Repozytorium

Ferroelectricity in ethylammonium bismuth-based organic–inorganic hybrid: (C2H5NH3)2[BiBr5].

Autorzy

Ryszard Jakubas

Anna Gągor

Maciej J. Winiarski

Maciej Ptak

Anna Piecha-Bisiorek

Agnieszka Ciżman

Rok wydania

2020

Czasopismo

Inorganic Chemistry

Numer woluminu

59

Strony

3417-3427

DOI

10.1021/acs.inorgchem.9b03193

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The (C2H5NH3)2[BiBr5] (EBB) crystals adopt the one-dimensional (1D) polymeric anionic form [BiBr5]∞2-, which is preferred by halobismuthates(III) exhibiting polar properties and realized in R2MX5 stoichiometry. Differential scanning calorimetry and dilatometric measurements reveal reversible structural phase transitions: at 160 K (phase I → phase II) and 120 K (phase II → phase III). The resolved crystal structures of EBB show the centrosymmetric space group in phase I (Aeam), polar (Pca21) in phase II, and polar (Aea2) in phase III. The presence of dielectric hysteresis loops in phases II and III evidence ferroelectric properties. The dielectric response [ε*(ω,T)] of EBB close to 160 K is characteristic of ferroelectrics with a critical slowing down process. The molecular mechanism of a paraelectric-ferroelectric phase transition at 160 K is explained as "order-disorder" (assigned to the dynamics of the ethylammonium cations) and dominating "displacive" (related to strong distortion of the 1D anionic network). The optical band gap obtained from UV-vis measurements is about 2.6 eV. The conduction band minimum is formed by the hybridized Bi 6p and Br 4p states. An analysis of the CSD results for haloantimonates(III) and halobismuthates(III) ferroelectrics characterized by [MX4]-, [M2X9]3-, [MX5]2-, and [M2X11]5- anions is given.

Słowa kluczowe

Amines, Insulators, Phase transitions, Cations, Polarization

Adres publiczny

http://dx.doi.org/10.1021/acs.inorgchem.9b03193

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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