Nucleation-mediated growth of chiral 3D organic–inorganic perovskite single crystals

• Published in: Nature chemistry Vol. 15; no. 11; pp. 1581 - 1590
• Main Authors: Chen, Gaoyu, Liu, Xiaoyu, An, Jiakun, Wang, Shibin, Zhao, Xiaokun, Gu, Zhongzheng, Yuan, Caojin, Xu, Xiangxing, Bao, Jianchun, Hu, Han-Shi, Li, Jun, Wang, Xun
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.11.2023; Nature Publishing Group
• Subjects: 639/638/298/398; 639/638/440/94; 639/638/549/933; Ammonium; Analytical Chemistry; Biochemistry; Cations; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Chirality; Circular polarization; Crystallization; Crystals; Inorganic Chemistry; Lead compounds; Metal halides; Nanoparticles; Nucleation; Optoelectronics; Organic Chemistry; Perovskite structure; Perovskites; Physical Chemistry; Polarized light; Reagents; Single crystals
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/s41557-023-01290-2

Although their zero- to two-dimensional counterparts are well known, three-dimensional chiral hybrid organic–inorganic perovskite single crystals have remained difficult because they contain no chiral components and their crystal phases belong to centrosymmetric achiral point groups. Here we report a general approach to grow single-crystalline 3D lead halide perovskites with chiroptical activity. Taking MAPbBr 3 (MA, methylammonium) perovskite as a representative example, whereas achiral MAPbBr 3 crystallized from precursors in solution by inverse temperature crystallization method, the addition of micro- or nanoparticles as nucleating agents promoted the formation of chiral crystals under a near equilibrium state. Experimental characterization supported by calculations showed that the chirality of the 3D APbX 3 (where A is an ammonium ion and X is Cl, Br or mixed Cl–Br or Br–I) perovskites arises from chiral patterns of the A-site cations and their interaction with the [PbX 6 ] 4− octahedra in the perovskite structure. The chiral structure obeys the lowest-energy principle and thereby thermodynamically stable. The chiral 3D hybrid organic–inorganic perovskites served in a circularly polarized light photodetector prototype successfully. While chiral hybrid organic–inorganic perovskites are promising materials for optoelectronic applications, the synthesis of three-dimensional single crystals has proven challenging. Now, a general strategy has been shown to synthesize chiral, three-dimensional perovskites by heterogeneous nucleation. The single-crystalline materials contain no chiral component; their chiroptical activity arises from supercells formed by chiral patterns of the A-site cations.