Order-disorder transition and phase separation in the MgB2 metallic sublattice induced by Al doping

MgB2 is a superconductor constituted by alternating Mg and B planar layers: doping of both the sublattices has been observed experimentally to destroy the outstanding superconductive properties of this simple material. In this study we present the investigation by first principles methods at atomistic scale of the phase separation induced by aluminum doping in the MgB2 lattice. The calculations were performed by Density Functional Theory in generalized gradient approximation and pseudopotentials. Orthorhombic oP36 supercells derived by the primitive hR3 MgB2 cell were built in order to simulate the aluminum-magnesium substitution in the 0-50% composition range. The computational results explained the occurrence of a phase separation in the Mg1-xAlxB2 system. The miscibility gap is predicted to be induced by an order-disorder transition in the metallic sublattice at high Al concentration. Indeed at 1000 K aluminum substitution takes place on random Mg sites for concentration up to 17% of the total metallic sites, whereas at Al content larger than 31% the substitution is energetically more favorable on alternated metallic layers (Mg undoped planes alternate with Mg-Al layers). The formation of this Al-rich phase lead at 50% doping to the formation of the double omega Mg1/2Al1/2B2 ordered lattice. From 17 to 31% the two phases, the disordered Mg1-xAlxB2 (x < 0.17) and the ordered Mg1/2+yAl1/2-yB2 (y < 0.19) lattices, coexist. This phase separation is driven by the balance of the enthalpy and entropy contributions to the Gibbs energy. Present DFTGGA calculations indicate that this thermodynamically predicted suppression of the Al doping disorder in the metallic sublattice of MgB2 occurs in parallel with the collapse of the superconductive properties of the material.