Thermochemical stability, and electronic and dielectric properties of Janus bismuth oxyhalide BiOX (X = Cl, Br, I) monolayers

Abstract

Ultrathin monolayers of bismuth oxyhalide materials BiOX (X = Cl, Br, I) grown along 〈001〉 are studied using first-principles density functional theory. Both pristine BiOX and Janus (X, X′ = Cl, Br, I) monolayers are investigated by analyzing their structural stability using formation enthalpy and phonon density of states. On the other hand, their thermochemical reactivity is understood from their surface energy trends in symmetric and asymmetric terminations. The theoretically measured optical band gaps and fundamental band gaps of these Janus monolayers are compared with their pristine counterparts BiOX and BiOX′ as well as to the known experimental measurements. All of the possible Janus monolayers possess structural, electronic and optical properties intermediate to the corresponding properties of the two associated pristine BiOX and BiOX′ monolayers. According to the formation enthalpy, stabilization is equally favorable for all the monolayers, whereas the lowest surface energy is found for BiOCl0.5Br0.5, leading to excellent thermochemical reactivity which is consistent with recent experimental measurements. The frequency dependent dielectric functions are simulated in the density functional perturbation theory limit, and the optical band gaps are estimated from the absorption and reflectance spectra, and are in excellent agreement with the known experimentally measured values. High frequency dielectric constants of these materials with 2D symmetry are estimated from G0W0 calculations including local field and spin-orbit effects. The larger dielectric constants and wider differences in the charge carriers' effective masses also provide proof that this new class of 2D materials has potential in photo-electrochemical applications. Thus, fabricating Janus monolayers of these oxyhalide compounds would open up a rational design strategy for tailoring their optoelectronic properties, which may offer guidance for the design of highly efficient optoelectronic materials for catalysis, valleytronic, and sensing applications.