Optical properties of two-dimensional tin nanosheets epitaxially grown on graphene.

Heterostacks formed by combining two-dimensional materials show novel properties which are of great interest for new applications in electronics, photonics and even twistronics, the new emerging field born after the outstanding discoveries on twisted graphene. Here, we report the direct growth of tin nanosheets at the two-dimensional limit via molecular beam epitaxy on chemical vapor deposited graphene on Al2O3(0001). The mutual interaction between the tin nanosheets and graphene is evidenced by structural and chemical investigations. On the one hand, Raman spectroscopy indicates that graphene undergoes compressive strain after the tin growth, while no charge transfer is observed. On the other hand, chemical analysis shows that tin nanosheets interaction with sapphire is mediated by graphene avoiding the tin oxidation occurring in the direct growth on this substrate. Remarkably, optical measurements show that the absorption of tin nanosheets exhibits a graphene-like behavior with a strong absorption in the ultraviolet photon energy range, therein resulting in a different optical response compared to tin nanosheets on bare sapphire. The optical properties of ultra-thin tin films therefore represent an open and flexible playground for the absorption of light in a broad range of the electromagnetic spectrum and technologically relevant applications for photon harvesting and sensors.

Stability and universal encapsulation of epitaxial Xenes.

In the realm of two-dimensional material frameworks, single-element graphene-like lattices, known as Xenes, pose several issues concerning their environmental stability, with implications for their use in technology transfer to a device layout. In this Discussion, we scrutinize the chemical reactivity of epitaxial silicene, taken as a case in point, in oxygen-rich environments. The oxidation of silicene is detailed by means of a photoemission spectroscopy study upon carefully dosing molecular oxygen under vacuum and subsequent exposure to ambient conditions, showing different chemical reactivity. We therefore propose a sequential Al2O3 encapsulation of silicene as a solution to face degradation, proving its effectiveness by virtue of the interaction between silicene and a silver substrate. Based on this method, we generalize our encapsulation scheme to a large number of metal-supported Xenes by taking into account the case of epitaxial phosphorene-on-gold.

Thickness determination of anisotropic van der Waals crystals by raman spectroscopy: the case of black phosphorus.

The large foreseeable use two-dimensional materials in nanotechnology consequently demands precise methods for their thickness measurements. Usually, having a quick and easy methodology is a key requisite for the inspection of the large number of flakes produced by exfoliation methods. An effective option in this respect relies on the measurement of the intensity of Raman spectra, which can be used even when the flakes are encapsulated by a transparent protective layer. However, when using this methodology, special attention should be paid to the crystalline anisotropy of the examined material. Specifically, for the case of black phosphorus flakes, the absolute experimental determination of the thickness is rather difficult because the material is characterized by a low symmetry and also because the Raman tensors are complex quantities. In this work, we exploited Raman spectroscopy to measure the thickness of black phosphorous flakes using silicon as reference material for intensity calibrations. We found out that we can determine the thickness of a flake above 5 nm with an accuracy of about 20%. We tested the reproducibility of the method on two different setups, finding similar results. The method can be applied also to other van der Waals materials with a Raman band characterized by the same Raman tensor.

Silicene, silicene derivatives, and their device applications.

Silicene, the ultimate scaling of a silicon atomic sheet in a buckled honeycomb lattice, represents a monoelemental class of two-dimensional (2D) materials similar to graphene but with unique potential for a host of exotic electronic properties. Nonetheless, there is a lack of experimental studies largely due to the interplay between material degradation and process portability issues. This review highlights the state-of-the-art experimental progress and future opportunities in the synthesis, characterization, stabilization, processing and experimental device examples of monolayer silicene and its derivatives. The electrostatic characteristics of the Ag-removal silicene field-effect transistor exhibit ambipolar charge transport, corroborating with theoretical predictions on Dirac fermions and Dirac cone in the band structure. The electronic structure of silicene is expected to be sensitive to substrate interaction, surface chemistry, and spin-orbit coupling, holding great promise for a variety of novel applications, such as topological bits, quantum sensing, and energy devices. Moreover, the unique allotropic affinity of silicene with single-crystalline bulk silicon suggests a more direct path for the integration with or revolution to ubiquitous semiconductor technology. Both the materials and process aspects of silicene research also provide transferable knowledge to other Xenes like stanene, germanene, phosphorene, and so forth.

Optical Conductivity of Two-Dimensional Silicon: Evidence of Dirac Electrodynamics.

The exotic electrodynamics properties of graphene come from the linearly dispersive electronic bands that host massless Dirac electrons. A similar behavior was predicted to manifest in freestanding silicene, the silicon counterpart of graphene, thereby envisaging a new route for silicon photonics. However, the access to silicene exploitation in photonics was hindered so far by the use of optically inappropriate substrates in experimentally realized silicene. Here we report on the optical conductivity of silicon nanosheets epitaxially grown on optically transparent Al2O3(0001) from a thickness of a few tens of nanometers down to the extreme two-dimensional (2D) limit. When a 2D regime is approached, a Dirac-like electrodynamics can be deduced from the observation of a low-energy optical conductivity feature owing to a silicene-based interfacing to the substrate.

Buckled two-dimensional Xene sheets.

Silicene, germanene and stanene are part of a monoelemental class of two-dimensional (2D) crystals termed 2D-Xenes (X = Si, Ge, Sn and so on) which, together with their ligand-functionalized derivatives referred to as Xanes, are comprised of group IVA atoms arranged in a honeycomb lattice - similar to graphene but with varying degrees of buckling. Their electronic structure ranges from trivial insulators, to semiconductors with tunable gaps, to semi-metallic, depending on the substrate, chemical functionalization and strain. More than a dozen different topological insulator states are predicted to emerge, including the quantum spin Hall state at room temperature, which, if realized, would enable new classes of nanoelectronic and spintronic devices, such as the topological field-effect transistor. The electronic structure can be tuned, for example, by changing the group IVA element, the degree of spin-orbit coupling, the functionalization chemistry or the substrate, making the 2D-Xene systems promising multifunctional 2D materials for nanotechnology. This Perspective highlights the current state of the art and future opportunities in the manipulation and stability of these materials, their functions and applications, and novel device concepts.

Towards a uniform and large-scale deposition of MoS2 nanosheets via sulfurization of ultra-thin Mo-based solid films.

Large-scale integration of MoS2 in electronic devices requires the development of reliable and cost-effective deposition processes, leading to uniform MoS2 layers on a wafer scale. Here we report on the detailed study of the heterogeneous vapor-solid reaction between a pre-deposited molybdenum solid film and sulfur vapor, thus resulting in a controlled growth of MoS2 films onto SiO2/Si substrates with a tunable thickness and cm(2)-scale uniformity. Based on Raman spectroscopy and photoluminescence, we show that the degree of crystallinity in the MoS2 layers is dictated by the deposition temperature and thickness. In particular, the MoS2 structural disorder observed at low temperature (<750 °C) and low thickness (two layers) evolves to a more ordered crystalline structure at high temperature (1000 °C) and high thickness (four layers). From an atomic force microscopy investigation prior to and after sulfurization, this parametrical dependence is associated with the inherent granularity of the MoS2 nanosheet that is inherited by the pristine morphology of the pre-deposited Mo film. This work paves the way to a closer control of the synthesis of wafer-scale and atomically thin MoS2, potentially extendable to other transition metal dichalcogenides and hence targeting massive and high-volume production for electronic device manufacturing.

Terahertz and Infrared Plasmon Polaritons in PtTe2 Type-II Dirac Topological Semimetal.

Surface plasmon polaritons (SPPs) are electromagnetic excitations existing at the interface between a metal and a dielectric. SPPs provide a promising path in nanophotonic devices for light manipulation at the micro and nanoscale with applications in optoelectronics, biomedicine, and energy harvesting. Recently, SPPs are extended to unconventional materials like graphene, transparent oxides, superconductors, and topological systems characterized by linearly dispersive electronic bands. In this respect, 3D Dirac and Weyl semimetals offer a promising frontier for infrared (IR) and terahertz (THz) radiation tuning by topologically-protected SPPs. In this work, the THz-IR optical response of platinum ditelluride (PtTe2) type-II Dirac topological semimetal films grown on Si substrates is investigated. SPPs generated on microscale ribbon arrays of PtTe2 are detected in the far-field limit, finding an excellent agreement among measurements, theoretical models, and electromagnetic simulation data. The far-field measurements are further supported by near-field IR data which indicate a strong electric field enhancement due to the SPP excitation near the ribbon edges. The present findings indicate that the PtTe2 ribbon array appears an ideal active layout for geometrically tunable SPPs thus inspiring a new fashion of optically tunable materials in the technologically demanding THz and IR spectrum.

Emerging Two-Dimensional Materials: Inspiring Nanotechnologies for Smart Energy Management.

Two-dimensional (2D) materials are a class of materials that can be reduced to a thickness of a few layers, exhibiting peculiar and innovative properties relative to their three-dimensional solid counterparts [...].

All-around encapsulation of silicene.

Silicene or the two-dimensional (2D) graphene-like silicon allotrope has recently emerged as a promising candidate for various applications in nanotechnology. However, concerns on the silicene stability still persist to date and need to be addressed aiming at the fabrication of competing and durable silicene-based devices. Here, we present an all-around encapsulation methodology beyond the current state-of-the-art silicene configuration, namely silicene sandwiched in between a capping layer (e.g., Al2O3) and the supporting substrate (e.g., Ag). In this framework, the insertion of one or two sacrificial 2D Sn layers enables the realization of different atomically thin encapsulation schemes, preserving the pristine properties of silicene while decoupling it from the growth template. On one hand, the epitaxy of a 2D Sn layer before silicene allows for the removal of the Ag substrate with no effect on silicene which in turn can be easily gated, for example, with an oxide layer on its top face. On the other hand, a full 2D encapsulation scheme, where top and bottom faces of silicene are protected by 2D Sn layers, gives rise to an atomically thin and cm2-scaled membrane preventing degradation of silicene for months. Both schemes thus constitute an advancement for the silicene stability and encapsulation in ambient conditions, paving the way to further exploitation in flexible electronics and photonics.

Solid phase crystallization of amorphous silicon at the two-dimensional limit.

The epitaxy of silicene-on-Ag(111) renewed considerable interest in silicon (Si) when scaled down to the two-dimensional (2D) limit. This remains one of the most explored growth cases in the emerging 2D material fashion beyond graphene. However, out of a strict silicene framework, other allotropic forms of Si still deserve attention owing to technological purposes. Here, we present 2D Solid Phase Crystallization (SPC) of Si starting from an amorphous-Si on Ag(111) in atomic coverage to gain a crystalline-Si layer by post-growth annealing below 450 °C, namely Complementary Metal Oxide Semiconductor (CMOS) Back-End-of-Line (BEOL) thermal budget limit. Moreover, considering the benefit of the 2D-SPC scheme, we managed to write crystalline-Si pixels on the amorphous-Si matrix. Our in situ and ex situ analyses show that an in-plane interface or a lateral heterojunction between amorphous and crystalline-Si is formed. This amorphous-to-crystalline phase transformation suggests that 2D silicon may stem from an epitaxially grown layer and thermal self-organization/assembling.

Crystal phase engineering of silicene by Sn-modified Ag(111).

The synthesis of silicene by direct growth on silver is characterized by the formation of multiple phases and domains, posing severe constraints on the spatial charge conduction towards a technological transfer of silicene to electronic transport devices. Here we engineer the silicene/silver interface by two schemes, namely, either through decoration by Sn atoms, forming an Ag2Sn surface alloy, or by buffering the interface with a stanene layer. Whereas in both cases Raman spectra confirm the typical features as expected from silicene, by electron diffraction we observe that a very well-ordered single-phase 4 × 4 monolayer silicene is stabilized by the decorated surface, while the buffered interface exhibits a sharp phase at all silicon coverages. Both interfaces also stabilize the ordered growth of a phase in the multilayer range, featuring a single rotational domain. Theoretical ab initio models are used to investigate low-buckled silicene phases (4 × 4 and a competing one) and various structures, supporting the experimental findings. This study provides new and promising technology routes to manipulate the silicene structure by controlled phase selection and single-crystal silicene growth on a wafer-scale.

Bendable Silicene Membranes.

Due to their superior mechanical properties, 2D materials have gained interest as active layers in flexible devices co-integrating electronic, photonic, and straintronic functions altogether. To this end, 2D bendable membranes compatible with the technological process standards and endowed with large-scale uniformity are highly desired. Here, it is reported on the realization of bendable membranes based on silicene layers (the 2D form of silicon) by means of a process in which the layers are fully detached from the native substrate and transferred onto arbitrary flexible substrates. The application of macroscopic mechanical deformations induces a strain-responsive behavior in the Raman spectrum of silicene. It is also shown that the membranes under elastic tension relaxation are prone to form microscale wrinkles displaying a local generation of strain in the silicene layer consistent with that observed under macroscopic mechanical deformation. Optothermal Raman spectroscopy measurements reveal a curvature-dependent heat dispersion in silicene wrinkles. Finally, as compelling evidence of the technological potential of the silicene membranes, it is demonstrated that they can be readily introduced into a lithographic process flow resulting in the definition of flexible device-ready architectures, a piezoresistor, and thus paving the way to a viable advance in a fully silicon-compatible technology framework.

Optothermal Raman Spectroscopy of Black Phosphorus on a Gold Substrate.

With black phosphorus being a promising two-dimensional layered semiconductor for application to electronics and optoelectronics, an issue remains as to how heat diffusion is managed when black phosphorus is interfaced with metals, namely in a typical device heterojunction. We use Raman spectroscopy to investigate how the laser-induced heat affects the phonon modes at the interface by comparing the experimental data with a finite element simulation based on a localized heat diffusion. The best convergence is found taking into account an effective interface thermal conductance, thus indicating that heat dissipation at the Au-supported black phosphorus nanosheets is limited by interface effect.

Closing the THz gap with Dirac semimetals.

High-performance THz photodetection is unprecedentedly accessed by integrating a topological Dirac (Weyl) semimetal in a carefully designed antenna at deep-subwavelength scales.

Ambient Pressure Chemical Vapor Deposition of Flat and Vertically Aligned MoS2 Nanosheets.

Molybdenum disulfide (MoS2) got tremendous attention due to its atomically thin body, rich physics, and high carrier mobility. The controlled synthesis of large area and high crystalline monolayer MoS2 nanosheets on diverse substrates remains a challenge for potential practical applications. Synthesizing different structured MoS2 nanosheets with horizontal and vertical orientations with respect to the substrate surface would bring a configurational versatility with benefit for numerous applications, including nanoelectronics, optoelectronics, and energy technologies. Among the proposed methods, ambient pressure chemical vapor deposition (AP-CVD) is a promising way for developing large-scale MoS2 nanosheets because of its high flexibility and facile approach. Here, we show an effective way for synthesizing large-scale horizontally and vertically aligned MoS2 on different substrates such as flat SiO2/Si, pre-patterned SiO2 and conductive substrates (TaN) benefit various direct TMDs production. In particular, we show precise control of CVD optimization for yielding high-quality MoS2 layers by changing growth zone configuration and the process steps. We demonstrated that the influence of configuration variability by local changes of the S to MoO3 precursor positions in the growth zones inside the CVD reactor is a key factor that results in differently oriented MoS2 formation. Finally, we show the layer quality and physical properties of as-grown MoS2 by means of different characterizations: Raman spectroscopy, scanning electron microscopy (SEM), photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS). These experimental findings provide a strong pathway for conformally recasting AP-CVD grown MoS2 in many different configurations (i.e., substrate variability) or motifs (i.e., vertical or planar alignment) with potential for flexible electronics, optoelectronics, memories to energy storage devices.

Optical and thermal responses of silicene in Xene heterostructures.

Stabilization of silicene and preservation of its structural and electronic properties are essential for its processing and future integration into devices. The stacking of silicene on stanene, creating a Xene-based heterostructure, proves to be a viable new route in this respect. Here we demonstrate the effectiveness of a stanene layer in breaking the strong interaction between silicene and the Ag(111) substrate. The role of stanene as a 'buffer' layer is investigated by analyzing the optical response of epitaxial silicene through both power-dependent Raman spectroscopy and reflectivity measurements in the near infrared (NIR)-ultraviolet (UV) spectral range. Finally, we point out a Xene-induced shift of the silver plasma edge that paves the way for the development of a new approach to engineering the metal plasmonic response.

Extreme Bendability of Atomically Thin MoS2 Grown by Chemical Vapor Deposition Assisted by Perylene-Based Promoter.

Shaping two-dimensional (2D) materials in arbitrarily complex geometries is a key to designing their unique physical properties in a controlled fashion. This is an elegant solution, taking benefit from the extreme flexibility of the 2D layers but requiring the ability to force their spatial arrangement from flat to curved geometries in a delicate balance among free-energy contributions from strain, slip-and-shear mechanisms, and adhesion to the substrate. Here, we report on a chemical vapor deposition approach, which takes advantage of the surfactant effects of organic molecules, namely the tetrapotassium salt of perylene-3,4,9,10-tetracarboxylic acid (PTAS), to conformally grow atomically thin layers of molybdenum disulphide (MoS2) on arbitrarily nanopatterned substrates. Using atomically resolved transmission electron microscope images and density functional theory calculations, we show that the most energetically favorable condition for the MoS2 layers consists of its adaptation to the local curvature of the patterned substrate through a shear-and-slip mechanism rather than strain accumulation. This conclusion also reveals that the perylene-based molecules have a role in promoting the adhesion of the layers onto the substrate, no matter the local-scale geometry.