Van der Waals epitaxy of tunable moirés enabled by alloying.

The unique physics in moiré superlattices of twisted or lattice-mismatched atomic layers holds great promise for future quantum technologies. However, twisted configurations are thermodynamically unfavourable, making accurate twist angle control during growth implausible. While rotationally aligned, lattice-mismatched moirés such as WSe2/WS2 can be synthesized, they lack the critical moiré period tunability, and their formation mechanisms are not well understood. Here, we report the thermodynamically driven van der Waals epitaxy of moirés with a tunable period from 10 to 45 nanometres, using lattice mismatch engineering in two WSSe layers with adjustable chalcogen ratios. Contrary to conventional epitaxy, where lattice-mismatch-induced stress hinders high-quality growth, we reveal the key role of bulk stress in moiré formation and its unique interplay with edge stress in shaping the moiré growth modes. Moreover, the superlattices display tunable interlayer excitons and moiré intralayer excitons. Our studies unveil the epitaxial science of moiré synthesis and lay the foundations for moiré-based technologies.

Uncovering Topological Edge States in Twisted Bilayer Graphene.

Twisted bilayer graphene (t-BLG) has recently been introduced as a rich physical platform displaying flat electronic bands, strongly correlated states, and unconventional superconductivity. Studies have hinted at an unusual Z2 topology of the moiré Dirac bands of t-BLG. However, direct experimental evidence of this moiré band topology and associated edge states is still lacking. Herein, using superconducting quantum interferometry, we reconstructed the spatial supercurrent distribution in t-BLG Josephson junctions and revealed the presence of edge states located in the superlattice band gaps. The absence of edge conduction in high resistance regions just outside the superlattice band gap confirms that the edge transport originates from the filling of electronic states located inside the band gap and further allows us to exclude several other edge conduction mechanisms. These results confirm the unusual moiré band topology of twisted bilayer graphene and will stimulate further research to explore its consequences.

Pnictogens Allotropy and Phase Transformation during van der Waals Growth.

With their ns2 np3 valence electronic configuration, pnictogens are the only system to crystallize in layered van der Waals (vdW) and quasi-vdW structures throughout the group. Light pnictogens crystallize in the A17 phase, and bulk heavier elements prefer the A7 phase. Herein, we demonstrate that the A17 of heavy pnictogens can be stabilized in antimonene grown on weakly interacting surfaces and that it undergoes a spontaneous thickness-driven transformation to the stable A7 phase. At a critical thickness of ∼4 nm, A17 antimony transforms from AB- to AA-stacked α-antimonene by a diffusionless shuffle transition followed by a gradual relaxation to the A7 phase. Furthermore, the competition between A7- and A17-like bonding affects the electronic structure of the intermediate phase. These results highlight the critical role of the atomic structure and substrate-layer interactions in shaping the stability and properties of layered materials, thus enabling a new degree of freedom to engineer their performance.

2D Antimony-Arsenic Alloys.

Alloying in group V 2D materials and heterostructures is an effective degree of freedom to tailor and enhance their physical properties. Up to date, black arsenic-phosphorus is the only 2D group V alloy that has been experimentally achieved by exfoliation, leaving all other possible alloys in the realm of theoretical predictions. Herein, the existence of an additional alloy consisting of 2D antimony arsenide (2D-Asx Sb1- x ) grown by molecular beam epitaxy on group IV semiconductor substrates and graphene is demonstrated. The atomic mixing of As and Sb in the lattice of the grown 2D layers is confirmed by low-energy electron diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. The As content in 2D-Asx Sb1- x is shown to depend linearly on the As4 /Sb4 deposition rate ratio and As concentrations up to 15 at% are reached. The grown 2D alloys are found to be stable in ambient conditions in a timescale of weeks but to oxidize after longer exposure to air. This study lays the groundwork for a better control of the growth and alloying of group V 2D materials, which is critical to study their basic physical properties and integrate them in novel applications.

Dynamics of Antimonene-Graphene Van Der Waals Growth.

Van der Waals (vdW) heterostructures have recently been introduced as versatile building blocks for a variety of novel nanoscale and quantum technologies. Harnessing the unique properties of these heterostructures requires a deep understanding of the involved interfacial interactions and a meticulous control of the growth of 2D materials on weakly interacting surfaces. Although several epitaxial vdW heterostructures have been achieved experimentally, the mechanisms governing their synthesis are still nebulous. With this perspective, herein, the growth dynamics of antimonene on graphene are investigated in real time. In situ low-energy electron microscopy reveals that nucleation predominantly occurs on 3D nuclei followed by a self-limiting lateral growth with morphology sensitive to the deposition rate. Large 2D layers are observed at high deposition rates, whereas lower growth rates trigger an increased multilayer nucleation at the edges as they become aligned with the Z2 orientation leading to atoll-like islands with thicker, well-defined bands. This complexity of the vdW growth is elucidated based on the interplay between the growth rate, surface diffusion, and edges orientation. This understanding lays the groundwork for a better control of the growth of vdW heterostructures, which is critical to their large-scale integration.

Alignment of semiconducting graphene nanoribbons on vicinal Ge(001).

Chemical vapor deposition of CH4 on Ge(001) can enable anisotropic growth of narrow, semiconducting graphene nanoribbons with predominately smooth armchair edges and high-performance charge transport properties. However, such nanoribbons are not aligned in one direction but instead grow perpendicularly, which is not optimal for integration into high-performance electronics. Here, it is demonstrated that vicinal Ge(001) substrates can be used to synthesize armchair nanoribbons, of which ∼90% are aligned within ±1.5° perpendicular to the miscut. When the growth rate is slow, graphene crystals evolve as nanoribbons. However, as the growth rate increases, the uphill and downhill crystal edges evolve asymmetrically. This asymmetry is consistent with stronger binding between the downhill edge and the Ge surface, for example due to different edge termination as shown by density functional theory calculations. By tailoring growth rate and time, nanoribbons with sub-10 nm widths that exhibit excellent charge transport characteristics, including simultaneous high on-state conductance of 8.0 µS and a high on/off conductance ratio of 570 in field-effect transistors, are achieved. Large-area alignment of semiconducting ribbons with promising charge transport properties is an important step towards understanding the anisotropic nanoribbon growth and integrating these materials into scalable, future semiconductor technologies.

Dynamics and Mechanisms of Exfoliated Black Phosphorus Sublimation.

We report on real time observations of the sublimation of exfoliated black phosphorus layers throughout annealing using in situ low energy electron microscopy. We found that sublimation manifests itself above 375 ± 20 °C through the nucleation and expansion of asymmetric, faceted holes with the long axis aligned along the [100] direction and sharp tips defined by edges consisting of alternating (10) and (11) steps. This thermally activated process repeats itself via successive sublimation of individual layers. Calculations and simulations using density functional theory and kinetic Monte Carlo allowed to determine the involved atomic pathways. Sublimation is found to occur via detachments of phosphorus dimers rather than single atoms. This behavior and the role of defects is described using an analytical model that captures all essential features. This work establishes an atomistic-level understanding of the thermal stability of exfoliated black phosphorus and defines the temperature window available for material and device processing.

Direct oriented growth of armchair graphene nanoribbons on germanium.

Graphene can be transformed from a semimetal into a semiconductor if it is confined into nanoribbons narrower than 10 nm with controlled crystallographic orientation and well-defined armchair edges. However, the scalable synthesis of nanoribbons with this precision directly on insulating or semiconducting substrates has not been possible. Here we demonstrate the synthesis of graphene nanoribbons on Ge(001) via chemical vapour deposition. The nanoribbons are self-aligning 3° from the Ge〈110〉 directions, are self-defining with predominantly smooth armchair edges, and have tunable width to <10 nm and aspect ratio to >70. In order to realize highly anisotropic ribbons, it is critical to operate in a regime in which the growth rate in the width direction is especially slow, <5 nm h(-1). This directional and anisotropic growth enables nanoribbon fabrication directly on conventional semiconductor wafer platforms and, therefore, promises to allow the integration of nanoribbons into future hybrid integrated circuits.

Dynamic imaging of a single gold nanoparticle in liquid irradiated by off-resonance femtosecond laser.

Plasmonic nanoparticles can lead to extreme confinement of the light in the near field. This unique ability of plasmonic nanoparticles can be used to generate nanobubbles in liquid. In this work, we demonstrate with single-particle monitoring that 100 nm gold nanoparticles (AuNPs) irradiated by off-resonance femtosecond (fs) laser in the tissue therapeutic optical window (λ = 800 nm), can act as a durable nanolenses in liquid and provoke nanocavitation while remaining intact. We have employed combined ultrafast shadowgraphic imaging, in situ dark field imaging and dynamic tracking of AuNP Brownian motion to ensure the study of individual AuNPs/nanolenses under multiple fs laser pulses. We demonstrate that 100 nm AuNPs can generate multiple, highly confined (radius down to 550 nm) and transient (life time < 50 ns) nanobubbles. The latter is of significant importance for future development of in vivo AuNP-assisted laser nanosurgery and theranostic applications, where AuNP fragmentation should be avoided to prevent side effects, such as cytotoxicity and immune system's response. The experimental results have been correlated with theoretical modeling to provide an insight to the AuNP-safe cavitation mechanism as well as to investigate the deformation mechanism of the AuNPs at high laser fluences.