Abstract
Novel GaN-based van der Walls (vdW) hetero-bilayer (HBL) is systemically studied through the first-principles density functional theory (DFT) framework to explore its optoelectronic property facilitated photocatalytic activity for hydrogen (H 2 ) fuel production. The vdW concept of planar GaN with GeC monolayer, together making stacked hetero-bilayer, shows unique and tunable optoelectronic properties that fulfill all the photocatalysis attributes. The confirmation of chemical and dynamical stabilities is made with negative interlayer binding energy and non-negative frequency in phonon spectra, respectively. Among the dynamically stable hetero-bilayers, binding energy in HBL 2 (AB1) is the lowest and interlayer distance ~2.954Å is the smallest. The HBLs are sensitive to the stacking arrangements, where HBL 2 demonstrates type-I direct bandgap and HBL 6 (AB6) is Type-II direct bandgap. The intrinsic HBLs show superior carrier mobility as their effective masses are lower from their constituent monolayers. Also, the intrinsic absorption coefficient of the HBLs increase as high as ~10 6 cm −1 , 10 times greater than conventional perovskite materials, which show outperforming optoelectronic conversion efficiency. Additionally, the HBLs are highly tunable in both bandgap and type due to biaxial strains and cross-plane electric fields. With biaxial strains, from compressive to tensile, both HBLs show monotonous bandgap lowering with a dominant direct-indirect bandgap splitting in HBL 2. Interestingly, for all the biaxial strains within the −6% to +6% range, both HBLs have sufficient kinetic overpotential for photocatalytic water splitting and an increase in visible peak by 3.5 (2) times in the HBL 6 (HBL 2). Electric fields also increase the photocatalytic water splitting performance with a net bandgap lowering and increasing the visible absorption peak by ~1.5 times compared with intrinsic HBLs. These promising properties that we have found in the planar GaN/GeC vdW hetero-bilayer are highly suggestive for the impending use of this material in photocatalytic water splitting technology to produce H 2 fuel.