Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors
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) structu...
| Main Authors: | , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2022-02-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202104141 |
| _version_ | 1818872422655328256 |
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| author | Jueli Shi Ethan A. Rubinstein Weiwei Li Jiaye Zhang Ye Yang Tien‐Lin Lee Changdong Qin Pengfei Yan Judith L. MacManus‐Driscoll David O. Scanlon Kelvin H.L. Zhang |
| author_facet | Jueli Shi Ethan A. Rubinstein Weiwei Li Jiaye Zhang Ye Yang Tien‐Lin Lee Changdong Qin Pengfei Yan Judith L. MacManus‐Driscoll David O. Scanlon Kelvin H.L. Zhang |
| author_sort | Jueli Shi |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-12-19T12:38:34Z |
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| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-12-19T12:38:34Z |
| publishDate | 2022-02-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj.art-bdf6f3bb0cd14226a6070d7b230d58a52022-12-21T20:21:03ZengWileyAdvanced Science2198-38442022-02-0196n/an/a10.1002/advs.202104141Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide SemiconductorsJueli Shi0Ethan A. Rubinstein1Weiwei Li2Jiaye Zhang3Ye Yang4Tien‐Lin Lee5Changdong Qin6Pengfei Yan7Judith L. MacManus‐Driscoll8David O. Scanlon9Kelvin H.L. Zhang10State Key Laboratory of Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 ChinaDepartment of Chemistry and Thomas Young Centre University College London London WC1H 0AJ UKMIIT Key Laboratory of Aerospace Information Materials and Physics College of Science Nanjing University of Aeronautics and Astronautics Nanjing 211106 ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 ChinaDiamond Light Source Ltd. Harwell Science and Innovation Campus Didcot OX11 0DE UKBeijing Key Laboratory of Microstructure and Property of Solids Faculty of Materials and Manufacturing Beijing University of Technology Beijing 100124 ChinaBeijing Key Laboratory of Microstructure and Property of Solids Faculty of Materials and Manufacturing Beijing University of Technology Beijing 100124 ChinaDepartment of Materials Science and Metallurgy University of Cambridge 27 Charles Babbage Road Cambridge CB3 0FS UKDepartment of Chemistry and Thomas Young Centre University College London London WC1H 0AJ UKState Key Laboratory of Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 ChinaAbstract 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.https://doi.org/10.1002/advs.202104141DFT calculationselectronic structuresp‐type oxide semiconductorsphotoemission spectroscopy |
| spellingShingle | Jueli Shi Ethan A. Rubinstein Weiwei Li Jiaye Zhang Ye Yang Tien‐Lin Lee Changdong Qin Pengfei Yan Judith L. MacManus‐Driscoll David O. Scanlon Kelvin H.L. Zhang Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors Advanced Science DFT calculations electronic structures p‐type oxide semiconductors photoemission spectroscopy |
| title | Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors |
| title_full | Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors |
| title_fullStr | Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors |
| title_full_unstemmed | Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors |
| title_short | Modulation of the Bi3+ 6s2 Lone Pair State in Perovskites for High‐Mobility p‐Type Oxide Semiconductors |
| title_sort | modulation of the bi3 6s2 lone pair state in perovskites for high mobility p type oxide semiconductors |
| topic | DFT calculations electronic structures p‐type oxide semiconductors photoemission spectroscopy |
| url | https://doi.org/10.1002/advs.202104141 |
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