Thionine Self-Assembled Structures on Graphene: Formation, Organization, and Doping.

The association of organic molecules with two-dimensional (2D) materials, creating hybrid systems with mutual influences, constitutes an important testbed for both basic science self-assembly studies and perspective applications. Following this concept, in this work, we show a rich phenomenology that is involved in the interaction of thionine with graphene, leading to a hybrid material formed by well-organized self-assembled structures atop graphene. This composite system is investigated by atomic force microscopy, electric transport measurements, Raman spectroscopy, and first principles calculations, which show (1) an interesting time evolution of thionine self-assembled structures atop graphene; (2) a highly oriented final molecular assembly (in accordance with the underlying graphene surface symmetry); and (3) a strong n-type doping effect introduced in graphene by thionine. The nature of the thionine-substrate interaction is further analyzed in experiments using mica as a polar substrate. The present results may help pave the way to achieve tailored 2D material hybrid devices via properly chosen molecular self-assembly processes.

Temperature-induced coexistence of a conducting bilayer and the bulk-terminated surface of the topological insulator Bi2Te3.

Topological insulators such as Bi2Se3 and Bi2Te3 have extremely promising transport properties, due to their unique electronic behavior: they are insulators in the bulk and conducting at the surface. Recently, the coexistence of two types of surface conducting channels has been observed for Bi2Se3, one being Dirac electrons from the topological state and the other electrons from a conventional two-dimensional gas. As an explanation for this effect, a possible structural modification of the surface of these materials has been hypothesized. Using scanning tunneling microscopy we have directly observed the coexistence of a conducting bilayer and the bare surface of bulk-terminated Bi2Te3. X-ray crystal truncation rod scattering was used to directly show the stabilization of this epitaxial bilayer which is primarily composed of bismuth. Using this information, we have performed density functional theory calculations to determine the electronic properties of the possible surface terminations. They can be used to understand recent angular resolved photoemission data which have revealed this dual surface electronic behavior.

Evidence of thickness-dependent surface-induced ferroelectricity in few-layer germanium sulfide obtained via scanning tunneling spectroscopy.

The discovery of ferroelectricity in two-dimensional van der Waals materials has sparked enormous interest from the scientific community, due to its possible applications in next-generation nanoelectronic devices, such as random-access memory devices, digital signal processors, and solar cells, among others. In the present study, we used vapor phase deposition to synthesize ultrathin germanium sulfide nano-flakes on a highly oriented pyrolytic graphite substrate. Nanostructures of variable thicknesses were characterized using scanning tunneling microscopy and spectroscopy. Tunneling currents under forward and backward biases were measured as a function of nano-flake thickness. Remarkably, we clearly observed a hysteresis pattern, which we attributed to surface ferroelectric behavior, consistent with the screening conditions of polarization charges. The effect increases as the number of layers is reduced. This experimental result may be directly applicable to miniaturized memory devices, given the two-dimensional nature of this effect.

Pressure tuning of minibands in MoS2/WSe2 heterostructures revealed by moiré phonons.

Moiré superlattices of two-dimensional heterostructures arose as a new platform to investigate emergent behaviour in quantum solids with unprecedented tunability. To glean insights into the physics of these systems, it is paramount to discover new probes of the moiré potential and moiré minibands, as well as their dependence on external tuning parameters. Hydrostatic pressure is a powerful control parameter, since it allows to continuously and reversibly enhance the moiré potential. Here we use high pressure to tune the minibands in a rotationally aligned MoS2/WSe2 moiré heterostructure, and show that their evolution can be probed via moiré phonons. The latter are Raman-inactive phonons from the individual layers that are activated by the moiré potential. Moiré phonons manifest themselves as satellite Raman peaks arising exclusively from the heterostructure region, increasing in intensity and frequency under applied pressure. Further theoretical analysis reveals that their scattering rate is directly connected to the moiré potential strength. By comparing the experimental and calculated pressure-induced enhancement, we obtain numerical estimates for the moiré potential amplitude and its pressure dependence. The present work establishes moiré phonons as a sensitive probe of the moiré potential as well as the electronic structures of moiré systems.

Electronic Band Tuning and Multivalley Raman Scattering in Monolayer Transition Metal Dichalcogenides at High Pressures.

Transition metal dichalcogenides (TMDs) possess spin-valley locking and spin-split K/K' valleys, which have led to many fascinating physical phenomena. However, the electronic structure of TMDs also exhibits other conduction band minima with similar properties, the Q/Q' valleys. The intervalley K-Q scattering enables interesting physical phenomena, including multivalley superconductivity, but those effects are typically hindered in monolayer TMDs due to the large K-Q energy difference (ΔEKQ). To unlock elusive multivalley phenomena in monolayer TMDs, it is desirable to reduce ΔEKQ, while being able to sensitively probe the valley shifts and the multivalley scattering processes. Here, we use high pressure to tune the electronic properties of monolayer MoS2 and WSe2 and probe K-Q crossing and multivalley scattering via double-resonance Raman (DRR) scattering. In both systems, we observed a pressure-induced enhancement of the double-resonance LA and 2LA Raman bands, which can be attributed to a band gap opening and ΔEKQ decrease. First-principles calculations and photoluminescence measurements corroborate this scenario. In our analysis, we also addressed the multivalley nature of the DRR bands for WSe2. Our work establishes the DRR 2LA and LA bands as sensitive probes of strain-induced modifications to the electronic structure of TMDs. Conversely, their intensity could potentially be used to monitor the presence of compressive or tensile strain in TMDs. Furthermore, the ability to probe K-K' and K-Q scattering as a function of strain shall advance our understanding of different multivalley phenomena in TMDs such as superconductivity, valley coherence, and valley transport.

Modulating the electronic properties along carbon nanotubes via tube-substrate interaction.

We study single wall carbon nanotubes (SWNTs) deposited on quartz. Their Raman spectrum depends on the tube-substrate morphology, and in some cases, it shows that the same SWNT-on-quartz system exhibits a mixture of semiconductor and metal behavior, depending on the orientation between the tube and the substrate. We also address the problem using electric force microscopy and ab initio calculations, both showing that the electronic properties along a single SWNT are being modulated via tube-substrate interaction.

Covalently Linked Porphyrins as One-Dimensional Conductors.

We apply first-principles calculations to address the problem of the formation and characterization of covalently linked porphyrin-like structures. We show that upon pressure a rehybridization process takes place which leads to one-dimensional compounds resembling nanothreads, in which carbon atoms are all 4-fold coordinated. We also show that the resulting nanostructures have metallic character and possess remarkable mechanical properties. Moreover, in the case of porphyrin-metal complexes, we find that the covalently linked structures may be a platform for the stabilization of straight metallic wires.

Interplay between structural deformations and flat band phenomenology in twisted bilayer antimonene.

In this work we apply first principles calculations to investigate the flat band phenomenology in twisted antimonene bilayer. We show that the relatively strong interlayer interactions which characterize this compound have profound effects in the emergence and properties of the flat bands. Specifically, when the moiré length becomes large enough to create well defined stacking patterns along the structure, out-of-plane displacements take place and are stabilized in the regions dominated by the AB stacking, leading to the emergence of flat bands. The interplay between structural and electronic properties allows for detection of flat bands in higher twist angles comparable to other two-dimensional materials. We also show that their energy position may be modulated by noncovalent functionalization with electron acceptor molecules.

First-principles investigation of electrochemical properties of gold nanoparticles.

A first-principles formalism is employed to investigate the effects of size and structure on the electronic and electrochemical properties of Au nanoparticles with diameters between 0.8 and 2.0 nm. We find that the behavior of the ionization potentials (IPs) and the electron affinities (EAs) as a function of cluster size can be separated into many-body and single-electron contributions. The many-body part is only (and continuously) dependent on particle size, and can be very well described in terms of the capacitance of classical spherical conductors for clusters with more the 55 atoms. For smaller clusters, molecule-like features lead the capacitance and fundamental gap to differ systematically from those of a classical conductor with decreasing size. The single-electron part fluctuates with particle structure. Upon calculating the neutral chemical potential micro(0) = (IP+EA)/2, the many-body contributions cancel out, resulting in fluctuations of micro(0) around the bulk Au work function, consistent with experimental results. The values of IP and EA changes upon functionalization with thiolated molecules, and the magnitude of the observed changes does not depend on the length of the alkane chain. The functionalization can also lead to a transition from metallic to non-metallic behavior in small nanoparticles, which is consistent with experimental observations.

Oxidation-driven formation of precisely ordered antimonene nanoribbons.

The control of geometric structure is a key aspect in the interplay between theoretical predictions and experimental realization in the science and applications of nanomaterials. This is particularly important in one-dimensional structures such as nanoribbons, in which the edge morphology dictates most of the electronic behavior in low energy scale. In the present work we demonstrate by means of first principles calculations that the oxidation of few-layer antimonene may lead to an atomic restructuring with formation of ordered multilayer zig-zag nanoribbons. The widths are uniquely determined by the number of layers of the initial structure, allowing the synthesis of ultranarrow ribbons and chains. We also show that the process may be extended to other compounds based on group V elements, such as arsenene. The characterization of the electronic structure of the resulting ribbons shows an important effect of stacking on band gaps and on modulation of electronic behavior.

Compression-Induced Modification of Boron Nitride Layers: A Conductive Two-Dimensional BN Compound.

The ability to create materials with improved properties upon transformation processes applied to conventional materials is the keystone of materials science. Here, hexagonal boron nitride (h-BN), a large-band-gap insulator, is transformed into a conductive two-dimensional (2D) material- bonitrol-that is stable at ambient conditions. The process, which requires compression of at least two h-BN layers and hydroxyl ions, is characterized via scanning probe microscopy experiments and ab initio calculations. This material and its creation mechanism represent an additional strategy for the transformation of known 2D materials into artificial advanced materials with exceptional properties.

Raman evidence for pressure-induced formation of diamondene.

Despite the advanced stage of diamond thin-film technology, with applications ranging from superconductivity to biosensing, the realization of a stable and atomically thick two-dimensional diamond material, named here as diamondene, is still forthcoming. Adding to the outstanding properties of its bulk and thin-film counterparts, diamondene is predicted to be a ferromagnetic semiconductor with spin polarized bands. Here, we provide spectroscopic evidence for the formation of diamondene by performing Raman spectroscopy of double-layer graphene under high pressure. The results are explained in terms of a breakdown in the Kohn anomaly associated with the finite size of the remaining graphene sites surrounded by the diamondene matrix. Ab initio calculations and molecular dynamics simulations are employed to clarify the mechanism of diamondene formation, which requires two or more layers of graphene subjected to high pressures in the presence of specific chemical groups such as hydroxyl groups or hydrogens.The synthesis of two-dimensional diamond is the ultimate goal of diamond thin-film technology. Here, the authors perform Raman spectroscopy of bilayer graphene under pressure, and obtain spectroscopic evidence of formation of diamondene, an atomically thin form of diamond.

Charge transfer between carbon nanotubes on surfaces.

The charge transfer between neighboring single-walled carbon nanotubes (SWNTs) on a silicon oxide surface was investigated as a function of both the SWNT nature (metallic or semiconducting) and the anode/cathode distance using scanning probe techniques. Two main mechanisms were observed: a direct electron tunneling described by the typical Fowler-Nordheim model, and indirect electron transfer (hopping) mediated by functional groups on the supporting surface. Both mechanisms depend on the SWNT nature and on the anode/cathode separation: direct electron tunneling dominates the charge transfer process for metallic SWNTs, especially for large distances, while both mechanisms compete with each other for semiconducting SWNTs, prevailing one over the other depending on the anode/cathode separation. These mechanisms may significantly influence the design and operation of SWNT-based electronic devices.

Chemical stabilization and improved thermal resilience of molecular arrangements: possible formation of a surface network of bonds by multiple pulse atomic layer deposition.

In this work, we make use of an atomic layer deposition (ALD) surface reaction based on trimethyl-aluminum (TMA) and water to modify O-H terminated self-assembled layers of octadecylphosphonic acid (OPA). The structural modifications were investigated by X-ray reflectivity, X-ray diffraction, and atomic force microscopy. We observed a significant improvement in the thermal stability of ALD-modified molecules, with the existence of a supramolecular packing structure up to 500 °C. Following the experimental observations, density functional theory (DFT) calculations indicate the possibility of formation of a covalent network with aluminum atoms connecting OPA molecules at terrace surfaces. Chemical stability is also achieved on top of such a composite surface, inhibiting further ALD oxide deposition. On the other hand, in the terrace edges, where the covalent array is discontinued, the chemical conditions allow for oxide growth. Analysis of the DFT results on band structure and density of states of modified OPA molecules suggests that besides the observed thermal resilience, the dielectric character of OPA layers is preserved. This new ALD-modified OPA composite is potentially suitable for applications such as dielectric layers in organic devices, where better thermal performance is required.

Asymmetric effect of oxygen adsorption on electron and hole mobilities in bilayer graphene: long- and short-range scattering mechanisms.

We probe electron and hole mobilities in bilayer graphene under exposure to molecular oxygen. We find that the adsorbed oxygen reduces electron mobilities and increases hole mobilities in a reversible and activated process. Our experimental results indicate that hole mobilities increase due to the screening of long-range scatterers by oxygen molecules trapped between the graphene and the substrate. First principle calculations show that oxygen molecules induce resonant states close to the charge neutrality point. Electron coupling with such resonant states reduces the electron mobilities, causing a strong asymmetry between electron and hole transport. Our work demonstrates the importance of short-range scattering due to adsorbed species in the electronic transport in bilayer graphene on SiO2 substrates.

Two-dimensional molecular crystals of phosphonic acids on graphene.

The synthesis and characterization of two-dimensional (2D) molecular crystals composed of long and linear phosphonic acids atop graphene is reported. Using scanning probe microscopy in combination with first-principles calculations, we show that these true 2D crystals are oriented along the graphene armchair direction only, thereby enabling an easy determination of graphene flake orientation. We have also compared the doping level of graphene flakes via Raman spectroscopy. The presence of the molecular crystal atop graphene induces a well-defined shift in the Fermi level, corresponding to hole doping, which is in agreement with our ab initio calculations.

Edge States and magnetism in carbon nanotubes with line defects.

We apply first-principles calculations to investigate the interplay between electronic and magnetic properties of carbon nanotubes with line defects. We consider three types of defects: lines of C--O--C epoxy groups, and defects resulting from the substitution of the oxygen atoms by CH2 or C2H4 divalent radicals. We find that the line defects behave as pairs of coupled graphene edge states, and a variety of electronic and magnetic ground states is predicted as a function of defect type, nanotube diameter, and a possibly applied transverse electric field.

Electron states in a lattice of Au nanoparticles: the role of strain and functionalization.

We make use of first-principles calculations to study the effects of functionalization and compression on the electronic properties of 2D lattices of Au nanoparticles. We consider Au38 particles capped by methylthiol molecules and possibly functionalized by the dithiolated conjugated molecules benzenedimethanethiol and benzenedicarbothialdehyde. We find that the nonfunctionalized lattices are insulating, with negligible band dispersions even for a compression of 20% of the lattice constant. Distinct behaviors of the dispersion of the lowest conduction band as a function of compression are predicted for functionalized lattices: The band dispersion of the benzenedimethanethiol-functionalized lattice increases considerably with compression, while that of the benzenedicarbothialdehyde-functionalized lattice decreases.