RESUMO
This contribution explores the systematic substitution of phosphorene monoflakes (Mfs) and biflakes (Bfs) with aluminum, silicon, and sulfur. These systems were investigated using density functional theory employing the TPSS exchange-correlation functional and complete active space self-consistent field (CASSCF) calculations. Al and Si substitution produces significant structural changes in both Mfs and Bfs compared to S-substituted and pristine systems. However, in Mfs, all heteroatoms generate a decrease in band gap and the ionization potentials (IP), and an increase in electron affinity (EA) in comparison with pristine phosphorene. Al doping improves the hole mobility in the phosphorene monoflake, while Si and S substitutions exhibit a similar behavior on EAs and reorganization energies. For Bfs, the presence of Si-Si and Al-P interlaminar interactions causes structural changes and higher binding energies for Si-Bfs and Al-Bfs. Regarding the electronic properties of Bfs, substitution with Si does not produce significant variations in the band gap. Nevertheless, it conduces the formation of hole transport materials, which does not occur in Si-Mfs. The same is observed for Al systems, whereas no correlation was identified between the doping level and reorganization energies for S complexes. The substitution with Al and S leads to an opposite behavior of the band gap and IP values, while the EA variation is similar. In summary, the nature of heteroatom and the doping degree can modify the semiconductor character and electronic properties of phosphorene mono- and biflakes, whose trends are closely related to the atomic properties considered. Overall, these computational calculations provide significant insights into the study of doped phosphorene materials.
RESUMO
The electronic structure of phosphorene nanoflakes (PNFs) doped with Al and Si has been explored using hybrid functional BHandHlyp/def2-SVP and complete active space (CASSCF) methods. Doping increases the bond length alternation and changes the overall PNF shape. Doping also decreases singlet-triplet splitting in the PNFs. This effect is most notable for Si doping where singlet and triplet states become virtually degenerated. Doping also reduces band gaps and changes the nature of the ground states for Si-doped systems. The ground state of Si-doped PNFs becomes polyradicalic. In general, dopants with even number of valence electrons promote polyradicalic ground state. Doped systems show increased electron affinities (EAs), while the ionization potentials are much less affected. Larger EAs are related with the delocalization of an extra electron over the empty or partially empty 3p orbitals of the dopants. Doping increases the reorganization energies in all cases. Al-doped PNFs are the hole transport materials while Si-doped nanoflakes tend to be electron transport systems. Graphical abstract.