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Modulation of the Bi3+ 6S2 lone pair state in perovskites for high-mobility p-type oxide semiconductors

DOI: 10.1002/advs.202104141 DOI Help

Authors: Jueli Shi (Xiamen University) , Ethan A. Rubinstein (University College London) , Weiwei Li (Nanjing University of Aeronautics and Astronautics; University of Cambridge) , Jiaye Zhang (Xiamen University) , Ye Yang (Xiamen University) , Tien-Lin Lee (Diamond Light Source) , Changdong Qin (Beijing University of Technology) , Pengfei Yan (Beijing University of Technology) , Judith L. Macmanus-Driscoll (University of Cambridge) , David O. Scanlon (University College London; Diamond Light Source) , Kelvin H.l. Zhang (Xiamen University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Advanced Science

State: Published (Approved)
Published: January 2022
Diamond Proposal Number(s): 24219

Open Access Open Access

Abstract: 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 Ba2BiMO6 (M = Bi, Nb, Ta) via the Bi 6s2 lone pair state to achieve p-type oxide semiconductors with high hole mobility up to 21 cm2 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 Ba2BiMO6. 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 me). 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 Ba2BiTaO6 and n-type Nb doped SrTiO3 exhibits high rectifying ratio of 1.3 × 104 at ±3 V, showing great potential in fabricating high-quality devices. This work provides deep insight into the electronic structure of Bi3+ based perovskites and guides the development of new p-type oxide semiconductors.

Journal Keywords: DFT calculations; electronic structures; p-type oxide semiconductors; photoemission spectroscopy

Diamond Keywords: Semiconductors

Subject Areas: Materials, Physics, Chemistry

Instruments: I09-Surface and Interface Structural Analysis

Added On: 10/01/2022 08:42

Advanced Science - 2022 - Shi - Modulation of the Bi3 6s2 Lone Pair State in Perovskites for High%E2%80%90Mobility p%E2%80%90Type Oxide.pdf

Discipline Tags:

Surfaces Hard condensed matter - electronic properties Physics Physical Chemistry Electronics Energy Materials Chemistry Materials Science interfaces and thin films Perovskites Metallurgy

Technical Tags:

Spectroscopy X-ray Photoelectron Spectroscopy (XPS) Hard X-ray Photoelectron Spectroscopy (HAXPES)