Band edge evolution of transparent Zn M2III O4 (MIII=Co, Rh, Ir) spinels

Matthew J. Wahila; Zachary W. Lebens-Higgins; Adam J. Jackson; David O. Scanlon; Tien Lin Lee; Jiaye Zhang; Kelvin H.L. Zhang; Louis F.J. Piper

doi:10.1103/PhysRevB.100.085126

Band edge evolution of transparent Zn M2III O4 (MIII=Co, Rh, Ir) spinels

Matthew J. Wahila^*
, Zachary W. Lebens-Higgins
, Adam J. Jackson
, David O. Scanlon
, Tien Lin Lee
, Jiaye Zhang
, Kelvin H.L. Zhang
, Louis F.J. Piper

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

ZnM2IIIO4 (MIII=Co, Rh, Ir) spinels have been recently identified as promising p-type semiconductors for transparent electronics. However, discrepancies exist in the literature regarding their fundamental optoelectronic properties. In this paper, the electronic structures of these spinels are directly investigated using soft/hard x-ray photoelectron and x-ray absorption spectroscopies in conjunction with density functional theory calculations. In contrast to previous results, ZnCo2O4 is found to have a small electronic band gap with forbidden optical transitions between the true band edges, allowing for both bipolar doping and high optical transparency. Furthermore, increased d-d splitting combined with a concomitant lowering of Zn s/p conduction states is found to result in a ZnCo2O4(ZCO)<ZnRh2O4(ZRO)≈ZnIr2O4(ZIO) band gap trend, finally resolving long-standing discrepancies in the literature.

Original language	English
Article number	085126
Journal	Physical Review B
Volume	100
Issue number	8
DOIs	https://doi.org/10.1103/PhysRevB.100.085126
Publication status	Published - 15 Aug 2019

Bibliographical note

Funding Information:
K.H.L.Z. is grateful for funding support from the Herchel Smith Fellowship by University of Cambridge and the Thousand Youth Talents Program of China. We thank Diamond Light Source for access to beamline I09 (SI 16005), which contributed to the results presented here. We also thank beamline scientist Christoph Schlueter at Diamond Light Source for their assistance. This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-18-1-0024. This work made use of the UCL Grace and Legion high-performance computing resources and the ARCHER U.K. National Supercomputing Service, via membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202). A.J.J. and D.O.S. acknowledge support from the EPSRC (EP/N01572X/1).

Funding Information:
K.H.L.Z. is grateful for funding support from the Herchel Smith Fellowship by University of Cambridge and the Thousand Youth Talents Program of China. We thank Diamond Light Source for access to beamline I09 (SI 16005), which contributed to the results presented here. We also thank beamline scientist Christoph Schlueter at Diamond Light Source for their assistance. This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-18-1-0024. This work made use of the UCL Grace and Legion high-performance computing resources and the ARCHER U.K. National Supercomputing Service, via membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202). A.J.J. and D.O.S. acknowledge support from the EPSRC (EP/N01572X/1)

Publisher Copyright:
© 2019 American Physical Society.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Condensed Matter Physics

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10.1103/PhysRevB.100.085126

Cite this

@article{8552e86503ce462bafa7b87dc0d981c6,

title = "Band edge evolution of transparent Zn M2III O4 (MIII=Co, Rh, Ir) spinels",

abstract = "ZnM2IIIO4 (MIII=Co, Rh, Ir) spinels have been recently identified as promising p-type semiconductors for transparent electronics. However, discrepancies exist in the literature regarding their fundamental optoelectronic properties. In this paper, the electronic structures of these spinels are directly investigated using soft/hard x-ray photoelectron and x-ray absorption spectroscopies in conjunction with density functional theory calculations. In contrast to previous results, ZnCo2O4 is found to have a small electronic band gap with forbidden optical transitions between the true band edges, allowing for both bipolar doping and high optical transparency. Furthermore, increased d-d splitting combined with a concomitant lowering of Zn s/p conduction states is found to result in a ZnCo2O4(ZCO)",

author = "Wahila, \{Matthew J.\} and Lebens-Higgins, \{Zachary W.\} and Jackson, \{Adam J.\} and Scanlon, \{David O.\} and Lee, \{Tien Lin\} and Jiaye Zhang and Zhang, \{Kelvin H.L.\} and Piper, \{Louis F.J.\}",

note = "Funding Information: K.H.L.Z. is grateful for funding support from the Herchel Smith Fellowship by University of Cambridge and the Thousand Youth Talents Program of China. We thank Diamond Light Source for access to beamline I09 (SI 16005), which contributed to the results presented here. We also thank beamline scientist Christoph Schlueter at Diamond Light Source for their assistance. This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-18-1-0024. This work made use of the UCL Grace and Legion high-performance computing resources and the ARCHER U.K. National Supercomputing Service, via membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202). A.J.J. and D.O.S. acknowledge support from the EPSRC (EP/N01572X/1). Funding Information: K.H.L.Z. is grateful for funding support from the Herchel Smith Fellowship by University of Cambridge and the Thousand Youth Talents Program of China. We thank Diamond Light Source for access to beamline I09 (SI 16005), which contributed to the results presented here. We also thank beamline scientist Christoph Schlueter at Diamond Light Source for their assistance. This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-18-1-0024. This work made use of the UCL Grace and Legion high-performance computing resources and the ARCHER U.K. National Supercomputing Service, via membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202). A.J.J. and D.O.S. acknowledge support from the EPSRC (EP/N01572X/1) Publisher Copyright: {\textcopyright} 2019 American Physical Society.",

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doi = "10.1103/PhysRevB.100.085126",

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volume = "100",

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AU - Jackson, Adam J.

AU - Scanlon, David O.

AU - Lee, Tien Lin

AU - Zhang, Jiaye

AU - Zhang, Kelvin H.L.

AU - Piper, Louis F.J.

N1 - Funding Information: K.H.L.Z. is grateful for funding support from the Herchel Smith Fellowship by University of Cambridge and the Thousand Youth Talents Program of China. We thank Diamond Light Source for access to beamline I09 (SI 16005), which contributed to the results presented here. We also thank beamline scientist Christoph Schlueter at Diamond Light Source for their assistance. This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-18-1-0024. This work made use of the UCL Grace and Legion high-performance computing resources and the ARCHER U.K. National Supercomputing Service, via membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202). A.J.J. and D.O.S. acknowledge support from the EPSRC (EP/N01572X/1). Funding Information: K.H.L.Z. is grateful for funding support from the Herchel Smith Fellowship by University of Cambridge and the Thousand Youth Talents Program of China. We thank Diamond Light Source for access to beamline I09 (SI 16005), which contributed to the results presented here. We also thank beamline scientist Christoph Schlueter at Diamond Light Source for their assistance. This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-18-1-0024. This work made use of the UCL Grace and Legion high-performance computing resources and the ARCHER U.K. National Supercomputing Service, via membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202). A.J.J. and D.O.S. acknowledge support from the EPSRC (EP/N01572X/1) Publisher Copyright: © 2019 American Physical Society.

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N2 - ZnM2IIIO4 (MIII=Co, Rh, Ir) spinels have been recently identified as promising p-type semiconductors for transparent electronics. However, discrepancies exist in the literature regarding their fundamental optoelectronic properties. In this paper, the electronic structures of these spinels are directly investigated using soft/hard x-ray photoelectron and x-ray absorption spectroscopies in conjunction with density functional theory calculations. In contrast to previous results, ZnCo2O4 is found to have a small electronic band gap with forbidden optical transitions between the true band edges, allowing for both bipolar doping and high optical transparency. Furthermore, increased d-d splitting combined with a concomitant lowering of Zn s/p conduction states is found to result in a ZnCo2O4(ZCO)

AB - ZnM2IIIO4 (MIII=Co, Rh, Ir) spinels have been recently identified as promising p-type semiconductors for transparent electronics. However, discrepancies exist in the literature regarding their fundamental optoelectronic properties. In this paper, the electronic structures of these spinels are directly investigated using soft/hard x-ray photoelectron and x-ray absorption spectroscopies in conjunction with density functional theory calculations. In contrast to previous results, ZnCo2O4 is found to have a small electronic band gap with forbidden optical transitions between the true band edges, allowing for both bipolar doping and high optical transparency. Furthermore, increased d-d splitting combined with a concomitant lowering of Zn s/p conduction states is found to result in a ZnCo2O4(ZCO)

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DO - 10.1103/PhysRevB.100.085126

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Band edge evolution of transparent Zn M2III O4 (MIII=Co, Rh, Ir) spinels

Abstract

Bibliographical note

ASJC Scopus subject areas

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