Large Piezoelectric Response and High Carrier Mobilities Enhanced via 6s2 Hybridization in Bismuth Chalcohalide Monolayers

In this study, we systematically investigated the piezoelectric and carrier transport properties of two-dimensional (2D) Bi-based chalcohalide monolayers (BiXY, X = Se, Te; Y = Br, I) using first-principles calculations. The phonon dispersion and elastic properties proved that BiXY monolayers are dynamically and mechanically stable. Our results reveal that the stereochemically active 6s² lone-pair electrons of Bi³⁺ play a crucial role in determining the structural and electronic characteristics of these systems. The simultaneous enhancement of Born effective charges and the strong sensitivity of atomic positions to external strain give rise to pronounced piezoelectric responses in BiXY monolayers. Specifically, the calculated piezoelectric coefficients (d₁₁) reached 13.16 and 17.76 pm/V for BiSeBr and BiSeI, respectively. The carrier transport properties were estimated using the deformation potential (DP) theory, which yielded upper-bound values under idealized conditions. For instance, in BiTeBr, the effective masses of electrons and holes were 0.15 and 0.40 m₀, respectively, leading to high carrier mobilities of 2736.1 and 2689.9 cm² V^-1 s^-1. These findings highlight the potential of Bi-based chalcohalide monolayers as promising candidates for next-generation multi-functional nanoelectronic and piezoelectric devices.