Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Sergio Conejeros; Muhammad Zamir Othman; Alex Croot; Judy Hart; Kane M O'Donnell; Paul W May; Neil L Allan

doi:10.1016/j.carbon.2020.09.065

Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Sergio Conejeros, Muhammad Zamir Othman, Alex Croot, Judy Hart, Kane M O'Donnell, Paul W May^*, Neil L Allan^*

^*Corresponding author for this work

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Abstract

We report calculated energetics (at the GGA, and at the B3LYP, HSE06 hybrid density functional levels of theory) and electronic properties (B3LYP, HSE06) of Li and N co-doped diamond containing LiNx clusters (x = 1–4). Defect energies and structural properties at the GGA and hybrid (B3LYP, HSE06) levels of theory are very similar. Our results for isolated Li and N dopants agree with previous work in that they are not suitable candidates for shallow n-type donors. Here, we investigate the effects of addition of N atoms as a co-dopant with Li, which vary with the Li:N ratio and whether Li is interstitial or substitutional. Reaction energies, geometries, bonding and densities of states (DOS) are examined. Nitrogen stabilises substitutional rather than interstitial lithium. Atom-projected DOS show that the chief contributions to the defect states are not from orbitals on the dopant atoms themselves but from states associated with neighbouring carbon atoms. Only the tetrahedral 1:4 cluster, LiCN₄, with substitutional Li is likely to behave as a shallow donor. We propose a non-molecular synthetic route for preparation of the LiCN₄-doped material via prior generation of the N₄V centre at temperatures at which Li is mobile but LiCN₄ clusters are not.

Original language	English
Pages (from-to)	857-868
Number of pages	12
Journal	Carbon
Volume	171
Early online date	25 Sep 2020
DOIs	https://doi.org/10.1016/j.carbon.2020.09.065
Publication status	Published - 1 Jan 2021

Bibliographical note

Funding Information:
The authors are grateful to the Public Service Department, Government of Malaysia, EPSRC grant EP/K030302/1 for financial support and Ben Truscott for his help with the software. S.C. gratefully acknowledges the Becas Chile program (CONICYT PAI/INDUSTRIA 74150058 ) for a postdoctoral grant at the University of Bristol , and FONDECYT Grant 11171063 . This work was carried out using the computational facilities of the Advanced Computing Research Centre, University of Bristol http://www.bris.ac.uk/acrc . The raw data for these calculations can be found on the University of Bristol data repository with d.o.i. 10.5523/bris.2ypb34qlp93ox2spy3k3ql4trd.

Funding Information:
The authors are grateful to the Public Service Department, Government of Malaysia, EPSRC grant EP/K030302/1 for financial support and Ben Truscott for his help with the software. S.C. gratefully acknowledges the Becas Chile program (CONICYT PAI/INDUSTRIA 74150058) for a postdoctoral grant at the University of Bristol, and FONDECYT Grant 11171063. This work was carried out using the computational facilities of the Advanced Computing Research Centre, University of Bristol http://www.bris.ac.uk/acrc. The raw data for these calculations can be found on the University of Bristol data repository with d.o.i. 10.5523/bris.2ypb34qlp93ox2spy3k3ql4trd.

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© 2020 Elsevier Ltd

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3 Article (Academic Journal)
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Predicted strong spin-phonon interactions in Li-doped diamond
Gentile, F., Mackrodt, W. C., Allan, N. L. & Dovesi, R., 1 Sep 2020, In: Physical Chemistry Chemical Physics. 2020, p. 20612-20617 6 p.
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A theoretical study of substitutional boron-nitrogen clusters in diamond
Croot, A., Othman, M. Z., Conejeros, S., Fox, N. & Allan, N., 24 Oct 2018, In: Journal of Physics Condensed Matter. 30, 42, 10 p., 425501.
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Investigations of the co-doping of boron and lithium into CVD diamond thin films
Halliwell, S., May, P., Fox, N. & Othman, Z., Jun 2017, In: Diamond and Related Materials. 76, p. 115-122 8 p.
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HPC (High Performance Computing) Facility
Polly E Eccleston (Other), Simon H Atack (Other), D A G Williams (Manager), Sadaf R Alam (Manager) & Steven A Chapman (Manager)
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Professor Paul W May
- Paul.Maybristol.acuk
- School of Chemistry - Professor of Physical Chemistry
- Soft Matter, Colloids and Materials
- Spectroscopy and Dynamics
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Cite this

@article{e680a6c4afce443089010a1ebd546e83,

title = "Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond",

abstract = "We report calculated energetics (at the GGA, and at the B3LYP, HSE06 hybrid density functional levels of theory) and electronic properties (B3LYP, HSE06) of Li and N co-doped diamond containing LiNx clusters (x = 1–4). Defect energies and structural properties at the GGA and hybrid (B3LYP, HSE06) levels of theory are very similar. Our results for isolated Li and N dopants agree with previous work in that they are not suitable candidates for shallow n-type donors. Here, we investigate the effects of addition of N atoms as a co-dopant with Li, which vary with the Li:N ratio and whether Li is interstitial or substitutional. Reaction energies, geometries, bonding and densities of states (DOS) are examined. Nitrogen stabilises substitutional rather than interstitial lithium. Atom-projected DOS show that the chief contributions to the defect states are not from orbitals on the dopant atoms themselves but from states associated with neighbouring carbon atoms. Only the tetrahedral 1:4 cluster, LiCN4, with substitutional Li is likely to behave as a shallow donor. We propose a non-molecular synthetic route for preparation of the LiCN4-doped material via prior generation of the N4V centre at temperatures at which Li is mobile but LiCN4 clusters are not.",

author = "Sergio Conejeros and Othman, {Muhammad Zamir} and Alex Croot and Judy Hart and O'Donnell, {Kane M} and May, {Paul W} and Allan, {Neil L}",

note = "Funding Information: The authors are grateful to the Public Service Department, Government of Malaysia, EPSRC grant EP/K030302/1 for financial support and Ben Truscott for his help with the software. S.C. gratefully acknowledges the Becas Chile program (CONICYT PAI/INDUSTRIA 74150058 ) for a postdoctoral grant at the University of Bristol , and FONDECYT Grant 11171063 . This work was carried out using the computational facilities of the Advanced Computing Research Centre, University of Bristol http://www.bris.ac.uk/acrc . The raw data for these calculations can be found on the University of Bristol data repository with d.o.i. 10.5523/bris.2ypb34qlp93ox2spy3k3ql4trd. Funding Information: The authors are grateful to the Public Service Department, Government of Malaysia, EPSRC grant EP/K030302/1 for financial support and Ben Truscott for his help with the software. S.C. gratefully acknowledges the Becas Chile program (CONICYT PAI/INDUSTRIA 74150058) for a postdoctoral grant at the University of Bristol, and FONDECYT Grant 11171063. This work was carried out using the computational facilities of the Advanced Computing Research Centre, University of Bristol http://www.bris.ac.uk/acrc. The raw data for these calculations can be found on the University of Bristol data repository with d.o.i. 10.5523/bris.2ypb34qlp93ox2spy3k3ql4trd. Publisher Copyright: {\textcopyright} 2020 Elsevier Ltd",

year = "2021",

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doi = "10.1016/j.carbon.2020.09.065",

language = "English",

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T1 - Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

AU - Conejeros, Sergio

AU - Othman, Muhammad Zamir

AU - Croot, Alex

AU - Hart, Judy

AU - O'Donnell, Kane M

AU - May, Paul W

AU - Allan, Neil L

N1 - Funding Information: The authors are grateful to the Public Service Department, Government of Malaysia, EPSRC grant EP/K030302/1 for financial support and Ben Truscott for his help with the software. S.C. gratefully acknowledges the Becas Chile program (CONICYT PAI/INDUSTRIA 74150058 ) for a postdoctoral grant at the University of Bristol , and FONDECYT Grant 11171063 . This work was carried out using the computational facilities of the Advanced Computing Research Centre, University of Bristol http://www.bris.ac.uk/acrc . The raw data for these calculations can be found on the University of Bristol data repository with d.o.i. 10.5523/bris.2ypb34qlp93ox2spy3k3ql4trd. Funding Information: The authors are grateful to the Public Service Department, Government of Malaysia, EPSRC grant EP/K030302/1 for financial support and Ben Truscott for his help with the software. S.C. gratefully acknowledges the Becas Chile program (CONICYT PAI/INDUSTRIA 74150058) for a postdoctoral grant at the University of Bristol, and FONDECYT Grant 11171063. This work was carried out using the computational facilities of the Advanced Computing Research Centre, University of Bristol http://www.bris.ac.uk/acrc. The raw data for these calculations can be found on the University of Bristol data repository with d.o.i. 10.5523/bris.2ypb34qlp93ox2spy3k3ql4trd. Publisher Copyright: © 2020 Elsevier Ltd

PY - 2021/1/1

Y1 - 2021/1/1

N2 - We report calculated energetics (at the GGA, and at the B3LYP, HSE06 hybrid density functional levels of theory) and electronic properties (B3LYP, HSE06) of Li and N co-doped diamond containing LiNx clusters (x = 1–4). Defect energies and structural properties at the GGA and hybrid (B3LYP, HSE06) levels of theory are very similar. Our results for isolated Li and N dopants agree with previous work in that they are not suitable candidates for shallow n-type donors. Here, we investigate the effects of addition of N atoms as a co-dopant with Li, which vary with the Li:N ratio and whether Li is interstitial or substitutional. Reaction energies, geometries, bonding and densities of states (DOS) are examined. Nitrogen stabilises substitutional rather than interstitial lithium. Atom-projected DOS show that the chief contributions to the defect states are not from orbitals on the dopant atoms themselves but from states associated with neighbouring carbon atoms. Only the tetrahedral 1:4 cluster, LiCN4, with substitutional Li is likely to behave as a shallow donor. We propose a non-molecular synthetic route for preparation of the LiCN4-doped material via prior generation of the N4V centre at temperatures at which Li is mobile but LiCN4 clusters are not.

AB - We report calculated energetics (at the GGA, and at the B3LYP, HSE06 hybrid density functional levels of theory) and electronic properties (B3LYP, HSE06) of Li and N co-doped diamond containing LiNx clusters (x = 1–4). Defect energies and structural properties at the GGA and hybrid (B3LYP, HSE06) levels of theory are very similar. Our results for isolated Li and N dopants agree with previous work in that they are not suitable candidates for shallow n-type donors. Here, we investigate the effects of addition of N atoms as a co-dopant with Li, which vary with the Li:N ratio and whether Li is interstitial or substitutional. Reaction energies, geometries, bonding and densities of states (DOS) are examined. Nitrogen stabilises substitutional rather than interstitial lithium. Atom-projected DOS show that the chief contributions to the defect states are not from orbitals on the dopant atoms themselves but from states associated with neighbouring carbon atoms. Only the tetrahedral 1:4 cluster, LiCN4, with substitutional Li is likely to behave as a shallow donor. We propose a non-molecular synthetic route for preparation of the LiCN4-doped material via prior generation of the N4V centre at temperatures at which Li is mobile but LiCN4 clusters are not.

U2 - 10.1016/j.carbon.2020.09.065

DO - 10.1016/j.carbon.2020.09.065

M3 - Article (Academic Journal)

VL - 171

SP - 857

EP - 868

JO - Carbon

JF - Carbon

SN - 0008-6223

ER -

Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Abstract

Bibliographical note

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Research output

Predicted strong spin-phonon interactions in Li-doped diamond

A theoretical study of substitutional boron-nitrogen clusters in diamond

Investigations of the co-doping of boron and lithium into CVD diamond thin films

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HPC (High Performance Computing) Facility

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Professor Paul W May

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