Issue 8, 2022

A one-dimensional perovskite with ferroelectric and switchable nonlinear optical properties: [azetidinium]CdCl3


Organic–inorganic perovskite hybrids (OIPHs) have been a topical area of interest in recent years. This stems from their key features such as facile and inexpensive solution based synthesis, high mechanical flexibility, structural tuneability, and chemical diversity, to name a few. Additionally, the frequently observed emergence of ferroelectric or piezoelectric properties along with optical properties renders them promising for photovoltaic energy conversion or mechanical energy harvesting applications. Herein, we report the synthesis of a novel ABX3-type ferroelectric crystal AZECdCl3 of formula [C3H8N]CdCl3, forming an infinite one-dimensional [{CdCl3}]n chain along the c direction, with azetidinium (AZE) cations C3H8N+ fitted in-between the inorganic chains. Calorimetric (DSC) measurements revealed that the crystal undergoes a complex sequence of phase transitions, at 495 K (discontinuous III), 202 K (continuous IIIII) and 167K (discontinuous IIIIV). AZECdCl3 is characterised by a strongly enhanced electric permittivity around the paraelectric–ferroelectric transition at 202 K, exhibiting excellent ferroelectric hysteresis loops with a spontaneous polarization (Ps) of 4 μC cm−2 (168 K) and with a relatively small coercive electric field (Ec) of 1.02 kV cm−1. The crystal exhibits also ferroelastic properties over all low temperature phases. The experimental value of Ps agrees with theoretical predictions based on density functional theory-based calculations. The temperature-resolved second-harmonic generation (SHG) measurements attest to the polar order of this phase. First-order phase transition IVIII was demonstrated to feature robust, high contrast SHG-off–SHG-on switching functionality. The broadband luminescence reveals thermal quenching when going from cryogenic temperatures to room temperature. The emission was assigned to the synergistic emissions of excitons due to the structural deformation of the lattice.

Graphical abstract: A one-dimensional perovskite with ferroelectric and switchable nonlinear optical properties: [azetidinium]CdCl3

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Article information

Article type
05 Nov 2021
12 Jan 2022
First published
13 Jan 2022
This article is Open Access
Creative Commons BY license

J. Mater. Chem. C, 2022,10, 3036-3047

A one-dimensional perovskite with ferroelectric and switchable nonlinear optical properties: [azetidinium]CdCl3

M. Rok, B. Zarychta, J. Trojan-Piegza, A. Bil, A. Piecha-Bisiorek, J. K. Zaręba, W. Medycki and R. Jakubas, J. Mater. Chem. C, 2022, 10, 3036 DOI: 10.1039/D1TC05355H

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