Using Graphdiyne Nanoribbons for Molecular Electronics Spectroscopy and Nucleobase Identification: A Theoretical Investigation.

In pursuit of fast, cost-effective, and reliable DNA sequencing techniques, a variety of two-dimensional (2D) material-based nanodevices such as solid-state nanopores and nanochannels have been explored and established. Given the promising potential of graphene for the design and fabrication of nanobiosensors, other 2D carbon allotropes such as graphyne and graphdiyne have also attracted a great deal of attention as candidate materials for the development of sequencing technology. Herein, employing the 2D electronic molecular spectroscopy (2DMES) method, we investigate the capability of graphdiyne nanoribbons (GDNRs) as the building blocks of a feasible, precise, and ultrafast sequencing device. Using first-principles calculations, we study the adsorption of four canonical nucleobases (NBs), i.e., adenine (A), cytosine (C), guanine (G), and thymine (T) on an armchair GDNR (AGDNR). Our calculations reveal that compared to graphene, graphdiyne demonstrates more distinct binding energies for different NBs, indicating its more promising ability to unambiguously recognize DNA bases. Utilizing the 2DMES technique, we calculate the differential conductance (Δg) of the studied NB-AGDNR systems and show that the resulting Δg maps, unique for each NB-AGDNR complex, can be used to recognize each individual NB without ambiguity. We also investigate the conductance sensitivity of the proposed nanobiosensor and show that it exhibits high sensitivity and selectivity toward various NBs. Thus, our proposed graphdiyne-based nanodevice would hold promise for next-generation DNA sequencing technology.

DNA/RNA sequencing using germanene nanoribbons via two dimensional molecular electronic spectroscopy: an ab initio study.

Developing fast, reliable, and cost effective, yet practical DNA/RNA sequencing methods and devices is a must. In this regard, motivated by the recently introduced two-dimensional electronic molecular spectroscopy (2DMES) technique for molecular recognition, and the compatibility of 2D layers of group IV elements with the current technology of manufacturing electronic devices, we investigate the capability of germanene nanoribbons (GeNRs) as a feasible, accurate, and ultra-fast sequencing device under the application of 2DMES. We show that by employing 2DMES, not only can GeNRs unambiguously distinguish different nucleobases to sequence DNA/RNA, they are also capable of recognizing methylated nucleobases that could be related to cancerous cell growth. Our calculations indicate that, compared to frequently used graphene layers, germanene provides more distinct adsorption energies for different nucleobases which implies its better ability to recognize various molecules unambiguously. By calculating the conductance sensitivity of the system for experimental purposes, we also show that the introduced sequencing device possesses a high sensitivity and selectivity characteristic. Thus, our proposed system would be a promising device for next-generation DNA sequencing technologies and would be realizable using the current protocols of fabricating electronic devices.

A Potassium Metal-Organic Framework based on Perylene-3,4,9,10-tetracarboxylate as Sensing Layer for Humidity Actuators.

We have synthesized a novel three-dimensional metal-organic-framework (MOF) based on the perylene-3,4,9,10-tetracarboxylate linker and potassium as metallic centre. We report the formation of this K-based MOF using conventional routes with water as solvent. This material displays intense green photoluminescence at room temperature, and displays an aggregation dependent quenching. Correlation of the optical properties with the crystalline packing was confirmed by DFT calculations. We also demonstrate its potential to build humidity actuators with a reversible and reproducible response, with a change of 5 orders of magnitudes in its impedance at about 40% relative humidity (RH). This 3D-MOF is based on an interesting perylene derivative octadentate ligand, a moiety with interesting fluorescent properties and known component in organic semiconductors. To the best of our knowledge, this is the first time to build such a printed and flexible actuator towards humidity with a reversible response, enabling precise humidity threshold monitoring.

Atomic-scale defects and electronic properties of a transferred synthesized MoS2 monolayer.

MoS2 monolayer samples were synthesized on a SiO2/Si wafer and transferred to Ir(111) for nano-scale characterization. The samples were extensively characterized during every step of the transfer process, and MoS2 on the final substrate was examined down to the atomic level by scanning tunneling microscopy (STM). The procedures conducted yielded high-quality monolayer MoS2 of milimeter-scale size with an average defect density of 2 × 1013 cm-2. The lift-off from the growth substrate was followed by a release of the tensile strain, visible in a widening of the optical band gap measured by photoluminescence. Subsequent transfer to the Ir(111) surface led to a strong drop of this optical signal but without further shifts of characteristic peaks. The electronic band gap was measured by scanning tunneling spectroscopy (STS), revealing n-doping and lateral nano-scale variations. The combined use of STM imaging and density functional theory (DFT) calculations allows us to identify the most recurring point-like defects as S vacancies.

Versatile synthesis and enlargement of functionalized distorted heptagon-containing nanographenes.

Highly distorted polycyclic aromatic hydrocarbons (PAHs) are predicted to be attractive goals in nanoscience owing to the new properties they can exhibit. We have shown that a variety of functionalized distorted heptagon-containing nanographenes can be easily prepared from simple building blocks by a sequence of Co-catalyzed cyclotrimerization and cyclodehydrogenation reactions. The versatility of this strategy allows easy subsequent enlargement of these nanostructures by Ni-catalyzed cross-coupling and final cyclodehydrogenation reactions. Soluble extended distorted nanographenes 1 and 2 containing heptagon and an edge-shared pentagon-heptagon combination have been synthesized. High distortion of the polycyclic backbone of 2 caused by non-hexagonal rings and a helicene moiety was confirmed by X-ray crystallography. Experimental data reveal promising optical and electronic properties for distorted PAHs with long fluorescence lifetimes (up to 14.5 ns) and low band gaps (down to 2.27 eV). This straightforward and versatile synthetic strategy, the observed long fluorescence lifetimes and the small optical and electrochemical band gaps for the presented compounds may promote the future implementation of distorted graphene molecules in electronic devices.

Adsorption of small inorganic molecules on a defective MoS2 monolayer.

We present a theoretical study of molecular adsorption on defects on a MoS2 monolayer. Based on Density Functional Theory, our calculations confirm that small inorganic molecules, such as CO2, CO, H2O, NO, NO2, H2 and N2, remain bonded to the pristine monolayer through weak van der Waals interactions, suggesting that the molecules may easily diffuse over the clean monolayer. On the other hand, the introduction of defects can lead to three different situations, depending on the defect and the molecule considered: physisorption, chemical (strong) bonding to the metallic defects, namely the Mo substitutional atoms on the S vacancies, and dissociation, that can take place spontaneously at 0 K in some specific cases or by the effect of thermal agitation in molecules such as CO2 or NO2 on the S vacancy. Our energetic and electronic analyses provide an explanation to such bonding possibilities, showing that in the low interacting situations, the molecules tend to adopt a planar configuration parallel to the monolayer, while a molecular rotation is favored in order to facilitate the bond formation on the reactive sites. Finally, the ab initio based Scanning Tunneling Microscopy (STM) simulations show the fingerprint of each molecule adsorbed on the most reactive site. This work opens the way to the possibility of tuning the catalytic properties of MoS2 by controlling the creation of specific defects in the MoS2 monolayer.

Atomistic boron-doped graphene field-effect transistors: a route toward unipolar characteristics.

We report fully quantum simulations of realistic models of boron-doped graphene-based field-effect transistors, including atomistic details based on DFT calculations. We show that the self-consistent solution of the three-dimensional (3D) Poisson and Schrödinger equations with a representation in terms of a tight-binding Hamiltonian manages to accurately reproduce the DFT results for an isolated boron-doped graphene nanoribbon. Using a 3D Poisson/Schrödinger solver within the non-equilibrium Green's function (NEGF) formalism, self-consistent calculations of the gate-screened scattering potentials induced by the boron impurities have been performed, allowing the theoretical exploration of the tunability of transistor characteristics. The boron-doped graphene transistors are found to approach unipolar behavior as the boron concentration is increased and, by tuning the density of chemical dopants, the electron-hole transport asymmetry can be finely adjusted. Correspondingly, the onset of a mobility gap in the device is observed. Although the computed asymmetries are not sufficient to warrant proper device operation, our results represent an initial step in the direction of improved transfer characteristics and, in particular, the developed simulation strategy is a powerful new tool for modeling doped graphene nanostructures.

Quantum transport in graphene nanoribbons: effects of edge reconstruction and chemical reactivity.

We present first-principles transport calculations of graphene nanoribbons with chemically reconstructed edge profiles. Depending on the geometry of the defect and the degree of hydrogenation, spectacularly different transport mechanisms are obtained. In the case of monohydrogenated pentagon (heptagon) defects, an effective acceptor (donor) character results in strong electron-hole conductance asymmetry. In contrast, weak backscattering is obtained for defects that preserve the benzenoid structure of graphene. Based on a tight-binding model derived from ab initio calculations, evidence for large conductance scaling fluctuations are found in disordered ribbons with lengths up to the micrometer scale.

Chemically induced mobility gaps in graphene nanoribbons: a route for upscaling device performances.

We report a first-principles based study of mesoscopic quantum transport in chemically doped graphene nanoribbons with a width up to 10 nm. The occurrence of quasi-bound states related to boron impurities results in mobility gaps as large as 1 eV, driven by strong electron-hole asymmetrical backscattering phenomena. This phenomenon opens new ways to overcome current limitations of graphene-based devices through the fabrication of chemically doped graphene nanoribbons with sizes within the reach of conventional lithography.

Anomalous doping effects on charge transport in graphene nanoribbons.

We present first-principles calculations of quantum transport in chemically doped graphene nanoribbons with a width of up to 4 nm. The presence of boron and nitrogen impurities is shown to yield resonant backscattering, whose features are strongly dependent on the symmetry and the width of the ribbon, as well as the position of the dopants. Full suppression of backscattering is obtained on the pi-pi* plateau when the impurity preserves the mirror symmetry of armchair ribbons. Further, an unusual acceptor-donor transition is observed in zigzag ribbons. These unconventional doping effects could be used to design novel types of switching devices.

Transport length scales in disordered graphene-based materials: strong localization regimes and dimensionality effects.

We report on a numerical study of quantum transport in disordered two dimensional graphene and graphene nanoribbons. By using the Kubo and the Landauer approaches, transport length scales in the diffusive (mean free path and charge mobilities) and localized regimes (localization lengths) are computed, assuming a short range disorder (Anderson-type). The electronic systems are found to undergo a conventional Anderson localization in the zero-temperature limit, in agreement with localization scaling theory. Localization lengths in weakly disordered ribbons are found to strongly fluctuate depending on their edge symmetry, but always remain several orders of magnitude smaller than those computed for 2D graphene for the same disorder strength. This pinpoints the role of transport dimensionality and edge effects.

Anderson localization in carbon nanotubes: defect density and temperature effects.

The role of irradiation induced defects and temperature in the conducting properties of single-walled (10, 10) carbon nanotubes has been analyzed by means of a first-principles approach. We find that divacancies modify strongly the energy dependence of the differential conductance, reducing also the number of contributing channels from two (ideal) to one. A small number of divacancies (5-9) brings up strong Anderson localization effects and a seemly universal curve for the resistance as a function of the number of defects. It is also shown that low temperatures, about 15-65 K, are enough to smooth out the fluctuations of the conductance without destroying the exponential dependence of the resistivity as a function of the tube length.