Homochirality to design high- T c lead-free ferroelastic semiconductors

• Published in: Journal of materials chemistry. C, Materials for optical and electronic devices Vol. 12; no. 17; pp. 6098 - 6105
• Main Authors: Deng, Bo-Wen, Rao, Zhi-Peng, Shen, Ming-Jing, Liang, Ke-Wei, Zhu, Yang, Wang, Zhi-Jie, Ding, Kun, Su, Chang-Yuan, Lun, Meng-Meng, Zhang, Zhi-Xu, Zhang, Yi, Fu, Da-Wei
• Format: Journal Article
• Language: English
• Published: 02.05.2024
• ISSN: 2050-7526; 2050-7534
• DOI: 10.1039/D4TC00428K

Ferroelastic semiconductor materials have garnered significant research interest due to their promising applications in the fields of shape memory, superelasticity, templated electronic nanostructures, mechanical switching, and optoelectronic transmission. However, the toxicity of lead-based structures and low phase-transition temperature ( T c ) greatly constrain the application scenarios of ferroelastic semiconductors. Here, using an H/OH-substitution-induced homochiral strategy, we synthesize a pair of lead-free ferroelastic semiconductors ( R / S -CTA) 2 SbCl 5 (CTA = 3-chloro-2-hydroxypropyltrimethyllammonium) having semiconductor properties with an indirect bandgap of 3.41 eV. They crystallized in the chiral space group P 2 1 2 1 2 1 at room temperature, and both undergo 422F222 type ferroelastic phase transitions with T c up to 410 K, accompanied by a large entropy change of 68.75 and 66.09 J mol −1 K −1 , respectively. Owing to the introduction of chirality, they exhibited temperature-dependent nonlinear second-harmonic generation (SHG) properties. Relatively, the achiral TMCP (TMCP = N , N , N -trimethylchloropropylamine) makes the phase transition properties of centrosymmetric TMCP 2 SbCl 5 ordinary compared to chiral R / S -pair. This is precisely the main starting point of homochiral strategies in phase transition and optical structure research, while arousing research interest. This work, which provides a new avenue for the design of high- T c lead-free ferroelastic semiconductor compounds, is a powerful motivation for the realization of multifunctional materials related to chirality.