Electrochimica Acta 338 (2020) 135884

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Applying neoteric MgTiO3-coated TiO2 nanoparticulate films as

scaffold layers in perovskite solar cells based on carbon counter
electrode for retarding charge recombination
Bowen Zhang a, b, *, Bo Zhang c, Shaowei Wang a, b, Shujuan Yao a, b, Hari Bala a, b, **,
Guang Sun a, b, Jianliang Cao a, b, Zhanying Zhang a, b
a
Henan Key Laboratory of Materials on Deep-Earth Engineering, School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo,
454000, China
b
Cultivating Base for Key Laboratory of Environment-friendly Inorganic Materials in University of Henan Province, Henan Polytechnic University, Jiaozuo,
454000, China
c
Office for Science and Technology, Henan Polytechnic University, Jiaozuo, 454000, China

a r t i c l e i n f o a b s t r a c t

Article history: MgTiO3-coated TiO2 mesoporous scaffold layers were fabricated and applied in perovskite solar cells
Received 23 July 2019 (PSCs) based on carbon counter electrode (CCE), in which TiO2 mesoporous layers were treated with
Received in revised form different concentration of Mg2þ solution. Compared with PSCs based on pure TiO2 mesoporous layer, the
31 December 2019
open circuit voltage (Voc) and circuit photocurrent density (Jsc) of MgTiO3/TiO2-based devices significant
Accepted 10 February 2020
improved. Intensive characterizations including scanning electron microscopy, electrochemical imped-
Available online 10 February 2020
ance spectroscopy can confirm that the presence of MgTiO3 shell layer can’t only retard charge recom-
bination at CH3NH3PbI3/TiO2 interface, but also have a strong effect on the perovskite film growth. Based
Keywords:
MgTiO3/TiO2
on the optimized treating concentration of 0.10 M, power conversion efficiency (PCE) of 10.39% could be
Mesorporous scaffold layer achieved for the hole-conductor-free PSCs with excellent long-term stability, suggesting immense po-
Hole-conductor-free tential for large-scale industrial production in the future.
Carbon counter electrode © 2020 Elsevier Ltd. All rights reserved.
Perovskite solar cell

1. Introduction alternative to silicon solar cell due to their advantages including

As new generation of thin-film solar cells, organic-inorganic
hybrid perovskites based solar cells (PSCs) have received consid-
erable attention owe to their numerous advantages including low
exciton binding energy [1,2], high extinction coefficient [3], ambi-
polar charge transport [4], and long carrier diffusion lengths [5,6].
Since the initial report on applying perovskite materials in solar
cells published back in 2009, impressive progress in enhancing the
photovoltaic performance has been made and their power con-
version efficiency (PCE) has skyrocketed to over 23% from 3.8%
[7e10]. And PSCs exhibit outstanding potential as an ideal
* Corresponding author. Henan Key Laboratory of Materials on Deep-Earth En-
gineering, School of Materials Science and Engineering, Henan Polytechnic Uni-
versity, Jiaozuo, 454000, China.
** Corresponding author. Henan Key Laboratory of Materials on Deep-Earth En-
gineering, School of Materials Science and Engineering, Henan Polytechnic Uni-
versity, Jiaozuo, 454000, China.
E-mail addresses: zhangbw@hpu.edu.cn (B. Zhang), hari@hpu.edu.cn (H. Bala).
simple manufacture, environment friendly, and high conversion
efficiency [11e15]. However, the hole transporting materials (HTM)
and noble metal electrodes (Au or Ag) applied in common PSCs
greatly raise production cost compared with other components in
such devices, limiting their application in fabricating low-cost
photovoltaic devices [16,17]. Furthermore, most of PSCs prepare
noble-metal electrodes via vacuum evaporation or sputtering
process. This could cause a lot of energy consumption and damage
the structural integrity of devices, hindering the large-scale pro-
duction of PSCs.
In order to develop new-type PSCs without HTM, more and
more scientists have devoted to find cheap and abundantly avail-
able materials for replacing the noble-metal CE. As a common and
inexpensive material, carbon has been applied in CE of PSCs owe to
its advantages including good conductivity and flexibility, tailor
preparing method and easy operating process, and similar work
function with Au electrode (Au (5.1 eV), carbon (5.0 eV))
[18e23]. Zhang et al. reported a screen-printing technique to pre-
pare hole-conductor-free mesoporous PSCs based on CCE [19]. Li

https://doi.org/10.1016/j.electacta.2020.135884
0013-4686/© 2020 Elsevier Ltd. All rights reserved.
2 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884
et al. communicated an investigation of PSCs using a mesoporous
TiO2/Al2O3 structure as a framework in combination with a
graphite/carbon black CE material [20]. Compared with noble-
metal CE-based PSCs, the devices based on CCE not only save the
HTM and simplifies the production process, but also greatly reduce
the material and production cost. This would offer a broader
prospect for the commercialization of this photovoltaic device.
Although the CCE-based PSCs exhibit low-cost and well-
stability, there are still some shortcomings that limit the develop-
ment of devices including low open circuit voltage (Voc) and
limited maximum PCE. There have been many attempts to improve
the photovoltaic properties of PSCs, such as using different meso-
porous scaffold materials (TiO2, ZrO2, Al2O3) and replacing the
constituent atom in perovskite structure of ABX3 [24e28]. For CCE-
based PSCs, the mesoporous scaffold layer plays an important role
in crystallization of perovskite films which can contribute to effi-
cient charge separation and transport. The ZrO2 or Al2O3 insulating
layer are often introduced to form TiO2eZrO2 or TiO2eAl2O3 double
mesoporous layer for preventing carriers recombination . However,
the CH3NH3PbI3 perovskite materials have a relatively short elec-
tron diffusion length. The presence of ZrO2 or Al2O3 insulating layer
increases the thickness of mesoporous layer and blocks the injec-
tion of electrons into TiO2 transport materials, which would in-
crease electrons transport resistance. Many attempts and efforts
have been made to solve the problem. An effective way is changing
the electrical properties of electron transport materials by material
engineering, such as doping method, surface coating, and forming
composite with other semiconductors [26,29e31]. Xiao et al. re-
ported the impact of W-doping TiO2 nanoparticles on the photo-
voltaic properties of hole transport material free PSCs that employ
CCE [26]. Nevertheless, to the best of our knowledge, studies on
controlling the carriers recombination between electron transport
materials and perovskite material by surface coating method have
been sparse.
In this work, MgTiO3 shells had grown onto TiO2 nanoparticles
to form MgTiO3eTiO2 core-shell structure mesoporous layer via a
simple sintering route. The introduction of MgTiO3 shell effectively
not only retarded the carrier recombination at the interface
Fig. 1. Schematic illustration of the fabrication route of CCE-based PSCs.
between TiO2 and CH3NH3PbI3, but also improved the crystalliza-
tion of perovskite films. This would lead to improvement of the Voc
and circuit photocurrent density (Jsc). Consequently, the PCE of solar
cell based on MgTiO3-coated TiO2 mesoporous layer increased from
4.98% to 10.39% compared to TiO2-based devices.
2. Experimental section
2.1. Materials
Patterned FTO glasses with a sheet resistance of 7U/sq were
purchased form from Shenzhen Huanan Xiangcheng Factory. PbI2
(99.999%) was obtained from Xian Polymer Light Technology Corp.
All of other reagents were purchased form Macklin. To synthesize
the methylammonium iodide (CH3NH3I, MAI), first hydroiodic acid
(30 mL, 57 wt% in water, Macklin) and methylamine (27.8 mL, 40%
in methanol, Macklin) were stirred at 0  C for 1 h. The mixture
solution was evaporating at 50  C for 1 h to obtain raw MAI. And the
white powder was washed for three times with diethyl ether and
dried in a vacuum oven overnight at 50  C. The TiO2 paste consisted
of TiO2 monocrystalline with average grain size of ~25 nm was
synthesized according to previous report with modifications [32].
2.2. Fabrication of CCE PSCs
The whole experimental process was finished at air with high
humidity of ~50%. Fig. 1 illustrates the fabrication process of the
MgTiO3/TiO2 core-shell nanoparticles based PSCs with CCE. FTO
glasses were respectively cleaned by using etergent, deionized
water, acetone and ethanol and dried in air. To prepare TiO2
compact layers, precursor solution of mixed CH3CH2OH, CH3COOH,
and Ti(OC4H9)4 was spin-coated at 3500 rpm for 30s on FTO glasses
and then annealed at 500  C for 30 min. After cooling to room
temperature, the substrates were treated for 30 min with 0.08 M
TiCl4 aqueous solution to improve the surface properties of TiO2
film. After that, a tailor-made TiO2 precursor (TiO2 paste dissolved
in ethanol) was spin-coated on TiO2 compact layer at 4000 r.p.m for
20s and annealed at 500  C for 30 min to obtain a mesoporous TiO2
 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884
Fig. 2. (a) XRD patterns of TiO2 mesoporous layer and MgTiO3-coated TiO2 mesoporous layer, (b) the top-view SEM image of MgTiO3-coated TiO2 films, and the corresponding EDX
elemental mapping of (c) Sn, (d) Ti, (e) O, and (f) Mg elements.
layer. Then the substrates were treating with TiCl4 aqueous solu-
tion at 70  C. Definitively, MgTiO3-coated TiO2 mesoporous layer
was prepared according to a previous report with modifications
[33]. First the obtained substrates were immersed into Mg(NO3)2
ethanol solution with different concentration (x ¼ 0.05 M, 0.10 M,
0.20 M, 0.40 M) for 90 s and then washed with ethanol and finally
sintered at 550  C. For comparison, a sample without treating by
Mg(NO3)2 (x ¼ 0 M) was prepared. After that, the mixture con-
taining MAI, PbI2 and NH4Cl additive (MAI:PbI2:NH4Cl ¼ 1:1:0.5)
was dissolved into component solvent consisting of dime-
thylformamide (DMF) and dimethyl sulfoxide (DMSO) with a vol-
ume ration of 8:2 to obtain perovskite precursor solution.
Subsequently the perovskite precursor solution was directly spin-
coating on MgTiO3-coated TiO2 mesoporous layer and then heat-
ed at 90  C for 50 min to form MAPbI perovskite film. Finally, CCE
was prepared by blade-coating carbon paste onto perovskite films
which sintered at 100  C for 10 min. The active area of solar cells
was determined as 0.20 cm2.
2.3. Characterization
Crystal structure and phase purity were obtained by employing
X-ray diffraction (XRD) on a Rigaku SmartLab diffractometer with
Cu Ka radiation. The core-shell structure of mesoporous layer was
clearly observed by the high-resolution transmission electron mi-
croscope (HRTEM, JEOL, JEM-2100). The field-emission scanning
electron microscopy (FESEM, Zeiss Supa 50 V P, Germany) was used
to observe the morphology of perovskite films and mesoporous
layer. Elemental analysis was performed by X-ray energy-dispersive
spectroscopy (EDX, INCAENERGY 250) integrated into the FESEM
system. Ultravioletevisible (UVevis) absorption spectra were
measured by using TU-1810 PCS UVeVis spectrophotometer (Bei-
jing Purkinje General Ins. Co. Ltd., China). Photovoltaic properties of
solar cells were tested by a keithley model 2602 A digital source
meter (Keithley, USA). The solar simulator (BOS-X-1000G of irra-
diance 1000 W/m2) was adjusted to AM 1.5G by a laser power
meter (PMA2100/PMA2144 Pyranometer, USA). Electrochemical
impedance spectrum was carried out using electrochemical work-
station (Parstat 2273, USA, Princeton). The contact angle machine
(Beijing Shangdetong Technology Co., Ltd, JC2000C, China) was
3
used to test the hydrophilia of CCE.
3. Results and discussion
For the CCE based mesoscopic PSCs, the mesoporous scaffold
layer could contribute to efficient charge separation and transport
[34]. XRD analysis was performed to study the crystal structure of
TiO2 mesoporous layer with and without treating by Mg2þ solution,
as shown in Fig. 2(a). As is observable, after treating by 0.10 M Mg2þ
solution, the two weak signals indexed to (101) and (113) planes of
MgTiO3 (perovskite, JCPDS no. 06e0494) slightly appeared at
21.28 and 40.78 , clearly demonstrating the formation of MgTiO3
in the film. The weakness of diffraction intensities of MgTiO3
indicate the coating of an only thin layer, but the diffraction peaks
of anatase TiO2 (JCPDS no. 21e1272) remained, which confirms the
fabrication of MgTiO3/TiO2 core-shell nanoparticles. Moreover, an
additional peak at 27.51 due to (101) plane of rutile TiO2 (JCPDS no.
21e1276) can be found, indicating that the crystal structure of TiO2
changed during high temperature calcination. From the top-view
SEM image of MgTiO3-coated TiO2 film based on x ¼ 0.10 M as
shown in Fig. 2(b), a uniform, flat and non-defective mesoporous
film can be directly examined and its phase composition and crystal
structure are further elucidated by EDX. As shown in Fig. 2(cef),
four elements including Sn, Ti, O, and Mg are simultaneously pre-
sented and Mg elements are randomly dispersed around Ti ele-
ments which uniform distributed in thin film. These findings
demonstrate that the MgTiO3-coated TiO2 mesoporous layer was
prepared through a pickling process.
The cross-sectional FESEM image of PSCs is shown in Fig. 3(a). It
is clearly seen that a compact carbon layer with thickness of about
9.29 mm is coated on the perovskite layer as CE. The carbon layer
consists of thin flaks with stratified arrangement that can contact
the interfacial by tight combination and can prevent perovskite film
from contacting with water vapor. This is beneficial for our devices
to enhance their stability. To further analysis the architecture
structure of devices, high-resolution FESEM image for perovskite/
MgTiO3@TiO2/FTO is show in Fig. 3(b). It can be observed that a
~330 nm of MAPbI3 perovskite capping layer covers on the MgTiO3-
coated TiO2 mesoporous layer which is fully infiltrated by perov-
skite crystal, and the thickness of mesoporous layer is about
4 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884

Fig. 3. Cross-section FESEM images of (a) PSCs and (b) perovskite/MgTiO3@TiO2/FTO,

(c) the top-view SEM image of MgTiO3-coated TiO2 mesoporous layer based on
x ¼ 0.10 M, (d) the HRTEM image of MgTiO3/TiO2 nanoparticles.

460 nm. The top-view SEM image for mesoporous layer is displayed
in Fig. 3(c). It is appeared that a large number of size-uniformity
particles accumulate together to form uniform film with meso-
porous structure. To further confirm the formation of core-shell
structure, the high-resolution TEM image of MgTO3-coated TiO2
powders detached from mesoporous layer is taken (Fig. 3(d)). It is
obvious that the distances of lattice fringes for TiO2 core are
approximately 0.35 nm, which corresponded to (101) plane of
anatase TiO2. And a number of relatively narrow lattice fringes on
the TiO2 surface are found and their interplannar distances are
about 0.22 nm consisted with (113) plane of MgTiO3, indicated that
the MgTiO3 shell layer was completely coated onto the TiO2 core.
The mesoporous scaffold layers have great influence on growth
and crystallization of perovskite film which can contribute to
improvement of photovoltaic properties of devices. The surface
morphology of perovskite films based on mesoporous layers
treated by different concentration of Mg2þ solution was charac-
terized and shown in Fig. 4. Form Fig. 4(a) and (b), it can be
observed that a great deal of snowflake-like crystal blocks with
average size of 20.35 mm grow on the TiO2 mesoporous layer
without treating. These crystal blocks consists of several dendritic Fig. 4. Surface SEM images of perovskite films on TiO2 mesoporous layer with treating
by x M Mg2þ solution: (a,b) x ¼ 0 M; (c,d) x ¼ 0.05 M; (e,f) x ¼ 0.10 M; (g,h) x ¼ 0.20 M;
broad arms that form a star-like shape and the average length and
(i,j) x ¼ 0.40 M.
diameters of broad arms respectively are 10.20 mm and 1.5 mm. A
large number of gaps appear in perovskite films, leading to expo-
sure of TiO2 mesoporous layers. This can make mesoporous layer photovoltaic properties. With increase of treating concentration,
directly contacts with CCE and cause charges recombination, the structure of perovskite crystals change to maple-leaf-like
resulting in decrease of photocurrent and PCE. For improving morphology and their mean size is about 20.82 mm. And these
photovoltaic performance, MgTiO3 maskant was introduced for crystals combine tightly to form a dense film and no gaps and
retarding charge recombination. Fig. 4(c) and (d) show the top- pinholes are found, indicated high coverage of perovskite films on
view SEM images of perovksite films based on TiO2 mesoporous the MgTiO3-coated TiO2 mesoporous layer based on x ¼ 0.10 M
layer with treating by 0.05 M Mg2þ solution. It is obvious that the (Fig. 4(e) and (f)). This is beneficial to carriers transport and reduces
average size of crystal blocks is increased to 25.77 mm compared recombination, which contributed to the improvement of devices
with perovksite film based on x ¼ 0 M. Many schistose crystals with performance. When treating concentration increase to 0.20 M, the
average length of 12.31 mm and diameters of 6.62 mm are ordered perovskite crystals present similar maple-leaf-like structure, but
accumulation that form hierarchical polygonal structure and joined some big voids appear among the crystals (Fig. 4(g) and (h)).
together to form a uniform and dense film that can fully cover on Compared with perovskite films based on x ¼ 0.20 M, the films
mesoporous layer. But there are a few tiny gaps appeared in based on x ¼ 0.40 M show similar morphology but smaller crystal
perovskite film, which may make against enhancement of size (~14.96 mm) and more voids (Fig. 4(i) and (j)), which is related
 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884 5

to the treating concentration of Mg2þ solution. Therefore, the

introduction of MgTiO3-coated TiO2 nanoparticles could promote
the crystallization of MAPbI3 perovskite crystals to obtained better
perovskite films.
For the mesoscopic PSCs without HTM, the perovskite films as
light absorber play a decisive role in exciton separation and carrier
transport which can affect the performance of devices. The quality
of perovskite films depends on a variety of factors including solvent
evaporation rate, crystallization rate of crystals, the additive, and
the mesoporous layer. When perovskite precursor was deposited in
TiO2 mesoporous layer by spin-coating method, the MAPbI3 crystal
seed random dispersed on TiO2 nanoparticles and scattered grew
after heat treatment to form snowflake-like structure with smaller
crystal size, leading to exposure of TiO2 mesoporous layer. With
treating of Mg2þ solution to TiO2 mesoporous layer, especially
treating concentration increase to 0.10 M, a uniform and dense
perovskite film consisted of maple-leaf-like crystals can fully cover
on mesoporous layer and no gaps and pinholes are observed,
indicated good crystallinity and high surface coverage of perovskite
films. This can be attributed to the perovskite crystal structure of
MgTiO3. When the MAPbI3 crystal seeds absorbed on the surface of
MgTiO3, the total potential energy of the whole system could be
reduced and the MAPbI3 crystals may nucleate and grow on MgTiO3
nanoparticles through heterogeneous nucleation rather than
forming separate nuclei by homogeneous nucleation. Thus, the
perovskite crystal seed would absorb and grow onto MgTiO3 shell
and rapid ordered crystallize to form a dense film. However, with
further increase of treating concentration, some voids appeared in
the perovskite film and the crystal size becoming smaller, which is
relate to high treating concentration of Mg2þ solution to TiO2
mesopourous layer. The introduction of MgTiO3 can promote rapid
crystallization of perovskite crystals, but excessive MgTiO3 may
lead to excessive crystallization rate, resulting in MAPbI3 speedy
growth and inability to interconnect in time.
The crystal structure and phase purity for perovskite films were
analyzed by XRD patterns, as shown in Fig. 5(a). The diffraction
peaks at 14.24 , 20.08 , 28.54 , 31.82 , and 40.7 can be found,
which are respectively corresponded to (110), (112), (220), (310), Fig. 5. (a) XRD patterns and (b) UVeVis absorption spectra for the perovskite films
and (224) planes of the tetragonal perovskite phase. A weak signal based on TiO2 mesoporous layer and MgTiO3-coated TiO2 mesoporous layer (x ¼ 0.05,
0.10, 0.20, 0.40 M).
at 12.38 due to PbI2 is observed for perovskite films based on TiO2
mesoporous layer without treating. When TiO2 mesoporous layer
was treated by 0.05 M of Mg2þ solution, the peaks from PbI2 is not Representative photocurrent density versus photovoltage (J-V)
observed, indicated better crystallinity of perovskite films. With the curves for the best performing devices as a variable of treating
increase of treating concentration, the peaks intensity from MAPbI3 concentration are shown in Fig. 6(a), and their photovoltaic pa-
reach a maximum when x ¼ 0.10 M and then drops down. And a rameters are also listed on Table 1. It can be observed that the de-
weak peak of PbI2 appears when treating concentration increase to vice based on x ¼ 0 M exhibits poor photovoltaic performance, such
0.04 M, suggesting incomplete reaction of PbI2 with MAI. From the as low Voc of 0.80 V and Jsc of 14.05 mA/cm2. This can be attributed
analysis results from SEM and XRD, we can confirm that the per- to the direct contact between TiO2 nanoparticles and perovksite
ovsktie film based on MgTiO3-coated TiO2 mesoporous layer with films. A large deal of charge recombination occurs on the interface
x ¼ 0.10 M exhibits best crystallinity and highest coverage, which of TiO2/MAPbI3, resulting in reduction of photocurrent. After
can contribute to improvement of devices performance. treating with Mg2þ solution, the TiO2 nanoparticles was coating by
Fig. 5(b) shows UVeVis absorption spectra of the MAPbI3 per- MgTiO3 layer to form core-shell structure, which can retard effec-
ovkste films grown on the TiO2 mesoporous layer treated with tively charge recombination. And the presence of MgTiO3-coated
varying Mg2þ solution. It is clear that the absorption edges of all TiO2 nanoparticles could promote crystallization of perovskite
films situate at ~780 nm, implying well light-harvesting ability films, which is beneficial to improve the performance of devices.
ranging from the visible-to-near-IR region. And the perovskite film From Fig. 6(a), it can be found that the Voc and Jsc of devices sig-
based on x ¼ 0.10 M exhibits top optical absorption intensity in the nificant increase since MgTiO3 coated on the TiO2 nanoparticles.
wavelength region from 550 to 800 nm, suggesting a complete The maximum value of Voc of 0.95 V and Jsc of 22.62 mA/cm2 can be
reaction from PbI2 into MAPbI3. However, optical absorption was obtained when the treating concentration is 0.10 M, corresponding
decreased when treating concentration further raise. This is owing to a maximum PCE of 10.39%. Increasing the concentration of Mg2þ
to thicker MgTiO3 shell layer lead to formation of worse quality of solution, which is related to the thickness of the MgTiO3 layer,
MAPbI3 films, which is corresponded to the above analysis results. would lead to a decrease of photocurrent density. This is attributed
To sum up, the perovskite film based on x ¼ 0.10 M shows the best to the negative effect of MgTiO3 shell on electron injection from the
experimental results, and the PSCs based on such a film should perovskite film into TiO2 particles. Fig. 6(b) shows the J-V curves of
show best photovoltaic behaviors.
6 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884

Fig. 6. (a) J-V cures of the PSCs based on different treating concentration (x ¼ 0, 0.05,
0.10, 0.20, and 0.40 M) under AM 1.5 illumination, (b) reverse and forward scan J-V
characteristics of PSCs based on x ¼ 0.10 M.
Fig. 7. (a) Schematic representation of the charge transfer mechanism in the PSCs
based on MgTiO3-coated TiO2 mesoporous layer, and (b) the corresponding band-
energy arrangement diagram.

observed from Fig. 4 that the MgTiO3 shell layers have negative
effect on crystallization of MAPbI3 perovskite film when the treat-
Table 1
The photovoltaic performance parameters of the devices. ing concentration is more than 0.10 M, which would lead to
decrease of Voc and Jsc. Furthermore, the thickness of MgTiO3 shell
x (M) Jsc (mA/cm2) Voc (mV) FF (%) h (%) Rtr (ohm) Rrec (ohm)
controlled by adjusting treatment concentration has an important
0.0 14.05 801 44.3 4.98 99.2 268.2 influence on carrier transport. When x > 0.10 M, the thick MgTiO3
0.05 21.03 923 45.6 8.84 70.6 600.3
shell would hinder electrons injecting into TiO2 nanoparticles from
0.10 22.62 953 48.2 10.39 55.7 673.8
0.20 19.55 931 44.8 8.15 74.6 514.3 perovskite film, resulting in decrease of Jsc and PCE.
0.40 17.20 901 44.1 6.82 96.8 391.8 To probe the effect of MgTiO3 shell layer on the retardation of
charge recombination, the electrochemical impedance spectros-
copy (EIS) of devices based on different treating concentration
the optimum performance devices based on x ¼ 0.10 M in forward under the same illumination at DC bias of 0.8 V was characterized
and reverse scan. As expected, the devices exhibit a tiny J-V hys- and shown in Fig. 8. Two semicircles are observed from the ob-
teresis, which is depending on the specific hole-conductor-free tained curves that are fitted using the equivalent circuit in the inset
mesoporous structure of devices. of Fig. 8(a), the corresponding values are listed in Table 1. The
Compared with pristine TiO2 based PSCs, the photovoltage semicircle situated at high frequency range (the first one) ascribed
performance of devices based on MgTiO3-coated TiO2 mesoporous to the carrier transport resistance (Rtr) while the second semicircle
layer are enhanced significantly, which is related to unique MgTiO3/ at low frequency range is considered to represent the recombina-
TiO2 core-shell structure. As illustrated in Fig. 7, the insulating tion resistance (Rrec) at the TiO2/perovsite interface [35e38].
MgTiO3 layer with large band gap energy (approximately 3.7 eV) is Fig. 8(b) shows the transport resistance Rtr and recombination Rrec
capable of blocking charge recombination at the TiO2/perovskite extracted under different treating concentration. It is obvious that
interface. Therefore, the Voc could improve when the MgTiO3 the Rtr first decrease and then increase with increase of treating
coating on TiO2 nanoparticles, indicating the effective retardation concentration along with an opposite trend for Rrec. When TiO2
of charge recombination. Moreover, the quality of perovskite film mesoporous layer was treated with Mg2þ solution, MgTiO3 coated
also plays an important role in performance of devices. It can be on TiO2 nanoparticles to form a blocking layer that retard
 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884
Fig. 8. (a) Representative Nyquist plots measured at 0.8 V applied bias for PSCs based
on x ¼ 0, 0.05, 0.10, 0.20, and 0.40 M and (b) the value of transfer resistance (Rtr, left)
recombination resistance (Rrec, right) versus treating concentration of Mg2þ solution.
The inset shows the equivalent circuit used for fitting the Nyquist plots.
Fig. 9. Statistic results of photovoltaic parameters for eight batches of devices based on different treating concentrations of Mg2þ solution.
7
effectively charge recombination to obtain a higher Rrec at TiO2/
perovskite interface. And MgTiO3 would promote crystallization of
MAPbI3 to form high-quality perovskite film, leading to a lower Rtr
at perovskite/CCE interface. But with further increase of treating
concentration, a thicker MgTiO3 shell layer was obtained on the
surface of TiO2, which could hinder carrier transport and have
negative effect on growth of perovsktie crystals. This could lead to
decrease of Rrec and rise of Rtr. Obviously, the PSCs based on
x ¼ 0.10 M shows higher Rrec and lower Rtr, implying slower
recombination and faster carrier transport. This provides more
evidence for the retarded charge recombination when MgTiO3/TiO2
core-shell nanoparticles were applied in PSCs.
To test the credibility of our devices, statistic data regarding the
numerical distribution of the photovoltaic parameters for 40
simultaneously prepared devices based on different treating con-
centration are obtained and shown in Fig. 9. Minimal fluctuations to
all parameters and similar changing tendency of Voc, Jsc, FF, and PCE
were observed, indicating the excellent repeatability of our devices.
And the devices based on based on x ¼ 0.10 M exhibit the optimal
photovoltaic performance, with average PCE of 9.96%, Voc of
956 mV, Jsc of 21.92 mA/cm2, and FF of 0.47. In summary, the
introduction of MgTiO3 is beneficial to improvement of perfor-
mance of CCE-based PSCs.
The stability of optimum PSCs based on x ¼ 0.10 M also was test
to ensure their long-term reliability, as shown in Fig. 10. The device
was stored in dark at air with high humidity of 50% and the values
of Voc and Jsc only reduce 1.05% and 6.99% after over 1000 h. And this
device exhibits outstanding stability as the PCE value remain
88.35% of its initial value, which is related to the unique architec-
ture structure of devices. It is reported that the HTM such as Spiro-
OmeTAD applied in metal-electrode mesoscopic PSCs could absorb
easily water vapor from the air, which can cause decomposition of
perovskite film. And the metal electrodes are generally prepared via
vacuum evaporation at high temperatures, which make against
improvement of devices stability. So the CCE-based devices without
HTM should exhibit excellent long-term stability. Fig. 11 displays
the variety of contact angles to H2O versus time on the surface of
8 B. Zhang et al. / Electrochimica Acta 338 (2020) 135884
Fig. 10. Stability test of the optimum PSCs based on x ¼ 0.10 M for 1008 h (42 days)
stored at air with high humidity of about 50% without light illumination.
Fig. 11. Contact angles for H2O on surface of CCE in PSCs: (a) 0 s, (b) 20 s, (c) 40 s, and
(d) 60 s.
CCE. It can be seen that the contact angle is determined as 118
when the droplet contact with the surface. After 60 s, an only 6
reduction can be observed, implying excellent hydrophobicity of
CCE. This hydrophobic behavior is related to the laminated con-
struction consisted of carbon layers and beneficial to enhancement
of stability of devices.
4. Conclusions
In summary, we present a simple sintering route to fabricate
MgTiO3-coated TiO2 mesoporous scaffold layers based on different
treating concentration. The MgTiO3/TiO2 core-shell structure can be
confirmed from analysis results of TEM. By employing MgTiO3 shell
layer, the photovoltaic performance of devices significant improve,
demonstrating that MgTiO3 shell as blocking layer could efficiently
prevent charge recombination at interface of MAPbI3/TiO2. Mean-
while, the introduction of MgTiO3 could promote crystallization of
MAPbI3 crystals, which is beneficial to formation of high quality of
perovskite film. The PSCs based on optimum treating concentration
of 0.10 M deliver a high PCE of 10.39%, which still remain 88.35%
after 1008 h stored at air with high humidity. Their excellent sta-
bility and simple preparation process offer a wide prospect for
future commercial application.
CRediT authorship contribution statement
Bowen Zhang: Conceptualization, Methodology, Writing -
original draft, Writing - review & editing. Bo Zhang: Validation,
Investigation. Shaowei Wang: Investigation. Shujuan Yao: Data
curation. Hari Bala: Resources, Funding acquisition. Guang Sun:
Project administration. Jianliang Cao: Supervision. Zhanying
Zhang: Supervision, Funding acquisition.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (61474038 and U1704255) and Doctoral Fund
of Henan Polytechnic University (760607/016).
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