For two-dimensional (2D) layered semiconductors, control over atomic defects and understanding of their electronic and optical functionality represent major challenges towards developing a mature semiconductor technology using such materials. Here, we correlate generation, optical spectroscopy, atomic resolution imaging, and ab initio theory of chalcogen vacancies in monolayer MoS2. Chalcogen vacancies are selectively generated by in-vacuo annealing, but also focused ion beam exposure. The defect generation rate, atomic imaging and the optical signatures support this claim. We discriminate the narrow linewidth photoluminescence signatures of vacancies, resulting predominantly from localized defect orbitals, from broad luminescence features in the same spectral range, resulting from adsorbates. Vacancies can be patterned with a precision below 10 nm by ion beams, show single photon emission, and open the possibility for advanced defect engineering of 2D semiconductors at the ultimate scale.

Atomistic van derWaals heterostacks are ideal systems for high-temperature exciton condensation because of large exciton binding energies and long lifetimes. Charge transport and electron energy-loss spectroscopy showed first evidence of excitonic many-body states in such two-dimensional materials. Pure optical studies, the most obvious way to access the phase diagram of photogenerated excitons have been elusive. We observe several criticalities in photogenerated exciton ensembles hosted in MoSe2-WSe2 heterostacks with respect to photoluminescence intensity, linewidth, and temporal coherence pointing towards the transition to a coherent quantum state. For this state, the occupation is 100% and the exciton diffusion length is increased. The phenomena survive above 10 kelvin, consistent with the predicted critical condensation temperature. Our study provides a first phase-diagram of manybody interlayer exciton states including Bose Einstein condensation.

Valley selective hybridization and residual coupling of electronic states in commensurate van der Waals heterobilayers enable the control of the orbital character of interlayer excitons. We demonstrate electric field control of layer index, orbital character, lifetime and emission energy of indirect excitons in MoS2/WS2 heterobilayers embedded in an vdW field effect structure. Different excitonic dipoles normal to the layers are found to stem from bound electrons and holes located in different valleys of MoS2/WS2 with a valley selective degree of hybridization. For the energetically lowest emission lines, coupling of electronic states causes a field-dependent level anticrossing that goes along with a change of the IX lifetime from 400 ns to 100 ns. In the hybridized regime the exiton is delocalized between the two constituent layers, whereas for large positive or negative electric fields, the layer index of the bound hole is field-dependent. Our results demonstrate the design of novel van der Waals solids with the possibility to in-situ control their physical properties via external stimuli such as electric fields.

Substrate, environment, and lattice imperfections have a strong impact on the local electronic structure and the optical properties of atomically thin transition metal dichalcogenides. We find by a comparative study of MoS2 on SiO2 and hexagonal boron nitride (hBN) using scanning tunneling spectroscopy (STS) measurements that the apparent bandgap of MoS2 on SiO2 is significantly reduced compared to MoS2 on hBN. The bandgap energies as well as the exciton binding energies determined from all-optical measurements are very similar for MoS2 on SiO2 and hBN. This discrepancy is found to be caused by a substantial amount of band tail states near the conduction band edge of MoS2 supported by SiO2. The presence of those states impacts the local density of states in STS measurements and can be linked to a broad red-shifted photoluminescence peak and a higher charge carrier density that are all strongly diminished or even absent using high quality hBN substrates. By taking into account the substrate effects, we obtain a quasiparticle gap that is in excellent agreement with optical absorbance spectra and we deduce an exciton binding energy of about 0.53 eV on SiO2 and 0.44 eV on hBN.

AbstractThis review aims to provide an overview over recent developments of light-driven currents with a focus on their application to layered van der Waals materials. In topological and spin-orbit dominated van der Waals materials helicity-driven and light-field-driven currents are relevant for nanophotonic applications from ultrafast detectors to on-chip current generators. The photon helicity allows addressing chiral and non-trivial surface states in topological systems, but also the valley degree of freedom in two-dimensional van der Waals materials. The underlying spin-orbit interactions break the spatiotemporal electrodynamic symmetries, such that directed currents can emerge after an ultrafast laser excitation. Equally, the light-field of few-cycle optical pulses can coherently drive the transport of charge carriers with sub-cycle precision by generating strong and directed electric fields on the atomic scale. Ultrafast light-driven currents may open up novel perspectives at the interface between photonics and ultrafast electronics.

Using Hall photovoltage measurements, we demonstrate that a linear transverse Hall-voltage can be induced in few layer WTe2 under circularly polarized light illumination. By applying a bias voltage along different crystal axes, we find that the photon-helicity induced Hall effect coincides with a particular crystal axis. Our results are consistent with the underlying Berry-curvature exhibiting a dipolar distribution due to the breaking of crystal inversion symmetry. Using a time-resolved optoelectronic auto-correlation spectroscopy, we find that the decay time of the detected Hall voltage exceeds the electron-phonon scattering time by orders of magnitude but is consistent with the comparatively long spin-lifetime of carriers in the momentum-indirect electron and hole pockets in WTe2. Our observation suggests, that a helicity induced non-equilibrium spin density on the Fermi surface after the initial charge carrier relaxation gives rise to a linear Hall effect.

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Integration of semiconducting transition metal dichalcogenides (TMDs) into functional optoelectronic circuitries requires an understanding of the charge transfer across the interface between the TMD and the contacting material. Here, we use spatially resolved photocurrent microscopy to demonstrate electronic uniformity at the epitaxial graphene/molybdenum disulfide (EG/MoS2) interface. A 10 larger photocurrent is extracted at the EG/MoS2 interface when compared to metal (Ti/Au) /MoS2 interface. This is supported by semi-local density-functional theory (DFT), which predicts the Schottky barrier at the EG/MoS2 interface to be ~2 lower than Ti/MoS2. We provide a direct visualization of a 2D material Schottky barrier through combination of angle resolved photoemission spectroscopy with spatial resolution selected to be ~300 nm (nano-ARPES) and DFT calculations. A bending of ~500 meV over a length scale of ~2-3 µm in the valence band maximum of MoS2 is observed via nano-ARPES. We explicate a correlation between experimental demonstration and theoretical predictions of barriers at graphene/TMD interfaces. Spatially resolved photocurrent mapping allows for directly visualizing the uniformity of built-in electric fields at heterostructure interfaces, providing a guide for microscopic engineering of charge transport across heterointerfaces. This simple probe-based technique also speaks directly to the 2D synthesis community to elucidate electronic uniformity at domain boundaries alongside morphological uniformity over large areas.