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Metal Acetylacetonate Series in Interface Engineering
Communication
for Full Low-Temperature-Processed, High-Performance,
and Stable Planar Perovskite Solar Cells with Conversion
Efficiency over 16% on 1 cm2 Scale
Wei Chen, Leiming Xu, Xiyuan Feng, Jiansheng Jie, and Zhubing He*
For the past several years, organic–inorganic hybrid pervoskite
materials have attracted tremendous attention of researchers
in such multidisciplinary areas as photovoltaics,[1,2] photo­
detectors,[3] lasers,[4] and light-emitting diodes.[5–7] With a certi-
fied 22.1% conversion efficiency in current record[8] and no sign
that it is reaching a bottleneck, perovskite solar cells (PSCs)
show big potential to be comparable to commercial crystal-
line silicon solar cells.[9,10] The initial device configuration of
PSCs originated from the dye sensitized solar cells, where both
mesoporous and compact metal oxide films serve as electron
collecting and transporting layer while the organic acceptor
molecules play as hole transport layer.[11] Although those
mesoporous PSCs have achieved over 20% conversion effi-
ciency,[12,13] complex structure, complicated carrier transport
routes, and tedious processes will cast a cloud in the scale-up
manufacture of PSCs. Owing to superior absorportion coef-
ficient and ultralong diffusion length of carriers in perovs-
kite layers,[14] much simpler planar heterojunction PSCs have
drawn much more attention of researchers. Till now, the planar
champion cell has achieved a record of over 19% conversion
efficiency.[15–17] Besides simple structure, low process temper-
ature is another merit of the planar PSCs,[18] which includes
both normal structured devices (n-i-p) and inverted ones (p-i-n).
However, without mesoporous scaffold, normal structured
planar PSCs generally suffer a serious hysteresis in I–V curves
under different scanning directions, due to the possible facts
that originated from the ion migration, surface states trap-
ping charge carriers, or dielectric polarization by ferroelectric
W. Chen, L. Xu, X. Feng, Prof. Z. He
Department of Materials Science and Engineering
Shenzhen Key Laboratory of Full Spectral Solar
Electricity Generation (FSSEG)
Southern University of Science and Technology, China
No. 1088, Xueyuan Rd. P.C. 518055
Shenzhen, Guangdong, P. R. China
E-mail: hezb@sustc.edu.cn
Prof. J. Jie
Institute of Functional Nano and Soft Materials (FUNSOM)
and Collaborative Innovation Center of Suzhou
Nano Science and Technology
Jiangsu Key Laboratory for Carbon-Based Functional
Materials and Devices
Soochow University, P.C. 215123
Suzhou, Jiangsu, P. R. China
DOI: 10.1002/adma.201603923
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properties,[17,19–23] whereas, the hysteresis effect could be
eliminated in such inverted planar PSCs as transparent
conductive oxide (TCO)/hole transport layer (e.g., poly(3,4-
ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS))/
perovskite/electron transport layer (e.g., phenyl-C61-butyric
acid methyl ester (PCBM))/metal electrode,[24–26] which also
demonstrated good performance and reproducibility. There-
fore, hysteresis-free, low process temperature and simpler
structure and process of the inverted planar PSCs with high
conversion efficiency are attracting more and more attention
of researchers. Besides performance, stability is another crucial
topic on the way to scale-up commercilization of PSCs, which
is influenced by at least three factors described below. First, per-
ovskite is very sensitive to humidity and easily decomposed by
a trace amount of hydramolecules,[27,28] which is a key concern
for even encapsulated PSCs working in an outdoor environ-
ment. Second, the chemical and thermal stability of materials
involved in the whole PSCs will shrink the process window
and herein determine the factual feasibility of the process in
manufacture. Last but not the least, ions moving in perovskite
induced by such fields as optical, electrical, thermal, etc., lead to
structure change of perovskite and hence deteriorate the perfor-
mance,[29] which threats the stability of PSCs in long-term uti-
lization. Although improving the perovskite itself by changing
composition is an important way to resolve those problems
listed above [Cs+, FA+, Br−, SCN−, etc.],[9,30–32] interface engi-
neering is also an indispensable pathway for the commercili-
zation of PSCs, as well as CdTe, Cu-In-Ga-Se (CIGS) thin film
solar cells.
Based on those understanding, we aim to resolve some of
the above concerns of PSCs through interface engineering.
As we know, the effective charge extraction of both holes and
electrons from the perovskite films originated from good band
alignment of solar cells and has contributed more to the high
performance of planar structure PSCs.[33] Various evaporated
and solution-processed inorganic and oganic cathode inter­
facial layers (CILs) have been successfully empolyed recently to
modulate the interfacial properties of the cathode in inverted
structure PSCs.[24,34–47] Nevertheless, most of them are either
sensitive to moisture, oxygen, and organic solvents in process,
or suffer from instability in thermal and light soaking environ-
ment, which is far from so called “multi-stability” with stability
both in manufacturing process and hereafter utilization envi-
ronment, and finally devite them from the way-out for the mass
production of PSCs. Besides, their high cost and complicated
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processes for the preparation of PSCs also hinder the utiliza- photoelectron spectrometer (UPS) data (Figure S2 and S3,

tion of PSCs in the future. Multistability, low cost, and simple
processed CILs are essential to the development of PSCs.
In this work, we employ a series of metal acetylacetonates
(MAcac, where M represents titanium (Ti), zirconium (Zr),
and hafnium (Hf)) as CILs to achieve both “multistable” and
high-performance planar PSCs. NiOx nanocrystal (NiOx NCs)
condensed thin film, instead of PEDOT:PSS, was employed
as hole transport layer (HTL) in our planar PSCs to minimize
the open circuit voltage (Voc) losses. PSCs with structure ITO/
NiOx/MAPbI3/PCBM/MAcac/Ag were fabricated to investi-
gate the impact of those interfacial layers on the performance
and stability of PSCs. The best photovoltaic performance was
achieved by using ZrAcac as interfacial layer, which demon-
strated a power conversion efficiency of 18.69% with a open cir-
cuit voltage (Voc) of 1.079 V and a short circuit current density
(Jsc) of 22.17 mA cm−2. In contrast to that of the control devices
(only 12.43%) without metal acetylacetonates CILs, the remark-
able performance enhancement is likely owing to minimum
contact barriers at PCBM/MAcac/Ag interface. Moreover, our
devices demonstrated excellent stabilities in inert environment
or when exposed to moisture, which attributed to the stable
NiOx HTL and multistability of the metal acetylacetonates CILs
film.
The device configuration of our inverted structure PSCs and
the chemical structure of the metal acetylacetonates interfacial
materials are presented in Figure 1A,B. The perovskite film was
sandwiched by NiOx and PCBM to form a p-i-n planar arch-
itechture, where the holes and electrons were transported to the
electrodes through NiOx and PCBM, respectively. Energy level
diagrams for different used layers are depicted in Figure 1C.
Energy values used here are quoted from literatures except
those of metal acetylacetonates interfacial materials which
were calculated from their absorption spectra and ultroviolet
Communication
Supporting Information).[48]
NiOx NCs were synthesized according to literature methods
with slight modification (see more details in the Supporting
Information).[49] The TEM and XRD characteristics reveal
that the obtained NiOx NCs are well-crystallized cubic struc-
ture (three main diffraction peaks at 2θ of 37.14°, 43.28°, and
62.69°) and have small sizes of ≈4–7 nm (Figure S1, Sup-
porting Information).[50] NiOx NCs were easily dissolved in
water and isopropanol mixed solvents to form a highly stable
ink and coated on ITO glass substrates at room temperature
without any thermal annealling. Atomic force microscopy
(AFM) images demonstrated that the as-prepared NiOx NCs
on ITO substrate were uniform and freeflaw films with nano-
structured morphology (Figure 1D and Figure S4, Supporting
Information).
Perovskite films were deposited on NiOx HTL by one-step
method with solvent engineering strategy (see more details in
the Supporting Information).[51] XRD pattern of the MAPbI3 on
ITO substrate confirmed the crystalline structure of the depos-
ited perovskite film, and no signal of PbI2 residue was observed
(Figure S5, Supporting Information). It is recognized that the
morphology of perovskite films was extremely important to
achieve high performance.[52] According to the SEM image in
Figure S5 (Supporting Information) and Figure 1E, uniform
and pinhole free perovskite films with large grain sizes (300 nm
to 1 µm) were obtained in our case. Large grain size and espe-
cially the compact, well-crystallized film morphology are pre-
requisites for a high device performance, since a higher density
of larger grains might have less grain boundary and positively
suppress charge recombination due to the localized less density
of charge traps in these regions.[53] Cross-section SEM image of
a typical device demonstrates a planar configuration that each
layer is uniform and able to be clearly distinguished (Figure 1F).

Figure 1. Device configuration and morphology characteristics of our inverted planar structure perovskite solar cell. A) Schematic diagram of various
stack layers in our perovskite solar cell architecture: ITO/NiOx/MAPbI3/PCBM/MAcac/Ag; B) molecular structures of the metal acetylacetonates CILs
studied here; C) schematic drawing of the band energy diagrams for the inverted structure perovskite solar cell; D) 2D topography AFM height images
of the NiOx NCs as coated on ITO substrate, the AFM image sizes are 10 µm × 10 µm for each image. The surface rms roughness is 11.37 nm;
E) surface SEM image of the MAPbI3 film prepared on NiOx-coated ITO substrate (scale bars: 500 nm); F) cross-sectional SEM image of the inverted
structure perovskite solar cell with ZrAcac cathode interfacial layer (scale bar: 500 nm).

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The estimated thickness of the absorber was ≈320 nm which is Figure S10–S12 (Supporting Information). The survey scan for
Communication

thick enough to fully utilize the solar spectrum (Figure S6, Sup-
porting Information). Moreover, the PCBM layer with average
thickness of 100 nm was fully covered on top of perovskite with
dense and uniform morphology and further confirmed by the
surface SEM and AFM images (Figure S7 and S8, Supporting
Information). The surface rms roughness for the perovskite
film was ≈12.7 nm. While the value was reduced to 2.8 nm after
coating with PCBM on top. Dense and uniform PCBM layers
are able to effectively isolate perovskite from electrodes to avoid
direct contact between them, which is critical to improve the
stability of PSCs.[44]
The MAcac CILs were then spun on the surface of the PCBM
layer with diluted methanol solution before evaporating the
silver electrode. As shown in Figure S7 (Supporting Informa-
tion), there was almost no influence on the morphology of the
PCBM layer after coating with CILs as well as its optical proper-
ties (Figure S6, Supporting Information). The rms roughness
for the PCBM/ZrAcac and PCBM/HfAcac did not vary while a
little increase for the PCBM/TiAcac was observed, when com-
pared with the existing PCBM layers (Figure S8, Supporting
Information). The homogeneous coverages of the MAcac CILs
were further confirmed by the energy-dispersive X-ray spec-
trometry (EDS) analysis. As shown in Figure S9 (Supporting
Information), homogenous color distribution for metal ele-
ments of the MAcac (Ti, Zr, Hf,) in the EDS mapping images
demonstrates excellent film quality of the coated MAcac CILs.
Note that there is no thermal annealing or any post-treat-
ment for the coated MAcac films. To identify the chemical
structure change of those coated MAcac films in contrast to
their corresponding source powders, we analyzed the chem-
ical components of the MAcac films prepared on glass sub-
strate by X-ray photoelectron spectroscopy (XPS), as shown in
both powder and thin film samples performed in the range of
0–1200 eV binding energy (BE) shows almost unmoved char-
acteristic peaks of the elements. More specifically, the XPS
spectra of the core level of Ti 2p, Zr 3d, and Hf 4f for the thin
film samples demonstrate similar spin–orbit doublet as com-
pared to the original powder samples.[48,54,55] The same results
were obtainted for the C 1s and O 1s XPS scan curves as well.
Those XPS analyses confirm our hypothesis that there was little
structure variation of the coated thin films in contrast to their
source powders.
The work function match at the PCBM/Ag cathode inter-
faces is very important for achieving high-performance inverted
planar PSCs.[25] The effect of MAcac CILs on the work function
of electrode is therefore investigated by scanning kelvin probe
microscopy (SKPM) and UPS. As shown in Figure 2A–D, the
surface potential of the evaporated silver can be largely reduced
after modified with thin layers of MAcac CILs. According to the
function ϕAg = ϕt - eVsp, where ϕt is the work function of conduc-
tive tip and Vsp the measured surface potential determined from
the surface potential profiles (Figure 2E). The work functions
ϕAg for these CILs modified silver were determined to be ≈4.25,
4.20, and 4.31 eV for TiAcac/Ag, ZrAcac/Ag, and HfAcac/Ag,
respectively, which is well consistent with the results calculated
from their UPS spectra (Figure 2F). It is already recognized that
the reduced work functions of Ag electrode by MAcac CILs are
derived from the dipoles formed along the interfaces,[47,48,56,57]
which leads to the ohmic contact between PCBM and Ag and
hence “barrier-free” electron extraction from PCBM to silver.
Interfacial charge-carrier characteristics were investigated by
steady-state and time-resolved photoluminescence (PL) spec-
troscopy. Figure S13 (Supporting Information) presented the
room-temperature PL spectra for the perovskite films correlated

Figure 2. The surface potential characteristics of the evaporated silver with and without metal acetylacetonates interfacial layers measured by scan-
ning kelvin probe microscopy (SKPM). A) Ag, B) TiAcac/Ag, C) ZrAcac/Ag, and D) HfAcac/Ag. The image sizes are 10 µm × 10 µm for each one;
E) the corresponding surface potential profiles (Vsp). F) Ultraviolet photoelectron spectroscopy (UPS) spectra of evaporated Ag with and without
metal acetylacetonates interfacial layers. G) Room-temperature photoluminescence (PL) decay curves for perovskite film on ITO, perovskite film on
NiOx/ITO, the device of PCBM/Ag, PCBM/TiAcac/Ag, PCBM/ZrAcac/Ag, and PCBM/HfAcac/Ag (excitation wavelength: 405 nm pulsed laser).

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to various interfaces. Perovskite-only films on glass demon- devices with MAcac CILs demonstrates huge improvement,

strate the highest PL intensity due to strong radiative recom-
bination of the photogenerated charge carriers. The PL density
of perovskite films on NiOx HTM was apparently decreased
due to obvious charge carrier transfer from perovskite to NiOx
HTM. A further quenching is expected for a complete device
where the charge carriers would transfer to the corresponding
contacts through the charge transport layers. The utmost PL
quenching was observed for the devices with MAcac CILs, dem-
onstrating the highest charge carrier transfer efficiency at those
interfaces. This phenomena is more clearly illustrated by the
following time-resolved PL spectra. As presented in Figure 2G,
the time-resolved PL spectra of the devices with MAcac CILs
show a fastest decay as compared to the control device and pure
perovskite films after excitation with a pulsed laser (405 nm).
Those results demonstrate that cathode interface modifi­
cation with MAcac would promote more efficient charge car-
rier transfer at cathode interfaces, and boost the performance
improvement of these inverted planar PSCs.
The photovoltaic performance for the inverted planar PSCs
with and without MAcac CILs is investigated in details. The
current density (J)–voltage (V) characteristics under AM 1.5 G
simulated sunlight (100 mW cm−2) are shown in Figure 3A and
a summary of the key parameters is displayed in Table 1. The
PCBM/Ag control device exhibits a power conversion efficiency
(PCE) of only 12.43%, with an open-circuit voltage (Voc) of
1.048 V, a short-circuit current density (Jsc) of 20.03 mA cm−2,
and a fill factor (FF) of 59.1%. Strikingly, employing the MAcac
as the CILs can significantly improve device performance, par-
ticularly Jsc and FF. As shown in Figure 3A, performance for
Communication
resulting in a optimal PCE of 18.36%, 18.69%, and 18.34%
for TiAcac, ZrAcac, and HfAcac, respectively, which substan-
tially surpass the performance of control device without CILs.
FF over 77% for all MAcac based devices can be achieved. The
enhanced Jsc and FF for those MAcac CILs modified devices can
be interpreted as a consequence of the reduced contact barrier
and enhanced charge carrier extraction efficiency at the PCBM/
Ag interface after integrating the MAcac CILs, which have been
demonstrated by above investigations. The increase of the Voc
for the MAcac-modified devices compared to the control one
can be ascribed to the reduced potential loss at the PCBM/Ag
interface due to better energy level alignment, which can be
further demonstrated by the dark current J–V curves. As shown
in Figure S14 (Supporting Information), dark J–V curves for
the devices with and without MAcac CILs showed quite dif-
ferent charge injection and rectification characteristics. Jo was
obviously suppressed due to the inserted MAcac CILs. The rela-
tion between Jo and Voc was given by the following equation:
kT  J sc 
Voc = ln  + 1 (1)
q  J0 
According to Equation (1), Jo was directly correlated with Voc,
smaller Jo results in a higher Voc.
Figure 3B presents the external quantum efficiency (EQE)
spectra of the corresponding solar cells. As shown, devices with
MAcac CILs exhibit a much higher photon-to-electron conver-
sion efficiency as compared to the control device. These results
confirm again that the interfacial modification with MAcac is

Figure 3. J–V characteristics and hysteresis behaviors for the inverted planar perovskite solar cells with various metal acetylacetonates: A) J–V curves
under the AM 1.5 G simulated sunlight illumination (100 mW cm−2) for the inverted planar perovskite solar cells with and without metal acetylaceton­
ates interfacial layers; B) external quantum efficiency (EQE) spectra for the corresponding devices; J–V curves for C) PCBM/TiAcac/Ag, D) PCBM/
ZrAcac/Ag, and E) PCBM/HfAcac/Ag devices under different scanning direction (short circuit (SC) to open circuit (OC); open circuit (OC) to short
circuit (SC)); and F) stable photocurrent output for the corresponding devices measured at the maximum power point.

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Table 1. Summary of the photovoltaic parameters for the inverted planar scanning direction. The PCE of the device with the ZrAcac
Communication

perovskite solar cells with and without various MAcac interfacial layers CIL could achieve 18.50% scanning from short circuit to open
under AM 1.5G simulated sunlight illumination (100 mW cm−2), the
optimal thicknesses of the corresponding MAcac CILs were presented
circuit, and 18.69% from open circuit to short circuit. For the
as well. TiAcac and HfAcac-based devices, there are no obvious varia-
tions as well in terms of PCE when changing the scanning
Devices Jsc Voc FF η Rs Rsh direction. Besides, as shown in Figure 3F, our MAcac-based
[mA cm−2] [V] [%] [%] [Ω cm2] [kΩ cm2] devices show an instant rise of the photocurrent to a maximum
PCBM/Ag 20.03 1.048 59.1 12.43 8.6 3.2 value during constant illumination and demonstrated a highly
stable output with no obvious loss after long-time light soaking
PCBM/TiAcac(9.0 nm)/Ag 22.14 1.076 77.6 18.36 2.1 5.7
(500 s). There are several explanations concerning this hyster-
PCBM/ZrAcac(8.3 nm)/Ag 22.17 1.079 78.1 18.69 1.7 6.3 esis effect and its possible mechanism is still under debate.[53]
PCBM/HfAcac(7.9 nm)/Ag 22.12 1.079 77.0 18.34 1.9 5.9 Here, we suppose that both ion migration and trap detrapping
processes may play a role based on our investigation and other
reports.[17,40,41,53] For the inverted structure devices, deposited
an effective way to improve device performance by reducing PCBM are able to diffuse into the grain boundary in perovs-
the contact barrier, improving charge extraction efficiency at kite film to passivate charge trap states at the interfaces and
the cathode. Note that the best device performance is achieved suppress the ion migration along grain boundaries of perovs-
by ZrAcac CIL and its similar structures and functionalities as kite, thus leading to an effective impact on the suppression of
TiAcac and HfAcac CILs. We thus employed the ZrAcac devices the hysteresis, which is consistent with our and other groups’
as a paradigm to investigate the impact of thickness of MAcac observations.[17,40,41,53,58]
CILs on the device efficiency. The J–V curves are presented in In order to demonstrate the superiority of this work toward
Figure S15 (Supporting Information). An optimal ZrAcac CIL mass production of PSCs, as a proof of scalable concept, devices
concentration of 1 m (≈8.3 nm) was found. Strikingly, devices with aperture area over 1 cm2 were fabricated by using ZrAcac
with ZrAcac CILs exhibit PCE over 17% in the wide range of as CIL. The J–V characteristics of the optimal device were pre-
CILs thicnesses (≈2.6–19.3 nm), which means that our metal sented in Figure 4A. The intact device photograph was shown
acetylacetonates CILs are thickness-insensitive (Table 2). This as well. Our champion cells in 1 cm2 size roll over 16% conver-
advantage that it affords broad process window, combined sion efficiency, which is very competitive in the reported planar
with full room-temperature process will make it more easily PSCs[44] and contribute more to the substantial commercializa-
scalable in future mass production. Furthermore, our devices tion of PSC techniques. The drop of Jsc, Voc, and FF for the large
based on ZrAcac CILs and NiOx HTM show excellent repeat- devices as compared to the small devices are mainly due to the
ability. Figure S16 (Supporting Information) shows the device increased series resistance of large device. Our large devices
statistics (Jsc, Voc, FF, and PCE) of 36 devices collected over also showed little hysteresis when the scan direction changed,
three different batches. All parameters show a narrow standard which is in accordance with the small ones (Figure 4A). EQE of
deviation, which is a metric for the reproducibility. our large devices showed an excellent response over the entire
It is well known that there is quite serious hysteresis for visible region with maximum peak value of 85.2% (Figure 4B).
the TiO2-based normal planar structure devices at different The integral Jsc from EQE is 20.54 mA cm−2, which is a little
scanning directions, which would significantly affect the low compared to the value from I–V curve (21.26 mA cm−2),
stable power output, and this hysteresis can be avoided when but within the measurement error caused by underestimated
inverted planar structures are employed. The photocurrent hys- spectral mismatch factor.
teresis effect of our MAcac CILs based inverted planar PSCs Afterward, the long-term device stability of high-performance
was investigated by varying the scan direction. As depicted ZrAcac devices in inert environment (H2O and O2 < 0.1 ppm)
in Figure 3C–E, all MAcac-based devices exhibited negligible was investigated at room temperature and in continuous light
hysteresis at a scanning rate of 30 mV s−1 regardless of the soaking. I–V curves were measured periodically to extract
the observed device parameters. Even though this stability
test protocol is not standard, it resembles the encapsulated
Table 2. Summary of the key photovoltaic parameters for the inverted devices under realistic operational conditions. As shown in
planar perovskite solar cells with ZrAcac interfacial layers under AM
1.5G simulated sunlight illumination (100 mW cm−2). Figure 5A,B, the device PCE maintained 87% of its initial value
after 1000 h storage. It is noteworthy that the Jsc and Voc did
Thickness Jsc Voc FF η
not drop significantly and that most degradation came from the
[nm] (C of ZrAcac) [mA cm−2] [V] [%] [%] FF due to interfacial degradation,[59] which is consistent with
previous reports.[60,61] This indicates that the stable NiOx HTM,
0 20.03 1.048 59.2 12.43
stable MAcac CILs, and high-quality perovskite film contribute
2.6 (0.2 m) 21.96 1.050 76.4 17.62
together to the enhanced device stability.[44,62]
5.5 (0.5 m) 21.76 1.067 76.3 17.72 Furthermore, we studied the ambient stability of the ZrAcac-
8.3 (1.0 m) 22.17 1.079 78.1 18.69 based devices and compared it with the control device (PCBM/
11.2 (1.5 m) 21.59 1.076 76.9 17.88 Ag), where the devices were kept in a dry box with controlled
relative humidity (RH) and temperature (50 ± 5%, 25 °C). As
14.5 (2 m) 21.83 1.074 73.7 17.29
shown in Figure 5C, PCE for ZrAcac-based device maintained
19.3 (3 m) 21.06 1.028 73.3 15.87
83.6% of its initial value after exposure to humid air over 30 d,

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Communication
Figure 4. A) I–V characteristics at different scan direction under AM 1.5 G simulated sunlight illumination (100 mW cm−2) for the optimal large area
device. The inset shows the corresponding photograph of a large area cell. B) The corresponding EQE spectrum for the optimal large area device.

while the control device was almost fully degraded. Additional
peaks in the XRD pattern of the degraded control device
originate from a MAPbI hydrate (CH3NH3PbI3·H2O) and PbI2
(Figure 5D), indicating the decomposition of the perovskite
layer.[63,64] In contrast, little detectable degradation products can
be identified in the XRD pattern of the ZrAcac-based device.
Metal acetylacetonates series has high pyrolysis temperature,
for example, 197 °C for ZrAcac,[65] and also has high hyrolysis
threshold owing to that Acac group has strong chelate bonding
to Zr(IV) ions, which is insensitive to water and chemicals.[66]
These merits of metal acetylacetonates have the potential of
expanding the process windows for PSCs. Additionally, the
hydrolysis and pyrolysis products of metal acetylacetonates,
such as ZrO2 or ZrO2(OH)x, are also very stable and hold high
dielectric constant for passivating the interface of PSCs. More-
over, it is the strong coordinating ability of Zr(IV) center ions
that lock the water and organic solvents before they penetrate
into the layers in solar cells below the metal acetylacetonates
film.[67] Those virtues from metal acetylacetonates potentially
contribute to the good stability of the PSCs.
In summary, by a full low-temperature (below 100 °C) pro-
cess, we successfully adopted a series of MAcac (where M
represents titanium (Ti), zirconium (Zr), and hafnium (Hf))
as CILs to achieve both “multistable” and high-performance
planar inverted PSCs in configuration of ITO/NiOx/MAPbI3/
PCBM/MAcac/Ag. All the three kinds of champion cells have
achieved over 18% conversion efficiency in small area, while
the optimal PCE of 18.69% was achieved for our ZrAacac CIL

Figure 5. Device stabilities for the inverted planar perovskite solar cells with ZrAcac CILs as representative; A) Normalized Jsc and Voc, and B) normal-
ized FF and PCE for the top performance solar cell with ZrAcac CIL in a duration over 1000 h of light soaking in inert environment; C) normalized
PCE for PCBM/Ag control and ZrAcac CILs devices before and after exposure to humidity (50 ± 5%, 25 °C). D) XRD patterns of intact PCBM/Ag and
PCBM/ZrAcac/Ag devices before and after exposure to humidity.

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based inverted planar PSCs without any current hysteresis.
Communication
Room temperature processed NiOx NCs were employed as
hole transport layer instead of PEDOT:PSS, which dramatically
suppress the Voc loss due to better energy level arrangement
at the anode interface. Those MAcac CILs were able to effec-
tively reduce interface energy barrier by so called dipole effect
yielded along CILs, and to enhance the electrons extraction to
form a barrier-free cathode interface. Moreover, our devices
demonstrated a significant stability in both light soaking and
ambient atmosphere owing to the hydromolecule-resist and
chemically stable MAcac CILs. Strikingly, stable and high-
performance planar PSCs in an aperture area of over 1 cm2
have been achieved with over 16% conversion efficiency, which
substantially paves a way for the future commercialization of
PSCs, especially for flexible solar cells in a low-temperature
process.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors thank Dr. H. Q. Yi (MSE Department of SUSTC),
Dr. Z. W. Liao, Dr. R. Gu, and Dr. Y. Qiu (Materials Characterization and
Preparation Center of SUSTC) for the characterizations involved in this
work. This work was funded by National Natural Science Foundation
of China (No. 11304147), Natural Science Foundation of Shenzhen
Innovation Committee (No. JCYJ20150529152146471), and the start-up
funding and internal funding (Nos. FRG-SUSTC1501A-61 and FRG-
SUSTC1501A-67) of the South University of Science and Technology of
China. This work was also supported by the Shenzhen Key Laboratory
Project (No. ZDSYS201602261933302).
Received: July 25, 2016
Revised: November 7, 2016
Published online: February 14, 2017
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