Advanced Science - 2019 - Yang - Achieving Long Term Operational Stability of Perovskite Solar Cells With A Stabilized

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Perovskite Solar Cells www.advancedscience.com
Achieving Long-Term Operational Stability of Perovskite

Solar Cells with a Stabilized Efficiency Exceeding 20%
after 1000 h
Tae-Youl Yang, Nam Joong Jeon, Hee-Won Shin, Seong Sik Shin, Young Yun Kim,
and Jangwon Seo*
degradation of PSCs.[2] This effect was

Perovskite solar cells (PSCs) with mesoporous TiO2 (mp-TiO2) as the significantly weakened by simply using
electron transport material attain power conversion efficiencies (PCEs) above UV-cut filters during light soaking tests in
22%; however, their poor long-term stability is a critical issue that must be TiO2-employed devices; however, the loss
of power is inevitable as well. Introduc-
resolved for commercialization. Herein, it is demonstrated that the long-term
tion of luminescent photo polymers into
operational stability of mp-TiO2 based PSCs with PCE over 20% is achieved PSCs for converting UV light to visible
by isolating devices from oxygen and humidity. This achievement attributes light is another solution, but is not cost
to systematic understanding of the critical role of oxygen in the degradation effective.[3] Imperfect interfaces, including
of PSCs. PSCs exhibit fast degradation under controlled oxygen charge recombination via deep traps at
atmosphere and illumination, which is accompanied by iodine migration into interfaces, are also known to induce the
stability loss under illumination. Surface
the hole transport material (HTM). A diffusion barrier at the HTM/perovskite
passivation of ETMs is considered as an
interface or encapsulation on top of the devices improves the stability against effective method to prevent the degrada-
oxygen under light soaking. Notably, a mp-TiO2 based PSC with a solid tion through this mechanism.[4]
encapsulation retains 20% efficiency after 1000 h of 1 sun (AM1.5G including Organic hole transport materials (HTMs)
UV) illumination in ambient air. are also essential components for highly
efficient mp-TiO2 based PSCs but are a
major cause of poor long-term stability,[5]
while HTM-free PSCs have showed excel-
The power conversion efficiency (PCE) of perovskite solar cells lent long-term operational stability.[6] Unlike Spiro-OMeTAD,
(PSCs) has exceeded 22% with mesoporous TiO2 (mp-TiO2) poly(triarylamine) (PTAA) combined with a quadruple-cation
as the electron transport material (ETM) on a transparent perovskite has showed excellent long-term thermal stability
conducting oxide.[1] Despite such high PCEs, poor long-term under illumination (without UV light) at inert nitrogen condi-
stability of mp-TiO2 based PSCs is a problematic issue for com- tion.[7] Under similar condition, PSCs with an inorganic HTM
mercialization. Photocatalytic chemical reaction with absorp- without any additives, CuSCN, showed long-term stability as
tion of ultraviolet (UV) light by TiO2 is considered to induce well as a high PCE above 20%.[8] Interestingly, although CuSCN-
incorporated PSCs were quite stable at high temperatures, long-
term stability under light soaking could not be achieved without
Dr. T.-Y. Yang, Dr. N. J. Jeon, Dr. S. S. Shin, Dr. Y. Y. Kim, Dr. J. Seo a barrier layer between CuSCN and Au.
Division of Advanced Materials It should be also noted that atom/ion migration from metal
Korea Research Institute of Chemical Technology (KRICT)
141 Gajeong-Ro, Yuseong-Gu, Daejeon 34114, Republic of Korea electrodes or the organometallic halide perovskites into the
E-mail: jwseo@krict.re.kr HTM is one of the leading causes of the degradation.[9] Recently,
Dr. H.-W. Shin[+] it is reported that the iodine migration in the perovskites is
Department of Energy Science enhanced by illumination, which can be associated with the
Sungkyunkwan University decomposition of the perovskite.[10] Thus, suppressing the
Suwon 16419, Republic of Korea
intrinsic degradation factors such as ion migration as well as
The ORCID identification number(s) for the author(s) of this article overcoming the extrinsic degradation factors such as humid air
can be found under https://doi.org/10.1002/advs.201900528.
and UV light is currently challenging to realize a long-term sta-
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, bility of PCSs including mp-TiO2 and organic HTMs under a
Weinheim. This is an open access article under the terms of the Creative
practical operating condition.
Commons Attribution License, which permits use, distribution and re-
production in any medium, provided the original work is properly cited. We reason that operational stability of PSCs correlates
[+]
with the external factors from the atmosphere because the
Present address: KOS Inc., 150 Jojeong-daero, Hanam-si, Gyeonggi-do
12930, Republic of Korea. stability of PSCs depends on encapsulations or the testing
atmosphere.[11,12] In PSCs with wider bandgap oxides, such as
DOI: 10.1002/advs.201900528 SnO2, as ETMs, long-term operational stability is not perfectly
Adv. Sci. 2019, 6, 1900528 1900528 (1 of 7) © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
21983844, 2019, 14, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/advs.201900528 by CochraneUnitedArabEmirates, Wiley Online Library on [23/05/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advancedscience.com
achieved.[13] The long-term operational stability of 1000 h in Most of them were carried out in ambient air including both
BaSnO3-based PSCs was realized only in a laminate cell. Even moisture and oxygen; they could not specify the reason of the
small amounts of oxygen can affect performances of PSCs degradation and were more focused on the moisture rather
since oxygen can easily react with halides.[14,15] It has also been than oxygen. Here, it is also demonstrated that mp-TiO2 based
demonstrated that oxygen induces photodegradation of methyl- PSCs have long-term stability under illumination including
ammonium lead iodide (MAPbI3).[16,17] Haque and co-workers UV if devices are immune to oxygen and humidity. PSCs
claimed that the degradation stems from the formation of reac- exceeding initial PCEs of 20% have a device structure com-
tive superoxide species in mediating halide vacancies in the posed of fluorine doped tin oxide (FTO)/d-TiO2/mp-TiO2/
perovskite materials.[16,18] In addition, organic semiconductors (FAPbI3)0.95(MAPbI3)0.05/PTAA/Au.
used as charge transport layers can also degrade when exposed When the devices are exposed to oxygen, PCE is reduced,
to oxygen and light.[19] Nevertheless, the effects of oxygen on and this degradation is accelerated by illumination. In order to
the long-term stability of PSCs have attracted only minor atten- clarify the effects of oxygen, the devices were illuminated in a
tion because it has been considered that the perovskites are gas-tight purging chamber with O2 (purity >99.999%) flow as
much less susceptible to oxygen, rather than humidity and described in Figure 1a. After devices were exposed to oxygen
heat, even though oxygen is one of the most exposure species with 1 sun illumination, PCE reduced in half within an hour,
during the manufacture and the operation of PCSs. It is critical (Figure 1b) which is much faster than the degradation in
that the combination of oxygen and light as accelerated aging bulk properties such as absorption and photoluminescence of
factors would cause the deterioration of the perovskites. perovskite films in literature. While all photovoltaic parameters
In this work, we investigate the effects of oxygen on the deg- (Jsc, Voc, and fill factor, FF) decreased with increasing the dura-
radation of PSCs under illumination and reveal that charge tion time of the O2–light exposure, FF was affected the most
transport from the perovskite to the HTM becomes ineffective among the performance factors. The large decrease in FF indi-
by iodine migration before the degradation of bulk perovskite. cates that transport of charge carriers becomes inefficient and/
Several papers have reported the degradation behavior of the or the nonradiative recombination of photo-excited carriers
devices and decomposition of perovskite materials by oxygen is enhanced. In addition, hysteresis in J–V curves increased
and ion migration; however, none of those have dealt with because the drop of PCE for a forward voltage scan was larger
influences of oxygen on the operational stability of the devices. than that for a reverse voltage scan. The broader hysteresis after
Figure 1. Variation of performances of perovskite solar cells (PSCs) with a device stack of FTO/d-TiO2/mp-TiO2/(FAPbI3)0.95(MAPbI3)0.05/
poly(triarylamine) (PTAA) /Au. a) A schematic of the test system for the O2–light exposure. b) Current density versus voltage (J–V) plots under 1 sun
illumination of pristine devices (black), and devices after 1 h of light soaking in O2 (red), and after 1 day of aging under dark and ambient air condi-
tions (blue). Plots of c) PCE, d) short-circuit current density (JSC), e) open-circuit voltage (VOC), and f) fill-factor (FF) as a function of the duration of
the O2–light exposure.
the exposure is likely to be caused by more unbalanced charge and illumination seems to accelerate the degradation in the
transport between electrons and holes near perovskite/ETM presence of O2. Considering the results of Ar-light exposure, we
or HTM interfaces.[20] The performance of the degraded PSC can also exclude photocatalytic effect of TiO2 with UV light as
was not recovered after aging the device in dark and in ambient one of the many causes of the photo-induced degradation of the
air. Such degradation could be observed regardless of the types devices.
of perovskites, ETMs, and HTMs as well as device structure In order to elucidate the cause of the degradation of PSCs
(Figures S1–S3, Supporting Information). by oxygen, we investigated the change in time-resolved photo
On the other hand, when PSC devices were exposed to luminescence (TRPL) of the perovskite thin film with and
Ar atmosphere under illumination or to O2 atmosphere in without charge transport layers according to the O2 exposure
the dark for an hour, a little degradation in Voc and FF was (Figure 2). When a perovskite single layer and a mp-TiO2/
observed, but their performances were completely recovered perovskite bilayer were exposed to O2 and light, photolumi-
after the 1 day aging in the dark (Figure S4, Supporting Infor- nescence (PL) decay curves were slightly extended (Figure 2a).
mation). However, even under dark conditions, the higher The PL enhancement in the perovskite under illumination in
pressure of O2 induced the permanent degradation of PCSs O2 atmosphere is explained by the curing of trapping sites as
(Figure S5, Supporting Information). Consequently, oxygen claimed in literature.[15] The transient behavior in the short-
ingress into PSCs is a main cause of the device degradation, time range (<100 ns) for the mp-TiO2/perovskite double layers,
Figure 2. Time-resolved photoluminescence (TRPL) decay curves of a) the perovskite film, b) perovskite film on TiO2 (d-TiO2/mp-TiO2), and c) perov-
skite film covered with PTAA. All samples are coated on FTO-coated glass substrates. d) TRPL decay curves of the perovskite (black) and PTAA-coated
perovskite (red) on FTO substrates, FTO/perovskite/PTAA stacked samples applied with the following consecutive sequences: after 1 h of O2–light
exposure (blue), then after removal of the PTAA layer (perovskite exposed to air again, magenta), and then after coating a new PTAA layer (green).
e) J–V curves for a device before (black) and after 1 h of the O2–light exposure (red), and after coating a new PTAA and Au on the device in which the
degraded PTAA was removed (blue). f) Nyquist plots at VOC and g) electrical resistance corresponding to semicircles in Nyquist plots as a function of
the duration of the O2–light exposure. Inset: An equivalent circuit for plotting the Nyquist plots (R_low represents a Warburg impedance).
which involves with the electron transport from the perovskite series resistance of the devices was significantly enlarged with
to the TiO2, did not change much by the O2–light exposure increasing the duration of the O2–light exposure. Such a similar
(Figure 2b). However, the PL decay curves for the perovskite/ observation was reported in a previous work where the device
PTAA bilayer were largely extended after the O2–light exposure. with MAPbI3 and Spiro-OMeTAD was exposed to light under
(Figure 2c) After O2 exposure under dark, only the perovskite/ ambient air condition.[12] Even though a humid air atmosphere,
PTAA sample showed slightly extended PL decay. These results this also supported our finding that the O2–light exposure could
indicate that the degradation of PSC devices by oxygen stems cause a deterioration of the perovskite/HTM interface of the
from the interruption of the transport of photo-excited holes device.
from the perovskite into PTAA. It should be noted that the optical absorbance, surface mor-
The hole transport can be hindered most probably due to the phology, and crystallinity of the perovskite film were not varied
barrier formation at the interface between the perovskite and the after the O2–light exposure for 2 h. (Figures S9 and S10, Sup-
HTM or the degradation of the HTM from reducing electrical porting Information). In addition, absorbance and conduct-
conductivity. We designed experiments to reveal where the hole ance of PTAA on a thin layer of the perovskite do not change
extraction is hindered: 1) only the PTAA layer in the degraded by the O2–light exposure (Figure S11, Supporting Information).
device was washed out by using toluene, and 2) then, a new These results indicate that rather than the bulk properties of
PTAA layer was recoated via spin-coating on top of the perov- the perovskite and PTAA, the interfacial properties are more
skite film in the degraded device and a new Au electrode was likely to be affected by the exposure.
deposited on top. TRPL measurements and J–V measurements Next, depth profiles of time-of-flight secondary ion mass
were conducted before and after the O2–light exposure and the spectrometry (ToF-SIMS) for the degraded PSC devices
removal and recoating of the PTAA layer (Figure 2d,e). were compared to that of a pristine device (Figure 3a,b). In
Interestingly, the device in which the PTAA layer was the degraded devices, interestingly, we observed no change in the
removed showed a similar PL decay curve to the degraded oxygen profile, whereas we found a large variation in the iodine
device by the O2–light exposure. It is likely that the PTAA in profile. Iodine concentration in the PTAA layer was increased
the degraded device cannot extracts holes. When a new PTAA after the O2–light exposure. The accumulation of iodine at the
layer was coated on the sample, the PL decay curve was short- Au/PTAA interface could also be identified. Larger amounts of
ened but was still much longer than that of the pristine sample iodine within PTAA and the interface were observed in devices
(denoted by Perov./PTAA). Replacing the PTAA layer restored with longer duration of the O2–light exposure (Figure 3c).
the performance of the PSC partly, but it was still not perfect The incorporation of iodine into PTAA seems to inhibit the
as well. The PCE of the devices rose from 11.0% to 16.2% for hole transport. The existence of iodine in PTAA stems from the
reverse scans by replacing the degraded PTAA with a new one diffusion of iodine from the perovskite to the PTAA layer by
but was lower than the initial PCE of 20.3%. While Jsc was O2 and light. Photo-excited holes bind with iodine ions, thus
fully recovered, FF increased from 51% to 67%; neither Voc nor forming neutral iodine.[10] The photo-excited neutral iodine
hysteresis was improved. Removing the PTAA and coating a with high activity might tend to diffuse into PTAA in which
new PTAA layer on a pristine sample have little effect on the iodine activity is much lower. In addition, several experimental
performance of the device (Figure S6, Supporting Information). results show that O2 provides enhanced iodine activity and cre-
The incomplete recovery of the PL decay curves and J–V curves ates iodine vacancies in the perovskite,[21] thereby activating
illustrate that the O2–light exposure induces degradation of the the diffusion of iodine out of the perovskite. The diffusion of
perovskite near the interface with the PTAA as well as degrada- iodine into PTAA was also observed in the degraded device by
tion of the PTAA layer. exposing to high-pressure O2 in the dark. If iodine is irrevers-
The interface between the PTAA and the Au electrodes does ibly removed by a condensed matter sink such as the HTM,
not contribute to the degradation by the O2–light exposure. the perovskite is eventually degraded into a nonstoichiometric
When Au electrodes on the degraded device were replaced by phase.
newly deposited Au electrodes after removing old ones, the To address the solution to prevent photo-induced degrada-
performance of the device was not recovered (Figure S7, Sup- tion in oxygen-contained atmosphere, we can consider two
porting Information). approaches: 1) suppression of the diffusion of iodine and
We also observed that interfacial adhesion between the 2) isolation of devices from oxygen. For the first solution, a
perovskite and the PTAA strengthened by the O2–light expo- np-Al2O3 layer was inserted between the perovskite and PTAA
sure in this experiment. In order to remove Au electrodes from as a diffusion barrier. This device showed good stability against
devices, a tape detaching method was employed. The PTAA the O2–light exposure (Figure 4a). The PCE of the devices was
layer on the degraded device was not completely removed by slightly decreased just after the exposure, but it was recovered
detaching tape, while the PTAA layer in pristine device was after aging for a day under dark in ambient air conditions.
removed clearly (Figure S8, Supporting Information). This The suppression of the iodine diffusion from the perovskite
result can be an evidence on chemical interaction between the into PTAA layer was apparently confirmed by ToF-SIMS depth
perovskite and the PTAA. profiling (Figure S12, Supporting Information). When the
The hindered hole transport leads to increase of series resist- np-Al2O3 layer was inserted not between the perovskite and
ance of the devices. The increase of series resistance can be PTAA but between PTAA and Au, it could not inhibit the
directly measured by analyzing impedance spectra (Figure 2f,g). degradation induced by the O2–light exposure (Figure S13,
Pristine PSC devices show two semicircles in Nyquist plots. Supporting Information). These findings imply that the
The first semicircle at high frequencies corresponding to np-Al2O3 layer is not enough as a barrier layer to prevent the
Figure 3. Depth profile of elements in PSCs from time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements a) before and b) after
1 h of O2–light exposure. c) Variation of depth profiles with increasing exposure duration. Diffusion of iodine ions within the PTAA especially increases
with longer exposure times to O2 and light. d) Schematic to describe the activation of iodine diffusion by oxygen and light.
outside oxygen from penetrating into the device but is still For the second solution, we have encapsulated PSC devices
effective to suppress iodine diffusion from the perovskite to by laminating face-sealing adhesive sheets on the top of the
the PTAA layer. The improved long-term stability of PSCs with devices. In order to remove trapped air during the lamination
adding of a np-Al2O3 buffer in a literature seems to attribute to and to improve the adhesion between the devices and the adhe-
this effect.[22] sive sheets, the encapsulated devices were aged in an autoclave.
Figure 4. Suppression of the degradation induced from exposure to O2 and long-term device stability of encapsulated perovskite solar cells. J–V scans
of devices a) with a np-Al2O3 layer between the perovskite and PTAA layers and b) with encapsulation. c) Shelf test results of the encapsulated device
under 85 °C and 85% RH conditions and d) long-term operational stability of the encapsulated devices under simulated real operating conditions
(maximum power point tracking under 1 sun AM1.5G illumination including UV without controlling temperature in ambient air).
Then, the devices were completely protected against the ingress (5000 rpm) step, 1 mL of ethyl ether was poured onto the substrate after
of oxygen and moisture. As shown in Figure 4b, the device is 15 s. The intermediate phase substrate was then put on a hot plate at
150 °C for 10 min. After that, PTAA were spin-coated as hole transport
not degraded at all after 2 h of the O2–light exposure.
materials. PTAA solution in toluene (11 mg mL−1) was prepared, and
We also examined the long-term stability of the encapsu- 3.7 µL Li-bis(trifluoromethanesulfonyl) imide (Li-TFSI) in acetonitrile
lated PSCs. First, we conducted a shelf test under 85 °C and (340 mg mL−1) and 3.7 µL 4-tert-butylpyridine (tBP) were added.
85% relative humidity (RH) conditions to evaluate encapsula- The PTAA solution was spin-coated on (FAPbI3)0.95(MAPbBr3)0.05/
tion efficiency (Figure 4c). PCE of the device was maintained mp-TiO2/d-TiO2/FTO substrate at 3000 rpm for 30 s. These all
up to 96% of its initial PCE after 1000 h (from 20.9% to 20.0%). processes were carried out in air with controlling temperature (≈23 °C)
In this case, only 0.9% efficiency decrease was found in early and humidity (≈20% RH). Finally, the 70 nm thick Au counter electrode
was deposited by thermal evaporation. The active area of this electrode
burn-in stage due to slight decrease of JSC and FF. There is no was fixed at 0.16 cm2.
additional drop in the device performance. This assures that Characterizations and Measurements: The morphologies of the
the encapsulation of the device is fairly solid. perovskite film coated with or without PTAA and the prepared devices
The long-term operational stability under real operating were investigated using field emission scanning electron microsope (FE-
conditions was also investigated with the encapsulated device SEM, Tescan Mira 3 LMU FEG).
(Figure 4d). Surprisingly, the PCE retained 96% of its initial The absorption spectra were obtained using a UV–vis
spectrophotometer (Shimadzu UV 2550) in the wavelength range of
value (20.6%) after 1000 h operation (maximum power point
300 to 900 nm.
tracking, MPPT) under 1 sun AM1.5G illumination of a xenon The photovoltaic properties of the devices were measured using
lamp including UV despite using mp-TiO2 as the ETM. The a solar simulator (Oriel Class A, 91195 A, Newport) with a source
final PCE from a J−V sweep was 20.0%. Even though PSCs meter (Keithley 2420) at AM1.5G 100 mA cm−2 of illumination and a
were encapsulated with the face-sealing adhesive sheets, the calibrated Si-reference cell certificated by National Renewable Energy
long-term stability of the PSCs was not guaranteed without Laboratory (NREL). The J−V curves were measured along reverse scan
direction from 1.3 to −0.2 V or forward scan direction from −0.2 to
the aging in the autoclave. As a result, a successful long-term
1.3 V. The step voltage and dwell time were fixed at 10 mV and 50 ms,
stability of PSCs can be realized by a solid encapsulation to respectively. The J–V curves of all the devices were measured in ambient
completely block oxygen and even moisture in the atmosphere, air (25 °C, ≈30% RH) by masking the active area using a metal mask
thereby impeding the ion movement as well as the sublimation with an area of 0.096 cm2.
of volatile components from the perovskite. Time-resolved photoluminescence decay profiles were measured
Overall, the effects of oxygen on the operational stability at 780 nm with 550 nm excitation of optical parameter oscillator laser
of PSCs were systemically investigated in this study. PSCs system (NT 342A-10-AW, EKSPLA). The pulse energy was strongly
attenuated to less than 1 µJ, in order to avoid nonlinear effects such
under illumination quickly degraded in oxygen atmosphere as exciton–exciton annihilation. Emissions from samples were collected
due to hindering charge transport from perovskite to HTMs. by a monochromator (SP2150, Princeton Instruments) equipped with a
We revealed that the degradation is induced by iodine diffu- photomultiplier tube (PMT, Hamamatsu H10721-20). The output signal
sion into the PTAA layer without applying electrical bias or from a PMT was recorded with a 500 MHz digital oscilloscope (DSO-X
heat. Diffusion of iodine from the perovskite into the PTAA 3054A, Agilent).
layer induces reduced hole transport ability near the interface Depth profiles of elements were measured by time-of-flight secondary
ion mass spectrometer (ION-TOF GmbH) equipped with a 1 keV Cs+
between the perovskite and the PTAA. Pure oxygen atmos-
primary ion beam for the sputtering and 30 keV Bi+ pulsed primary ion
phere is an accelerated condition as compared with ambient beam for the analysis.
atmosphere; however, it seems that oxygen has critical role on Impedance spectroscopy measurements were performed by using
the photo-induced degradation of PSCs. Long-term stability of an electrochemical impedance spectroscopy (model PGSTAT302N,
mp-TiO2 applied PSCs can be simply attained by protecting the AUTOLAB). The AC voltage was 0.2 V, and the frequency was swept
devices from oxygen and moisture, since even a small amount from 1 MHz to 10 mHz. The values of resistance and capacitance were
determined by fitting the Nyquist plots of the impedance (Z′′ vs Z′)
of oxygen notably affects the photo-induced degradation of
using the software ZView (Version 3.1c, Scribner Associates Inc.).
PSCs for a long-term period. The X-ray diffraction (XRD) spectra were measured using a Rigaku
Smart Lab X-ray diffractometer to identify the crystal phase of the
prepared films.
Experimental Section Long-Term Stability Tests: For long-term stability tests, PSC devices
were encapsulated by laminating face-sealing adhesive sheets developed
Device Fabrication: A 60 nm thick dense blocking layer of TiO2 for organic electronic devices.[23] The lamination was conducted at 60 °C
(bl-TiO2) was deposited onto an FTO (Pilkington, TEC8) substrate of roll temperature in dry air.
by spray pyrolysis deposition carried out using a 20 × 10−3 m Damp-heat shelf test was carried out in the chamber in which
titanium diisopropoxide bis(acetylacetonate) solution (Aldrich) at temperature and relative humidity were maintained at 85 °C and 85%
450 °C. 100 nm thick mesoporous TiO2 (TiO2 nanoparticles: average RH, respectively. PCE of the device was periodically measured under
particle size = ≈50 nm, crystalline phase = anatase) films were AM1.5G simulated sun light after cooling the device down to room
spin-coated onto the bl-TiO2/FTO substrate using diluted pastes temperature.
(SC-HT040, ShareChem, Korea) and were calcined at 500 °C for 1 h Long-term operational stability tests were performed by maximum
in air to remove the organic portion. To fabricate perovskite solar power point tracking using a source meter (Keithley 2420, USA)
cells based on (FAPbI3)0.95(MAPbBr3)0.05, the perovskite solution operated by the self-written software with a perturb–observe algorithm.
was prepared by dissolving 889 mg mL−1 of FAPbI3, 33 mg mL−1 of A 450 W xenon lamp (Oriel, USA) with an AM1.5G filter was used as
MAPbBr3, and 33 mg mL−1 of MACl in DMF/DMSO (8:1 v/v) mixed a light source, and light intensity was calibrated by a silicon reference
solvent. Then, the solution was coated onto the mp-TiO2/bl-TiO2/ cell. The temperature of the devices under the light soaking was not
FTO substrate by two consecutive spin-coating steps, at 1000 and controlled. Ambient temperature and humidity were maintained at 25 °C
5000 rpm for 5 and 20 s, respectively. During the second spin-coating and 30% RH, respectively.
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S. M. Zakeeruddin, M. Grätzel, Science 2017, 358, 768.
Supporting Information is available from the Wiley Online Library or [9] a) E. Bi, H. Chen, F. Xie, Y. Wu, W. Chen, Y. Su, A. Islam, M. Grätzel,
from the author. X. Yang, L. Han, Nat. Commun. 2017, 8, 15330; b) G. Divitini,
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Acknowledgements A. Hagfeldt, M. Grätzel, ACS Nano 2016, 10, 6306; d) Q. Jeangros,
T.-Y.Y. and N.J.J. contributed equally to this work. The authors are M. Duchamp, J. Werner, M. Kruth, R. E. Dunin-Borkowski,
grateful to Hee Won Seo at the KAIST Analysis Center for Research B. Niesen, C. Ballif, A. Hessler-Wyser, Nano Lett. 2016, 16, 7013;
Advancement (KARA) for ToF-SIMS measurements and to LG Chem. e) S. Kim, S. Bae, S.-W. Lee, K. Cho, K. D. Lee, H. Kim, S. Park,
Ltd. for providing the encapsulation sheets. This work was supported G. Kwon, S.-W. Ahn, H.-M. Lee, Y. Kang, H.-S. Lee, D. Kim,
by the Korea Institute of Energy Technology Evaluation and Planning Sci. Rep. 2017, 7, 1200; f) Z. Li, C. Xiao, Y. Yang, S. P. Harvey,
(KETEP) and the Ministry of Trade Industry & Energy (MOTIE) of the D. H. Kim, J. A. Christians, M. Yang, P. Schulz, S. U. Nanayakkara,
Republic of Korea (No. 20163010012470), the National Research C.-S. Jiang, J. M. Luther, J. J. Berry, M. C. Beard, M. M. Al-Jassim,
Council of Science & Technology (NST) (No. CAP-18-05-KAERI), and K. Zhu, Energy Environ. Sci. 2017, 10, 1234; g) J. Yang, T. L. Kelly,
also the Global Frontier R&D Program on Center for Multiscale Energy
Inorg. Chem. 2017, 56, 92; h) T. Zhang, X. Meng, Y. Bai, S. Xiao,
System (NRF-2016M3A6A7945503) and the Basic Science Research
C. Hu, Y. Yang, H. Chen, S. Yang, J. Mater. Chem. A 2017, 5,
Program (NRF-2015R1A6A3A04058164) through the National Research
1103.
Foundation (NRF) funded by the Ministry of Science and ICT (MSIT) of
the Republic of Korea. [10] G. Y. Kim, A. Senocrate, T.-Y. Yang, G. Gregori, M. Graetzel, J. Maier,
Nat. Mater. 2018, 17, 445.
[11] K. Domanski, E. A. Alharbi, A. Hagfeldt, M. Grätzel, W. Tress,
Nat. Energy 2018, 3, 61.
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Advanced Science - 2019 - Yang - Achieving Long Term Operational Stability of Perovskite Solar Cells With A Stabilized

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Perovskite Solar Cells www.advancedscience.com

Achieving Long-Term Operational Stability of Perovskite

degradation of PSCs.[2] This effect was

Supporting Information [8] N. Arora, M. I. Dar, A. Hinderhofer, N. Pellet, F. Schreiber,

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