Electroluminescent vertical tunneling junctions based on WSe2 monolayer quantum emitter arrays: Exploring tunability with electric and magnetic fields.

We experimentally demonstrate the creation of defects in monolayer WSe2 via nanopillar imprinting and helium ion irradiation. Based on the first method, we realize atomically thin vertical tunneling light-emitting diodes based on WSe2 monolayers hosting quantum emitters at deterministically specified locations. We characterize these emitters by investigating the evolution of their emission spectra in external electric and magnetic fields, as well as by inducing electroluminescence at low temperatures. We identify qualitatively different types of quantum emitters and classify them according to the dominant electron-hole recombination paths, determined by the mechanisms of intervalley mixing occurring in fundamental conduction and/or valence subbands.

Resonant Band Hybridization in Alloyed Transition Metal Dichalcogenide Heterobilayers.

Bandstructure engineering using alloying is widely utilized for achieving optimized performance in modern semiconductor devices. While alloying has been studied in monolayer transition metal dichalcogenides, its application in van der Waals heterostructures built from atomically thin layers is largely unexplored. Here, heterobilayers made from monolayers of WSe2 (or MoSe2) and MoxW1 - xSe2 alloy are fabricated and nontrivial tuning of the resultant bandstructure is observed as a function of concentration x. This evolution is monitored by measuring the energy of photoluminescence (PL) of the interlayer exciton (IX) composed of an electron and hole residing in different monolayers. In MoxW1 - xSe2/WSe2, a strong IX energy shift of ≈100 meV is observed for x varied from 1 to 0.6. However, for x < 0.6 this shift saturates and the IX PL energy asymptotically approaches that of the indirect bandgap in bilayer WSe2. This observation is theoretically interpreted as the strong variation of the conduction band K valley for x > 0.6, with IX PL arising from the K - K transition, while for x < 0.6, the bandstructure hybridization becomes prevalent leading to the dominating momentum-indirect K - Q transition. This bandstructure hybridization is accompanied with strong modification of IX PL dynamics and nonlinear exciton properties. This work provides foundation for bandstructure engineering in van der Waals heterostructures highlighting the importance of hybridization effects and opening a way to devices with accurately tailored electronic properties.

Emergence of Highly Linearly Polarized Interlayer Exciton Emission in MoSe2/WSe2 Heterobilayers with Transfer-Induced Layer Corrugation.

The availability of accessible fabrication methods based on deterministic transfer of atomically thin crystals has been essential for the rapid expansion of research into van der Waals heterostructures. An inherent issue of these techniques is the deformation of the polymer carrier film during the transfer, which can lead to highly nonuniform strain induced in the transferred two-dimensional material. Here, using a combination of optical spectroscopy, atomic force, and Kelvin probe force microscopy, we show that the presence of nanometer scale wrinkles formed due to transfer-induced stress relaxation can lead to strong changes in the optical properties of MoSe2/WSe2 heterostructures and the emergence of linearly polarized interlayer exciton photoluminescence. We attribute these changes to local breaking of crystal symmetry in the nanowrinkles, which act as efficient accumulation centers for interlayer excitons due to the strain-induced interlayer band gap reduction. Surface potential images of the rippled heterobilayer samples acquired using Kelvin probe force microscopy reveal variations of the local work function consistent with strain-induced band gap modulation, while the potential offset observed at the ridges of the wrinkles shows a clear correlation with the value of the tensile strain estimated from the wrinkle geometry. Our findings highlight the important role of the residual strain in defining optical properties of van der Waals heterostructures and suggest effective approaches for interlayer exciton manipulation by local strain engineering.

Moiré-Modulated Conductance of Hexagonal Boron Nitride Tunnel Barriers.

Monolayer hexagonal boron nitride (hBN) tunnel barriers investigated using conductive atomic force microscopy reveal moiré patterns in the spatial maps of their tunnel conductance consistent with the formation of a moiré superlattice between the hBN and an underlying highly ordered pyrolytic graphite (HOPG) substrate. This variation is attributed to a periodc modulation of the local density of states and occurs for both exfoliated hBN barriers and epitaxially grown layers. The epitaxial barriers also exhibit enhanced conductance at localized subnanometer regions which are attributed to exposure of the substrate to a nitrogen plasma source during the high temperature growth process. Our results show clearly a spatial periodicity of tunnel current due to the formation of a moiré superlattice and we argue that this can provide a mechanism for elastic scattering of charge carriers for similar interfaces embedded in graphene/hBN resonant tunnel diodes.

Observing Imperfection in Atomic Interfaces for van der Waals Heterostructures.

Vertically stacked van der Waals heterostructures are a lucrative platform for exploring the rich electronic and optoelectronic phenomena in two-dimensional materials. Their performance will be strongly affected by impurities and defects at the interfaces. Here we present the first systematic study of interfaces in van der Waals heterostructure using cross-sectional scanning transmission electron microscope (STEM) imaging. By measuring interlayer separations and comparing these to density functional theory (DFT) calculations we find that pristine interfaces exist between hBN and MoS2 or WS2 for stacks prepared by mechanical exfoliation in air. However, for two technologically important transition metal dichalcogenide (TMDC) systems, MoSe2 and WSe2, our measurement of interlayer separations provide the first evidence for impurity species being trapped at buried interfaces with hBN interfaces that are flat at the nanometer length scale. While decreasing the thickness of encapsulated WSe2 from bulk to monolayer we see a systematic increase in the interlayer separation. We attribute these differences to the thinnest TMDC flakes being flexible and hence able to deform mechanically around a sparse population of protruding interfacial impurities. We show that the air sensitive two-dimensional (2D) crystal NbSe2 can be fabricated into heterostructures with pristine interfaces by processing in an inert-gas environment. Finally we find that adopting glovebox transfer significantly improves the quality of interfaces for WSe2 compared to processing in air.

Exfoliation of natural van der Waals heterostructures to a single unit cell thickness.

Weak interlayer interactions in van der Waals crystals facilitate their mechanical exfoliation to monolayer and few-layer two-dimensional materials, which often exhibit striking physical phenomena absent in their bulk form. Here we utilize mechanical exfoliation to produce a two-dimensional form of a mineral franckeite and show that the phase segregation of chemical species into discrete layers at the sub-nanometre scale facilitates franckeite's layered structure and basal cleavage down to a single unit cell thickness. This behaviour is likely to be common in a wider family of complex minerals and could be exploited for a single-step synthesis of van der Waals heterostructures, as an alternative to artificial stacking of individual two-dimensional crystals. We demonstrate p-type electrical conductivity and remarkable electrochemical properties of the exfoliated crystals, showing promise for a range of applications, and use the density functional theory calculations of franckeite's electronic band structure to rationalize the experimental results.

Sub-bandgap Voltage Electroluminescence and Magneto-oscillations in a WSe2 Light-Emitting van der Waals Heterostructure.

We report on experimental investigations of an electrically driven WSe2 based light-emitting van der Waals heterostructure. We observe a threshold voltage for electroluminescence significantly lower than the corresponding single particle band gap of monolayer WSe2. This observation can be interpreted by considering the Coulomb interaction and a tunneling process involving excitons, well beyond the picture of independent charge carriers. An applied magnetic field reveals pronounced magneto-oscillations in the electroluminescence of the free exciton emission intensity with a 1/B periodicity. This effect is ascribed to a modulation of the tunneling probability resulting from the Landau quantization in the graphene electrodes. A sharp feature in the differential conductance indicates that the Fermi level is pinned and allows for an estimation of the acceptor binding energy.