Lead-free Dion–Jacobson halide perovskites CsMX2Y2 (M = Sb, Bi and X, Y = Cl, Br, I) used for optoelectronic applications via first principle calculations

In this study, all-inorganic two-dimensional Dion–Jacobson halide perovskites (DJ-HPs) CsMX2Y2 (M = Sb, Bi; and X/Y= I/I, I/Br, Br/Br, I/Cl, Br/Cl, Cl/Cl) have been studied for photovoltaic, photoemission and other potential applications in optoelectronic devices using first principle calculations within the framework of density functional theory (DFT). The ground state crystal symmetry is tetragonal with a P4/mmm (No. 123) space group. In these compounds, Cs+ is a spacer cation, which separates the octahedral layers and balances the charge. The corner sharing M-centered (Sb, Bi) [MX2Y4]3– unit constructs the 2D [MX2Y2]nn– plane, where the X and Y (halogens) atoms occupy the out of plane apical and in-plane bridging sites, respectively. The DJ-HPs with P4/mmm crystal symmetry exhibit pseudo-direct band gap semiconducting nature and the spin orbit (SO) effect reduces the band gaps as well as splits the Sb/Bi-p orbital in the bottom of conduction band (CB) and X/Y-p orbital at the top of valence band (VB). Among these DJ-HPs, the band gap energies of CsSbI2Cl2 (0.87 eV), CsSbBr2Cl2 (1.00 eV), CsSbCl4 (1.40 eV), CsBiI4 (1.10 eV), CsBiI2Br2 (1.40 eV) and CsBiBr4 (1.60 eV) lie in a band gap energy range (0.9–1.6 eV) suitable for photovoltaic applications. The M-s (Sb-5s and Bi-6s) and X/Y-p (Cl-3p, Br-4p and I-5p) orbitals are responsible for the electron transition from the valence to conduction band, while the spacer cation (Cs+) has a limited effect on the charge carrier mobility. The effective masses of the charge carriers and exciton binding energies of these materials are suitable for solar cell and optoelectronic applications. From the optical coefficients it is clear that these DJ-HPs have excellent response to the incident photons in the visible and ultraviolet light region. •New Dion–Jacobson two dimensional halide are investigated for optoelectronic applications.•These compounds belongs to tetragonal symmetry having space group P4/mmm.•Band gap of these semiconductors are pseudo direct and spin orbit (SO) effect increases from Sb to Bi and Cl to I.•The effective masses of the carriers are increasing linearly with the increasing band gaps.