Intriguing electronic, optical and photocatalytic performance of BSe, M2CO2 monolayers and BSe–M2CO2 (M = Ti, Zr, Hf) van der Waals heterostructures

Abstract

Using density functional (DFT) theory calculations, we have investigated the electronic band structure, optical and photocatalytic response of BSe, M₂CO₂ (M = Ti, Zr, Hf) monolayers and their corresponding BSe–M₂CO₂ (M = Ti, Zr, Hf) van der Waals (vdW) heterostructures. Optimized lattice constant, bond length, band structure and bandgap values, effective mass of electrons and holes, work function and conduction and valence band edge potentials of BSe and M₂CO₂ (M = Ti, Zr, Hf) monolayers are in agreement with previously available data. Binding energies, interlayer distance and Ab initio molecular dynamic simulations (AIMD) calculations show that BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures are stable with specific stacking and demonstrate that these heterostructures might be synthesized in the laboratory. The electronic band structure shows that all the studied vdW heterostructures have indirect bandgap nature – with the CBM and VBM at the Γ–K and Γ-point of BZ for BSe–Ti₂CO₂, respectively; while for BSe–Zr₂CO₂ and BSe–Hf₂CO₂ vdW heterostructures the CBM and VBM lie at the K-point and Γ-point of BZ, respectively. Type-II band alignment in BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures prevent the recombination of electron–hole pairs, and hence are crucial for light harvesting and detection. Absorption spectra are investigated to understand the optical behavior of BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures, where the lowest energy transitions are dominated by excitons. Furthermore, BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures are found to be potential photocatalysts for water splitting at pH = 0, and exhibit enhanced optical properties in the visible light zones.