Ana Laura Elías

Extraordinary Room-Temperature Photoluminescence in Triangular WS2 Monolayers

Individual monolayers of metal dichalcogenides are atomically thin two-dimensional crystals with attractive physical properties different from those of their bulk counterparts. Here we describe the direct synthesis of WS2 monolayers with triangular morphologies and strong room-temperature photoluminescence (PL). The Raman response as well as the luminescence as a function of the number of S-W-S layers is also reported. The PL weakens with increasing number of layers due to a transition from direct band gap in a monolayer to indirect gap in multilayers. The edges of WS2 monolayers exhibit PL signals with extraordinary intensity, around 25 times stronger than that at the platelets center. The structure and chemical composition of the platelet edges appear to be critical for PL enhancement.

Identification of individual and few layers of WS2 using Raman Spectroscopy

The Raman scattering of single- and few-layered WS2 is studied as a function of the number of S-W-S layers and the excitation wavelength in the visible range (488, 514 and 647 nm). For the three excitation wavelengths used in this study, the frequency of the A1g(Γ) phonon mode monotonically decreases with the number of layers. For single-layer WS2, the 514.5 nm laser excitation generates a second-order Raman resonance involving the longitudinal acoustic mode (LA(M)). This resonance results from a coupling between the electronic band structure and lattice vibrations. First-principles calculations were used to determine the electronic and phonon band structures of single-layer and bulk WS2. The reduced intensity of the 2LA mode was then computed, as a function of the laser wavelength, from the fourth-order Fermi golden rule. Our observations establish an unambiguous and nondestructive Raman fingerprint for identifying single- and few-layered WS2 films.

Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing.

Graphene is a two-dimensional network in which sp2-hybridized carbon atoms are arranged in two different triangular sub-lattices (A and B). By incorporating nitrogen atoms into graphene, its physico-chemical properties could be significantly altered depending on the doping configuration within the sub-lattices. Here, we describe the synthesis of large-area, highly-crystalline monolayer N-doped graphene (NG) sheets via atmospheric-pressure chemical vapor deposition, yielding a unique N-doping site composed of two quasi-adjacent substitutional nitrogen atoms within the same graphene sub-lattice (N2AA). Scanning tunneling microscopy and spectroscopy (STM and STS) of NG revealed the presence of localized states in the conduction band induced by N2AA-doping, which was confirmed by ab initio calculations. Furthermore, we demonstrated for the first time that NG could be used to efficiently probe organic molecules via a highly improved graphene enhanced Raman scattering.

Controlled synthesis and transfer of large-area WS2 sheets: from single layer to few layers.

The isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-area (~1 cm(2)) WS2 sheets with thicknesses ranging from monolayers to a few layers. During synthesis, WOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures (750-950 °C). An efficient route to transfer the synthesized WS2 films onto different substrates such as quartz and transmission electron microscopy (TEM) grids has been satisfactorily developed using concentrated HF. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of single-, bi-, and few-layered WS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layers, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This method has also proved successful in the synthesis of heterogeneous systems of MoS2 and WS2 layers, thus shedding light on the controlled production of heterolayered devices from transition metal chalcogenides.

Longitudinal Cutting of Pure and Doped Carbon Nanotubes to Form Graphitic Nanoribbons Using Metal Clusters as Nanoscalpels

We report the use of transition metal nanoparticles (Ni or Co) to longitudinally cut open multiwalled carbon nanotubes in order to create graphitic nanoribbons. The process consists of catalytic hydrogenation of carbon, in which the metal particles cut sp(2) hybridized carbon atoms along nanotubes that results in the liberation of hydrocarbon species. Observations reveal the presence of unzipped nanotubes that were cut by the nanoparticles. We also report the presence of partially open carbon nanotubes, which have been predicted to have novel magnetoresistance properties.(1) The nanoribbons produced are typically 15-40 nm wide and 100-500 nm long. This method offers an alternative approach for making graphene nanoribbons, compared to the chemical methods reported recently in the literature.

Band Gap Engineering and Layer-by-Layer Mapping of Selenium-Doped Molybdenum Disulfide

Ternary two-dimensional dichalcogenide alloys exhibit compositionally modulated electronic structure, and hence, control of dopant concentration within each individual layer of these compounds provides a powerful tool to efficiently modify their physical and chemical properties. The main challenge arises when quantifying and locating the dopant atoms within each layer in order to better understand and fine-tune the desired properties. Here we report the synthesis of molybdenum disulfide substitutionally doped with a broad range of selenium concentrations, resulting in over 10% optical band gap modulations in atomic layers. Chemical analysis using Z-contrast imaging provides direct maps of the dopant atom distribution in individual MoS2 layers and hence a measure of the local optical band gaps. Furthermore, in a bilayer structure, the dopant distribution is imaged layer-by-layer. This work demonstrates that each layer in the bilayer system contains similar local Se concentrations, randomly distributed, providing new insights into the growth mechanism and alloying behavior in two-dimensional dichalcogenide atomic layers. The results show that growth of uniform, ternary, two-dimensional dichalcogenide alloy films with tunable electronic properties is feasible.

New First Order Raman-active Modes in Few Layered Transition Metal Dichalcogenides

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.

CVD-grown monolayered MoS2 as an effective photosensor operating at low-voltage

We report the fabrication of a photosensor based on as-grown single crystal monolayers of MoS2 synthesized by chemical vapor deposition (CVD). The measurements were performed using Au/Ti leads in a two terminal configuration on CVD-grown MoS2 on a SiO2/Si substrate. The device was operated in air at room temperature at low bias voltages ranging from −2 V to 2 V and its sensing capabilities were tested for two different excitation wavelengths (514.5 nm and 488 nm). The responsivity reached 1.1 mA W−1 when excited with a 514.5 nm laser at a bias of 1.5 V. This responsivity is one order of magnitude larger than that reported from photo devices fabricated using CVD-grown multilayered WS2. A rectifying-effect was observed for the optically excited current, which was four times larger in the direct polarization bias when compared to the reverse bias photocurrent. Such rectifying behavior can be attributed to the asymmetric electrode placement on the triangular MoS2 monocrystal. It is envisioned that these components could eventually be used as efficient and low cost photosensors based on CVD-grown transition metal dichalcogenide monolayers.

Extraordinary Second Harmonic Generation in Tungsten Disulfide Monolayers

We investigate Second Harmonic Generation (SHG) in monolayer WS2 both deposited on a SiO2/Si substrate or suspended using transmission electron microscopy grids. We find unusually large second order nonlinear susceptibility, with an estimated value of deff ~ 4.5 nm/V nearly three orders of magnitude larger than other common nonlinear crystals. In order to quantitatively characterize the nonlinear susceptibility of two-dimensional (2D) materials, we have developed a formalism to model SHG based on the Greens function with a 2D nonlinear sheet source. In addition, polarized SHG is demonstrated as a useful method to probe the structural symmetry and crystal orientation of 2D materials. To understand the large second order nonlinear susceptibility of monolayer WS2, density functional theory based calculation is performed. Our analysis suggests the origin of the large nonlinear susceptibility in resonance enhancement and a large joint density of states, and yields an estimate of the nonlinear susceptibility value deff = 0.77 nm/V for monolayer WS2, which shows good order-of-magnitude agreement with the experimental result.

Super-stretchable graphene oxide macroscopic fibers with outstanding knotability fabricated by dry film scrolling.

Graphene oxide (GO) has recently become an attractive building block for fabricating graphene-based functional materials. GO films and fibers have been prepared mainly by vacuum filtration and wet spinning. These materials exhibit relatively high Youngs moduli but low toughness and a high tendency to tear or break. Here, we report an alternative method, using bar coating and drying of water/GO dispersions, for preparing large-area GO thin films (e.g., 800-1200 cm(2) or larger) with an outstanding mechanical behavior and excellent tear resistance. These dried films were subsequently scrolled to prepare GO fibers with extremely large elongation to fracture (up to 76%), high toughness (up to 17 J/m(3)), and attractive macroscopic properties, such as uniform circular cross section, smooth surface, and great knotability. This method is simple, and after thermal reduction of the GO material, it can render highly electrically conducting graphene-based fibers with values up to 416 S/cm at room temperature. In this context, GO fibers annealed at 2000 °C were also successfully used as electron field emitters operating at low turn on voltages of ca. 0.48 V/μm and high current densities (5.3 A/cm(2)). Robust GO fibers and large-area films with fascinating architectures and outstanding mechanical and electrical properties were prepared with bar coating followed by dry film scrolling.