Band alignment of monolayer CaP${}_3$, CaAs${}_3$, BaAs${}_3$ and the role of $p$-$d$ orbital interactions in the formation of conduction band minima

Abstract

Recently, a number of new two-dimensional (2D) materials based on puckered phosphorene and arsenene have been predicted with moderate band gaps, good absorption properties and carrier mobilities superior to transition metal dichalcogenides. For heterojunction applications, it is important to know the relative band alignment of these new 2D materials. We report the band alignment of puckered CaP${}_3$, CaAs${}_3$ and BaAs${}_3$ monolayers at the quasiparticle level of theory (G${}_0$W${}_0$), calculating band offsets for isolated monolayers according to the electron affinity rule. Our calculations suggest that monolayer CaP${}_3$, CaAs${}_3$ and BaAs${}_3$ all form type-II (staggered) heterojunctions. Their quasiparticle gaps are 2.1 (direct), 1.8 (direct) and 1.5 eV (indirect), respectively. We also examine trends in the electronic structure in the light of chemical bonding analysis. We show that the indirect band gap in monolayer BaAs${}_3$ is caused by relatively strong As $3p$ - Ba $5d$ bonding interactions that stabilize the conduction band away from the $\Gamma$ point between $\Gamma$ and $S$.

arXiv comment23 pages, 4 figures

References in corpus (20)

• Black phosphorus field-effect transistors
• Tunable Band Gap and Anisotropic Optical Response in Few-layer Black Phosphorus
• The PseudoDojo: Training and grading a 85 element optimized norm-conserving pseudopotential table
• Nonlocal van der Waals density functional: The simpler the better
• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Absolute energy level positions in tin and lead based halide perovskites
• Predicting Band Gaps with Hybrid Density Functionals
• GeP3: A small indirect band gap 2D crystal with high carrier mobility and strong interlayer quantum confinement
• Truncation of Periodic Image Interactions for Confined Systems
• PyProcar: A Python library for electronic structure pre/post-processing
• Van der Waals Materials for Atomically-Thin Photovoltaics: Promise and Outlook
• Quasiparticle GW calculations for solids, molecules and 2D materials
• Coulomb-hole summations and energies for GW calculations with limited number of empty orbitals: a modified static remainder approach
• Quasiparticle band-edge energy and band offsets of monolayer of molybdenum and tungsten chalcogenide
• A New Two-Dimensional Functional Material with Desirable Bandgap and Ultrahigh Carrier Mobility
• Non-uniform sampling schemes of the Brillouin zone for many-electron perturbation-theory calculations in reduced dimensionality
• Why Two-Dimensional Semiconductors Generally Have Low Electron Mobility
• Theoretical studies of electronic transport in mono- and bi-layer phosphorene: A critical overview
• Electronic properties of Pb-I deficient lead halide perovskites
• $\mathrm{BaA}{\mathrm{s}}_3$: A narrow gap 2D semiconductor with vacancy-induced semiconductor-metal transition