Communication
pubs.acs.org/JACS
A Three-Dimensional Molecular Perovskite Ferroelectric: (3-
Ammoniopyrrolidinium)RbBr3
Qiang Pan,†,‡ Zhi-Bo Liu,†,‡ Yuan-Yuan Tang,†,‡ Peng-Fei Li,†,‡ Rong-Wei Ma,†,‡ Ru-Yuan Wei,†,‡
Yi Zhang,†,‡ Yu-Meng You,†,‡ Heng-Yun Ye,*,†,‡ and Ren-Gen Xiong*,†,‡
†
Ordered Matter Science Research Center and ‡Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics,
Southeast University, Nanjing 211189, P. R. China
*
S Supporting Information
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ABSTRACT: It is known that CH3NH3PbI3 is partic-
ularly promising for next-generation solar devices; there-
fore, molecular perovskite structures have recently received
Downloaded via UNIV DA CORUNA on January 28, 2021 at 15:19:03 (UTC).
extraordinary attention from the academic community
because of their potential in producing unique physical
properties. However, although great efforts have been
made, molecular ferroelectrics with three-dimensional
(3D) perovskite structures are still rare. So far, reported
perovskite-like molecular ferroelectrics are basically one- or
two-dimensional, significantly deviating from the inorganic
perovskite ferroelectrics. Thus, their ferroelectric proper-
ties have to be greatly improved to meet the requirements
of practical applications. Here, we report a 3D molecular
perovskite ferroelectric: (3-ammoniopyrrolidinium)RbBr3
[(AP)RbBr3], with a high Curie temperature (Tc = 440 K)
beyond that of BaTiO3. To the best of our knowledge,
such above-room-temperature ferroelectricity in the 3D
molecular perovskite compound is unprecedented. Fur-
thermore, (AP)RbBr3 has great potential for applications
due to its high thermal stability, ultrafast polarization
reversal (greater than 20 kHz), and fascinating multiaxial
characteristic. This finding opens a new avenue to the
design and controllable synthesis of molecular ferroelectric
perovskites, where the metal ion, halogen ion, and organic
cation can be easily tuned.
F or centuries, perovskitesof simplest generic formula
ABX3 (A, B = two different cations, X = anion)have
intrigued chemists, physicists, and material scientists. Thanks to
the unique three-dimensional (3D) structure of corner-sharing
BX6 octahedra enclosing nominal 12-coordinate holes occupied
by the A cations, they have rich and excellent physical
properties, such as colossal magnetoresistive effects, super-
conductivity, ionic conductivity, and good dielectric- and
ferroelectric-related properties, which are of great importance
in microelectronics and telecommunications.1 Recently, organ-
ic−inorganic hybrid perovskites have attracted tremendous
interest because of their low production costs, simple
processing, and biocompatibility. For example, CH3NH3PbX3
(X = I, Br, or Cl) perovskites have been recognized as
promising light-harvesting materials for future high-perform-
ance and ultralow-cost-per-watt photovoltaic devices.2
One of the important properties of perovskites, ferroelec-
tricity, has also been discovered in a few perovskite-type
© 2017 American Chemical Society
hybrids. Among them, the structures of metal formate
frameworks resemble the cubic perovskite structure, except
that the bridging formate ligand is a multiatomic group.3
However, the low Tc below room temperature and the uniaxial
characteristics severely limit their application potential.4 Here,
we find that (3-ammoniopyrrolidinium)RbBr3 [(AP)RbBr3],
adopting the 3D perovskite structure, undergoes a distinct
transition from the paraelectric point group m3̅m to the
ferroelectric point group m at around 440 K. As far as we are
aware, it is the first example of a high-temperature molecular
3D perovskite ferroelectric. Very importantly, (AP)RbBr3
possesses 12 equivalent ferroelectric axes, which provide
possible ferroelectric-related applications in polycrystalline
forms.
The crystals of (AP)RbBr3 can be easily synthesized by
evaporation of the aqueous solution containing equal molar
amounts of the organic ammonium and RbBr. The presence of
HBr in the solution contributes to forming large crystals. The
purity of the bulk phase was verified by infrared spectroscopy
and powder X-ray diffraction (Figures S1 and S2).
(AP)RbBr3 has the familiar crystal structure of a 3D
framework of corner-sharing RbBr6 octahedra, where the AP
cations are confined in the cavities enclosed by the octahedra
(Figure 1). This arrangement of corner-sharing octahedra is
common in the transition metal halides and halometalates of
Sn(II), Pb(II), Sb(III), and Bi(III) ions, but rare in alkali metal
halides.5 At room temperature, the crystal is polar, with space
group Ia (the nonstandard set of the space group facilitates the
comparison of the ferroelectric and paraelectric structures), and
shows strong optical nonlinear behavior (Figure 2a). Organic
molecules included in such organometal frameworks, such as
dimethylammonium, methylammonium, and imidazonium,
usually have large freedom of motion; thus, they are normally
disordered.6 In our case, the AP cation is well ordered and
aligned in the lattice at room temperature. As shown in Figure
S3, the primary ammonium heads are oriented along the c-
direction, and the N atoms of the rings are located on the left of
the molecules. Such an alignment should induce a polarization
along the a- and c-directions. In order to estimate the
spontaneous polarization, we performed calculations with a
point charge model. By assuming that the positive charges of
the AP cation are located on the two N atoms, we obtained the
Received: January 16, 2017
Published: March 1, 2017
3954 DOI: 10.1021/jacs.7b00492
J. Am. Chem. Soc. 2017, 139, 3954−3957
Journal of the American Chemical Society
Figure 1. Top: Crystal structures of (a) BaTiO3 and (b) (AP)RbBr3 in
the ferroelectric phase. Bottom: Structural unit of (AP)RbBr3 in (c)
the ferroelectric phase and (d) the paraelectric phase. In (d), the
atoms corresponding to the AP cation are shown in the space-filling
mode.
Figure 2. Ferroelectricity and related properties of (AP)RbBr3. (a)
Temperature dependence of the SHG signal of the polycrystalline
sample. (b) DSC data in heating and cooling runs. (c) Temperature
dependence of the real part of the complex dielectric permittivity (ε =
ε′ − iε″, where ε′ and ε″ are the real and imaginary parts,
respectively), measured along the [1 1 1] direction. (d) Applied-
voltage dependence of the spontaneous polarization at various
frequencies, measured from a Sawyer−Tower circuit.
polarization of 3.0 μC cm−2, with components of 2.5 μC cm−2
along the a-axis and 1.7 μC cm−2 along the c-axis.
Thermogravimetric analysis reveals high thermal stability up
to 570 K. A structural phase transition was observed around
440 K (Figure S4) and confirmed by the reversible thermal
anomalies in the differential scanning calorimetry (DSC)
measurement (Figure 2b). The vanishing of the second-
harmonic generation (SHG) signal in the high-temperature
phase (HTP) also reveals a high-temperature phase transition
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from the polar room-temperature phase (RTP) into a
centrosymmetric HTP.
The high-temperature structure determined at 453 K has a
face-centered cubic (FCC) structure, space group Pm3̅m
(Figure 1b). The relationship between cells of two temperature
phases is aHTP ≈ 0.5aRTP, bHTP ≈ 0.5bRTP + 0.5cRTP, and cHTP ≈
−0.5bRTP + 0.5cRTP. The ac-plane of the RTP corresponds to
the (0 1 1) plane of the HTP (Figure S5). Both the Rb atom
and the AP cation in the HTP are located on the special sites of
m3̅m. The twist octahedron of the alkali metal halide
framework become the regular octahedron. The high site
symmetry of m3̅m requires a total disorder of the AP cation,
and accordingly, the AP cation was modeled with a spherical
structure regardless of its molecular geometry. The large
entropy change (ΔS) of 36.66 J/(mol·K) supports such a
transition. From the Boltzmann equation, ΔS = R ln N, where
R is the gas constant and N is the ratio of the numbers of
respective geometrically distinguishable orientations, we obtain
N1 = 82.22. The AP cation can be considered to undergo a
high degree of dynamic reorientation (tumbling), which
compiles the isotropic cubic phase.
Therefore, the ferroelectric origin is due to the freezing of the
dynamics of the dipolar molecule and the subsequent alignment
of the dipoles, which is different from the off-center
displacement of the central Ti atom in BaTiO3. We notice
that this situation is very similar to that recently observed for
the quinuclidinium, 3-hydroxylquinuclidinium, and tetraethy-
lammonium salts.7 In those cases, the high-temperature phase
becomes the cubic plastic phase, because the molecules have
spherical geometries. The 3D spherical molecular structures,
such as tetramethylammonium, adamantane, 1,4-
diazabicyclo[2.2.2]octane, tend to exhibit dynamical disorder
in the close-packed crystals because of weak van der Waals
interactions. In our case, AP has a geometry significantly
deviating from the spherical geometry. The transition to a freely
rotating state should be due to the spacious cavity enclosed by
the RbBr6 octahedral frame. According to the symmetry
change, (AP)RbBr3 belongs with m3̅mFm(s) among the 88
species of ferroelectrics, where s indicates that the spontaneous
polarization vector lies in the (0 1 1) face of the m3̅m phase.8
Such a species has 24 crystallographically equivalent polar-
ization vector directions (Figure 3), much greater than the six
in BaTiO3, which allows more tunability in polarization
direction.
The large dielectric anomalies of the single-crystal and
polycrystalline samples around Tc = 440 K reveal the
ferroelectric nature of the high-temperature phase transition
Figure 3. Analyses of polarization directions: (a) 24 possible
equivalent polarization directions of (AP)RbBr3 in the ferroelectric
phase and (b) 6 possible equivalent polarization directions of BaTiO3
within space group P4mm.
DOI: 10.1021/jacs.7b00492
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Journal of the American Chemical Society
(Figures 2c, S6, and S7). The dielectric permittivity jump
around Tc reveals the character of the first-order transition,
consistent with that revealed by the sharp peaks in the thermal
analysis. The excellent reversibility is consistent with the good
stability of the alkali metal halide framework. Compared with
BaTiO3, (AP)RbBr3 has the smaller dielectric permittivity (a
few hundred for BaTiO3) and higher Tc. Tc is the temperature
where ferroelectric materials lose their spontaneous polar-
ization. Since this type of ferroelectric phase transition is driven
by thermal activation, the height of the energy barrier between
the ordered and disordered states is directly related to the
transition temperature. In this case, considering the AP cation
to have a relatively big volume but to be restricted in a three-
dimensional {RbBr3}n2n− cage, a higher energy is needed to
reach its disordered state (a more quantitative analysis based on
DSC data can be found in Figure S8). On the other hand, this
phase transition also involves distortion of the host metal halide
framework, resulting in giant symmetry changes from the
monoclinic to the cubic system. All these changes undoubtedly
require large energy to activate the phase transition, leading to a
higher Curie temperature.
Polarization reversal was investigated on a thin-film capacitor
with the configuration of ITO (indium−tin oxide glass)/thin
crystallite/GaIn because of the high coercive field (see
Supporting Information for experimental details). The polar-
ization−field dependence at various temperatures and
frequencies was recorded. The remnant polarization (Pr) and
the shape of the loops change little as the temperature increases
from 303 to 333 K (Figure S9), and a similar frequency
dependence was observed. As shown in Figure 2d, the high
rectangularity is retained up to 20 kHz without any significant
change of Pr. The measured Pr is around 2.3 μC cm−2, a little
smaller than the calculated value. Compared with the values of
recently developed molecular ferroelectrics, the Pr of (AP)-
RbBr3 is moderate. For a thin crystallite of 700 nm thickness,
the coercive voltage for the polarization reversal is about 38 V,
corresponding to a coercive field (Ec) of 542 kV/cm. Such a
high coercive field is due to the surface effect as well as the fact
that the polarization reversal involves a great amplitude of
reorientation of the cations.
Considering that domain structure and domain dynamics are
important for understanding the ferroelectric mechanism and
practical applications, we studied domain properties with the
help of piezoresponse force microscopy (PFM). PFM is a
general ferroelectric characterization method which provides
information on the magnitude [by recording the vertical and
lateral (VPFM and LPFM) amplitude images] and direction
(by recording the VPFM and LPFM phase images) of the
polarization. By applying DC voltage to the conductive tip, one
can easily manipulate the local polarization direction and study
the polarization reversal process. Figure 4a,b demonstrates the
stripe-like domain structure in an area of 1 × 1 μm2 of an as-
grown thin crystallite. The neighboring domains have about
180° phase contrast and nearly the same vertical amplitudes,
indicating 180° domains. More measurements revealed the
existence of non-180° domains, as shown in the area enclosed
by the red rectangle in Figure S10. This result is consistent with
the symmetry change in the ferroelectric m3̅mFm(s) species.
To test the polarization reversal properties, we measured the
phase and amplitude by scanning the applied tip voltage from
−15 to 15 V (Figure 4c,d). The typical rectangular phase
hysteresis loop and butterfly amplitude loop were developed,
due to ferroelectric polarization reversal. We then carried out
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Figure 4. Domain structure recorded for an as-grown crystal. (a,b)
VPFM phase and amplitude images. (c,d) Phase and amplitude signals
as functions of the tip voltage for a selected point, showing local PFM
hysteresis loops.
local polarization manipulation experiments by writing in the
selected rectangle areas. As shown in Figure 5, clear and
successive reversals of phase contrasts (∼180°) were
demonstrated at different tip bias. The generated domain
shapes deviated from the rectangle due to domain diffusion,
which may be caused by the roughness of the sample surface.
The domain manipulation indicates that the polarization
direction of the crystallite is switchable in a controllable
manner. The written domains are stable and remain unchanged
after 9 h (Figure S11).
The frequency (speed) of polarization reversal is closely
related to the ferroelectric domain dynamics during the
ferroelectric switching. Typically, the polarization reversal
involves the following steps: (1) domain nucleation, (2)
forward extension, and (3) lateral expansion. Among those
steps, the reversal time is normally limited by the lateral
expansion speed of the domain. In our case, the lateral
movement of domain walls can be easily activated and rapidly
diffused, as shown by the PFM switching results (Figure 5),
indicating that the fast lateral expansion of domains in this
material can be achieved. On the other hand, our ferroelectric
hysteresis loop measurement is based on a microcrystal with
thickness of ∼700 nm. Such small thickness also reduces the
forward extension time, leading to a high switching frequency.
In summary, we have rationally designed a 3D molecular
perovskite ferroelectric. The properties revealed suggest great
application potential of this kind of material. For example, good
thermal stability and high Tc of molecular ferroelectrics have
been intensively pursued. The exceptional thermal stability and
unprecedentedly high Tc seems to be inborn for the alkali metal
perovskites owing to the stability of the alkali metal halide
framework. The realization of ultrafast polarization would be an
important factor in improving the realistic device speed. Finally,
the multiaxial characteristic gives it more polarization states and
makes polycrystalline applications possible. Considering that
both the framework and the cation have much room to be
designed and tailored, one can expect more alkali metal halide
perovskite ferroelectrics to be discovered with better properties
and greater application potential.
DOI: 10.1021/jacs.7b00492
J. Am. Chem. Soc. 2017, 139, 3954−3957
Journal of the American Chemical Society
Figure 5. Domain manipulation. The panels in each row are arranged
in the sequence topographic image (left), VPFM amplitude image
(middle), and VPFM phase image (right). (a) Images for the initial
state of the as-grown crystallite. (b) Images for the state after the first
switching operation in the region of the blue rectangle, produced by
scanning with the tip bias of 11 V. (c) Images for the state after the
succeeding back-switching operation in the region of the smaller red
rectangle, produced by scanning with the tip bias of −8 V. (d) Images
for the state after the succeeding back-switching operation in the
region of the smaller blue rectangle, produced by scanning with the tip
bias of 9 V.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.7b00492.
Supplementary methods and Figures S1−S11 (PDF)
X-ray crystallographic data for (AP)RbBr3, 293 K (CIF)
X-ray crystallographic data for (AP)RbBr3, 453 K (CIF)
■ AUTHOR INFORMATION
Corresponding Authors
*hyye@seu.edu.cn
*xiongrg@seu.edu.cn
ORCID
Yi Zhang: 0000-0002-6375-1712
Ren-Gen Xiong: 0000-0003-2364-0193
Notes
The authors declare no competing financial interest.
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Communication
■ ACKNOWLEDGMENTS
This work was supported by 973 project (2014CB932103) and
the National Natural Science Foundation of China (21290172,
91422301, 21427801, and 21573041).
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DOI: 10.1021/jacs.7b00492
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