A Three-Dimensional Lead Halide Perovskite-Related Ferroelectric

Article abstract of DOI:10.1021/jacs.0c00375

Three-dimensional (3D) organic-inorganic lead halides represented by [CH₃NH₃]PbI₃ perovskite have attracted great interest for their diverse functional properties and promising optoelectronic applications. However, 3D lead halides are still very rare and their ferroelectricity remains controversial. Here, we report an unprecedented 3D lead halide perovskite-related ferroelectric [2-trimethylammonioethylammonium]Pb₂Cl₆ ([TMAEA]Pb₂Cl₆), which contains a 3D lead chloride framework of corner- A nd edge-sharing PbCl₆ octahedral, with the [TMAEA]⁺ cations occupying the voids of the framework. [TMAEA]Pb₂Cl₆ shows a ferroelectric-to-paraelectric phase transition with the Curie temperature as high as 412 K, a typical ferroelectric hysteresis loop at 293 K with a spontaneous polarization of 1 μC/cm², and a clear ferroelectric domain switching. To the best of our knowledge, [TMAEA]Pb₂Cl₆ is the first 3D lead halide showing such an excellent ferroelectricity. Additionally, it also exhibits a semiconducting property with a direct band gap of 3.43 eV. This finding enriches the family of 3D hybrid lead halides and inspires the exploration of 3D lead halide ferroelectrics.

Full text of DOI:10.1021/jacs.0c00375

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Communication
A Three-Dimensional Lead Halide Perovskite-Related Ferroelectric
Han-Yue Zhang, Xian-Jiang Song, Hao Cheng, Yu-Ling Zeng,
Yi Zhang, Peng-Fei Li, Wei-Qiang Liao, and Ren-Gen Xiong
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c00375 • Publication Date (Web): 23 Feb 2020
Downloaded from pubs.acs.org on February 24, 2020
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A Three-Dimensional Lead Halide Perovskite-Related Ferroelectric
Han-Yue Zhang,† Xian-Jiang Song,† Hao Cheng,§ Yu-Ling Zeng,§ Yi Zhang,† Peng-Fei Li,§ Wei-Qiang
Liao,§ and Ren-Gen Xiong*,†,§
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†Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics, Southeast University, Nanjing 211189,
People’s Republic of China
§Ordered Matter Science Research Center, Nanchang University, Nanchang 330031, People’s Republic of China
Supporting Information Placeholder
facilitating the separation of photoexcited carriers.9 This unique
ABSTRACT: Three-dimensional (3D) organic-inorganic lead
feature results in some extraordinary optoelectronic phenomena in
ferroelectric semiconductors, such as the switchable photovoltaic
effects and large photovoltage in BiFeO3.10 Researchers also
deemed that the possible ferroelectricity in 3D [CH3NH3]PbI3
contributed to its outstanding photovoltaic performance.11
Combined with the ferroelectricity, semiconducting property, and
the advantages of low cost, easy processing, and mechanical
flexibility within a single molecular compound, the organic-
inorganic lead halide ferroelectric semiconductors (OLHFS) are
promising for next-generation optoelectronic devices.12 In this
context, some one-dimensional (1D) and two-dimensional (2D)
halides represented by [CH3NH3]PbI3 perovskite have attracted
great interest for their diverse functional properties and promising
optoelectronic applications. However, 3D lead halides are still
very rare and their ferroelectricity remains controversial. Here, we
report an unprecedented 3D lead halide perovskite-related
ferroelectric
[2-trimethylammonioethylammonium]Pb2Cl6
([TMAEA]Pb2Cl6), which contains a 3D lead chloride framework
of corner- and edge-sharing PbCl6 octahedral, with the
[TMAEA]+ cations occupying the voids of the framework.
[TMAEA]Pb2Cl6 shows
a ferroelectric-to-paraelectric phase
transition with the Curie temperature as high as 412 K, a typical
ferroelectric hysteresis loop at 293 K with a spontaneous
polarization of 1 μC/cm2, and a clear ferroelectric domain
switching. To the best of our knowledge, [TMAEA]Pb2Cl6 is the
first 3D lead halide showing such an excellent ferroelectricity.
Additionally, it also exhibits semiconducting property with a
direct bandgap of 3.43 eV. This finding enriches the family of 3D
hybrid lead halides, and inspires the exploration of 3D lead halide
ferroelectrics.
OILHs were recently discovered as OLHFS,7,12,13 such as the 1D
13a
[(CH3)3NCH2I]PbI3
and the 2D (benzylammonium)2PbCl4,7a
[cyclohexylammonium]PbBr4,7b
[4,4-
[2-
diflorocyclohexylammonium]2PbI4,13b
fluorobenzylammonium]2PbCl4,13c [ethylammonium]4Pb3Br10,13d
[4-aminotetrahydropyran]2PbBr4,13e
and
[R-1-(4-
chlorophenyl)ethylammonium]2PbI4.13f Nevertheless, whether the
3D [CH3NH3]PbI3 has ferroelectricity or not is still under debate
due to the lack of convinced evidence to prove its
ferroelectricity.14 And the centrosymmetric Pm3m space group in
[CH3NH3]PbCl3 and [CH3NH3]PbBr3 fails to meet the polar
symmetry for ferroelectrics.15 To date, genuine 3D OLHFS are
still not documented, though ferroelectricity have been found in
other 3D organic-inorganic hybrids,16 such as the metal-formate
[NH4][M(HCOO)3] (M = Mn, Fe, Co, Ni, Zn),16a the alkali-metal
halide perovskite [3-ammoniopyrrolidinium]RbBr3,16c and the
Organic-inorganic lead halides (OILHs) with perovskite or
perovskite-related crystal structures have gained worldwide
attention in recent years as promising semiconductors for
applications in solar cells, smart photovoltaic windows,
photodetectors, light emitting diodes, etc.1,2 Among them, the
three-dimensional (3D) APbX3 (A = organic cation, X = Cl, Br, I)
perovskites are particularly attractive because of their unique 3D
structures and superior optoelectronic properties.2 APbX3 adopts
the cubic perovskite structure, which is composed of a 3D lead
halide framework of corner-sharing PbX6 octahedra, with A
cations residing in the holes formed by adjacent PbX6 octahedra.3
To obey the Goldschmidt tolerance factor rule, the A cation is
limited to the small size [CH3NH3]+ and [NH2(CH)NH2]+ cations.4
Great efforts have been made to extend the family of 3D OILHs,
however, 3D OILHs still remain very sparse.3,5 Organic-inorganic
hybrid crystal structures derived from perovskite are rich,6 and the
connectivity of the PbX6 octahedra is diverse, varying from
corner-sharing to face-sharing to edge-sharing,3 but most of
OILHs are of the zero-, one- or two-dimensional structure.3
Discovering a new 3D OILHs is a great challenge.
metal-free
diazabicyclo[2.2.2]octonium]NH4I3.16d
Here, we find that [2-trimethylammonioethylammonium]Pb2Cl6
([TMAEA]Pb2Cl6), which adopts 3D perovskite-related
perovskite
[N-methyl-N'-
a
structure consisting of a 3D lead chloride framework of corner-
and edge-sharing PbCl6 octahedral, shows a clear ferroelectricity
with a high Curie temperature of 412 K and a spontaneous
polarization of 1 μC/cm2 and semiconducting property with a
direct bandgap of 3.43 eV. As far as we know, [TMAEA]Pb2Cl6
is the first example of 3D OLHFS. This finding opens up
possibilities for exploring new 3D organic-inorganic lead halides,
especially the 3D lead halide ferroelectric semiconductors.
[TMAEA]Pb2Cl6 was prepared by reacting stoichiometric
amounts of the synthesized [TMAEA]Cl2 and the PbCl2 in the
concentrated hydrochloric acid. We used the powder X-ray
diffraction determination to confirm the phase purity of
[TMAEA]Cl2 and [TMAEA]Pb2Cl6 (Figures S1 and S2), and the
thermogravimetric analysis to show the thermal stability of
[TMAEA]Pb2Cl6 up to about 580 K (Figure S3). [TMAEA]Pb2Cl6
crystallizes in the orthorhombic polar space group Pma2 (point
Besides semiconductors, structurally, the free motion of organic
cation in the space enclosed by the PbX6 octahedra makes OILHs
candidates for ferroelectrics,7 which possess spontaneous
polarization (Ps) and are able to switch the Ps under an external
electric filed.8 The Ps can induce a built-in electric field,
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group mm2 (C2v)) at 293 K (room-temperature phase, RTP)
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(Table S1), different from the cubic centrosymmetric Pm3m one
in [CH3NH3]PbCl3.15 The crystal structure of [TMAEA]Pb2Cl6
contains 3D lead-chloride inorganic frameworks of corner- and
edge-sharing PbCl6 octahedral, of which the voids are occupied
by the [TMAEA]+ organic cations, adopting an organic-inorganic
perovskite-related structure (Figure 1).17 In the PbCl6 octahedron,
the Pb center is coordinated by six bridging Cl atoms with Cl–Pb–
Cl bond angles of 81.6(3)–176.2(4)° (Table S2), showing a
distorted coordination geometry. The PbCl6 octahedron connects
with an adjacent one through the edge-sharing mode to form a
[Pb2Cl6]2- dimer, which further links with adjacent dimers through
the corner-sharing mode to form a 3D network (Figure S4).
OILHs featuring both edge- and corner-sharing modes are rare,
though it was also found in the 1D lead-bromide perovskite-
related (C6H16N2)3Pb2Br10 and the 2D one (C5H14N2)2Pb3Br10.17
Each cavity of the 3D network in [TMAEA]Pb2Cl6 are composed
of twelve PbCl6 octahedral, which are large enough to
accommodate the [TMAEA]+ cations (Figure 1a). Between the
anionic framework and [TMAEA]+ cations, there are weak N–
H···Cl hydrogen-bonding interactions with an average N···Cl
distance of 3.291 Å (Figure S5a). The [TMAEA]+ cation lies on a
symmetry position of the mirror plane parallel to the bc plane, and
shows a two-fold orientational disorder (Figure S5b). As Figure
1c shows, the polar [TMAEA]+ cations are arranged in the c-axis
with one orientation, which will results in a spontaneous
polarization.
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Figure 1. (a, b) 3D perovskite-related structure of
[TMAEA]Pb2Cl6 at 293 K. (c) Packing view of the structure at
293 K. (d) Packing view of the structure at 423 K. The red dash
line denotes a mirror plane.
Differential scanning calorimetry (DSC) analysis reflects that
[TMAEA]Pb2Cl6 experiences two phase transitions at around T1
= 361 K and T2 = 412 K, respectively (Figure 2a). We thus further
determined the crystal structure of [TMAEA]Pb2Cl6 at 393 K in
the intermediate-temperate phase (ITP) and at 423 in the high-
temperature phase (HTP). In ITP, [TMAEA]Pb2Cl6 has the same
Pma2 space group as in RTP (Table S1), and both the 3D anionic
framework and [TMAEA]+ cations show no obvious change from
RTP to ITP (Table S2 and Figure S5), which indicates that the
phase transition at T1 is an isostructural one. However, in HTP, the
space group of [TMAEA]Pb2Cl6 becomes the orthorhombic
centrosymmetric Pmma (point group mmm (D2h)) (Table S1). The
Pb–Cl bond distances and Cl–Pb–Cl bond angles of PbCl6
octahedron are comparable to those in ITP (Table S2). While the
[TMAEA]+ cation becomes four-fold orientationally disordered,
since its symmetry positon changes to two mirror plane parallel to
the bc and ac plane, respectively (Figure S5d). The orientations of
the [TMAEA]+ cation are related by the mirror plane (Figure 1d),
leading to the offset of dipolar moments. The phase transition at
T2 can thus be ascribed to the orientation change of [TMAEA]+
cations.
Figure 2. Ferroelectric and related properties of [TMAEA]Pb2Cl6
. (a) DSC curves. (b) Temperature-dependent ε′ at 1 MHz in the
heating run. (c) Temperature-dependent SHG intensity. Inset:
SHG intensity of [TMAEA]Pb2Cl6 and KDP at 293 K. (d) P–E
hysteresis loop recorded at 293 K.
The phase transition of [TMAEA]Pb2Cl6 at T2 is the
mmmFmm2 type ferroelectric one,18 accompanied by the
symmetry breaking of 8 symmetry elements (E, 2σv, i, σh, 2C2′,
and C2) in mmm (D2h) point group decreasing to 4 symmetry
elements (E, 2σv, and C2) in mm2 (C2v) point group. The Curie
temperature of [TMAEA]Pb2Cl6 (T2, 412 K) is higher than those
of most of molecular ferroelectrics including the lead halide
Real part (ε′) of the dielectric permittivity of [TMAEA]Pb2Cl6
presents a remarkable anomaly near T2 (Figure 2b), further
verifying the phase transition at T2. No obvious dielectric anomaly
was observed during the phase transition at T1, maybe due to its
isostructural nature. We also employed the second harmonic
generation (SHG) experiment to investigate the phase transition
(Figure 2c). [TMAEA]Pb2Cl6 displays a clear SHG signal with
the intensity about one fifth of that of KH2PO4 (KDP) at 293 K,
according with the polar Pma2 space group. As temperature
increases, the SHG intensity weakens gradually, and reduces to
zero near T2. This manifests that the phases below and above T2
are non-centrosymmetric and centrosymmetric ones, respectively,
corresponding to the polar Pma2 space group in RTP and ITP and
the centrosymmetric Pmma space group in HTP.
ones,8
[cyclohexylammonium]2PbBr4
such
as
[(CH3)3NCH2I]PbI3
(312
and
K),13a
[4,4-
(363
K),7b
diflorocyclohexylammonium]2PbI4 (377 K),13b and even higher
than the 393 K of inorganic perovskite ferroelectric BaTiO3. We
then confirm that [TMAEA]Pb2Cl6 is a ferroelectric by the
observation of
a typical polarization−electric field (P−E)
hysteresis loop at 293 K (Figure 2d). The saturate spontaneous
polarization value of [TMAEA]Pb2Cl6 is about 1 μC/cm2, which is
larger than those of the first molecular ferroelectric Rochelle salt
(0.25 μC/cm2),8 the molecular perovskite [NMe4]CdBr3 (0.12
μC/cm2),19a and the recently discovered anti-perovskite
[(CH3)3NH]3(MnBr3)(MnBr4) (0.45 μC/cm2).19b
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Figure 4. UV-vis absorption spectra of [TMAEA]Pb2Cl6.
Ultraviolet-visible (UV-vis) absorption spectra
of
[TMAEA]Pb2Cl6 shows a sharp absorption in the UV region at
around 370 nm (Figure 4), indicating the direct bandgap
semiconductor nature, which is commonly seen in lead halide
perovskite.2,7 The Tauc plot reveals a bandgap of approximately
3.43 eV, which is slightly smaller than that (3.65 eV) of the 2D
lead-chloride perovskite ferroelectric (benzylammonium)2PbCl4,7a
while slightly larger than that (3.16 eV) of the 3D lead-chloride
perovskite [CH3NH3]PbCl3.20
In conclusion, we presented a 3D lead halide perovskite-related
ferroelectric [TMAEA]Pb2Cl6, which contains a unique 3D lead-
chloride framework of both corner-sharing and edge-sharing
PbCl6 octahedral. [TMAEA]Pb2Cl6 shows a ferroelectric phase
transition at the high Curie temperature of 412 K and a clear
Figure 3. Domain structure and polarization switching for
[TMAEA]Pb2Cl6. (a) Lateral PFM amplitude and (b) phase
images for a region of 5 × 5 m. (c, d) Lateral PFM amplitude and
phase of the region marked by white dashed box in a and b
overlaid on the 3D topographic image, respectively. (e) Measured
PFM switching spectroscopy on an arbitrary point of the thin film.
(f) Box-in-box domain pattern created by three steps electric
poling.
ferroelectricity at room temperature with
a spontaneous
polarization of
1
μC/cm2. [TMAEA]Pb2Cl6 also possesses
semiconducting property with a direct bandgap of 3.43 eV. As the
first example of 3D lead halide ferroelectric showing a clear
ferroelectricity, the finding of [TMAEA]Pb2Cl6 throws light on
the exploration of more excellent 3D lead halide ferroelectrics
with tremendous application potential.
Further, we performed Piezoresponse Force Microscopy (PFM)
measurements to examine the ferroelectricity of [TMAEA]Pb2Cl6
in its thin film samples. The lateral PFM imaging shows that the
shape of the spontaneous domains is highly irregular. An example
was shown in Figure 3a and b. Domain walls can be clearly
observed in the amplitude image and the phase contrasts between
the adjacent domains are 180˚. The vertical PFM imaging for this
region shows weak amplitude response and blurry phase contrast
(Figure S6b and c), indicating the polarization of this region
predominantly lies in the in-plane direction. It is clearly show the
domain pattern appears to be closely related to the grain structure
of the thin film (topographic image see Figure S6a). Hence, to
exclude the issue that the PFM contrast comes from the
topography, we overlaid the PFM images on the 3D topographic
image. As shown in Figure 3c and d, the 3D images demonstrate
that the domain structure have no correlation with the
morphology.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Experimental details, supporting figures S1−S7, supporting
Tables S1 and S2, and X-ray crystallographic data (CIF) for this
article.
Corresponding Author
*xiongrg@seu.edu.cn
Notes
The authors declare no competing financial interest.
Next, we carried out polarization switching tests by PFM.
Firstly, the PFM switching spectroscopy on a single point of the
thin film was obtained. The hysteretic phase loops and typical
butterfly shape of amplitude loops evidence the robust
ferroelectric polarization in [TMAEA]Pb2Cl6 (Figure 3e). Regard
to a larger region of polarization switching, we write the domains
in the central region of a selected region with three steps electric
poling. Finally, a box-in-box domain pattern was created (Figure
3f), further confirming the switchable polarization in
[TMAEA]Pb2Cl6. Detailed description of the switching
experiments refers to Figure S7.
ACKNOWLEDGMENT
This work was supported by the National Natural Science
Foundation of China (21991142, 21831004 and 21427801).
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