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Atomically thin materials offer multiple opportunities for layer-by-layer control of their electronic properties. While monolayer graphene (MLG) is a zero-gap system, Bernal-stacked bilayer graphene (BLG) acquires a finite band gap when the symmetry between the layers' potential energy is broken, usually, via a large electric field applied in double-gate devices. Here, we introduce an asymmetric twistronic stack comprising both MLG and BLG, synthesized via low-pressure chemical vapor deposition (LP-CVD) on Cu. Although a large ($\sim30^{\circ}$) twist angle decouples the MLG and BLG electronic bands near Fermi level, we find that the layer degeneracy in the BLG subsystem is lifted, producing a gap in the absence of external fields. The built-in interlayer asymmetry originates from proximity-induced energy shifts in the outermost layers and requires a displacement field of $0.14$ V/nm to be compensated. The latter corresponds to a $\sim10$ meV intrinsic BLG gap, a value confirmed by our thermal-activation measurements. The present results highlight the role of structural asymmetry and encapsulating environment, expanding the engineering toolbox for monolithically-grown graphene multilayers., Comment: 23 pages, 4 figures and supporting information

Semiconducting transition metal dichalcogenides (MX$_2$) occur in 2H and rhombohedral (3R) polytypes, respectively distinguished by anti-parallel and parallel orientation of consecutive monolayer lattices. In its bulk form, 3R-MX$_2$ is ferroelectric, hosting an out-of-plane electric polarisation, the direction of which is dictated by stacking. Here, we predict that twin boundaries, separating adjacent polarization domains with reversed built-in electric fields, are able to host two-dimensional electrons and holes with an areal density reaching $\sim 10^{13} {\rm cm}^{-2}$. Our modelling suggests that n-doped twin boundaries have a more promising binding energy than p-doped ones, whereas hole accumulation is stable at external surfaces of a twinned film. We also propose that assembling pairs of mono-twin films with a `magic' twist angle $\theta^*$ that provides commensurability between the moir\'e pattern at the interface and the accumulated carrier density, should promote a regime of strongly correlated states of electrons, such as Wigner crystals, and we specify the values of $\theta^*$ for homo- and heterostructures of various TMDs., Comment: 12 pages, 8 Figures

Understanding and controlling the electrical properties of solution-processed 2D materials is key to further printed electronics progress. Here we demonstrate that the thermolysis of the aromatic intercalants utilized in nanosheet exfoliation for graphene laminates opens the route to achieving high intrinsic mobility and simultaneously controlling doping type ($n$- and $p$-) and concentration over a wide range. We establish that the intra-flake mobility is high by observing a linear magnetoresistance of such solution-processed graphene laminates and using it to devolve the inter-flake tunneling and intra-layer magnetotransport. Consequently, we determine the temperature dependences of the inter- and intra-layer characteristics, which both appear to be dominated by phonon-assisted processes at temperature $T>$20 Kelvin. In particular, we identify the efficiency of phonon-assisted tunneling as the main limiting factor for electrical conductivity in graphene laminates at room temperature. We also demonstrate a thermoelectric sensitivity of around 50 ${\mu}$V K$^{-1}$ in a solution-processed metal-free graphene-based thermocouple.

Polytypes of tetralayer graphene (TLG: Bernal, rhombohedral and mixed stacking) are crystalline structures with different symmetries. Among those, mixed-stacking tetralayers lack inversion symmetry, which allows for intrinsic spontaneous out-of-plane electrical polarisation, inverted in the mirror-image pair, ABCB and ABAC stackings. Here, we compare the intrinsic polarisation of such TLGs with the symmetry-breaking effect of a substrate, which can also generate out-of-plane electric dipole moments with different sizes in all four polytypes, including ABCB and ABAC twins. We analyse their temperature and magnetic field dependence, in view of understanding the origin of the recently measured Kelvin probe force microscopy maps of tetralayer flakes, and notice that the intrinsic contribution could be singled out based on magnetic field dependence of polarisation measured at low temperatures., Comment: 11 pages, 6 figures

Ferroelectricity (Valasek, J. Phys. Rev. 1921, 17, 475) - a spontaneous formation of electric polarisation - is a solid state phenomenon, usually, associated with ionic compounds or complex materials. Here we show that, atypically for elemental solids, few-layer graphenes can host an equilibrium out-of-plane electric polarisation, switchable by sliding the constituent graphene sheets. The systems hosting such effect include mixed-stacking tetralayers and thicker (5-9 layers) rhombohedral graphitic films with a twin boundary in the middle of a flake. The predicted electric polarisation would also appear in marginally (small-angle) twisted few-layer flakes, where lattice reconstruction would give rise to networks of mesoscale domains with alternating value and sign of out-of-plane polarisation., Comment: 25 pages, 7 figures

Van der Waals assembly enables exquisite design of electronic states in two-dimensional (2D) materials, often by superimposing a long-wavelength periodic potential on a crystal lattice using moir\'e superlattices. Here we show that electronic states in three-dimensional (3D) crystals such as graphite can also be tuned by the superlattice potential arising at the interface with another crystal, namely, crystallographically aligned hexagonal boron nitride. Such alignment is found to result in a multitude of Lifshitz transitions and Brown-Zak oscillations for near-surface 2D states whereas, in high magnetic fields, fractal states of Hofstadter's butterfly extend deep into graphite's bulk. Our work shows a venue to control 3D spectra by using the approach of 2D twistronics.

We theoretically investigate 3D layered crystals of alternating graphene and hBN layers with different symmetries. Depending on the hopping parameters between the graphene layers, we find that these synthetic 3D materials can feature semimetallic, gapped, or Weyl semimetal phases. Our results demonstrate that 3D crystals stacked from individual 2D materials represent a synthetic materials class with emergent properties different from their constituents.

Massless Dirac fermions have been observed in various materials such as graphene and topological insulators in recent years, thus offering a solid-state platform to study relativistic quantum phenomena. Single quantum dots (QDs) and coupled QDs formed with massless Dirac fermions can be viewed as artificial relativistic atoms and molecules, respectively. Such structures offer a unique platform to study atomic and molecular physics in the ultra-relativistic regime. Here, we use a scanning tunneling microscope to create and probe single and coupled electrostatically defined graphene QDs to unravel the unique magnetic field responses of artificial relativistic nanostructures. Giant orbital Zeeman splitting and orbital magnetic moment are observed in single graphene QDs. While for coupled graphene QDs, Aharonov Bohm oscillations and strong Van Vleck paramagnetic shift are observed. Such properties of artificial relativistic atoms and molecules can be leveraged for novel magnetic field sensing modalities.

Topologically protected flat surface bands make thin films of rhombohedral graphite an appealing platform for searching for strongly correlated states of 2D electrons. In this work, we study rhombohedral graphite with a twin boundary stacking fault and analyse the semimetallic and topological properties of low-energy bands localised at the surfaces and at the twinned interface. We derive an effective 4-band low energy model, where we implement the full set of Slonczewski-Weiss-McClure (SWMcC) parameters, and find the conditions for the bands to be localised at the twin boundary, protected from the environment-induced disorder. This protection together with a high density of states at the charge neutrality point, in some cases -- due to a Lifshitz transition, makes this system a promising candidate for hosting strongly-correlated effects., Comment: 8 pages, 5 figures

Here we investigate how charge density waves (CDW), inherent to a monolayer, are effected by creating twisted van der Waals structures. Homobilayers of metallic transition metal dichalcogenides (TMDs), at small twist angles where there is significant atomic reconstruction, are utilised as an example to investigate the interplay between the moir\'e domain structure and CDWs of different periods. For $\sqrt{3}\times\sqrt{3}$ CDWs, there is no geometric constraint to prevent the CDWs from propagating throughout the moir\'e structure. Whereas for $2\times2$ CDWs, to ensure the CDWs in each layer have the most favourable interactions in the domains, the CDW phase must be destroyed in the connecting domain walls. For $3\times3$ CDWs with twist angles close to 180 degree, moir\'e-scale triangular structures can form; while close to 0 degree, moir\'e-scale dimer domains occur. The star-of-David CDW ($\sqrt{13}\times\sqrt{13}$) is found to host CDWs in the domains only, since there is one low energy stacking configuration, similar to $2\times2$ CDWs. These predictions are offered for experimental verification in twisted bilayer metallic TMDs which host CDWs, and we hope this will stimulate further research on the interplay between the moir\'e supperlattice and CDW phases intrinsic to the comprising 2D materials.

We report experimental investigations of transport through bilayer graphene (BLG)/chromium trihalide (CrX$_3$; X=Cl, Br, I) van der Waals interfaces. In all cases, a large charge transfer from BLG to CrX$_3$ takes place (reaching densities in excess of $10^{13}$ cm$^{-2}$), and generates an electric field perpendicular to the interface that opens a band gap in BLG. We determine the gap from the activation energy of the conductivity and find excellent agreement with the latest theory accounting for the contribution of the $\sigma$ bands to the BLG dielectric susceptibility. We further show that for BLG/CrCl$_3$ and BLG/CrBr$_3$ the band gap can be extracted from the gate voltage dependence of the low-temperature conductivity, and use this finding to refine the gap dependence on the magnetic field. Our results allow a quantitative comparison of the electronic properties of BLG with theoretical predictions and indicate that electrons occupying the CrX$_3$ conduction band are correlated.

We build a microscopic model to study the intra- and inter-layer superexchange due to electrons hopping in chromium trihalides ($\mathrm{CrX}_3$, X= Cl, Br, and I). In evaluating the superexchange, we identify the relevant intermediate excitations in the hopping. In our study, we find that the intermediate hole-pairs excitations in the $p$-orbitals on X ion play a crucial role in mediating various types of exchange interactions. In particular, the inter-layer antiferromagnetic exchange may be realized by the hole-pair-mediated superexchange. Interestingly, we also find that these virtual hopping processes compete with each other leading to weak intra-layer ferromagnetic exchange. In addition, we also study the spin-orbit coupling effects on the superexchange and investigate the Dzyaloshinskii-Moriya interaction. Finally, we extract the microscopic model parameters from density functional theory for analyzing the exchange interactions in a monolayer $\mathrm{CrI}_3$., Comment: 18 pages, 4 figures, minor corrections with more references added

Light-emitting electronic devices are ubiquitous in key areas of current technology, such as data communications, solid-state lighting, displays, and optical interconnects. Controlling the spectrum of the emitted light electrically, by simply acting on the device bias conditions, is an important goal with potential technological repercussions. However, identifying a material platform enabling broad electrical tuning of the spectrum of electroluminescent devices remains challenging. Here, we propose light-emitting field-effect transistors based on van der Waals interfaces of atomically thin semiconductors as a promising class of devices to achieve this goal. We demonstrate that large spectral changes in room-temperature electroluminescence can be controlled both at the device assembly stage -- by suitably selecting the material forming the interfaces -- and on-chip, by changing the bias to modify the device operation point. Even though the precise relation between device bias and kinetics of the radiative transitions remains to be understood, our experiments show that the physical mechanism responsible for light emission is robust, making these devices compatible with simple large areas device production methods.

Twisted heterostructures of two-dimensional crystals offer almost unlimited scope for the design of novel metamaterials. Here we demonstrate a room-temperature ferroelectric semiconductor that is assembled using mono- or few- layer MoS2. These van der Waals heterostructures feature broken inversion symmetry, which, together with the asymmetry of atomic arrangement at the interface of two 2D crystals, enables ferroelectric domains with alternating out-of-plane polarisation arranged into a twist-controlled network. The latter can be moved by applying out-of-plane electrical fields, as visualized in situ using channelling contrast electron microscopy. The interfacial charge transfer for the observed ferroelectric domains is quantified using Kelvin probe force microscopy and agrees well with theoretical calculations. The movement of domain walls and their bending rigidity also agrees well with our modelling results. Furthermore, we demonstrate proof-of-principle field-effect transistors, where the channel resistance exhibits a pronounced hysteresis governed by pinning of ferroelectric domain walls. Our results show a potential venue towards room temperature electronic and optoelectronic semiconductor devices with built-in ferroelectric memory functions., Comment: 15 pages, 3 figures

Lattice reconstruction in twisted transition-metal dichalcogenide (TMD) bilayers gives rise to piezo- and ferroelectric moir\'e potentials for electrons and holes, as well as a modulation of the hybridisation across the bilayer. Here, we develop hybrid $\mathbf{k}\cdot \mathbf{p}$ tight-binding models to describe electrons and holes in the relevant valleys of twisted TMD homobilayers with parallel (P) and anti-parallel (AP) orientations of the monolayer unit cells. We apply these models to describe moir\'e superlattice effects in twisted WSe${}_2$ bilayers, in conjunction with microscopic \emph{ab initio} calculations, and considering the influence of encapsulation, pressure and an electric displacement field. Our analysis takes into account mesoscale lattice relaxation, interlayer hybridisation, piezopotentials, and a weak ferroelectric charge transfer between the layers, and describes a multitude of possibilities offered by this system, depending on the choices of P or AP orientation, twist angle magnitude, and electron/hole valley., Comment: 44 pages, 27 figures, 6 appendices. For v2: Modelling and analysis for Q-point bands and minibands added

We use a hybrid k dot p theory - tight binding (HkpTB) model to describe interlayer coupling simultaneously in both Bernal and twisted graphene structures. For Bernal-aligned interfaces, HkpTB is parametrized using the full Slonczewski-Weiss-McClure (SWMcC) Hamiltonian of graphite, which is then used to refine the commonly used minimal model for twisted interfaces, by deriving additional terms that reflect all details of the full SWMcC model of graphite. We find that these terms introduce some electron-hole asymmetry in the band structure of twisted bilayers, but in twistronic multilayer graphene, they produce only a subtle change of moire miniband spectra, confirming the broad applicability of the minimal model for implementing the twisted interface coupling in such systems.

The tuneability and control of quantum nanostructures in two-dimensional materials offer promising perspectives for their use in future electronics. It is hence necessary to analyze quantum transport in such nanostructures. Material properties such as a complex dispersion, topology, and charge carriers with multiple degrees of freedom, are appealing for novel device functionalities but complicate their theoretical description. Here, we study quantum tunnelling transport across a few-electron bilayer graphene quantum dot. We demonstrate how to uniquely identify single- and two-electron dot states' orbital, spin, and valley composition from differential conductance in a finite magnetic field. Furthermore, we show that the transport features manifest splittings in the dot's spin and valley multiplets induced by interactions and magnetic field (the latter splittings being a consequence of bilayer graphene's Berry curvature). Our results elucidate spin- and valley-dependent tunnelling mechanisms and will help to utilize bilayer graphene quantum dots, e.g., as spin and valley qubits., Comment: 18 pages, 12 figures

Bloch states of electrons in honeycomb two-dimensional crystals with multi-valley band structure and broken inversion symmetry have orbital magnetic moments of a topological nature. In crystals with two degenerate valleys, a perpendicular magnetic field lifts the valley degeneracy via a Zeeman effect due to these magnetic moments, leading to magnetoelectric effects which can be leveraged for creating valleytronic devices. In this work, we demonstrate that trilayer graphene with Bernal stacking, (ABA TLG) hosts topological magnetic moments with a large and widely tunable valley g-factor, reaching a value 1050 at the extreme of the studied parametric range. The reported experiment consists in sublattice-resolved scanning tunneling spectroscopy under perpendicular electric and magnetic fields that control the TLG bands. The tunneling spectra agree very well with the results of theoretical modeling that includes the full details of the TLG tight-binding model and accounts for a quantum-dot-like potential profile formed electrostatically under the scanning tunneling microscope tip., Comment: Manuscript and Supporting Information updated

The functional form of Coulomb interactions in the transition metal dichalcogenides and other van der Waals solids is critical to many of their unique properties, e.g. strongly-correlated electron states, superconductivity and emergent ferromagnetism. This paper presents measurements of key excitonic energy levels in MoSe2/WSe2 heterostructures. These measurements are obtained from resonance Raman experiments on specific Raman peaks only observed at excited states of the excitons. This data is used to validate a model of the Coulomb potential in these structures which predicts the exciton energies to within ~5 meV / 2.5%. This model is used to determine the effect of heterostructure formation on the single-particle band gaps of the layers and will have a wide applicability in designing the next generation of more complex transition metal dichalcogenide structures., Comment: 19 pages, 3 figures and an additional 14 pages, 7 figures of supplimentary info. Submitted to IOP 2D Materials

We develop the theory of collective modes supported by a Fermi liquid of electrons in pristine graphene. Under reasonable assumptions regarding the electron-electron interaction, all the modes but the plasmon are over-damped. In addition to the $SU(2)$ symmetric spin mode, these include also the valley imbalance modes obeying a $U(1)$ symmetry, and a $U(2)$ symmetric valley spin imbalance mode. We derive the interactions and diffusion constants characterizing the over-damped modes. The corresponding relaxation rates set fundamental constraints on graphene valley- and spintronics applications., Comment: 7 pages + 12 pages 1 figure supplemental material

Hybridisation of electronic bands of two-dimensional materials, assembled into twistronic heterostructures, enables one to tune their optoelectronic properties by selecting conditions for resonant interlayer hybridisation. Resonant interlayer hybridisation qualitatively modifies the excitons in such heterostructures, transforming these optically active modes into superposition states of interlayer and intralayer excitons. For MoSe$_2$/WSe$_2$ heterostructures, strong hybridization occurs between the holes in the spin-split valence band of WSe$_2$ and in the top valence band of MoSe$_2$, especially when both are bound to the same electron in the lowest conduction band of WSe$_2$. Here we use resonance Raman scattering to provide direct evidence for the hybridisation of excitons in twistronic MoSe$_2$/WSe$_2$ structures, by observing scattering of specific excitons by phonons in both WSe$_2$ and MoSe$_2$. We also demonstrate that resonance Raman scattering spectroscopy opens up a wide range of possibilities for quantifying the layer composition of the superposition states of the exciton and the interlayer hybridisation parameters in heterostructures of two-dimensional materials., Comment: 32 pages, 5 figures, 8 supplementary figures, 8 supplementary tables. 2D Mater. (2021)

In two-dimensional heterostructures, crystalline atomic layers with differing lattice parameters can stack directly one on another. The resultant close proximity of atomic lattices with differing periodicity can lead to new phenomena. For umklapp processes, this opens the possibility for interlayer umklapp scattering, where interactions are mediated by the transfer of momenta to or from the lattice in the neighbouring layer. Using angle-resolved photoemission spectroscopy to study a graphene on InSe heterostructure, we present evidence that interlayer umklapp processes can cause hybridization between bands from neighbouring layers in regions of the Brillouin zone where bands from only one layer are expected, despite no evidence for moir/'e-induced replica bands. This phenomenon manifests itself as 'ghost' anti-crossings in the InSe electronic dispersion. Applied to a range of suitable 2DM pairs, this phenomenon of interlayer umklapp hybridization can be used to create strong mixing of their electronic states, giving a new tool for twist-controlled band structure engineering., Comment: Main paper: 21 pages, 4 figures. Supplementary Material: 12 pages, 7 figures

Understanding and tuning correlated states is of great interest and significance to modern condensed matter physics. The recent discovery of unconventional superconductivity and Mott-like insulating states in magic-angle twisted bilayer graphene (tBLG) presents a unique platform to study correlation phenomena, in which the Coulomb energy dominates over the quenched kinetic energy as a result of hybridized flat bands. Extending this approach to the case of twisted multilayer graphene would allow even higher control over the band structure because of the reduced symmetry of the system. Here, we study electronic transport properties in twisted trilayer graphene (tTLG, bilayer on top of monolayer graphene heterostructure). We observed the formation of van Hove singularities which are highly tunable by twist angle and displacement field and can cause strong correlation effects under optimum conditions, including superconducting states. We provide basic theoretical interpretation of the observed electronic structure., Comment: 16 pages, 9 figures

III-VI post-transition metal chalcogenides (InSe and GaSe) are a new class of layered semiconductors, which feature a strong variation of size and type of their band gaps as a function of number of layers (N). Here, we investigate exfoliated layers of InSe and GaSe ranging from bulk crystals down to monolayer, encapsulated in hexagonal boron nitride, using Raman spectroscopy. We present the N-dependence of both intralayer vibrations within each atomic layer, as well as of the interlayer shear and layer breathing modes. A linear chain model can be used to describe the evolution of the peak positions as a function of N, consistent with first principles calculations., Comment: 6 pages, 5 figures

We perform a $\mathbf{k \cdot p}$ theory analysis of the spectra of the lowest energy and excited states of the excitons in few-layer atomically thin films of InSe taking into account in-plane electric polarizability of the film and the influence of the encapsulation environment. For the thinner films, the lowest-energy state of the exciton is weakly indirect in momentum space, with its dispersion showing minima at a layer-number-dependent wave number, due to an inverted edge of a relatively flat topmost valence band branch of the InSe film spectrum and we compute the activation energy from the momentum dark exciton ground state into the bright state. For the films with more than seven In$_2$Se$_2$ layers, the exciton dispersion minimum shifts to $\Gamma$-point., Comment: 12 pages, 7 figures

Structural engineering of van der Waals heterostructures via stacking and twisting has recently been used to create moir\'e superlattices, enabling the realization of new optical and electronic properties in solid-state systems. In particular, moir\'e lattices in twisted bilayers of transition metal dichalcogenides (TMDs) have been shown to lead to exciton trapping, host Mott insulating and superconducting states, and act as unique Hubbard systems whose correlated electronic states can be detected and manipulated optically. Structurally, these twisted heterostructures also feature atomic reconstruction and domain formation. Unfortunately, due to the nanoscale sizes (~10 nm) of typical moir\'e domains, the effects of atomic reconstruction on the electronic and excitonic properties of these heterostructures could not be investigated systematically and have often been ignored. Here, we use near-0$^o$ twist angle MoSe$_2$/MoSe$_2$ bilayers with large rhombohedral AB/BA domains to directly probe excitonic properties of individual domains with far-field optics. We show that this system features broken mirror/inversion symmetry, with the AB and BA domains supporting interlayer excitons with out-of-plane (z) electric dipole moments in opposite directions. The dipole orientation of ground-state $\Gamma$-K interlayer excitons (X$_{I,1}$) can be flipped with electric fields, while higher-energy K-K interlayer excitons (X$_{I,2}$) undergo field-asymmetric hybridization with intralayer K-K excitons (X$_0$). Our study reveals the profound impacts of crystal symmetry on TMD excitons and points to new avenues for realizing topologically nontrivial systems, exotic metasurfaces, collective excitonic phases, and quantum emitter arrays via domain-pattern engineering., Comment: 29 pages, 4 figures in main text, 6 figures in supplementary information

When two-dimensional atomic crystals are brought into close proximity to form a van der Waals heterostructure, neighbouring crystals can start influencing each others electronic properties. Of particular interest is the situation when the periodicity of the two crystals closely match and a moir\'e pattern forms, which results in specific electron scattering, reconstruction of electronic and excitonic spectra, crystal reconstruction, and many other effects. Thus, formation of moir\'e patterns is a viable tool of controlling the electronic properties of 2D materials. At the same time, the difference in the interatomic distances for the two crystals combined, determines the range in which the electronic spectrum is reconstructed, and thus is a barrier to the low energy regime. Here we present a way which allows spectrum reconstruction at all energies. By using graphene which is aligned simultaneously to two hexagonal boron nitride layers, one can make electrons scatter in the differential moir\'e pattern, which can have arbitrarily small wavevector and, thus results in spectrum reconstruction at arbitrarily low energies. We demonstrate that the strength of such a potential relies crucially on the atomic reconstruction of graphene within the differential moir\'e super-cell. Such structures offer further opportunity in tuning the electronic spectra of two-dimensional materials., Comment: 35 pages, 15 figures

Van der Waals (vdW) materials offer new ways to assemble artificial electronic media with properties controlled at the design stage, by combining atomically defined layers into interfaces and heterostructures. Their potential for optoelectronics stems from the possibility to tailor the spectral response over a broad range by exploiting interlayer transitions between different compounds with an appropriate band-edge alignment. For the interlayer transitions to be radiative, however, a serious challenge comes from details of the materials --such as lattice mismatch or even a small misalignment of the constituent layers-- that can drastically suppress the electron-photon coupling. The problem was evidenced in recent studies of heterostructures of monolayer transition metal dichalcogenides, whose band edges are located at the K-point of reciprocal space. Here we demonstrate experimentally that the solution to the interlayer coupling problem is to engineer type-II interfaces by assembling atomically thin crystals that have the bottom of the conduction band and the top of the valence band at the $\Gamma$-point, thus avoiding any momentum mismatch. We find that this type of vdW interfaces exhibits radiative optical transition irrespective of lattice constant, rotational/translational alignment of the two layers, or whether the constituent materials are direct or indirect gap semiconductors. The result, which is robust and of general validity, drastically broadens the scope of future optoelectronics device applications based on 2D materials.

We describe how the out-of-plane dielectric polarizability of monolayer graphene influences the electrostatics of bilayer graphene -- both Bernal (BLG) and twisted (tBLG). We compare the polarizability value computed using density functional theory with the output from previously published experimental data on the electrostatically controlled interlayer asymmetry potential in BLG and data on the on-layer density distribution in tBLG. We show that monolayers in tBLG are described well by polarizability $\alpha_{exp} = 10.8 \unicode{x212B}^3$ and effective out-of-plane dielectric susceptibility $\epsilon_z = 2.5$, including their on-layer electron density distribution at zero magnetic field and the inter-layer Landau level pinning at quantizing magnetic fields., Comment: 4 pages

Van der Waals heterostructures form a massive interdisciplinary research field, fueled by the rich material science opportunities presented by layer assembly of artificial solids with controlled composition, order and relative rotation of adjacent atomic planes. Here we use atomic resolution transmission electron microscopy and multiscale modeling to show that the lattice of MoS$_2$ and WS$_2$ bilayers twisted to a small angle, $\theta<3^{\circ}$, reconstructs into energetically favorable stacking domains separated by a network of stacking faults. For crystal alignments close to 3R stacking, a tessellated pattern of mirror reflected triangular 3R domains emerges, separated by a network of partial dislocations which persist to the smallest twist angles. Scanning tunneling measurements show that the electronic properties of those 3R domains appear qualitatively different from 2H TMDs, featuring layer-polarized conduction band states caused by lack of both inversion and mirror symmetry. In contrast, for alignments close to 2H stacking, stable 2H domains dominate, with nuclei of an earlier unnoticed metastable phase limited to $\sim$ 5nm in size. This appears as a kagome-like pattern at $\theta\sim 1^{\circ}$, transitioning at $\theta\rightarrow 0$ to a hexagonal array of screw dislocations separating large-area 2H domains.

Of the two stable forms of graphite, hexagonal (HG) and rhombohedral (RG), the former is more common and has been studied extensively. RG is less stable, which so far precluded its detailed investigation, despite many theoretical predictions about the abundance of exotic interaction-induced physics. Advances in van der Waals heterostructure technology have now allowed us to make high-quality RG films up to 50 graphene layers thick and study their transport properties. We find that the bulk electronic states in such RG are gapped and, at low temperatures, electron transport is dominated by surface states. Because of topological protection, the surface states are robust and of high quality, allowing the observation of the quantum Hall effect, where RG exhibits phase transitions between gapless semimetallic phase and gapped quantum spin Hall phase with giant Berry curvature. An energy gap can also be opened in the surface states by breaking their inversion symmetry via applying a perpendicular electric field. Moreover, in RG films thinner than 4 nm, a gap is present even without an external electric field. This spontaneous gap opening shows pronounced hysteresis and other signatures characteristic of electronic phase separation, which we attribute to emergence of strongly-correlated electronic surface states., Comment: 18 pages, 12 figures

Control over the electronic spectrum at low energy is at the heart of the functioning of modern advanced electronics: high electron mobility transistors, semiconductor and Capasso terahertz lasers, and many others. Most of those devices rely on the meticulous engineering of the size quantization of electrons in quantum wells. This avenue, however, hasn't been explored in the case of 2D materials. Here we transfer this concept onto the van der Waals heterostructures which utilize few-layers films of InSe as quantum wells. The precise control over the energy of the subbands and their uniformity guarantees extremely high quality of the electronic transport in such systems. Using novel tunnelling and light emitting devices, for the first time we reveal the full subbands structure by studying resonance features in the tunnelling current, photoabsorption and light emission. In the future, these systems will allow development of elementary blocks for atomically thin infrared and THz light sources based on intersubband optical transitions in few-layer films of van der Waals materials., Comment: 12 pages, 3 figures

Topologically non-trivial states characterized by Berry curvature appear in a number of materials ranging from spin-orbit-coupling driven topological insulators to graphene. In multivalley conductors, such as mono- and bilayer graphene, despite a zero total Chern number for the entire Brillouin zone, Berry curvature with different signs concentrated in different valleys can affect the observable material's transport characteristics. Here we consider thin films of rhombohedral graphite, which appear to retain truly two-dimensional properties up to tens of layers of thickness and host two-dimensional electron states with a large Berry curvature, accompanied by a giant intrinsic magnetic moment carried by electrons. The size of Berry curvature and magnetization in the vicinity of each valley can be controlled by electrostatic gating leading to a tuneable anomalous Hall effect and a peculiar structure of the two-dimensional Landau level spectrum., Comment: 24 pages, 7 figures

Due to their unique two-dimensional nature, charge carriers in semiconducting transition metal dichalcogenides (TMDs) exhibit strong unscreened Coulomb interactions and sensitivity to defects and impurities. The versatility of van der Waals layer stacking allows spatially separating electrons and holes between different TMD layers with staggered band structure, yielding interlayer few-body excitonic complexes whose nature is still debated. Here we combine quantum Monte Carlo calculations with spectrally and temporally resolved photoluminescence measurements on a top- and bottom-gated MoSe2/WSe2 heterostructure, and identify the emitters as impurity-bound interlayer excitonic complexes. Using independent electrostatic control of doping and out-of-plane electric field, we demonstrate control of the relative populations of neutral and charged complexes, their emission energies on a scale larger than their linewidth, and an increase of their lifetime into the microsecond regime. This work unveils new physics of confined carriers and is key to the development of novel optoelectronics applications.

Atomically-thin layers of two-dimensional materials can be assembled in vertical stacks held together by relatively weak van der Waals forces, allowing for coupling between monolayer crystals with incommensurate lattices and arbitrary mutual rotation. A profound consequence of using these degrees of freedom is the emergence of an overarching periodicity in the local atomic registry of the constituent crystal structures, known as a moir\'e superlattice. Its presence in graphene/hexagonal boron nitride (hBN) structures led to the observation of electronic minibands, whereas its effect enhanced by interlayer resonant conditions in twisted graphene bilayers culminated in the observation of the superconductor-insulator transition at magic twist angles. Here, we demonstrate that, in semiconducting heterostructures built of incommensurate MoSe2 and WS2 monolayers, excitonic bands can hybridise, resulting in the resonant enhancement of the moir\'e superlattice effects. MoSe2 and WS2 are specifically chosen for the near degeneracy of their conduction band edges to promote the hybridisation of intra- and interlayer excitons, which manifests itself through a pronounced exciton energy shift as a periodic function of the interlayer rotation angle. This occurs as hybridised excitons (hX) are formed by holes residing in MoSe2 bound to a twist-dependent superposition of electron states in the adjacent monolayers. For heterostructures with almost aligned pairs of monolayer crystals, resonant mixing of the electron states leads to pronounced effects of the heterostructure's geometrical moir\'e pattern on the hX dispersion and optical spectrum. Our findings underpin novel strategies for band-structure engineering in semiconductor devices based on van der Waals heterostructures., Comment: 43 pages, 14 figures, includes supplementary information

We demonstrate that, at the onset of conduction, an electrostatically defined quantum wire in bilayer graphene (BLG) with an interlayer asymmetry gap may act as a 1D semimetal, due to the multiple minivalley dispersion of its lowest subband. Formation of a non-monotonic subband coincides with a near-degeneracy between the bottom edges of the lowest two subbands in the wire spectrum, suggesting an $8e^2/h$ step at the conduction threshold, and the semimetallic behaviour of the lowest subband in the wire would be manifest as resonance transmission peaks on an $8e^2/h$ conductance plateau., Comment: 9 pages, 8 figures (including appendices)

Atomically thin films of III-VI post-transition metal chalcogenides (InSe and GaSe) form an interesting class of two-dimensional semiconductor that feature strong variations of their band gap as a function of the number of layers in the crystal [1-4] and, specifically for InSe, an earlier predicted crossover from a direct gap in the bulk [5,6] to a weakly indirect band gap in monolayers and bilayers [7-11]. Here, we apply angle resolved photoemission spectroscopy with submicrometer spatial resolution ($\mu$ARPES) to visualise the layer-dependent valence band structure of mechanically exfoliated crystals of InSe. We show that for 1 layer and 2 layer InSe the valence band maxima are away from the $\mathbf{\Gamma}$-point, forming an indirect gap, with the conduction band edge known to be at the $\mathbf{\Gamma}$-point. In contrast, for six or more layers the bandgap becomes direct, in good agreement with theoretical predictions. The high-quality monolayer and bilayer samples enables us to resolve, in the photoluminescence spectra, the band-edge exciton (A) from the exciton (B) involving holes in a pair of deeper valence bands, degenerate at $\mathbf{\Gamma}$, with the splitting that agrees with both $\mu$ARPES data and the results of DFT modelling. Due to the difference in symmetry between these two valence bands, light emitted by the A-exciton should be predominantly polarised perpendicular to the plane of the two-dimensional crystal, which we have verified for few-layer InSe crystals.

Two-dimensional semiconductors - atomic layers of materials with covalent intra-layer bonding and weak (van der Waals or quadrupole) coupling between the layers - are a new class of materials with great potential for optoelectronic applications. Among those, a special position is now being taken by post-transition metal chalcogenides (PTMC), InSe and GaSe. It has recently been found that the band gap in 2D crystals of InSe more than doubles in the monolayer compared to thick multilayer crystals, while the high mobility of conduction band electrons is promoted by their light in-plane mass. Here, we use Raman and PL measurements of encapsulated few layer samples, coupled with accurate atomic force and transmission electron microscope structural characterisation to reveal new optical properties of atomically thin GaSe preserved by hBN encapsulation. The band gaps we observe complement the spectral range provided by InSe films, so that optical activity of these two almost lattice-matched PTMC films and their heterostructures densely cover the spectrum of photons from violet to infrared. We demonstrate the realisation of the latter by the first observation of interlayer excitonic photoluminescence in few-layer InSe-GaSe heterostructures. The spatially indirect transition is direct in k-space and therefore is bright, while its energy can be tuned in a broad range by the number of layers., Comment: 8 pages 4 figures

Geometrical moir\'e patterns, generic for almost aligned bilayers of two-dimensional (2D) crystals with similar lattice structure but slightly different lattice constants, lead to zone folding and miniband formation for electronic states. Here, we show that moir\'e superlattice (mSL) effects in $\mathrm{MoSe}_2/\mathrm{WS}_2$ and $\mathrm{MoTe}_2/\mathrm{MoSe}_2$ heterobilayers that feature alignment of the band edges are enhanced by resonant interlayer hybridization, and anticipate similar features in twisted homobilayers of TMDs, including examples of narrow minibands close to the actual band edges. Such hybridization determines the optical activity of interlayer excitons in transition-metal dichalcogenide (TMD) heterostructures, as well as energy shifts in the exciton spectrum. We show that the resonantly hybridized exciton (hX) energy should display a sharp modulation as a function of the interlayer twist angle, accompanied by additional spectral features caused by umklapp electron-photon interactions with the mSL. We analyze the appearance of resonantly enhanced mSL features in absorption and emission of light by the interlayer exciton hybridization with both intralayer A and B excitons in $\mathrm{MoSe}_2/\mathrm{WS}_2$, $\mathrm{MoTe}_2/\mathrm{MoSe}_2$, $\mathrm{MoSe}_2/\mathrm{MoS}_2$, $\mathrm{WS}_2/\mathrm{MoS}_2$, and $\mathrm{WSe}_2/\mathrm{MoSe}_2$., Comment: Final published version, with updated title and abstract, minor corrections to equations, and 4 new figures added

We present measurements of quantized conductance in electrostatically induced quantum point contacts in bilayer graphene. The application of a perpendicular magnetic field leads to an intricate pattern of lifted and restored degeneracies with increasing field: at zero magnetic field the degeneracy of quantized one-dimensional subbands is four, because of a twofold spin and a twofold valley degeneracy. By switching on the magnetic field, the valley degeneracy is lifted. Due to the Berry curvature states from different valleys split linearly in magnetic field. In the quantum Hall regime fourfold degenerate conductance plateaus reemerge. During the adiabatic transition to the quantum Hall regime, levels from one valley shift by two in quantum number with respect to the other valley, forming an interweaving pattern that can be reproduced by numerical calculations.

We present a density functional theory parametrized hybrid k$\cdot$p tight binding model for electronic properties of atomically thin films of transition-metal dichalcogenides, 2H-$MX_2$ ($M$=Mo, W; $X$=S, Se). We use this model to analyze intersubband transitions in $p$- and $n$-doped $2{\rm H}-MX_2$ films and predict the line shapes of the intersubband excitations, determined by the subband-dependent two-dimensional electron and hole masses, as well as excitation lifetimes due to emission and absorption of optical phonons. We find that the intersubband spectra of atomically thin films of the 2H-${MX_2}$ family with thicknesses of $N=2$ to $7$ layers densely cover the infrared spectral range of wavelengths between $2$ and $30\ {\rm \mu m}$. The detailed analysis presented in this paper shows that for thin $n$-doped films, the electronic dispersion and spin-valley degeneracy of the lowest-energy subbands oscillate between odd and even number of layers, which may also offer interesting opportunities for quantum Hall effect studies in these systems., Comment: 20 pages, including 17 figures and 5 appendices

The chirality of electronic Bloch bands is responsible for many intriguing properties of layered two-dimensional materials. We show that in bilayers of transition metal dichalcogenides (TMDCs), unlike in few-layer graphene and monolayer TMDCs, both intra-layer and inter-layer couplings give important contributions to the Berry-curvature in the $K$ and $-K$ valleys of the Brillouin zone. The inter-layer contribution leads to the stacking dependence of the Berry curvature and we point out the differences between the commonly available 3R type and 2H type bilayers. Due to the inter-layer contribution the Berry curvature becomes highly tunable in double gated devices. We study the dependence of the valley Hall and spin Hall effects on the stacking type and external electric field. Although the valley and spin Hall conductivities are not quantized, in MoS$_2$ 2H bilayers they may change sign as a function of the external electric field which is reminiscent of the behaviour of lattice Chern insulators., Comment: 19 pages, 6 figures

We present theoretical results for the radiative rates and doping-dependent photoluminescence spectrum of interlayer excitonic complexes localized by donor impurities in MoSe$_2$/WSe$_2$ twisted heterobilayers, supported by quantum Monte Carlo calculations of binding energies and wave-function overlap integrals. For closely aligned layers, radiative decay is made possible by the momentum spread of the localized complexes' wave functions, resulting in few $\mu$s$^{-1}$ radiative rates. For strongly misaligned layers, the short-range interaction between the carriers and impurity provides a finite radiative rate with a strong asymptotic twist angle dependence $\propto \theta^{-8}$. Finally, phonon-assisted recombination is considered, with emission of optical phonons in both layers resulting in additional weaker emission lines, redshifted by the phonon energy., Comment: 19 pages, including 11 figures and 5 appendices

We propose atomic films of n-doped $\gamma$-InSe as a platform for intersubband optics in the infrared (IR) and far infrared (FIR) range, coupled to out-of-plane polarized light. Depending on the film thickness (number of layers) of the InSe film these transitions span from $\sim 0.7$ eV for bilayer to $\sim 0.05$ eV for 15-layer InSe. We use a hybrid $\mathbf{k} \cdot \mathbf{p}$ theory and tight-binding model, fully parametrized using density functional theory, to predict their oscillator strengths and thermal linewidths at room temperature.

We determine conditions for the formation of compressible stripes near the quantum Hall effect (QHE) edges of top-gated epitaxial graphene on Si-terminated SiC (G/SiC) and compare those to graphene exfoliated onto insulating substrate in the field-effect-transistor (GraFET) geometry. For G/SiC, a large density of localised surface states on SiC just underneath graphene layer and charge transfer between them lead both to doping of graphene and to screening of potential profile near its edge. This suppresses formation of compressible stripes near QHE edges in graphene, making them much narrower than the corresponding compressible stripes in GraFETs., Comment: 6 pages, version accepted to PRB but with reduced resolution of spectrum figures