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ARTICLE
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Enhanced stability and optoelectronic properties of MAPbI3 films

with cationic surface active agent for perovskite solar cells
Received 00th January 20xx, He Zhaoa,b, Shirong Wanga,b,*, Mengna Suna,b, Fei Zhanga,b, Xianggao Lia,b,*, Yin Xiaoa,b
Accepted 00th January 20xx
The insufficient stability of perovskite solar cells (PSCs) has considerably restrained its development and application. Herein,
DOI: 10.1039/x0xx00000x we demonstrate an approach to prepare the PSCs with high stability and efficiency by adding n-octyltrimethylammonium
bromide (OTAB) into precursor solution. In the resultant films, the charge trap density exhibits a significant reduction and
www.rsc.org/
the long-term stability shows a remarkable enhancement. With adding 0.5 mg mL-1 OTAB, the power conversion efficiency
(PCE) of the PSCs reaches 18.32% under simulated AM 1.5G solar illumination, which increases 16% comparing to the pristine
devices. Moreover, the OTAB modified devices demonstrate both excellent performance in high temperature (70 , 40f
5% relative humidity) and high humidity (25 , 75f5% relative humidity) environment. These results indicate a very
promising method to improve comprehensive performance of the PSCs.

propitious to improve the device efficiency and long-term

Introduction stability. Yet by simulating degradation process of MAPbI 3,
Azpiroz et al.7 have found the MAI-terminated surfaces are
Organictinorganic halide perovskite solar cells (PSCs), mostly
easily subject to solvation, due to the nucleophilic substitution
based on methylammonium lead iodide (MAPbI 3), have brought
of dangling I ions on the surface by H2O, and the PbI2-
about widespread attention in the field of photovoltaic
terminated surfaces with vacancy defects are also prone to
generation in recent years. Owing to strong light absorption
degradation reaction. Therefore, fabricating hydrophobic layer
with a wide range of infrared-visible spectral regions,1,2 high
and reducing the surface defects seem to be crucial to stabilize
carrier mobility3 and low exciton recombination rate 4 of the
the perovskite films, which was verified by a large amount
perovskite materials, the power conversion efficiency (PCE) of
of research. For instance, Tripathi et al.15 have reported a
PSCs has increased rapidly and exceeded 22% in 2016.5
neutral surfactant polymer poly[9,9-bis (3[-(N,N-
Although the PCE of PSCs is already near silicon solar cells, a
dimethylamino)-propyl)-2,7-fluorene)-alt-2,7-(9,9-
critical problem, low ambient stability, severely impedes its
dioctylfluorene)] (PFN-P1) as modifier to improve the
industrial production and commercial application. 6-8 Thus, for
performance of the solar cells by passivating the trap states and
the extension of the service life, various methods have been
forming the hydrophobic layer, where the PCE was increased
explored, including device encapsulation, new perovskite
from 12.3% to 13.2%, and the encapsulated devices just slightly
materials development, crystallization control, interface
decayed after 6 months in ambient air. Phenylethylammonium
modification and so on.9-11 ,}Á À ŒU ]š[• v}š (µv u vš o
iodide (PEAI) as an organic halide salt was applied to self-
solution to the problem of low ambient stability by packaging
assemble at the lattice surface and grain boundaries of
solar cells. In addition, the efficiency of new materials solar cells
perovskite grains.16 Consequently, a high stability FAPbI 3 solar
like all-inorganic perovskite solar cells, 2D or 3D/2D perovskite
cell with the PCE of 17.7% was developed. Besides that, choline
bilayer heterojunction solar cells were generally lower than
chloride,17 PC61BM,18 PMMA19 etc. have been doped into
15%, despite improved stability.12,13 So there is still a better
perovskite films to improve device performance. Even so, it has
strategy for optimizing devices performance by additive
yet been a big challenge to select an additive with combined
modification.
functions, such as film morphology optimization, defect
In accordance with the additives functionalities, Huang et al.14
passivation, hydrophobicity improvement, perovskite
divided them into several categories: polymer, fullerene,
decomposition inhibition etc., to build the high efficiency solar
inorganic acids, organic halide salts etc. Some could passivate
cells with long-term stability of the thermal and humidity,
surface defect, some could manipulate the film morphology,
especially for MAPbI3-based solar cells.14,20,21 To date, this kind
while others could form protective layer. All of above are
of PSC with over 18% PCE and excellent hygrothermal stability
and is seldom reported.20
a School of Chemical Engineering and Technology, Tianjin University, Tianjin 300354, Herein, we report the use of a quaternary ammonium halides
China. *Email: [email protected]; E-mail: [email protected]
b Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), additive, n-octyltrimethylammonium bromide (OTAB), to
Tianjin 300072, China. enhance the stability and performance of the PSCs. As a cationic
• o šŒ}v] ^µ‰‰o u všary Information (ESI) available. See
surface active agent, the OTAB molecular has a relative long
DOI: 10.1039/x0xx00000x

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alkyl chain and can bind with MAPbI3 at grain surface to form š}v]šŒ]o •}oµš]}v v îõ …> ð-tert-butylpyridine. Finally,
hydrophobic film, which is able to resist water molecules under high vacuum, 80 nm of gold was deposited on the top of
invasion and hinder the decomposition product of MAPbI 3 the HTM layer by thermal evaporation using a shadow mask to
diffusing to environment. Compared to conventional amine pattern the electrodes.

Journal of Materials Chemistry A Accepted Manuscript

halide treatment22-25, this strategy can also modulate film Characterizations
morphology, passivate charged defects efficiently and The X-ray photoelectron spectroscopy (XPS) of perovskite films
significantly improve the PSCs performance. As a result, the PCE was carried out by a PHI 5000 VersaProbe XPS system using
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of OTAB modified devices is significantly improved to 18.32%, u}v} ZŒ}u š]Ì o <r ytray photons. The surface
while the champion non-additive device is just 15.80%. morphologies of the perovskite films and the cross-section
Furthermore, the OTAB modified devices without encapsulation images were measured on a scanning electron microscope
demonstrate both excellent performance in high temperature (SEM, SUPRA 55VP, ZEISS). The X-ray diffraction (XRD) data was
environment (70 , 40 f 5% relative humidity) and high recorded by X-ray diffractometer (Mini Flex 600, Rigaku) in the
humidity environment (25 , 75f5% relative humidity). Œ vP î}Aíì-60° with Cu K=1 radiation. Ultraviolettvisible (UV-
Vis) absorption was obtained by a Thermo Evolution 300
UV/Visible spectrometer. Time-resolved photoluminescence
Experimental
(TRPL) spectra was measured by exciting the perovskite films
Materials deposited on FTO substrate at 485 nm on Edinburgh
All chemicals were used as received without any other Instruments (FLS 980, UK). The electrochemical impedance
refinement unless otherwise specified. FTO-coated glass (<15 spectroscopy (EIS) was performed by electrochemical
Ol•‹µ Œ • Á • ‰µŒ Z • (Œ}u E]‰‰}v ^Z š 'o •• workstation (Vertex. One. EIS, Ivium) with alternating current
Corporation. Titanium diisopropoxide bis(acetylacetonate) was amplitude of 10 mV. The current density-voltage (J-V) curves of
obtained from Energy Chemical Corporation. Methylamine perovskite solar cells were measured with a Keithley 2400
solution (40 % in methanol), HI (57 wt% in water) and n-butanol source meter using a solar simulator (Solarbeam-2, Crowntech)
were purchased from Aladdin. PbI2 and spiro-OMeTAD were at 100 mW cm-2 illumination (AM 1.5G), and all devices were
received from Luminescence Technology Corporation. Dimethyl applied to a mask of 0.06 cm2. The incident photon-to-electron
sulphoxid ~ D^K•U EUE;-dimethylformamide (DMF) and n- conversion efficiency (IPCE) was recorded by an IPCE testing
octyltrimethylammonium bromide (OTAB) were acquired from system (E0201a, Chinese Academy of Science).
J&K chemical Corporation. CH3NH3I (MAI) was prepared
according to the reported procedure.26
Perovskite solar cells fabrication
Results and discussions
The single fluorine-doped tin oxide (FTO) glass substrates were The structure of perovskite solar cells based on
sequentially washed by detergent, toluene, acetone, and FTO/TiO2/MAPbI3/spiro-OMeTAD/Au is shown in Figure 1a. The
ethanol. After the substrates drying completely in the air, the perovskite layers were fabricated with spin-coating of precursor
compact layer of TiO2 (c-TiO2) was deposited on the cleaned FTO solutions containing equivalent MAI and PbI 2 with OTAB as
by spin-coating a precursor solution of titanium diisopropoxide additive in amount of 0, 0.1 mg mL -1, 0.5 mg mL-1, 1 mg mL-1 and
bis(acetylacetonate) in n-butanol (v: v=1:16) at 2000 rpm for 30 3 mg mL-1 on to mesoporous TiO2. As a quaternary ammonium
s, soon afterwards calcining at 500°C for 30 min in air. The cation, OTAB cannot form the 3D perovskite crystal owing to its
mesoporous TiO2 layer was coated on the c-TiO2/FTO substrate excessive ionic radius. However, by Coulomb interaction, the
by spin-coating the 30 nm TiO2 particle paste diluted in ethanol additive is able to graft on the surface of MAPbI 3 crystal and
(w: w=1:6) at 4500 rpm for 20 s, then sintering at 500 °C for 30 form a protective layer (Figure 1c),27 which is validated with X-
min. The perovskite precursor solution was prepared from ray photoelectron spectroscopy of perovskite film (Figure 2a).
1.55M Pb2+ with different concentration of OTAB in the mixed Comparing to pristine film, the I 3d3/2 peak of OTAB modified
solvents of DMF and DMSO (v: v=9:1), and the perovskite film sample moves from 629.6 eV to 628.8 eV and I 3d5/2 peak moves
was obtained from depositing the precursor solution by a from 618.2 eV to 617.4 eV. This peak shifting is arised from
consecutive two-step spin-coating process at 1000 and 6000 increasing electron cloud density of I- ion interacting with OTA+
rpm for 10 and 30 s, respectively. During the second step 20 s ion and indicates the chemisorption of OTA+ onto crystal
(}Œ šZ v }( šZ ‰Œ} µŒ U íìì …> }( Zo}Œ} vÌ v ~ • surface. (The radius of alkyl group in OTA + is larger than H in
was dripped onto the substrate. Thereafter, the substrate was CH3NH3+, which inclines to weaken the interaction between
heated at 100°C for 1 h on a hot plate. After cooling down to quaternary ammonium cation and I- ion and leading to a higher
room temperature, the hole transport material (HTM) was spin- the electron cloud density of interacting I - ion.) For the
coated on the top of perovskite film at 4000 rpm for 20s. The meantime, the N 1s peak shifting (Figure S1) and a great
HTM solution was prepared by dissolving 72.3 mg spiro- increasing ratio of C atom on the OTAB modified film surface
KD d ]v í u> Zo}Œ} vÌ v Á]šZ šZ ]š]}v }( íóXñ …> }( (Table S1) also hint OTA+ ion enriched on grain surface.
520 mg mL-1 lithium bis(trifluoromethylsulphonyl)imide

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Figure 1. (a) The device structure of perovskite solar cells. (b) Molecule structures of OTAB. (c) Schematic model of the OTAB
grafting on the surface of a MAPbI3 film.

Figure 2b shows the X-ray diffraction spectra of perovskite film OTAB increases above 1 mg mL-1, the peak intensities decrease
prepared with different amounts of OTAB. All XRD patterns rapidly which mainly due to the dispersive action of OTAB. As a
•Z}Á• u ]v ]((Œ š]}v ‰ l• š CíðXô£U îôXõ£U v ïîXï£U type of surface active agent, alkyl amine cation with a long chain
respectively, assigning to the (110), (220), and (310) crystal could bind to the uncoordinated I atoms on the surface of
planes of the perovskite structure, 28 which means the addition crystal13 to reduce the surface energy. Therefore, the MAPbI3
of OTAB cannot destroy the intrinsic crystal structure of pristine grain size and crystallinity could be decreased by adding a
material as the additive just replaces methyl amine cation on sufficient amount of OTAB, resulting in diffraction peak
the surface of MAPbI3 crystal. However, when the content of reduction.

Figure 2. (a) I 3d3/2 and I 3d5/2 XPS spectra of MAPbI3 films with and without OTAB modified. (b) XRD spectra of the MAPbI3/
mesoporous TiO2/ FTO films with different concentrations of OTAB.

To further investigate whether the OTAB modified crystal films According to classical nucleation theory, the film formation is a
are compact and uniform or not, MAPbI 3 thin film was analyzed four-step process, which commences with the formation of
by SEM (Figure 3a-e). Obviously, some pinholes could be stable crystal nucleus, and then develops in turn to island
observed in the perovskite thin films without OTAB, while the structure, network structure and continue layer.29 At the first
films prepared with 0.1 mg mL-1 to 0.5 mg mL-1 OTAB solution step, both homogeneous and heterogeneous nucleation rate of
shown compact arrangement, increasing coverage and more MAPbI3 exponentially decreases with nucleation barrier ¿)Áâà
uniform crystallites than the pristine thin film. Similar effect has and ¿)ÁØç respectively,30 and the ¿)Áâà can be further
been observed when adding other low surface energy additive expressed by
7
molecules into MAPbI3 precursor solutions, causing the v sxèJÛÌÅ
¿)Áâà L èNÞ7 ® J ® ¿)Ï E vèNÞ6 ® J ® ÛÌÅ L 6 (1)
promoting of the crystallization and surface coverage of u u¿)Ï
perovskite films.27 Nevertheless, when the additive where NÞ is critical nucleus radius, J is the quantity of critical
concentration is over 1 mg mL-1, the perovskite gain size nucleus per unit volume, ¿)Ï is the change of free energy
becomes smaller and compactness of film turn to worse, which between nucleus and solution per unit volume and ÛÌÅ is
is well consistent with XRD spectra as mentioned above. These ‰ Œš] o [• •µŒ( v ŒPÇX D vÁZ]o šZ Z š Œ}P v }µ•
phenomenon is mainly due to the presence of OTAB which can nucleation barrier ¿)ÁØç is given by
influence the film forming process.
¿)ÁØç L ¿)Áâà ® B:à; O ¿)Áâà (2)

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where à is the contact angle and r O B:à; O s . Thus low promoted by reducing interfacial energy, and then the continue
‰ Œš] o [• •µŒ( v ŒPÇ Œ o š • š} Z]PZ vµ o š]}v Œ š U ÁZ] Z film is achieved. Stated thus, appropriate amount of OTAB
means OTAB additive is able to increase the nucleating rate and additive is conducive to depositing high quality perovskite film.
adverse to form coarse grain. Nevertheless, in the ensuing Figure 3f demonstrates the UV-Vis absorption spectra of the

Journal of Materials Chemistry A Accepted Manuscript

}µŒ• }( ŒÇ•š o PŒ}ÁšZU o}Á ‰ Œš] o [• •µŒ( v ŒPÇ u Ç have MAPbI3 thin films deposited on the FTO glass. As can be seen,
contributed to the fabrication of high quality film with dense with the increase of OTAB content, UV-Vis absorption intensity
structure. It can be supposed that the grain size increases with is firstly increased and then decreased. A maximum value can
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interfacial energy in the stage of developing network structure. be attained at the concentration of 0.5 mg mL -1 in precursor
In addition, based on classical film formation theory, secondary solutions, probably attributing to the improvement of surface
nucleation process generating in the channel or pinhole will be coverage and crystal morphology revealed in Figure 3c.31,32

Figure 3. Top-view SEM images of MAPbI3 films prepared on the mesoporous TiO2 substrate with different concentrations of OTAB:
(a) 0 mg mL-1; (b) 0.1 mg mL-1; (c) 0.5 mg mL-1; (d) 1 mg mL-1; (e) 3 mg mL-1. (f) UV-Vis absorption spectra of MAPbI3 films at different
concentration of OTAB.

The hydrophobicity of perovskite was confirm by contact angle the perovskite, could be represented the extent of MAPbI3
test between MAPbI3 film and water, which could reveal the decomposition.20,35 After aging for 120 days at 70°C, 40f5%
stability of the film in humid air.33,34 As shown in Figure S2, the relative humidity, the peak intensity ratio of non-additive film
contact angle (E) of control sample is 47.6°, and when adding rose to 20.4% while the additive modified films were almost no
0.1 mg mL-1 OTAB, the value of E increases to 54.8°. While with rise. In high humidity environment, the OTAB modified films
the addition of 0.5 mg mL-1, 1 mg mL-1 and 3 mg mL-1 OTAB, the also showed the excellent stability after aging for 120 days. We
contact angles are all 58° approximately. On one hand it found the non-additive film completely degraded into PbI2.
illustrates that using OTAB can increase the hydrophobicity There were no diffraction peaks of perovskite could be
remarkably; on the other hand, it illustrates the similar observed and the color of film turned to yellow (Figure S3). In
distribution state of 0.5-3 mg mL-1 OTAB in perovskite thin films. contrast, the peak intensity ratio of OTAB modified films just
In order to validate the influence of OTAB on environment increased to 12.3%. These results indicate the OTAB can
stability, the durable XRD measurement was conducted as well. improve the stability prominently, which is conducive to
In Figure 4, the ratio of peak intensities located at 13.4° prolong cells lifetime.36,37
corresponded to the (001) face of the PbI 2 to the (110) face of

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Figure 4. XRD spectra of the MAPbI3 films without and with OTAB modified on the mesoporous TiO2 substrate, which were exposed
to (a, b) 70°C, 40f5% relative humidity and (c, d) 25°C, 65f5% relative humidity.

The MAPbI3 films with and without OTAB modified were placed check trap state density in the perovskite layer. The curves
in a nearly 100% relative humidity environment, then the could be fitted with bi-exponential decay function:40
evolution of perovskite microstructure with increasing aging
; L #5 ‡š’:FP¤ì5 ; E #6 ‡š’:FP¤ì6 ; E U4 (3)
time was tracked by SEM shown in Figure 5. We observed
decomposition preferred to start from pinholes and the where #5 and #6 are the relative amplitudes, ì5 and ì6 are the
boundaries between small and larger grains. This is mainly due lifetimes of the fast and slow recombination, respectively. In
to the secondary grain growth of perovskite films which can perovskite films, the slow recombination primarily due to trap-
widen boundary gaps.30 While by adding OTAB, the assisted recombination causes most of photoluminescence
hydrophobic molecules cover MAPbI3 grain surface and retard decay. The film with OTAB shows longer fluorescence lifetime
crystal degradation prominently.38 Moreover, because of high (ì L ì5 E ì6 ) of ì=183.9 ns, while the film without OTAB only
uniformity and compactness of additive modified films, there is exhibits the lifetime of ì=81.5 ns. This result is attributed to the
few space for H2O molecules invading into perovskite films.20 protective and passivation effect of OTAB. In accordance with
Even after aging 240 min, the undecomposed part of OTAB previous theory and experiments, the atom vacancies at grain
modified film presented relatively higher quality than surface such as I- and MA+ vacancies are the main sources of the
control ones (Figure 5f, l). defect states.38 While OTAB molecules are expected to adsorb
To study the surface and interfacial defects of perovskite film, onto perovskite surface, and thus it would inhibit the loss of
the steady-state and time-resolved photoluminescence (PL) MA+ and I- by evaporation during the thermal annealing
was measured in Figure 6a-b. Compared to the control film, process. Meantime, the OTA+ cation can passivate MA+
with adding 0.5 mg mL -1 OTAB, the intensity of steady-state PL vacancies by occupying lattice sites to recompense the MA+ loss
spectrum displays a significant enhancement, which suggests on film surface, leading to a lower defect density and superior
the fewer surface defects and higher crystallinity of perovskite electronic quality for the OTAB modified films.17,41
thin film.37,39 The TRPL decay measurement of MAPbI3 film with
and without OTAB on FTO glass was performed in Figure 6b to

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charge and . is the thickness of the MAPbI3 film. The values of

tÝ4 Ý8Í¿Å
0çåÔãæ L (4) VTFL for perovskite films without and with OTAB modified are
A.6
0.622 V and 0.181 V, assigned to the electron trap density of
where Ý4 is the dielectric constant of vacuum permittivity, Ý is 2.52H1016 cm-3 and 7.33H1015 cm-3, respectively. The defect

Journal of Materials Chemistry A Accepted Manuscript

the relative dielectric constant of MAPbI3, A is the elementary density of OTAB modified film is much lower than the contrast
film, which is corresponding to the steady-state PL and TRPL.
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Figure 6. (a) Steady-state photoluminescence spectra and (b) time-resolved photoluminescence spectra of the perovskite films
with and without OTAB. Current densitytvoltage characteristics of ITO/MAPbI3/Au devices (c) without OTAB and (d) with 0.5 mg
mL-1 OTAB.

Figure S4 exhibits the cross sectional SEM image of perovskite V curves under AM 1.5G illumination with the light intensity of
solar cell with 0.5 mg mL-1 OTAB modified. Figure 7a shows the 100 mW cm-2, and there photovoltaic parameters are
EIS measurement in the darkness to access the ability of summarized in Table 1. To contract device, the short-circuit
blocking charge recombination in devices. 44 The recombination current density (Jsc) is 21.53 mA cm-2, the open-circuit voltage
resistance (Rrec) in simplified equivalent circuit (inset of Figure (Voc) is 0.97 V, the fill factor (FF) is 0.75 and thus the PCE is
7a) reflects the charge recombination at two interface of 15.80%. By comparison, the OTAB modified device exhibits a
TiO2/MAPbI3 and MAPbI3/HTM.46,47 Under 0.8 V bias voltage, remarkable enhancement for both Jsc of 22.50 mA cm-2, Voc of
the Rrec of the PSCs without and with OTAB modified are 1002 1.04 V and FF of 0.78. Hence, the champion cells with 0.5 mg
3 and 2335 3 respectively. The higher Rrec means the lower mL-1 additive treatment presents an excellent PCE of 18.32%.
recombination rate arising from the high quality of the MAPbI3 We attribute the performance enhancement to carrier
films. This implies the higher open-circuit voltage (Voc) and fill transport improvement and defect density reduction in OTAB
factor (FF) in the PSCs with OTAB modified. 46-48 Furthermore, modified perovskite layer.17,20 Besides, by modification, the
the EIS characterization under 1 sun light illumination was hysteresis effect of PSCs can be significantly reduced owing to the
performed to understand effective charge-transfer dynamics as passivation effect of OTAB molecules.32,50
well (Figure 7b). Because of the larger photocurrent than dark As presented in Figure S7, the stabilized current density and PCE
current, the recombination resistance becomes unapparent. 49 were monitored at the maximum power point. The OTAB
Under this circumstance, charge transfer resistance (Rct) of modified devices displays not only a stable power output for
OTAB modified device is lower than non-additive device while 1300s, but also a fast photovoltaic response to light on.
series resistance (Rs) is slightly higher than the pristine one, Corresponding IPCE spectra of two devices are illustrated in
which can contribute to the improvement of MAPbI 3 film Figure 7d. By integrating the IPCE spectrum, the Jsc of cells with
morphology and the insulation of OTAB molecular layer. Other and without OTAB modified are 21.91 mA cm-2 and 20.69 mA
EIS tests under different bias voltage were shown in Figure S5 cm-2, respectively, which are approached to the J sc values
and Figure S6. obtained from the J-V curves. The statistics of performance
In accordance with the optimization experiments, the devices parameters distribution were also tested by characterizing
with and without 0.5 mg mL -1 additive were fabricated to test J- about 8 cells for each OTAB concentration. In Figure 8, the cells

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with 0.5 mg mL-1 additive exhibit an excellent reproducibility by

the narrow photovoltaic parameters distribution.

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Figure 7. (a) Nyquist plots of the PSCs measured in the dark with 0.8 V bias voltage. (b) Nyquist plots of the PSCs measured under
1 sun light illumination with 0.8 V bias voltage. (c) Current densitytvoltage characteristics of the PSCs with and without OTAB under
simulated AM 1.5G solar illumination of 100 mW cm-2. (d) IPCE spectra of the corresponding PSCs.

Table 1. Device parameters of the best-performing perovskite solar cells without and with 0.5 mg mL-1 OTAB modified under AM
1.5G illumination.
Sample Direction Jsc (mA cm-2) Voc (V) FF PCE (%)

reverse 21.53 0.97 0.75 15.80

MAPbI3 without OTAB
forward 20.94 0.96 0.71 14.29
reverse 22.50 1.04 0.78 18.32
MAPbI3 with OTAB
forward 22.34 1.04 0.75 17.43

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Figure 8. The photovoltaic parameters distribution for devices with different concentrations of OTAB. (a) V oc, (b) Jsc, (c) FF, (d) PCE.

The long-term stability of PSCs is a challenging issue that is Meanwhile, there was almost no photo-electricity response for
relevant to thermal and humidity. Therefore we executed the the non-additive devices. This significant improvement for
stability test of the PSCs without encapsulation under high OTAB modified devices is mainly ascribed to the hydrophobicity
temperature and high humidity environment, respectively enhancement and defect passivation at MAPbI3 film
(Figure 9 and Figure S8). After aging at 70 , 40f5% relative surface.31,50,51 Additionally, the OTAB protective layer may
humidity for 60 days, the devices with adding 0.5 mg mL-1 OTAB hinder the decomposition product of MAPbI3, such as MAI and
still kept 92% of the initial PCE value, while the PCE of control HI, diffusing to environment, which can regenerate the
devices decreased to 26% under the same condition. Then aging perovskite phase by reacted with PbI 2 in the film.52,53 Similar
at 25 , 75f5% relative humidity for 30 days, the PCE of OTAB phenomenon has been observed when fabricating long chain
modified devices dropped 18% compared to initial value. molecule layer on perovskite films.52

Figure 9. The evolution of normalized (a) V oc, (b) Jsc, (c) FF and (d) PCE for devices with and without OTAB modified under 70 , 40
f5% relative humidity for 60 days and normalized (e) Voc, (f) Jsc, (g) FF and (h) PCE under 25 , 75f5% relative humidity for 30
days.

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17 X. Zheng, B. Chen, J. Dai, Y. Fang, Y. Bai, Y. Lin, H. Wei, X. C.

Zeng and J. Huang, Nat. Energy, 2017, 2, 17102.
Conclusions 18 F. Zhang, W. Shi, J. Luo, N. Pellet, C. Yi, X. Li, X. Zhao, T. J. S.
Dennis, X. Li, S. Wang, Y. Xiao, S. M. Zakeeruddin, D. Bi and M.
In summary, we have demonstrated a new quaternary Graetzel, Adv. Mater., 2017, 29, 1606806.

Journal of Materials Chemistry A Accepted Manuscript

ammonium halide additive (OTAB) in MAPbI 3 film to enhance 19 D. Bi, C. Yi, J. Luo, J.-D. Decoppet, F. Zhang, S. M. Zakeeruddin,
the devices performance and the environmental stability. With X. Li, A. Hagfeldt and M. Gratzel, Nat. Energy, 2016, 1, 16142.
adding 0.5 mg mL-1 OTAB, a prominent increased PCE of devices 20 M. Sun, F. Zhang, H. Liu, X. Li, Y. Xiao and S. Wang, J. Mater.
Chem. A, 2017, 5, 13448-13456.
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from 15.80% to 18.32% was achieved by improving the

21 A. M. A. Leguy, Y. Hu, M. Campoy-Quiles, M. I. Alonso, O. J.
morphology of MAPbI3 thin films and reducing the defect Weber, P. Azarhoosh, M. van Schilfgaarde, M. T. Weller, T.
v•]šÇ }( ‰ Œ}À•l]š •µŒ( X tZ š[• u}Œ U šZ šZ Œu o v Bein, J. Nelson, P. Docampo and P. R. F. Barnes, Chem. Mater.,
humidity stability of OTAB modified devices was much better 2015, 27, 3397-3407.
than control devices. This result may provide a simple and 22 X. Li, M. I. Dar, C. Y. Yi, J. S. Luo, M. Tschumi, S. M. Zakeeruddin,
efficient method to enhance performance and stability of PSCs. M. K. Nazeeruddin, H. W. Han and M. Gratzel, Nat. Chem.,
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23 F. Wang, W. Geng, Y. Zhou, H.-H. Fang, C.-J. Tong, M. A. Loi, L.-
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Conflicts of interest 24 F. Jafarzadeh, S. Javadpour and M. H. Shariat, Ceram. Int.,
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This work was supported by the National Key R&D Program of 27 D. Q. Bi, P. Gao, R. Scopelliti, E. Oveisi, J. S. Luo, M. Gratzel, A.
China (2016YFB0401303), the National Nature Science Hagfeldt and M. K. Nazeeruddin, Adv. Mater., 2016, 28, 2910-
Foundation of China (21676188), the Key Projects in National 2915.
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K. Noel, A. A. Haghighirad, V. M. Burlakov, D. W. deQuilettes,
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The passivation and hydrophobic effects can enhance the stability and optoelectronic properties of
MAPbI3 films significantly.