Article

Cite This: Chem. Mater. 2019, 31, 6231−6238 pubs.acs.org/cm

Cesium Lead Mixed-Halide Perovskites for Low-Energy Loss Solar

Cells with Efficiency Beyond 17%
Haoran Wang,‡ Hui Bian,‡ Zhiwen Jin,*,† Hong Zhang,†,∥ Lei Liang,‡ Jialun Wen,‡ Qian Wang,*,†
Liming Ding,*,§ and Shengzhong Frank Liu*,‡
†
School of Physical Science and Technology & Key Laboratory for Magnetism and Magnetic Materials of MoE & Key Laboratory of
Special Function Materials and Structure Design, MoE & National & Local Joint Engineering Laboratory for Optical Conversion
Materials and Technology and ∥Electron Microscopy Centre, School of Physical Science and Technology, Lanzhou University,
Lanzhou 730000, China
‡
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Materials Science & Engineering,
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Shaanxi Normal University, Xi’an 710119, P. R. China

§
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Center for Excellence in Nanoscience (CAS), Key Laboratory of Nanosystem and Hierarchical Fabrication (CAS), National Center
for Nanoscience and Technology, Beijing 100190, China
*
S Supporting Information

ABSTRACT: In spite of rapid progress in cesium lead halide (CsPbX3)

perovskites solar cells (PSCs), their power conversion efficiencies (PCEs)
achieved to date leave much space for further improvement, principally as a
result of their large energy losses (Eloss). Herein, after incorporating 5% of Br
ions into the CsPbI3 film as the mixed-halide CsPbI2.85Br0.15-absorber layer,
the optimized PSCs obtain a record reverse scan PCE of 17.17% and
stabilized PCE of 16.83% with lower Eloss of 0.58 eV. A record PCE of 12.28
and 13.14% are also achieved for large areas (1 cm2) and flexible substrates,
respectively. More importantly, the optimized devices exhibit excellent
thermal and compositional stability. Further characterizations have proved the
much enhanced PCE and stability original from the Br induced suppressing
bulk trap-assisted nonradiative recombination and lattice strain relaxation.

■ INTRODUCTION
Benefiting from excellent optical absorption, low trap density,
long charge lifetime, high carrier mobility, and small exition
bonding energy, organic−inorganic hybrid PSCs have made
huge progress in both device preparation and component
regulation.1−4 Simultaneously, the most celebrated PSCs have
obtained power conversion efficiency (PCE) of 24.2%.5 It is a
matter of regret that the volatile and thermally unstable nature
of the organic cations is the major concern for large-scale
commercial applications.6−8 Surprisingly, because the perov-
skites of CsPbX3 have excellent composition stability, they
have taken an important position in the emerging materials of
perovskites and will make a significant contribution to the
development.9−11
For the reported CsPbX3 (X = Br, I) PSCs, the obtained
PCEs (Figure 1a) and open-circuit voltage (VOC) (Figure 1b)
are plotted versus optical band gap (Eg). Clearly, according to
the Shockley−Queisser (S−Q) limit, an appropriate Eg for
photovoltaic materials is on a par with low Eloss (described by
the equation: Eloss = Eg − qVOC) in terms of importance.12−14
For a fixed Eg, the high PCE of PSCs owes to the high VOC
with low Eloss.15−18 According to the statistics in Figure 1, Eloss
for most CsPbX3 (X = Br, I) PSCs lies between 0.7 and 1 eV,
much larger than the hybrid ones (0.4−0.5 eV).19−21 Hence,
large Eloss has become a major obstacle to final efficiency.
Initially, CsPbI2Br, by virtue of its excellent phase stability
and reasonable Eg (1.91 eV),22−24 has made great pro-
gress.25−27 For example, Yan et al. reported a SnO2/ZnO
bilayered electron transport layer resulting in pretty good
results.28 The as-optimized PSC achieves low Eloss (0.69 eV)
with large VOC (1.23 V) and delivers a high PCE of 14.6%. By
optimizing the crystallization process to suppress bulk trap-
assisted nonradiative recombination, Bai et al. reported
CsPbI2Br PSCs exhibiting admirable PCE of up to 14.81%
with a VOC of 1.22 V, achieving an Eloss of 0.68 eV.29
Most recently, although facing the challenge of phase
transition,30−32 CsPbI3 played an extremely important role in
further improving the PCE of CsPbX3 PSCs for its more
suitable Eg (∼1.7 eV).33−35 Surprisingly, CsPbI3 QD-based
PSCs attain a much lower Eloss (0.52 eV), reported by
Swarnkar et al.36 For a recently reported CsPbI3 QD device
with more suitable materials as the hole transport layer (HTL),
corresponding to a further reduced Eloss of 0.45 eV, they
Received: June 9, 2019
Revised: July 30, 2019
Published: July 31, 2019

© 2019 American Chemical Society 6231 DOI: 10.1021/acs.chemmater.9b02248

Chem. Mater. 2019, 31, 6231−6238
Chemistry of Materials
Figure 1. Device Performance compared with reported CsPbX3 PSCs.
(a) Reported efficiency as a function of Eg. (b) Reported VOC as a
function of Eg.
obtained an excellent PCE of 12.55% with VOC of 1.28 V.37
However, the chain capping agents result in high electrical
resistance and poor charge-carrier properties.38−40 Later, a
record 15.7% PCE of CsPbI3 thin-film PSCs has been
successfully achieved by the solvent-controlled growth film,
with an Eloss of 0.65 eV reported by You et al.41 Almost in the
same period, Jin et al. fabricated the distorted phase (lower-
symmetry orthorhombic42−44) CsPbI3 film via the intermedi-
ate HPbI3+x.45,46 Then, the relevant solar cell achieved a PCE
of 15.1% and VOC of 1.06 V (Eloss of 0.63 eV). Most recently,
Zhao et al. reported that CsPbI3 perovskite solar cells (PSCs)
exhibited maximal PCE up to 17.06% and stabilized PCE of
16.3%, with an Eloss of 0.62 eV.47
However, paying close attention to the line of S−Q limit in
Figure 1, there is still a long way that needs us to make up for
CsPbX3 PSCs. Further suppression of trap-assisted non-
radiative recombination in inorganic CsPbX3 film is urgently
needed.48 Herein, compared with that of other reported
Figure 2. Dynamic annealing process and microstructure of the fabricated films and devices. (a) Dynamic annealing process of the optimized
CsPbI2.85Br0.15 film and (b) pristine CsPbI3 film; (c−g) EDS mapping images for the optimized CsPbI2.85Br0.15 film; AFM images for (h) the
pristine CsPbI3 film and (i) optimized CsPbI2.85Br0.15 film; (j) cross-sectional SEM image of the completed optimized CsPbI2.85Br0.15 PSC.
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CsPbX3 PSCs, a record reverse scan PCE of 17.17% with
16.83% stable output for mixed-halide CsPbI2.85Br0.15 solar
cells have been achieved, with a lower Eloss of 0.58 eV and
higher VOC of 1.135 V. Also, more importantly, the devices
have excellent thermal and compositional stability compared
with that of CsPbI3.
■ RESULTS AND DISCUSSION
The energy level of pristine and optimized devices is also given
in Figure S1a. In order to clearly identify the effects of Br
incorporated into the CsPbI3 film, the PSC-based mixed-halide
CsPbIxBr3−x-absorber layer with different Br content (for 0, 2,
5, and 10%, successively) was fabricated and compared, and
the typical J−V curves can be seen in Figure S1b with the
detailed data summarized in Table S1. Apparently, the device
performance reaches the best condition with the Br content of
5%. The density functional theory (DFT, shown in Figure
S2a−d) currently affirms the perovskites of CsPbIxBr3−x as
direct band gap semiconductors. Meanwhile, as shown in
Figure S2e−h, judging from the calculation of density-of-states,
in comparison to the pristine film, Br has much higher
electronegativity and ionization potential than iodine. Thus, it
results in the appearance of Br-rich occupied levels lying
deeper in the valence band after the substitution of iodides by
bromides.49 These results led to the obvious increase of the
carrier mobility (Table S2).
Scanning electron microscopy (SEM) images shown in
Figure S3a−d are used to determine the morphological
transformation of the CsPbIxBr3−x films, which are fabricated
with different Br contents for 0, 2, 5, and 10%, successively.
Apparently, the grain size is mostly distributed from 400 to 500
nm with an increased bromine content from 0 to 10%. Images
of the optimized CsPbI2.85Br0.15 (5% Br) and pristine CsPbI3
films at different durations of annealing in nitrogen atmosphere
are shown in Figure 2a,b, respectively. In the first instance,
both of the CsPbI2.85Br0.15 and CsPbI3 films show a bright
yellow color. The CsPbI2.85Br0.15 film transforms into a black
phase in 3 min, which is because of a complete crystallization
process with the pure black phase after 10 min. In contrast, the
crystallization process of the CsPbI3 film becomes much slower
than that of CsPbI2.85Br0.15, resulting in an annealing time of 25
min. It turns out that the addition of Br can accelerate the
crystallization rate and induce nucleation.
In order to clearly identify the element distribution, energy-
dispersive X-ray spectroscopy (EDX) mapping was conducted
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Chemistry of Materials
Figure 3. Crystallization mechanism analysis and film property characterization. (a,b) PL spectra and XRD patterns of the pristine CsPbI3 film for
different annealing points of time; (c,d) PL spectra and XRD patterns of the optimized CsPbI2.85Br0.15 film for different points of time; (e)
schematic diagram for Br-driven crystalline grain growth. (f) Absorption spectra; (g) decay curves; (h) VB XPS spectra; (i) Mott−Schottky fitting
to the CV data.
on the CsPbI2.85Br0.15 film, accompanied with the images
presented in Figure 2c−g, which draws a conclusion that all of
the elements, especially Br, have a uniform distribution
throughout the film sample. The detailed results of EDX
analysis of the grain boundaries (red point) and grains (blue
point) shown in Figure S4 further confirm the results. The
atomic force microscopy (AFM) images are obtained to study
the film surface roughness. It is obvious that the CsPbI2.85Br0.15
film (Figure 2h,i) shows a smoother surface and the smaller
crystals were distributed homogeneously. Then, the cross
section of the optimized device CsPbI2.85Br0.15 shown in Figure
2j shows a continuous homogeneous morphology, with a
thickness of 400 nm.
From other reports, the composition of perovskites
fabricated using HPbI3 is questioned. They believe that
HPbI3 should be DMAPbI3.50,51 However, we found in their
studies that they synthesized neat DMAI powder, fabricated
the CsxDMA1−xPbI3 film, and studied its properties. Here, the
1H NMR spectrum (Figure S5) shows the HPbI3 powder and
the related CsPbI3 film dissolved in DMSO-d6. Clearly, a signal
at d = 8.15 ppm corresponds to protons in −NH2+−. However,
from the EDX analysis and the XPS spectra, atom N is hard to
detect. Hence, we believe during the HPbI3 synthesis process,
only a small part of dimethylformamide (DMF) is transformed
into DMAI. In other words, the films fabricated in our work are
mainly CsPbI3 with only little DMA+ doped into the films,
which could be ignored. In the future, the film composition
should be studied in detail.
In order to explain the mechanism of the crystallization
process in detail, the photoluminescence (PL) spectra and X-
ray diffraction (XRD) were conducted on CsPbI3 and
CsPbI2.85Br0.15 films, which were fabricated at different
annealing grades. The structure of PL samples present as
glass/CsPbX3 film, then, 510 nm light was used for the photon
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excitation light incidented from the CsPbX3 side of the film. As
we all know, in the case of substitution, the XRD peak shifted
to the smaller numerical value of 2θ, indicating the
incorporation of larger halide ions into the lattice sites of
CsPbX3.52 Clearly, as shown in Figure 3a,b, no matter for PL
or XRD, there was no obvious shift in the peak position. The
complete XRD patterns are given in Figure S6, and they
confirm that the finally obtained crystal structure is the γ phase,
according to the early reports.45 After 25 min, the center of the
PL peak is at 726 nm and 28.7°. In contrast, it is obvious that
the peak of CsPbI2.85Br0.15 films exhibit a palpable continuous
change for red shift shown in Figure 3c, as the annealing time
continues to grow. Moreover, the intensity of the sample
would gradually increase as time goes by, till the broad
emission band centers at 716 nm. What is more, Figure 3d
shows that for the XRD peak intensities, there is palpable
change for different annealing points of time. Following the
passage of time, a monotonic shift of the XRD peaks to the
smaller numerical value of 2θ finally fixed at 28.9°.
As shown in Figure 3e, a summing-up of the mechanisms of
CsPbX3 formation is outlined, and the control variable is with
Br or without Br. In the beginning, Br was distributed evenly in
the precursor solution. In the initial annealing process, Br-rich
CsPbI3−xBrx was quickly formed, and right after, I was inserted
into the CsPbI3−xBrx lattice during the annealing process,
leading to expansion of the crystalline lattice. Meanwhile, in
virtue of the addition of Br, the whole crystallization process is
accelerated, forming highly crystalline and uniform perovskite
layers. The visible-light absorption spectra of the pristine film
and optimized film are presented in Figure 3f, with their
thicknesses controlled to be one and the same in the
meantime. In addition, Eg is calculated to be 1.703 and
1.715 eV for the pristine and optimized film, respectively. It is
clear that only a slight blue shift could be observed, indicating
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Chemistry of Materials Article

Table 1. Key Parameters of the Fabricated Pristine CsPbI3 Film and Optimized CsPbI2.85Br0.15 Film
sample μe (cm2 V−1 S−1) ne(traps) (cm−3) σe (Ω−1 cm−1) μh (cm2 V−1 S−1) nh(traps) (cm−3) σh (Ω−1 cm−1) τave (ns) VB (eV) Vbl (V)
−9
pristine 21.28 1.29 × 10 16
2.90 × 10 16.10 2.89 × 10 15
1.83 × 10−7 3.08 0.87 0.76
optimized 24.51 1.17 × 1016 1.14 × 10−8 19.02 1.78 × 1015 8.71 × 10−7 53.11 1.04 0.85

Figure 4. TAS properties. TAS spectra recorded following 500 nm laser pulse excitation: (a,c) for the pristine CsPbI3 film; (b,d) for the optimized
CsPbI2.85Br0.15 film; (e) transient bleach recovery recorded at the bleach maximum for the pristine CsPbI3 film at 711 nm and for the optimized
CsPbI2.85Br0.15 film at 693 nm.

Figure 5. Device Performance. (a) J−V characteristics under both the reverse and forward scan directions with an area of 0.09 cm2; (b) EQE and
the integrated product of the EQE curves; (c) PCE and JSC measured as a function of time for the cells biased at 0.95 V; (d) PCE distribution
histograms of about 60 devices; J−V characteristics of the optimized devices: (e) on the glass substrate with an area of 1 cm2; (f) on the PET/ITO/
TiO2 substrate with an area of 0.09 cm2.

that the loss caused by Br in the samples can almost be
ignored. The carrier extraction dynamics was investigated
through the samples with the structure of the glass/CsPbX3
6234
film, conducted via time-resolved PL (TRPL) (showed in
Figure 3g). Then, 510 nm light was used for the photon
excitation light incident from the side of the film with glass. By
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Chemistry of Materials
Figure 6. Device stability investigation. Images of the pristine CsPbI3 film and optimized CsPbI2.85Br0.15 film: (a) stored in N2 for 30 days; (b)
under light illumination in N2 for 300 h; (c) stored at 80 °C in N2 for 15 days; (d) exposure to air with 40−50% for 5 h; (e−h) long-term stability
of normalized PCEs of fabricated PSCs stored in abovementioned ambient conditions in proper sequence.
using the bi-exponential decay function [amplitudes (Ai) and
times (τi)], the TRPL decay curves were acquired, and the
corresponding key parameters were listed in Table 1. Then, the
average recombination lifetime (τave) was estimated using the
following equation53
∑ A i τi 2
τave =
∑ A i τi
Also, the PL lifetime increases from 3.08 to 53.11 ns with the
doping of Br, indicating that the treatment of Br doping
effectively reduced the density of defect states, leading to
availably improved hole extraction efficiency and then reduced
recombination loss. We also measured the trap state density of
the CsPbI3 films to explore the influence of Br doping. We
chalked up dark current voltage (I−V) characteristics (shown
in Figure S7) for the electron-only device and hole-only device
successively to make a thorough inquiry about the trap
densities. It is worth noting that the trap-filled limit voltage
(VTFL) that is the applied voltage at the kink point was
calculated using54
entrapL2
VTFL =
2ε0ε
Then, the carrier dynamics parameter represented by trap
state density (ntrap), conductivity (σ), and carrier mobility (μ)
was fitted and calculated, with the key parameters summarized
in Table 1. In order to further explore and study the band
alignment and interface around the heterojunction of the
pristine and optimized film, valence band (VB) XPS spectra
were also estimated, which is shown in Figure 3h. The VB
energy revealed the shift of the surface energy levels after the
Br doping, which can be derived from the intersection of the
linear portion of the spectra near the Fermi edge.55 Such
improvement could be beneficial for enhancing built-in electric
field. Capacitance−voltage (C2−−V) measurements were also
Article
performed to measure the built-in potential (Figure 3i), which
can be obtained on the basis of the Mott−Schottky equation56
1 2(V − V )
= 2 bi
C 2
A eεε0NA (3)
We further conducted a dynamical optical investigation by
transient absorption spectroscopy (TAS, exciting with 500 nm
(1)
pump pulses). As shown in Figure 4a−d, a negative band peak
appears at 711 and 692 nm for the pristine and optimized
films, respectively, because of state filling of the conduction
and valence band and be assigned to photobleaching (PB),57
The PB band decreases in the time range investigated (Figure
4e). Because most of the traps are expected to be filled, PB
decay mainly mirrors the electron hole recombination.58 Here,
the PB signal for the optimized film decays more slowly, which
could suppress bulk trap-assisted nonradiative recombination
after Br mixing.59
When attention is paid to Figure 5a, the typical J−V curves
(measured by the reverse and forward scan directions) of the
best-performing device can be seen. This proves that the device
shows negligible hysteresis. In Figure 5b, the measure of the
EQE spectrum was carried out on the champion cell and the
integral current density is also presented. After that, as shown
(2) in Figure 5c, when measured for over 600 s, the PCE was
measured to be 16.83% with a stable J (17.71 mA/cm2), and
the devices were based on the VMP values of 0.95 V. Figure 5d
shows that after approximately 60 individual devices were
measured, the devices were confirmed to have excellent
reproducibility. To verify the uniform high quality of the
CsPbI2.85Br0.15 films, the device with an area of 1 cm2 is
fabricated, and its typical J−V curve can be seen in Figure 5e,
resulting in a JSC of 19.01 mA/cm2, a VOC of 1.044 V, and an
FF of 61.9%, with an overall PCE of 12.28%. Finally, a flexible
CsPbI2.85Br0.15 PSC was fabricated on a polyethylene
terephthalate (PET) substrate (shown in Figure 5f), with a
JSC of 18.73 mA/cm2, a VOC of 0.964 V, and an FF of 72.8%,
with an overall PCE of 13.14%. These values are also the
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Chemistry of Materials
record ones reported now to the inorganic PSCs.60 However,
these efforts are a preliminary attempt toward large-area
preparation and flexible applications of high-efficiency CsPbI3
PSCs, and there is still a long way to go toward industrial
implementation.
Images and performance of the fabricated optimized
CsPbI2.85Br0.15 and pristine CsPbI3 films at different durations
of storage with different strict external conditions are shown in
Figure 6. When the films were stored in N2 for 1 month
(shown in Figure 6a), nearly no decay of PCE was detected for
their corresponding PSC. After exposing the films under light
illumination in N2, both the films did not show any changes
(Figure 6b), and the PSC still retained 95% of the initial value
after 300 h. In order to verify the thermal stability of the
sample, we put the sample on a hot platform at 80 °C for 6
days (shown in Figure 6c). The pristine films quickly showed
yellow spots in 2 days, and most areas turned yellow after 6
days, resulting approximately in 30% decay for the PCE. As a
control, the optimized films did not show any changes with the
PSC dropped to 90% of the initial value. On exposing the films
to higher relative humidity (RH%: 40−50%, Figure 6d), after 5
h, the PSC of CsPbI2.85Br0.15 can continue to maintain
excellent performance with the value dropping to ∼80% of
the initial condition. In sharp contrast, the pristine film
changed quickly to the yellow phase, and the device PCE
dropped below 40% of its initial value. Detailed degradation
rate and related changes of the fabricated devices can be seen
in Figure 6e,f. The reason for the long-term stability is closely
related to the doping treatment using Br for the CsPbI3-
absorber layer, resulting in lattice shrinkage and suppression of
atomic vacancies.61
■
CONCLUSIONS
By optimizing with Br concentration, CsPbI2.85Br0.15 PSCs are
fabricated with an Eloss as low as 0.58 eV, and the best-
performing device demonstrates a record PCE of 17.17%.
Simultaneously, it also caused a positive impact in the stability
of devices after continuous light soaking or long-term exposure
in the ambient condition. Further characterizations found that
the role of Br is effectively suppressing bulk trap-assisted
nonradiative recombination and lattice strain relaxation. This
kind of an optimization method is greatly beneficial for their
various scientific and application investigations in inorganic
perovskite devices. With further exploration, inorganic CsPbX3
PSCs are potentially becoming the prevailing thin-film
technology of next-generation photovoltaic devices in the
near-future.
■
EXPERIMENTAL SECTION
Preparation of PVK Solution. The precursor solution of CsPbI3
was prepared by using CsI (0.18 g) and HPbI3 (0.44 g) dissolved in 1
mL of DMF/DMSO (v/v 9:1) and stirring for 24 h in a glovebox
which is filled with nitrogen. The precursor solutions of CsPbI3−xBrx
were prepared by fully replacing HPbI3 with PbBr2, the molar ratios of
which ranged from 0 to 10%.
Preparation of HTL Solution. The HTL solution used PTAA
(36 mg), tert-butylpyridine (TBP, 36 μL), and a sulfonyl imide (Li-
TFSI, 22 μL, 520 mg Li-TFSI in 1 mL acetonitrile) dissolved in 1 mL
of chlorobenzene solution.
Assembly of PSCs. First, clean FTO-coated glass was immersed
in a 40 mM TiCl4 aqueous solution for 30 min at 70 °C to form TiO2.
For the flexible device, the PET substrate was used with 160 nm
indium tin oxide (ITO). Right after that, 40 nm TiO2 was deposited
onto the ITO by atomic layer deposition. Second, the CsPbX3 layer
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was fabricated onto the O2-plasma-treated substrate. The speed was
increased to 3500 rpm and maintained 40 s. Third, the HTL film was
prepared by spin-coating the PTAA solution at 5000 rpm for 30 s.
Then, the oxidation process was performed overnight. Finally, the
gold electrode was thermally evaporated to 80 nm thickness.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.9b02248.
Experimental procedures; energy levels; J−V curves;
DFT calculation; top-view SEM images; EDS elemental
analysis; 1H NMR spectra; XRD patterns; trap density of
the fabricated films and the properties of the related
devices (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jinzw@lzu.edu.cn (Z.J.).
*E-mail: qianwang@lzu.edu.cn (Q.W.).
*E-mail: ding@nanoctr.cn (L.D.).
*E-mail: szliu@dicp.ac.cn (S.F.L.).
ORCID
Haoran Wang: 0000-0002-0771-7827
Hui Bian: 0000-0002-5761-2601
Zhiwen Jin: 0000-0002-5256-9106
Qian Wang: 0000-0003-2286-9164
Liming Ding: 0000-0001-6437-9150
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
H.W. and H.B. contributed equally to this work. This work was
funded by the National Natural Science Foundation of China
(61704099, 51773045, 21572041 and 21772030), National
Key Research and Development Program of China
(2017YFA0206600), Natural Science Foundation of Shaanxi
Province (2018JQ6072), the basic scientific research business
expenses of the central university, and Open Project of Key
Laboratory for Magnetism and Magnetic Materials of the
Ministry of Education, Lanzhou University
(LZUMMM2019001/LZUMMM2019005). In addition, we
wish to thank the Electron Microscopy Centre of Lanzhou
University for the microscopy and microanalysis of our
specimens.
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6238 DOI: 10.1021/acs.chemmater.9b02248

Chem. Mater. 2019, 31, 6231−6238