Local p‐ and n‐Type Doping of an Oxide Semiconductor via Electric‐Field‐Driven Defect Migration

Local acceptor and donor doping is achieved in a semiconducting oxide by controlled splitting of oxygen interstitial‐vacancy pairs under applied d.c. voltage. The separated oxygen defects are demonstrated to form interstitial‐rich (p‐type) and vacancy‐rich (n‐type) regions, comparable to dipolar npn‐junctions, enabling transient functionalization. Abstract Layered oxides exhibit high ionic mobility and chemical flexibility, attracting interest as cathode materials for lithium‐ion batteries and the pairing of hydrogen production and carbon capture. Recently, layered oxides emerged as highly tunable semiconductors. For example, by introducing anti‐Frenkel defects, the electronic hopping conductance in hexagonal manganites is increased locally by orders of magnitude. Here, local acceptor and donor doping in Er(Mn,Ti)O3 is demonstrated, facilitated by the controlled splitting of anti‐Frenkel defects under applied d.c. voltage. By combining density functional theory calculations, scanning probe microscopy, atom probe tomography, and scanning transmission electron microscopy, it is shown that the oxygen defects can readily be moved through the layered crystal structure, leading to nano‐sized interstitial‐rich (p‐type) and vacancy‐rich (n‐type) regions. The resulting pattern is comparable to dipolar npn‐junctions and stable on the timescale of days. These findings reveal the possibility of temporarily functionalizing oxide semiconductors at the nanoscale, giving additional opportunities for the field of oxide electronics and the development of transient electronics in general. Local acceptor and donor doping is achieved in a semiconducting oxide by controlled splitting of oxygen interstitial-vacancy pairs under applied d.c. voltage. The separated oxygen defects are demonstrated to form interstitial-rich (p-type) and vacancy-rich (n-type) regions, comparable to dipolar npn-junctions, enabling transient functionalization. Abstract Layered oxides exhibit high ionic mobility and chemical flexibility, attracting interest as cathode materials for lithium-ion batteries and the pairing of hydrogen production and carbon capture. Recently, layered oxides emerged as highly tunable semiconductors. For example, by introducing anti-Frenkel defects, the electronic hopping conductance in hexagonal manganites is increased locally by orders of magnitude. Here, local acceptor and donor doping in Er(Mn,Ti)O 3 is demonstrated, facilitated by the controlled splitting of anti-Frenkel defects under applied d.c. voltage. By combining density functional theory calculations, scanning probe microscopy, atom probe tomography, and scanning transmission electron microscopy, it is shown that the oxygen defects can readily be moved through the layered crystal structure, leading to nano-sized interstitial-rich (p-type) and vacancy-rich (n-type) regions. The resulting pattern is comparable to dipolar npn-junctions and stable on the timescale of days. These findings reveal the possibility of temporarily functionalizing oxide semiconductors at the nanoscale, giving additional opportunities for the field of oxide electronics and the development of transient electronics in general. Advanced Science, Volume 12, Issue 43, November 20, 2025.