187 research outputs found
Cu-doped Pb(PO)O, and V doped SrTiO -- a tutorial on electron-crystal lattice coupling in insulating materials with transition metal dopants
We provide two pedagogical examples to understand the mechanisms at play in
stabilizing an insulating state, and an impurity level in the bandgap in two
insulators using DFT+U: Cu-doped Pb(PO)O and V-doped SrTiO
transition metal-doped insulators. We find both to be insulating, with isolated
impurity (flat) bands, regardless of doping location. In both cases, the
electron degeneracy and crystal lattice symmetry are broken, leading to an
insulating state, and a magnetically and orbitally polarized impurity state
within the gap, clearly separated from the valence and conduction bands. We
also resolve previously noticed inconsistencies between DFT and experiment
regarding doping site energetics, crystal structure, and transparency in
Cu-doped phosphate lead apatite 'LK-99'. Doping one of each type of site in the
same unit cell ( doping) also simply leads to two spin-polarized
impurity bands in the material's gap. The local transition metal ion sites may
behave like color centers (or f-centers), possibly giving color at low
temperatures to what we predict to be a transparent, insulating material in the
recently synthesized LK-99. Weak ferromagnetism may be possible due to the
relatively delocalized unpaired spins in the valence band. Further work should
take into account the possibility of further changes in stoichiometry,
different doping locations, supercell effects, and quantification of magnetic
exchange interactions
Trigonal Symmetry Breaking and its Electronic Effects in Two-Dimensional Dihalides and Trihalides
We study the consequences of the approximately trigonal () point
symmetry of the transition metal (M) site in two-dimensional van der Waals
MX dihalides and MX trihalides. The trigonal symmetry leads to a 2-2-1
orbital splitting of the transition metal shell, which may be tuned by the
interlayer distance, and changes in the ligand-ligand bond lengths. Orbital
order coupled to various lower symmetry lattice modes may lift the remaining
orbital degeneracies, and we explain how these may support unique electronic
states using ZrI and CuCl as examples, and offer a brief overview of
possible electronic configurations in this class of materials. By building and
analysing Wannier models adapted to the appropriate symmetry we examine how the
interplay among trigonal symmetry, electronic correlation effects, and -
orbital charge transfer leads to insulating, orbitally polarized magnetic
and/or orbital-selective Mott states. Our work establishes a rigorous framework
to understand, control, and tune the electronic states in low-dimensional
correlated halides. Our analysis shows that trigonal symmetry and its breaking
is a key feature of the 2D halides that needs to be accounted for in search of
novel electronic states in materials ranging from CrI to -RuCl
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