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Palladium diselenide (PdSe2)—a layered van der Waals material—is attracting significant attention for optoelectronics due to the wide tunability of its band gap from the infrared through the visible range as a function of the number of layers. However, there continues to be disagreement over the precise nature and value of the optical band gap of bulk PdSe2, owing to the rather small value of this gap that complicates experimental measurements and their interpretation. Here, we design and employ a Wannier-localized optimally tuned screened range-separated hybrid (WOT-SRSH) functional to investigate the electronic band structures and optical absorption spectra of bulk and monolayer PdSe2. In particular, we account carefully for the finite exciton center-of-mass momentum within a time-dependent WOT-SRSH framework to calculate the indirect optical gap and absorption onset accurately. Our results agree well with the best available photoconductivity measurements, as well as with state-of-the-art many-body perturbation theory calculations, confirming that bulk PdSe2 has an optical gap in the mid-infrared (upper bound of 0.44 eV). More generally, this work further bolsters the utility of the WOT-SRSH approach for predictive modeling of layered semiconductors. 

MoSi2N4 is a two-dimensional ternary nitride semiconductor that has attracted attention for its excellent mechanical and thermal properties. Theoretical studies predict that zigzag edges of this material can host magnetic edge states and Dirac fermions, but the stability of such edges has not been examined. Here, we present a density functional theory study of the electronic and thermodynamic properties of MoSi2N4 edges. We develop a (partial) ternary phase diagram that identifies a region of chemical potentials within which MoSi2N4 is stable over competing elemental or binary phases. Based on this phase diagram, we determine the thermodynamic stability of several armchair and zigzag edges and elucidate their electronic structures. Bare zigzag edges, predicted to host exotic electronic states, are found to be substantially higher in energy than armchair edges and, thus, unlikely to occur in practice. However, with hydrogen passivation, these zigzag edges can be stabilized relative to their armchair counterparts while retaining metallicity and magnetic order. Our analysis provides a solid thermodynamic basis for further exploration of MoSi2N4 in nanoscale electronics and spintronics. 

Abstract Above‐band gap optical excitation of non‐centrosymmetric semiconductors can lead to the spatial shift of the center of electron charge in a process known as shift current. Shift current is investigated in single‐crystal SnS₂, a layered semiconductor with the band gap of ≈2.3 eV, by THz emission spectroscopy and first principles density functional theory (DFT). It is observed that normal incidence excitation with above gap (400 nm; 3.1 eV) pulses results in THz emission from 2H SnS₂() polytype, where such emission is nominally forbidden by symmetry. It is argued that the underlying symmetry breaking arises due to the presence of stacking faults that are known to be ubiquitous in SnS₂single crystals and construct a possible structural model of a stacking fault with symmetry properties consistent with the experimental observations. In addition to shift current, it is observed THz emission by optical rectification excited by below band gap (800 nm; 1.55 eV) pulses but it requires excitation fluence more than two orders of magnitude higher to produce same signal amplitude. These results suggest that ultrafast shift current in which can be excited with visible light in blue–green portion of the spectrum makes SnS₂a promising source material for THz photonics. 

Computational spectrometry is an emerging field that uses photodetection in conjunction with numerical algorithms for spectroscopic measurements. Compact single photodetectors made from layered materials are particularly attractive since they eliminate the need for bulky mechanical and optical components used in traditional spectrometers and can easily be engineered as heterostructures to optimize device performance. However, such photodetectors are typically nonlinear devices, which adds complexity to extracting optical spectra from their response. Here, we train an artificial neural network to recover the full nonlinear spectral photoresponse of a single GeSe-InSe p-n heterojunction device. The device has a spectral range of 400 to 1100 nm, a small footprint of ~25 × 25 square micrometers, and a mean reconstruction error of 2 × 10⁻⁴for the power spectrum at 0.35 nanometers. Using our device, we demonstrate a solution to metamerism, an apparent matching of colors with different power spectral distributions, which is a fundamental problem in optical imaging.