Valence band modification of Cr2O3 by Ni-doping: Creating a high figure of merit p-type TCO

Elisabetta Arca; Aoife B. Kehoe; Tim D. Veal; Aleksey Shmeliov; David O. Scanlon; Clive Downing; Dermot Daly; Daragh Mullarkey; Igor V. Shvets; Valeria Nicolosi; Graeme W. Watson

doi:10.1039/c7tc03545d

Valence band modification of Cr₂O₃ by Ni-doping: Creating a high figure of merit p-type TCO

Elisabetta Arca^*, Aoife B. Kehoe, Tim D. Veal, Aleksey Shmeliov, David O. Scanlon, Clive Downing, Dermot Daly, Daragh Mullarkey, Igor V. Shvets, Valeria Nicolosi, Graeme W. Watson

^*Corresponding author for this work

Chemistry

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

Abstract

p-Type transparent conductors and semiconductors still suffer from remarkably low performance compared to their more widespread n-type counterparts, despite extensive investigation into their development. In this contribution, we present a comparative study on the defect chemistry of potential p-type transparent conducting oxides Mg-doped and Ni-doped Cr₂O₃. Conductivities as high as 28 S cm^-1 were achieved by Ni-doping. By benchmarking crystallography and spectroscopy characterization against density functional theory calculations, we show that the incorporation of Ni into Cr₂O₃ contributes to the composition of the valence band, making the formed holes more delocalized, while Mg states do not interact with the valence band in Mg-doped Cr₂O₃. Furthermore, it is experimentally proven that Ni has a higher solubility in Cr₂O₃ than Mg, at least in the highly non-thermodynamic deposition conditions used for these experiments, which directly translates into a higher acceptor concentration. The combination of these two effects means that Ni is a more effective acceptor in Cr₂O₃ than Mg and explains the improved conductivity observed for the former.

Original language	English
Pages (from-to)	12610-12618
Number of pages	9
Journal	Journal of Materials Chemistry C
Volume	5
Issue number	47
DOIs	https://doi.org/10.1039/c7tc03545d
Publication status	Published - 2017

Bibliographical note

Funding Information:
Calculations were performed on ARCHER via membership of the Materials Chemistry Consortium (funded by EPSRC grant number EP/L000202), the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC) platform Fionn (project tcche056b), and the Lonsdale and Kelvin clusters maintained by TCHPC.

Funding Information:
This research was supported by SFI through the PI programme (grant numbers 12/IA/1414 and SFI12/IA/1264). E. Arca acknowledges SFI for the Advance Award Fellowship (grant number SFI14/ADV/IA2641). T. D. Veal acknowledges support from the EPSRC (grant no. EP/N015800/1). D. O. Scanlon acknowledges the EPSRC grant number EP/N01572X/1. V. Nicolosi, A. Shmeliov, D. Daly and C. Downing acknowledge SFI infrastructure funding for the NION UltraSTEM 200 and AMBER centre.

Publisher Copyright:
© 2017 The Royal Society of Chemistry.

ASJC Scopus subject areas

General Chemistry
Materials Chemistry

Access to Document

10.1039/c7tc03545d

Cite this

@article{11cb093a9f46446f894aa94df80e0ede,

title = "Valence band modification of Cr2O3 by Ni-doping: Creating a high figure of merit p-type TCO",

abstract = "p-Type transparent conductors and semiconductors still suffer from remarkably low performance compared to their more widespread n-type counterparts, despite extensive investigation into their development. In this contribution, we present a comparative study on the defect chemistry of potential p-type transparent conducting oxides Mg-doped and Ni-doped Cr2O3. Conductivities as high as 28 S cm-1 were achieved by Ni-doping. By benchmarking crystallography and spectroscopy characterization against density functional theory calculations, we show that the incorporation of Ni into Cr2O3 contributes to the composition of the valence band, making the formed holes more delocalized, while Mg states do not interact with the valence band in Mg-doped Cr2O3. Furthermore, it is experimentally proven that Ni has a higher solubility in Cr2O3 than Mg, at least in the highly non-thermodynamic deposition conditions used for these experiments, which directly translates into a higher acceptor concentration. The combination of these two effects means that Ni is a more effective acceptor in Cr2O3 than Mg and explains the improved conductivity observed for the former.",

author = "Elisabetta Arca and Kehoe, {Aoife B.} and Veal, {Tim D.} and Aleksey Shmeliov and Scanlon, {David O.} and Clive Downing and Dermot Daly and Daragh Mullarkey and Shvets, {Igor V.} and Valeria Nicolosi and Watson, {Graeme W.}",

note = "Funding Information: Calculations were performed on ARCHER via membership of the Materials Chemistry Consortium (funded by EPSRC grant number EP/L000202), the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC) platform Fionn (project tcche056b), and the Lonsdale and Kelvin clusters maintained by TCHPC. Funding Information: This research was supported by SFI through the PI programme (grant numbers 12/IA/1414 and SFI12/IA/1264). E. Arca acknowledges SFI for the Advance Award Fellowship (grant number SFI14/ADV/IA2641). T. D. Veal acknowledges support from the EPSRC (grant no. EP/N015800/1). D. O. Scanlon acknowledges the EPSRC grant number EP/N01572X/1. V. Nicolosi, A. Shmeliov, D. Daly and C. Downing acknowledge SFI infrastructure funding for the NION UltraSTEM 200 and AMBER centre. Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7tc03545d",

language = "English",

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T2 - Creating a high figure of merit p-type TCO

AU - Arca, Elisabetta

AU - Kehoe, Aoife B.

AU - Veal, Tim D.

AU - Shmeliov, Aleksey

AU - Scanlon, David O.

AU - Downing, Clive

AU - Daly, Dermot

AU - Mullarkey, Daragh

AU - Shvets, Igor V.

AU - Nicolosi, Valeria

AU - Watson, Graeme W.

N1 - Funding Information: Calculations were performed on ARCHER via membership of the Materials Chemistry Consortium (funded by EPSRC grant number EP/L000202), the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC) platform Fionn (project tcche056b), and the Lonsdale and Kelvin clusters maintained by TCHPC. Funding Information: This research was supported by SFI through the PI programme (grant numbers 12/IA/1414 and SFI12/IA/1264). E. Arca acknowledges SFI for the Advance Award Fellowship (grant number SFI14/ADV/IA2641). T. D. Veal acknowledges support from the EPSRC (grant no. EP/N015800/1). D. O. Scanlon acknowledges the EPSRC grant number EP/N01572X/1. V. Nicolosi, A. Shmeliov, D. Daly and C. Downing acknowledge SFI infrastructure funding for the NION UltraSTEM 200 and AMBER centre. Publisher Copyright: © 2017 The Royal Society of Chemistry.

PY - 2017

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N2 - p-Type transparent conductors and semiconductors still suffer from remarkably low performance compared to their more widespread n-type counterparts, despite extensive investigation into their development. In this contribution, we present a comparative study on the defect chemistry of potential p-type transparent conducting oxides Mg-doped and Ni-doped Cr2O3. Conductivities as high as 28 S cm-1 were achieved by Ni-doping. By benchmarking crystallography and spectroscopy characterization against density functional theory calculations, we show that the incorporation of Ni into Cr2O3 contributes to the composition of the valence band, making the formed holes more delocalized, while Mg states do not interact with the valence band in Mg-doped Cr2O3. Furthermore, it is experimentally proven that Ni has a higher solubility in Cr2O3 than Mg, at least in the highly non-thermodynamic deposition conditions used for these experiments, which directly translates into a higher acceptor concentration. The combination of these two effects means that Ni is a more effective acceptor in Cr2O3 than Mg and explains the improved conductivity observed for the former.

AB - p-Type transparent conductors and semiconductors still suffer from remarkably low performance compared to their more widespread n-type counterparts, despite extensive investigation into their development. In this contribution, we present a comparative study on the defect chemistry of potential p-type transparent conducting oxides Mg-doped and Ni-doped Cr2O3. Conductivities as high as 28 S cm-1 were achieved by Ni-doping. By benchmarking crystallography and spectroscopy characterization against density functional theory calculations, we show that the incorporation of Ni into Cr2O3 contributes to the composition of the valence band, making the formed holes more delocalized, while Mg states do not interact with the valence band in Mg-doped Cr2O3. Furthermore, it is experimentally proven that Ni has a higher solubility in Cr2O3 than Mg, at least in the highly non-thermodynamic deposition conditions used for these experiments, which directly translates into a higher acceptor concentration. The combination of these two effects means that Ni is a more effective acceptor in Cr2O3 than Mg and explains the improved conductivity observed for the former.

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