Tuning Defects in a Halide Double Perovskite with Pressure

Dopant defects in semiconductors can trap charge carriers or ionize to produce charge carriers playing a critical role in electronic transport. Halide perovskites are a technologically important semiconductor family with a large pressure response. Yet, to our knowledge, the effect of high pressures on defects in halide perovskites has not been experimentally investigated. Here, we study the structural, optical, and electronic consequences of compressing the small-bandgap double perovskites Cs₂AgTlX₆(X = Cl or Br) up to 56 GPa. Mild compression to 1.7 GPa increases the conductivity of Cs₂AgTlBr₆by ca. 1 order of magnitude and decreases its bandgap from 0.94 to 0.7 eV. Subsequent compression yields complex optoelectronic behavior: The bandgap varies by 1.2 eV and conductivity ranges by a factor of 10⁴. These conductivity changes cannot be explained by the evolving bandgap. Instead, they can be understood as tuning of the bromine vacancy defect with pressure varying between a delocalized shallow defect state with a small ionization energy and a localized deep defect state with a large ionization energy. Activation energy measurements reveal that the shallow-to-deep defect transition occurs near 1.5 GPa, well before the cubic-to-tetragonal phase transition. An analysis of the orbital interactions in Cs₂AgTlBr₆illustrates how the bromine vacancy weakens the adjacent Tl s-Br p antibonding interaction, driving the shallow-to-deep defect transition. Our orbital analysis leads us to propose that halogen vacancies are most likely to be shallow donors in halide double perovskites that have a conduction band derived from the octahedral metal's s orbitals.