Broad background in electron diffraction of 2D materials as a signature of their superior quality.

An unusually broad bell-shaped component (BSC) has been previously observed in surface electron diffraction on different types of 2D systems. It was suggested to be an indicator of uniformity of epitaxial graphene (Gr) and hexagonal boron nitride (hBN). In the current study we use low-energy electron microscopy and micro-diffraction to directly relate the BSC to the crystal quality of the diffracting 2D material. Specially designed lateral heterostructures were used to map the spatial evolution of the diffraction profile across different 2D materials, namely pure hBN, BCN alloy and pure Gr, where the alloy region exhibits deteriorated structural coherency. The presented results show that the BSC intensity has a minimum in the alloyed region, consequently showing that BSC is sensitive to the lateral domain size and homogeneity of the material under examination. This is further confirmed by the presence of a larger number of sharp moiré spots when the BSC is most pronounced in the pure hBN and Gr regions. Consequently, it is proposed that the BSC can be used as a diagnostic tool for determining the quality of the 2D materials.

Linewidth Narrowing with Ultimate Confinement of an Alkali Multipole Plasmon by Modifying Surface Electronic Wave Functions with Two-Dimensional Materials.

This work demonstrates significant line narrowing of a surface multipole plasmon (MP) by modifying the surface electronic wave function with two-dimensional materials (2DMs): graphene and hexagonal boron nitride. This is found in an optical reflectivity of alkali atoms (Cs or K) on an Ir(111) surface covered with the 2DMs. The reduction in reflectivity induced by deposition of the alkali atoms becomes as large as 20% at ∼2 eV, which is ascribed to a MP of a composite of alkali/2DM/alkali/Ir multilayer structure. The linewidth of the MP band becomes as narrow as 0.2 eV by the presence of the 2DM between the two alkali layers. A numerical simulation by time-dependent density functional theory with a jellium model reveals that the density of states of the surface localized state is sharpened remarkably by the 2DMs that decouple the outermost alkali layer from the Ir bulk. Consequently, a local field enhancement of an order of 10^{5} is achieved by ultimate confinement of the MP within the outermost alkali layer. This work leads to a novel strategy for reducing plasmon dissipation in an atomically thin layer via atomic scale modification of surface structure.

Energy-Dependent Chirality Effects in Quasifree-Standing Graphene.

We present direct experimental evidence of broken chirality in graphene by analyzing electron scattering processes at energies ranging from the linear (Dirac-like) to the strongly trigonally warped region. Furthermore, we are able to measure the energy of the van Hove singularity at the M point of the conduction band. Our data show a very good agreement with theoretical calculations for free-standing graphene. We identify a new intravalley scattering channel activated in case of a strongly trigonally warped constant energy contour, which is not suppressed by chirality. Finally, we compare our experimental findings with T-matrix simulations with and without the presence of a pseudomagnetic field and suggest that higher order electron hopping effects are a key factor in breaking the chirality near to the van Hove singularity.

The backside of graphene: manipulating adsorption by intercalation.

The ease by which graphene is affected through contact with other materials is one of its unique features and defines an integral part of its potential for applications. Here, it will be demonstrated that intercalation, the insertion of atomic layers in between the backside of graphene and the supporting substrate, is an efficient tool to change its interaction with the environment on the frontside. By partial intercalation of graphene on Ir(111) with Eu or Cs we induce strongly n-doped graphene patches through the contact with these intercalants. They coexist with nonintercalated, slightly p-doped graphene patches. We employ these backside doping patterns to directly visualize doping induced binding energy differences of ionic adsorbates to graphene through low-temperature scanning tunneling microscopy. Density functional theory confirms these binding energy differences and shows that they are related to the graphene doping level.

Strain-Enhanced Large-Area Monolayer MoS2 Photodetectors.

In this study, we show a direct correlation between the applied mechanical strain and an increase in monolayer MoS2 photoresponsivity. This shows that tensile strain can improve the efficiency of monolayer MoS2 photodetectors. The observed high photocurrent and extended response time in our devices are indicative that devices are predominantly governed by photogating mechanisms, which become more prominent with applied tensile strain. Furthermore, we have demonstrated that a nonencapsulated MoS2 monolayer can be used in strain-based devices for many cycles and extensive periods of time, showing endurance under ambient conditions without loss of functionality. Such robustness emphasizes the potential of MoS2 for further functionalization and utilization of different flexible sensors.

Interplay of Kinetic Limitations and Disintegration: Selective Growth of Hexagonal Boron Nitride and Borophene Monolayers on Metal Substrates.

The CVD growth of bielemental 2D-materials by using molecular precursors involves complex formation kinetics taking place at the surface and sometimes also subsurface regions of the substrate. Competing microscopic processes fundamentally limit the parameter space for optimal growth of the desired material. Kinetic limitations for diffusion and nucleation cause a high density of small domains and grain boundaries. These are usually overcome by increasing the growth temperature and decreasing the growth rate. In contrast, the nature of molecular precursors with limited thermal stability can result in dissociation and preferential desorption, leading to an undesired or ill-defined composition of the 2D-material. Here we demonstrate these constraints in a combined low-energy electron diffraction and low-energy electron microscopy study by examining the selective formation of single-layer hexagonal boron nitride (hBN) and borophene on Ir(111) using a borazine precursor. We derive a temperature-pressure phase diagram and apply classical nucleation theory to describe our results. By considering the competing processes, we find an optimum growth temperature for hBN of 950 °C. At lower temperatures, the hBN island density is increased, while at higher temperatures the precursor disintegrates and borophene is formed. Our results introduce an additional aspect that must be considered in any high-temperature growth of bielemental 2D-materials from single molecular precursors.

Unidirectional Nano-modulated Binding and Electron Scattering in Epitaxial Borophene.

A complex interplay between the crystal structure and the electron behavior within borophene renders this material an intriguing 2D system, with many of its electronic properties still undiscovered. Experimental insight into those properties is additionally hampered by the limited capabilities of the established synthesis methods, which, in turn, inhibits the realization of potential borophene applications. In this multimethod study, photoemission spectroscopies and scanning probe techniques complemented by theoretical calculations have been used to investigate the electronic characteristics of a high-coverage, single-layer borophene on the Ir(111) substrate. Our results show that the binding of borophene to Ir(111) exhibits pronounced one-dimensional modulation and transforms borophene into a nanograting. The scattering of photoelectrons from this structural grating gives rise to the replication of the electronic bands. In addition, the binding modulation is reflected in the chemical reactivity of borophene and gives rise to its inhomogeneous aging effect. Such aging is easily reset by dissolving boron atoms in iridium at high temperature, followed by their reassembly into a fresh atomically thin borophene mesh. Besides proving electron-grating capabilities of the boron monolayer, our data provide comprehensive insight into the electronic properties of epitaxial borophene which is vital for further examination of other boron systems of reduced dimensionality.

Macroscopic Single-Phase Monolayer Borophene on Arbitrary Substrates.

A major challenge in the investigation of all 2D materials is the development of synthesis protocols and tools which would enable their large-scale production and effective manipulation. The same holds for borophene, where experiments are still largely limited to in situ characterizations of small-area samples. In contrast, our work is based on millimeter-sized borophene sheets, synthesized on an Ir(111) surface in ultrahigh vacuum. Besides high-quality macroscopic synthesis, as confirmed by low-energy electron diffraction (LEED) and atomic force microscopy (AFM), we also demonstrate a successful transfer of borophene from Ir to a Si wafer via electrochemical delamination process. Comparative Raman spectroscopy, in combination with the density functional theory (DFT) calculations, proved that borophene's crystal structure has been preserved in the transfer. Our results demonstrate successful growth and manipulation of large-scale, single-layer borophene sheets with minor defects and ambient stability, thus expediting borophene implementation into more complex systems and devices.

Electronic Structure of Quasi-Freestanding WS2/MoS2 Heterostructures.

Growth of 2D materials under ultrahigh-vacuum (UHV) conditions allows for an in situ characterization of samples with direct spectroscopic insight. Heteroepitaxy of transition-metal dichalcogenides (TMDs) in UHV remains a challenge for integration of several different monolayers into new functional systems. In this work, we epitaxially grow lateral WS2-MoS2 and vertical WS2/MoS2 heterostructures on graphene. By means of scanning tunneling spectroscopy (STS), we first examined the electronic structure of monolayer MoS2, WS2, and WS2/MoS2 vertical heterostructure. Moreover, we investigate a band bending in the vicinity of the narrow one-dimensional (1D) interface of the WS2-MoS2 lateral heterostructure and mirror twin boundary (MTB) in the WS2/MoS2 vertical heterostructure. Density functional theory (DFT) is used for the calculation of the band structures, as well as for the density of states (DOS) maps at the interfaces. For the WS2-MoS2 lateral heterostructure, we confirm type-II band alignment and determine the corresponding depletion regions, charge densities, and the electric field at the interface. For the MTB, we observe a symmetric upward bend bending and relate it to the dielectric screening of graphene affecting dominantly the MoS2 layer. Quasi-freestanding heterostructures with sharp interfaces, large built-in electric field, and narrow depletion region widths are proper candidates for future designing of electronic and optoelectronic devices.

Two Phases of Monolayer Tantalum Sulfide on Au(111).

We prepared monolayers of tantalum sulfide on Au(111) by evaporation of Ta in a reactive background of H2S. Under sulfur-rich conditions, monolayers of 2H-TaS2 formed, whereas under sulfur-poor conditions TaS2-x with 0 ≤ x ≤ 1 were found. We identified this phase as TaS, a structure that can be derived from 2H-TaS2 by removal of the bottom S layer.

Segregation-Enhanced Epitaxy of Borophene on Ir(111) by Thermal Decomposition of Borazine.

Like other 2D materials, the boron-based borophene exhibits interesting structural and electronic properties. While borophene is typically prepared by molecular beam epitaxy, we report here on an alternative way of synthesizing large single-phase borophene domains by segregation-enhanced epitaxy. X-ray photoelectron spectroscopy shows that borazine dosing at 1100 °C onto Ir(111) yields a boron-rich surface without traces of nitrogen. At high temperatures, the borazine thermally decomposes, nitrogen desorbs, and boron diffuses into the substrate. Using time-of-flight secondary ion mass spectrometry, we show that during cooldown the subsurface boron segregates back to the surface where it forms borophene. In this case, electron diffraction reveals a (6 × 2) reconstructed borophene χ6-polymorph, and scanning tunneling spectroscopy suggests a Dirac-like behavior. Studying the kinetics of borophene formation in low energy electron microscopy shows that surface steps are bunched during the borophene formation, resulting in elongated and extended borophene domains with exceptional structural order.

Anomalous Temperature Dependence of Exciton Spectral Diffusion in Tetracene Thin Film.

In this work, an ultrafast spectral diffusion of the lowest exciton in a tetracene ultrathin film is studied by two-dimensional electronic spectroscopy. From the analysis of the nodal line slope, the frequency-fluctuation correlation function (FFCF) of the exciton band is extracted. The FFCF contains two components with decay times of 400 and 80 fs; while the former can be understood by a linear exciton-phonon coupling model, the latter shows an order of magnitude increase in its amplitude from 96 to 186 K that cannot be explained by the same model. A novel scheme of the energy-gap fluctuations is examined, in which an intramolecular high-frequency mode causes the spectral diffusion that is enhanced through an anharmonic coupling to low-frequency phonon modes. This finding provides a valuable input for future theoretical predictions on the ultrafast nonadiabatic dynamics of the molecular exciton.

Equilibrium shape of single-layer hexagonal boron nitride islands on iridium.

Large, high-quality layers of hexagonal boron nitride (hBN) are a prerequisite for further advancement in scientific investigation and technological utilization of this exceptional 2D material. Here we address this demand by investigating chemical vapor deposition synthesis of hBN on an Ir(111) substrate, and focus on the substrate morphology, more specifically mono-atomic steps that are always present on all catalytic surfaces of practical use. From low-energy electron microscopy and atomic force microscopy data, we are able to set up an extended Wulff construction scheme and provide a clear elaboration of different interactions governing the equilibrium shapes of the growing hBN islands that deviate from the idealistic triangular form. Most importantly, intrinsic hBN edge energy and interaction with the iridium step edges are examined separately, revealing in such way the importance of substrate step morphology for the island structure and the overall quality of 2D materials.