Gallium nitride (GaN) is an important commercial semiconductor for solid-state lighting applications. Atomically thin GaN, a recently synthesized two-dimensional material, is of particular interest because the extreme quantum confinement enables additional control of its light-emitting properties. We performed first-principles calculations based on density functional and many-body perturbation theory to investigate the electronic, optical, and excitonic properties of monolayer and bilayer two-dimensional (2D) GaN as a function of strain. Our results demonstrate that light emission from monolayer 2D GaN is blueshifted into the deep ultraviolet range, which is promising for sterilization and water-purification applications. Light emission from bilayer 2D GaN occurs at a similar wavelength to its bulk counterpart due to the cancellation of the effect of quantum confinement on the optical gap by the quantum-confined Stark shift. Polarized light emission at room temperature is possible via uniaxial in-plane strain, which is desirable for energy-efficient display applications. We compare the electronic and optical properties of freestanding two-dimensional GaN to atomically thin GaN wells embedded within AlN barriers in order to understand how the functional properties are influenced by the presence of barriers. Our results provide microscopic understanding of the electronic and optical characteristics of GaN at the few-layer regime.

We determine the fundamental electronic and optical properties of the high-thermal-conductivity III-V semiconductor boron arsenide (BAs) using density functional and many body perturbation theory including quasiparticle and spin-orbit coupling corrections. We find that the fundamental band gap is indirect with a value of 2.049 eV, while the minimum direct gap has a value of 4.135 eV. We calculate the carrier effective masses and report smaller values for the holes than the electrons, indicating higher hole mobility and easier p-type doping. The small difference between the static and high frequency dielectric constants indicates that BAs is only weakly ionic. We also observe that the imaginary part of the dielectric function exhibits a strong absorption peak, which corresponds to parallel bands in the band structure. Our estimated exciton binding energy of 43 meV indicates that excitons are relatively stable against thermal dissociation at room temperature. Our work provides theoretical insights on the fundamental electronic properties of BAs to guide experimental characterization and device applications.

We present experimental results confirming extreme quantum confinement in GaN/Al x Ga1–x N (x = 0.65 and 1.0) nanowire and planar heterostructures, where the GaN layer thickness is of the order of a monolayer. The results were obtained from temperature- and excitation-dependent and time-resolved photoluminescence measurements. In the GaN/AlN nanowire heterostructure array sample, the measured emission peak at 300 K is ∼5.18–5.28 eV. This is in excellent agreement with the calculated optical gap of 5.23 eV and 160–260 meV below the calculated electronic gap of 5.44 eV, suggesting that the observed emission is excitonic in nature with an exciton binding energy of ∼160–260 meV. Similarly, in the monolayer GaN/Al0.65Ga0.35N planar heterostructure, the measured emission peak at 300 K is 4.785 eV and in good agreement with the calculated optical gap of 4.68 eV and 95 meV below the calculated electronic gap of 4.88 eV. The estimated exciton binding energy is 95 meV and in close agreement with our theoretical calculations. Excitation-dependent and time-resolved photoluminescence data support the presence of excitonic transitions. Our results indicate that deep-ultraviolet excitonic light sources and microcavity devices can be realized with heterostructures incorporating monolayer-thick GaN.

Ultrawide-band-gap (UWBG) semiconductors are promising for fast, compact, and energyefficient power-electronics devices. Their wider band gaps result in higher breakdown electric fields that enable high-power switching with a lower energy loss. Yet, the leading UWBG semiconductors suffer from intrinsic materials limitations with regards to their doping asymmetry that impedes their adoption in CMOS technology. Improvements in the ambipolar doping of UWBG materials will enable a wider range of applications in power electronics as well as deep-UV optoelectronics. These advances can be accomplished through theoretical insights on the limitations of current UWBG materials coupled with the computational prediction and 2 experimental demonstration of alternative UWBG semiconductor materials with improved doping and transport properties. As an example, we discuss the case of rutile GeO2 (r-GeO2), a waterinsoluble GeO2 polytype which is theoretically predicted to combine an ultra-wide gap with ambipolar dopability, high carrier mobilities, and a higher thermal conductivity than β-Ga2O3. The subsequent realization of single-crystalline r-GeO2 thin films by molecular beam epitaxy provides the opportunity to realize r-GeO2 for electronic applications. Future efforts towards the predictive discovery and design of new UWBG semiconductors include advances in first-principles theory and high-performance computing software, as well as the demonstration of controlled doping in high-quality thin films with lower dislocation densities and optimized film properties.

Power electronics seek to improve power conversion of devices by utilizing materials with a wide bandgap, high carrier mobility, and high thermal conductivity. Due to its wide bandgap of 4.5 eV, β-Ga2O3 has received much attention for high-voltage electronic device research. However, it suffers from inefficient thermal conduction that originates from its low-symmetry crystal structure. Rutile germanium oxide (r-GeO2) has been identified as an alternative ultra-wide-bandgap (4.68 eV) semiconductor with a predicted high electron mobility and ambipolar dopability; however, its thermal conductivity is unknown. Here, we characterize the thermal conductivity of r-GeO2 as a function of temperature by first-principles calculations, experimental synthesis, and thermal characterization. The calculations predict an anisotropic phonon-limited thermal conductivity for r-GeO2 of 37 W m−1 K−1 along the a direction and 58 W m−1 K−1 along the c direction at 300 K where the phonon-limited thermal conductivity predominantly occurs via the acoustic modes. Experimentally, we measured a value of 51 W m−1 K−1 at 300 K for hot-pressed, polycrystalline r-GeO2 pellets. The measured value is close to our directionally averaged theoretical value, and the temperature dependence of ∼1/T is also consistent with our theory prediction, indicating that thermal transport in our r-GeO2 samples at room temperature and above is governed by phonon scattering. Our results reveal that high-symmetry UWBG materials, such as r-GeO2, may be the key to efficient power electronics.

We performed first-principles calculations based on density functional theory and many-body perturbation theory to investigate the electronic and optical properties of monolayer, bilayer, and bulk litharge α-PbO, including spin–orbit coupling effects. The fundamental gap is direct for the monolayer (4.48 eV) and indirect for the bilayer (3.44 eV) and the bulk material (2.45 eV). The exciton binding energies are large for the monolayer (1.1 eV) and the bilayer (0.9 eV), indicating that excitons are stable at room temperature. However, the lowest-energy excitons for the monolayer and the bilayer are dark with radiative lifetimes on the order of milliseconds. A pronounced van Hove singularity in the valence band of the few-layer structures suggests it becomes a multiferroic two-dimensional material upon hole doping. Our results indicate strong optical absorbance in the vacuum UV region and transparency in the visible and near UV for monolayer PbO, suggesting applications for atomically thin solar-blind UV photodetectors.

Diamond and cBN are two of the most promising ultra-wide-band-gap (UWBG) semiconductors for applications in high-power high-frequency electronic devices. Yet despite extensive studies on carrier transport in these materials, there are large discrepancies in their reported carrier mobilities.In this work, we investigate the phonon-and dopant-limited electron and hole mobility of cBN and diamond with atomistic first-principles calculations in order to understand their fundamental upper bounds to carrier transport. Our results show that although the phonon-limited electron mobilities are comparable between cBN and diamond, the hole mobility is significantly lower in cBN due to its heavier hole effective mass. Moreover, although lattice scattering dominates the mobility at low doping, neutral impurity scattering becomes the dominant scattering mechanism at higher dopant concentrations due to the high dopant ionization energies. Our analysis provides critical insights and reveals the intrinsic upper limits to the carrier mobilities of diamond and cBN as a function of doping and temperature for applications in high-power electronic devices.

Group-III nitrides are established commercial semiconductors that were recently synthesized in 2D form. We apply first-principles calculations to determine the electronic properties of polar hydrogen-passivated monolayers and bilayers of BN, AlN, GaN, and InN. We find that hydrogen-passivated AlN, GaN, and InN monolayers are stable under standard conditions. Our results indicate that antialigned bilayer orientations, which cancel the polarization fields, yield wide band gaps by quantum confinement. However, the band gaps are narrower in bilayers with aligned polarizations, due to the strong quantum-confined Stark effect. Strongly bound interlayer excitons form in structures with aligned polarizations due to the spatial separation of electron and hole wave functions on different monolayers. Our results demonstrate that the stacking orientation acts as an additional degree of freedom to tune the band gap of polar 2D bilayers, as well as to control the direct or interlayer nature of excitons for optoelectronic and excitonic applications.