Influence of the second layer on geometry and spectral properties of doped two-dimensional hexagonal boron nitride

Influence of the additional layer of hexagonal boron nitride (h-BN) on structure, energetics, and electronic spectra of a layer doped with magnesium, silicon, phosphorus, aluminum, or carbon atoms has been examined by theoretical methods. The h-BN layers are modeled as BN clusters of over thirty atoms with the defect in the center. The calculations show that atom positions undergo some modifications in the presence of the second layer, which in several cases lead to significant changes in electronic spectra, like (i) modifications of the character of some states from local excitation to a partial charge transfer; (ii) redshift of the majority of lowest excitations; (iii) absence or appearance of new states in comparison with the monolayers. For instance, a zero-intensity excitation below 4 eV for the carbon atom in place of boron transforms into a dipole-allowed one in the presence of the second layer. A comparison of the interaction energies of doped and undoped clusters shows a strong dependence of the stabilizing of destabilizing effect on the dopant atom, the replaced atom, and in some cases also on the stacking type (AA’ or AB). The stabilization energy per BN pair, calculated for two undoped clusters, is equal to − 31 and − 28 meV for the AA’ and AB stacking, respectively, thus confirming a larger stability of the AA’ stacking for the h-BN case. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s00894-020-04456-8) contains supplementary material, which is available to authorized users.