Revealing the electronic, optical and photocatalytic properties of PN-M2CO2 (P = Al, Ga; M = Ti, Zr, Hf) heterostructures

Abstract

Using DFT, the electronic structure, optical, and photocatalytic properties of PN (P = Ga, Al) and M₂CO₂ (M = Ti, Zr, Hf) monolayers and their PN-M₂CO₂ van der Waals heterostructures (vdWHs) are investigated. Optimized lattice parameters, bond length, bandgap, conduction and valence band edges show the potential of PN (P = Ga, Al) and M₂CO₂ (M = Ti, Zr, Hf) monolayers in photocatalytic applications, and the application of the present approach to combine these monolayers and form vdWHs for efficient electronic, optoelectronic and photocatalytic applications is shown. Based on the same hexagonal symmetry and experimentally achievable lattice mismatch of PN (P = Ga, Al) with M₂CO₂ (M = Ti, Zr, Hf) monolayers, we have fabricated PN-M₂CO₂ vdWHs. Binding energies, interlayer distance and AIMD calculations show the stability of PN-M₂CO₂ vdWHs and demonstrate that these materials can be easily fabricated experimentally. The calculated electronic band structures show that all the PN-M₂CO₂ vdWHs are indirect bandgap semiconductors. Type-II[-I] band alignment is obtained for GaN(AlN)-Ti₂CO₂[GaN(AlN)-Zr₂CO₂ and GaN(AlN)-Hf₂CO₂] vdWHs. PN-Ti₂CO₂ (PN-Zr₂CO₂) vdWHs with a PN(Zr₂CO₂) monolayer have greater potential than a Ti₂CO₂(PN) monolayer, indicating that charge is transfer from the Ti₂CO₂(PN) to PN(Zr₂CO₂) monolayer, while the potential drop separates charge carriers (electron and holes) at the interface. The work function and effective mass of the carriers of PN-M₂CO₂ vdWHs are also calculated and presented. A red (blue) shift is observed in the position of excitonic peaks from AlN to GaN in PN-Ti₂CO₂ and PN-Hf₂CO₂ (PN-Zr₂CO₂) vdWHs, while significant absorption for photon energies above 2 eV for AlN-Zr₂CO₂, GaN-Ti₂CO₂ and PN-Hf₂CO₂, give them good optical profiles. The calculated photocatalytic properties demonstrate that PN-M₂CO₂ (P = Al, Ga; M = Ti, Zr, Hf) vdWHs are the best candidates for photocatalytic water splitting.