Interface coupling in Au-supported MoS2-WS2 heterobilayers grown by pulsed laser deposition.

Van der Waals heterostructures of transition metal dichalcogenides (TMDs) are promising systems for engineering functional layered 2D materials with tailored properties. In this work, we study the growth of WS2/MoS2 and MoS2/WS2 heterobilayers by pulsed laser deposition (PLD) under ultra-high vacuum conditions. Using Au(111) as growth substrate, we investigated the heterobilayer morphology and structure at the nanoscale by in situ scanning tunneling microscopy. Our experiments show that the heterostructure growth can be controlled with high coverage and thickness sensitivity by tuning the number of laser pulses in the PLD process. Raman spectroscopy complemented our investigation, revealing the effect of the interaction with the metallic substrate on the TMD vibrational properties and a strong interlayer coupling between the MoS2 and WS2 layers. The transfer of the heterobilayers on a silica substrate via a wet etching process shows the possibility to decouple them from the native metallic substrate and confirms that the interlayer coupling is not substrate-dependent. This work highlights the potential of the PLD technique as a method to grow TMD heterostructures, opening to new perspectives in the synthesis of complex 2D layered materials.

Steric hindrance in the on-surface synthesis of diethynyl-linked anthracene polymers.

Hybrid sp-sp2 structures can be efficiently obtained on metal substrates via on-surface synthesis. The choice of both the precursor and the substrate impacts on the effectiveness of the process and the stability of the formed structures. Here we demonstrate that using anthracene-based precursor molecules on Au(111) the formation of polymers hosting sp carbon chains is affected by the steric hindrance between aromatic groups. In particular, by scanning tunneling microscopy experiments and density functional theory simulations we show that the de-metalation of organometallic structures induces a lateral separation of adjacent polymers that prevents the formation of ordered domains. This study contributes to the understanding of the mechanisms driving the on-surface synthesis processes, a fundamental step toward the realization of novel carbon-based nanostructures with perspective applications in nanocatalysis, photoconversion, and nano-electronics.

Interface-Driven Assembly of Pentacene/MoS2 Lateral Heterostructures.

Mixed-dimensional van der Waals heterostructures formed by molecular assemblies and 2D materials provide a novel platform for fundamental nanoscience and future nanoelectronics applications. Here we investigate a prototypical hybrid heterostructure between pentacene molecules and 2D MoS2 nanocrystals, deposited on Au(111) by combining pulsed laser deposition and organic molecular beam epitaxy. The obtained structures were investigated in situ by scanning tunneling microscopy and spectroscopy and analyzed theoretically by density functional theory calculations. Our results show the formation of atomically thin pentacene/MoS2 lateral heterostructures on the Au substrate. The most stable pentacene adsorption site corresponds to MoS2 terminations, where the molecules self-assemble parallel to the direction of MoS2 edges. The density of states changes sharply across the pentacene/MoS2 interface, indicating a weak interfacial coupling, which leaves the electronic signature of MoS2 edge states unaltered. This work unveils the self-organization of abrupt mixed-dimensional lateral heterostructures, opening to hybrid devices based on organic/inorganic one-dimensional junctions.

Hydrophilic Character of Single-Layer MoS2 Grown on Ag(111).

The study of MoS2/metal interfaces is crucial for engineering efficient semiconductor-metal contacts in 2D MoS2-based devices. Here we investigate a MoS2/Ag heterostructure fabricated by growing a single MoS2 layer on Ag(111) by pulsed laser deposition under ultrahigh vacuum (UHV) conditions. The surface structure is observed in situ by scanning tunneling microscopy, revealing the hexagonal moiré pattern characteristic of the clean MoS2/Ag(111) interface. Ex situ Raman spectroscopy reveals an anomalous behavior of vibrational modes, induced by the strong MoS2-Ag interaction. After few-hours exposure to ambient conditions the Raman response significantly changes and the formation of molybdenum oxysulfides is revealed by X-ray photoelectron spectroscopy. These effects are due to the interplay with water vapor and can be reversed by a moderate UHV annealing. A polymeric (PMMA) capping is demonstrated to hinder water-induced modifications, preserving the original interface quality for months.

Structural, Electronic, and Vibrational Properties of a Two-Dimensional Graphdiyne-like Carbon Nanonetwork Synthesized on Au(111): Implications for the Engineering of sp-sp2 Carbon Nanostructures.

Graphdiyne, atomically thin two-dimensional (2D) carbon nanostructure based on sp-sp2 hybridization is an appealing system potentially showing outstanding mechanical and optoelectronic properties. Surface-catalyzed coupling of halogenated sp-carbon-based molecular precursors represents a promising bottom-up strategy to fabricate extended 2D carbon systems with engineered structure on metallic substrates. Here, we investigate the atomic-scale structure and electronic and vibrational properties of an extended graphdiyne-like sp-sp2 carbon nanonetwork grown on Au(111) by means of the on-surface synthesis. The formation of such a 2D nanonetwork at its different stages as a function of the annealing temperature after the deposition is monitored by scanning tunneling microscopy (STM), Raman spectroscopy, and combined with density functional theory (DFT) calculations. High-resolution STM imaging and the high sensitivity of Raman spectroscopy to the bond nature provide a unique strategy to unravel the atomic-scale properties of sp-sp2 carbon nanostructures. We show that hybridization between the 2D carbon nanonetwork and the underlying substrate states strongly affects its electronic and vibrational properties, modifying substantially the density of states and the Raman spectrum compared to the free standing system. This opens the way to the modulation of the electronic properties with significant prospects in future applications as active nanomaterials for catalysis, photoconversion, and carbon-based nanoelectronics.

Scanning tunneling microscopy and Raman spectroscopy of polymeric sp-sp2 carbon atomic wires synthesized on the Au(111) surface.

Long linear carbon nanostructures based on sp-hybridization can be synthesized by exploiting on-surface synthesis of halogenated precursors evaporated on Au(111), thus opening a way to investigations by surface-science techniques. By means of an experimental approach combining scanning tunneling microscopy and spectroscopy (STM and STS) with ex situ Raman spectroscopy we investigate the structural, electronic and vibrational properties of polymeric sp-sp2 carbon atomic wires composed by sp-carbon chains connected through phenyl groups. Density-functional-theory (DFT) calculations of the structure and the electronic density of states allow us to simulate STM images and to compute Raman spectra. The comparison of experimental data with DFT simulations unveil the properties and the formation stages as a function of the annealing temperature. Atomic-scale structural information from STM complement the Raman sensitivity to the single molecular bond to open the way to detailed understanding of these novel carbon nanostructures.

Pulsed laser deposition of single-layer MoS2 on Au(111): from nanosized crystals to large-area films.

Molybdenum disulphide (MoS2) is a promising material for heterogeneous catalysis and novel two-dimensional (2D) optoelectronic devices. In this work, we synthesized single-layer (SL) MoS2 structures on Au(111) by pulsed laser deposition (PLD) under ultra-high vacuum (UHV) conditions. By controlling the PLD process, we were able to tune the sample morphology from low-coverage SL nanocrystals to large-area SL films uniformly wetting the whole substrate surface. We investigated the obtained MoS2 structures at the nanometer and atomic scales by means of in situ scanning tunneling microscopy/spectroscopy (STM/STS) measurements, to study the interaction between SL MoS2 and Au(111)-which for example influences MoS2 lattice orientation-the structure of point defects and the formation of in-plane MoS2/Au heterojunctions. Raman spectroscopy, performed ex situ on large-area SL MoS2, revealed significant modifications of the in-plane E12g and out-of-plane A1g vibrational modes, possibly related to strain and doping effects. Charge transfer between SL MoS2 and Au is also likely responsible for the total suppression of excitonic emission, observed by photoluminescence (PL) spectroscopy.