Centimeter‐Sized Piezoelectric Single Crystal of Chiral Bismuth‐Based Hybrid Halide with Superior Electrostrictive Coefficient

Abstract

The lead‐free hybrid perovskite piezoelectrics possess advantages of easy processing, light weight, and low‐toxicity over inorganic ceramics. However, the lack of understanding in structure–property relationships hinders exploration of new molecular piezoelectric crystals with excellent performances. Herein, by introducing chiral α‐phenylethylammonium (α‐PEA+) cations into bismuth‐based hybrid halides, centimeter‐sized (R‐α‐PEA)4Bi2I10 and (S‐α‐PEA)4Bi2I10 single crystals with a superior piezoelectric voltage coefficient g22 of 309 mV m N−1, are obtained. Structural rigidity in crystals leads to a remarkable electrostrictive coefficient Q22 of 25.8 m4 C−2, nearly 20 times higher than that of poly(vinylidene fluoride) (PVDF), which is beneficial to improve piezoelectricity with the synergistic effect of chirality. Moreover, the as‐grown crystals show outstanding phase stability from 173 K to ≈470 K. This work suggests a design strategy based on rigidity and chirality to exploit novel piezoelectrics among hybrid metal halides.

Chiral zero-dimensional hybrid organic–inorganic metal halides based on nipecotic acid and tetrabromocuprate

“…Organic-inorganic hybrid metal halides combine the properties of inorganic and organic components and have the characteristics of flexible crystal structure, highly adjustable band gap, and luminescence effect. [1][2][3] They can be widely used in ferroelectric materials, 4 piezoelectric material, 5 and other materials. [6][7][8] The introduction of chiral organic molecules into organic-inorganic hybrid metal halides can obtain organic-inorganic metal halides with chiral properties.…”

Precise Manipulation the Efficient Multi‐Exciton Emission with High Thermal Stability in Hybrid Manganese‐Antimony Chloride for Optical Thermometry, Anti‐Counterfeiting, and Information Encryption

“…Zero-dimensional (0D) organic-inorganic hybrid metal halides (OHMHs) have emerged as promising candidates in the field of advanced anti-counterfeiting luminescent materials due to their unique and diverse "host-guest" structures, highly efficient stimulated emission, and tunable photoluminescent properties. [9][10][11][12][13] Currently, there are numerous anti-counterfeiting applications based on zero-dimensional materials, such as Cu-based, [14] Sbbased, [11] Zr-based, [15] and In-based. [5] But most of these materials are usually limited to two emission colors, so information can only be decrypted through one key.…”

Synthesis and Optical Properties of One Year Air-Stable Chiral Sb(III) Halide Semiconductors

“…Although there are some studies evaluating the stability of various lead-free metal halides based on Bi­(III) and Sb­(III) for up to a year, − there are only scarce reports about the environmental stability of chiral lead-free MHS. In particular, Wu et al developed a 1D semiconductor, namely, (C 9 H 14 N)­SbCl 4 (C 9 H 14 N = N , N ,4-trimethylaniline) with high second harmonic generation (SHG) response, which is air-stable for 3 months, Moon et al reported the synthesis of 0D [(( R / S )-C 8 H 12 N) 4 ]­[Bi 2 Br 10 ], (C 8 H 12 N = 1-phenyl-ethylammonium) which is stable in humid air for 1 month, Tao et al, acquired the 0D ( R -α-PEA) 4 Bi 2 I 10 and ( S -α-PEA) 4 Bi 2 I 10 compounds which are air-stable for 4 months, while Maiti and Pal synthesized the 0D ( R / S -MBA) 4 Bi 2 Br 10 materials which are air-stable for 15 days …”