02 July 2024 | Haining Zheng, Arup Ghosh, M. J. Swamynadhan, Qihan Zhang, Walter P. D. Wong, Zhenyue Wu, Rongrong Zhang, Jingsheng Chen, Fanica Cimpoesu, Saurabh Ghosh, Branton J. Campbell, Kai Wang, Alessandro Stroppa, Ramanathan Mahendiran & Kian Ping Loh
This study reports the coexistence of ferroelectric, magnetic, and crystallographic chirality in hybrid organic-inorganic perovskites [(R/S)-β-methylphenethylamine]₂CuCl₄. The material exhibits in-plane ferroelectricity and A-type antiferromagnetic order, with chirality-dependent magnetic circular dichroism (MCD) arising from the field-induced Zeeman effect. Through Landau symmetry mode analysis, a novel mechanism for chirality transfer is proposed, involving the coupling of non-chiral distortions characterized by a pseudo-scalar quantity, ξ = p · r, which distinguishes between (R)- and (S)-chirality based on its sign. The reversal of this descriptor's sign is associated with coordinated transitions in ferroelectric distortions, Jahn-Teller antiferro-distortions, and Dzyaloshinskii-Moriya vectors, indicating the mediating role of crystallographic chirality in magnetoelectric correlations.
Chirality, a property of non-superposability between an object and its mirror image, is crucial in various fields, enabling phenomena such as spin-orbit coupling and topological spin arrangements. Chiral crystals, with reduced symmetry, can induce polar electric long-range orders. Chirality-induced spin selectivity allows spin polarization manipulation without external magnetic fields, offering potential for spin filters and non-volatile magnetic memories. However, designing single-phase chiral multiferroics is challenging due to the mutual exclusivity of ferroelectric and magnetic orders.
Layered Cu²+-based hybrid organic-inorganic perovskites (HOlPs) are ideal candidates for chiral multiferroics. These materials exhibit corner-sharing CuCl₆ octahedral frames connected by organic cations through hydrogen bonding. Ferroelectricity arises from organic ligand disorder-to-order phase transitions and induced structural distortions in the inorganic octahedra. Cooperative Jahn-Teller (J-T) tilted ordering provides a ferromagnetic superexchange pathway along Cu²+-Cl⁻-Cu²+ bridges, enabling multiferroic behavior. Incorporating chiral organic ligands enables chirality transfer across the organic-inorganic framework, which is coupled with the helical distortion of CuCl₆ anionic cages.
The study demonstrates the coexistence of chirality, electric, and magnetic orders in HOIP-based chiral multiferroics (R/S)-(MPA)₂CuCl₄, which display intralayer ferroelectricity and A-type antiferromagnetic order. These materials exhibit chirality-dependent MCD characters. Through Landau-type symmetry-mode analysis, a peculiar chirality transfer mechanism is revealed, where two non-chiral structural distortions hybridize to break all improper symmetries Sₙ in the structure, rendering structural chirality. This chirality transfer mechanism is parametrized by a pseudo-scalar order parameterThis study reports the coexistence of ferroelectric, magnetic, and crystallographic chirality in hybrid organic-inorganic perovskites [(R/S)-β-methylphenethylamine]₂CuCl₄. The material exhibits in-plane ferroelectricity and A-type antiferromagnetic order, with chirality-dependent magnetic circular dichroism (MCD) arising from the field-induced Zeeman effect. Through Landau symmetry mode analysis, a novel mechanism for chirality transfer is proposed, involving the coupling of non-chiral distortions characterized by a pseudo-scalar quantity, ξ = p · r, which distinguishes between (R)- and (S)-chirality based on its sign. The reversal of this descriptor's sign is associated with coordinated transitions in ferroelectric distortions, Jahn-Teller antiferro-distortions, and Dzyaloshinskii-Moriya vectors, indicating the mediating role of crystallographic chirality in magnetoelectric correlations.
Chirality, a property of non-superposability between an object and its mirror image, is crucial in various fields, enabling phenomena such as spin-orbit coupling and topological spin arrangements. Chiral crystals, with reduced symmetry, can induce polar electric long-range orders. Chirality-induced spin selectivity allows spin polarization manipulation without external magnetic fields, offering potential for spin filters and non-volatile magnetic memories. However, designing single-phase chiral multiferroics is challenging due to the mutual exclusivity of ferroelectric and magnetic orders.
Layered Cu²+-based hybrid organic-inorganic perovskites (HOlPs) are ideal candidates for chiral multiferroics. These materials exhibit corner-sharing CuCl₆ octahedral frames connected by organic cations through hydrogen bonding. Ferroelectricity arises from organic ligand disorder-to-order phase transitions and induced structural distortions in the inorganic octahedra. Cooperative Jahn-Teller (J-T) tilted ordering provides a ferromagnetic superexchange pathway along Cu²+-Cl⁻-Cu²+ bridges, enabling multiferroic behavior. Incorporating chiral organic ligands enables chirality transfer across the organic-inorganic framework, which is coupled with the helical distortion of CuCl₆ anionic cages.
The study demonstrates the coexistence of chirality, electric, and magnetic orders in HOIP-based chiral multiferroics (R/S)-(MPA)₂CuCl₄, which display intralayer ferroelectricity and A-type antiferromagnetic order. These materials exhibit chirality-dependent MCD characters. Through Landau-type symmetry-mode analysis, a peculiar chirality transfer mechanism is revealed, where two non-chiral structural distortions hybridize to break all improper symmetries Sₙ in the structure, rendering structural chirality. This chirality transfer mechanism is parametrized by a pseudo-scalar order parameter