First-principles study on the electronic structures and optical properties of Mg-doped KDP crystal

First-principles method was employed to study the defect formation energy, electronic structure, and optical properties of Potassium Dihydrogen Phosphate (KDP) crystals doped with Mg in both paraelectric phase (PE-KDP) and ferroelectric phase (FE-KDP). Additionally, we employed the HSE hybrid density functional to address the issue of “band gap” and utilized the finite size correction-finite volume (FNV) method to rectify defect formation energies. Due to hybridization of Mg-3s orbitals with O-2p orbitals, a defect energy level is created at the conduction band minimum (CBM), resulting in the band gap of Mg-doped KDP crystals being smaller than that of perfect crystals. Moreover, the incorporation of Mg leads to significant lattice distortions and alters bond lengths, particularly the O–Mg bonds, which are stretched by 0.65–0.77 Å. The optical spectra also have been obtained under the consideration of electron-phonon coupling. The absorption peak locates at 4.37 eV (284 nm) in PE-KDP. The absorption peak locates at 4.66 eV (266 nm) in FE-KDP. Moreover, the significant Stokes shifts (3.67 eV and 2.9 eV) observed in Mg-doped KDP crystals were attributed to lattice relaxation energy and distortions induced by the substitution. The calculated results indicate that the quality of the KDP crystals may be reduce by introducing Mg-impurities. The work provides valuable insights into the optical characteristics of Mg-doped KDP crystals and their potential applications in laser technology.