Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton–phonon coupling in two-dimensional materials. We present here resonant Raman experiments of ...single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin–orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin–orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton–phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton–phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic).
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Although the main Raman features of semiconducting transition metal dichalcogenides are well known for the monolayer and bulk, there are important differences exhibited by few layered systems which ...have not been fully addressed. WSe2 samples were synthesized and ab-initio calculations carried out. We calculated phonon dispersions and Raman-active modes in layered systems: WSe2, MoSe2, WS2 and MoS2 ranging from monolayers to five-layers and the bulk. First, we confirmed that as the number of layers increase, the E', E″ and E2g modes shift to lower frequencies, and the A'1 and A1g modes shift to higher frequencies. Second, new high frequency first order A'1 and A1g modes appear, explaining recently reported experimental data for WSe2, MoSe2 and MoS2. Third, splitting of modes around A'1 and A1g is found which explains those observed in MoSe2. Finally, exterior and interior layers possess different vibrational frequencies. Therefore, it is now possible to precisely identify few-layered STMD.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
The magnetic and electronic properties of MoS(2) nanoribbons with zigzag and armchair edges are investigated using LSDA-DFT. We found that the properties of the nanoribbons are very different from ...bulk MoS(2) due to edge states. Armchair nanoribbons could be metallic and exhibit a magnetic moment; however, when passivating with hydrogen, they become semiconducting. Zigzag nanoribbons are metallic and exhibit unusual magnetic properties regardless of passivation. Our results could explain the recent evidence of ferromagnetism in flat MoS(2) clusters, and motivate the synthesis of novel MoS(2) nanosystems.
Crossing single-walled carbon nanotubes can be joined by electron beam welding to form molecular junctions. Stable junctions of various geometries are created in situ in a transmission electron ...microscope. Electron beam exposure at high temperatures induces structural defects which promote the joining of tubes via cross-linking of dangling bonds. The observations are supported by molecular dynamics simulations which show that the creation of vacancies and interstitials induces the formation of junctions involving seven- or eight-membered carbon rings at the surface between the tubes.
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Substitutional phosphorus doping in single-wall carbon nanotubes (SWNTs) is investigated by density functional theory and resonance Raman spectroscopy. Electronic structure calculations predict ...charge localization on the phosphorus atom, generating nondispersive valence and conduction bands close to the Fermi level. Besides confirming sustitutional doping, accurate analysis of electron and phonon renormalization effects in the double-resonance Raman process elucidates the different nature of the phosphorus donor doping (localized) when compared to nitrogen substitutional doping (nonlocalized) in SWNTs.
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First-principles density functional theory calculations are performed on dopamine–graphene systems in the presence of an external electric field. The graphene lattice is also modified via ...substitutional boron- and nitrogen-doping, and via the introduction of defects (monovacancy and Thrower–Stone–Wales). The geometry optimization, electronic density of states, cohesive energy, electronic charge density, and wave functions are analyzed. Our results revealed that dopamine is anchored on the surface of graphene via a physisorption mechanism, and the cohesive strength varies as B-doped > N-doped > vacancy defect > Thrower–Stone–Wales defect. Boron-doped graphene exhibits valence states with dopamine molecules; furthermore, this system showed the strongest cohesive energy. When an electric field is applied, we observe shifts in the valence states near the Fermi level producing a decrease in the molecule–layer interaction. We envisage that the present results could help in developing novel biosensors based on doped/defective graphene field-effect transistor devices.
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Gold nanoparticles were selectively attached to chemically functionalized surface sites on nitrogen-doped carbon (CN x ) nanotubes. A cationic polyelectrolyte was adsorbed on the surface of the ...nanotubes by electrostatic interaction between carboxyl groups on the chemically oxidized nanotube surface and polyelectrolyte chains. Negatively charged 10 nm gold nanoparticles from a gold colloid suspension were subsequently anchored to the surface of the nanotubes through the electrostatic interaction between the polyelectrolyte and the nanoparticles. This approach provides an efficient method to attach other nanostructures to carbon nanotubes and can be used as an illustrative detection of the functional groups on carbon nanotube surfaces.
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Nitrogen-doped carbon nanotubes have been synthesized using pyrolysis and characterized by scanning tunneling spectroscopy and transmission electron microscopy. The doped nanotubes are all metallic ...and exhibit strong electron donor states near the Fermi level. Using tight-binding and ab initio calculations, we observe that pyridine-like N structures are responsible for the metallic behavior and the prominent features near the Fermi level. These electron rich structures are the first example of n-type nanotubes, which could pave the way to real molecular heterojunction devices.
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A thermal stability study of graphene nanoribbons annealed up to 2800°C is presented. We noted a progressive annihilation of lattice defects as the heat treatment temperature is raised. Single and ...multiple loop formation were observed on the ribbons edges as the temperature increases.
We present a high temperature heat treatment study of CVD-grown graphene nanoribbons annealed up to 2800°C, demonstrating a progressive annihilation of lattice defects as the heat treatment temperature is raised. Starting at 1500°C, single and multiple loop formation were observed on the ribbons edges as the temperature was increased. The structural changes of the samples are documented by X-ray diffraction, Raman spectroscopy, TGA, SEM, and HRTEM. This work indicates that nanoribbon annealing eventually leads to defect-free samples, through graphitization and edge loop formation. The annealed material exhibits structural differences that could be tailored for a variety of specific applications.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The dependence of the radial breathing modes (RBMs) and the tangential mode (G-band) of triple-wall carbon nanotubes (TWCNTs) under hydrostatic pressure is reported. Pressure screening effects are ...observed for the innermost tubes of TWCNTs similar to what has been already found for DWCNTs. However, using the RBM pressure coefficients in conjunction with the histogram of the diameter distribution, we were able to separate the RBM Raman contribution related to the intermediate tubes of TWCNTs from that related to the inner tubes of DWCNTs. By combining Raman spectroscopy and high-pressure measurements, it was possible to identify these two categories of inner tubes even if the two tubes exhibit the same diameters because their pressure response is different. Furthermore, it was possible to observe similar RBM profiles for the innermost tubes of TWCNTs using different resonance laser energies but also under different pressure conditions. This is attributed to changes in the electronic transition energies caused by small pressure-induced deformations. By using Raman spectroscopy, it was possible to estimate the displacement of the optical energy levels with pressure.
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