Electronic stabilization by occupational disorder in the ternary bismuthide Li_3–x–y In _x Bi (x ≃ 0.14, y ≃ 0.29)

Abstract

A ternary derivative of Li3Bi with the composition Li3–x–yInxBi (x ≃ 0.14, y ≃ 0.29) was produced by a mixed In+Bi flux approach. The crystal structure adopts the space group Fdm (No. 227), with a = 13.337 (4) Å, and can be viewed as a 2 × 2 × 2 superstructure of the parent Li3Bi phase, resulting from a partial ordering of Li and In in the tetrahedral voids of the Bi fcc packing. In addition to the Li/In substitutional disorder, partial occupation of some Li sites is observed. The Li deficiency develops to reduce the total electron count in the system, counteracting thereby the electron doping introduced by the In substitution. First‐principles calculations confirm the electronic rationale of the observed disorder.