Nanoscale mapping of quasiparticle band alignment.

Control of atomic-scale interfaces between materials with distinct electronic structures is crucial for the design and fabrication of most electronic devices. In the case of two-dimensional materials, disparate electronic structures can be realized even within a single uniform sheet, merely by locally applying different vertical gate voltages. Here, we utilize the inherently nano-structured single layer and bilayer graphene on silicon carbide to investigate lateral electronic structure variations in an adjacent single layer of tungsten disulfide (WS2). The electronic band alignments are mapped in energy and momentum space using angle-resolved photoemission with a spatial resolution on the order of 500 nm (nanoARPES). We find that the WS2 band offsets track the work function of the underlying single layer and bilayer graphene, and we relate such changes to observed lateral patterns of exciton and trion luminescence from WS2.

Excitonic Effects in Tungsten Disulfide Monolayers on Two-Layer Graphene.

Light emission in atomically thin heterostructures is known to depend on the type of materials and the number and stacking sequence of the constituent layers. Here we show that the thickness of a two-dimensional substrate can be crucial in modulating the light emission. We study the layer-dependent charge transfer in vertical heterostructures built from monolayer tungsten disulfide (WS2) on one- and two-layer epitaxial graphene, unravelling the effect that the interlayer electronic coupling has on the excitonic properties of such heterostructures. We bring evidence that the excitonic properties of WS2 can be effectively tuned by the number of supporting graphene layers. Integrating WS2 monolayers with two-layer graphene leads to a significant enhancement of the photoluminescence response, up to 1 order of magnitude higher compared to WS2 supported on one-layer graphene. Our findings highlight the importance of substrate engineering when constructing atomically thin-layered heterostructures.

Thickness-Dependent Hydrophobicity of Epitaxial Graphene.

This article addresses the much debated question whether the degree of hydrophobicity of single-layer graphene (1LG) is different from that of double-layer graphene (2LG). Knowledge of the water affinity of graphene and its spatial variations is critically important as it can affect the graphene properties as well as the performance of graphene devices exposed to humidity. By employing chemical force microscopy with a probe rendered hydrophobic by functionalization with octadecyltrichlorosilane (OTS), the adhesion force between the probe and epitaxial graphene on SiC has been measured in deionized water. Owing to the hydrophobic attraction, a larger adhesion force was measured on 2LG Bernal-stacked domains of graphene surfaces, thus showing that 2LG is more hydrophobic than 1LG. Identification of 1LG and 2LG domains was achieved through Kelvin probe force microscopy and Raman spectral mapping. Approximate values of the adhesion force per OTS molecule have been calculated through contact area analysis. Furthermore, the contrast of friction force images measured in contact mode was reversed to the 1LG/2LG adhesion contrast, and its origin was discussed in terms of the likely water depletion over hydrophobic domains as well as deformation in the contact area between the atomic force microscope tip and 1LG.

Carrier type inversion in quasi-free standing graphene: studies of local electronic and structural properties.

We investigate the local surface potential and Raman characteristics of as-grown and ex-situ hydrogen intercalated quasi-free standing graphene on 4H-SiC(0001) grown by chemical vapor deposition. Upon intercalation, transport measurements reveal a change in the carrier type from n- to p-type, accompanied by a more than three-fold increase in carrier mobility, up to µh ≈ 4540 cm(2) V(-1) s(-1). On a local scale, Kelvin probe force microscopy provides a complete and detailed map of the surface potential distribution of graphene domains of different thicknesses. Rearrangement of graphene layers upon intercalation to (n + 1)LG, where n is the number of graphene layers (LG) before intercalation, is demonstrated. This is accompanied by a significant increase in the work function of the graphene after the H2-intercalation, which confirms the change of majority carriers from electrons to holes. Raman spectroscopy and mapping corroborate surface potential studies.

Band gap expansion, shear inversion phase change behaviour and low-voltage induced crystal oscillation in low-dimensional tin selenide crystals.

In common with rocksalt-type alkali halide phases and also semiconductors such as GeTe and SnTe, SnSe forms all-surface two atom-thick low dimensional crystals when encapsulated within single walled nanotubes (SWNTs) with diameters below ∼1.4 nm. Whereas previous density functional theory (DFT) studies indicate that optimised low-dimensional trigonal HgTe changes from a semi-metal to a semi-conductor, low-dimensional SnSe crystals typically undergo band-gap expansion. In slightly wider diameter SWNTs (∼1.4-1.6 nm), we observe that three atom thick low dimensional SnSe crystals undergo a previously unobserved form of a shear inversion phase change resulting in two discrete strain states in a section of curved nanotube. Under low-voltage (i.e. 80-100 kV) imaging conditions in a transmission electron microscope, encapsulated SnSe crystals undergo longitudinal and rotational oscillations, possibly as a result of the increase in the inelastic scattering cross-section of the sample at those voltages.

Confined crystals of the smallest phase-change material.

The demand for high-density memory in tandem with limitations imposed by the minimum feature size of current storage devices has created a need for new materials that can store information in smaller volumes than currently possible. Successfully employed in commercial optical data storage products, phase-change materials, that can reversibly and rapidly change from an amorphous phase to a crystalline phase when subject to heating or cooling have been identified for the development of the next generation electronic memories. There are limitations to the miniaturization of these devices due to current synthesis and theoretical considerations that place a lower limit of 2 nm on the minimum bit size, below which the material does not transform in the structural phase. We show here that by using carbon nanotubes of less than 2 nm diameter as templates phase-change nanowires confined to their smallest conceivable scale are obtained. Contrary to previous experimental evidence and theoretical expectations, the nanowires are found to crystallize at this scale and display amorphous-to-crystalline phase changes, fulfilling an important prerequisite of a memory element. We show evidence for the smallest phase-change material, extending thus the size limit to explore phase-change memory devices at extreme scales.

Evidence for metal-semiconductor transitions in twisted and collapsed double-walled carbon nanotubes by scanning tunneling microscopy.

The atomic and electronic structure of a twisted and collapsed double-walled carbon nanotube was characterized using scanning tunneling microscopy and spectroscopy. It was found that the deformation opens an electronic band gap in an otherwise metallic nanotube, which has major ramifications on the use of carbon nanotubes for electronic applications. Fundamentally, the importance of the intershell interaction in this double-walled carbon nanotube points to the potential of a reversible metal-semiconductor junction, which can have device applications, as well as a caution in the design of semiconductor components based on carbon nanotubes. Lattice registry effects between the two neighboring walls evidenced by atomically resolved images confirm earlier first principle calculations indicating that the helicity influences the collapsed structure and show excellent agreement with the predicted twisted-collapse mode.

Registry-induced electronic superstructure in double-walled carbon nanotubes, associated with the interaction between two graphene-like monolayers.

Prior to the implementation of multi-walled carbon nanotubes in microelectronic devices, investigating their electronic structure down to the nanometer scale is necessary. In that prospect, we used scanning tunneling microscopy (STM) to study the detailed atomic scale structure of double-walled carbon nanotubes, each comprising two rolled monolayers of graphene. Atomically resolved STM images usually displayed a motif and periodicity similar to that found in graphite but, on selected regions, atomically resolved motifs with a clearly defined superstructure were observed. This phenomenon has been reported previously but without a suitable explanation. We discuss the origin of this behavior in terms of modified stacking sequences due to the mismatch in registry between the chiral angles of the inner and the outer shells, associated with the interaction between the two carbon monolayers. These phenomena must be taken into account for the realization of lateral interference devices based on carbon nanotubes or graphene layers.

Inner-tube chirality determination for double-walled carbon nanotubes by scanning tunneling microscopy.

Evidence for modified electronic structure in double-walled carbon nanotubes with respect to their individual inner and outer constituent single-walled nanotubes is provided by scanning tunneling microscopy and spectroscopy experiments. The contribution originating from the inner tube to the local density of states of the double-walled system was identified in agreement with previous theoretical calculations. Consequently, the chiral index for the inner tube was extracted based on the additional van Hove singularities present in the experimental tunneling spectra.