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We conduct a systematic investigation of the role of Hubbard U corrections in electronic structure calculations of two-dimensional (2D) materials containing 3d transition metals. Specifically, we use density functional theory (DFT) with the PBE and PBE+U approximations to calculate the crystal structure, band gaps, and magnetic parameters of 638 monolayers. Based on a comprehensive comparison to experiments we first establish that inclusion of the U correction worsens the accuracy for the lattice constant. Consequently, PBE structures are used for subsequent property evaluations. The band gaps show significant dependence on the U-parameter. In particular, for 134 (21%) of the materials the U parameter leads to a metal-insulator transition. For the magnetic materials we calculate the magnetic moment, magnetic exchange coupling, and magnetic anisotropy parameters. In contrast to the band gaps, the size of the magnetic moments shows only weak dependence on U. Both the exchange energies and magnetic anisotropy parameters are systematically reduced by the U correction. On this basis we conclude that the Hubbard U correction will lead to lower predicted Curie temperatures in 2D materials. All the calculated properties are available in the Computational 2D Materials Database (C2DB).

Intercalation (ic) of metal atoms into the van der Waals (vdW) gap of layered materials constitutes a facile strategy to create new materials whose properties can be tuned via the concentration of the intercalated atoms. Here we perform systematic density functional theory calculations to explore various properties of an emergent class of crystalline 2D materials (ic-2D materials) comprising vdW homobilayers with native metal atoms on a sublattice of intercalation sites. From an initial set of 1348 ic-2D materials, generated from 77 vdW homobilayers, we find 95 structures with good thermodynamic stability (formation energy within 200 meV/atom of the convex hull). A significant fraction of the semiconducting host materials are found to undergo an insulator to metal transition upon self-intercalation with only PdS$_2$, PdSe$_2$, and GeS$_2$ maintaining a finite electronic gap. In five cases, self-intercalation introduces magnetism. In general, self-intercalation is found to promote metallicity and enhance the chemical reactivity on the basal plane. Based on the calculated H binding energy we find that self-intercalated SnS$_2$ and Hf$_3$Te$_2$ are promising candidates for hydrogen evolution catalysis. All the stable ic-2D structures and their calculated properties can be explored in the open C2DB database.

Intermetallics are an important playground to stabilize a large variety of physical phenomena, arising from their complex crystal structure. The ease of their chemical tuneabilty makes them suitable platforms to realize targeted electronic properties starting from the symmetries hidden in their unit cell. Here, we investigate the family of the recently discovered intermetallics MCo$_2$Al$_9$ (M: Sr, Ba) and we unveil their electronic structure for the first time. By using angle-resolved photoelectron spectroscopy and density functional theory calculations, we discover the existence of Dirac-like dispersions as ubiquitous features in this family, coming from the hidden kagome and honeycomb symmetries embedded in the unit cell. Finally, from calculations, we expect that the spin-orbit coupling is responsible for opening energy gaps in the electronic structure spectrum, which also affects the majority of the observed Dirac-like states. Our study constitutes the first experimental observation of the electronic structure of MCo$_2$Al$_9$ and proposes these systems as hosts of Dirac-like physics with intrinsic spin-orbit coupling. The latter effect suggests MCo$_2$Al$_9$ as a future platform for investigating the emergence of non-trivial topology.

Recent theoretical and experimental studies suggest that van der Waals heterostructures with n- and p-doped bilayers of transition metal dichalcogenides are promising facilitators of exciton superfluidity. Exciton superfluidity in such bilayer systems is often modelled by solving a mean-field gap equation defined for only the conduction and valence band of the electron and hole material respectively. A key quantity entering the gap equation is the effective Coulomb potential acting as the bare interaction in the subspace of the model. Since the model only includes a few bands around the Fermi energy the effective model interaction is partially screened. Although the screening is a material dependent quantity it has in previous works been accounted for in an ad hoc manner, by assuming a static dielectric constant of 2 for a wide range of different materials. In this work we show that the effective model interaction can be derived from first principles using open source code frameworks. Using this novel ab initio downfolding procedure we show that the material dependent screening is essential to predict both magnitude and trends of exciton binding energies and superfluid properties. Furthermore, we suggest new material platforms of both transition metal oxides and dichalcogenides with superior properties compared to the standard devices with two transition metal dichalcogenide layers., Comment: 16 pages, 8 figures

Stacking of two-dimensional (2D) materials has emerged as a facile strategy for realising exotic quantum states of matter and engineering electronic properties. Yet, developments beyond the proof-of-principle level are impeded by the vast size of the configuration space defined by layer combinations and stacking orders. Here we employ a density functional theory (DFT) workflow to calculate interlayer binding energies of 8451 homobilayers created by stacking 1052 different monolayers in various configurations. Analysis of the stacking orders in 247 experimentally known van der Waals crystals is used to validate the workflow and determine the criteria for realizable bilayers. For the 2586 most stable bilayer systems, we calculate a range of electronic, magnetic, and vibrational properties, and explore general trends and anomalies. We identify an abundance of bistable bilayers with stacking order-dependent magnetic or electrical polarisation states making them candidates for slidetronics applications.

We explore a new platform for realising excitonic insulators, namely van der Waals (vdW) bilayers comprising 2D Janus materials. In previous studies, Type-II heterobilayers have been brought to the excitonic insulating regime by tuning the band alignment using external gates. In contrast, the Janus bilayers of the current work represent intrinsic excitonic insulators. We first conduct ab initio calculations to obtain the quasiparticle band structures, screened Coulomb interaction, and interlayer exciton binding energies of the bilayers. These ab initio-derived quantities are then used to construct a BCS-like Hamiltonian of the exciton condensate. By solving the mean-field gap equation, we identify 16 vdW Janus bilayers with insulating ground states and superfluid properties. Our calculations expose a new class of advanced materials that are likely to exhibit novel excitonic phases at low temperatures, and highlight the subtle competition between interlayer hybridization, spin-orbit coupling, and dielectric screening that govern their properties., Comment: 5 figures, 10 pages

Antimonene -- a single layer of antimony atoms -- and its few layer forms are among the latest additions to the 2D mono-elemental materials family. Numerous predictions and experimental evidence of its remarkable properties including (opto)electronic, energetic or biomedical, among others, together with its robustness under ambient conditions, have attracted the attention of the scientific community. However, experimental evidence of its electrical properties is still lacking. Here, we characterized the electronic properties of mechanically exfoliated flakes of few-layer (FL) antimonene of different thicknesses (~ 2-40 nm) through photoemission electron microscopy, kelvin probe force microscopy and transport measurements, which allows us to estimate a sheet resistance of ~ 1200 $\Omega$sq$^{-1}$ and a mobility of ~ 150 cm$^2$V$^{-1}$s$^{-1}$ in ambient conditions, independent of the flake thickness. Alternatively, our theoretical calculations indicate that topologically protected surface states (TPSS) should play a key role in the electronic properties of FL antimonene, which supports our experimental findings. We anticipate our work will trigger further experimental studies on TPSS in FL antimonene thanks to its simple structure and significant stability in ambient environments.

A mismatch of atomic registries between single-layer transition metal dichalcogenides (TMDs) in a two dimensional van der Waals heterostructure produces a moir\'e superlattice with a periodic potential, which can be fine-tuned by introducing a twist angle between the materials. This approach is promising both for controlling the interactions between the TMDs and for engineering their electronic band structures, yet direct observation of the changes to the electronic structure introduced with varying twist angle has so far been missing. Here, we probe heterobilayers comprised of single-layer MoS$_2$ and WS$_2$ with twist angles of $(2.0 \pm 0.5)^{\circ}$, $(13.0 \pm 0.5)^{\circ}$, and $(20.0 \pm 0.5)^{\circ}$ and investigate the differences in their electronic band structure using micro-focused angle-resolved photoemission spectroscopy. We find strong interlayer hybridization between MoS$_2$ and WS$_2$ electronic states at the $\bar{\mathrm{\Gamma}}$-point of the Brillouin zone, leading to a transition from a direct bandgap in the single-layer to an indirect gap in the heterostructure. Replicas of the hybridized states are observed at the centre of twist angle-dependent moir\'e mini Brillouin zones. We confirm that these replica features arise from the inherent moir\'e potential by comparing our experimental observations with density functional theory calculations of the superlattice dispersion. Our direct visualization of these features underscores the potential of using twisted heterobilayer semiconductors to engineer hybrid electronic states and superlattices that alter the electronic and optical properties of 2D heterostructures., Comment: 31 pages, 6 figures in the main text and 5 figures in the supporting information

Core level binding energies and absorption edges are at the heart of many experimental techniques concerned with element-specific structure, electronic structure, chemical reactivity, elementary excitations and magnetism. X-ray photoemission spectroscopy (XPS) in particular, can provide information about the electronic and vibrational many-body interactions in a solid as these are reflected in the detailed energy distribution of the photoelectrons. Ultrafast pump-probe techniques add a new dimension to such studies, introducing the ability to probe a transient state of the many-body system. Here we use a free electron laser to investigate the effect of a transiently excited electron gas on the core level spectrum of graphene, showing that it leads to a large broadening of the C 1s peak. Confirming a decade-old prediction, the broadening is found to be caused by an exchange of energy and momentum between the photoemitted core electron and the hot electron system, rather than by vibrational excitations. This interpretation is supported by a line shape analysis that accounts for the presence of the excited electrons. Fitting the spectra to this model directly yields the electronic temperature of the system, in agreement with electronic temperature values obtained from valence band data. Furthermore, making use of time- and momentum-resolved C 1s spectra, we illustrate how the momentum change of the outgoing core electrons leads to a small but detectable change in the time-resolved photoelectron diffraction pattern and to a nearly complete elimination of the core level binding energy variation associated with the narrow $\sigma$-band in the C 1s state. The results demonstrate that the XPS line shape can be used as an element-specific and local probe of the excited electron system and that X-ray photoelectron diffraction investigations remain feasible at very high electronic temperatures., Comment: 16 pages, 12 figures

We report direct measurements via angle-resolved photoemission spectroscopy (ARPES) of the electronic dispersion of single-layer CoO$_2$. The Fermi contour consists of a large hole pocket centered at the $\overline{\Gamma}$ point. To interpret the ARPES results, we use density functional theory (DFT) in combination with the multi-orbital Gutzwiller Approximation (DFT+GA), basing our calculations on crystalline structure parameters derived from x-ray photoelectron diffraction and low-energy electron diffraction. Our calculations are in good agreement with the measured dispersion. We conclude that the material is a moderately correlated metal. We also discuss substrate effects, and the influence of hydroxylation on the CoO$_2$ single-layer electronic structure.

We apply an intense infrared laser pulse in order to perturb the electronic and vibrational states in the three-dimensional charge density wave material 1$T$-VSe$_2$. Ultrafast snapshots of the light-induced hot carrier dynamics and non-equilibrium quasiparticle spectral function are collected using time- and angle-resolved photoemission spectroscopy. The hot carrier temperature and time-dependent electronic self-energy are extracted from the time-dependent spectral function, revealing that incoherent electron-phonon interactions heat the lattice above the charge density wave critical temperature on a timescale of $(200 \pm 40)$~fs. Density functional perturbation theory calculations establish that the presence of hot carriers alters the overall phonon dispersion and quenches efficient low-energy acoustic phonon scattering channels, which results in a new quasi-equilibrium state that is experimentally observed., Comment: 24 pages including supplemental material, 4 figures in the main text and 4 figures in the supplemental material

There is immense interest in how the local environment influences the electronic structure of materials at the single layer limit. We characterize moir\'e induced spatial variations in the electronic structure of in-situ grown monolayer V2S3 on Au(111) by means of low temperature scanning tunneling microscopy and spectroscopy. We observe a long-range modulation of the integrated local density of states (LDOS), and quantify this modulation with respect to the moir\'e superstructure for multiple orientations of the monolayer with respect to the substrate. Scanning tunneling spectroscopy reveals a prominent peak in the LDOS, which is shifted in energy at different points of the moir\'e superstructure. Comparing ab initio calculations with angle-resolved photoemission, we are able to attribute this peak to bands that exhibit a large out-of-plane d-orbital character. This suggests that the moir\'e driven variations in the measured density of states is driven by a periodic modulation of the monolayer-substrate hybridization.

A cardinal obstacle to performing quantum-mechanical simulations of strongly-correlated matter is that, with the theoretical tools presently available, sufficiently-accurate computations are often too expensive to be ever feasible. Here we design a computational framework combining quantum-embedding (QE) methods with machine learning. This allows us to bypass altogether the most computationally-expensive components of QE algorithms, making their overall cost comparable to bare Density Functional Theory (DFT). We perform benchmark calculations of a series of actinide systems, where our method describes accurately the correlation effects, reducing by orders of magnitude the computational cost. We argue that, by producing a larger-scale set of training data, it will be possible to apply our method to systems with arbitrary stoichiometries and crystal structures, paving the way to virtually infinite applications in condensed matter physics, chemistry and materials science., Comment: Main text (6 pages, 4 figures ) and supplemental material (5 pages)

The quantum-spin-Hall (QSH) phase of 2D topological insulators has attracted increased attention since the onset of 2D materials research. While large bulk gaps with vanishing edge gaps in atomically thin layers have been reported, verifications of the QSH phase by resistance measurements are comparatively few. This is partly due to the poor uniformity of the bulk gap induced by the substrate over a large sample area and/or defects induced by oxidation. Here, we report the observation of the QSH phase at room-temperature in the 1T'-phase of few-layer MoS2 patterned onto the 2H semiconducting phase using low-power and short-time laser beam irradiation. Two different resistance measurements reveal hallmark transport conductance values, ~e2/2h and e2/4h, as predicted by the theory. Magnetic-field dependence, scanning tunneling spectra, and calculations support the emergence of the room-temperature QSH phase. Although further experimental verification is still desirable, our results provide feasible application to room-temperature topological devices.

The possibility of triggering correlated phenomena by placing a singularity of the density of states near the Fermi energy remains an intriguing avenue towards engineering the properties of quantum materials. Twisted bilayer graphene is a key material in this regard because the superlattice produced by the rotated graphene layers introduces a van Hove singularity and flat bands near the Fermi energy that cause the emergence of numerous correlated phases, including superconductivity. While the twist angle-dependence of these properties has been explored, direct demonstration of electrostatic control of the superlattice bands over a wide energy range has, so far, been critically missing. This work examines a functional twisted bilayer graphene device using in-operando angle-resolved photoemission with a nano-focused light spot. A twist angle of 12.2$^{\circ}$ is selected such that the superlattice Brillouin zone is sufficiently large to enable identification of van Hove singularities and flat band segments in momentum space. The doping dependence of these features is extracted over an energy range of 0.4 eV, expanding the combinations of twist angle and doping where they can be placed at the Fermi energy and thereby induce new correlated electronic phases in twisted bilayer graphene., Comment: 16 pages, 4 figures. A revised version of the manuscript has been accepted for publication in Advanced Materials

Two-dimensional perovskites, in which inorganic layers are stabilized by organic spacer molecules, are attracting increasing attention as a more robust analogue to the conventional three-dimensional metal-halide perovskites. However, reducing the perovskite dimensionality alters their optoelectronic properties dramatically, yielding excited states that are dominated by bound electron-hole pairs known as excitons, rather than by free charge carriers common to their bulk counterparts. Despite the growing interest in two-dimensional perovskites for both light harvesting and light emitting applications, the full impact of the excitonic nature on their optoelectronic properties remains unclear, particularly regarding the spatial dynamics of the excitons within the two-dimensional (2D) plane. Here, we present direct measurements of in-plane exciton transport in single-crystalline layered perovskites. Using time-resolved fluorescence microscopy, we show that excitons undergo an initial fast, intrinsic normal diffusion through the crystalline plane, followed by a transition to a slower subdiffusive regime as excitons get trapped. Interestingly, the early intrinsic exciton diffusivity depends sensitively on the exact composition of the perovskite, such as the choice of organic spacer. We attribute these changes in exciton transport properties to strong exciton-phonon interactions and the formation of large exciton-polarons. Our findings provide a clear design strategy to optimize exciton transport in these systems., Comment: 22 pages, 4 figures, and supporting information

We present a theoretical study of the phase-coherent DC conductivity of few-layered antimonene in the presence of surface disorder. It is well known that while a single layer is a trivial semiconductor, multiple layers (typically a minimum of $\approx$ 7) turn into a semi-metal with a nontrivial topological invariant featuring protected and decoupled surface states. We employ the finite-size Kubo formalism based on density functional theory calculations to show that the conductivity is amply dominated by the topological surface states even without bulk disorder. More importantly, the conductivity of the surface states does not show traces of a metal-insulator transition while the bulk ones can be driven towards an insulating phase in presence of only surface disorder. These results suggest that few-layered antimonene, despite not being insulating in the bulk, can present many of the advantages attributed to topological insulators under very general experimental conditions.

We predict that long-lived excitons with very large binding energies can also exist in a single or few layers of monochalcogenides such as GaSe. Our theoretical study shows that excitons confined by a radial local strain field are unable to recombine despite of electrons and holes co-existing in space. The localized single-particle states are calculated in the envelope function approximation based on a three-band $\boldsymbol{k}\cdot \boldsymbol{p}$ Hamiltonian obtained from DFT calculations. The binding energy and the decay rate of the exciton ground state are computed after including correlations in the basis of electron-hole pairs. The interplay between the localized strain and the caldera-type valence band, characteristic of few-layered monochalcogenides, creates localized electron and hole states with very different quantum numbers which hinders the recombination even for singlet excitons., Comment: 6 pages, 4 figures

Few-layer GaSe is one of the latest additions to the family of 2D semiconducting crystals whose properties under strain are still relatively unexplored. Here, we study rippled nanosheets that exhibit a periodic compressive and tensile strain of up to 5%. The strain profile modifies the local optoelectronic properties of the alternating compressive and tensile regions, which translates into a remarkable shift of the optical absorption band-edge of up to 1.2 eV between crests and valleys. Our experimental observations are supported by theoretical results from density functional theory calculations performed for monolayers and multilayers (up to 7 layers) under tensile and compressive strain. This large band gap tunability can be explained through a combined analysis of the elastic response of Ga atoms to strain and the symmetry of the wave functions., Comment: Main text: 10 pages, 3 figures. Supp. Info: 10 pages, 7 figures

We study the magneto-optical response of noble metal nanoparticle clusters. We consider the interaction between the light-induced dipoles of particles. In the presence of a magnetic field, the simplest achiral cluster, a dimer, exhibits circular dichroism (CD). The CD of a dimer depends on the directions of the magnetic field and the light wave vector. The CD of a populous cluster weakly depends on the magnetic field. Upon scattering from the cluster, an incident linearly polarized light with polarization azimuth $\varphi$, becomes elliptically polarized. The polarization azimuth rotation and ellipticity angle variation are sinusoidal functions of $2 \varphi$. The anisotropy and the chirality of the cluster control the amplitude and offset of these sinusoidal functions. The Faraday rotation and Faraday ellipticity are also sinusoidal functions of $2 \varphi$. Near the surface plasmon frequency, Faraday rotation and Faraday ellipticity increase.