The ability to directly observe electronic band structure in modern nanoscale field-effect devices could transform understanding of their physics and function. One could, for example, visualize local changes in the electrical and chemical potentials as a gate voltage is applied. One could also study intriguing physical phenomena such as electrically induced topological transitions and many-body spectral reconstructions. Here we show that submicron angle-resolved photoemission (-ARPES) applied to two-dimensional (2D) van der Waals heterostructures affords this ability. In graphene devices, we observe a shift of the chemical potential by 0.6 eV across the Dirac point as a gate voltage is applied. In several 2D semiconductors we see the conduction band edge appear as electrons accumulate, establishing its energy and momentum, and observe significant band-gap renormalization at low densities. We also show that -ARPES and optical spectroscopy can be applied to a single device, allowing rigorous study of the relationship between gate-controlled electronic and excitonic properties.Angle resolved photoemission spectroscopy (ARPES), in which the energy and momentum of photoemitted electrons are measured from a sample subjected to a spectrally narrow ultraviolet or X-ray excitation, is a powerful technique that yields the momentum-dependent single-electron band structure and chemical potential in a solid with essentially no assumptions. It probes only electron states near the surface, and so cannot be applied to conventional semiconductor devices. It is, however, very effective when applied to 2D materials and has been used extensively to study the bands in graphene 1 , monolayer transition metal dichalcogenides 2-7 , and others 8,9 . Furthermore, µ-ARPES (with a micron-scale beam spot) can be performed 10 on 2D heterostructures (2DHSs) 11 made of stacked exfoliated 2D materials 12-14 , suggesting the possibility of monitoring electronic structure during actual device operation. We demonstrate here that momentum-resolved electronic spectra can indeed be obtained during reversible electrostatic gating, enabling direct visualization of chemical potential shifts and band structure changes controlled by the gate electric field.A limitation of ARPES is that it probes only occupied electron states, and so a semiconductor must first be electron-doped in order to obtain a signal from the conduction band. The usual approach is to deposit alkali metal atoms 1-7,15 which act as an n-type dopant, but this has several limitations: the density cannot be controlled accurately; it can only be reversed by high-temperature annealing; it introduces disorder through the random positions of the dopants; and it chemically perturbs the electronic structure in ways that are hard to calculate. Electrostatic doping has none of these disadvantages, and the accessible carrier densities are most relevant to practical devices.We first validate our technique using graphene, and then go on to apply it to the 2D transition metal dichalcogenide (TMD) sem...

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 1 arXiv:1901.06943v1 [cond-mat.mtrl-sci] 21 Jan 2019 weakly indirect band gap in monolayers and bilayers. 7-11 Here, we apply angle resolved photoemission spectroscopy with submicrometer spatial resolution (µARPES) 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 Γ-point, forming an indirect gap, with the conduction band edge known to be at the Γ-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 Γ, with the splitting that agrees with both µARPES 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. KeywordsARPES, indium selenide, 2D materials, density functional theory, photoluminescence, spinorbit coupling Two-dimensional materials (2DM) and their van der Waals heterostructures, constructed by the mechanical assembly of individual 2D crystals, have a great potential for optoelectronic applications. 12 The fast growing family of 2DM 13 includes 2D insulators, 2D semiconductors with various band gaps, 2D metals and even 2D superconductors, with electronic and optical properties that often differ from their bulk allotropes. 14 In this family, post-transition metal monochalcogenides (PTMC), III-VI compounds such as GaSe and InSe, are emerging as important materials to study, due to their interesting layer-dependent optical properties and exceptionally high carrier mobility. [1][2][3][4]8,15,16 Both GaSe and InSe display a pronounced quantum confinement effect: an increase of the band gap upon decreasing the number of layers, L, which is stronger in InSe 3,11 than in GaSe 17 films as revealed recently by photolu-

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 Moiré-induced replica bands. This phenomenon manifests itself as ‘ghost’ anti-crossings in the InSe electronic dispersion. Applied to a range of suitable two-dimensional material 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.

Alloying enables engineering of the electronic structure of semiconductors for optoelectronic applications. Due to their similar lattice parameters, the two-dimensional semiconducting transition metal dichalcogenides of the MoWSeS group (MX2 where M = Mo or W and X = S or Se) can be grown as high-quality materials with low defect concentrations. Here we investigate the atomic and electronic structure of Mo(1−x)W x S2 alloys using a combination of high-resolution experimental techniques and simulations. Analysis of the Mo and W atomic positions in these alloys, grown by chemical vapour transport, shows that they are randomly distributed, consistent with Monte Carlo simulations that use interaction energies determined from first-principles calculations. Electronic structure parameters are directly determined from angle resolved photoemission spectroscopy measurements. These show that the spin–orbit splitting at the valence band edge increases linearly with W content from MoS2 to WS2, in agreement with linear-scaling density functional theory predictions. The spin–orbit splitting at the conduction band edge is predicted to reduce to zero at intermediate compositions. Despite this, polarisation-resolved photoluminescence spectra on monolayer Mo0.5W0.5S2 show significant circular dichroism, indicating that spin-valley locking is retained. These results demonstrate that alloying is an important tool for controlling the electronic structure of MX2 for spintronic and valleytronic applications.