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Oxychalcogenides for transparent p-type conductors

Oxychalcogenides for transparent p-type conductors
Oxychalcogenides for transparent p-type conductors
The quinary layered oxychalcogenide, Sr3Sc2O5Cu2S2, was used as a prototype to investigate the effect of composition and structure, on transparency and conductivity of analogous materials. A selection of analogues was computationally screened for predicted stability and optical transparency. The compounds Ba3Sc2O5Cu2S2 and Ca3Al2O5Cu2S2 were both expected to show band gap energies higher than 3.1 eV and conductivities higher than that of the prototype. The compound Ba3Sc2O5Cu2S2 was successfully synthesised here by solid-state reaction at 800 oC for 12 h, apparently for the first time. Its measured band-gap energy was 3.24 eV. Synthesis of Ca3Al2O5Cu2S2 was not achieved. It was concluded that a high-pressure synthetic route would be required to realise this compound.

The compounds intermediate between the prototype and new member BaxSr3-xSc2O5Cu2S2 where x = 1 and 2, were also successfully synthesised. Refinement of their crystal structures showed a preference of barium for the ‘intra-layer’ site in the perovskite layer, as rationalised by the Goldschmidt tolerance factor. The perovskite A site mixing yielded extreme bond distances and angles in the conductive copper sulfide layer of x = 2, beyond the range spanned by the end-members. Williamson-Hall analysis revealed increased strain and reduced crystallite size for the intermediates and general anisotropic growth of these compounds favouring the direction of conduction, as confirmed by scanning-electron microscopy.

The successful syntheses of the analogous compounds Ba3Sc2O5Cu2S2, Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2Se2, Ba3In2O5Cu2Se2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2 were also reported here, for the first time to the authors knowledge. It was found that the increased radius of the perovskite M cation, increased the basal lattice parameter and linked coinage metal-metal distance, expected to benefit transparency. However, observed reductions in band-gap energy for both the indium and yttrium analogues, relative to those of the scandium compounds, were rationalised by electronegativity and (n-1)d-orbital occupancy, respectively. The coinage metal-chalcogenide distance increased, and angle deviated from the ideal tetrahedral, with increasing M cation radius, in all cases. Barium and scandium proved to be the optimal candidate perovskite layer cations. Substitution of selenium and silver into the conductive layer was expected to increase conductivity at the expense of an observed decrease in band gap for the scandium analogues.

The compounds Ba3Sc2O5Cu2S2 and Ba3Sc2O5Cu2Se2 showed promise as improved transparent p-type conductors. Their compositions and structures suggested improved conductivity compared to that of Sr3Sc2O5Cu2S. The 3.05 eV band gap of Ba3Sc2O5Cu2Se2 may be increased above the visible light threshold by p-type doping. A preliminary investigation saw the prototype successfully doped by 5 at. % sodium with an accompanied Moss-Burstein shift in band gap energy of + 0.5 eV to 3.2 eV.
University of Southampton
Limburn, Gregory James
afd49e4c-1afa-4c37-b608-fa0581d380f7
Limburn, Gregory James
afd49e4c-1afa-4c37-b608-fa0581d380f7
Hyett, Geoffrey
4f292fc9-2198-4b18-99b9-3c74e7dfed8d

Limburn, Gregory James (2019) Oxychalcogenides for transparent p-type conductors. University of Southampton, Doctoral Thesis, 202pp.

Record type: Thesis (Doctoral)

Abstract

The quinary layered oxychalcogenide, Sr3Sc2O5Cu2S2, was used as a prototype to investigate the effect of composition and structure, on transparency and conductivity of analogous materials. A selection of analogues was computationally screened for predicted stability and optical transparency. The compounds Ba3Sc2O5Cu2S2 and Ca3Al2O5Cu2S2 were both expected to show band gap energies higher than 3.1 eV and conductivities higher than that of the prototype. The compound Ba3Sc2O5Cu2S2 was successfully synthesised here by solid-state reaction at 800 oC for 12 h, apparently for the first time. Its measured band-gap energy was 3.24 eV. Synthesis of Ca3Al2O5Cu2S2 was not achieved. It was concluded that a high-pressure synthetic route would be required to realise this compound.

The compounds intermediate between the prototype and new member BaxSr3-xSc2O5Cu2S2 where x = 1 and 2, were also successfully synthesised. Refinement of their crystal structures showed a preference of barium for the ‘intra-layer’ site in the perovskite layer, as rationalised by the Goldschmidt tolerance factor. The perovskite A site mixing yielded extreme bond distances and angles in the conductive copper sulfide layer of x = 2, beyond the range spanned by the end-members. Williamson-Hall analysis revealed increased strain and reduced crystallite size for the intermediates and general anisotropic growth of these compounds favouring the direction of conduction, as confirmed by scanning-electron microscopy.

The successful syntheses of the analogous compounds Ba3Sc2O5Cu2S2, Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2Se2, Ba3In2O5Cu2Se2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2 were also reported here, for the first time to the authors knowledge. It was found that the increased radius of the perovskite M cation, increased the basal lattice parameter and linked coinage metal-metal distance, expected to benefit transparency. However, observed reductions in band-gap energy for both the indium and yttrium analogues, relative to those of the scandium compounds, were rationalised by electronegativity and (n-1)d-orbital occupancy, respectively. The coinage metal-chalcogenide distance increased, and angle deviated from the ideal tetrahedral, with increasing M cation radius, in all cases. Barium and scandium proved to be the optimal candidate perovskite layer cations. Substitution of selenium and silver into the conductive layer was expected to increase conductivity at the expense of an observed decrease in band gap for the scandium analogues.

The compounds Ba3Sc2O5Cu2S2 and Ba3Sc2O5Cu2Se2 showed promise as improved transparent p-type conductors. Their compositions and structures suggested improved conductivity compared to that of Sr3Sc2O5Cu2S. The 3.05 eV band gap of Ba3Sc2O5Cu2Se2 may be increased above the visible light threshold by p-type doping. A preliminary investigation saw the prototype successfully doped by 5 at. % sodium with an accompanied Moss-Burstein shift in band gap energy of + 0.5 eV to 3.2 eV.

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Gregory Limburn Thesis - Version of Record
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Published date: November 2019

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Local EPrints ID: 435764
URI: http://eprints.soton.ac.uk/id/eprint/435764
PURE UUID: 8c129783-11e3-4f72-8a68-cce497626ca9
ORCID for Geoffrey Hyett: ORCID iD orcid.org/0000-0001-9302-9723

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Date deposited: 20 Nov 2019 17:30
Last modified: 05 May 2021 04:01

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Contributors

Author: Gregory James Limburn
Thesis advisor: Geoffrey Hyett ORCID iD

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