Solar Energy Materials & Solar Cells 159 (2017) 143–150

Contents lists available at ScienceDirect

Solar Energy Materials & Solar Cells

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

Improvement of photovoltaic performance of perovskite solar cells

with a ZnO/Zn2SnO4 composite compact layer
Weixin Li a,b,c, Qinghui Jiang a,b, Junyou Yang a,b,n, Yubo Luo a,b, Xin Li a,b, Yaru Hou a,b,
Shuqin Zhou a,b
a
State Key Laboratory of Materials Processing and Die & Mould Technology, Huazhong University of Science and Technology, No. 1037 Luoyu Road, Wuhan
430074, PR China
b
Shenzhen Institute of Huazhong University of Science and Technology, PR China
c
Hubei Province Key Laboratory of Refractories and Ceramics & Ministry-Province Jointly-Constructed Cultivation Base for State Key Laboratory, Wuhan
University of Science and Technology, No. 947 Heping Avenue, Wuhan 430081, PR China

art ic l e i nf o a b s t r a c t

Article history: In this study, ZnO/Zn2SnO4 (ZSO) composite is synthesized as a promising alternative compact layer to
Received 27 May 2016 TiO2 by spray pyrolysis method. Owing to the ZnO/ZSO composite possesses higher carrier mobility and
Received in revised form suitable band gap structure, it will behave well in the application of solar cells. The characterization
15 July 2016
results show that the ZnO/ZSO composite compact layer manifests better optical transmittance, en-
Accepted 9 September 2016
Available online 15 September 2016
hanced electrons collective efficiency and superior electrical conductivity. Consequently, the corre-
sponding photo-current is improved effectively when compared with that of TiO2 compact layer. The
Keywords: optimum efficiency of perovskite solar cell based on the ZnO/ZSO composite compact layer reaches
Perovskite 12.03% at AM 1.5 solar light of 100 mW cm
2, which is 18% higher than that of perovskite solar cell based
Compact layer
on the TiO2 compact layer.
Solar cell
& 2016 Published by Elsevier B.V.

1. Introduction electron in perovskite is excited from the valence band to the

Due to their intrinsic optimum band gap of 1.55 eV, high ab-
sorption coefficient (4104 cm
1), long hole-electron diffusion
length (100–1000 nm) and superior ambipolar carrier transport
properties, the organic/inorganic hybrid perovskite materials have
been proved to be excellent light energy harvesters [1–4]. Since
the organic/inorganic hybrid perovskite solar cell (PSC) was re-
ported by Miyasaka [5] in 2009, a research boom of PSC has up
surged around the world, and a power conversion efficiency ex-
ceeding 20% has been reported recently [6–8]. Typically, a per-
ovskite solar cell is assembled like a sandwich structure with solid
light absorber layer between efficient electron selective contacts
and hole transporting materials (HTM) [9,10]. According to the cell
structure, the perovskite solar cells can be classified into two
types, namely the mesoporous and the planar heterojunction solar
devices, both of which could be fabricated via single step, two
sequential and vapor deposition methods [11–13].
The general working mechanism of PSC based on mesoporous
TiO2 is similar to that of dye-sensitized solar cells. Namely, an
n
Corresponding author at: State Key Laboratory of Materials Processing and Die
& Mould Technology, Huazhong University of Science and Technology, No. 1037
Luoyu Road, Wuhan 430074, PR China.
E-mail address: jyyang@mail.hust.edu.cn (J. Yang).
conduction band under solar irradiance, followed by the injection
of the electron into TiO2 and hole into the HTM layer with the
circuit completed by transporting the electron in TiO2 via the ex-
ternal circuit to recombine with holes at the counter electrode
[14]. Based on the mechanism stated above, the compact electron
transport layer plays a critical role in facilitating electrons trans-
portation and suppressing recombination between the FTO and
HTM layer [15–17]. In this regard, tremendous efforts have been
made on exploiting suitable compact layers (CLs) for effective
charge separation and carrier extraction [18]. Choi and Song et al.
have studied the relationship between the morphology of a con-
ventional TiO2 layer on the FTO and the electron transport prop-
erties [19].
However, the TiO2 CL commonly used in PSC behaves poor in
electron extraction owing to its relatively low carrier mobility [20].
Hence, semiconductors with larger carrier mobility have also been
employed as the alternative CLs like SnO2 and ZnO [21–23]. Dong
et al. [24] reported a higher short-circuit in the PSC based on a
SnO2 CL fabricated by the sol-gel method than that of the PSC
based on a TiO2 CL. Liu et al. [12] applied a ZnO nanoparticle film
as the CL in the PSC and achieved the efficiency of 15.7%. Besides,
Zn2SnO4 (ZSO) as a spinel structure compound has always been
adopted as a transport-conducting oxide for optoelectronic appli-
cations due to its high stability and electron mobility [25].

http://dx.doi.org/10.1016/j.solmat.2016.09.007
0927-0248/& 2016 Published by Elsevier B.V.
144 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150
Actually, owing to its higher charge injection and electron diffu-
sion efficiency than that of TiO2 [26], ZSO is also a very promising
alternative to the TiO2 CL in PSC. Recently, Oh et al. [27] adopted
the spin-coating method to fabricate a ZSO CL and the PSC based
on the 300 nm thick mesoporous ZSO layer manifests a PCE of 7%.
Given that composite electrodes combine two semiconductors into
one thus they can compensate each other, electrodes such as TiO2-
ZnO, SnO2-TiO2, and ZnO-Zn2SnO4 have been applied in dye-sen-
sitized solar cells and quantum dots sensitized solar cells to en-
hance the photovoltaic performance [28]. Thereby, a composite CL,
which has rarely been adopted in PSC, would also be beneficial to
its photovoltaic performance.
In this scenario, we fabricated a composite ZnO/ZSO CL through
a facile spray pyrolysis route to replace the traditional TiO2 CL in
PSCs in this paper. Considering ZnO possesses a superior electronic
mobility of 205–300 cm2 V s
1 than that of ZSO with 10–
15 cm2 V s
1 [29,30], ZnO can effectively facilitate the transpor-
tation of electrons. On the other side, the inherent larger band gap
with higher conduction band edge of ZSO benefits for restricting
the recombination process and improving the open-circuit voltage.
Given that the energy band structure is similar with that of TiO2
and the mobility of TiO2 is less than 1 cm2 V
1 S
1 [31,32], it is
expected that the ZnO/ZSO composite CL may exhibit a superior
photovoltaic performance in contrast with that based on a con-
ventional TiO2 CL. The effects of the composite ZnO/ZSO CL on the
performance of PSCs have been investigated, and the electron
dynamics of the ZnO/ZSO-based perovskite solar cells have been
compared with the conventional TiO2-based counterpart. The re-
sults demonstrate that the PSC based on composite ZnO/ZSO CL
manifests better photovoltaic performance than that of the PSC
based on TiO2 CL.
2. Experimental section
2.1. Reagents and materials
Lead iodide (99.999% trace metals basis) and N,N-dimethyl
formamide (DMF) were purchased from Alfa Aesar. Li-bis-(tri-
fluoromethanesulfonyl) imide (Li-TFSI), 4-tert-butylpyridine (TBP)
and methylamine (33 wt% in absolute ethanol) were purchased
from Aladdin Reagents. Hydroiodic acid (57 wt% in water, 99.99%)
was purchased from Sigma-Aldrich. Titanium (IV) acetylacetonate
(75% in isopropanol) was purchased from TCI in Japan. Spiro-
OMeTAD (2,2’,7,7’-tetrakis(N,N-di-4-methoxyphenylamino)-9,9’-
spriobifluorene, 99.0%) and TiO2 pastes were obtained from Wu-
han Jingge Technology of Solar Cell Co., Ltd. Isopropanol, n-butyl
alcohol, ZnCl2, SnCl4, zinc powder, ethanol were purchased from
Sinopharm Chemical Reagent Co., Ltd. (China). All of the used re-
agents were analytical grade without further purification.
2.2. Synthesis of TiO2 and ZnO/ZSO compact layer on transparent
conducting substrate
Fluorine-doped SnO2-coated transparent conduction glass
substrates (FTO) were etched with metallic Zn powder and HCl
(2 M), then cleaned with ethanol, acetone and deionized water
under an ultrasonic condition for 30 min, lastly dried in an oven.
To remove the organic impurities, the FTO substrates were an-
nealed at 500 °C for 30 min. Different compact layers were de-
posited on each FTO substrate using the spray-pyrolysis method.
For TiO2 compact layer, a solution containing 100 μL titanium (IV)
acetylacetonate in 1 mL n-butyl alcohol was sprayed on the
cleaned FTO substrates which were placed on a hot plate with
450 °C. After spraying, the compact layer was kept at 450 °C for
30 min on the hot plate. To deposit the ZnO/ZSO layer, solution
containing ZnCl2 and SnCl4 (mole ratio of Zn/Sn is 2) in iso-
propanol was adopted with the same spray-pyrolysis process of
synthesis TiO2 layer. Lastly, the obtained ZnO/ZSO layer was an-
nealed at 600 °C for 30 min under flow N2 atmosphere. For TiO2
mesoporous layer, a commercial TiO2 paste (20 nm) was diluted
with ethanol (1:3 wt ratio), and spin-coated on the CL coated FTO
substrate, followed by annealing at 500 °C for 30 min under an
ambient atmosphere.
2.3. Device fabrication
CH3NH3I was synthesized as described earlier [33] via reacting
30 mL of methylamine and 32.3 mL of hydroiodic acid in a 250 mL
round bottom flask at 0 °C for 2 h with continuously stirring. The
precipitate was recovered by putting the solution in the vacuum
oven under 60 °C for 6 h. The obtained raw product of methy-
lammonium iodide (CH3NH3I) was washed with diethylether until
the powder become white. After filtration, the solids were col-
lected and dried at 60 °C in a vacuum oven for 24 h. The synthesis
of CH3NH3PbI3 on the mesoporous TiO2 surface was carried out by
a two-step deposition method [11] and we did some modification
to optimize the morphology of CH3NH3PbI3. At the beginning, a
460 mg mL
1 PbI2 solution dissolved in N,N-dimethyl formamide
(DMF) was dropped onto the TiO2 film and spin coated at
3000 rpm for 60 s, followed by annealing at 70 °C for 30 min. In
the second step, the cell was dipped into a beaker containing
10 mg mL
1 CH3NH3I solution (dissolved in isopropanol) and then
the whole beaker was put on the hot plate at 70 °C for 10 min.
After that, the film was taken out and washed with isopropanol
followed by annealing at 70 °C for another 30 min. During the
dipping and annealing, CH3NH3PbI3 was formed, as indicated by
the dark brown color of the electrode. Subsequently, the spir-
oOMeTAD based hole transporting layer which contained 72.3 mg
of spiroOMeTAD, 28.8 μL of 4-tert-butylpyridine and 17.5 μL of Li-
bis-(tri-fluoromethanesulfonyl) imide (Li-TFSI) solution (520 mg of
Li-TFSI in 1 mL of acetonitrile), all dissolved in 1 mL of chlor-
obenzene, was deposited onto the perovskite-coated substrate by
spin coating at 3000 rpm for 60 s. Finally, 80 nm of gold was de-
posited through thermal evaporation as the counter electrode. The
cells were characterized under an Air Mass 1.5 Global (AM 1.5 G)
solar simulator with an irradiation intensity of 100 mW cm
2 and
the active area was 0.1 cm2.
2.4. Characterization
X-ray diffraction (XRD) patterns were recorded with a Philip
X’pert X-ray diffractometer equipped with Cu Kα irradiation (λ
1.5406 Å). The morphology were observed through a Nova Nano-
SEM 450 field emission scanning electron microscope (FE-SEM).
The square average roughness of CL was characterized by the
atomic force microscope (AFM, SPM9700, Shimadzu). UV–vis light
absorption spectra were recorded with a Lambda 35 (Perkin El-
mer) ultraviolet visible (UV–vis) spectrophotometer. The photo-
luminescence spectrum was obtained by a VG Multilab 2000 X-ray
photoelectron spectroscopy (XPS). The photovoltaic measure-
ments of the PSCs were performed with the aid of a CHI604D
electrochemical workstation under a simulated sunlight (Chang
Tuo, incident light intensity 100 mW cm
2). The internal im-
pedance of the PSCs were measured by electrochemical im-
pedance spectroscopy (EIS) using an Autolab PGSTAT 30 equip-
ment (Eco Chemie B.V., Utrecht, The Netherlands) with the fre-
quency ranging from 0.01 Hz to 100 kHz at room temperature
under dark condition with the applied bias voltage and AC am-
plitude of 0.8 V and 10 mV, respectively.
 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150
3. Results and discussion
Fig. 1(a) and (b) shows the XRD patterns of CH3NH3PbI3
(MAPbI3) and ZnO/ZSO, respectively. In Fig. 1(a), the strong dif-
fraction peak located at 14.0°, 28.3°, 31.7° correspond well to the
(110), (220), (312) crystal planes of CH3NH3PbI3, while the small
diffraction peak at 12.7° belongs to that of PbI2, indicating that
most of PbI2 has converted into the tetragonal CH3NH3PbI3 and
only a small amount of PbI2 is remained or decomposed in the
two-step deposition process. This phenomenon usually appears in
the fabrication process of MAPbI3 via the two-step deposition and
is believed to have a passivation function [34]. The characteristic
diffraction peaks of hexagonal ZnO (JCPDS card No. 01-079-0206)
and cubic ZSO (JCPDS card No. 01-074-2184) can be detected in
Fig. 1(b).
To further confirm the phase composition of ZnO/ZSO CL, the
ZnO/ZSO CL was characterized by X-ray photoelectron spectroscopy
(XPS) and the results are shown in Fig. 2. Fig. 2(a) and (b) shows the
O 1s and Sn 3d5/2 spectra of bare FTO. Fig. 2(c)–(e) shows the spectra
of O 1s, Sn 3d5/2 and Zn 2p3/2 of ZnO/ZSO CL, respectively. When
compared with Fig. 2(a), the peak of O 1s in Fig. 2(c) moves toward to
lower binding energy, which means that the chemical environment
around O element is changed after the deposition of ZnO/ZSO CL. The
O element is not only bonded with Sn but also bonded with Zn. The
binding energy peak at 530.29 eV in Fig. 2(c) is in accordance with
the peak of O 1s of metal oxide (530.7 eV), while the peak at
531.79 eV is ascribed to the weakly bound oxygen on the surface of
the sample [35]. It can be seen that the peak of Sn 3d5/2 shifts to
lower binding energy by comparing Fig. 2(b) with (d). Taking the
asymmetry of Sn 3d5/2 peak into consideration and applying the
Gaussian fitting, we obtained two peaks at 486.05 eV and 486.56 eV,
suggesting that Sn4 þ ions occupy different lattice positions owing to
different chemical environment. Fig. 2(e) illustrates the inner elec-
tron energy spectrum of Zn. After the peak-differentiating and imi-
tating, two peaks at 1021.38 eV and 1022.00 eV are obtained. The
peak at 1021.38 eV is identified as the characteristic binding energy
peak of Zn 2p3/2 in ZnO and the peak at 1022.00 eV corresponds to
the electron energy spectrum peak of Zn 2p3/2 in ZSO [36]. The re-
sults of XPS confirm that the CL is composed by ZnO and ZSO as is
verified by XRD.
Fig. 3(a)–(c) shows the top images of the bare FTO, TiO2 CL
coated and ZnO/ZSO CL coated FTO substrate, respectively. It can
be seen that the surface of bare FTO substrate consists of many
smooth SnO2 particles. After deposited with TiO2 or ZnO/ZSO, the
surface of FTO substrate is covered by numerous nanoparticles and
formed a thin compact layer (seen in Fig. 3(b) and (c)).
The cross-sectional images of TiO2 CLs and ZnO/ZSO CLs are
shown in Fig. 4 to further confirm the morphology of CLs. Fig. 4(a–
e) are the TiO2 CLs with 40, 60, 80, 100, 120 nm and Fig. 4(f–h) are
Fig. 1. XRD patterns of (a) CH3NH3PbI3 and (b) ZnO/ZSO CL.
145
the ZnO/ZSO CLs with 15, 35, 55, 75, 95 nm, respectively. As it is
shown in the cross-sectional images, on the surface of the FTO
substrates, a layer of compact nanoparticles exists. Moreover, dif-
ferent thicknesses can be obtained via controlling the number of
spraying cycles. Through the AFM characterization, the square
average roughness of TiO2 and ZnO/ZSO CLs with different thick-
ness are obtained and listed in Table 1. The roughness increases
with the thickness. It is understandable that continuous spray
pyrolysis will supply crystal nucleus thus leading to the growth
and stack of nanoparticles. The smoother surface is believed to be
beneficial to electric contact between the mesoporous layer and
the CL [37].
Fig. 5 shows the top-view images of the perovskite (MAPbI3)
deposited on the TiO2 porous film. It can be seen that the MAPbI3
crystal particles are compactly and homogenously covered on the
surface of TiO2. Fig. 6(a) and (b) give the cross-sectional images of
PSCs based on the TiO2 and ZnO/ZSO CLs, respectively. To in-
vestigate the influence of CLs, the structure above the CL was
fabricated by the same method. The counter electrode of Au is
about 80 nm, the HTM layer is around 345 nm and the TiO2 me-
soporous layer is about 365 nm. As shown in Fig. 6, no crack or
pinhole can be seen in the cross-sectional images indicating that
the morphology of perovskite solar cell is acceptable.
To study the impacts of CLs on the performance of PSCs, Fig. 7
displays the optical transmittance spectra of TiO2 CLs and ZnO/ZSO
CLs with different thickness. As the refractive index of both ZnO
and ZSO are lower than that of TiO2, the optical transmittance of
ZnO/ZSO CL is better than that of TiO2 CL suggesting that the ZnO/
ZSO CLs possess better optical property. That is to say, for the ZnO/
ZSO CL, more photon flux can reach the CH3NH3PbI3 layer for
photo-generate carriers. Besides, it is understandable that the
transmittance decreases along with the increase of the CLs thick-
ness. It is worthwhile to note that when the ZnO/ZSO CL is very
thin, its transmittance is even higher than that of the bare FTO
substrate. Compared with bare FTO substrate, the existence of very
thin layer of nanoparticles may change the incident light pathway
thus reducing the refraction loss and allowing more light be de-
tected by the UV–vis device. Besides, ZSO is a wide-band semi-
conductor with low extinction coefficient and possesses a lower
refractive index (1.37) than that of SiO2 (1.5) [38] leading to the
better transmittance property. Based on the above analysis, the
extremely thin composite ZnO/ZSO layer manifests impressive
transmittance.
Fig. 8 shows the photovoltaic performance of PSCs based on
different thickness of TiO2 CLs. The corresponding photovoltaic
parameters are summarized in Table 2. Initially, the power con-
version efficiency (PCE) of perovskite solar cells increases with the
thickness of TiO2 CLs. When the thickness of TiO2 CL is 100 nm, the
optimum performance is achieved with the PCE of 10.14% and the
146 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150

Fig. 2. XPS spectrum of FTO (a) O 1s, (b) Sn 3d5/2 and ZnO/ZSO (c) O 1s, (d) Sn 3d, (e) Zn 2p3/2.

Fig. 3. SEM images of (a) bare FTO substrate, (b) TiO2 CL coated FTO substrate, (c) ZnO/ZSO CL coated FTO substrate.

Fig. 4. SEM images of cross-section (a–e) compact layer of TiO2 with different thickness; (f–h) compact layer of ZnO/ZSO with different thickness.

short-circuit current of 16.77 mA cm
2. Further increasing the the photovoltaic performance of perovskite solar cells increase
thickness of TiO2 CLs will lead to the decline of PCE. Fig. 9 is the with the thickness of ZnO/ZSO CLs at first and then degrade. The
photovoltaic parameters comparison of perovskite solar cells maximum PCE of 12.03% is achieved when the ZnO/ZSO CL is
based on different thickness of TiO2 CLs. 75 nm with the corresponding short-circuit reaching
Fig. 10 shows the photovoltaic performance of PSCs based on 19.71 mA cm
2. Compared with the TiO2 CLs, the ZnO/ZSO CLs
different thickness of ZnO/ZSO CLs. The corresponding photo- improve the short-circuit current of PSCs more efficiently, thus
voltaic parameters are listed in Table 3. Similar with the TiO2 CLs, enhancing the photovoltaic performance.
 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150 147

Table 1
Root mean square roughness (RMS) for TiO2 and ZnO/ZSO compact layers with
different thickness.

Thickness (nm) 40 60 80 100 120

TiO2 (nm) 14.19 16.15 18.64 20.40 22.72
Thickness (nm) 15 35 55 75 95
ZnO/ZSO (nm) 15.04 17.16 19.72 21.49 23.85

Fig. 8. I–V curves of perovskite solar cells based on different thickness of TiO2 CLs.

Table 2
Photovoltaic parameters of the best perovskite solar cells based on different
thickness of TiO2 CLs.

TiO2 (nm) Jsc (mA cm
2) Voc (V) FF η (%)

40 14.39 1.012 0.53 7.49

Fig. 5. The top-view SEM images of the perovskite (MAPbI3) on the TiO2 porous 60 14.91 1.023 0.57 8.64
film. 80 15.74 1.029 0.58 9.40
100 16.77 1.050 0.58 10.14
120 16.15 1.029 0.58 9.61

TiO2. Fig. 11(a) illustrates the photoluminescence (PL) quenching

Fig. 6. Device structure of the perovskite solar cells based on (a) TiO2 and (b) ZnO/
ZSO compact layer.
To gain more insight into the fundamental reason why the com-
posite ZnO/ZSO CL behaves better than the TiO2 CL, the electron
property of the 75 nm ZnO/ZSO is compared with that of the 100 nm
spectra of MAPbI3 deposited on a 75 nm ZnO/ZSO CL and a 100 nm
TiO2 CL, respectively. Compared with the MAPbI3/FTO sample, a
significant reduction of PL intensity is observed in the MAPbI3/ZnO/
ZSO/FTO and MAPbI3/TiO2/FTO. As regards the MAPbI3/ZnO/ZSO/FTO
sample, the PL quenching phenomenon is more distinct. That is to
say, the photo-generate electrons are more easily extracted in the
ZnO/ZSO CL. It can be attributed to the suitable energy band struc-
ture. Owing to the lower conduction band location of ZnO/ZSO than
that of TiO2, the driving force of electron injection from mesoporous
TiO2 to ZnO/ZSO CL is enhanced. Hence, the excitons in the per-
ovskite can be more efficiently dissociated at the interface between
the perovskite and the ZnO/ZSO CL. Consequently, the ZnO/ZSO CL
manifests superior electron collection capacity. To investigate the
electrical conductivity of TiO2 CL and ZnO/ZSO CL, linear sweep
voltammetry (LSV) measurements were conducted, and the results
are shown in Fig. 11(b). The symmetrical dummy cells were as-
sembled as a sandwich structure with two identical CLs on both sides
and the HTM layer in the middle. The ZnO/ZSO CL shows higher
current density indicating that the ZnO/ZSO CL possesses higher

Fig. 7. Optical transmittance spectra of TiO2 CLs and ZnO/ZSO CLs with different thicknesses.
148 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150

Fig. 9. Box chart of photovoltaic parameters comparison of perovskite solar cells based on different thickness TiO2 CLs. The data were statistically analyzed from 10 cells.

Fig. 10. I–V curves of perovskite solar cells based on different thickness of ZnO/ZSO
CLs.

Table 3
Photovoltaic parameters of the best perovskite solar cells based on different
thickness of ZnO/ZSO CLs.

ZnO/ZSO (nm) Jsc (mA cm
2) Voc (V) FF η (%)

15 16.81 0.991 0.54 8.93

35 17.89 1.004 0.56 10.11
55 18.50 1.021 0.58 10.96
75 19.71 1.035 0.59 12.03
95 18.41 1.027 0.60 11.31

electrical conductivity. Consequently, the electron transportation is

more favorable in the ZnO/ZSO CL, the result of which is in ac-
Fig. 11. (a) Photoluminescence spectra of MAPbI3 deposited on the top of FTO, TiO2
cordance with the theoretical conclusion that the carrier mobility of
CL and ZnO/ZSO CL, (b) Linear sweep voltammetry curves of TiO2/HTM/TiO2 and
ZnO and ZSO are higher than that of TiO2. Based on the above ana- ZnO/ZSO/HTM/ ZnO/ZSO.
lysis, the enhanced short-circuit current of PSCs based on the ZnO/
ZSO CL is originated from the better electron collective ability and
higher carrier mobility.
 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150
Fig. 12. Impedance spectroscopy of the device based on 75 nm ZnO/ZSO and
100 nm TiO2 CL under dark conditions.
Although the PSC based on ZnO/ZSO CL shows superior pho-
tovoltaic performance, the open-circuit voltage of it is slightly
lower than that of cell based on TiO2 CL. To analyze the re-
combination in the cells, EIS characterization was employed under
dark condition with a bias voltage of 0.8 V. Fig. 12 gives the Ny-
quist plot of PSCs based on 75 nm ZnO/ZSO CL and 100 nm TiO2 CL
with the equivalent circuit shown in the inset of Fig. 12. The large
arc is attributed to the inner recombination resistance of the PSCs.
The cell based on TiO2 CL manifests larger recombination re-
sistance thus leading to higher open-circuit voltage. It is specu-
lated that the recombination in cell based on ZnO/ZSO CL is likely
caused by the higher roughness verified by AFM results. However,
the series resistance (Rs) of the cell based on ZnO/ZSO CL is lower
than that of the cell based on TiO2 CL due to the fact that the
thickness of ZnO/ZSO CL is smaller and the carrier mobility of the
ZnO/ZSO CL appears to be higher based on the conductivity
measurements.
Fig. 13. Box chart of photovoltaic parameters comparison of perovskite solar cells based on different thickness ZnO/ZSO CLs. The data were statistically analyzed from 10
cells.
149
Fig. 13 is photovoltaic parameters comparison of perovskite
solar cells based on different thickness of ZnO/ZSO CLs. It can be
seen that short-circuit current and open-circuit voltage increased
with thickness at first and then declined. The thin CL may cause
more recombination due to the non-uniform coverage. As can be
seen from Fig. 14, the dark current of cells assembled by FTO/ZnO/
ZSO CL/HTM/Au decreased with the increasing thickness of CLs.
Therefore, thicker ZnO/ZSO CL can effectively reduce back re-
combination of electrons thus improving short-circuit current and
open-circuit voltage. However, the thicker CLs will lead to lower
optical transmittance thus restricting further increase of short-
circuit current. Meanwhile, the roughness will increase with
thicker CLs as well, which will increase the probability of re-
combination. Consequently, the optimum thickness of ZnO/ZSO CL
is 75 nm.
4. Conclusion
In summary, composite ZnO/ZSO CL was synthesized via spray
pyrolysis route to substitute the conventional TiO2 CL. This kind of
composite CL can combine the merits of both ZnO and ZSO thus
exhibiting superior application in photovoltaic devices. Generally,
ZnO/ZSO CL shows better optical transmittance owing to its lower
refractive index. The photovoltaic performance of PSCs based on
different thickness of CLs is investigated. An optimum thickness of
75 nm ZnO/ZSO CL is formed, while an optimum thickness of
100 nm TiO2 CL is obtained. Through the PL characterization, it can
be found that perovskite solar cell based on 75 nm ZnO/ZSO CL
manifests superior electron collective property. Besides, ZnO/ZSO
CL with a thickness of 75 nm possesses better electron con-
ductivity than TiO2 CL with a thickness of 100 nm, thus facilitating
the transportation of electrons. Hence, the perovskite solar cell
based on 75 nm ZnO/ZSO CL shows an enhanced photo-current,
attaining 19.71 mA cm
2 with an overall PCE of 12.03%.
150 W. Li et al. / Solar Energy Materials & Solar Cells 159 (2017) 143–150
Fig. 14. Dark current-voltage curves of FTO/ZnO/ZSO CL/HTM/Au cells with differ-
ent thickness of ZnO/ZSO CL.
Acknowledgement
This work is co-financed by National Natural Science Founda-
tion of China (Grant Nos. 51572098 and 51272080), National Basic
Research Program of China (Grant No. 2013CB632500), Natural
Science Foundation of Hubei Province (Grant No. 2015CFB432),
Open Fund of State Key Laboratory of Advanced Technology for
Materials Synthesis and Processing, Wuhan University of Tech-
nology Grant (No. 2016-KF-5). The technical assistance from the
Analytical and Testing Center of HUST is likewise gratefully
acknowledged.
References
[1] S. De Wolf, J. Holovsky, S.-J. Moon, P. Löper, B. Niesen, M. Ledinsky, F.-J. Haug,
J.-H. Yum, C. Ballif, J. Phys. Chem. Lett. 5 (2014) 1035–1039.
[2] G. Xing, N. Mathews, S. Sun, S.S. Lim, Y.M. Lam, M. Grätzel, S. Mhaisalkar, T.
C. Sum, Science 342 (2013) 344–347.
[3] S.D. Stranks, G.E. Eperon, G. Grancini, C. Menelaou, M.J.P. Alcocer, T. Leijtens, L.
M. Herz, A. Petrozza, H.J. Snaith, Science 342 (2013) 341–344.
[4] H. AitDads, S. Bouzit, L. Nkhaili, A. Elkissani, A. Outzourhit, Sol. Energy Mater.
Sol. Cells 148 (2016) 30–33.
[5] A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, J. Am. Chem. Soc. 131 (2009)
6050–6051.
[6] W.S. Yang, J.H. Noh, N.J. Jeon, Y.C. Kim, S. Ryu, J. Seo, S. Seok II, Science 348
(2015) 1234–1237.
[7] F. Bella, Electrochim. Acta 175 (2015) 151–161.
[8] N.J. Jeon, J.H. Noh, W.S. Yang, Y.C. Kim, S. Ryu, J. Seo, S. Seok II, Nature 517
(2015) 476–480.
[9] M. Liu, M.B. Johnston, H.J. Snaith, Nature 501 (2013) 395–398.
[10] J.T.-W. Wang, J.M. Ball, E.M. Barea, A. Abate, J.A. Alexander-Webber, J. Huang,
M. Saliba, I. Mora-Sero, J. Bisquert, H.J. Snaith, R.J. Nicholas, Nano Lett. 14
(2014) 724–730.
[11] J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M.K. Nazeeruddin,
M. Grätzel, Nature 499 (2013) 316–319.
[12] D. Liu, T.L. Kelly, Nat. Photon. 8 (2014) 133–138.
[13] L. Huang, Z. Hu, J. Xu, X. Sun, Y. Du, J. Ni, H. Cai, J. Li, J. Zhang, Sol. Energy Mater.
Sol. Cells 149 (2016) 1–8.
[14] A.K. Chandiran, A. Yella, M.T. Mayer, P. Gao, M.K. Nazeeruddin, M. Grätzel, Adv.
Mater. 26 (2014) 4309–4312.
[15] H. Liu, Z. Huang, S. Wei, L. Zheng, L. Xiao, Q. Gong, Nanoscale 8 (2016)
6209–6221.
[16] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Chem. Rev. 110 (2010)
6595–6663.
[17] J. Burschka, A. Dualeh, F. Kessler, E. Baranoff, N.-L. Cevey-Ha, C. Yi, M.
K. Nazeeruddin, M. Grätzel, J. Am. Chem. Soc. 133 (2011) 18042–18045.
[18] D. Liu, J. Yang, T.L. Kelly, J. Am. Chem. Soc. 136 (2014) 17116–17122.
[19] J. Choi, S. Song, M.T. Hörantner, H.J. Snaith, T. Park, ACS Nano (2016).
[20] A.R. Pascoe, S. Meyer, W. Huang, W. Li, L. Benesperi, N.W. Duffy, L. Spiccia,
U. Bach, Y.-B. Cheng, Adv. Funct. Mater. (2015).
[21] W. Ke, G. Fang, J. Wang, P. Qin, H. Tao, H. Lei, Q. Liu, X. Dai, X. Zhao, ACS Appl.
Mater. Interfaces 6 (2014) 15959–15965.
[22] W. Ke, G. Fang, Q. Liu, L. Xiong, P. Qin, H. Tao, J. Wang, H. Lei, B. Li, J. Wan,
G. Yang, Y. Yan, J. Am. Chem. Soc. 137 (2015) 6730–6733.
[23] M.H. Kumar, N. Yantara, S. Dharani, M. Grätzel, S. Mhaisalkar, P.P. Boix,
N. Mathews, Chem. Commun. 49 (2013) 11089–11091.
[24] Q. Dong, Y. Shi, K. Wang, Y. Li, S. Wang, H. Zhang, Y. Xing, Y. Du, X. Bai, T. Ma, J.
Phys. Chem. C 119 (2015) 10212–10217.
[25] F.D. Giacomo, V. Zardetto, A. D’Epifanio, S. Pescetelli, F. Matteocci, S. Razza, A.
D. Carlo, S. Licoccia, W.M.M. Kessels, M. Creatore, T.M. Brown, Adv. Energy
Mater. 5 (2015) 1401808.
[26] S.S. Mali, C.S. Shim, C.K. Hong, Sci. Rep. 5 (2015) 11424.
[27] L.S. Oh, D.H. Kim, J.A. Lee, S.S. Shin, J.-W. Lee, I.J. Park, M.J. Ko, N.-G. Park, S.
G. Pyo, K.S. Hong, J.Y. Kim, J. Phys. Chem. C 118 (2014) 22991–22994.
[28] L.-B. Li, Y.-F. Wang, H.-S. Rao, W.-Q. Wu, K.-N. Li, C.-Y. Su, D.-B. Kuang, ACS
Appl. Mater. Interfaces 5 (2013) 11865–11871.
[29] T.J. Coutts, D.L. Young, X. Li, W.P. Mulligan, X. Wu, J. Vac. Sci. Technol. A 18
(2000) 2646–2660.
[30] L. Loh, J. Briscoe, S. Dunn, ACS Appl. Mater. Interfaces 7 (2015) 152–157.
[31] M. Quintana, T. Edvinsson, A. Hagfeldt, G. Boschloo, J. Phys. Chem. C 111 (2007)
1035–1041.
[32] E. Hendry, M. Koeberg, B. O’Regan, M. Bonn, Nano Lett. 6 (2006) 755–759.
[33] J.A. Christians, R.C. Fung, P.V. Kamat, J. Am. Chem. Soc. 16 (2013) 758–764.
[34] T.-Y. Hsieh, T.-C. Wei, K.-L. Wu, M. Ikegami, T. Miyasaka, Chem. Commun. 51
(2015) 13294–13297.
[35] M. Chen, X. Wang, Y.H. Yu, Z.L. Pei, X.D. Bai, C. Sun, R.F. Huang, L.S. Wen, Appl.
Surf. Sci. 158 (2000) 134–140.
[36] S.W. Gaarenstroom, N. Winograd, J. Chem. Phys. 67 (1977) 3500–3506.
[37] D. Yang, R. Yang, J. Zhang, Z. Yang, S. Liu, C. Li, Energy Environ. Sci. 8 (2015)
3208–3214.
[38] S.S. Shin, W.S. Yang, J.H. Noh, J.H. Suk, N.J. Jeon, J.H. Park, J.S. Kim, W.M. Seong,
S. Seok II, Nat. Commun. 6 (2015) 7410.