Anomalous Polarons in Two‐Dimensional Organometallic Perovskite Ferroelectric

The concept of ferroelectric polarons is proposed to partially explain the exceptional optoelectronic properties observed in lead halide perovskites (LHPs). It is intriguing but unclear how this proposal, which involves local or transient polarizations, applies in general to 2D LHPs with long-range ferroelectricity. Here, this work presents a pioneering time-domain experimental investigation of polarons in ferroelectric (IA)₂(MA)₂Pb₃Br₁₀ (IMPB; IA is isoamylammonium and MA is methylammonium) using transient absorption spectroscopy. Compared to non-ferroelectric LHPs, IMPB exhibits several distinct polaronic properties closely associated with macroscopic polarizations of ferroelectricity, including a prolonged polaron formation time (≈1.1 ps), a Stark splitting of the bleaching (≈63 meV), and a giant polaron Mott density (≈7.6 × 10¹⁸ cm^-3). These findings broaden the realm of 2D polaron systems and reveal the decisive role of static/unidirectional polarizations on polaron physics in 2D LHPs.