An Unprecedented Biaxial Trilayered Hybrid Perovskite Ferroelectric

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An Unprecedented Biaxial Trilayered Hybrid Perovskite Ferroelectric with Directionally-Tunable Photovoltaic Effects Sasa Wang, Xitao Liu, Lina Li, Chengmin Ji, Zhihua Sun, Zhenyue Wu, Maochun Hong, and Junhua Luo J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b02558 • Publication Date (Web): 02 May 2019 Downloaded from http://pubs.acs.org on May 2, 2019

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An Unprecedented Biaxial Trilayered Hybrid Perovskite Ferroelectric with Directionally-Tunable Photovoltaic Effects Sasa Wang,†, ‡ Xitao Liu,† Lina Li,†,* Chengmin Ji,† Zhihua Sun,†,* Zhenyue Wu,†, ‡ Maochun Hong† and Junhua Luo†,* †State

Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China ‡University of Chinese Academy of Sciences, Beijing, 100049, China Supporting Information Placeholder ABSTRACT: Multiaxial molecular ferroelectrics, in which multiple-directional switching of spontaneous polarization creates diverse properties, have shown many intriguing advantages as indispensable complements to conventional inorganic oxides. Despite recent blooming advances, multiaxial molecular ferroelectric with bulk photovoltaic effects still remains a huge blank. Herein, we report a biaxial lead-halide ferroelectric, EA4Pb3Br10 (1, EA = ethylammonium), which adopts the unique trilayered perovskite motif with a high Curie temperature of ~384 K. Particularly, for 1, the distinct symmetry breaking with 4/mmmFmm2 species leads to the emergence of four equivalent polarization directions in the ferroelectric phase. Based on its biaxial nature, the bulk photovoltaic effect of 1 can be facilely tuned between such multiple directions through electric poling. As far as we know, this is the first report on biaxial hybrid perovskite ferroelectric showing directionally-tunable photovoltaic activity. This work allows for an avenue to control bulk physical properties of multiaxial molecular ferroelectrics, and highlights their potentials for further application in the field of smart devices.

Ferroelectrics, which enable switching of spontaneous polarization (Ps) under an external electric field, have sparked great interest for their promising applications in ferroelectric random access memory, piezoelectric devices, capacitors, sensors, and optoelectronic devices.1-5 It is noteworthy that to achieve the optimal polarization, the uniaxial ferroelectric must be well oriented to the polar axis. In contrast, the polarization can be switched more easily in multiaxial ferroelectrics and a larger polarization can be obtained after poling, owing to the capable of multiple equivalent polarization directions.6,7 Moreover, the polarization axis of the as-grown crystals can be feasibly controlled by external electric field, providing a facile way to control the polarization direction of the crystal.8,9 In this aspect, as indispensable complements to conventional inorganic oxides, multiaxial molecular ferroelectrics, especially multiaxial organicinorganic hybrid ferroelectrics have been recently investigated, such as large piezoelectric effect of ~185 pC/N for TMCM-MnCl3 (TMCM = Me3NCH2Cl),10 the fastest polarization switching of 100 kHz for the thin films of [Hdabco]ReO4 (dabco = 1,4diazabicyclo[2.2.2]octane),11 and an unprecedented bondswitching phase transition for [(CH3)3NOH]2[KFe(CN)6],12 etc. Meanwhile, the spontaneous polarization in ferroelectrics could create an ultrahigh built-in electric field thus promotes the desirable separation of photoexcited carriers.13-15 This feature

renders ferroelectrics promising candidates for photovoltaic application.16,17 For instance, it has been deemed that intriguing optoelectronic performances of [CH3NH3]PbI3 might be related to its large polarization and domain structures.18-20 Furthermore, organic-inorganic hybrid perovskites display great structural tunability and variability, which provides an infinite possibility in the design of new ferroelectrics.21-25 Recent advance has witnessed the booming of hybrid perovskite-type ferroelectrics, especially their application in photoelectric conversion, as exemplified by (C4H9NH3)2CsPb2Br7 and bis(cyclohexylaminium)PbBr4.26,27 For multiaxial ferroelectrics, their multiple polarization directions characteristic offers an opportunity for the orientation control of its bulk photovoltaic effects. However, multiaxial molecular ferroelectrics with tunable photovoltaic effects remain a huge blank, which are highly desirable for the development of high-performance smart optoelectronic devices. Herein, we report a biaxial ferroelectric, EA4Pb3Br10 (1, EA = ethylammonium), adopting a unique trilayered perovskite motif with the simple EA as template cation. It undergoes a distinct phase transition from the paraelectric 4/mmm to ferroelectric mm2 at ~384 K, suggesting its biaxial nature. Emphatically, bulk photovoltaic effects of 1 were easily tuned between such polarization directions (i.e. the crystallographic a- and c- axes) by electric poling, relying on the multiple-directional tunability along the two axes. To our knowledge, 2D trilayered hybrid perovskite that shows biaxial ferroelectricity and directionally-tunable photovoltaic activity is unprecedented. This work allows for an avenue to control bulk physical properties of multiaxial molecular ferroelectrics, and highlights their potentials for further application in the field of smart devices. Structural analyses reveal that 1 adopts a unique 2D trilayered perovskite architecture and crystallizes in the polar orthorhombic space group C2cb at room temperature (Table S1), consistent with previously report.28 Usually, for multilayered perovskite, (B)2(A)n−1PbnX3n+1, cation A is the “perovskitizer” that occupies the central cavity of corner-sharing PbX6 octahedra, and cation B is the “spacer” that confined in the interlayer space of inorganic sheets.29 For 1, however, the EA cations act as both the “perovskitizer” cation and “spacer” cation, forming a distinct trilayered motif via N−H···Br hydrogen bonds (Figure S3). This architecture can be regarded as a derivative of the threedimensional (3D) MAPbBr3, where the symmetry is tailored to 2D by replacing the MA with relatively large EA cation, as illustrated in Scheme 1. As is known, the MA cations are

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pertains to typical biaxial ferroelectric, which is the first example of 2D trilayered organic-inorganic hybrid biaxial ferroelectric. Variable-temperature second harmonic generation (SHG) measurement was performed to verify symmetry breaking of 1 during its phase transition. As illustrated in Figure 2a, the SHG

Scheme 1. Diagram for the tailoring of a 3D prototype of MAPbBr3 into the 2D trilayered perovskite ferroelectric EA4Pb3Br10. The H atoms are omitted for clarity. dynamically disordered with a nearly-spherical shape in MAPbBr3 thus meeting the requirement of highly-symmetric structure.30 However, in EA4Pb3Br10, the EA cations are totally ordered resulting from the strong N−H∙∙∙Br hydrogen bonds. Meanwhile, the corner-sharing PbBr6 octahedrons are extremely distorted to accommodate the additional −CH2− group, as exemplified by the Br−Pb−Br bond angles and Pb−Br bond lengths (Table S2). Consequently, the negative charged PbBr6 octahedrons deviate away from their ideal octahedral symmetry, together with the tilting of the positively charged centers of organic cations, making a crucial contribution to the formation of molecular dipole moment (Figure S4a). Upon heating, 1 undergoes a ferroelectric phase transition at ~384 K (Tc), and adopts a centrosymmetric space group I4/mmm. It is obvious that the distorted inorganic framework turns into highly symmetric configuration at high temperature phase (HTP). Meanwhile, the EA cations become highly disordered with the N and the terminal C atom situate in the fourfold rotation axis, while the middle C atom are uniformly distributed around the fourfold rotation axis (Figure S4b). The relationship of lattice cells between HTP and low temperature phase (LTP) is aLTP ≈ aHTP + bHTP, bLTP ≈ cHTP, cLTP ≈ aHTP - bHTP (Figure 1a). The ab-plane of

Figure 1. (a) Projection figure of the crystal cell of 1 at ferroelectric phase, the cell with blue edges represent that of its tetragonal paraelectric phase. (b) The scheme drawing of the four equivalent polarization directions for the ferroelectric species 4/mmmFmm2.

Figure 2. (a) Variable-temperature SHG signals of 1. (b) P−E hysteresis loops measured along the crystallographic a-, b-, and caxes. signal of 1 is almost zero at HTP, indicating the centrosymmetric characteristic of the paraelectric phase, as supported by the crystal structure of 390 K. Apparently, it increases gradually as temperature decreases below Tc, the SHG-active state is in good accordance with the polar structure at LTP. The obvious change of SHG signal fits well with the DSC, variable-temperature PXRD patterns, and dielectric results (Figures S5-S7). Further, biaxial ferroelectricity of 1 is definitely validated by P−E hysteresis loops (Figure 2b). The explored Ps value of ~3.5 μC/cm2 is approximately to the calculated result (Figure S16), and larger than other multiaxial ferroelectrics, such as (R)-(–)-3hydroxlyquinuclidinium (∼2.4 μC/cm2),32 and [(CH3)3NOH]2[KFe(CN)6] (∼0.58 μC/cm2).12 It should be emphasized that the rectangular P−E hysteresis loops can be realized not only along a-axis but also along c-axis, which is distinct from the linear P−E relationship of b-axis. The P−E hysteresis loops anisotropy of 1 coincids well with its biaxial feature, making it definitely different with that of previously reported uniaxial ferroelectrics. Besides, the P−E hysteresis loop remains well-defined rectangular after exposed to ambient conditions for two weeks, confirming its good stability (Figure S8). As far as we are aware, this biaxial nature is reminiscent of an avenue to tune bulk photoelectric properties of 1, that is, the multiple-directional control of polarization by an external electric poling. Before correlating the polarization switching with bulk photovoltaic effect (BPVE) of 1, we studied the magnitude of its optical band gap. As depicted in Figure 3a, 1 displays an absorption cut-off around 460 nm, the estimated band gap (~2.70 eV, inset of Figure 3a) is slightly larger than the calculated one (~2.30 eV), but on par with that of BiFeO3 (~2.67 eV).33 Considering Rashba effect in the polar structure, 1 should be a direct band gap semiconductor, stemmed from Pb-5p and Br-4p states of the inorganic framework (Figures S9 and S10).28,34 Such a moderate band gap implies the potentials of 1 for photovoltaic application.

the HTP corresponds to the ac-plane of the LTP. The symmetry change of 1 satisfies the requirement of the Aizu rule 4/mmmFmm2, which is among the 88 species ferroelectric phase transitions.31 Considering the number of symmetry operations in the HTP and LTP, there are four equivalent polarization directions (r = 16/4) in the ferroelectric phase (Figure 1b). Therefore, 1


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Figure 3. (a) Optical absorption spectrum of 1. Inset: the band gap obtained from absorption spectrum. (b) I–V curves of 1 measured along the crystallographic a-axis in the dark and illuminated with 405 nm laser light. Inset: the logarithmic I–V curves. (c) Enlarged version of I–V curves in the low bias region. (d) Temperature-dependence of the short circuit current of 1. Subsequently, bulk photovoltaic properties of 1 were measured on single crystals with lateral two-probe device under 405 nm laser light (Figure S11). As shown in Figure 3b, upon irradiation, the current increases sharply from ~164 pA to ~178 nA (Vbias = 10 V), the large “on/off” ratio (~103) is comparable with those of other hybrid perovskite-based detectors.35 This performance manifests the potential of 1 as promising photoelectric material. Remarkably, in the low bias region, BPVEs were facilely acquired along a-axis (Figure 3c). The open circuit voltage (Voc) and short circuit current (Isc) of 1 is estimated as -0.49 V/+7.26 nA for polarization up state, and +0.52 V/-6.36 nA for polarization down state. With the inversion of polarization states, the signs of Voc and Isc have been switched; this suggests that BPVE of 1 is highly relevant to the built-in electric field stemmed from its ferroelectricity. Moreover, the Isc exhibits a temperaturedependent variation with a sharp decrease in the vicinity of Tc, and vanishes fully at the paraelectric phase (Figure 3d). This tendency legibly reveals the close relationship between BPVE and ferroelectricity, which has been verified in ferroelectrics of BiFeO3 and TTF-CA.36,37 Besides, the almost unchanged photocurrent after turning light on/off for several cycles and the steady-state feature of Isc and Voc reveals good stability of the crystal-based photovoltaic device (Figures S12-S14). Such excellent properties make 1 a potential candidate for photovoltaic device application. Most significantly, BPVEs of 1 can be tuned between its equivalent polarization directions, which involves with the orientation control of its polarization under an external electric field. As shown in the inset of Figure 3c, identical to that of its aaxis, BPVEs were also achieved along the crystallographic c-axis (with b-axis shows almost negligible levels of BPVEs, Figure S15). This feature is in stark contrast to that of previously reported uniaxial ferroelectrics. From the viewpoint of crystallography, the Ps direction of a ferroelectric is determined by the symmetry breaking from paraelectric phase (PEP) to ferroelectric phase (FEP).38-41 At FEP, 1 belongs to the space group of C2cb, the polarization of which is restricted to the [100]FEP-direction according to crystallographic symmetry (Figure 4a). However, at PEP, 1 adopts a higher symmetric space group of

Figure 4. Schematic illustration of the flexible alteration of Ps directions under external electric poling. (a) The Ps direction along a-axis (yellow arrows) of 1 at FEP. (b) Four equivalent [110]directions at PEP (red arrows) for symmetry breaking of 4/mmmFmm2. (c) Variation of Ps direction during PEP-to-FEP under an applied electric poling. I4/mmm with two equivalent axes, corresponding to four directions of [110] , [110] , [110] , [110] (Figure 4b). During symmetry-breaking phase transition upon cooling, one of such equivalent axes becomes the polarization axis of its FEP. Accordingly, the entire crystal chooses its polar twofold axis randomly without an electric field. However, under an applied electric field, the polarization axis can be selected by a controllable manner, which is aligned tightly with the applied electric field. As a result, the crystal exhibits polarization directions different from that of the as-grown one (Figure 4c). Thus, after poling, a similar photovoltaic current reversal was observed along the crystallographic c-axis. This result discloses the close relationship between BPVE and electric polarization, and further verifies the biaxial ferroelectric character of 1. In conclusion, we reported a biaxial molecular ferroelectric, EA4Pb3Br10, adopting a unique trilayered perovskite architecture with one single-cation template. Most strikingly, 1 exhibits the directionally-tunable photovoltaic behaviours; that is, the bulk photovoltaic effects can be easily tuned between its equivalent polarization directions under an applied electric poling. This unprecedented performance depends on the multiple-directional switching of polarization, fully different from the known uniaxial ferroelectrics. As a pioneering exploration, 1 should be the first hybrid perovskite biaxial ferroelectric that shows directionallytunable photovoltaic activity. This work opens a new pathway to control bulk physical properties of multiaxial molecular ferroelectrics, and sheds light on their potentials for further smartdevice application.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the internet: http://pubs.acs.org. Crystal data of EA4Pb3Br10, PXRD patterns, and additional data



X-ray crystallographic data of 1 at 280 K (CIF) and 390 K (CIF)

AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected] *[email protected]

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported by National Natural Science Foundation of China (21601188, 21622108, 21833010, 21875251, 21525104, 21571178, 51502288, and 91422301), the NSF of Fujian Province (2016J06012, 2018H0047 and 2016J01082), L.L. thanks the supports from Youth Innovation Promotion of CAS (2015240), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20010200).

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An Unprecedented Biaxial Trilayered Hybrid Perovskite Ferroelectric

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