Efficient and improved prediction of the band offsets at semiconductor heterojunctions from meta-GGA density functionals: A benchmark study.

Accurate theoretical prediction of the band offsets at interfaces of semiconductor heterostructures can often be quite challenging. Although density functional theory has been reasonably successful to carry out such calculations, efficient, accurate semilocal functionals are desirable to reduce the computational cost. In general, the semilocal functionals based on the generalized gradient approximation (GGA) significantly underestimate the bulk bandgaps. This, in turn, results in inaccurate estimates of the band offsets at the heterointerfaces. In this paper, we investigate the performance of several advanced meta-GGA functionals in the computational prediction of band offsets at semiconductor heterojunctions. In particular, we investigate the performance of r2SCAN (two times revised strongly constrained and appropriately normed functional), rMGGAC (revised semilocal functional based on cuspless hydrogen model and Pauli kinetic energy density functional), mTASK (modified Aschebrock and Kümmel meta-GGA functional), and local modified Becke-Johnson exchange-correlation functionals. Our results strongly suggest that these meta-GGA functionals for supercell calculations perform quite well, especially, when compared to computationally more demanding GW calculations. We also present band offsets calculated using ionization potentials and electron affinities, as well as band alignment via the branch point energies. Overall, our study shows that the aforementioned meta-GGA functionals can be used within the density functional theory framework to estimate the band offsets in semiconductor heterostructures with predictive accuracy.

First-Principles Identification of Single Photon Emitters Based on Carbon Clusters in Hexagonal Boron Nitride.

A recent study associates carbon with single photon emitters (SPEs) in hexagonal boron nitride (h-BN). This observation, together with the high mobility of carbon in h-BN, suggests the existence of SPEs based on carbon clusters. Here, by means of density functional theory calculations, we studied clusters of substitutional carbon atoms up to tetramers in h-BN. Two different conformations of neutral carbon trimers have zero-point line energies and shifts of the phonon sideband compatible with typical photoluminescence spectra. Moreover, some conformations of two small C clusters next to each other result in photoluminescence spectra similar to those found in the experiments. We also showed that vacancies are unable to reproduce the typical features of the phonon sideband observed in most measurements because of the large spectral weight of low-energy breathing modes, ubiquitous in such defects.

Bandgap of two-dimensional materials: Thorough assessment of modern exchange-correlation functionals.

The density-functional theory (DFT) approximations that are the most accurate for the calculation of bandgap of bulk materials are hybrid functionals, such as HSE06, the modified Becke-Johnson (MBJ) potential, and the GLLB-SC potential. More recently, generalized gradient approximations (GGAs), such as HLE16, or meta-GGAs, such as (m)TASK, have also proven to be quite accurate for the bandgap. Here, the focus is on two-dimensional (2D) materials and the goal is to provide a broad overview of the performance of DFT functionals by considering a large test set of 298 2D systems. The present work is an extension of our recent studies [T. Rauch, M. A. L. Marques, and S. Botti, Phys. Rev. B 101, 245163 (2020); Patra et al., J. Phys. Chem. C 125, 11206 (2021)]. Due to the lack of experimental results for the bandgap of 2D systems, G0W0 results were taken as reference. It is shown that the GLLB-SC potential and mTASK functional provide the bandgaps that are the closest to G0W0. Following closely, the local MBJ potential has a pretty good accuracy that is similar to the accuracy of the more expensive hybrid functional HSE06.

Erratum: Spin Chirality Tuning and Topological Semimetals in Strained HgTe_{x}S_{1-x} [Phys. Rev. Lett. 114, 236805 (2015)].

This corrects the article DOI: 10.1103/PhysRevLett.114.236805.

Spin Chirality Tuning and Topological Semimetals in Strained HgTe(x)S(1-x).

By means of detailed electronic structure calculations, we show that strained HgTe(x)S(1-x) alloys show a surprisingly rich topological phase diagram. In the strong topological insulator phase, the spin chirality of the topological nontrivial surface states can be reversed by adjusting the alloy concentration x and the strain. On top of this, we predict two semimetallic topological phases, namely, a Dirac semimetal and a Weyl semimetal. The topological phases are characterized by their Z2 invariants and their mirror Chern numbers.

Dual topological character of chalcogenides: theory for Bi2Te3.

A topological insulator is realized via band inversions driven by the spin-orbit interaction. In the case of Z2 topological phases, the number of band inversions is odd and time-reversal invariance is a further unalterable ingredient. For topological crystalline insulators, the number of band inversions may be even but mirror symmetry is required. Here, we prove that the chalcogenide Bi2Te3 is a dual topological insulator: it is simultaneously in a Z2 topological phase with Z2 invariants (ν0;ν1ν2ν3) = (1;0 0 0) and in a topological crystalline phase with mirror Chern number -1. In our theoretical investigation we show in addition that the Z2 phase can be broken by magnetism while keeping the topological crystalline phase. As a consequence, the Dirac state at the (111) surface is shifted off the time-reversal invariant momentum Γ; being protected by mirror symmetry, there is no band gap opening. Our observations provide theoretical groundwork for opening the research on magnetic control of topological phases in quantum devices.

Electronic Structure and Epitaxy of CdTe Shells on InSb Nanowires.

Indium antimonide (InSb) nanowires are used as building blocks for quantum devices because of their unique properties, that is, strong spin-orbit interaction and large Landé g-factor. Integrating InSb nanowires with other materials could potentially unfold novel devices with distinctive functionality. A prominent example is the combination of InSb nanowires with superconductors for the emerging topological particles research. Here, the combination of the II-VI cadmium telluride (CdTe) with the III-V InSb in the form of core-shell (InSb-CdTe) nanowires is investigated and potential applications based on the electronic structure of the InSb-CdTe interface and the epitaxy of CdTe on the InSb nanowires are explored. The electronic structure of the InSb-CdTe interface using density functional theory is determined and a type-I band alignment is extracted with a small conduction band offset ( ⩽0.3 eV). These results indicate the potential application of these shells for surface passivation or as tunnel barriers in combination with superconductors. In terms of structural quality, it is demonstrated that the lattice-matched CdTe can be grown epitaxially on the InSb nanowires without interfacial strain or defects. These shells do not introduce disorder to the InSb nanowires as indicated by the comparable field-effect mobility measured for both uncapped and CdTe-capped nanowires.

Electronic Structure of Molecules, Surfaces, and Molecules on Surfaces with the Local Modified Becke-Johnson Exchange-Correlation Potential.

The knowledge of electronic properties of matter is the key to the understanding of its properties and to propose useful applications. To model hybrid organic/inorganic systems with the plane-wave approach, large supercells with many atoms are usually necessary to minimize artificial interactions between periodic images. For such systems, accurate approximations to the exchange-correlation functional of density functional theory, such as hybrid functionals, become computationally expensive, and cheaper approaches need to be considered. Here, we apply the local modified Becke-Johnson exchange-correlation potential to free molecules and surfaces and study its accuracy for calculated ionization potentials. This quantity being important to understand the band alignment of composite heterogeneous systems, we demonstrate the application of the potential to the electronic structure calculation of an exemplary composite semiconductor/molecule system, namely, a F6-TCNNQ molecule adsorbed on a hydrogenated Si(111) surface.

Local Modified Becke-Johnson Exchange-Correlation Potential for Interfaces, Surfaces, and Two-Dimensional Materials.

The modified Becke-Johnson meta-GGA potential of density functional theory has been shown to be the best exchange-correlation potential to determine band gaps of crystalline solids. However, it cannot be consistently used for the electronic structure of nonperiodic or nanostructured systems. We propose an extension of this potential that enables its use to study heterogeneous, finite, and low-dimensional systems. This is achieved by using a coordinate-dependent expression for the parameter c that weights the Becke-Russel exchange, in contrast to the original global formulation, where c is just a fitted number. Our potential takes advantage of the excellent description of band gaps provided by the modified Becke-Johnson potential and preserves its modest computational effort. Furthermore, it yields with one single calculation band diagrams and band offsets of heterostructures and surfaces. We exemplify the usefulness and efficiency of our local meta-GGA potential by testing it for a series of interfaces (Si/SiO2, AlAs/GaAs, AlP/GaP, and GaP/Si), a Si surface, and boron nitride monolayer.

Impact of the Topological Surface State on the Thermoelectric Transport in Sb2Te3 Thin Films.

Ab initio electronic structure calculations based on density functional theory and tight-binding methods for the thermoelectric properties of p-type Sb2Te3 films are presented. The thickness-dependent electrical conductivity and the thermopower are computed in the diffusive limit of transport based on the Boltzmann equation. Contributions of the bulk and the surface to the transport coefficients are separated, which enables to identify a clear impact of the topological surface state on the thermoelectric properties. When the charge carrier concentration is tuned, a crossover between a surface-state-dominant and a Fuchs-Sondheimer transport regime is achieved. The calculations are corroborated by thermoelectric transport measurements on Sb2Te3 films grown by atomic layer deposition.