Ferroelectric, Switchable Dielectric and Nonlinear Optical Properties in Inorganic-Organic Lead-Free 1D Hybrids Based on Bi(III) and Azetidine: (C₃NH₈)₂[BiCl₅], (C₃NH₈)₂[BiBr₅].

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL The Journal of Physical Chemistry Letters Pub Date : 2024-11-15 DOI:10.1021/acs.jpclett.4c02695

Magdalena Rok, Bartosz Zarychta, Jan K Zaręba, Aleksandra Krupińska, Błażej Dziuk, Piotr Durlak, Rafał Janicki, Ryszard Jakubas, Grażyna Bator, Wojciech Medycki, Michaela Zamponi, Anna Piecha-Bisiorek

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Abstract

This study investigates lead-free organic-inorganic hybrids (C₃NH₈)₂[BiCl₅] (ABC) and (C₃NH₈)₂[BiBr₅] (ABB), focusing on their structural, dielectric, ferroelectric, and optical properties. Both compounds exhibit paraelectric (I) to ferroelectric (II) phase transitions (PTs) at 230/233 K and 228/229 K, respectively, transitioning from orthorhombic (Pnma) to monoclinic (P2₁) phases, with distorted [BiX₆]^3- octahedra forming 1D chains. Quasielastic neutron scattering and solid-state ¹H NMR studies reveal the localized motion of azetidinium cations. Dielectric measurements of ABC and ABB show step-like permittivity changes by 11-12 units post-transition I → II, demonstrating reversible switching behavior. Absorption studies reveal band gaps of 3.24 eV for ABC and 2.76 eV for ABB, classifying them as insulators. Luminescence spectra at 77K display 578 nm (ABC) and 708 nm (ABB) emissions, attributed to ³P_1,0 → ¹S₀ transitions. Both compounds demonstrate stable second harmonic generation (SHG) switching of the on-off type. The switching performance is evaluated over multiple thermal cycles using the t_req metric, which decreases with increasing temperature change rate and indicates that ABB's SHG switching is approximately 30% faster than that of ABC.

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基于 Bi(III)和氮杂环丁烷的无机-有机无铅一维杂化物：(C3NH8)2[BiCl5]、(C3NH8)2[BiBr5]的铁电性、可切换介电性和非线性光学特性。

本研究调查了无铅有机无机杂化物 (C3NH8)2[BiCl5] (ABC) 和 (C3NH8)2[BiBr5] (ABB)，重点研究了它们的结构、介电、铁电和光学特性。这两种化合物分别在 230/233 K 和 228/229 K 时表现出介电（I）到铁电（II）的相变（PTs），从正方晶相（Pnma）过渡到单斜晶相（P21），扭曲的 [BiX6]3- 八面体形成一维链。准弹性中子散射和固态 1H NMR 研究揭示了氮杂环丁烷阳离子的局部运动。对 ABC 和 ABB 的介电测量显示，在 I → II 转变后，介电系数发生了 11-12 个单位的阶梯状变化，证明了其可逆转换行为。吸收研究显示，ABC 和 ABB 的带隙分别为 3.24 eV 和 2.76 eV，因此它们被归类为绝缘体。77K 时的发光光谱显示出 578 纳米（ABC）和 708 纳米（ABB）的发射光谱，这归因于 3P1,0 → 1S0 转变。这两种化合物都显示出稳定的开关型二次谐波发生（SHG）开关。开关性能通过多个热循环使用 treq 指标进行评估，该指标随温度变化率的增加而降低，表明 ABB 的 SHG 开关速度比 ABC 快约 30%。

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来源期刊

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.