4.7 Article

Luminescence and Dielectric Switchable Properties of a 1D (1,1,1-Trimethylhydrazinium)PbI3 Hybrid Perovskitoid

Journal

INORGANIC CHEMISTRY
Volume 61, Issue 51, Pages 20886-20895

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c0328720886

Keywords

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Funding

  1. National Science Centre, Poland [UMO-2020/37/N/ST5/02257]

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The synthesis and investigation of a novel one-dimensional organic-inorganic hybrid perovskite with unique physicochemical properties are reported. The crystal structure and phase transitions of the material are studied, and its optical properties are characterized, suggesting potential applications.
The synthesis and investigation of the physicochemical properties of a novel one-dimensional (1D) hybrid organic-inorganic perovskitoid templated by the 1,1,1-trimethylhydrazinium (Me(3)Hy(+)) cation are reported. (Me(3)Hy)[PbI3] crystallizes in the hexagonal P6(3)/m symmetry and undergoes two phase transitions (PTs) during heating (cooling) at 322 (320) and 207 (202) K. Xray diffraction data and temperature-dependent vibrational studies show that the second-order PT to the high-temperature hexagonal P6(3)/mmc phase is associated with a weak change in entropy and is related to weak structural changes and different confinement of cations in the available space. The second PT to the lowtemperature orthorhombic Pbca phase that corresponds to the high change in entropy and dielectric switching is associated with an ordering of the trimethylhydrazinium cations, re-arrangement and strengthening of hydrogen bonds, and slightly shifted lead-iodide octahedral chains. The high-pressure Raman data revealed two additional PTs, one between 2.8 and 3.2 GPa, related to the symmetry decrease, ordering of the cations, and inorganic chain distortion, and the other in the 6.4-6.8 GPa range related to the partial and reversible amorphization. Optical studies revealed that (Me(3)Hy)[PbI3] has a wide band gap (3.20 eV) and emits reddishorange excitonic emission at low temperatures with an activation energy of 65 meV.

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