of more than 20 mA cm2 Jsc,
consequently yielding a high PCE of 12.2%, which is attributed
to superior recombination-blocking and electron-transport
properties of the Lt-ALD-TiOx layer (see below). The crosssectional transmission electron microscopy (TEM) images for
the Lt-ALD-TiOx layer in Fig. 2a clearly display conformal
coating on the surface of the ITO layer. The high-resolution
TEM image shows that the thickness of the TiOx compact layer
is approximately 20 nm. Given that the lattice image is not
observed, the TiOx compact layer is considered to be amorphous by reason of the low temperature process (80
C).
A thick (100 nm) TiOx layer deposited via the same process
shows no indexable X-ray diraction (grazing incidence) peak
(see Fig. S1(a), ESI), supporting the formation of the amorphous-like TiOx layer. Energy dispersive X-ray spectroscopic
(EDS) mapping of each element demonstrates that the amorphous layer is composed of Ti, distinguishable from the In
detected ITO layer. To characterize the photovoltaic performance of the Lt-ALD-TiOx layer, two other TiOx compact electron collection layers, commonly used in dye-sensitized solar
cells and perovskite solar cells, were prepared by a conventional
solution process, at the same process temperature of 80
C. The
rst layer, denoted as Et-TiOx, was prepared using an ethanolbased solution containing titanium isopropoxide (TTIP),
distilled water, and diluted nitric acid. The other sample (Bt-

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Fig. 2 (a) Cross-sectional TEM (a-1 and a-2), scanning TEM (a-3) and
EDS mapping (a-4 and a-5) images of Lt-ALD-TiOx on the ITO
substrate. Scale bar: 100 nm (a-1), 10 nm (a-2 and a-3), and 25 nm (a-4
and a-5). (b) Average JV characteristics of the exible devices with
dierent TiOx layers. (c) TRPL trace at 770 nm with 670 nm excitation.
The TRPL trace could be clearly distinguished from the instrumental
response function. Average life times were convoluted to be 383 ns,
435 ns, and 537 ns respectively in the dierent TiOx layers. All the
convoluted parameters are listed in Table S2. See the ESI for details.
(d) Nyquist plots of each exible perovskite solar cell in the opencircuit state. The low Z region (red squared) is magnied in the inset.

TiOx) was fabricated from a butanol-based TTIP solution.12,14

The mixed halide perovskite layer on each TiOx layer has the
same crystal structure (Fig. S1(b), ESI). The photovoltaic
performance of the exible perovskite solar cells employing the
Lt-ALD-, Et-, and Bt-TiOx layers respectively on the PEN/ITO
substrates is presented in Fig. 2b. All device performances are
summarized in Table S1, ESI. It is notable that exible devices
with the Lt-ALD-TiOx layer achieve average characteristic values
of 18.4 mA cm2 Jsc, open circuit voltage (Voc) of 0.89 V, ll factor
(FF) of 0.58 and 9.42% PCE, thus exhibiting superior performance compared to devices employing Et- and Bt-TiOx (4.24%
and 1.22% PCE, respectively). To conrm the reproducibility of
the photovoltaic properties, we fabricated and characterized
100 devices. Histograms for the cell performance parameters of
all devices are presented in Fig. S2, ESI. Half of the solar cells
employing Lt-ALD-TiOx layers showed over 9% PCE at 1 sun
illumination, further, 35% of the cells had a PCE above 10%.
Moreover, the average Jsc was nearly 19 mA cm2, which is much
greater than in other compact electron collection layer based
solar cells. The device shows some hysteresis in the JV curves
during back and forward scans, but the average eciency of
those scans is similar to the saturated static PCE which is
obtained by applying the maximum power output potential (see
Fig. S3, ESI). The electron injection from CH3NH3PbI(3x)Clx
into the TiOx layer and the transport properties in the TiOx layer
had a great inuence on the higher photocurrent density of the
Lt-ALD-TiOx layer based solar cells.
Time-resolved photoluminescence (TRPL) characteristics of
the exible perovskite solar cells were measured to conrm the

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relaxation dynamics at the interfaces between each TiOx and

CH3NH3PbI(3x)Clx layers. The TRPL decays for each solar cell
were convoluted using three exponential functions and are
plotted in Fig. 2c. The convoluted parameters are listed in Table
S2, ESI. In the case of Lt-ALD-TiOx, the intensity weighed
average PL lifetime (383 ns) is faster than those of Et- and BtTiOx (435 and 537 ns, respectively). Since the faster electron
injection process from CH3NH3PbI(3x)Clx into TiOx is indispensable for PL quenching and shortening of the PL lifetime of
perovskite, it could be concluded that the Lt-ALD-TiOx sample
showed better solar cell performance due to the faster electron
injection process even though organic defects in Et- and Bt-TiOx
were not considered (see Fig. S4 and S5, ESI). Fig. 2d presents
the impedance spectra for each exible device, measured in the
frequency range of 102 Hz to 2 MHz at an open circuit potential
under 1 sun illumination. The Lt-ALD-TiOx layer based solar cell
exhibits the lowest ending resistance of the semicircles, indicating the smallest internal resistance among all of the dierent
solar cells. Although the exact impedance components have not
been interpreted so far, the radius of the impedance semicircles corresponds to the internal resistances of the TiOx/
CH3NH3PbI(3x)Clx interface, the TiOx layer itself and the ITO/
TiOx interface. Therefore, the exible perovskite solar cell containing a Lt-ALD-TiOx layer possesses superior charge injection
characteristics and low internal resistance. The origin of the
dierent charge collection properties is considered to be due to
imperfections such as residual chemicals, hydroxyl groups, and
Ti3+ ions, in comparison with other solar cells based on Et- and
Bt-TiOx layers. To investigate chemical conditions, such as
surface defects and residual organic compounds in each TiOx
layer, Fourier transform infrared (FT-IR) and X-ray photoelectron (XPS) spectra were considered (Fig. S4 and S5, ESI). The
FT-IR spectra for each TiOx layer clearly demonstrate that both
the solution based TiOx layers (Et- and Bt-TiOx) possess many
residual organics and hydroxyl groups, as evidenced by the
appearance of OH (32003400 cm1) and CH stretching
absorbance peaks (28502970 cm1). On the other hand, any
absorbance peaks corresponding to residual species are not
observed in the Lt-ALD-TiOx layer. The residual species in the
solution-based TiOx layers were due to the insucient baking
temperature. The XPS of Ti 2p3/2 and O 1s spectra, shown in
Fig. S5, ESI clearly exhibits the negligible presence of nonstoichiometric point defects such as Ti3+ ions and oxygen
vacancies in the Lt-ALD-TiOx layer.15 Both the solution based Etand Bt-TiOx layers contain relatively high amounts of Ti3+ ions
(457 eV) and hydroxyl groups (531 eV).16 Therefore, a large
amount of residual organics, hydroxyl groups, and point defects
in solution based TiOx layers may impede electron injection and
transport, thereby contributing to the deterioration of the
photovoltaic properties.
From the viewpoint of utilization of the exible perovskite
solar cells, operation under various light illumination conditions and the mechanical bending stability are of great importance. Systematic studies for light illumination and mechanical
bending stability have not been reported to date for the exible
perovskite solar cell. Fig. 3a shows the JV characteristics under
various light intensities ranging from 0.4 to 1 sun. Jsc decreases

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from 19.05 to 8.77 mA cm2 with decreasing light intensity.

However, even at 0.4 sun light illumination, Voc remains
between 0.9 and 0.82 V, thereby the PCE under 0.4 sun illumination is similar to that for 1 sun illumination. Relatively
constant Voc values under inadequate illumination conditions
are ascribed to the reduced charge recombination due to the
negligible surface and sub-bandgap states in the perovskite
layer.17 The JV curves at dierent light incidence angles (q),
from 0
to 45
are also shown in Fig. 3b. The dependence of the
photovoltaic property on the incidence light angle displays a
similar trend to that for light intensity. Voc also is almost
unchanged (from 0.9 to 0.88 V), although the normalized Jsc
decreases by 30%. But, the eciencies on the basis of the
eective active area, calculated by the multiplied active area and
cos(q), remain nearly constant in the tested angle range. Over 1
micrometer diusion length of the CH3NH3PbI(3x)Clx perovskite absorber and its 330 nm thick multilayered device structure led to excellent PCE consistency under substandard
eective light intensities.18
In order to verify the device stability against mechanical
bending of the exible device, a bending test was performed
taking into account the bending radii and cycles. The PCE of the
exible perovskite solar cells was measured aer they were bent

Fig. 3 (a) JV curves of the designed exible perovskite solar cells at

various light intensities ranging from 1 to 0.4 sun. The inset shows PCE
as a function of light intensity. (b) JV curves at various light incident
angles (q) from 0
to 45
. The inset shows the normalized eective
PCEs which are obtained using the eective active area. (c) Normalized
PCE measured after bending the substrate within a specied radius of
400 mm to 1 mm. The inset shows the real images attached on the
human neck, wrist, and nger corresponding to 400 nm, 10 nm and 4
nm bending radii, respectively. The error bar represents standard
deviation from 4 devices. (d) Normalized PCE of exible perovskite
devices as a function of bending cycles with dierent radii of 400, 10,
and 4 mm. The inset shows the real images taken during the bending
tests. The error bar represents the standard deviation from 4 devices.

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repeatedly with dierent radii of curvature. The PCE exhibited

no signicant decrease in eciency even with 1 mm of bending
radii, retaining 93% of the original PCE value (Fig. 3c). As the
next step, we evaluated the eects of mechanical bending on
device performance during 1000 consecutive bending cycles at
three dierent values of radii of curvature, i.e., at 400 mm, 10
mm, and 4 mm, respectively (R400, R10, and R4). The exible
perovskite solar cells revealed fairly promising mechanical
bending stability. Their performance was maintained without
any reduction in PCE during the 1000 bending cycles when the
device was bent with R400. The device with R10 also exhibited no
signicant decrease in PCE, retaining over 95% of its initial PCE
(Fig. 3d) without deterioration of the key photovoltaic properties such as Jsc, Voc, and ll factor (Fig. S6, ESI). For R4, 90% of
the initial PCE remained aer 25 cycles. However, aer 1000
cycles with R4, the PCE decreased by approximately 50%
compared with the initial eciency. These results demonstrated that the designed exible devices possess good bending
durability. However, under an acute bending radius such as R4,
cell performance is degraded due to the limitation of exibility
in the PEN/ITO substrate, corresponding well with the expectations reported by Kelly et al.9
To nd out the origin of fatigue, we prepared three kinds of
multilayer structures, i.e. PEN/ITO, PEN/ITO/TiOx/perovskite/
spiro-MeOTAD (full device only without Ag electrode), and PEN/
TiOx/perovskite/spiro-MeOTAD (full device without the ITO
layer and Ag electrode), respectively, and measured the change
in the electrical resistance of each structure with compressive
strain using the in situ resistance-measurement compressive
test system reported in a previous work (schematically shown in
Fig. S7a, ESI).19 Fig. 4a shows the relative resistance changes
(DR/R0 (%)) as a function of the bending cycles at the radius of
curvature R4. In the case of the PEN/ITO substrate, a drastic
increase in resistance is observed at the outset. When the TiOx/
perovskite/spiro-MeOTAD layers are deposited on just the PEN/
ITO substrate, the resistance is not changed until 250 cycles
have passed. Aer 260 bending cycles, the resistance is abruptly
increased, indicating that a fracture occurs inside the exible
device. In contrast, no abrupt resistance change of the exible
device without the ITO layer (PEN/TiOx/perovskite/spiro-MeOTAD) is observed for 300 cycles, only a gradual increase of 15%.
Therefore, we suggest that the performance degradation of
exible devices as a result of repeated mechanical bending can
be attributed to the fractures in the ITO layer, which induce an
abrupt increase in series resistance. The SEM images of the
ruptured PEN/ITO/TiOx/perovskite and PEN/TiOx/perovskite
samples aer 300 bending cycles at R4 clearly exhibit the origin
of the abrupt fracture in the exible solar cell. For more obvious
observations, the spiro-MeOTAD layer was omitted. Fig. 4b
shows that the large crack lines are formed perpendicular to the
bending direction, which is typical of the rupture behavior
displayed by an ITO layer coated onto a exible substrate
because of the dierence in Young's modulus between the ITO
and the exible substrate.20 The magnied image (Fig. 4b-1)
shows that the perovskite layer near the cracked ITO peels o.
Fig. 4b-2 demonstrates that the crack propagates in the region
of ITO and PEN/ITO/TiOx/perovskite, implying that the origin of

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4. Experimental

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4.1. Materials
Ethanol and 1-butanol were purchased from Dychemi and
Tokyo Chemical Industry, respectively. Nitric acid (HNO3) was
purchased from Junsei Chemical. Spiro-MeOTAD was
purchased from the Luminescence Technology Corp. The other
materials were purchased from Sigma-Aldrich. All materials
were used as received. CH3NH3I was prepared by synthesizing
according to a previously reported method.13
4.2. Formation of the compact electron collection layer

Fig. 4 (a) In situ resistance change (DR/R0 (%)) of the designed

multilayered structure (see Fig. S7bd, ESI, for the details of the
method). The lower panel shows the magnied plot of the upper panel
(yellow squared region). (b-1 and c-1) Low-magnication SEM images
of the designed multilayer structures (PEN/ITO/TiOx/perovskite and
PEN/TiOx/perovskite, respectively) after 300 bending cycles. Scale bar:
100 mm. Fig. (b-2), (b-3), (c-2), and (c-3) show magnied SEM images
corresponding to the green and red regions in Fig. 4b and c. Scale bars:
5 mm.

the crack is the ITO fracture. However, in the case of TiOx/

perovskite layers prepared on only PEN exible substrates
without ITO, the fracture and delamination are not observed
aer the bending test, indicating that the fatigue phenomenon
of the exible perovskite solar cells with a large bending radius
of R4 originates from the fracture in the brittle ITO layer. This
attests that the inorganicorganic halide perovskite materials
themselves possess excellent mechanical properties, which can
contribute to the realization of wearable solar cells, well beyond
the capabilities of current exible thin lm solar cells, once the
brittle ITO transparent conducting lms are substituted with
highly bendable conducting layers such as metal-transparent
conducting
lm
composite
layers,11
poly(3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS), or
nanostructured metal web layers.

3.

Conclusions

Highly ecient and decidedly bending durable perovskite solar

cells were fabricated in a low temperature process employing a
20 nm-thick, low-impurity, amorphous TiOx layer, thus
providing a promising approach to the development of practical
wearable perovskite solar cells. By studying the TiOx nanolayer
deposition technology, the layer qualities such as charge
transport property and mechanical durability can be enhanced
against bending or folding of the device. The observation of the
unaltered
PEN/TiOx
nanolayer/perovskite/spiro-MeOTAD
multilayer aer several bending tests signies that the bending
durability of the TiOx nanolayer-employed perovskite solar cells
can be improved if that of the transparent conducting substrate
is achieved.

920 | Energy Environ. Sci., 2015, 8, 916921

Lt-ALD-TiOx was deposited in a lab-scale plasma enhanced

atomic layer deposition (PEALD) system. The Lt-ALD-TiOx layer
was systematically investigated using titanium(IV) isopropoxide
(TTIP, UPChem) as the Ti precursor. For PEALD, high-purity O2
was employed as the oxygen source and high-purity Ar was used
as the TTIP carrier and purging gas; these gas ows were
controlled by a mass ow controller. Each deposition cycle
comprised 10 s of pre-purging, 3 s of TTIP source injection, and
nally 1 s of O2 ow. Aer O2 exposure plasma was enhanced at
300 W power, 10 s of Ar ow was followed by the post-purging
per cycle.
step. The growth rate of the Lt-ALD-TiOx lm was 0.5 A
Et- and Bt-TiOx layers were prepared via the solution process as
reported elsewhere.12,14 Each TiOx layer underwent spin coating
at 2000 rpm and 3000 rpm for 30 s, respectively, then was baked
at 80
C for 15 min and cooled down to room temperature.
4.3. Solar cell fabrication
The solar cells were fabricated on PEN/ITO substrates (Peccell,
PECP-IP, 13 U sq1), which were washed for 15 min each with
acetone, deionized water, and ethyl alcohol in an ultrasonic
bath. First, each TiOx compact electron collection layer (Et-, Btand Lt-ALD-TiOx) was coated onto PEN/ITO as mentioned
above. Aer deposition, the CH3NH3PbI(3x)Clx solution
(CH3NH3IPbCl2 3 : 1 molar ratio, 42 wt% in N,N-dimethylformamide (DMF)) was spin-coated at 2000 rpm for 45 s,
and then dried on a 95
C hot plate for 2 h. Subsequently, 25 ml
of a hole transport layer (80 mg of 2,20 ,7,70 -tetrakis(N,N-di-pmethoxyphenyl-amine)-9,90 -spirobiuorene (spiro-MeOTAD),
8.4 ml of 4-tert-butylpyridine, and 51.6 ml of bis (triuoromethane) sulfonamide lithium salt (Li-TFSI) solution (154 mg
ml1 in acetonitrile), the whole mixture was dissolved in 1 ml
chlorobenzene) was formed aer spin coating at 2500 rpm for
45 s. All processes were carried out under controlled atmospheric conditions and a humidity of <0.5 ppm. Finally, a 100
nm thick Ag electrode was deposited by thermal evaporation at
106 bar with a shadow mask.
4.4. Characterization
The cross-sectional structure and thickness of the exible
perovskite solar cells were characterized using eld-emission
scanning electron microscopy (FESEM, JSM-7600F, Jeol).
Cross-sectional TEM, STEM and EDS images (HRTEM, JEM2100F, JEOL) of the Lt-ALD-TiO x were obtained with the aid of

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a focused ion beam system (FIB system, Helios 650, FEI).

Crystallinity of the 100 nm thick Lt-ALD-TiOx layers deposited on a glass substrate was analyzed by using a Grazing
incidence X-ray diractometer (New D8 advance, Bruker)
with 1
incidence angle. The infrared spectra (IR) of the TiOx
layers were recorded on an FT-IR spectrometer (Nicolet 6700,
Thermo Scientic) in the range of 6004000 cm1 with a Ge
window. The chemical states of Ti and O in TiOx were
analyzed using X-ray photoelectron spectroscopy (XPS, Sigma
Probe, ThermoVG, UK). The currentvoltage characteristics
of the solar cells were measured under solar-simulated
light (Newport Oriel Solar 3A Class AAA, 64023A) with the
aid of a potentiostat (CHI 600D, CH Instruments). The AM
1.5G sun light (100 mA cm2) was calibrated using a
standard Si-solar cell (Oriel, VLSI standards). Solar light
intensity from 0.4 to 1 sun was adjusted using a standard Sisolar cell by tuning the light sensor current (Newport
Oriel digital exposure controller, Model 68945). Impedance
spectroscopy was carried out at an open-circuit state by
applying an AC amplitude signal of 5 mV and frequency
from 102 Hz to 2 MHz, using the same potentiostat under 1
sun light illumination. Time-resolved photoluminescence
was measured at 770 nm using a time-correlated single
photon counting method (FluoTime 200, PicoQuant
BmbH) employing a 670 nm diode laser (LDH-P-C-670,
PicoQuant BmbH) with a 715 nm long-pass lter to block any
scattered light. Excitation intensity was controlled using a
series of neutral density lters in order to avoid nonlinear
eects such as exciton-charge annihilation. In situ resistance
measurements of the designed multilayered lms (Fig. S7,
ESI) with R10 compressive bending were conducted using
a micro-compressive machine (MMT-500N, Shimadzu)
equipped with an electrically contactable jig. All tests were
conducted at 0.2 Hz bending frequency at room
temperature. As the lms were bent by compressive stress,
the electrical resistance was measured with an Agilent
34410A multimeter.

Acknowledgements
This work was supported by the Global Frontier R&D Program at
the Center for Multiscale Energy System (2012M3A6A7054861).
Also this work was supported by the National Research Foundation of Korea (NRF) funded by the Ministry of Education,
Science and Technology (2012M3A7B4049967 and NRF2014R1A4A1008474). Characterization of the crystal structure
and TEM analysis were supported by the Research Institute of
Advanced Materials (RIAM) and XPS analysis was supported by
the National Center for Inter-University Research Facilities
(NCIRF). Especially, this paper is dedicated to our late mentor,
Prof. Kug Sun Hong.

This journal is The Royal Society of Chemistry 2015

Energy & Environmental Science

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