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Two-dimensional (2D) materials tend to have the preferably formation ofvacancies at the outer surface. Here, contrary to the normal notion, we reveala type of vacancy that thermodynamically initiates from the interior part ofthe 2D backbone of germanium selenide ({\gamma}-GeSe). Interestingly, theGe-vacancy (VGe) in the interior part of {\gamma}-GeSe possesses the lowestformation energy amongst the various types of defects considered. We also finda low diffusion barrier (1.04 eV) of VGe which is a half of those of sulfurvacancy in MoS2. The facile formation of mobile VGe is rooted in theantibonding coupling of the lone-pair Ge 4s and Se 4p states near the valenceband maximum, which also exists in other gamma-phase MX (M=Sn, Ge; X=S, Te).The VGe is accompanied by a shallow acceptor level in the band gap and inducesstrong infrared light absorption and p-type conductivity. The VGe located inthe middle cationic Ge sublattice is well protected by the surface Se layers-afeature that is absent in other atomically thin materials. Our work suggeststhat the unique well-buried inner VGe, with the potential of formingstructurally protected ultrathin conducting filaments, may render the GeSelayer an ideal platform for quantum emitting, memristive, and neuromorphicapplications.

nanoscale horizons

Abnormal behavior of preferred formation of cationic vacancy from the  interior in {\gamma}-GeSe monolayer with the stereo-chemical antibonding  lone-pair state