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Article
Unprecedented ferroelectric-antiferroelectric-paraelectric phase
transitions discovered in an organic-inorganic hybrid perovskite
Peng-Fei Li, Wei-Qiang Liao, Yuan-Yuan Tang, Heng-Yun Ye, Yi Zhang, and Ren-Gen Xiong
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 08 Jun 2017
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1
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7 Unprecedented ferroelectric-antiferroelectric-paraelectric phase
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9 transitions discovered in an organic-inorganic hybrid perovskite
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11 Peng-Fei Li, Wei-Qiang Liao, Yuan-Yuan Tang, Heng-Yun Ye, Yi Zhang*, Ren-Gen Xiong*
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Ordered Matter Science Research Center, Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics,
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14 Southeast University, Nanjing 211189, P. R. China
15 ABSTRACT: As a promising candidate for energy storage capacitors, antiferroelectric (AFE) materials have attracted great concern
16 due to their congenital advantages of large energy storage ability from double polarization versus electric field (P−E) hysteresis char-
17 acteristics in contrast to ferroelectrics and linear dielectrics. However, antiferroelectricity has only been discovered in inorganic oxides
18 and some hydrogen-bonded molecular systems. In view of the structural diversity and unique physical properties of organic-inorganic
19 hybrid system, it remains a great opportunity to introduce antiferroelectricity into organic-inorganic hybrid perovskites. Here, we
20 report polarizable antiparallel dipole arrays can be realized in an organic-inorganic hybrid perovskite, (3-pyrrolinium)CdBr3, which
21 not only exhibits an excellent ferroelectric property (with a high spontaneous polarization of 7.0 µC/cm2), but also presents a striking
22 antiferroelectric characteristic revealed by clear double P−E hysteresis loops. To the best of our knowledge, it is the first time that
23 such successive ferroelectric−antiferroelectric−paraelectric phase transitions have been discovered in organic-inorganic perovskites.
24 Besides, a giant dielectric constant of 1600 even at high frequency of 1000 kHz and a bulk electrocaloric effect with entropy change
25 of 1.18 J•K-1kg-1 under 7.41 kV/cm are also observed during the phase transition. Apparently, the combined striking antiferroelectric
26 characteristic and giant dielectric constant make (3-pyrrolinium)CdBr3 a promising candidate for next generation high-energy-storage
27 capacitors.
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31 fore, it remains both a great opportunity and challenge to ex-
INTRODUCTION plore new AFE materials with unique properties like low-den-
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33 Electrical energy storage has attracted worldwide concern for sity, easy processing and flexible structural tunability.7 Cur-
34 the present threat of energy crisis and global warming. In order rently, active research has been focused on hybrid organic-inor-
35 to effectively reduce the production of greenhouse gases along ganic perovskites for various applications like electric, magnetic,
36 with the rapid development of electronic industry, there has luminescent and photovoltaic devices.8 Constructing new elec-
been increasing demand for high-energy-storage capacitors tric ordering materials based on organic-inorganic hybrids has
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over the past decades.1 Among the homogeneous-structured di- also been proven to be one of the most feasible strategies.9 Very
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electrics used for energy storage capacitors, antiferroelec- recently, we have successfully designed a three-dimensional or-
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tric(AFE) material is considered as one of the most promising ganic-inorganic perovskite ferroelectric, (3-ammoniopyrroli-
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candidates due to its congenital advantages of large energy stor- dinium)RbBr3, which shows extraordinary high Curie tempera-
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age ability from polarization vs. electric field(P−E) characteris- ture and ultrafast polarization switching.10 In addition, organic-
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tics in contrast to ferroelectrics and linear dielectrics.2 Structur- inorganic perovskites with one-dimensional hexagonal stacking
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ally, AFE materials with adjacent dipoles (in a single domain) frameworks can also be structurally engineered to show excel-
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45 polarized in antiparallel directions display a typical double P−E lent ferroelectricity.11 However, reports of organic-inorganic
hysteresis loop when subjected to a strong electric field.3 The perovskite AFE systems have still remained sparse. This situa-
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electric field induced AFE to ferroelectric phase transition gen- tion is quite similar to aforementioned inorganic oxides, indi-
47 cating that polarizable antiparallel dipole arrays can hardly form
erally leads to a large lattice strain and high electrostatic energy
48 in homogeneous crystalline materials. On the other hand, as a
density.4 In addition, the high dielectric constant and the dis-
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tinct phase transition in AFE materials also provide great oppor- vital criterion for AFE, double P−E hysteresis loops have always
50
tunities for the realization of high-energy storage density and been hard to demonstrate in AFE materials since their switching
51 field is usually larger than the break down field. Although some
fast discharging rates in high performance capacitors.
52 new compounds were claimed to have AFE property, double
53 Homogeneous-structured AFE materials have so far been dis-
covered mainly in inorganic oxides, such as PbZrO3, PbHfO3 P−E hysteresis loops are rarely observed experimentally.
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55 and NaNbO3 with perovskite structure5 and some molecular- In the course of exploring high-performance electric ordering
56 based crystals like ammonium dihydrogen phosphate(ADP)6. materials based on organic-inorganic hybrids, we found a new
Compared with the abundant structural diversity of dielectrics compound (3-pyrrolinium)CdBr3, which not only exhibits an
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and ferroelectrics, such a small amount of existing AFE materi- excellent ferroelectric property (with a high spontaneous polar-
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als has become a big hindrance for further development of tech- ization of 7.0 µC/cm2) and presents a striking antiferroelectric
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nical implementation in high-energy-storage capacitors. There- characteristic revealed by clear double P−E hysteresis loops. Be-
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sides, a giant dielectric constant of 1600 even at high frequency
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of 1 MHz and a bulk electrocaloric effect with entropy change reversible heat anomalies at 246.6/244.2 K (T1) and
1 of 1.18 J•K-1kg-1 under 7.41 kV/cm are also observed during the 237.9/235.2 K (T2) in the heating/cooling runs, with the nar-
2 ferroelectric-to-antiferroelectric phase transition. Apparently, row temperature hysteresis of 2.4 K and 2.7 K, respectively, in-
3 the combined striking antiferroelectric characteristic and giant dicative of two typical second-order phase transitions. For con-
4 dielectric constant make (3-pyrrolinium)CdBr3 a promising venience, the three solid phases of 1 are marked according to
5 candidate for next generation high-energy-storage capacitors. these two phase transitions, as the low-temperature phase
6 To the best of our knowledge, it is the first time that such suc- (LTP), the intermediate-temperature phase (ITP) and the
7 cessive ferroelectric−antiferroelectric−paraelectric phase tran- high-temperature phase (HTP), respectively.
8 sitions have been discovered in organic-inorganic perovskites.
9 In view of the structural diversity of organic-inorganic hybrid
10 system, the present work will undoubtedly stimulate a research
11 upsurge about structure-property relationships toward high
12 performance ferroelectric and/or antiferroelectric devices.
13
14 EXPERIMENTAL SECTION
15 DSC, SHG and XRD measurements: Differential scanning calo-
16 rimetry (DSC) measurements were performed on a Perki-
17 nElmer Diamond DSC under nitrogen atmosphere in aluminum
18 crucibles with a heating or cooling rate of 10 K/min. For second
19 harmonic generation (SHG) experiments, an unexpanded laser
20 beam with low divergence (pulsed Nd:YAG at a wavelength of
21 1064 nm, 5 ns pulse duration, 1.6 MW peak power, 10 Hz repe-
22 tition rate) was used. The instrument model is Ins 1210058,
23 INSTEC Instruments, while the laser is Vibrant 355 II, Figure 1. DSC curves of 1.
24 OPOTEK. The numerical values of the nonlinear optical coef- To deeply understand the phase transition mechanism, we
25 ficients for SHG have been determined by comparison with a determined the crystal structures of 1 at 293, 238 and 203 K by
26 KDP reference. Variable-temperature X-ray diffraction analysis single-crystal X-ray diffraction, respectively (Figure 2). The
27 was carried out using a Rigaku Saturn 724+ CCD diffractometer structure of the HTP is solved in the orthorhombic space group
28 with Mo-Kα radiation (λ = 0.71073 Å). Data collection, cell Cmcm, which is isostructural to our recently reported AMX3 an-
29 refinement and data reduction was performed using Rigaku alogues.12 It contains infinite columns of face-sharing CdBr6 oc-
30 CrystalClear 1.3.5. The structures were solved by direct tahedra separated by the 3-pyrrolinium cations (Figure 2a), ar-
31 methods and refined by the full-matrix method based on F2 ranged in the same manner as the NiO6 unities and Ba cations
32 using the SHELXTL software package. All non-hydrogen atoms in the hexagonal 2-H BaNiO3.13 The geometric parameters of
33 were refined anisotropically and the positions of all hydrogen the organic and inorganic parts are unexceptional. In term of
34 atoms were generated geometrically. polarization, the characteristic feature of the HTP is that the or-
35 Dielectric, ferroelectric and pyroelectric measurements: For die- ganic cation is located on a crystallographic mirror plane with a
36 lectric, ferroelectric and pyroelectric measurements, the sam- disordered fashion, and thus the polarization is cancelled out,
37 ples were made with single-crystals cut into the form of thin leading to no alignment of polarization in the c-direction. The
38 plate perpendicular to the crystal c-axis. Silver conduction paste ITP and the LTP have similar packing structures as that of the
39 deposited on the plate surfaces was used as the electrodes. Com- HTP, showing the pseudo symmetry to the HTP. Therefore,
40 plex dielectric permittivity were measured with a TH2828A im- the other possible space groups different from Cmcm were cho-
41 pedance analyzer over the frequency range from 1 kHz to 1000 sen for the ITP and LTP based on the antiferroelectriciy and
42 kHz with an applied electric field of 0.5 V. Dielectric hysteresis ferroelectricity, respectively.
43 loops were recorded on a Radiant Precision Premier II. Pyroe- The ITP assumes the space group ‘C 2/m 1 1’ (we chose the
44 lectric property was measured with an electrometer/high re- nonstandard unit cell setting so that the directions of the axis
45 sistance meter (Keithley 6517B) with a heating or cooling rate are close to those in the HTP, which facilitates the comparison
46 of 10 K/min. The bias electric field dependence of dielectric and the understanding of the transition mechanisms). The
47 constant was measured with an Alpha-A High performance Fre- structure can also be refined in the space group of the HTP
48 quency Analyzer at 10 kHz. (Cmcm) or the LTP (Cmc21), we did not refine it in the space
49 group Cmcm or Cmc21, because the antiferroelectricity for this
RESULTS AND DISCUSSION phase require antiparallel alignment of the dipoles. The mod-
50
51 Colorless rod-like crystals of (3-pyrrolinium)CdBr3 (1) with elled 3-pyrrolinium cation remains disordered. However, the ra-
52 size 3 × 3 × 15 mm3 were grown by slow evaporation of a clear tios the N and C for the two atoms bonded by the double bond
53 aqueous solution containing equal molar amounts of CdBr2 and are 0.7: 0.3 and 0.3: 0.7. As shown in Figure 2b, such a model
54 pyrroline hydrobromide at room temperature (Supporting In- indicates that there are anti-parallel electric dipole moments
55 formation, Figure S1). Phase purity of 1 was confirmed by pow- along the c-axis. The LTP assumes the space group Cmc21. As
der X-ray diffraction and IR analysis (Figures S2 and S3). To shown in Figure 2c, the orientations of the cations become the
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confirm the phase transition behavior of 1, we firstly carried out same, and thus the crystal should display a net polarization.
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differential scanning calorimetry (DSC) measurement. As
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shown in Figure 1, the DSC curves clearly present two pairs of
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suggests a second-order phase transition feature.

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14 Figure 3. SHG intensity of 1 as a function of temperature.
15 The temperature dependence of the complex dielectric con-
16 stant (ε = ε′ − iε″, where ε′ is the real part of the complex
17 constant, and ε″ is the imaginary part of the complex constant)
18 has been proved to be another effective way to detect structural
19 phase transition, the reason of which is that the macroscopic di-
20 electric response is sensitive to the variation of the microscopic
21 structure. The real part (ε′) as a function of temperature, meas-
22 ured at different frequencies along the c-axis, are shown in Fig-
23 ure 4a. As the temperature decreases to in the vicinity of the T1,
24 ε′ increases slowly and presents a tiny frequency independent
25 dielectric anomaly. At the lower temperature, the ε′ shows rap-
26 idly changing, accompanied with a giant frequency dependent
27 dielectric responses at T2. The peak values increase from 1600
28 to 2500 as the measurement frequencies decrease from 1000
29 kHz to 1 kHz. In addition, dielectric anisotropy measurement is
30 one of the most feasible strategies to further investigate the in-
31 Figure 2. Perspective views of 1 in the (a) HTP, (b) ITP and (c) trinsic structural changes in the phase transition processes. As
32 LTP, showing the similarities of the crystal packings and differ- shown in Figure S4, the values of ε′ along the c-axis are obvi-
33 ences of the orientational states of the cations and the lattices. ously larger than those along the b- and a-axis. The remarkable
34 In (b), the atoms with the probability of N of 70% are shown in dielectric anisotropy is related to the placement and motion of
35 blue, while the atoms with probability of C of 70% are shown in the cations. It can be seen from the structure in the ITP that the
36 brown. The pink planes indicate the (pseudo) crystallographic disordered 3-pyrrolinium cation takes two positions, arousing
37 mirror planes. the motions both in the plane parallel to the bc-plane and per-
38 pendicular to the a-axis. The in-plane motion only yields a very
The SHG (second harmonic generation) signal is sensitive to
39 weak dipole moment component in the a-axis, which leads to a
the lack of inversion symmetry, thus the SHG technique has
40 small dielectric change. Furthermore, comparing the structure
been developed as an indispensable supplementary approach to
41 of the HTP and LTP, the N atoms show obvious shift along the
detect the symmetry change accompanying the structural phase
42 c-direction, which will lead to large dielectric response.
transition.14 In order to further confirm the reasonable space
43 groups, determined from the structural analyses, the tempera-
44 ture dependent SHG measurements of 1 were performed. As
45 shown in Figure 3, SHG intensity is zero above T1, suggesting
46 that 1 is centrosymmetric in the HTP, since only non-centro-
47 symmetric solid is SHG active in principle. With the tempera-
48 ture decreasing between T1 and T2, SHG intensity remains zero,
49 indicating that 1 also belongs to centrosymmetric in the ITP.
50 When the temperature deep cooled below T2, non-zero values
51 of the SHG intensity emerge, unambiguously revealing that 1 is
52 non-centrosymmetric in the LTP. Therefore, the SHG conclu-
53 sions match well with the results of crystal structure analyses.
54 Furthermore, the continuous increase of SHG intensity near T2
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1 (a)
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32 Figure 4. Dielectric properties in 1. (a) Real part of the complex Figure 5. (a) P–E hysteresis loops of 1 measured along the c-axis
33 dielectric constant (ε′) of 1 along the c-axis at different frequen- at HTP, ITP and LTP. (b) I–E curves of 1 measured along the
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cies. (b) Plot showing the dependence of the real part ε′ of the c-axis at HTP, ITP and LTP.
35 complex dielectric constant of 1 on the bias electric field.
36 The measurement of P−E hysteresis loop is one of the most
37 Significantly, besides large dielectric anomalies, antiferroelet- direct methods to determine the ferroelectricity and antiferroe-
38 rics and ferroelectrics, display strong nonlinear dielectric re- lectricity. As depicted in Figure 5a, the polarization response to
39 sponse because of switchable spontaneous polarization. Hence, the applied field is linear at 248 K in the HTP, as expected for
40 the bias-field dependence of ε′ was investigated in the three ordinary dielectrics under a smaller field. With the temperature
41 phases. As presented in Figure 4b, ε′ remains unchanged with decreasing below T1, a characteristic double hysteresis P−E
42 the changes of the electric field and shows linear dielectric prop- loops become visible at 245 K, showing one distinct features of
erties in the HTP. Whereas, ε′ in the ITP shows an exciting dou- the antiferroelectrics. The forward phase switching field (EF)
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ble butterfly shape under circular function of external DC elec- and the backward switching field (EA) can be estimated by ex-
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tric field, indicating a striking feature of antiferroelectric. As the trapolating the two steepest sections of the hysteresis loop and
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electric-field increase from zero to maximum values, ε′ increases obtaining their intersections with the horizontal axis. Moreover,
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firstly, and reaches the first peak value at the phase switching the better double hysteresis loops can be obtained with larger
47
from AFE to FE state and then decreases gradually. Similarly, as saturated polarization and smaller switching field as the temper-
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electric field decreases from maximum values to zero, dielectric ature decreases (Figure 5a and Figure S5a). However, when the
49
constant also increases firstly and then declines. A second peak temperature drops down below T2, the double hysteresis loops
50 change to single hysteresis loop in the LTP, revealing a transi-
51 value at the phase transformation from FE to AFE state is ob-
tained in this course. Dramatically, under the same external DC tion from antiferroelectric to ferroelectric phase. At the same
52 time, the saturated polarization Ps reaches the maximum value
53 electric field modulate, the dielectric constant change a double
butterfly shape to single butterfly shape in the process of trans- of about 5.65 μC·cm−2 at 223 K, which is fairly consistent with
54 the estimated Ps value (5.48 μC·cm−2) according to point elec-
55 forming from ITP to LTP. The butterfly curve in the LTP indi-
cated that the ε′ shows non-linearity in response to the polari- tric charge model (Supporting Information, Table S1). The cor-
56 responding coercive field is about 3.5 kV·cm−1. Furthermore, ac-
57 zation switching, which is one of the characters for other well
studied ferroelectrics. cording to the P–E loop measured at 245 K in the ITP (Figure
58 S6), we estimate that the maximum energy storage density is
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about 0.4-0.6 J·cm-3, the energy-storage efficiency of

1 (C4NH10)CdBr3 was 85% at 245 K for an applied electric field
2 of 32 kV·cm-1.
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19 Figure 6. (a) The temperature dependence of spontaneous
20 polarization by integrating the pyroelectric current. Figure 7. (a) The relation of polarization change and (b)
21 Electrocaloric entropy change (ΔS) as a function of
Ferroelectric as a special kind of pyroelectric, shows a sensitive
22 temperature for different external electric fields.
spontaneous polarization response to the temperature. Obvi-
23 ously pyroelectric effect can be generated during the ferroelec-
24 tric-antiferroelectric and ferroelectric-paraelectric phase transi-
25 tion. The polarization and current as a function of temperature
26 for compound 1 are shown in Figure 6. As the temperature is
27 above T2, the electric current keeps unchanged, while a sharp
28 change of the current occurs in the vicinity of T2. By integrating
29 the pyroelectric current, we can see that the polarization values
30 increase with decreasing temperature below T2, basically con-
31 sistent with those measured by the P−E hysteresis loops. More-
32 over, the tendency of polarization versus temperature is similar
33 as that of the SHG signal, which can be explained by the Landau
34 theory equation, χ(2) = 6ε0β′Ps, where the ε0 andβ′ are tempera-
35 ture-independent.
36 Electrocaloric (EC) effect, the reverse course of pyroelectric ef-
37 fect, is the change in temperature of a material upon the appli-
38 cation or removal of an electric field. According to the measure-
39 ment results of P−E loops as a function of temperature (Figure
40 S7), we obtain the relation of polarization change under
41 different external electric fields (Figure 7a). The entropy Figure 8. Variation of polarization (a) and total energy (b) as a
42 change can be obtained through the variation of the Maxwell function of the dynamic path connecting the ferroelectric (λ =
43 1 𝐸𝐸 𝜕𝜕𝜕𝜕
equation, ∆S = − ∫𝐸𝐸 2 � � 𝑑𝑑𝑑𝑑. As shown in Figure 7b, the en- 1) to antiferrroelectric (λ = 0) configuration.
44 𝜌𝜌 1𝜕𝜕𝜕𝜕
tropy change with temperature during in the process of phase In order to gain deep insight into the ferroelectric-to-antifer-
45
transition shows a peak value of entropy change about 1.18 J·K- roelectric phase transition, density functional theory calculation
46 1
·kg-1 under 7.41 kV/cm, which is comparable to those bulk in- was carried out to evaluate the polarization dynamics. A dy-
47
organic ferroelectric oxides.15 namic path between the ferroelectric to antiferrroelectric con-
48
figuration is constructed based on the crystal structure obtained
49
from the single crystal X-ray diffraction. Accordingly, the struc-
50
ture of low temperature ferroelectric phase at 223 K is used as
51
the ferroelectric configuration (λ = 1), while the antiferrroelec-
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tric (λ = 0) configuration is obtained from the matrix transfor-
53
mation of the coordinates of λ = 1 considering both the rotation
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and displacement of the organic cations. The variation of polar-
55 ization and total energy as a function of the dynamic path is
56 shown in Figure 8, from which the ferroelectric polarization
57
with 6.0 µC/cm2 along c-axis can be extracted from the initial
58
point of λ = 1 configuration. While the value of polarization
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gradually decreased to zero toward the λ = 0 AFE state with an REFERENCES

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32 the Internet at http://pubs.acs.org.” (11) (a) Ye, H. Y.; Zhang, Y.; Fu, D. W.; Xiong, R. G. Angew. Chem. Int. Ed.
33 2014, 53, 11242; (b) Zhang, Y.; Liao, W.-Q.; Fu, D.-W.; Ye, H.-Y.; Chen,
34 Supplementary methods and Figures S1−S7 Z.-N.; Xiong, R.-G. J. Am. Chem. Soc. 2015, 137, 4928; (c) Ye, H.-Y.; Zhou,
Q.; Niu, X.; Liao, W.-Q.; Fu, D.-W.; Zhang, Y.; You, Y.-M.; Wang, J.; Chen,
35 Z.-N.; Xiong, R.-G. J. Am. Chem. Soc. 2015, 137, 13148; (d) Zhang, Y.; Liao,
36 AUTHOR INFORMATION W. Q.; Fu, D. W.; Ye, H. Y.; Liu, C. M.; Chen, Z. N.; Xiong, R. G. Adv.
37 Corresponding Author Mater. 2015, 27, 3942.
38 (12) Zhang, Y.; Ye, H.-Y.; Zhang, W.; Xiong, R.-G. Inorg. Chem. Front. 2014,
yizhang1980@seu.edu.cn, xiongrg@seu.edu.cn 1, 118.
39
Notes (13) Lander, J. J. Acta Crystallogr. 1951, 4, 148.
40 The authors declare no competing financial interest. (14) Shi, P.-P.; Tang, Y.-Y.; Li, P.-F.; Liao, W.-Q.; Wang, Z.-X.; Ye, Q.;
41 Xiong, R.-G. Chem. Soc. Rev. 2016, 45, 3811.
42 ACKNOWLEDGMENT (15) Moya, X.; Kar-Narayan, S.; Mathur, N. Nat. Mater. 2014, 13, 439.
43
This work was supported by 973 project (2014CB932103) and the
44 National Natural Science Foundation of China (21290172,
45 91422301, 21427801, and 21522101).
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