Computationally Driven Discovery of Layered Quinary Oxychalcogenides: Potential p-Type Transparent Conductors?

Benjamin A.D. Williamson; Gregory J. Limburn; Graeme W. Watson; Geoffrey Hyett; David O. Scanlon

doi:10.1016/j.matt.2020.05.020

Computationally Driven Discovery of Layered Quinary Oxychalcogenides: Potential p-Type Transparent Conductors?

Benjamin A.D. Williamson^*, Gregory J. Limburn, Graeme W. Watson, Geoffrey Hyett^*, David O. Scanlon^*

^*Corresponding author for this work

Chemistry

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

Abstract

n-type transparent conductors (TCs) are key materials in the modern optoelectronics industry. Despite years of research, the development of a high-performance p-type TC has lagged far behind that of its n-type counterparts, delaying the advent of “transparent electronics”-based p-n junctions. Here, we propose the layered oxysulfide [Cu₂S₂][Sr₃Sc₂O₅] as a structural motif for discovering p-type TCs. We have used density functional theory to screen 24 compositions based on this motif in terms of their thermodynamic and dynamic stability and their electronic structure, thus predicting two p-type TCs and eight other stable systems with semiconductor properties. Following our predictions, we have successfully synthesized our best candidate p-type TC, [Cu₂S₂][Ba₃Sc₂O₅], which displays structural and optical properties that validate our computational models. It is expected that the design principles emanating from this analysis will move the field closer to the realization of a high figure-of-merit p-type TC. This work has predicted and experimentally realized the p-type transparent conductor [Cu₂S₂][Ba₃Sc₂O₅], and at the same time has developed design principles for layered oxychalcogenide materials of this structure type. The layered oxychalcogenide materials offer a large configurational space of potentially stable compounds with tunable functional properties for a wide range of applications. The longer-term ambitions of the research are to use the combined methods of density functional theory and experiments to search for and understand further layered oxychalcogenide structure types and configurations for different semiconductor applications. This research has the potential to affect the types of electronic devices by bringing us closer to the realism of transparent electronics. The research presented will also further the development of applications for which transparent conductors are essential, such as solar cells. The realization of transparent electronics is hindered by the lack of a suitable high-mobility p-type transparent conductor (TC). This work used ab initio simulations to search for a p-type TC based on the layered oxychalcogenide [Cu₂S₂][A₃M₂O₅] structure. The main result of this study was the discovery of the optimum p-type oxychalcogenide TC, [Cu₂S₂][Ba₃Sc₂O₅], predicted to have a higher optical band gap, better hole mobility, and greater stability than its parent compound [Cu₂S₂][Ba₃Sc₂O₅]; this was verified experimentally.

Original language	English
Pages (from-to)	759-781
Number of pages	23
Journal	Matter
Volume	3
Issue number	3
DOIs	https://doi.org/10.1016/j.matt.2020.05.020
Publication status	Published - 2 Sept 2020

Bibliographical note

Funding Information:
B.A.D.W. would like to acknowledge useful discussions with Dr. A.M. Ganose, Dr. C.N. Savory, and Dr. D.W. Davies. B.A.D.W. would like to acknowledge Mr. K. Spooner for his assistance in the n-type TC BoltzTraP data. G.J.L. would like to acknowledge experimental support from Mr. D. Salazar-Marcano, Mr. P. Bayliss, and Mr. N. Davis. Thank you to Mr. C. Tang for performing the synchrotron diffraction experiment. G.J.L. and G.H. would also like to thank Prof. G. Reid and Prof. A. Hector, and Dr. D. Bradshaw and Dr. S. Cosham for useful discussions. This work made use of the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) via our membership of the UK's HEC Materials Chemistry Consortium, which is also funded by the EPSRC ( EP/L000202 ). The UCL Legion and Grace HPC Facilities (Legion@UCL and Grace@UCL) were also used in the completion of this work. G.J.L. and G.H. would like to acknowledge support from the EPSRC ( EP/T011793/1 ) and use of the Diamond I11 Rapid Access beamtime: EE16644. D.O.S. would like to acknowledge support from the EPSRC ( EP/N01572X/1 ), and B.A.D.W. and D.O.S. would like to acknowledge support from the European Research Council (grant 758345 ). D.O.S. acknowledges membership of the Materials Design Network.

Publisher Copyright:
© 2020 The Authors

Keywords

DFT
inorganic
layered compounds
MAP2: Benchmark
materials prediction
mixed anion semiconductors
oxychalcogenides
p-type
photocatalysts
photovoltaics
transparent conductors

ASJC Scopus subject areas

General Materials Science

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@article{23f8d828145245e2ad0ea84e3486b746,

title = "Computationally Driven Discovery of Layered Quinary Oxychalcogenides: Potential p-Type Transparent Conductors?",

abstract = "n-type transparent conductors (TCs) are key materials in the modern optoelectronics industry. Despite years of research, the development of a high-performance p-type TC has lagged far behind that of its n-type counterparts, delaying the advent of “transparent electronics”-based p-n junctions. Here, we propose the layered oxysulfide [Cu2S2][Sr3Sc2O5] as a structural motif for discovering p-type TCs. We have used density functional theory to screen 24 compositions based on this motif in terms of their thermodynamic and dynamic stability and their electronic structure, thus predicting two p-type TCs and eight other stable systems with semiconductor properties. Following our predictions, we have successfully synthesized our best candidate p-type TC, [Cu2S2][Ba3Sc2O5], which displays structural and optical properties that validate our computational models. It is expected that the design principles emanating from this analysis will move the field closer to the realization of a high figure-of-merit p-type TC. This work has predicted and experimentally realized the p-type transparent conductor [Cu2S2][Ba3Sc2O5], and at the same time has developed design principles for layered oxychalcogenide materials of this structure type. The layered oxychalcogenide materials offer a large configurational space of potentially stable compounds with tunable functional properties for a wide range of applications. The longer-term ambitions of the research are to use the combined methods of density functional theory and experiments to search for and understand further layered oxychalcogenide structure types and configurations for different semiconductor applications. This research has the potential to affect the types of electronic devices by bringing us closer to the realism of transparent electronics. The research presented will also further the development of applications for which transparent conductors are essential, such as solar cells. The realization of transparent electronics is hindered by the lack of a suitable high-mobility p-type transparent conductor (TC). This work used ab initio simulations to search for a p-type TC based on the layered oxychalcogenide [Cu2S2][A3M2O5] structure. The main result of this study was the discovery of the optimum p-type oxychalcogenide TC, [Cu2S2][Ba3Sc2O5], predicted to have a higher optical band gap, better hole mobility, and greater stability than its parent compound [Cu2S2][Ba3Sc2O5]; this was verified experimentally.",

keywords = "DFT, inorganic, layered compounds, MAP2: Benchmark, materials prediction, mixed anion semiconductors, oxychalcogenides, p-type, photocatalysts, photovoltaics, transparent conductors",

author = "Williamson, {Benjamin A.D.} and Limburn, {Gregory J.} and Watson, {Graeme W.} and Geoffrey Hyett and Scanlon, {David O.}",

note = "Funding Information: B.A.D.W. would like to acknowledge useful discussions with Dr. A.M. Ganose, Dr. C.N. Savory, and Dr. D.W. Davies. B.A.D.W. would like to acknowledge Mr. K. Spooner for his assistance in the n-type TC BoltzTraP data. G.J.L. would like to acknowledge experimental support from Mr. D. Salazar-Marcano, Mr. P. Bayliss, and Mr. N. Davis. Thank you to Mr. C. Tang for performing the synchrotron diffraction experiment. G.J.L. and G.H. would also like to thank Prof. G. Reid and Prof. A. Hector, and Dr. D. Bradshaw and Dr. S. Cosham for useful discussions. This work made use of the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) via our membership of the UK's HEC Materials Chemistry Consortium, which is also funded by the EPSRC ( EP/L000202 ). The UCL Legion and Grace HPC Facilities (Legion@UCL and Grace@UCL) were also used in the completion of this work. G.J.L. and G.H. would like to acknowledge support from the EPSRC ( EP/T011793/1 ) and use of the Diamond I11 Rapid Access beamtime: EE16644. D.O.S. would like to acknowledge support from the EPSRC ( EP/N01572X/1 ), and B.A.D.W. and D.O.S. would like to acknowledge support from the European Research Council (grant 758345 ). D.O.S. acknowledges membership of the Materials Design Network. Publisher Copyright: {\textcopyright} 2020 The Authors",

year = "2020",

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doi = "10.1016/j.matt.2020.05.020",

language = "English",

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journal = "Matter",

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T2 - Potential p-Type Transparent Conductors?

AU - Williamson, Benjamin A.D.

AU - Limburn, Gregory J.

AU - Watson, Graeme W.

AU - Hyett, Geoffrey

AU - Scanlon, David O.

N1 - Funding Information: B.A.D.W. would like to acknowledge useful discussions with Dr. A.M. Ganose, Dr. C.N. Savory, and Dr. D.W. Davies. B.A.D.W. would like to acknowledge Mr. K. Spooner for his assistance in the n-type TC BoltzTraP data. G.J.L. would like to acknowledge experimental support from Mr. D. Salazar-Marcano, Mr. P. Bayliss, and Mr. N. Davis. Thank you to Mr. C. Tang for performing the synchrotron diffraction experiment. G.J.L. and G.H. would also like to thank Prof. G. Reid and Prof. A. Hector, and Dr. D. Bradshaw and Dr. S. Cosham for useful discussions. This work made use of the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) via our membership of the UK's HEC Materials Chemistry Consortium, which is also funded by the EPSRC ( EP/L000202 ). The UCL Legion and Grace HPC Facilities (Legion@UCL and Grace@UCL) were also used in the completion of this work. G.J.L. and G.H. would like to acknowledge support from the EPSRC ( EP/T011793/1 ) and use of the Diamond I11 Rapid Access beamtime: EE16644. D.O.S. would like to acknowledge support from the EPSRC ( EP/N01572X/1 ), and B.A.D.W. and D.O.S. would like to acknowledge support from the European Research Council (grant 758345 ). D.O.S. acknowledges membership of the Materials Design Network. Publisher Copyright: © 2020 The Authors

PY - 2020/9/2

Y1 - 2020/9/2

N2 - n-type transparent conductors (TCs) are key materials in the modern optoelectronics industry. Despite years of research, the development of a high-performance p-type TC has lagged far behind that of its n-type counterparts, delaying the advent of “transparent electronics”-based p-n junctions. Here, we propose the layered oxysulfide [Cu2S2][Sr3Sc2O5] as a structural motif for discovering p-type TCs. We have used density functional theory to screen 24 compositions based on this motif in terms of their thermodynamic and dynamic stability and their electronic structure, thus predicting two p-type TCs and eight other stable systems with semiconductor properties. Following our predictions, we have successfully synthesized our best candidate p-type TC, [Cu2S2][Ba3Sc2O5], which displays structural and optical properties that validate our computational models. It is expected that the design principles emanating from this analysis will move the field closer to the realization of a high figure-of-merit p-type TC. This work has predicted and experimentally realized the p-type transparent conductor [Cu2S2][Ba3Sc2O5], and at the same time has developed design principles for layered oxychalcogenide materials of this structure type. The layered oxychalcogenide materials offer a large configurational space of potentially stable compounds with tunable functional properties for a wide range of applications. The longer-term ambitions of the research are to use the combined methods of density functional theory and experiments to search for and understand further layered oxychalcogenide structure types and configurations for different semiconductor applications. This research has the potential to affect the types of electronic devices by bringing us closer to the realism of transparent electronics. The research presented will also further the development of applications for which transparent conductors are essential, such as solar cells. The realization of transparent electronics is hindered by the lack of a suitable high-mobility p-type transparent conductor (TC). This work used ab initio simulations to search for a p-type TC based on the layered oxychalcogenide [Cu2S2][A3M2O5] structure. The main result of this study was the discovery of the optimum p-type oxychalcogenide TC, [Cu2S2][Ba3Sc2O5], predicted to have a higher optical band gap, better hole mobility, and greater stability than its parent compound [Cu2S2][Ba3Sc2O5]; this was verified experimentally.

AB - n-type transparent conductors (TCs) are key materials in the modern optoelectronics industry. Despite years of research, the development of a high-performance p-type TC has lagged far behind that of its n-type counterparts, delaying the advent of “transparent electronics”-based p-n junctions. Here, we propose the layered oxysulfide [Cu2S2][Sr3Sc2O5] as a structural motif for discovering p-type TCs. We have used density functional theory to screen 24 compositions based on this motif in terms of their thermodynamic and dynamic stability and their electronic structure, thus predicting two p-type TCs and eight other stable systems with semiconductor properties. Following our predictions, we have successfully synthesized our best candidate p-type TC, [Cu2S2][Ba3Sc2O5], which displays structural and optical properties that validate our computational models. It is expected that the design principles emanating from this analysis will move the field closer to the realization of a high figure-of-merit p-type TC. This work has predicted and experimentally realized the p-type transparent conductor [Cu2S2][Ba3Sc2O5], and at the same time has developed design principles for layered oxychalcogenide materials of this structure type. The layered oxychalcogenide materials offer a large configurational space of potentially stable compounds with tunable functional properties for a wide range of applications. The longer-term ambitions of the research are to use the combined methods of density functional theory and experiments to search for and understand further layered oxychalcogenide structure types and configurations for different semiconductor applications. This research has the potential to affect the types of electronic devices by bringing us closer to the realism of transparent electronics. The research presented will also further the development of applications for which transparent conductors are essential, such as solar cells. The realization of transparent electronics is hindered by the lack of a suitable high-mobility p-type transparent conductor (TC). This work used ab initio simulations to search for a p-type TC based on the layered oxychalcogenide [Cu2S2][A3M2O5] structure. The main result of this study was the discovery of the optimum p-type oxychalcogenide TC, [Cu2S2][Ba3Sc2O5], predicted to have a higher optical band gap, better hole mobility, and greater stability than its parent compound [Cu2S2][Ba3Sc2O5]; this was verified experimentally.

KW - DFT

KW - inorganic

KW - layered compounds

KW - MAP2: Benchmark

KW - materials prediction

KW - mixed anion semiconductors

KW - oxychalcogenides

KW - p-type

KW - photocatalysts

KW - photovoltaics

KW - transparent conductors

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ER -

Computationally Driven Discovery of Layered Quinary Oxychalcogenides: Potential p-Type Transparent Conductors?

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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