Novel One-Dimensional Organic–Inorganic Hybrid Halide Perovskite Material with Coexistence of High Phase Transition Temperature and Corresponding Dielectric Response

Abstract

Organic−inorganic hybrid perovskite materials have attracted much attention because they combine the advantages of the organic and inorganic components at the molecular level. Organic−inorganic hybrid materials have both the structural variability and the flexibility of organic components, as well as magnetic, electrical, and thermal properties of inorganic components. A novel one-dimensional organic−inorganic hybrid halide perovskite material [Et 3 NCH 2 Br][PbBr 3 ] (compound 1) undergoes a high-temperature phase transition at around 429.3 K, which is triggered by the order−disorder change of cations. Differential scanning calorimetry, a dielectric test, and single-crystal X-ray diffraction indicate that compound 1 exhibits structural phase transition from the P2 1 /c to P6 3 /m space group and a prominent dielectric anomaly. Strikingly, the bandgap of compound 1 is 3.12 eV. It is believed that our findings will contribute to an alternative pathway for the design of multifunctional materials.

Intermolecular Forces Regulating the Phase-Transition Temperatures in Organic–Inorganic Hybrid Materials

“…It may be due to the increase in the distance between the anionic backbones from the one-dimensional chain structure ( 1 ) to the zero-dimensional structure ( 2 ), so the bandgap value decreases from 3.31 to 2.26 eV. Zhang et al found in their study that the bandgap value gradually decreases as the sizes of the cations increase for fixed anions. , With the introduction of F and COOH, the cations become larger, and the bandgap value decreases, which is consistent with the above reports. This finding is of great significance for the design of novel materials with specific electronic properties, especially in the research and development of materials in the fields of semiconductors, optoelectronic devices, and energy storage, where the bandgap value can be optimized by precisely regulating the cation size to enhance the material properties, and technological progress.…”

Successive high-temperature phase transitions triggered dielectric switching in a one-dimensional hybrid perovskite with blue emission

“…Such arrangement enables cations to have greater freedom of dynamic movement. 26,28 And each trans -4-methylcyclohexylammonium cation is bound to the adjacent two inorganic chains through N–H⋯Cl hydrogen bonding interactions with the average donor–acceptor distance of about 3.31 Å, forming two-dimensional hydrogen-bonded networks along ab -plane (Fig. S2a and b†).…”

“…Exploration for materials with high-temperature phase transition is critical for advancing the field of hybrid perovskites, which has a direct bearing on the effectiveness of the material in harsh working conditions and holds great promise for applications in electronic and optoelectronic devices, particularly in the realm of switches and memories. 21–23 Despite the extensive array of efforts directed towards manipulating phase transition temperatures through strategies such as halogen substitution, modulation of intermolecular interactions, and engineering of void occupancy, 24–28 reports on hybrid perovskite phase transition materials that capitalize on the synergistic effects of symmetry breaking and unconventional configuration changes are notably scarce. In recent studies focused on phase transition hybrid crystals, it has been discovered that certain organic cations with adaptable cis / trans -configurations can serve as unique components.…”