Bias Tunable Transport Modulation and Gas Selectivity in Layered BiOI: A DFT NEGF Study

Abstract

Understanding the interplay between adsorption energetics and charge-transport modulation is essential for the rational design of low-power and bias-tunable gas sensors. Here, we present a comprehensive first-principles study of gas selectivity in layered bismuth oxyiodide (BiOI) by integrating density functional theory with nonequilibrium Green's function transport calculations. The adsorption and bias-dependent transport responses toward NO2, NH3, CO2, and representative volatile organic compounds are systematically examined. While NH3 and NO2 exhibit strong chemisorption and localized electronic perturbations, CO2 interacts through weak physisorption, demonstrating that adsorption strength alone does not determine sensing performance. Instead, the evolution of transmission channels near the Fermi level governs the sensing response. Bias-dependent calculations reveal an electrically tunable sensitivity hierarchy, in which weakly adsorbed CO2 preserves conductive pathways and exhibits pronounced low-bias sensitivity despite minimal charge transfer. Recovery-time analysis further highlights the trade-off between transport modulation and reversibility for strongly adsorbed species. These results establish a transport-centered selectivity framework for layered BiOI and provide mechanistic insight into electric-field-controlled gas sensing under ambient conditions.