Modulation of the Bi(3+) 6s(2) Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors

Oxide semiconductors are key materials in many technologies from flat‐panel displays，solar cells to transparent electronics. However, many potential applications are hindered by the lack of high mobility p‐type oxide semiconductors due to the localized O‐2p derived valence band (VB) structure. In this work, the VB structure modulation is reported for perovskite Ba(2)BiMO(6) (M = Bi, Nb, Ta) via the Bi 6s(2) lone pair state to achieve p‐type oxide semiconductors with high hole mobility up to 21 cm(2) V(−1) s(−1), and optical bandgaps widely varying from 1.5 to 3.2 eV. Pulsed laser deposition is used to grow high quality epitaxial thin films. Synergistic combination of hard x‐ray photoemission, x‐ray absorption spectroscopies, and density functional theory calculations are used to gain insight into the electronic structure of Ba(2)BiMO(6). The high mobility is attributed to the highly dispersive VB edges contributed from the strong coupling of Bi 6s with O 2p at the top of VB that lead to low hole effective masses (0.4–0.7 m (e)). Large variation in bandgaps results from the change in the energy positions of unoccupied Bi 6s orbital or Nb/Ta d orbitals that form the bottom of conduction band. P–N junction diode constructed with p‐type Ba(2)BiTaO(6) and n‐type Nb doped SrTiO(3) exhibits high rectifying ratio of 1.3 × 10(4) at ±3 V, showing great potential in fabricating high‐quality devices. This work provides deep insight into the electronic structure of Bi(3+) based perovskites and guides the development of new p‐type oxide semiconductors.