Fundamental Principles for Calculating Charged Defect Ionization Energies in Ultrathin Two-Dimensional Materials
Abstract
Defects in two-dimensional (2D) materials are becoming prominent candidates for quantum emitters and scalable optoelectronic applications. However, several physical properties that characterize their behavior, such as charged defect ionization energies, are difficult to simulate with conventional first-principles methods, mainly because of the weak and anisotropic dielectric screening caused by the reduced dimensionality. We establish fundamental principles for accurate and efficient calculations of charged defect ionization energies and electronic structure in ultrathin 2D materials. We propose to use the vacuum level as the reference for defect charge transition levels (CTLs) because it gives robust results insensitive to the level of theory, unlike commonly used band-edge positions. Furthermore, we determine the fraction of Fock exchange in hybrid functionals for accurate band gaps and band-edge positions of 2D materials by enforcing the generalized Koopmans’ condition of localized defect states. We found that the obtained fractions of Fock exchange vary significantly from 0.2 for bulk hexagonal boron nitride (h-BN) to 0.4 for monolayer h-BN, whose band gaps are also in good agreement with experimental results and calculated GW results. The combination of these methods allows for the reliable and efficient prediction of defect ionization energies (the difference between CTLs and band-edge positions). We motivatemore »
- Authors:
-
- Univ. of California Santa Cruz, Santa Cruz, CA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1490339
- Alternate Identifier(s):
- OSTI ID: 1488641
- Grant/Contract Number:
- AC02-06CH11357; AC02-05CH11231; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Materials
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 12; Journal ID: ISSN 2475-9953
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Quantum informatoin science; Quantum materials
Citation Formats
Smart, Tyler J., Wu, Feng, Govoni, Marco, and Ping, Yuan. Fundamental Principles for Calculating Charged Defect Ionization Energies in Ultrathin Two-Dimensional Materials. United States: N. p., 2018.
Web. doi:10.1103/PhysRevMaterials.2.124002.
Smart, Tyler J., Wu, Feng, Govoni, Marco, & Ping, Yuan. Fundamental Principles for Calculating Charged Defect Ionization Energies in Ultrathin Two-Dimensional Materials. United States. https://doi.org/10.1103/PhysRevMaterials.2.124002
Smart, Tyler J., Wu, Feng, Govoni, Marco, and Ping, Yuan. Thu .
"Fundamental Principles for Calculating Charged Defect Ionization Energies in Ultrathin Two-Dimensional Materials". United States. https://doi.org/10.1103/PhysRevMaterials.2.124002. https://www.osti.gov/servlets/purl/1490339.
@article{osti_1490339,
title = {Fundamental Principles for Calculating Charged Defect Ionization Energies in Ultrathin Two-Dimensional Materials},
author = {Smart, Tyler J. and Wu, Feng and Govoni, Marco and Ping, Yuan},
abstractNote = {Defects in two-dimensional (2D) materials are becoming prominent candidates for quantum emitters and scalable optoelectronic applications. However, several physical properties that characterize their behavior, such as charged defect ionization energies, are difficult to simulate with conventional first-principles methods, mainly because of the weak and anisotropic dielectric screening caused by the reduced dimensionality. We establish fundamental principles for accurate and efficient calculations of charged defect ionization energies and electronic structure in ultrathin 2D materials. We propose to use the vacuum level as the reference for defect charge transition levels (CTLs) because it gives robust results insensitive to the level of theory, unlike commonly used band-edge positions. Furthermore, we determine the fraction of Fock exchange in hybrid functionals for accurate band gaps and band-edge positions of 2D materials by enforcing the generalized Koopmans’ condition of localized defect states. We found that the obtained fractions of Fock exchange vary significantly from 0.2 for bulk hexagonal boron nitride (h-BN) to 0.4 for monolayer h-BN, whose band gaps are also in good agreement with experimental results and calculated GW results. The combination of these methods allows for the reliable and efficient prediction of defect ionization energies (the difference between CTLs and band-edge positions). We motivate and generalize these findings with several examples including different defects in monolayer to few-layer h-BN, monolayer MoS2, and graphane. Lastly, we show that increasing the number of layers of h-BN systematically lowers defectionization energies, mainly through CTLs shifting towards vacuum, with conduction band minima kept almost unchanged.},
doi = {10.1103/PhysRevMaterials.2.124002},
journal = {Physical Review Materials},
number = 12,
volume = 2,
place = {United States},
year = {Thu Dec 20 00:00:00 EST 2018},
month = {Thu Dec 20 00:00:00 EST 2018}
}
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