Electrically Switchable Polarization in Bi₂O₂Se Ferroelectric Semiconductors

Abstract Atomically 2D layered ferroelectric semiconductors, in which the polarization switching process occurs within the channel material itself, offer a new material platform that can drive electronic components toward structural simplification and high‐density integration. Here, a room‐temperature 2D layered ferroelectric semiconductor, bismuth oxychalcogenides (Bi₂O₂Se), is investigated with a thickness down to 7.3 nm (≈12 layers) and piezoelectric coefficient (d₃₃) of 4.4 ± 0.1 pm V⁻¹. The random orientations and electrically dependent polarization of the dipoles in Bi₂O₂Se are separately uncovered owing to the structural symmetry‐breaking at room temperature. Specifically, the interplay between ferroelectricity and semiconducting characteristics of Bi₂O₂Se is explored on device‐level operation, revealing the hysteresis behavior and memory window (MW) formation. Leveraging the ferroelectric polarization originating from Bi₂O₂Se, the fabricated device exhibits “smart” photoresponse tunability and excellent electronic characteristics, e.g., a high on/off current ratio > 10⁴ and a large MW to the sweeping range of 47% at V_GS = ±5 V. These results demonstrate the synergistic combination of ferroelectricity with semiconducting characteristics in Bi₂O₂Se, laying the foundation for integrating sensing, logic, and memory functions into a single material system that can overcome the bottlenecks in von Neumann architecture.