Limits to Hole Mobility and Doping in Copper Iodide

Joe Willis; Romain Claes; Qi Zhou; Matteo Giantomassi; Gian-Marco Rignanese; Geoffroy Hautier; David O. Scanlon

doi:10.1021/acs.chemmater.3c01628

Limits to Hole Mobility and Doping in Copper Iodide

Joe Willis, Romain Claes, Qi Zhou, Matteo Giantomassi, Gian-Marco Rignanese, Geoffroy Hautier^*, David O. Scanlon^*

^*Corresponding author for this work

Chemistry

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Abstract

Over one hundred years have passed since the discovery of the p-type transparent conducting material copper iodide, predating the concept of the “electron–hole” itself. Supercentenarian status notwithstanding, little is understood about the charge transport mechanisms in CuI. Herein, a variety of modeling techniques are used to investigate the charge transport properties of CuI, and limitations to the hole mobility over experimentally achievable carrier concentrations are discussed. Poor dielectric response is responsible for extensive scattering from ionized impurities at degenerately doped carrier concentrations, while phonon scattering is found to dominate at lower carrier concentrations. A phonon-limited hole mobility of 162 cm² V^–1 s^–1 is predicted at room temperature. The simulated charge transport properties for CuI are compared to existing experimental data, and the implications for future device performance are discussed. In addition to charge transport calculations, the defect chemistry of CuI is investigated with hybrid functionals, revealing that reasonably localized holes from the copper vacancy are the predominant source of charge carriers. The chalcogens S and Se are investigated as extrinsic dopants, where it is found that despite relatively low defect formation energies, they are unlikely to act as efficient electron acceptors due to the strong localization of holes and subsequent deep transition levels.

Original language	English
Journal	Chemistry of Materials
Early online date	25 Oct 2023
DOIs	https://doi.org/10.1021/acs.chemmater.3c01628
Publication status	E-pub ahead of print - 25 Oct 2023

Bibliographical note

Acknowledgments:
J.W. and R.C. acknowledge fruitful discussions with Dr Andrea Crovetto, Dr Alex Squires, Dr Alex Ganose, Dr Chris Savory, and Dr Guillaume Brunin. J.W. and D.O.S. acknowledge Diamond Light Source Ltd for cosponsorship of an EngD studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1), support for EPSRC Grant number EP/N01572X/1, and from the European Research Council, ERC (grant no. 758345). This work used the ARCHER and ARCHER2 UK National Supercomputing Service (https://www.archer2.ac.uk), via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431, and EP/T022213). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources (Thomas and Young), which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). The authors acknowledge the use of the UCL Myriad, Kathleen, and Thomas High Performance Computing Facilities (Myriad@UCL, Kathleen@UCL, and Thomas@UCL), and associated support services, in the completion of this work. R.C. acknowledges financial support from the Communauté Française de Belgique, grant ARC 18/23-093. G.M.R. acknowledges financial support from the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS). Computational resources were provided by the Consortium des Équipements de Calcul Intensif, funded by the F.R.S.- FNRS under grant no. 2.5020.11 and by the Walloon Region. The present research benefited from computational resources made available on the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under grant no. 1117545. G.H. acknowledges funding by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05-CH11231: Materials Project program KC23MP. The work has received partial support from the European Union’s Horizon 2020 research and innovation program, grant no. 951786 through the Center of Excellence NOMAD.

Keywords

copper
charge transport
holes
mobility
scattering
CuI
defects
densityfunctionaltheory/DFT

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Cite this

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title = "Limits to Hole Mobility and Doping in Copper Iodide",

abstract = "Over one hundred years have passed since the discovery of the p-type transparent conducting material copper iodide, predating the concept of the “electron–hole” itself. Supercentenarian status notwithstanding, little is understood about the charge transport mechanisms in CuI. Herein, a variety of modeling techniques are used to investigate the charge transport properties of CuI, and limitations to the hole mobility over experimentally achievable carrier concentrations are discussed. Poor dielectric response is responsible for extensive scattering from ionized impurities at degenerately doped carrier concentrations, while phonon scattering is found to dominate at lower carrier concentrations. A phonon-limited hole mobility of 162 cm2 V–1 s–1 is predicted at room temperature. The simulated charge transport properties for CuI are compared to existing experimental data, and the implications for future device performance are discussed. In addition to charge transport calculations, the defect chemistry of CuI is investigated with hybrid functionals, revealing that reasonably localized holes from the copper vacancy are the predominant source of charge carriers. The chalcogens S and Se are investigated as extrinsic dopants, where it is found that despite relatively low defect formation energies, they are unlikely to act as efficient electron acceptors due to the strong localization of holes and subsequent deep transition levels.",

keywords = "copper, charge transport, holes, mobility, scattering, CuI, defects, densityfunctionaltheory/DFT",

author = "Joe Willis and Romain Claes and Qi Zhou and Matteo Giantomassi and Gian-Marco Rignanese and Geoffroy Hautier and Scanlon, {David O.}",

note = "Acknowledgments: J.W. and R.C. acknowledge fruitful discussions with Dr Andrea Crovetto, Dr Alex Squires, Dr Alex Ganose, Dr Chris Savory, and Dr Guillaume Brunin. J.W. and D.O.S. acknowledge Diamond Light Source Ltd for cosponsorship of an EngD studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1), support for EPSRC Grant number EP/N01572X/1, and from the European Research Council, ERC (grant no. 758345). This work used the ARCHER and ARCHER2 UK National Supercomputing Service (https://www.archer2.ac.uk), via our membership of the UK{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431, and EP/T022213). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources (Thomas and Young), which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). The authors acknowledge the use of the UCL Myriad, Kathleen, and Thomas High Performance Computing Facilities (Myriad@UCL, Kathleen@UCL, and Thomas@UCL), and associated support services, in the completion of this work. R.C. acknowledges financial support from the Communaut{\'e} Fran{\c c}aise de Belgique, grant ARC 18/23-093. G.M.R. acknowledges financial support from the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS). Computational resources were provided by the Consortium des {\'E}quipements de Calcul Intensif, funded by the F.R.S.- FNRS under grant no. 2.5020.11 and by the Walloon Region. The present research benefited from computational resources made available on the Tier-1 supercomputer of the F{\'e}d{\'e}ration Wallonie-Bruxelles, infrastructure funded by the Walloon Region under grant no. 1117545. G.H. acknowledges funding by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05-CH11231: Materials Project program KC23MP. The work has received partial support from the European Union{\textquoteright}s Horizon 2020 research and innovation program, grant no. 951786 through the Center of Excellence NOMAD.",

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T1 - Limits to Hole Mobility and Doping in Copper Iodide

AU - Willis, Joe

AU - Claes, Romain

AU - Zhou, Qi

AU - Giantomassi, Matteo

AU - Rignanese, Gian-Marco

AU - Hautier, Geoffroy

AU - Scanlon, David O.

N1 - Acknowledgments: J.W. and R.C. acknowledge fruitful discussions with Dr Andrea Crovetto, Dr Alex Squires, Dr Alex Ganose, Dr Chris Savory, and Dr Guillaume Brunin. J.W. and D.O.S. acknowledge Diamond Light Source Ltd for cosponsorship of an EngD studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1), support for EPSRC Grant number EP/N01572X/1, and from the European Research Council, ERC (grant no. 758345). This work used the ARCHER and ARCHER2 UK National Supercomputing Service (https://www.archer2.ac.uk), via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431, and EP/T022213). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources (Thomas and Young), which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). The authors acknowledge the use of the UCL Myriad, Kathleen, and Thomas High Performance Computing Facilities (Myriad@UCL, Kathleen@UCL, and Thomas@UCL), and associated support services, in the completion of this work. R.C. acknowledges financial support from the Communauté Française de Belgique, grant ARC 18/23-093. G.M.R. acknowledges financial support from the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS). Computational resources were provided by the Consortium des Équipements de Calcul Intensif, funded by the F.R.S.- FNRS under grant no. 2.5020.11 and by the Walloon Region. The present research benefited from computational resources made available on the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under grant no. 1117545. G.H. acknowledges funding by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05-CH11231: Materials Project program KC23MP. The work has received partial support from the European Union’s Horizon 2020 research and innovation program, grant no. 951786 through the Center of Excellence NOMAD.

PY - 2023/10/25

Y1 - 2023/10/25

N2 - Over one hundred years have passed since the discovery of the p-type transparent conducting material copper iodide, predating the concept of the “electron–hole” itself. Supercentenarian status notwithstanding, little is understood about the charge transport mechanisms in CuI. Herein, a variety of modeling techniques are used to investigate the charge transport properties of CuI, and limitations to the hole mobility over experimentally achievable carrier concentrations are discussed. Poor dielectric response is responsible for extensive scattering from ionized impurities at degenerately doped carrier concentrations, while phonon scattering is found to dominate at lower carrier concentrations. A phonon-limited hole mobility of 162 cm2 V–1 s–1 is predicted at room temperature. The simulated charge transport properties for CuI are compared to existing experimental data, and the implications for future device performance are discussed. In addition to charge transport calculations, the defect chemistry of CuI is investigated with hybrid functionals, revealing that reasonably localized holes from the copper vacancy are the predominant source of charge carriers. The chalcogens S and Se are investigated as extrinsic dopants, where it is found that despite relatively low defect formation energies, they are unlikely to act as efficient electron acceptors due to the strong localization of holes and subsequent deep transition levels.

AB - Over one hundred years have passed since the discovery of the p-type transparent conducting material copper iodide, predating the concept of the “electron–hole” itself. Supercentenarian status notwithstanding, little is understood about the charge transport mechanisms in CuI. Herein, a variety of modeling techniques are used to investigate the charge transport properties of CuI, and limitations to the hole mobility over experimentally achievable carrier concentrations are discussed. Poor dielectric response is responsible for extensive scattering from ionized impurities at degenerately doped carrier concentrations, while phonon scattering is found to dominate at lower carrier concentrations. A phonon-limited hole mobility of 162 cm2 V–1 s–1 is predicted at room temperature. The simulated charge transport properties for CuI are compared to existing experimental data, and the implications for future device performance are discussed. In addition to charge transport calculations, the defect chemistry of CuI is investigated with hybrid functionals, revealing that reasonably localized holes from the copper vacancy are the predominant source of charge carriers. The chalcogens S and Se are investigated as extrinsic dopants, where it is found that despite relatively low defect formation energies, they are unlikely to act as efficient electron acceptors due to the strong localization of holes and subsequent deep transition levels.

KW - copper

KW - charge transport

KW - holes

KW - mobility

KW - scattering

KW - CuI

KW - defects

KW - densityfunctionaltheory/DFT

U2 - 10.1021/acs.chemmater.3c01628

DO - 10.1021/acs.chemmater.3c01628

M3 - Article

SN - 0897-4756

JO - Chemistry of Materials

JF - Chemistry of Materials

ER -

Limits to Hole Mobility and Doping in Copper Iodide

Abstract

Bibliographical note

Keywords

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