Polycyclic aromatic hydrocarbons (PAHs) provide a versatile platform for engineering electronic functionality at the molecular scale; however, achieving precise control over their surface assembly and emergent properties remains a significant challenge. Here, we investigate the growth and electronic behavior of a large nanographene molecule (C96-tBu8) on Au(111) using two complementary deposition methods: pulsed-valve injection and molecular beam epitaxy (MBE). Low-temperature scanning tunneling microscopy and spectroscopy (STM/STS) reveal that the deposition pathway governs distinct growth regimes, ranging from highly ordered extended monolayers to isolated molecules and anisotropic stripe-like nanostructures. A clear size-dependent evolution of the electronic structure is observed: small assemblies exhibit a semiconducting gap on the order of 1 eV, whereas larger assemblies display a finite density of states near the Fermi level. Rather than indicating a fully metallic state, this behavior is more appropriately described as a transition toward a reduced-gap regime associated with increased electronic delocalization. This evolution is attributed to the interplay between quantum confinement, intermolecular electronic coupling, and molecule-substrate interactions. Overall, these findings establish a correlation between growth dynamics, structural organization, and electronic properties, demonstrating that surface assembly provides an effective route to tune functionality within a single molecular system. This work highlights large nanographenes as promising building blocks for nanoscale electronic and quantum architectures.

ABSTRACT Polycyclic aromatic hydrocarbons (PAHs) offer a unique platform for bridging molecular design and nanoscale functionality owing to their tunable structures. Beyond their intrinsic electronic properties, PAHs exhibit significant potential for directed self‐assembly, enabling the formation of ordered nanostructures with tailored functionalities. Here, we report the on‐surface self‐assembly of quantum dot‐like nanostructures and nanoribbons from two closely related PAH molecules, C₉₆H24(C₁2H25)₆ (C96‐A) and C₉₆H3₀ (C96), deposited on Au(111) via molecular beam epitaxy. Scanning tunneling microscopy and spectroscopy (STM/STS) reveal a structural evolution from ordered single molecules to extended nanoribbons, with the latter exhibiting a narrow electronic bandgap of 0.8 eV. X‐ray photoelectron spectroscopy (XPS) indicates a single carbon chemical environment, while near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy confirms a flat‐lying molecular orientation. Density functional theory (DFT) calculations corroborate the experimental findings and provide insight into the self‐assembly mechanisms. These results highlight the potential of engineered PAHs for the bottom‐up fabrication of nanoscale electronic materials.

Phosphorene, a semiconducting two-dimensional material, has recently attracted huge interest due to its potential applications in opto-electronics. The first attempts to synthesize phosphorene were based mainly on mechanical and chemical exfoliations. A few years later, different groups reported the synthesis of phosphorene using the molecular beam epitaxy process, which opened the way for research on physical properties. In this article, we report phosphorus growth on an Au(110) substrate via molecular beam epitaxy. The atomically resolved scanning tunneling microscopy images exhibit a self-assembled phosphorus-dimer structure, which is converted into phosphorus chains when increasing the phosphorus coverage. The chemical composition of the obtained structures is determined via Auger electron and X-ray photoelectron spectroscopies. Density functional theory calculations support the experimental findings.

2D materials beyond graphene and in particular 2D semiconductors have raised interest due to their unprecedented electronic properties, such as high carrier mobility or tunable bandgap. Blue phosphorene is an allotrope of black phosphorene that resembles graphene as it presents a honeycomb structure. However, it is known to have semiconductor character and the crucial point is to determine whether this hexagonal phase of phosphorene presents Dirac fermions as in graphene. Here, the first compelling experimental evidence of Dirac fermions in blue phosphorene layer grown on Cu(111) surface is presented. The results highlight the formation of a highly ordered blue phosphorene sheet with a clear Dirac cone at the high symmetry points of the Brillouin Zone. The charge carriers behave as massless relativistic particles. Therefore, all the expectations held for graphene, such as high‐speed electronic devices based on ballistic transport at room temperature, may also be applied to blue phosphorene.

Silicene is a two-dimensional (2D) material with very promising electronic properties for applications in silicon modern technology. However, the first experimental synthesis of silicene on metallic surfaces shows strong interactions between the silicene and its substrate, which can alter its electronic properties. Here, we report on the first steps of silicene growth on an insulating surface (NaCl) using scanning tunneling microscopy (STM), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and angle-resolved photoemission spectroscopy (ARPES). We demonstrate the importance of temperature annealing in the growth of silicene on NaCl. Indeed, after deposition of silicon on the NaCl/Ag(110) surface, we observe the following stages: (i) at room temperature, the silicon atoms accumulate on top of the NaCl layer without any given order. (ii) At 60 °C, silicon dimers start to grow on the NaCl. (iii) At 140 °C, these dimers form a 2D silicon chains on the surface. (iv) After a post-annealing at 200 °C, evident 2D silicon nanoribbons with a honeycomb-like structure were observed. Our results of the first silicene growth stages on an insulating surface are a necessary step for exploring its growth mechanism further.

This work reports on the electron-induced modification of NaCl thin film grown on Ag(110). We show using low energy electron diffraction that electron beam bombardment leads to desorption and formation of Cl vacancy defects on NaCl surface. The topographic structure of these defects is studied using scanning tunneling microscopy (STM) showing the Cl defects as depressions on the NaCl surface. Most of the observed defects are mono-atomic vacancies and are located on flat NaCl terraces. Auger electron spectroscopy confirms the effect of electron exposure on NaCl thin films showing Cl atoms desorption from the surface. Using density functional theory taken into account the van der Waals dispersion interactions, we confirm the observed experimental STM measurements with STM simulation. Furthermore, comparing the adsorption of defect free NaCl and defective NaCl monolayer on Ag(110) surfaces, we found an increase of the adhesion energy and the charge transfer between the NaCl film and the substrate due to the Cl vacancy. In details, the adhesion energy increases between the NaCl film and the metallic Ag substrate from 30.4 meV Å-2for the NaCl film without Cl vacancy and from 39.5 meV Å-2for NaCl film with a single Cl vacancy. The charge transfer from the NaCl film to the Ag substrate is enhanced when the vacancy is created, from 0.63e-to 1.25e-.

In order to understand the adsorption process of selenium (Se) and Se-based molecules on noble metal surfaces, we report here on the properties of a thin film of Se on Cu(100) substrate. The deposition was carried out by incubating of a clean Cu(100) surface into Na2Se solution under controlled conditions. The film properties were analysed as a function of the annealing temperature of the sample, using Low Energy Electron Diffraction (LEED) and photoemission techniques. A progressive structural transition from disordered thick layer to a two-dimensional Copper Selenide CuSe thin layer is obtained upon the thermal treatment. Our study proves that a large scale, well-ordered, and highly-stabilized metal chalcogenide layer can be produced for promising use in potential applications.

Blue phosphorene (blue-P) has attracted considerable attention due to its potential applications in optical and electronic devices. However, its synthesis has remained a challenge. Here, we report an experimental investigation of the first steps of blue-P growth on Au(111) surface by molecular-beam epitaxy. The structure was characterized by in situ low temperature scanning tunneling microscopy, low-energy electron diffraction, combined with density functional theory calculations. We reveal two-dimensional (2D) phosphorus clusters (P-clusters) formed on surface at 150 degrees C, where the most prevalent structure of P-clusters is composed of triangles with six protrusions. We also demonstrate the transformation of these P-clusters into a single layer of blue-P after post-annealing at 260 degrees C. Our observation of the growth process is a necessary step for exploring the growth mechanisms further. (C) 2019 Elsevier Ltd. All rights reserved.

Silicene, a new 2D material has attracted intense research because of the ubiquitous use of silicon in modern technology. However, producing free-standing silicene has proved to be a huge challenge. Until now, silicene could be synthesized only on metal surfaces where it naturally forms strong interactions with the metal substrate that modify its electronic properties. Here, the authors report the first experimental evidence of silicene nanoribbons on an insulating NaCl thin film. This work represents a major breakthrough, for the study of the intrinsic properties of silicene, and by extension to other 2D materials that have so far only been grown on metal surfaces.

The emergence of peculiar phenomena in 1D phosphorene chains (P chains) has been proposed in theoretical studies, notably the Stark and Seebeck effects, room temperature magnetism, and topological phase transitions. Attempts so far to fabricate P chains, using the top-down approach starting from a few layers of bulk black phosphorus, have failed to produce reliably precise control of P chains. We show that molecular beam epitaxy gives a controllable bottom-up approach to grow atomically thin, crystalline 1D flat P chains on a Ag(111) substrate. Scanning tunneling microscopy, angle-resolved photoemission spectroscopy, and density functional theory calculations reveal that the armchair-shaped chains are semiconducting with an intrinsic 1.80 ± 0.20 eV band gap. This could make these P chains an ideal material for opto-electronic devices.

The synthesis of blue phosphorene by molecular beam epitaxy (MBE) has recently come under the spotlight due to its potential applications in electronic and optoelectronic devices. However, this synthesis remains a significant challenge. The surface reactivity between the P atoms and the Au atoms should be considered for the P/Au(111) system. In the MBE process, the temperature of the substrate is a key parameter for the growth of blue phosphorene. During the initial growth stage, irregularly shaped Phosphorus clusters grow on top of Au(111) surface at room temperature. When the substrate temperature is increased, these clusters transform into a phosphorene-like structure with a honeycomb lattice. An atom exchange reaction is observed between the P and first layer Au atoms under thermal activation at higher temperature, where the P atoms replace Au atoms to form a blue phosphorene structure within the top Au layer and at the step edges.

This work relates to direct synthesis of the two-dimensional (2D) transition metal dichalchogenide (TMD) PtSe2 using an original method based on chemical deposition during immersion of a Pt(111) surface into aqueous Na2Se solution. Annealing of the sample induces significant modifications in the structural and electronic properties of the resulting PtSe2 film. We report systematic investigations of temperature dependent phase transitions by combining synchrotron based high-resolution X-ray photoemission (XPS), low temperature scanning tunnelling microscopy (LT-STM) and low energy electron diffraction (LEED). From the STM images, a phase transition from TMD 2H-PtSe2 to Pt2Se alloy monolayer structure is observed, in agreement with the LEED patterns showing a transition from (4 × 4) to (√3 × √3)R30° and then to a (2 × 2) superstructure. This progressive evolution of the surface reconstruction has been monitored by XPS through systematic de-convolution of the Pt4f and Se3d core level peaks at different temperatures. The present work provides an alternative method for the large scale fabrication of 2D transition metal dichalchogenide films.

We report on the oxidation of self-assembled silicene nanoribbons grown on the Ag (110) surface using scanning tunneling microscopy and high-resolution photoemission spectroscopy. The results show that silicene nanoribbons present a strong resistance towards oxidation using molecular oxygen. This can be overcome by increasing the electric field in the STM tunnel junction above a threshold of +2.6 V to induce oxygen dissociation and reaction. The higher reactivity of the silicene nanoribbons towards atomic oxygen is observed as expected. The HR-PES confirm these observations: even at high exposures of molecular oxygen, the Si 2p core-level peaks corresponding to pristine silicene remain dominant, reflecting a very low reactivity to molecular oxygen. Complete oxidation is obtained following exposure to high doses of atomic oxygen; the Si 2p core level peak corresponding to pristine silicene disappears.

We present an experimental investigation of a new polymorphic 2D single layer of phosphorus on Ag(111). The atomically-resolved scanning tunneling microscopy (STM) images show a new 2D material composed of freely-floating phosphorus pentamers organized into a 2D layer, where the pentamers are aligned in close-packed rows. The scanning tunneling spectroscopy (STS) measurements reveal a semiconducting character with a band gap of 1.20 eV. This work presents the formation at low temperature (LT) of a new polymorphic 2D phosphorus layer composed of a floating 2D pentamer structure. The smooth curved terrace edges and a lack of any clear crystallographic orientation with respect to the Ag(111) substrate at room temperature indicates a smooth potential energy surface that is reminiscent of a liquid-like growth phase. This is confirmed by density functional theory (DFT) calculations that find a small energy barrier of only 0.17 eV to surface diffusion of the pentamers (see Supplemental Material). The formation of extended, homogeneous domains is a key ingredient to opening a new avenue to integrate this new 2D material into electronic devices.

The number of two-dimensional (2D) materials has grown steadily since the discovery of graphene. Each new 2D material demonstrated unusual physical properties offering a large flexibility in their tailoring for high-tech applications. Here, we report on the formation and characterization of an uncharted 2D material: ‘Cu 2 Te alloy monolayer on Cu(111) surface’. We have successfully grown a 2D binary Te-Cu alloy using a straightforward approach based on chemical deposition method. Low electron energy diffraction (LEED) and scanning tunneling microscopy (STM) results reveal the existence of a well-ordered alloy monolayer characterized by (√3 × √3)R30° superstructure, while the x-ray photoemission spectroscopy (XPS) measurements indicate the presence of single chemical environment of the Te atoms associated with the Te-Cu bonding. Analysis of the valence band properties by angle resolved photoemission spectroscopy (ARPES); in particular the electronic states close to the Fermi level suggests a strong hybridization between Te and Cu electronic states leading to an appearance of new dispersive bands localized at the surface alloy, which is confirmed by first-principles calculations. These bands are strongly influenced by the surface reconstruction and undergo a back-folding at the boundaries of the reduced surface Brillouin zone (SBZ). More interesting, a band gap of about 0.91 eV and a Rashba splitting in the conduction band are obtained. These findings taken together clearly prove the presence of 2D-type electron system within the Cu 2 Te alloy layer, which is promising for spintronic application.

The oxidation of the Ni(111) surface under ultrahigh-vacuum conditions is studied experimentally with low-energy electron diffraction and high-resolution X-ray photoelectron spectroscopy. Exposure of the clean Ni(111) surface to molecular oxygen at room temperature followed by annealing at 400 K leads to the formation of two different structures (2x2) and (3 root 3 x 3 root 3)R30 degrees, prior to the formation of the NiO(111) monolayer. The O 1s core levels indicate that the obtained oxide is terminated by oxygen atoms while the valence band measurements clearly reveal the band gap of NiO. The energy difference between the Fermi level and the maximum of the valance band is extracted and is found to be 0.47 eV.

Two-dimensional (2D) chalcogen-based layers have proven to be the next generation of materials for potential high-tech applications, and it is very important to control their properties at the nanoscale. Herein, we discuss the structural and electronic properties of Au(111) surface after being exposed to high temperature vapor deposition of Tellurium (Te) in ultrahigh vacuum. The scenarios entailing the formation of 2D AuTe2 metal dichalcogenide or rather Au-Te alloy monolayer (ML) or even Tellurene single layer deserved to be addressed. In this purpose, low energy electron diffraction (LEED) supported by scanning tunneling microscopy (STM) shows the existence of several surface reconstructions depending on the Te film thickness in the sub-monolayer regime. We observed that the well-known spin-split Shockley state of the Au(111) surface survives the Te deposition and is even shifted to higher binding energy, suggesting a charge transfer at the interface. For a coverage of 0.33 ML of Te, new dispersive bands are observed by angle-resolved photoemission (ARPES), which arise from a strong hybridization between the electronic states of Te and Au. With a substantially low intensity and a back-folding at the boundaries of the reduced surface Brillouin zone (R-SBZ), these electronic bands represent a proof of the existence of a naturel 2D electron gas, strongly disturbed by the surface reconstruction. It is therefore possible that an Au-Te alloy is formed at the surface. By increasing the coverage to 0.5 ML, a rich, thickness-dependent transition develops from the surface alloy to Tellurene-like structure and completely excludes the growth of AuTe2 monolayer. Both the surface alloy and the Tellurene monolayer have a semiconductor character with a gap in the occupied states of about 0.65 eV.

In this paper we report on the first steps of silicene growth on Ag(111) using scanning tunneling microscopy. We show that the topmost atomic layer is composed of both silicon and silver. The STM observations are consistent with an exchange process between the silicon and silver atoms preferentially taking place at the step edges of the Ag substrate. In addition, silicon stripes are observed as precursors of the formation of the silicene sheet.

Phosphorene is a new 2D material composed of a single or few atomic layers of black phosphorus. Phosphorene has both an intrinsic tunable direct bandgap and high carrier mobility values, which make it suitable for a large variety of optical and electronic devices. However, the synthesis of single-layer phosphorene is a major challenge. The standard procedure to obtain phosphorene is by exfoliation. More recently, the epitaxial growth of single-layer phosphorene on Au(111) was investigated by molecular beam epitaxy and the obtained structure described as a blue phosphorene sheet. In the present study, large areas of high-quality monolayer phosphorene, with a bandgap value equal to at least 0.8 eV, are synthesized on Au(111). The experimental investigations, coupled with density functional theory calculations, give evidence of two distinct phases of blue phosphorene on Au(111), instead of one as previously reported, and their atomic structures are determined.