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Communication
Discovery of an Unprecedented Above-Room-Temperature
Antiferroelectric in Two-dimensional Hybrid Perovskite
Zhenyue Wu, Xitao Liu, Chengmin Ji, Lina Li, Sasa Wang, Yu
Peng, Kewen Tao, Zhihua Sun, Maochun Hong, and Junhua Luo
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b13827 • Publication Date (Web): 18 Feb 2019
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Page 1 of 6 Journal of the American Chemical Society

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7 Discovery of an Unprecedented Above-Room-Temperature
8
9
Antiferroelectric in Two-dimensional Hybrid Perovskite
10 Zhenyue Wu†,§, Xitao Liu†,*, Chengmin Ji†, Lina Li†, Sasa Wang†,§, Yu Peng†,§, Kewen Tao†, Zhihua
11
12
Sun†,*, Maochun Hong†, Junhua Luo†,*
13 †StateKey Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of
14 Sciences, Fuzhou, Fujian, 350002, P. R. China
15 §University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100039, P. R. China
16
17 Supporting Information Placeholder
18
19 ABSTRACT: Antiferroelectric materials have been regarded as and further fabricate high-performance electronic energy storage
promising candidate for electronic energy storage devices, due to devices.
20
21 their natural double polarization versus electric field (P–E) Recently, two-dimensional (2D) organic-inorganic
hysteresis loops. Currently, two-dimensional organic-inorganic Ruddlesden-Popper hybrid perovskites have been explored for
22
hybrid perovskites with structural diversity and tunability, have multiple applications,8 benefitting from their structural
23 received blooming interests, whereas above-room-temperature tunability,9 superior stability,10 and congenital quantum-well
24 antiferroelectrics are still unreported in this perovskite system. effects.11 One of the most pregnant characteristics is that the
25 Herein, for the first time, we successfully acquire a two- dynamic motions of organic cation residing between two adjacent
26 dimensional Ruddlesden-Popper hybrid perovskite inorganic perovskite layers can be subtly controlled by applying
27 antiferroelectric, ((CH3)2CHCH2NH3)2CsPb2Br7 (1), which external stimulation;12 namely, molecular dipole may be
28 shows an above-room-temperature Curie temperature at 353 K, regenerated or reoriented in this process, which has been availably
29 trigging by the synergistic dynamic motion of inorganic Cs atoms employed to assemble electric ordering materials.13 For instance,
30 and organic i-BA cations. Intriguingly, the antiferroelectricity of 1 above-room-temperature perovskite ferroelectrics,
existing over a wide temperature range of 298~353 K are revealed (cyclohexylaminium)2PbBr4, (benzylammonium)2PbCl4 and
31
by the distinct double P–E hysteresis loops. Besides, 1 possesses (butylammonium)2(formamidinium)Pb2Br7 have been
32 remarkable energy storage efficiency up to 69%, comparable to successfully achieved in 2D organic-inorganic Ruddlesden-Popper
33 those of some reported inorganic antiferroelectric ceramics, hybrids.14 In comparison with exuberantly developed hybrid
34 promoting 1 potential application in energy storage devices. This ferroelectric, up to now, antiferroelectric in the class of organic-
35 work provides an avenue to construct novel antiferroelectric inorganic hybrids only was observed in the perovskite-like
36 materials for high-performance electronic device applications. compound, (3-pyrrolinium)CdBr3, of which antiparallel
37 arrangement of adjacent dipoles is induced by disordered organic
38 moieties in homogeneous crystal lattice.15 The fly in the ointment
39 is that its antiferroelectricity merely appears at low temperature
Energy storage materials have attracted tremendous attention on and a relatively narrow temperature range of 237-246 K.
40 account of the increasing demands for renewable energy sources Therefore, continued endeavors should be devoted to increasing
41 over the last decade.1 Particularly, antiferroelectric substance, as phase transition energy barrier to construct above-room-
42 one remarkable category of dielectric materials, is being temperature antiferroelectric in versatile 2D organic-inorgnaic
43 considered as promising candidate for high-energy storage hybrid perovskites,15-16 in spite of lacking the relevant knowledge
44 applications.2 From the structural viewpoint, antiferroelectric, regarding the control of antiparallel arrangements of the adjacent
45 with antiparallel arrangement of adjacent dipoles, displays the dipoles together with higher phase transition energy barrier in
46 characteristic double polarization versus electric field (P–E) homogeneous crystal.
47 hysteresis loops when applied electric field reaches a certain
In this work, we discover an unprecedented above-room-
critical value.3 Distinguishing from ferroelectric and linear
48 temperature antiferroelectric in the class of 2D hybrid perovskite,
dielectric materials, the electric field triggered transformation
49 from antiferroelectric to ferroelectric states generally generates
(i-BA)2CsPb2Br7 (1) (i-BA is isobutylammonium), which exhibits
50 an antiferroelectric-to-paraelectric phase transition at 353 K,
exceptional energy storage capacities,4 as confirmed by previous
51 triggered by synergistic dynamic motions of inorganic Cs atoms
researches.5 However, the current reports on antiferroelectric
and organic i-BA cations. Strikingly, antiferroelectric behavior of 1
52 materials are considerably scarce, which are dominated by limited
is evidenced by the notable double P–E hysteresis loops over a
53 the inorganic oxides6 (e.g. PbZrO3, AgNbO3, PbHfO3 etc) and
wide temperature range of 298-353 K, along with the remarkable
54 hydrogen-bonded organic compounds7 (e.g. NH4H2PO4,
polarization of ~6.3 μC/cm2. To the best of our knowledge, 1 is
55 NH4HSO4, 2-trifluoromethylbenzimidazole, etc), unfavorable to
the first above-room-temperature antiferroelectric in 2D organic-
56 expand practical device applications. In this context, it is highly
inorganic Ruddlesden-Popper hybrid perovskites. Besides, 1
imperative to explore new type of antiferroelectric material system
57 enables an evident energy storage efficiency up to ~69%,
58 comparable to those of some inorganic antiferroelectric ceramics,
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which makes 1 a potential candidate for energy storage materials. At high temperature phase (360 K), 1 still crystallizes in
1 We believe that this finding illuminates the potential of organic- orthorhombic centrosymmetric space group Cmca. Dramatically,
2 inorganic hybrid perovskite for constructing new antiferroelectric inorganic Cs atoms are located in the middle of cavities, which
3 materials for future high-performance electronic energy storage resembles that of classical cubic perovskite prototype of CsPbBr3
4 devices. (Figure 1b). For organic moieties, i-BA cations become a highly
disordered state at high temperature paraelectric phase. The two
5
ordered carbon atoms in the middle of i-BA cation are on the 2-
6 fold rotation axis, while the two methyl and amine groups show
7 remarkably disordered and have 2-fold rotation axis symmetry,
8 which satisfies demands of crystallographic symmetry (Figure S7).
9 Therefore, thermally triggered order-disorder dynamic
10 transformation of organic moieties and displacement of inorganic
11 Cs atoms synergistically lead to above-room-temperature
12 antiferroelectric-paraelectric phase transition behavior of 1.
13
14
15
16
17
18
19
20
21
22 Figure 2. Dielectric and thermal properties for compound 1. a)
Figure 1. Comparison of the crystal structures of 1 at different
23 temperatures. Crystal packing of 1 viewed along the c-axis
Temperature dependence of the complex permittivity measured at
24 different frequency. Inset: bulk high quality single-crystal was
direction at (a) antiferroelectric phase (293 K) and (b)
25 used to measure the complex permittivity of 1. b) DSC traces in
paraelectric phase (360 K), respectively. All hydrogen atoms were
the heating and cooling cycles.
26 removed for clarity.
27 Bulk crystals of 1, with a size up to 8 × 2.5 × 1.5 mm3, were
28 obtained by temperature-cooling method from its saturated HBr
29 solution (Figure S1), and the phase purity was further verified by
30 powder X-ray diffraction (Figure S2). In order to promote the
31 comprehension of structural phase transition mechanisms of 1, at
32 low temperature phase (293 K), the nonstandard orthorhombic
33 space group of Pmnb was selected to refine it so that the unit cell
parameters are consistent with those of high temperature phase
34
(Table S1). Single-crystal structural analyses uncover that 1
35 possesses typical 2D sandwich-like architecture, and the inorganic
36 perovskite bilayers, separated by organic i-BA+ cations, infinitely
37 extend along the crystal bc-plane. As depicted in Figure 1a,
38 inorganic alkali metal Cs+ ions, which are confined in the cavities
39 constructed by the corner-sharing PbBr6 octahedra (Figure S4),
40 exhibit distinct shift along its crystallography b-axis orientation. It
41 is considerably interesting that displacement directions of
42 inorganic Cs+ ions in two adjacent layers are antiparallel, which
obviously distinguishes from previously reported hybrid
43
perovskite.12a Similar to inorganic Cs+ ions, the organic i-BA+
44 moieties arrangement in between two adjacent layers are also
45 antiparallel along b-axis direction. Consequently, the combination
46 of dynamic movement of organic and inorganic cations gives rise
47 to antiparallel alignment of adjacent dipoles along its b-axis
48 direction, thereby resulting in macroscopic zero net spontaneous
49 polarization, which suggests the possible antiferroelectricity of 1.
50 Compared with its crystallography b-axis orientation, the
51 orientation of the N atoms of two adjacent i-BA cations and the
displacement of inorganic Cs+ ions are opposite along the c-axis at
52
some single bilayer (Figure S5), showing that the anisotropic of
53 the antiferroelectricity. In addition, the 2D inorganic perovskite
54 bilayers are stabilized by forming weak N-H···Br hydrogen bonds Figure 3. Antiferroelectric properties and corresponding current
55 interaction with NH3+ of organic i-BA cations (Figure S6). Such signals of 1. (a) The electric polarization as a function of the
56 configuration has been discovered in some classical inorganic electric field (P–E) hysteresis loops for 1 performed at different
57 perovskites compounds17 and 2D hybrid Ruddlesden-Popper temperature at 40 Hz. (b) Current versus electric field (I–E)
58 perovskites14b, 18. curves for 1 at different temperature at 40 Hz.
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At the critical transition temperature, the temperature Figure 4. (a) Schematic diagram for the calculation of energy
1 dependence of the dielectric constant commonly exhibits an storage properties of antiferroelectric materials. (b) The energy
2 apparent anomaly, which is an effective indicator of the existence density and energy efficiency of 1 as a function of temperature at
3 of structure phase transition.19 As depicted in Figure 2a, the real fixed electric field of 94 kV/cm.
4 part (ε′) of the complex permittivity measured along the Further, the recoverable energy density (Wrec) and energy
antiparallel dipole direction (b-axis) shows evident peak
5 efficiency (η) are important metrics to appraise the energy storage
anomalies at different frequency. The phase transition Curie performances for practical application. As displayed in Figure 4a
6 temperature (Tc) of 1 is estimated to be approximately 353 K
7 and Figure S12, the Wrec (blue areas) and η of 1 can be estimated
(Figure S8), which is higher than those of some reported 𝑃 𝑊rec
8
𝑚𝑎𝑥
antiferroelectric materials, such as, [H-55dmbp][Hca] (Tc = 318 by the definition equations: 𝑊rec = ∫𝑃𝑟 𝐸𝑑𝑃; 𝜂 = 𝑊rec + 𝑊loss ,
9 K),20 [Cu(HCOO)2(H2O)2] 2H2O (Tc = 235 K),21 where Pmax and Pr are the maximum polarization and remnant
10 [La2Cu3[NH(CH2COO)2]6] (Tc = 350 K).22 Furthermore, polarization, respectively, E represents the applied electric field
11 differential scanning calorimetry (DSC) curves for polycrystalline and Wloss is energy loss (green areas in Figure 4a). The
12 samples of 1 expressly disclose one pairs of computational value of Wrec is 0.26 J/cm3 at room temperature
13 exothermic/endothermic peaks in cooling and heating model (Figure 4b). With increasing temperature, the Wrec is slightly
(Figure 2b and S9), which is fully consistent with temperature- reduced, resulting from the decrease values of Pmax and EFE-AFE
14
dependent dielectric constant and powder X-ray diffraction results accompanying incremental temperature. Significantly, the η values
15 (Figure S2). of 1 show well thermal stability during the whole temperature
16 range. The η value reaches up to 69% at 298 K for an applied
The double hysteresis loop, which is one of most powerful
17 external electric field of 94 kV/cm, which is comparable to those
evidence to ascertain antiferroelectricity, appears when the
18 antiparallel dipoles transform into parallel arrangement along the of inorganic antiferroelectric ceramics, such as,
19 same direction by applying an enough external electric field. The Ag(Nb0.85Ta0.15)O3 (69%),5a (Pb0.965La0.035)(Zr0.9Ti0.1)0.99125O3
20 representative P–E double hysteresis loops over a wide (65%),23 (Pb0.95Sr0.05)ZrO3 (68%)24 and even larger than those
21 temperature range of 298-353 K at electric field of 94 kV/cm for 1 found in AgNbO3 (40%),25 (Ag0.97Bi0.01)NbO3 (55%),26 AgNbO3-
22 were obtained by deducting the normal resistance constituents 0.1 wt% MnO2 (52%).27
23 (Figure 3a and S10). At room temperature, 298K, 1 shows perfect In summary, we obtain above-room-temperature
24 P–E double hysteresis loop, making it a promising application in antiferroelectric based on 2D hybrid Ruddlesden-Popper
electronic energy storage devices. The corresponding polarization perovskite, (i-BA)2CsPb2Br7. Interestingly, the antiferroelectricity
25
value is estimated to be 6.3 μC/cm2. Such value is comparable to of 1, which is induced by synergistic dynamic motion of inorganic
26 Cs atoms and organic i-BA cations, is evidenced by the obvious
other some antiferroelectrics, including 2-
27 trifluoromethylbenzimidazole (5.9 μC/cm2) and 2- double P–E hysteresis loops at relatively wide temperature range
28 difluoromethylbenzimidazole (6 μC/cm2).7d Meanwhile, the of 298-353 K. To the best of our knowledge, such an above-room-
29 forward switching field from antiferroelectric to ferroelectric temperature antiferroelectric in 2D hybrid Ruddlesden-Popper
30 conversion (EAFE-FE) and backward switching field from perovskite is unprecedented. In addition, the energy storage
31 ferroelectric to antiferroelectric conversion (EFE-AFE) were efficiency η of 1 show well thermal stability, and the η value is
32 acquired from current peaks of I–E curves. From the Figure 3b, we estimated to be as high as 69% at 94 kV/cm at room temperature.
33 can clearly observe that the values of EAFE-FE and EFE-AFE are 75 Considering the diversity and tunability of hybrid perovskites, we
kV/cm and 40 kV/cm, respectively. As the temperature increases, believe this finding not only opens up a pathway for the design of
34
the switching field is gradually reductive, indicating that the new antiferroelectric materials, but also further promotes the
35 understanding of structure-property relationships in hybrid
electric field induced the dipoles transform from antiparallel
36 (antiferroelectric state) to parallel arrangement (ferroelectric perovskite system.
37 state) becomes easier at higher temperature. The phenomenon of
38 reduced switching electric field is mainly due to the flattened free ASSOCIATED CONTENT
39 energy barrier between antiferroelectric and ferroelectric states
40 with augmenting temperature. Additionally, Figure S11 presents Supporting Information
41 P–E hysteresis loops and I–E curves at variable frequency. Upon Experimental methods and Supporting Figures S1-S8; X-ray
42 increasing frequency, both polarization P and EFE-AFE apparently crystallographic data for 1, at 293 K and 360 K.
43 increase, while EAFE-FE correspondingly reduces. Above critical
44
phase transition Curie temperature (at 358 K), the linear behavior AUTHOR INFORMATION
of P–E and I–E curves reveal that 1 hold high-temperature
45 paraelectric phase. So far as we are aware, 1 should be the first Corresponding Author
46 above-room-temperature antiferroelectric based on a 2D organic- xtliu@fjirsm.ac.cn; sunzhihua@fjirsm.ac.cn;
47 inorganic hybrid Ruddlesden-Popper perovskite.
48 jhluo@fjirsm.ac.cn
49 Notes
50
The authors declare no competing financial interests.
51
52 ACKNOWLEDGMENT
53
54 This work was financially supported by the National Natural
55 Science Foundation of China (21833010, 21525104, 21875251,
21622108 and 51502288), the NSF of Fujian Province
56
(2018H0047, 2016J06012 and 2016J01082), the Strategic Priority
57 Research Program of the Chinese Academy of Sciences
58
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(XDB20010200), and the Youth Innovation Promotion of CAS
1 (2015240).
2
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