Stacking effects in van der Waals heterostructures of blueP and Janus XYO (X = Ti, Zr, Hf: Y = S, Se) monolayers

Using first-principles calculations, the geometry, electronic structure, optical and photocatalytic performance of blueP and XYO (X = Ti, Zr, Hf; Y = S, Se) monolayers and their corresponding van der Waal heterostructures in three possible stacking patterns, are investigated. BlueP and XYO (X = Ti, Zr, Hf; Y = S, Se) monolayers are indirect bandgap semiconductors. A tensile strain of 8(10)% leads to TiSeO(ZrSeO) monolayers transitioning to a direct bandgap of 1.30(1.61) eV. The calculated binding energy and AIMD simulation show that unstrained(strained) blueP and XYO (X = Ti, Zr, Hf; Y = S, Se) monolayers and their heterostructures are thermodynamically stable. Similar to the corresponding monolayers, blueP-XYO (X = Ti, Zr, Hf: Y = S, Se) vdW heterostructures in three possible stacking patterns are indirect bandgap semiconductors with staggered band alignment, except blueP-TiSeO vdW heterostructure, which signifies straddling band alignment. Absorption spectra show that optical transitions are dominated by excitons for blueP and XYO (X = Ti, Zr, Hf; Y = S, Se) monolayers and the corresponding vdW heterostructures. BothEVBandECBin TiSO, ZrSO, ZrSeO and HfSO monolayers achieve energetically favorable positions, and therefore, are suitable for water splitting at pH = 0, while TiSeO and HfSeO monolayers showed good response for reduction and fail to oxidise water. All studied vdW heterostructures also show good response to any produced O2, while specific stacking reduces H+to H2 © The Royal Society of Chemistry 2021.