Perspective
Cite This: J. Am. Chem. Soc. 2018, 140, 8051−8059 pubs.acs.org/JACS
Multiaxial Molecular Ferroelectric Thin Films Bring Light to Practical
Applications
Yuan-Yuan Tang,‡ Peng-Fei Li,‡ Wei-Qiang Liao,† Ping-Ping Shi,‡ Yu-Meng You,‡
and Ren-Gen Xiong*,†,‡
†
Ordered Matter Science Research Center, Nanchang University, Nanchang 330031, People’s Republic of China
‡
Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics, Southeast University, Nanjing 211189, People’s
Republic of China
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
ABSTRACT: Though dominating most of the practical
applications, inorganic ferroelectric thin films usually
suffer from the high processing temperatures, the
Downloaded via ETH ZURICH on June 8, 2022 at 13:54:21 (UTC).
substrate limitation, and the complicated fabrication
techniques that are high-cost, energy-intensive, and
time-consuming. By contrast, molecular ferroelectrics
offer more opportunities for the next-generation flexible
and wearable devices due to their inherent flexibility,
tunability, environmental-friendliness, and easy process-
ability. However, most of the discovered molecular
ferroelectrics are uniaxial, one major obstacle for
improving the thin-film performance and expanding the
application potential. In this Perspective, we overview the
recent advances on multiaxial molecular ferroelectric thin
films, which is a solution to this issue. We describe the
strategies for screening multiaxial molecular ferroelectrics
and characterizations of the thin films, and highlight their
advantages and future applications. Upon rational and
precise design as well as optimizing ferroelectric perform-
ance, the family of multiaxial molecular ferroelectric thin
films surely will get booming in the near future and inject
vigor into the century-old ferroelectric field.
■
INTRODUCTION
Over the past century, ferroelectrics, as an indispensable class
of functional materials, have become key components in
manifold areas such as ferroelectric random access memories
(FeRAM), capacitors, sensors, infrared detectors, surface
acoustic wave devices, and microactuators.1,2 Among their
versatile physical properties including dielectricity, piezo-
electricity, pyroelectricity, and nonlinear optical activity, the
most intrinsic and valuable feature is of course the switchable
spontaneous polarization (Ps) under an external electric field
(E) greater than the coercive field (Ec). Based on this, FeRAM,
the “real” application of ferroelectrics, is built by storing
electronic information on the positive and negative remnant
polarization (Pr) states.3 Nevertheless, it was realized in
practice until the booming of integrated ferroelectrics during
the 1980s, while the next decades have witnessed the shift in
emphasis from single crystals and bulk ceramics to thin films.4,5
In addition to the smaller size, lightweight, and diverse
microlevel structures, the supreme advantage of ferroelectric
© 2018 American Chemical Society
thin films is to overcome the initial barrier to the development
of ferroelectric memories, i.e., lower operating voltage.6
According to the Kay−Dunn law: Ec = bd−2/3 and coercive
voltage Vc = bd1/3 (d is film thickness and b is a d-independent
constant), for typical ferroelectrics with Ec of about 50 kV/cm,
only applying a Vc up to kV can lead to polarization switching
in mm-level bulk devices; whereas for submicrometer films, the
high Ec is able to be achieved by just a few volts, permitting
integration into silicon technology.7 Apparently, the rise of
ferroelectric thin films perfectly meets the growing demand for
miniaturized multifunctional devices, and now they are being
widely used in commercial products of memories, micro-
devices, and microwave electronic components.
Although the history of ferroelectrics began with the
molecular compound, Rochelle salt,8 it is the later inorganic
ferroelectrics like BaTiO3 (BTO), Pb(Zr, Ti)O3 (PZT), and
LiNbO3 (LNO) that have long occupied the mainstream with
robust properties and great utilization potential. To date, a
number of inorganic ferroelectric thin films have been
intensively developed and broadly exploited, while the
processing issue is always the main disadvantageous factor in
successful device design.9 They not only contain environ-
mentally harmful metals, but also suffer from the high
processing temperatures that result in significant integration
problems.10 Furthermore, it is particularly difficult to grow
high-quality epitaxial or single-crystalline films, without careful
selection of appropriate substrates, because the lattice and
thermal mismatch between them will cause strain and worsen
the useful characteristics.11 Most importantly, the properties of
the as-grown inorganic ferroelectric thin films rely heavily on
the complicated, high-cost, energy-intensive, and time-
consuming fabrication techniques involving magnetron sput-
tering, pulsed laser deposition, molecular beam epitaxy, and
metal−organic chemical vapor deposition.12 All of these
unfavorable facts stimulate the desire for finding new
ferroelectric systems as viable alternatives or supplements to
the inorganic ones. Consequently, researchers renewed interest
in molecular ferroelectrics with superiorities of lightweight, low
cost, environmental friendliness, mechanical flexibility, ease of
low-temperature processing, structural tunability, low acoustic
impedance, and biocompatibility.13−15
Received: May 1, 2018
Published: June 12, 2018
8051 DOI: 10.1021/jacs.8b04600
J. Am. Chem. Soc. 2018, 140, 8051−8059
Journal of the American Chemical Society Perspective

Table 1. Division of the Multiaxial and Uniaxial Ferroelectric Phase Transitions

Multiaxiala Uniaxiala
Triclinic 1̅F1 (2)
Monoclinic 2F1 (2/2); mF1 (2); 2/mF1 (4) 2/mFm (2); 2/mF2 (2)
Orthorhombic 222F1 (4/2); mm2F1 (4/2); mm2Fm (2/2); mmmF1 (8); mmmFm (4) 222F2 (2); mmmFmm2 (2)
Tetragonal 4F1 (4/2); 4̅F1 (4/2); 4/mF1 (8); 4/mFm (4); 422F1 (8/2); 422F2(s) (4); 4mmF1 (8/2); 4mmFm (4/2); 4̅F2 (2); 4/mF4 (2); 422F4 (2);
4̅2mF1 (8/2); 4̅2mF2(s) (4); 4̅2mFm (4/2); 4/mmmF1 (16); 4/mmmFm (s) (8); 4/mmmFm(p) (8); 4/ 4̅2mFmm2 (2); 4/mmmF4mm
mmmFmm2(s) (4) (2)
Trigonal 3F1 (3/2); 3̅F1 (6); 32F1 (6/2); 32F2 (3/2); 3mF1 (6/2); 3mFm (3/2); 3̅mF1 (12); 3̅mF2 (6); 3̅mFm (6) 3̅F3 (2); 32F3 (2); 3̅mF3m (2)
Hexagonal 6F1 (6/2); 6̅F1 (6/2); 6̅Fm (3/2); 6/mF1 (12); 6/mFm (6); 622F1 (12/2); 622F2(s) (6); 6mmF1 (12/2); 6̅F3 (2); 6/mF6 (2); 622F6 (2);
6mmFm (6/2); 6̅m2F1 (12/2); 6̅m2Fm(s) (6/2); 6̅m2Fm(p) (6/2); 6̅m2F mm2 (3/2); 6/mmmF1 (24); 6̅m2F3m (2); 6/mmmF6mm (2)
6/mmmFm(s) (12); 6/mmmFm(p) (12); 6/mmmFmm2(s) (6)
Cubic 23F1 (12/2); 23F2 (6); 23F3 (4/2); m3̅F1 (24); m3̅Fm(12); m3̅Fmm2 (6); m3̅F3 (8); 432F1 (24/2);
432F2(s) (12); 432F4 (6); 432F3 (8); 4̅3mF1 (24/2); 4̅3mFm (12/2); 4̅3mFmm2 (6); 4̅3m F3m (4/2);
m3̅mF1 (48); m3̅mFm(s) (24); m3̅mFm (p) (24); m3̅mFmm2 (12); m3̅mF4mm (6); m3̅mF3m (8)
a
“F” means ferroelectric phase transition. The number of polarization directions are included in the round brackets, and those ones with “/2”
represent reorientable ferroelectrics, in which the spontaneous polarization cannot be switched by 180°.

In the past decade, the emerging molecular ferroelectrics

have definitely pointed out the bright future.16 Even the large
Ps and high Curie temperature (Tc), once regarded as the
major obstacles to the development of molecular ferroelectrics,
have been successfully attained.17,18 Benefiting from the easy
deposition of thin-films by simple, low-cost, and low-
temperature solution methods, molecular ferroelectric thin
films become a hot topic as a matter course.19,20 Nonetheless,
it is a wonder that they are still far below the practical
application level now, despite the ongoing efforts. Taking
croconic acid as an example, its single crystal has a large Ps of
20 μC·cm−2,21 comparable to that of BTO, however, the Pr of
thin film is as small as 0.4 μC·cm−2.22 Actually, not just in
molecular ferroelectrics, such limited performance of thin films
has also been found in LNO, whose use in turn is restricted to
bulk crystals.23 What they have in common is uniaxial nature,
so that under an applied electric field the random grains in
polycrystalline state can only be polarized between two
opposite polarization directions to show a very weak
macroscopic polarization. By contrast, for the majority of
inorganic ferroelectrics like BTO, the polarization in each grain
can be switched more easily between multiple directions to
achieve an excellent ferroelectric performance. In general, the
maximum remnant polarization (Pr)max that may be gained in
polycrystalline state is dependent on the available ferroelectric
axes. For those cases with one, three, four, and six axes, the
corresponding (Pr)max are 0.25, 0.83, 0.87, 0.91Ps for the single-
crystal sample, respectively.4 Given this fact, introducing
multiaxial nature into molecular ferroelectrics will make
considerable contribution to enhancing usability in polycrystal-
line thin-film form. It is no doubt that, only if the performance
of molecular ferroelectric thin films could be much improved,
it is possible to envision their future uses as promising
alternatives to the conventional inorganic family.
Aimed at moving molecular ferroelectrics from curiosity-
driven discoveries to real-world applications, the principal
problem to solve is how to rationally design and effectively
identify outstanding multiaxial molecular ferroelectrics as well
as thin films. Herein, this Perspective focuses on the recent
developments and future directions of multiaxial molecular
ferroelectric thin films, being helpful to address the grand
challenges facing the inorganic ones. In light of the developed
key design strategies and the vital explorations on high-quality
thin films, the family of multiaxial molecular ferroelectrics will
get greatly enriched, and thus inspire technological evolution
in the next-generation flexible and wearable devices.
8052
■ WHAT ARE MULTIAXIAL MOLECULAR
FERROELECTRICS?
Ferroelectricity is a bulk property that is hard to predict and
design via a bottom-up approach. However, there have been
some empirical guidelines for identifying ferroelectrics: (i) the
ferroelectric phase belongs to one of the 10 polar point groups:
1 (C1), 2 (C2), m (C1h), mm2 (C2v), 4 (C4), 4mm (C4v), 3
(C3), 3m (C3v), 6 (C6), and 6mm (C6v); and (ii) there is a
structural phase transition occurring at Tc.24 The condition (i)
is essential for the occurrence of ferroelectricity while (ii) is
generally true in most ferroelectrics. Accompanying the
transition from the high-temperature, high-symmetry para-
electric phase to the low-temperature, low-symmetry ferro-
electric phase, symmetry breaking happens with losing some
symmetry elements, and hence Ps emerges. In view of the
Curie principle, the ferroelectric point group should be a
subgroup of both paraelectric point group and symmetry group
of Ps.16 In other words, a paraelectric point group normally
owns several isomorphic subgroups, whose polar direction
corresponds to the direction of Ps, and the maximal one
comprising the most symmetry elements along the polarization
direction is the ferroelectric point group. Accordingly, given a
known paraelectric point group, the number of polarization
directions in the ferroelectric phase can be defined as n = Np/
Nf, where Np and Nf represent the respective orders of
paraelectric and ferroelectric point groups, known as the sum
of symmetry elements. In this manner, when n = 2, the
ferroelectrics are uniaxial with only two opposite polarization
directions, and certainly multiaxial ferroelectrics are charac-
terized by more than two polarization directions.
On account of the group-to-subgroup relationship deter-
mined by the Curie principle, Aizu has derived 88 species of
potential ferroelectric phase transitions.25 This enables one to
judge directly the occurrence of multiaxial ferroelectricity by
evaluating the n, since the Np and Nf are already got for all the
32 crystallographic point groups.26 As depicted in Table 1, the
greater the symmetry change between paraelectric phase and
ferroelectric phase is, the more equivalent polarization
directions a ferroelectric will have. In the case of LNO, since
both the paraelectric space group R3̅c and the ferroelectric R3c
belong to the trigonal crystal system, their lattice symmetries
are so close that uniaxial nature arises. 27 Likewise,
diisopropylammonium bromide, as a representative molecular
ferroelectric with a high Tc and a large Ps that can get on par
with BTO, is also uniaxial with an Aizu notation of 2/mF2.17
DOI: 10.1021/jacs.8b04600
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Journal of the American Chemical Society Perspective

Figure 1. Schematic illustration for the variation of equivalent polarization orientations n of BTO undergoing the m3̅mF4mm (n = 6), m3̅mFmm2
(n = 12), m3̅mF3m (n = 8) ferroelectric transitions.

Table 2. Summary of Recently Discovered Multiaxial Molecular Ferroelectrics

Formulaa Tc (K) Symmetry change Aizu notation (n) Pr/Vc of filmb ref
[Hdabco]ClO4 377 Pm21n↔P4/mmm 4/mmmFmm2 (4) 4.0/25 (298 K) 31
[Hdabco]BF4 374 Pm21n↔P4/mmm 4/mmmFmm2 (4) 4.9/10 (298 K) 32
[Hdabco]ReO4 377.1, 499.6 Cm↔P4mm↔Pm3̅m m3̅mFm (24), m3̅mF4mm (6) 9.0/10 (298 K) 34
[gua]ClO4 454 R3m↔Pm3̅m m3̅mF3m (8) 8.1/30 (298 K) 35
[Et4N]ClO4 378 Fm3̅m↔Cc m3̅mFm (24) 7.0 (298 K) 37
[qui]IO4 322 Pmn21↔Pm3̅m m3̅mFmm2 (12) 6.7 (298 K) 38
[qui]ReO4 345, 367 Pmn21↔R3m↔Pm3̅m m3̅mFmm2 (12), m3̅mF3m (8) 5.2/50 (298 K) 39
[hqu]Cl 340 F432↔P41 432F4 (6) 1.7/15 (298 K) 40
[apd]RbBr3 440 Iac↔Pm3̅m m3̅mFm (24) 2.3/38 (303 K) 43
[MeHdabco]RbI3 430 R3↔P432 432F3 (8) 6.8/39 (298 K) 44
[tmno]2[KFe(CN)6] 402 Cc↔ Fm3̅m m3̅mFm (24) 1.25/35 (298 K) 45
[tmcm]MnCl3 406 Cc↔ P63/mmc 6/mmmFm (12) 4.0 (363 K) 47
[tmbm]MnBr3 415 Cc↔ P63/mmc 6/mmmFm (12) 3.5 (348 K) 48
a
Hdabco = monoprotonated 1,4-diazabicyclo[2.2.2]octane; gua = guanidinium; qui = quinuclidinium; hqu = (R)-(−)-3-hydroxlyquinuclidinium;
apd = 3-ammoniopyrrolidinium; MeHdabco = protonated N-methyl-1,4-diazoniabicyclo[2.2.2]octane; tmno = protonated trimethylamine N-oxide;
tmcm = trimethylchloromethylammonium; tmbm = trimethylbromomethylammonium. bμC·cm−2/V. cNonstandard space group. The
corresponding chemical structures for these compounds are shown in Table S1 of the Supporting Information.

Notably, it is found that those ferroelectric transitions from
cubic crystal system to the one with much lower symmetry are
generally multiaxial, and the n can even reach 48 (Table 1).
For instance, because of the successive phase transitions from
cubic Pm3̅m (Np = 48) to tetragonal P4mm (Nf = 8) at 393 K,
to orthorhombic Amm2 (Nf = 4) at 278 K, and then to R3m
(Nf = 6) at 183 K, BTO is a typical multiaxial ferroelectric
having 6, 12, and 8 equiv polarization directions in the three
ferroelectric phases, respectively (Figure 1).
reported ferroelectrics. Typically, early in 1999, some simple
organic salts of monoprotonated 1,4-diazabicyclo [2.2.2]octane
(Hdabco) were confirmed as ferroelectrics.28−30 In the vicinity
of the respective Tc of 377 and 374 K, [Hdabco]ClO4 and
[Hdabco]BF4 experience symmetry breaking from the
tetragonal paraelectric space group P4/mmm to the ortho-
rhombic ferroelectric Pm21n. From Table 1, we recognized that
the two with the same Aizu notation of 4/mmmFmm2 should
be biaxial and own 4 equiv polarization directions.31,32 Their

■ STRATEGIES FOR SCREENING MULTIAXIAL

MOLECULAR FERROELECTRICS
Molecular ferroelectrics, which possess diverse structural and
chemical variability exceeding the inorganic systems, can offer
substantial opportunities for introducing or tuning physical
properties by modulations on the molecular structures. Thanks
to the prominent structural tunability, a much broader design
flexibility can be expected for multiaxial molecular ferro-
electrics. Experimentally, there have most recently been
obtained a dozen multiaxial molecular ferroelectrics (Table
2), from which several accessible screening strategies are
proposed and summarized preliminarily as follows.
As described above, a structural phase transition associated
with significantly reduced crystal symmetry is necessary for
multiaxial molecular ferroelectrics. Taking advantage of this
characteristic enables multiaxial ferroelectricity, which re-
searchers previously ignored, to be identified by reviewing
8053
ferroelectric properties come from the ordering and relative
displacement of the components in crystal lattice, which is
common for molecular ferroelectrics. In particular, dabco is a
spherical molecule that often displays orientational disorder or
conformational transformation, and is thus capable of inducing
a high symmetry. With a drop in temperature, the broken high
lattice symmetry, stemming from the freezing of molecular
rotations, is especially suitable for accessing multiaxial feature.
By focusing on such type of spherical moieties and considering
the crystal symmetry requirement, more examples are about to
be obtainable during searching the database.
In fact, the above spherical molecule-based ferroelectrics
could have had the possibility to crystallize in the space group
with a higher symmetry, rather than in the tetragonal one. It is
supposed that [Hdabco]ClO4 and [Hdabco]BF4 may melt or
decompose before further reaching the possible high-symmetry
paraelectric phase. Instead, owing to the tremendously good
thermal stability, their following analogue, [Hdabco]ReO4,
DOI: 10.1021/jacs.8b04600
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Journal of the American Chemical Society
does undergo two distinct phase transitions from the
paraelectric Pm3̅m to the ferroelectric P4mm at 499.6 K and
to the monoclinic ferroelectric Cm at 377.1 K.33 The Tc of
499.6 K is the highest one among the current molecular
ferroelectrics, and above it, the detected cubic phase endows
[Hdabco]ReO 4 a multiaxial nature surpassing that of
[Hdabco]ClO4 and [Hdabco]BF4.34 Specifically, the ferro-
electric phase transitions with Aizu notations of m3̅mFm and
m3̅mF4mm give rise to 24 and 6 equiv polarization directions,
respectively (Figure 2). The spherical molecules are nearly
Figure 2. Crystal structures in ferroelectric Cm (a) and P4mm phase
(c) of [Hdabco]ReO4. (b, d) The 24 and 6 equiv polarization
directions arise in the two ferroelectric phases.
freely rotating in the high-temperature paraelectric phase to get
in an isotropic plastic state, and when the temperature
decreases, their rotations are slowing down to arouse an
identical orientation and the resultant multiaxial ferroelec-
tricity. At this point, plastic phase with the highest cubic
symmetry, in which the molecules show rotator-like motions
and lose orientational order, becomes a simple design
approach to acquire more ferroelectric axes. Remarkably,
when looking back to the discovered molecular ferroelectrics
through this idea, the scope is not just confined in spherical
molecules, but should be extended to other components that
are easy to be rotational or severely orientationally disordered
in the similar way. The multiaxial nature of [gua]ClO4 (gua =
guanidinium), where the planar [gua]+ cation usually has a C3
reorientation, is thereby distinguished.35 Years ago, it has been
found to crystallize in the polar space group R3m at room
temperature and to undergo a ferroelectric phase transition at a
high Tc of 454 K.36 On the basis of variable-temperature
powder X-ray diffraction (PXRD) measurements, the para-
electric phase is refined in the space group of Pm3̅m and
deduced as plastic. The Aizu notation is m3̅mF3m, so there
exist 8 equiv polarization directions, resembling what happens
to BTO below 183 K. As a consequence of the replacement of
[gua]+ by [Et4N]+ cation that also facilitates intense molecular
dynamics, a new multiaxial molecular ferroelectric is designed
and constructed smoothly. Similar to [gua]ClO4, [Et4N]ClO4
adopts a cubic space group in the plastic phase above Tc of 378
K, that is, Fm3̅m, but upon cooling it is broken into the
8054
Perspective
monoclinic Cc.37 With the same m3̅mFm Aizu notation as
[Hdabco]ReO4, as many as 24 equiv polarization directions are
available in [Et4N]ClO4.
Except for dabco, another famous spherical molecule,
quinuclidinium (qui), which bears a very analogous structure
to the former, has been developed as desirable unit for evoking
multiaxial ferroelectricity, too.38−40 For [qui]IO4, the ferro-
electric phase transition occurs at around 322 K, and it is no
suprise that in the paraelectric phase it belongs to the cubic
Pm3̅m, just as [Hdabco]ReO4 does.38 To satisfy such high
crystallographic symmetry, severely orientational disorder is
manifested by the spherical cations and anions, meaning a
collaborative flipping (Figure 3). In the low-temperature
Figure 3. Comparison of crystal structures of [qui]IO4 in paraelectric
(a) and ferroelectric phase (b).
ferroelectric phase, the disappearance of disorder is accom-
panied by the symmetry breaking to the orthorhombic space
group Pmn21. Obviously, the same Aizu notation of m3̅mFmm2
as that of BTO is indicative of 12 equiv polarization directions.
Similarly, the transition from Pm3̅m above 367 K to Pmn21
below 345 K is also presented in [qui]ReO4.39 The difference
is the presence of an intermediate ferroelectric phase between
them, which adopts the R3m space group and allows 8 equiv
polarization directions. Based on the two examples, research
goes further into the homochiral [hqu]Cl (hqu = (R)-(−)-3-
hydroxlyquinuclidinium), showing the valuable role of
molecular modifications.40 Among the 10 ferroelectric point
groups, 5 ones are enantiomorphic, i.e., 1 (C1), 2 (C2), 4 (C4),
3 (C3), and 6 (C6). The compounds comprising homochiral
molecules are more likely to crystallize in these enantiomor-
phic polar point groups, thereby helping to introduce
ferroelectricity more effectively. Herein, upon a H atom at
the 3-site of [qui]+ is substituted by a hydroxyl group, the
spherical geometry gets modified slightly, and a homochiral
[hqu]+ molecule is achieved. By assembling it with a carefully
chosen Cl− anion, [hqu]Cl adopts the expected enantiomor-
phic polar space group P41 in the ferroelectric phase. Then,
above 340 K, the severely disordered [hqu]+ cations experience
highly dynamic reorientation and are modeled with spherical
structure. Thus, a cubic-enantiomorphic space group F432 is
generated in the plastic paraelectric phase. The Aizu notation
of 432F4 signifies the multiaxial nature of [hqu]Cl, in which
the polarization can be switched between 6 equiv directions. It
is postulated that the unique availability of holding homochiral
molecules in molecular ferroelectrics, which is impossible in
the inorganic cousins, will provide an easy path to develop
multiaxial ferroelectricity.
Thus, far, the presented examples basically center on simple
organic salts, while the origin of multiaxial ferroelectricity is
DOI: 10.1021/jacs.8b04600
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Journal of the American Chemical Society Perspective

principally attributed to the relative large displacement
between cations and anions. However, beyond them there
remain countless intriguing structures and complicated ferro-
electric mechanisms to explore. In this respect, ABX 3
perovskites (A, B are two different cations, and X is anion),
where the A cations are enclosed in the three-dimensional
(3D) framework of corner-sharing BX6 octahedrons, deserve
special attention. It is well-known that the kinds of
extraordinary merits of the star inorganic ferroelectrics like
BTO and PZT are inseparable from such unique 3D perovskite
structure. In recent years, note that organic−inorganic
perovskites have also flourished and emerged as competitive
ferroelectric candidates.41 Given the distinctive structural
variability and tunability,42 they shed light on the possible
bottom-up approach to design multiaxial organic−inorganic
perovskite ferroelectrics. With an eye to this, excitedly three
excellent cases were harvested, namely [apd]RbBr3 (apd = 3-
ammoniopyrrolidinium),43 [MeHdabco]RbI3 (MeHdabco =
protonated N-methyl-1,4-diazoniabicyclo[2.2.2] octane),44
(Figure 4) and [tmno]2[KFe(CN)6] (tmno = protonated
Besides the intrinsic ferroelectricity, piezoelectricity also
definitely stands out as the most dominant and extensively
studied property of ferroelectrics.4 A number of inorganic
ferroelectrics like BTO and PZT display large piezoresponse
and have long been put into practice.2 Indeed, whether before
the flourishment of ferroelectric memories or even until now,
various piezoelectric devices such as sensors, transducers and
actuators keep occupying an important position in the
ferroelectric markets. In this regard, the combination of
exceptional ferroelectric and piezoelectric performances should
be a persistent goal for molecular ferroelectrics. Therefore, the
piezoelectric properties of multiaxial molecular ferroelectrics
become a matter of concern. Intriguingly, the above-mentioned
[gua]ClO4 is the first example of molecular ferroelectrics
displaying piezoelectric activity in the powder form after
poling, with a piezoelectric coefficient (d33) of 10 pC·N−1
being comparable to those of its single crystals (15 pC·N−1)
and LNO (8 pC·N−1).35 This behavior is analogous to
inorganic ferroelectrics and might be bounded up with the
multiaxial nature. More impressively, the largest d33 (185 pC·
N−1, Figure 5) among known molecule-based peizoelectrics
(e.g., ∼20 pC·N−1 for PVDF), close to that of BTO (190 pC·
N1− along the [111] direction), has been found in the single
crystal of a one-dimensional organic−inorganic perovskite
[tmcm]MnCl3 (tmcm = trimethylchloro-methylammonium)

Figure 4. Crystal structures of [MeHdabco]RbI3 in ferroelectric phase

and paraelectric phase. The blue arrows in the paraelectric phase
indicate 8 equiv polarization directions.

trimethylamine N-oxide).45 This type of structure is charac-

terized by dynamic organic cations confined in the 3D anionic
cages that afford enough spacious cavity for their rotations or
motions. In the paraelectric phase, the confined cation
undergoes a highly dynamic disorder in the cubic anionic
cage, while in the ferroelectric phase the cation becomes totally
ordered with specific orientations. A cubic-to-distorted phase
transition, triggered by disordering-to-ordering of the cationic
guests and tilting of the anionic octahedra, evolves a multiaxial
ferroelectricity, like the inorganic perovskite ferroelectrics.
Along with the phase transitions occurring at 440, 402, and
430 K, respectively, both [apd]RbBr3 and [tmno]2[KFe-
(CN)6] bear the Aizu notation of m3̅mFm and have 24
equiv polarization directions, and those of [MeHdabco]RbI3
are 432F3 and 8. Naturally, these achievements in multiaxial
3D organic−inorganic perovskite ferroelectrics are all under
precise structural design, particularly for [MeHdabco]RbI3. At
first, what caught our interest is [H2dabco]RbX3 (X = Cl, Br,
I),44,46 unfortunately they adopt the nonpolar space groups
and experience nonferroelectric phase transitions. To improve
that, a N-methyl is added on the nonpolar [H2dabco]2+ to
reduce the high molecular symmetry of D3h down to C3v and to
bring in a molecular dipole moment. Finally, the resulting
[MeHdabco] 2+ molecule is packed in the larger RbI 3 Figure 5. Crystal structures of [tmcm]MnCl3 in ferroelectric (a) and
framework. Just as expected, such a subtle molecular design paraelectric phase (b). (c) Illustration of the 12 equiv polarization
strategy did induce crystallization in polar space group and directions. (d) Temperature and frequency dependent piezoelectric
permit ferroelectricity. coefficient (d33).

8055 DOI: 10.1021/jacs.8b04600

J. Am. Chem. Soc. 2018, 140, 8051−8059
Journal of the American Chemical Society
very recently.47 Above 406 K, its paraelectric phase belongs to
a centrosymmetric hexagonal space group P63/mmc, in which
the molecular tumbling of [tmcm]+, derived from the spherical
[Me4N]+ cation, is modeled with 12-fold orientational diorder.
Conversely, the cations get freezed in the ferroelectric phase to
give a polar space group Cc and 12 equiv polarization
directions (Aizu notation 6/mmmFm). In addition, its
analogue [tmbm]MnBr3 (tmbm = trimethylbromomethylam-
monium) also has a large d33 of 112 pC/N along polar axis,
which undergoes a phase transition from a hexagonal (P63/
mmc) to a monoclinic (Cc) phase at 415 K.48 In these two
multiaxial ferroelectrics, the noteworthy piezoresponsivity is
supposed to come from a striking change of the polarization
due to the rotation of the polarization direction. These findings
denote that the well-designed multiaxial molecular ferro-
electrics have much to offer in not only ferroelectric field, but
also the uses of molecular piezoelectrics in microrobotics,
bioimplanted sensors, flexible and wearable devices, and so
on.49,50
■
MOLECULAR FERROELECTRIC THIN FILMS
Molecular ferroelectric thin films can be prepared via a simple
and low-cost full-solution procedure, in contrast to the
complicated procedures of inorganic ferroelectric films.33 The
common procedure is illustrated by uniaxial ferroelectric
(Im)ClO4 (Im = imidazolium) via a spin-coating approach.34
The as-grown single-crystalline film on substrate is about 2 μm
in thickness and shows different crystal planes, including the
preferred (102̅) plane which is approximately perpendicular to
the polar axis. According to the polarization vector analysis, the
measurement on the (102̅) plane can show comparable
performance of its bulk single crystal sample. Apart from this
lucky preferred orientation of (Im)ClO4 thin film, it is
generally hard to control the specific polarization orientations
of single-crystalline thin films in uniaxial molecular ferro-
electrics.
This difficulty can be largely overcome by multiaxial
molecular ferroelectric thin films. For example, the plastic
crystal (qui)(IO4) undergoes a ferroelectric phase tranistion
between the paraelectric phase Pm3̅m and ferroelectric phase
Pmn21. It has 12 symmetrically equivalent polarization
orientations, i.e., 6-fold polar axes. Such a multiaxial
ferroelectricity does not require any orientation-controlled
growth of the film on specific substrate. Therefore, the film
growth is greatly simplified. The aqueous precursor solution
containing 200 mg (qui)(IO4) per mililiter was spreaded on
various substrates, including ITO-coated glass or flexible
polyethylene terephthalate (PET) (conductive ITO as the
bottom electrode), SiO2/Si, single-crystalline silicon and so on.
The as-prepared thin-films with large area, high uniformity, and
high-coverage were obtained with controlled substrate temper-
ature and edge-pinned-crystallization. Therefore, there is no
need to grow single-crystalline film on specific substrates.
■
CHARACTERIZATIONS AND PERFOMANCES OF
MULTIAXIAL MOLECULAR FERROELECTRIC THIN
FILMS
Just like all the other functional materials, the final goal of
multiaxial ferroelectrics is to be applied in practice in the near
future. When moving forward to device fabrication, the first
level of control is achieved by modulating the molecular
structure, and the second one is achieved by optimizing thin
8056
Perspective
film properties. For that matter, characterizations and perform-
ances of multiaxial molecular ferroelectric thin films are of top
priority. With respect to the above screened multiaxial
molecular ferroelectrics, one of the key advantages resides in
the fact that their Tc are all above room temperature (as listed
in Table 1), varying between 322 and 500 K. Some of them
have even higher Tc than BTO (393 K), such as [Hdabco]-
ReO4, [gua]ClO4, [apd]RbBr3, and [MeHdabco]RbI3.34,43,44
The high Tc means that these ferroelectrics can be applicable in
a wider range of temperatures and is quite an important
characteristic for forthcoming device design.
From the application point of view, polarization switching
performance maintaining in the thin films is surely worth
exploring in the first place. Unique features that are highly
desirable for FeRAM devices include the large Pr for high-
density memories, the low-voltage operation (all Si devices
work at ≤5 V), and the fast polarization switching for high-
speed operation. The Pr is extracted from the polarization−
electric field (P−E) hysteresis loops measured by standard
Sawyer−Tower circuit usually. The ferroelectric thin film is
made into a capacitor with a typical sandwich-like architecture
(GaIn/thin film/ITO) where the bottom electrode is the
conductive ITO coated on the substrate while the top
electrode is liquid GaIn eutectic with the diameter of ∼0.5
mm. High-quality polycrystalline thin films of these multiaxial
samples are found to exhibit comparable Pr values with the
single-crystal samples, distinct from the uniaxial ones which
perform considerably more poorly in thin film than in bulk. For
example, the cold-pressed powder and polycrystalline thin film
samples of [gua]ClO4 have the large Pr of 5.1 and 8.1 μC·cm−2,
respectively, comparable with the measured Ps (8.4 μC·cm−2)
of the single crystal.35,36 On the other hand, among the
reported multiaxial molecular ferroelectrics, [Hdabco]ReO434
has the highest Pr of 9 μC·cm−2 at 298 K while [qui]IO4,38
[Et4N]ClO4,37 and [Medabco]RbI344 have the similar Pr values
between 6.7 and 8.1 μC·cm−2 at 298 K (Table 1). These values
are comparable with 8 μC·cm−2 for the ferroelectric polymer
poly(vinylidene-fluoride) (PVDF) and could be an important
step toward the development of cheap and flexible nonvoltatile
memory.13
For a number of ferroelectric candidates, the Ec is always so
high that verifying the ferroelectricity in the single-crystal form
becomes somewhat difficult. From the Kay-Dunn law, the
magnitude of the Ec may be as much as an order of magnitude
higher in thin films than in bulk materials, but the
corresponding low Vc will make the detection of ferroelectricity
easier and provide hope for low-voltage operation. Most of the
reported multiaxial molecular ferroelectrics display large Ec
values, because the reorientational motions of the polar cations
in the crystal lattice is energy-demanding under electric field,
similar to the PVDF (Ec = 500 kV·cm−1).13 However, it is the
high-quality films with suitable thickness that facilitate easy
realization of polarization switching at low voltage. For
example, polarization switching in [Hdabco]BF432 and
[Hdabco]ReO434 thin films with respective thicknesses of
∼150 and ∼600 nm can be achieved at a low voltage down to
4.2 and 10 V. In the cases of other multiaxial ferroelectric thin
films, the fine P−E hysteresis loops are all detectable at
relatively lower Vc than 50 V. Of particular note is [qui]ReO4
that previously demonstrated ferroelectricity in just a small
temperature window of 22 K (from 345 to 367 K), owing to
the presence of a large Ec in the bulk crystal sample.51 At that
time, for the sake of extending its working temperature range
DOI: 10.1021/jacs.8b04600
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Journal of the American Chemical Society
and expanding the application potential, one should determine
that whether the room-temperature phase below 345 K is
ferroelectric. Not surprisingly, it turned out that a 1.5 μm thick
film of [qui]ReO4 displays P−E hysteresis loops with good
rectangularity at room temperature, with a considerably large
Pr of 5.2 μC·cm−2 and a low Vc of 50 V.39
In the past, it was thought that molecular ferroelectrics had
few advantages in fast polarization switching, while most of
them can be operated at frequencies no more than 500 Hz.
This situation has changed in multiaxial molecular ferro-
electrics, and the thin films of [Hdabco]ClO4, [Hdabco]BF4,
and [Hdabco]ReO4 show well-defined rectangular ferroelectric
loops at relatively high frequencies of 10, 20, and 100 kHz,
respectively, at room temperature (Figure 6). Such high
polarization switching rates are unprecedented in molecular
ferroelectric thin films but will open a new avenue for FeRAM
applications.
Figure 6. Room-temperature ferroelectric hysteresis loops of the thin
film of [Hdabco]ReO4 at different AC frequencies (Hz).
Ferroelectric domain structures of the thin films are studied
by piezoresponse force microscopy (PFM) imaging at the
nanometer scale which affords the information on the
orientation of the domain polarization and piezoelectric
coefficient.52−55 A typical domain structure is the stripe
pattern, where the adjacent domains should be 180° when they
have the equal amplitude signals and 180° phase contrasts in
both out-of-plane and in-plane PFM images, and non-180°
when the amplitude signals are significantly different. Figure 7a
shows the non-180° stripe domains in the [Hdabco]BF4 thin
film, like that found in BiFeO3 (BFO).56 In some cases, two
types of non-180° stripe domains with different directions
would intersect each other to form the herringbone pattern.
For example, [tmcm]MnCl3, [tmbm]MnBr3 and [Hdabco]-
ReO4 all can exhibit the beautiful herringbone domains, as
depicted in Figure 7b,c, which also exist in BTO.57 In addition
to these, some irregular domain patterns would also appear due
to the coexistence of multiple domains with various directions.
Using PFM, we can further understand the polarization
switching behavior, the most important feature for ferroelectric
materials. First, local PFM spectroscopic experiments would be
measured, where the characteristic bipolar piezoelectric
hysteresis and butterfly loops are typical for the successful
switching of ferroelectric domains (Figure 7d). Subsequently,
by applying DC bias tip voltage, the domain switching process
of thin film can be intuitively observed. Figure 7e displays the
8057
Perspective
classical box-in-box bipolar domain patterns in the
[tmno]2[KFe(CN)6] thin film after applying reversed DC
bias in the center. This result demonstrates that the
polarization of ferroelectric domain can be switched forth
and back. Moreover, we also can visualize the non-180°
rotation of polarization direction by employing PFM. As
shown in Figure 7f, when a tip bias under −25 V was used to
pole the center region in the [MeHdabco]RbI3 film, a
bidomain-pattern emerged with different amplitude intensities,
indicating such polarization rotation has an angle of less than
180° and appears to be a ferroelastic switching. This means
that a larger spontaneous polarization can be obatained in the
corresponding polycrystalline samples after poling, promoting
their practical applications in the thin-film form.
■ OPPORTUNITIES AND CHALLENGES
The current development of multiaxial molecular ferroelectric
thin films is filling the gap between pure fundamental research
and practical applications of molecular ferroelectrics. From the
viewpoint of practical applications, some candidates show
promising properties for the use in devices, e.g., [Hdabco]-
ReO4 and [tmcm]MnCl3. In the light of the useful design
principles and the structural diversity, the family of multiaxial
molecular ferroelectrics can get greatly enriched, providing
deep insight into the structure−property relationship. More-
over, multiple properties would be introduced, along with the
ferroelectricity, due to the diversity of molecules such as
chirality. An interesting example is the homochiral molecular
ferroelectrics with potential applications in electro-optics,
molecular recognition and chiral induction. It is expected
that the multiaxial molecular ferroelectric thin films with
superior features will help to address the grand challenges
facing the inorganic ones and inspire technological evolution in
the next-generation flexible, wearable electronics. These
developments will inject new vitality to the century-old
ferroelectric field and attract the widespread interest of
researchers from the multiple subjects.
In order to develop multiaxial molecular ferroelectrics,
researchers are encouraged to pay more attention to the
concept of “ferroelectric chemistry”, which refers not only to
the chemical design of molecular ferroelectrics from the
molecular level, but also to the potential applications of
ferroelectricity in the chemical field, such as surface catalysis.58
From a chemist’s point of view, the design strategy and/or
optimization of ferroelectricity lie in the delicate modification
of flexible organic dipoles. Taking the nonpolar tetramethy-
lammonium [Me4N]+ cation as a prototype, through slight
structural substitution by one chlorine atom, the resultant
polar trimethylchloromethylammonium [Me3NCH2Cl]+ could
greatly influence the ferroelectric/piezoelectric properties in
one-dimensional metal halides. However, the systematic study
is further needed to clarify the underlying mechanisms. For
example, through halogen substitution by fluorine
[Me 3 NCH 2 F] + , chlorine [Me 3 NCH 2 Cl] + , bromine
[Me3NCH2Br]+ and iodine [Me3NCH2I]+, or other organic
substituent group like ethyl group [Me3NEt]+, together with
the structural variability tuned by the metal and halide ions
from the inorganic parts, we can constitute a huge class of
potential multiaxial ferroelectrics. Based on these, superior
ferroelectricity, piezoelectricity or nonlinear optical properties
can be envisioned.
Different from the aforementioned one-dimensional ABX3
organic−inorganic hybrid hexagonal perovskites, the develop-
DOI: 10.1021/jacs.8b04600
J. Am. Chem. Soc. 2018, 140, 8051−8059
Journal of the American Chemical Society Perspective

Figure 7. (a) Out-of-plane PFM amplitude image in the thin film of [Hdabco]BF4. (b) In-plane amplitude image in the thin film of
[Hdabco]ReO4. (c) Out-of-plane phase image in the thin film of [tmcm]MnCl3. (d) Out-of-plane phase and amplitude signals as functions of the
tip voltage for a selected point in the thin film of [qui]IO4, showing local PFM hysteresis loops. (e) Out-of-plane phase image recorded after writing
an area of 15 × 15 μm with +70 V and then the central 8 × 8 μm square with −70 V using a biased conductive tip in the thin film of
[tmno]2[KFe(CN)6]. (f) Out-of-plane amplitude image recorded after the switching produced by scanning with a tip bias of −25 V in the thin film
of [MeHdabco]RbI3.

ment and rational design of three-dimensional ABX3 cubic curiosity-driven research to problem-driven research. This
perovskites seem more attractive due to their structural trend calls for efficient collaborations among researchers in the
similarity to BTO and inherent multiaxial nature. For recently fields of chemistry, physics, materials, microelectronics and so
developed ferroelectric perovskites based on alkali halide on. It is reasonable to believe that these efforts will pave the
framework, the embedded polar divalent organic cations can be way for practicable applications of the molecular polycrystal-
extended to N-methyl-1,4-diazoniabicyclo[2.2.2]octane, trie- line ferroelectrics in the future, as the inorganic ceramic
thylenediamine-N-oxide, even some divalent chiral organic ferroelectrics.
cations such as 3-ammonioquinuclidine and 3-ammoniopyrro-
lidine. In pursuit of more lightweight and structural flexible
molecular ferroelectrics in perovskite system, the providential
■
*
ASSOCIATED CONTENT
S Supporting Information
effective molecular radius affords NH4+ cation to be ideal to The Supporting Information is available free of charge on the
construct metal-free molecular perovskite functional materials, ACS Publications website at DOI: 10.1021/jacs.8b04600.
such as superconductor, ferromagnetic and ferroelectric. The Chemical structures of recently discovered multiaxial
effective ion radius of NH4+ cation (1.46 Å) falls in between
the gap of K+ (1.38 Å) and Rb+ (1.52 Å), providing infinite molecular ferroelectrics (PDF)
combinations with halide anions and bivalent organic cation to
form 3D metal-free ABX3 type perovskite materials.
Besides, benefited by the possible natural sublimation
■ AUTHOR INFORMATION
Corresponding Author
character of electroneutral single-molecule organic com- *xiongrg@seu.edu.cn
pounds, single-molecule organic ferroelectric will facilitate ORCID
solvent-free film fabrication process like thermal evaporation. Yuan-Yuan Tang: 0000-0002-8369-572X
The ability of thermal evaporation will bring the possibility of
Wei-Qiang Liao: 0000-0002-5359-7037
large-scale integration based on multiaxial molecular ferro-
electrics.
Yu-Meng You: 0000-0002-4258-8733
However, there are still some challenges to overcome. The Ren-Gen Xiong: 0000-0003-2364-0193
number of multiaxial molecular ferroelectrics is limited. The Notes
overall performances of the thin films need further The authors declare no competing financial interest.
optimization. In particular, some advantages of the molecular
ferroelectrics over the inorganic ceramics are practicably
disadvantageous, such as aqueous solubility and thermal
■ ACKNOWLEDGMENTS
This work was supported by 973 project (2014CB932103) and
instability. It is becoming clear that the study of multiaxial the National Natural Science Foundation of China (21290172
molecular ferroelectric thin films needs a shift from the and 91622113).
8058 DOI: 10.1021/jacs.8b04600
J. Am. Chem. Soc. 2018, 140, 8051−8059
Journal of the American Chemical Society
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