Atomic networks as highways for holes in oxygen-deficient amorphous oxides

Oxygen-deficient amorphous tellurium oxides ($a$-TeO${}_x$) have recently challenged the intrinsic hole mobility limits of amorphous oxides, with thin-film transistors reaching mobilities up to 15 cm${}^2$V${}^{-1}$s${}^{-1}$ upon Se doping. However, the atomistic origins of this behavior, and its seeming contradiction with established semiconductor physics, have remained unresolved. Here, we combine machine-learning-accelerated ab initio molecular dynamics with hybrid-functional defect calculations to establish a new microscopic picture. We show that substantial oxygen loss drives spontaneous segregation into interpenetrating $a$-Te and $a$-TeO${}_2$ domains, rather than forming dispersed oxygen vacancies. The diffuse Te-$5p$ states from the $a$-Te network supply percolative pathways for holes, so mobility rises monotonically with oxygen deficiency, enabling mobilities that exceed current records. Doped Se incorporates into the $a$-Te domain, enhancing the connectivity of conductive pathways, thereby increasing hole mobility. Similar behavior in amorphous SeO${}_x$ suggests domain percolation as a general route to high-mobility p-type transport in amorphous oxides.