Project description:Penta-graphene is a quasi-two-dimensional carbon allotrope consisting of a pentagonal lattice in which both sp2 and sp3-like carbons are present. Unlike graphene, penta-graphene exhibits a non-zero bandgap, which opens the possibility of its use in optoelectronic applications. However, as the observed bandgap is large, gap tuning strategies such as doping are required. In this work, density functional theory calculations are used to determine the effects of the different number of line defects of substitutional nitrogen or silicon atoms on the penta-graphene electronic behavior. Our results show that this doping can induce semiconductor, semimetallic, or metallic behavior depending on the doping atom and targeted hybridization (sp2 or sp3-like carbons). In particular, we observed that nitrogen doping of sp2-like carbons atoms can produce a bandgap modulation between semimetallic and semiconductor behavior. These results show that engineering line defects can be an effective way to tune penta-graphene electronic behavior.
Project description:Trilayer graphene is of particular interest to the 2D materials community because of its unique tunable electronic structure. However, to date, there is a lack of fundamental understanding of the properties of epitaxial trilayer graphene on silicon carbide. Here, following successful synthesis of large-area uniform trilayer graphene, atomic force microscopy (AFM) showed that the trilayer graphene on 6H-SiC(0001) was uniform over a large scale. Additionally, distinct defects, identified as flower-shaped domains and isolated wrinkle structures, were observed randomly on the surface using scanning tunneling microscopy and spectroscopy (STM/STS). These carbon nanostructures formed during growth, has different structural and electronic properties when compared with the adjacent flat regions of the graphene. Finally, using low temperature STM/STS at 4K, we found that the isolated wrinkles showed an irreversible rotational motion between two 60° configurations at different densities of states.
Project description:In van der Waals bonded or rotationally disordered multilayer stacks of two-dimensional (2D) materials, the electronic states remain tightly confined within individual 2D layers. As a result, electron-phonon interactions occur primarily within layers and interlayer electrical conductivities are low. In addition, strong covalent in-plane intralayer bonding combined with weak van der Waals interlayer bonding results in weak phonon-mediated thermal coupling between the layers. We demonstrate here, however, that Coulomb interactions between electrons in different layers of multilayer epitaxial graphene provide an important mechanism for interlayer thermal transport, even though all electronic states are strongly confined within individual 2D layers. This effect is manifested in the relaxation dynamics of hot carriers in ultrafast time-resolved terahertz spectroscopy. We develop a theory of interlayer Coulomb coupling containing no free parameters that accounts for the experimentally observed trends in hot-carrier dynamics as temperature and the number of layers is varied.
Project description:The effects of different types of defects (vacancy, Stone-Wales defects, and heteroatom doping) and varying defect concentrations (single and double defects) on the structure, electronic, and optical properties of graphene quantum dots (GQDs) are systematically investigated using time-dependent density functional theory (TD-DFT). The results reveal that most defects induce noticeable structural distortions, with increasing deformation at higher defect concentrations. Compared to pristine GQD model C96 (with a maximum absorption peak at 592 nm), the absorption spectra of 6 defective C96 exhibit blue shifts ranging from 554 to 591 nm, while 12 defective C96 lead to red shifts (598-668 nm). The HOMO-LUMO gaps vary from 0.62 to 2.04 eV (2.10 eV for pristine C96). Quantitative analysis of the absorption spectra and molecular orbital energy levels demonstrate that the electronic and optical properties of defective C96 strongly depend on the types, concentrations, and locations of defects. NTO analysis illustrates that higher electron localization exists in defective C96, which is attributed to the disruption of the original π-conjugation caused by structural distortions and different orbital hybridizations. These findings offer a comprehensive insight into the impact of defects on GQDs and provide valuable guidance for exploiting the unique features of GQDs to expand new applications in various fields.
Project description:In recent years, graphene oxide has been considered as a soluble precursor of graphene for electronic applications. However, the performance lags behind that of graphene due to lattice defects. Here, the relation between the density of defects in the range of 0.2 % and 1.5 % and the transport properties is quantitatively studied. Therefore, the related flakes of monolayers of graphene were prepared from oxo-functionalized graphene (oxo-G). The morphologic structure of oxo-G was imaged by atomic force microscopy (AFM) and scanning tunneling microscopy (STM). Field-effect mobility values were determined to range between 0.3 cm2 V-1 s-1 and 33.2 cm2 V-1 s-1 , which were inversely proportional to the density of defects. These results provide the first quantitative description of the density of defects and transport properties, which plays an important role for potential applications.
Project description:Graphene decorated with 5d transitional metal atoms is predicted to exhibit many intriguing properties; for example iridium adatoms are proposed to induce a substantial topological gap in graphene. We extensively investigated the conductivity of single-layer graphene decorated with iridium deposited in ultra-high vacuum at low temperature (7 K) as a function of Ir concentration, carrier density, temperature, and annealing conditions. Our results are consistent with the formation of Ir clusters of ~100 atoms at low temperature, with each cluster donating a single electronic charge to graphene. Annealing graphene increases the cluster size, reducing the doping and increasing the mobility. We do not observe any sign of an energy gap induced by spin-orbit coupling, possibly due to the clustering of Ir.
Project description:Finding alternative ways to tailor the electronic properties of a catalyst to actively and selectively drive reactions of interest has been a growing research topic in the field of electrochemistry. In this Letter, we investigate the tuning of the surface electronic properties of electrocatalysts via polymer modification. We show that when a nickel oxide water oxidation catalyst is coated with polytetrafluoroethylene, stable Ni-CF x bonds are introduced at the nickel oxide/polymer interface, resulting in shifting of the reaction selectivity away from the oxygen evolution reaction and toward hydrogen peroxide formation. It is shown that the electron-withdrawing character of the surface fluorocarbon molecule leaves a slight positive charge on the water oxidation intermediates at the adjacent active nickel sites, making their bonds weaker. The concept of modifying the surface electronic properties of an electrocatalyst via stable polymer modification offers an additional route to tune multipathway reactions in polymer/electrocatalyst environments, like with ionomer-modified catalysts or with membrane electrode assemblies.
Project description:The climate change due to human activities stimulates the research on new energy resources. Hydrogen has attracted interest as a green carrier of high energy density. The sustainable production of hydrogen is achievable only by water electrolysis based on the hydrogen evolution reaction (HER). Graphitic materials are widely utilized in this technology in the role of conductive catalyst supports. Herein, by performing dynamic and steady-state electrochemical measurements in acidic and alkaline media, we investigated the bidirectional electrocatalysis of the HER and hydrogen oxidation reaction (HOR) on metal- and defect-free epigraphene (EG) grown on 4H silicon carbide (4H-SiC) as a ground level of structural organization of general graphitic materials. The absence of any signal degradation illustrates the high stability of EG. The experimental and theoretical investigations yield the coherent conclusion on the dominant HER pathway following the Volmer-Tafel mechanism. We ascribe the observed reactivity of EG to its interaction with the underlying SiC substrate that induces strain and electronic doping. The computed high activation energy for breaking the O-H bond is linked to the high negative overpotential of the HER. The estimated exchange current of HER/HOR on EG can be used in the evaluation of complex electrocatalytic systems based on graphite as a conducing support.
Project description:The electronic and optical response of Bernal stacked bilayer graphene with geometry modulation and gate voltage are studied. The broken symmetry in sublattices, one dimensional periodicity perpendicular to the domain wall and out-of-plane axis introduces substantial changes of wavefunctions, such as gapless topological protected states, standing waves with bonding and anti-bonding characteristics, rich structures in density of states and optical spectra. The wavefunctions present well-behaved standing waves in pure system and complicated node structures in geometry-modulated system. The optical absorption spectra show forbidden optical excitation channels, prominent asymmetric absorption peaks, and dramatic variations in absorption structures. These results provide that the geometry-modulated structure with tunable gate voltage could be used for electronic and optical manipulation in future graphene-based devices.
Project description:Edge-decorated graphene nanoribbons are investigated with the density functional theory; they reveal three stable geometric structures. The first type is a tubular structure formed by the covalent bonds of decorating boron or nitrogen atoms. The second one consists of curved nanoribbons created by the dipole-dipole interactions between two edges when decorated with Be, Mg, or Al atoms. The final structure is a flat nanoribbon produced due to the repulsive force between two edges; most decorated structures belong to this type. Various decorating atoms, different curvature angles, and the zigzag edge structure are reflected in the electronic properties, magnetic properties, and bonding configurations. Most of the resulting structures are conductors with relatively high free carrier densities, whereas a few are semiconductors due to the zigzag-edge-induced anti-ferromagnetism.