Interface Engineering of Monolayer MoS2/GaN Hybrid Heterostructure: Modified Band Alignment for Photocatalytic Water Splitting Application by Nitridation Treatment

Interface engineering is a key strategy to deal with the two-dimensional (2D)/three-dimensional (3D) hybrid heterostructure, since the properties of this atomic-layer-thick 2D material can easily be impacted by the substrate environment. In this work, the structural, electronic, and optical properties of the 2D/3D heterostructure of monolayer MoS2 on wurtzite GaN surface without and with nitridation interfacial layer are systematically investigated by first-principles calculation and experimental analysis. The nitridation interfacial layer can be introduced into the 2D/3D heterostructure by remote N2 plasma treatment to GaN sample surface prior to stacking monolayer MoS2 on top. The calculation results reveal that the 2D/3D integrated heterostructure is energetically favorable with a negative formation energy. Both interfaces demonstrate indirect band gap, which is a benefit for longer lifetime of the photoexcited carriers. Meanwhile, the conduction band edge and valence band edge of the MoS2 side increases after nitridation treatment. The modification to band alignment is then verified by X-ray photoelectron spectroscopy measurement on MoS2/GaN heterostructures constructed by a modified wet-transfer technique, which indicates that the MoS2/GaN heterostructure without nitridation shows a type-II alignment with a conduction band offset (CBO) of only 0.07 eV. However, by the deployment of interface nitridation, the band edges of MoS2 move upward for ∼0.5 eV as a result of the nitridized substrate property. The significantly increased CBO could lead to better electron accumulation capability at the GaN side. The nitridized 2D/3D heterostructure with effective interface treatment exhibits a clean band gap and substantial optical absorption ability and could be potentially used as practical photocatalyst for hydrogen generation by water splitting using solar energy.