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Nano Energy (2015) 11, 728–735

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanoenergy

RAPID COMMUNICATION

TiO2 nanotube arrays based flexible


perovskite solar cells with transparent carbon
nanotube electrode
Xiaoyan Wanga,1, Zhen Lia,1, Wenjing Xuc,
Sneha A. Kulkarnia, Sudip K. Batabyala, Sam Zhangd,
Anyuan Caoc, Lydia Helena Wonga,b,n

a
Energy Research Institute @ NTU (ERI@N), Nanyang Technological University, Techno Plaza,
50 Nanyang Drive, 637553 Singapore, Singapore
b
School of Materials Science and Engineering, Nanyang Technological University (NTU), Block N4.1,
Nanyang Avenue, 639798 Singapore, Singapore
c
Department of Materials Science and Engineering, College of Engineering, Peking University,
Beijing 100871, People’s Republic of China
d
School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue,
Singapore 639798, Singapore

Received 4 September 2014; received in revised form 5 November 2014; accepted 25 November 2014
Available online 9 December 2014

KEYWORDS Abstract
Perovskite solar cell; A solid-state, flexible solar cell based on titanium (Ti) foil/TiO2 nanotubes (TNTs) with organic–
Flexible; inorganic halide perovskite absorber and transparent carbon nanotube electrode is demon-
Titanium foil; strated. TNT arrays together with an inherent blocking layer were simultaneously formed on Ti
TiO2 nanotubes; foil during one-step anodization. TNT arrays serve as deposition scaffold and electron conductor
Carbon nanotubes;
for perovskite absorber. Transparent conductive carbon nanotube network is laminated on top
Anodization
of perovskite and serves as hole collector as well as transparent electrode for light illumination.
Under AM 1.5, 100 mW cm  2 illumination, power conversion efficiency of 8.31% has been
achieved, which is among the highest for TiO2 nanotube based flexible solar cells. Interestingly,
up to 100 mechanical bending cycles show little deterioration to the device performance,
demonstrating good flexibility of the Ti foil based perovskite solar cells. The Ti foil based

n
Corresponding author at: Energy Research Institute @ NTU (ERI@N), Nanyang Technological University, Techno Plaza, 50 Nanyang Drive,
637553 Singapore, Singapore.
E-mail address: lydiawong@ntu.edu.sg (L.H. Wong).
1
Equal contribution to the work.

http://dx.doi.org/10.1016/j.nanoen.2014.11.042
2211-2855/& 2014 Elsevier Ltd. All rights reserved.
TiO2 nanotube arrays based flexible perovskite solar cells with transparent carbon nanotube electrode 729

solid-state, flexible perovskite solar cells have great potential for applications in building
photovoltaics and wearable electronic devices.
& 2014 Elsevier Ltd. All rights reserved.

Introduction stainless steel fibers, yielding efficiency of 3.3% [14]. However,


solid-state flexible perovskite solar cells based on TiO2 nano-
As a new member of the next generation photovoltaic tubes have not been reported so far.
materials, organometal halide perovskite (e.g., CH3NH3PbI3, In Ti foil based perovskite devices, the opaque Ti foil
CH3NH3PbI3 xClx) was first demonstrated for efficient solar hinders the light absorption from the photoanode, so the
cells in 2009 [1], and soon become the most important device will not work using a conventional metallic counter
candidate to replace silicon, with low material cost and high electrode and therefore a transparent counter electrode is
efficiency. Owing to the high light absorption coefficient required. Transparent graphene [25] and carbon nanotubes
(1.5  104 cm  1 at 550 nm) [2] and long electron–hole diffu- (CNT) [20–23,26,27] have been successfully employed as the
sion length ( 100 nm for CH3NH3PbI3 [3,4] and 1 μm for counter electrode in DSSC devices. Recently, transparent CNT
CH3NH3PbI3 xClx [4]), perovskite solar cells have achieved a networks had been proved to be good hole conductor for
stunning success in a very short period in terms of efficiency, perovskite solar cells [14,28]. These works inspired our
i.e., from 4% in 2009 [1] to 10% in 2012 [5,6], then 15% in 2013 proposed flexible perovskite solar cell architecture with Ti
[7] and 19.3% at present [8]. foil as a working electrode, TNT as mesoporous layer for
The rapid and significant progress in perovskite solar cell perovskite loading and carbon nanotubes as hole conductor
triggers vigorous research interest, as well as commercialization and transparent electrode for light illumination. To date, it is
efforts. Flexibility is one of the development directions, which the first attempt of Ti metal foil substrate based flexible
can be beneficial for both production (with roll-to-roll appr- perovskite solar cell and a decent power conversion efficiency
oaches) and applications (easy installation on buildings and of 8.31% has been achieved.
integration on wearable devices). Flexible perovskite solar cells
have been reported by a few groups since end of 2013 [9–14]. Experimental
Polyethylene terephthalate (PET) coated by conductive indium
tin oxide (ITO) was adopted as the flexible substrates [9–13].
Fabrication of TiO2 nanotube arrays
PCBM and PEDOT:PSS were used as electron and hole transport
layers, yielding efficiencies of 4.5%  9.2% [9–12]. In addition,
Two kinds of Ti foils with different thicknesses (125 μm, 99.7%
low-temperature processed ZnO layer has also been used as
purity, Sigma-Aldrich; 25 μm, 99.98% purity, Sigma-Aldrich)
electron transport layer in flexible perovskite solar cells on PET
were employed. Prior to anodization, Ti foils were degreased
substrate [13]. The efficiency limitation of the flexible per-
ultrasonically in acetone, ethanol and deionized (DI) water for
ovskite solar cells on PET substrates may lie in the high series
20 min each and dried by air stream. Highly-ordered TiO2
resistance of ITO on PET substrates. In contrast, conductive
nanotube arrays were prepared by electrochemically anodiza-
metal foils possess better conductivity and mechanical robust-
tion at 20 V for 10 min at room temperature ( 20 1C). The
ness compared to PET substrates. Furthermore, metal substrate
anodizations were carried out with a two-electrode configura-
can tolerate high temperature treatment for sintering TiO2.
tion with Ti foil as the working electrode and platinum gauze
Among the electron transport materials used in perovskite solar
as the counter electrode. The electrolyte solution was ethy-
cell, TiO2 is still holding the efficiency record [8]. Meso-porous
lene glycol (extra pure, Merck) containing 0.3 wt% ammonium
TiO2 scaffold is also essential for solving the hysteresis problem
fluoride (98+%, Reagent, Sigma-Aldrich) and 2 vol% DI water.
of perovskite solar cells [15].
After anodization, the as-anodized TNT samples were rinsed in
Titanium (Ti) foils with TiO2 nanoparticles, nanotubes, or
DI water to remove the electrolyte and then dried in air. For
nanowires have been applied in flexible dye-sensitized solar
application in solar cells, the as-grown TNTs were subjected to
cells (DSSCs) as photoanodes [16–23]. In particular, TiO2 nano-
thermal annealing at 450 1C for 3 h to convert amorphous
tube (TNT) arrays can be grown on Ti foil by a facile elec-
titania into anatase phase. For better cell performance, the
trochemical anodization, which is a scaleable production
TNTs were also treated in 40 mM TiCl4 aqueous solution at
technique. However, flexible DSSCs with TNT arrays have shown
70 1C for 10 h and then rinsed with ethanol and DI water.
relatively poor performance with efficiencies lower than 4%
[17,19] and all these devices required liquid electrolyte, which
will cause sealing difficulty in large-scale production. To Synthesis of carbon nanotubes
replace dye absorber in DSSCs, efficient perovskite absorbers
will greatly increase the light absorption. More importantly, CNT network films were synthesized using the floating
the monolithic all-solid-state device structure for perovskite catalyst chemical vapor deposition (CVD) method using a
absorber will render the flexible solar cells better performance tube furnace [29]. Ferrocene (0.36 M) as catalyst and sulfur
stability during deformations. Recently Gao and co-authors (0.036 M) as growth promotion agent were dissolved in
reported perovskite sensitized liquid solar cells with TNTs on xylene to form a uniform precursor solution. The tempera-
rigid FTO glass [24]. Fiber shaped, flexible perovskite solar cells ture for CVD was set to 1150 1C. Then 2500 sccm Ar and
have also been demonstrated with TiO2 nanoparticle coated on 600 sccm H2 were introduced into the quartz tube as carrier
730 X. Wang et al.

gas. When the temperature and gas flow stabilized, the the gas flow to the end of the quartz tube with a temperature
precursor solution was injected into the quartz tube at a of 100–150 1C, where it was collected on a nickel foil.
preheating zone of the furnace with a temperature of Individual nanotubes assembled into bundles with diameter
180 1C. The precursor vaporized and was transported into of tens of nanometers and interweave to form a free standing
the center zone of the furnace by the gas flow for CNT CNT film.
growth. CNTs grew from the floating Fe catalyst in the carrier
gas flow. As shown in the Supporting materials (Fig. S1), the
Deposition of perovskite absorber
attained carbon nanotubes are mainly single and double-
walled carbon nanotubes with diameters between 1 and
2 nm. After growth, the CNTs formed an aerosol carried by Perovskite absorber was deposited on TNT arrays by a
sequential method. 1 M lead iodide (PbI2) were dissolved in
N,N-dimethylformamide overnight under stirring condition at
70 1C. The PbI2 solution was spin coated on TNTs at 6000 rpm
for 5 s, followed by drying on a hot plate at 70 1C for 30 min. In
order to convert PbI2 into CH3NH3PbI3, the PbI2 loaded TNT
samples were immersed in 8 mg mL  1 CH3NH3I solution in
2-propanol for 30 min. Subsequently, the samples were rinsed
with 2-propanol and then dried at 70 1C for 30 min again.

Assembly of perovskite solar cell device

CNT films on nickel foil was lifted off by a taped substrate and
transferred on the top of perovskite sensitized TNT/Ti foil
[24]. Several drops of toluene were used to wet CNT film for
Fig. 1 Schematic of solid-state perovskite solar cells based on improving the contact between CNTs and perovskite surface.
Ti foil/TiO2 nanotubes and carbon nanotubes. After toluene vaporization, a hole transport materials, namely

Fig. 2 (a) XRD patterns of the phase structures of TiO2 nanotubes/Ti, PbI2/TiO2 nanotubes/Ti and perovskite/TiO2 nanotubes/Ti. TiO2, PbI2
and perovskite peaks are marked by black box, circle and star respectively and the rest peaks from Ti substrate; (b) cross-sectional
morphology of perovskite/TiO2 nanotubes/Ti electrode; (c) tilted scanning electron image of CNT film covering partially on perovskite
surface; (d) magnified top morphology of CNT covered perovskite.
TiO2 nanotube arrays based flexible perovskite solar cells with transparent carbon nanotube electrode 731

spiro-OMeTAD (2,20 ,7,70 -tetrakis-(N,N-di-p-methoxyphenyla- and CNT networks composite with spiro-OMeTAD. Dense TNT
mined) 9,90 -spirobifluorene) in chlorobenzene (120 mg mL  1) arrays grown on Ti foil by electrochemical anodization serve both
were spin coated on CNTs covered substrate with a speed of as a scaffold for perovskite deposition and as an electron
4000 rpm for better hole collection. Prior to cell testing, collector. CNT network acts as hole collector and transparent
both Ti foil and CNT electrodes were soldered for better electrode. For better hole collection, the hole transport material
electrical contact. spiro-OMeTAD is infiltrated in carbon nanotubes network [28].
Light comes from CNT side, as indicated by arrow in Fig. 1. Since
Film characterization and cell testing Ti foil and CNT network are flexible materials, the integrated
solar cell device is expected to show good flexibility.
Highly ordered TiO2 nanotubes arrays are formed on Ti foil by
The phase structure of the TNT arrays, the deposited PbI2
electrochemical anodization [30,31]. The as-anodized TNTs are
and perovskite films were investigated by X-ray diffraction
amorphous in nature. To facilitate electron transport, amor-
(XRD, Bruker-AXS D8 Advance). The cross-sectional mor-
phous nanotubes are converted into anatase phase by thermal
phology of perovskite sensitized TNTs and top views of CNT
annealing at 450 1C for 3 h, as shown in the XRD patterns in
covered perovskite layers were examined by field-emission
Fig. 2(a). CH3NH3PbI3 perovskite are formed on TNT arrays by a
scanning electron microscope (FESEM, JSM-7600). The pho-
sequential deposition method [7]. In the first step, PbI2 was
tocurrent density–voltage (J–V) performance of the cell
deposited on nanotubes by spin coating, as revealed by the two
devices was characterized using solar simulator (San-EI
peaks at 12.72 1 and 39.52 1 in the XRD patterns Fig. 2(a)).
Electric, XEC-301S) under AM 1.5 with illumination from
Thereafter, soaking of PbI2 loaded nanotube substrates in
the CNT side. The illumination area was determined by the
CH3NH3I solution and subsequent drying process at 70 1C lead
black mask with an area of 0.16 cm2 (small area testing) and
to formation of CH3NH3PbI3. The characteristics XRD peaks of
0.36 cm2 (larger area for bending testing). Incident photon
CH3NH3PbI3 are indicated by black stars in Fig. 2(a). It is in well
to current conversion efficiency (IPCE) was determined
agreement with previous report [32].
using PVE300 (Bentham), with a dual xenon/quartz halogen
Cross-sectional morphology of perovskite loaded TiO2 nano-
light source, measured in DC mode and no bias light used.
tubes is presented in Fig. 2(b). The tube arrays formed on Ti foil
are 300 nm in length and 60 nm in diameter. A dense layer
Results and discussion of perovskite nanocrystals with a size of 100–400 nm completely
covers the nanotubes. The flexible CNT network is transferred
The cell configuration is shown in Fig. 1. From bottom to top in on top of the perovskite layer as the counter electrode, as
sequence are Ti foil, TNT arrays loaded with perovskite absorber shown in the tilted SEM image of Fig. 2(c). The CNT transfer

Fig. 3 (a) Characteristic photocurrent–voltage curves of TNT and CNT based perovskite solar cells with different Ti foil thickness
and with/without TiCl4 treatment; (b) IPCE of 25-μm-thick Ti based perovskite solar cells with/without TiCl4 treatment. The table
summarizes performance parameters with standard deviations calculated from different batches of devices fabricated under
identical fabrication conditions, together with the attained best value shown in brackets.
732 X. Wang et al.

procedure is described in previous report [28]. The CNT film is (125 μm and 25 μm) were used in perovskite solar cell
highly transparent with transmittance between 60% and 80% all fabrication. For both thick and thin Ti foil based perovskite
over the CH3NH3PbI3 absorption wavelength range from 300 to devices, TiCl4 treatment was employed to improve the
800 nm (see Fig. S2 in Supporting information). The CNT photovoltaic performance. TiCl4 treatment has been widely
network is closely adhered to the perovskite by van der Waal used in dye-sensitized solar cells [36–38] and perovskite
force. From the magnified top morphology of CNT/perovskite in solar cells [5,7,28]. It fills the voids and cracks in TiO2
Fig. 2(d), it shows that the bundled CNT networks are sparse blocking layer and therefore decreases recombination in
with pores for light transmittance. In order to enhance hole solar cells. Fig. 3 shows the device performances of the
collection in perovskite solar cells, spiro-OMeTAD are infiltrated TNT/CNT perovskite solar cells with different Ti foil thick-
into CNT networks by spin coating [28]. nesses and with/without TiCl4 treatment. The combined
Noticeably, there is a very thin TiO2 compact layer J–V curves are presented in Fig. 3(a) and the corresponding
formed between the TNT arrays and Ti foil during anodiza- photovoltaic parameters are summarized in the table. Solar
tion (Fig. 2(b)) [33–35]. The simultaneous anodic formation cells fabricated on 25 μm Ti foil exhibited higher photo-
of the TiO2 blocking layer and nanotube scaffold has great voltage (0.83 vs. 0.70 V for non-TiCl4-treated tubes; 0.99 vs.
advantages. The one-step anodization exempts the complex 0.78 V for TiCl4-treated tubes) and improved fill factor (0.63
fabrication process of sequential depositing blocking layer vs. 0.62 for non-TiCl4-treated tubes; 0.68 vs. 0.62 for TiCl4-
and meso-porous TiO2 layers. It is also highly controllable treated tubes), in comparison to 125 μm Ti foil based solar
with the ability of forming uniform coating over large area, cells. The Voc and fill factor improvement may be ascribed
which is desirable for large scale production. to the smaller surface roughness of the thinner Ti foil, as
The thickness of Ti foil affects the device flexibility. shown in Fig. S3 of the Supporting information. It is
Herein, two kinds of Ti foils with different thicknesses presumable that the smoother Ti surface improves the

Fig. 4 (a) Photograph of Ti foil/TNT and CNT based flexible perovskite solar cells; (b) combined J–V curves of flexible device with
different bending cycles; (c) plot of photovoltaic parameters as a function of bending cycles.
TiO2 nanotube arrays based flexible perovskite solar cells with transparent carbon nanotube electrode 733

flatness of perovskite layer and reduces the unfavorable perovskite solar cells on Ti metal foil substrate. The Ti foil/
current shunting, thus in return increases the Voc and fill TNTs act as scaffold for perovskite loading and electron
factor. transport layer, while the transparent CNT top electrode
As evident in Fig. 3(a), TiCl4 treatment after anodization acts as hole collecting layer and light transmission. With
is beneficial to enhance all photovoltaic parameters, includ- 25 μm Ti foil and TiCl4 treatment to TiO2 nanotube arrays,
ing photocurrent, Voc, fill factor and thus power conversion power conversion efficiency up to 8.31% has been achieved.
efficiency. Notably, Voc is greatly improved after TiCl4 The solar cells on Ti foil maintain good performance after
treatment (0.78 vs. 0.70 V for 125-μm-thick Ti; 0.99 vs. 100 mechanical bending cycles, indicating their excellent
0.83 V for 25-μm-thick Ti). It can be ascribed to the flexibility. Considering the high efficiency, good flexibility
reduction of recombination sites by the newly formed and simple fabrication technique, Ti foil/TNTs based flexible
nanoparticles from TiCl4 treatment. The slight improvement perovskite solar cells holds a promising future for roof-top
of photocurrent can be also shown from the IPCE of photovoltaics and power sources for wearable devices.
perovskite solar cells with/without TiCl4 treatment, as
displayed in Fig. 3(b). From 400 nm to 700 nm, TiCl4 treated
TNTs exhibit higher IPCE, which indicates a higher charge Acknowledgement
separation efficiency thus results in photocurrent increase.
Noticeably, the IPCE is relatively low at wavelength Funding from National Research Foundation (NRF), Singa-
between 300 and 400 nm due to the strong light absorption pore, is acknowledged through CRP Award no. NRF-CRP4-
of spiro-OMeTAD in this wavelength region (Fig. S2 in the 2008-03 and the Singapore-Berkeley Research Initiative for
Supporting information). Further improvement of photocur- Sustainable Energy (SinBeRISE) CREATE program. X. Wang
rent can be expected by adapting HTM materials with better wishes to thank the support from the World Future Founda-
transparency. For the 25-μm-thick Ti foils, the best per- tion (WFF) as a recipient for the 2014 WFF PhD Prize.
ovskite solar cells with TiCl4 treatment yield efficiency of
8.31%. The obtained efficiency is among the highest
reported for flexible perovskite solar cells [10–13]. Appendix A. Supporting information
Besides photovoltaic performance, tolerance to mechan-
ical bending is another important factor of consideration for
Supplementary data associated with this article can be
flexible perovskite solar cells. A photograph of flexible TNT/
found in the online version at http://dx.doi.org/10.1016/
CNT perovskite solar cell is shown in Fig. 4(a). The 25-μm-
j.nanoen.2014.11.042.
thick Ti foil based devices were used to investigate solar cell
flexibility. The solar cell with length of 2.5 cm was bended
to a bending radius of 0.75 cm by mechanical force up to
100 cycles. The dependence of the device performances on
bending cycles is presented in Fig. 4(b and c). J–V curves in References
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the Postdoctoral Research work in National
D. LeClere, G.E. Thompson, J.M. Macak, P. Schmuki, Adv.
University of Singapore and in Nanyang
Mater. 20 (2008) 4135–4139.
Technological University he joined as a
[34] A. Ghicov, P. Schmuki, Chem. Commun. (2009) 2791–2808.
senior scientist in Energy Research Institute
[35] Q.A.S. Nguyen, Y.V. Bhargava, V.R. Radmilovic, T.M. Devine,
in NTU (ERI@N). His research work is in
Electrochim. Acta 54 (2009) 4340–4344.
synthesis and application of nanostructured
[36] P. Roy, D. Kim, I. Paramasivam, P. Schmuki, Electrochem.
materials for energy harvesting and storage.
Commun. 11 (2009) 1001–1004.
Solution processing of inorganic and hybrid
[37] D. Kim, P. Roy, K. Lee, P. Schmuki, Electrochem. Commun. 12
materials for device fabrication is of his special interest. His
(2010) 574–578.
research focus is on the development of absorber materials and
[38] X. Wang, L. Sun, S. Zhang, X. Wang, ACS Appl. Mater.
electrode materials for photovoltaic’s devices.
Interfaces (2014) 1361–1365.

Prof. Sam Zhang received Ph.D. degree in


Ceramics in 1991 from The University of
Dr. Xiaoyan Wang received her Bachelor and Wisconsin-Madison, USA and is a tenured full
Master degree in Materials Science and Engi- professor (since 2006) at School of Mechanical
neering from BeiHang University, Beijing, in and Aerospace Engineering, NTU. He serves as
2006 and 2009, respectively. In February Editor-in-Chief for Nanoscience and Nano-
2014, she received her PhD degree from technology Letters and Principal Editor for
Nanyang Technological University, Singapore. Journal of Materials Research (USA). He has
She won the 2014 “World Future Foundation” been in processing and characterization of
outstanding Ph.D thesis prize. She is currently nanocomposite thin films and coatings for
a research fellow in Energy Research Institute more than 20 years and has published more
@ NTU (ERI@N). She is now working on CIGS than 280 peer reviewed international papers,
thin film solar cell and organic–inorganic 12 books, 20 book chapters and guest-edited more than 10 Journal
perovskite solar cells. volumes. His papers have been cited 4532 times and his h-index is 37.
TiO2 nanotube arrays based flexible perovskite solar cells with transparent carbon nanotube electrode 735

Prof. Anyuan Cao received his PhD degree Prof. Lydia Helena Wong received B. Appl.
in Mechanical Engineering from Tsinghua Sci. with Honors and Ph.D. in Materials
University. He has spent 3 years in Rensse- Science and Engineering from NTU. After-
laer Polytechnic Institute as a postdoc wards, she worked as a Senior Engineer at
researcher, and 3 years in the University of the Technology Development Department of
Hawaii at Manoa as an assistant professor. Chartered Semiconductor Manufacturing
He is currently a professor in the Depart- (Global Foundries) and was a Visiting Scien-
ment of Materials Science and Engineering, tist at Stanford University developing
College of Engineering, Peking University. organic photovoltaic materials at the
His research areas include controlled synth- Department of Chemical Engineering. She
esis of macroscopic structures based on is currently an Assistant Professor at the
carbon nanotubes and graphene, self- School of Materials Science and Engineer-
assembly, nanocomposites, nanoelectronics, energy and environ- ing, NTU. Her research group currently focuses on the investigation
mental applications. He has published over 100 peer-reviewed of non-toxic and abundant metal oxides and chalcopyrite materials
journal papers. for solar harvesting applications.

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