Unraveling the Impact of Graphene Addition to Thermoelectric SrTiO3and La-Doped SrTiO3Materials: A Density Functional Theory Study

Joshua Tse; Alex Aziz; Joseph M. Flitcroft; Jonathan M. Skelton; Lisa J. Gillie; Stephen C. Parker; David J. Cooke; Marco Molinari

doi:10.1021/acsami.1c10865

Unraveling the Impact of Graphene Addition to Thermoelectric SrTiO₃and La-Doped SrTiO₃Materials: A Density Functional Theory Study

Joshua Tse, Alex Aziz, Joseph M. Flitcroft, Jonathan M. Skelton, Lisa J. Gillie, Stephen C. Parker, David J. Cooke, Marco Molinari

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

13 Citations (SciVal)

Abstract

We present a detailed theoretical investigation of the interaction of graphene with the SrO-terminated (001) surface of pristine and La-doped SrTiO3. The adsorption of graphene is thermodynamically favorable with interfacial adsorption energies of -0.08 and -0.32 J/m2 to pristine SrTiO3 and La-doped SrTiO3 surfaces, respectively. We find that graphene introduces C 2p states at the Fermi level, rendering the composite semimetallic, and thus the electrical properties are predicted to be highly sensitive to the amount and quality of the graphene. An investigation of the lattice dynamics predicts that graphene adsorption may lead to a 60-90% reduction in the thermal conductivity due to a reduction in the phonon group velocities, accounting for the reduced thermal conductivity of the composite materials observed experimentally. This effect is enhanced by La doping. We also find evidence that both La dopant ions and adsorbed graphene introduce low-frequency modes that may scatter heat-carrying acoustic phonons, and that, if present, these effects likely arise from stronger phonon-phonon interactions.

Original language	English
Pages (from-to)	41303-41314
Number of pages	12
Journal	ACS Applied Materials and Interfaces
Volume	13
Issue number	34
Early online date	18 Aug 2021
DOIs	https://doi.org/10.1021/acsami.1c10865
Publication status	Published - 1 Sept 2021

Bibliographical note

Funding Information:
J.M.S. is grateful to UK Research and Innovation (UKRI) for the award of a Future Leaders Fellowship (MR/T043121/1), and to the University of Manchester for the previous support of a UoM Presidential Fellowship. S.C.P. thanks the EPSRC for funding (EP/P007821/1). Calculations were performed on the Balena HPC facility at the University of Bath, the Orion computing facility at the University of Huddersfield, the ARCHER UK National Supercomputing Service via our membership of the UK HEC Materials Chemistry Consortium (MCC; EPSRC EP/L000202, EP/R029431, EP/T022213), and the THOMAS facility at the UK Materials and Molecular Modelling Hub (MMM hub; EPSRC EP/P020194/1). The authors would also like to acknowledge computing time granted through the Spanish Supercomputing Network, RES, on the Tirant 3 supercomputer located at the University of Valencia (QS-2019-3-0025 and QS-2020-1-0021). Finally, this work also used the Isambard UK National Tier-2 HPC Service ( http://gw4.ac.uk/isambard/ ) via the Resource Allocation Panel (RAP) Open Access to Tier-2 call, operated by the GW4 and the UK Met Office and funded by the EPSRC (EP/P020224/1).

Keywords

electronic structure
graphene adsorption on perovskite oxides
graphene/strontium titanate composite materials
structural dynamics
thermal transport
thermoelectrics

ASJC Scopus subject areas

General Materials Science

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10.1021/acsami.1c10865Licence: CC BY

Cite this

@article{017fe9f5b8214d5b8acf82d5d0f09371,

title = "Unraveling the Impact of Graphene Addition to Thermoelectric SrTiO3and La-Doped SrTiO3Materials: A Density Functional Theory Study",

abstract = "We present a detailed theoretical investigation of the interaction of graphene with the SrO-terminated (001) surface of pristine and La-doped SrTiO3. The adsorption of graphene is thermodynamically favorable with interfacial adsorption energies of -0.08 and -0.32 J/m2 to pristine SrTiO3 and La-doped SrTiO3 surfaces, respectively. We find that graphene introduces C 2p states at the Fermi level, rendering the composite semimetallic, and thus the electrical properties are predicted to be highly sensitive to the amount and quality of the graphene. An investigation of the lattice dynamics predicts that graphene adsorption may lead to a 60-90% reduction in the thermal conductivity due to a reduction in the phonon group velocities, accounting for the reduced thermal conductivity of the composite materials observed experimentally. This effect is enhanced by La doping. We also find evidence that both La dopant ions and adsorbed graphene introduce low-frequency modes that may scatter heat-carrying acoustic phonons, and that, if present, these effects likely arise from stronger phonon-phonon interactions. ",

keywords = "electronic structure, graphene adsorption on perovskite oxides, graphene/strontium titanate composite materials, structural dynamics, thermal transport, thermoelectrics",

author = "Joshua Tse and Alex Aziz and Flitcroft, {Joseph M.} and Skelton, {Jonathan M.} and Gillie, {Lisa J.} and Parker, {Stephen C.} and Cooke, {David J.} and Marco Molinari",

note = "Funding Information: J.M.S. is grateful to UK Research and Innovation (UKRI) for the award of a Future Leaders Fellowship (MR/T043121/1), and to the University of Manchester for the previous support of a UoM Presidential Fellowship. S.C.P. thanks the EPSRC for funding (EP/P007821/1). Calculations were performed on the Balena HPC facility at the University of Bath, the Orion computing facility at the University of Huddersfield, the ARCHER UK National Supercomputing Service via our membership of the UK HEC Materials Chemistry Consortium (MCC; EPSRC EP/L000202, EP/R029431, EP/T022213), and the THOMAS facility at the UK Materials and Molecular Modelling Hub (MMM hub; EPSRC EP/P020194/1). The authors would also like to acknowledge computing time granted through the Spanish Supercomputing Network, RES, on the Tirant 3 supercomputer located at the University of Valencia (QS-2019-3-0025 and QS-2020-1-0021). Finally, this work also used the Isambard UK National Tier-2 HPC Service ( http://gw4.ac.uk/isambard/ ) via the Resource Allocation Panel (RAP) Open Access to Tier-2 call, operated by the GW4 and the UK Met Office and funded by the EPSRC (EP/P020224/1). ",

year = "2021",

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doi = "10.1021/acsami.1c10865",

language = "English",

volume = "13",

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journal = "ACS Applied Materials and Interfaces",

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T1 - Unraveling the Impact of Graphene Addition to Thermoelectric SrTiO3and La-Doped SrTiO3Materials

T2 - A Density Functional Theory Study

AU - Tse, Joshua

AU - Aziz, Alex

AU - Flitcroft, Joseph M.

AU - Skelton, Jonathan M.

AU - Gillie, Lisa J.

AU - Parker, Stephen C.

AU - Cooke, David J.

AU - Molinari, Marco

N1 - Funding Information: J.M.S. is grateful to UK Research and Innovation (UKRI) for the award of a Future Leaders Fellowship (MR/T043121/1), and to the University of Manchester for the previous support of a UoM Presidential Fellowship. S.C.P. thanks the EPSRC for funding (EP/P007821/1). Calculations were performed on the Balena HPC facility at the University of Bath, the Orion computing facility at the University of Huddersfield, the ARCHER UK National Supercomputing Service via our membership of the UK HEC Materials Chemistry Consortium (MCC; EPSRC EP/L000202, EP/R029431, EP/T022213), and the THOMAS facility at the UK Materials and Molecular Modelling Hub (MMM hub; EPSRC EP/P020194/1). The authors would also like to acknowledge computing time granted through the Spanish Supercomputing Network, RES, on the Tirant 3 supercomputer located at the University of Valencia (QS-2019-3-0025 and QS-2020-1-0021). Finally, this work also used the Isambard UK National Tier-2 HPC Service ( http://gw4.ac.uk/isambard/ ) via the Resource Allocation Panel (RAP) Open Access to Tier-2 call, operated by the GW4 and the UK Met Office and funded by the EPSRC (EP/P020224/1).

PY - 2021/9/1

Y1 - 2021/9/1

N2 - We present a detailed theoretical investigation of the interaction of graphene with the SrO-terminated (001) surface of pristine and La-doped SrTiO3. The adsorption of graphene is thermodynamically favorable with interfacial adsorption energies of -0.08 and -0.32 J/m2 to pristine SrTiO3 and La-doped SrTiO3 surfaces, respectively. We find that graphene introduces C 2p states at the Fermi level, rendering the composite semimetallic, and thus the electrical properties are predicted to be highly sensitive to the amount and quality of the graphene. An investigation of the lattice dynamics predicts that graphene adsorption may lead to a 60-90% reduction in the thermal conductivity due to a reduction in the phonon group velocities, accounting for the reduced thermal conductivity of the composite materials observed experimentally. This effect is enhanced by La doping. We also find evidence that both La dopant ions and adsorbed graphene introduce low-frequency modes that may scatter heat-carrying acoustic phonons, and that, if present, these effects likely arise from stronger phonon-phonon interactions.

AB - We present a detailed theoretical investigation of the interaction of graphene with the SrO-terminated (001) surface of pristine and La-doped SrTiO3. The adsorption of graphene is thermodynamically favorable with interfacial adsorption energies of -0.08 and -0.32 J/m2 to pristine SrTiO3 and La-doped SrTiO3 surfaces, respectively. We find that graphene introduces C 2p states at the Fermi level, rendering the composite semimetallic, and thus the electrical properties are predicted to be highly sensitive to the amount and quality of the graphene. An investigation of the lattice dynamics predicts that graphene adsorption may lead to a 60-90% reduction in the thermal conductivity due to a reduction in the phonon group velocities, accounting for the reduced thermal conductivity of the composite materials observed experimentally. This effect is enhanced by La doping. We also find evidence that both La dopant ions and adsorbed graphene introduce low-frequency modes that may scatter heat-carrying acoustic phonons, and that, if present, these effects likely arise from stronger phonon-phonon interactions.

KW - electronic structure

KW - graphene adsorption on perovskite oxides

KW - graphene/strontium titanate composite materials

KW - structural dynamics

KW - thermal transport

KW - thermoelectrics

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DO - 10.1021/acsami.1c10865

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