Electronic structure of boron-doped finite graphene sheets: unrestricted DFT and complete active space calculations

B3LYP and complete active space methods were applied to study graphene nanoribbons (GNRs) doped with boron atoms. The restricted B3LYP solutions were found to be unstable in all but two cases, and the complete active space calculations prove the multiconfigurational character of the ground state contributing with two most important configurations. The exception is the structure c4 where the system has single reference ground state in spite of the instability of the restricted wavefunction.

The distance between dopant atoms, their mutual position and their location within the nanoribbon impact the relative stability of doped nanoribbons. B doping does not modify the ionisation potentials of doped GNRs. However, it notably increases the electron affinity of the core-doped nanoribbons. The doping also has a notable impact on the reorganisation energy of the nanoribbons. The reorganisation energy of B-doped GNRs is higher than the corresponding reorganisation energy of pristine and nitrogen-doped GNRs.     

Electronic,transport, magnetic,and optical properties of graphene nanoribbons and their optical sensing applications: A comprehensive review

Low dimensional materials have attracted great research interest from both theoretical and experimental point of views. These materials exhibit novel physical and chemical properties due to the confinement effect in low dimensions. The experimental observations of graphene open a new platform to study the physical properties of materials restricted to two dimensions. This featured article provides a review on the novel properties of quasi one-dimensional (1D) material known as graphene nanoribbon. Graphene nanoribbons can be obtained by unzipping carbon nanotubes (CNT) or cutting the graphene sheet. Alternatively, it is also called the finite termination of graphene edges. It gives rise to different edge geometries, namely zigzag and armchair, among others. There are various physical and chemical techniques to realize these materials. Depending on the edge type termination, these are called the zigzag and armchair graphene nanoribbons (ZGNR and AGNR). These edges play an important role in controlling the properties of graphene nanoribbons. The present review article provides an overview of the electronic, transport, optical, and magnetic properties of graphene nanoribbons. However, there are different ways to tune these properties for device applications. Here, some of them, such as external perturbations and chemical modifications, are highlighted. Few applications of graphene nanoribbon have also been briefly discussed.     

Dynamical and Static Spin Susceptibilities of Doped Gapped Graphene Nanoribbon Due to Local Electronic Interaction

We present the behaviors of both dynamical and static spin susceptibilities of doped gapped armchair graphene nanoribbon using the Green’s function approach in the context of Hubbard model Hamiltonian. Specially, the effects of spin polarization and gap parameter on the spin excitation modes of armchair graphene nanoribbon are investigated via calculating correlation function of spin density operators. Our results show the increase of electron concentration leads to disappear low frequency spin excitation mode for gapless case. We also show that low frequency excitation mode for both gapped and gapless nanoribbon disappears under spin full polarization condition. Finally, the electron density dependence of static charge structure factor of armchair graphene nanoribbon is studied. The effects of both gap parameter and magnetic ordering on the static structure factor are discussed in details.     

Effects of the nitrogen doping configuration and site on the thermal conductivity of defective armchair graphene nanoribbons

The influence of the nitrogen (N) doping configuration on the thermal conductivity (TC) of armchair graphene nanoribbons (AGNRs) of size 15.7 nm × 7.26 nm was investigated using classical molecular dynamics (MD) simulations with the optimized Tersoff potential at room temperature. The effect of changing the N-doping site in defects on the TC of AGNRs was also investigated in detail. The variations with N concentration of the TCs of AGNRs presenting graphitic N (quarternary N), pyridinic N, and pyrrolic N doping configurations were studied. Results of MD simulations showed that, among these three doping configurations, pyridinic N was associated with the highest TC, and pyrrolic N with the lowest TC. The highest TC values were obtained when the N dopant atoms were located at the edges and at defects in the AGNR. The presence of both pyrrolic N and Stone–Wales type 1 (SW-1) defects led to a higher TC than the presence of both pyrrolic N and SW-2 defects. Phonon–defect scattering was found to be influenced by changes in C–C bond orientation. SW-1 defects were found to exert a greater influence on the TC than graphitic N doping. Furthermore, the influence on the TC of the N-doping site location in SW-1 defects was examined. Doping the central sites of SW-1 defects was found to yield higher TC values than doping the edge sites of defects. Graphitic-N doping of the more central sites in a SW-1 defect led to a higher TC than the random graphitic-N doping of sites in a SW-1 defect.     

Influence of defect locations and nitrogen doping configurations on the mechanical properties of armchair graphene nanoribbons

The effect of defect locations on the mechanical properties of armchair graphene nanoribbons (AGNRs) and the various configurations of nitrogen (N) doping on the mechanical properties of AGNRs were examined using molecular dynamics (MD) simulations. The variation of the Young’s modulus (YM) and the ultimate tensile strength (UTS) of pyridinic-N, graphitic-N, and pyrrolic-N by increasing the concentration of N doping was investigated. The results of MD simulations show that the defect location has a significant effect on the UTS and failure strain (FS) of AGNRs in both vertical and horizontal directions. In the horizontal direction, variations of the UTS and FS are lower than in the vertical direction. On the other hand, the variations of the YM is almost similar in vertical and horizontal directions. The results of this work indicate that the UTS and FS of AGNRs are more sensitive than the YM of AGNRs for different defect directions. Pyridinic-N improves the mechanical properties of the defective AGNR and performs better YM and UTS values than the graphitic-N. Substitution N atoms, which are located at the defective sites and/or at the edges of AGNRs, are mechanically more favorable. Pyrrolic-N configuration has the lowest mechanical properties among the other configurations. Furthermore, pyrrolic-N with Stone-Wales-1 (SW-1) type of defect has higher mechanical properties than pyrrolic-N with Stone-Wales-2 (SW-2) type of defect.     

Boron- and nitrogen-doped carbon nanotubes and graphene

Multi-walled, single-walled and double-walled carbon nanotubes as well as graphene can be doped with boron and nitrogen. B₂H₆ has been generally used as the boron source while NH₃ or pyridine is employed as the nitrogen source. Doping carbon nanotubes and graphene with boron and nitrogen brings about significant changes in the electronic structure and properties. Such doping not only results in desirable properties but also allows manipulation of properties for specific purposes. Doping with boron- and nitrogen-causes marked changes in the Raman spectra of the carbon nanostructures. In this article, we present the synthesis, characterization and properties of boron- and nitrogen-doped carbon nanotubes and graphene.     

Chemical Synthesis of 3D Graphene‐Like Cages for Sodium‐Ion Batteries Applications

Sodium (Na) super ion conductor structured Na₃V₂(PO₄)₃ (NVP) is extensively explored as cathode material for sodium‐ion batteries (SIBs) due to its large interstitial channels for Na⁺ migration. The synthesis of 3D graphene‐like structure coated on NVP nanoflakes arrays via a one‐pot, solid‐state reaction in molten hydrocarbon is reported. The NVP nanoflakes are uniformly coated by the in situ generated 3D graphene‐like layers with the thickness of 3 nm. As a cathode material, graphene covered NVP nanoflakes exhibit excellent electrochemical performances, including close to theoretical reversible capacity (115.2 mA h g^?1 at 1 C), superior rate capability (75.9 mA h g^?1 at 200 C), and excellent cyclic stability (62.5% of capacity retention over 30000 cycles at 50 C). Furthermore, the 3D graphene‐like cages after removing NVP also serve as a good anode material and deliver a specific capacity of 242.5 mA h g^?1 at 0.1 A g^?1. The full SIB using these two cathode and anode materials delivers a high specific capacity (109.2 mA h g^?1 at 0.1 A g^?1) and good cycling stability (77.1% capacity retention over 200 cycles at 0.1 A g^?1).     

Mechanical properties of pristine and nanoporous graphene

We present molecular dynamics simulations of monolayer graphene under uniaxial tensile loading. The Morse, bending angle, torsion and Lennard-Jones potential functions are adopted within the mdFOAM library in the OpenFOAM software, to describe the molecular interactions in graphene. A well-validated graphene model using these set of potentials is not yet available. In this work, we investigate the accuracy of the mechanical properties of graphene when derived using these simpler potentials, compared to the more commonly used complex potentials such as the Tersoff-Brenner and AIREBO potentials. The computational speed up of our approach, which scales O(1.5N), where N is the number of carbon atoms, enabled us to vary a larger number of system parameters, including graphene sheet orientation, size, temperature and concentration of nanopores. The resultant effect on the elastic modulus, fracture stress and fracture strain is investigated. Our simulations show that graphene is anisotropic, and its mechanical properties are dependant on the sheet size. An increase in system temperature results in a significant reduction in the fracture stress and strain. Simulations of nanoporous graphene were created by distributing vacancy defects, both randomly and uniformly, across the lattice. We find that the fracture stress decreases substantially with increasing defect density. The elastic modulus was found to be constant up to around 5% vacancy defects, and decreases for higher defect densities.     

Electrochemically Synthesized Polypyrrole/Graphene Composite Film for Lithium Batteries

A polypyrrole/reduced graphene oxide (PPy/r‐GO) composite film is prepared by inducing electrochemical reduction of graphene oxide incorporated into PPy as the dopant. This film has a wrinkled surface morphology with a porous structure as revealed by scanning electron microscopy. Its porous structure is attributed to the physical nature of the GO sheets, providing a templating effect during PPy deposition. This PPy/r‐GO composite is characterized using in‐situ UV–visible spectroelectrochemistry as well as Raman and Fourier‐transform IR spectroscopy. The PPy/r‐GO material shows greatly improved electrochemical properties, i.e., a high rate capability and excellent cycling stability when used as a cathode material in a lithium ion battery. It also delivers a large reversible capacity when used as an anode material, and this is mainly attributed to the reduced graphene oxide (r‐GO) component.     

Modelling the effects of hydrogen passivation and strain on the field emission from armchair-graphene nanoribbon using a modified non-equilibrium Green’s function method

In this report, we introduced a modified non-equilibrium Green’s function method to investigate the structural effects on the field emission current from an armchair graphene nanoribbon. We introduce a modified self-energy which is useful to study the effects of potential barrier in the field emission devices. Investigation into the effects of hydrogen passivation and applied strain can be realised using our modified formalism. Also a practical method to consider the effect of device parameters, such as channel length, anode–cathode separation and gate potential can be provided by the proposed formalism. The quantum effects of the emitter’s structure on the field emission are achievable by our introduced method.     

Computational investigation of double nitrogen doping on graphene

Density functional theory (DFT) calculations were performed to study doping of two nitrogen atoms at different positions on a finite-sized graphene model of C₈₂H₂₄. We examined 21 structures of double nitrogen doped graphene to calculate their relative stabilities. The structure with two nitrogen atoms located apart is the most stable among the positional isomers considered in this study. For double nitrogen doping within a six-membered ring, the 1,4-position is more preferred than 1,3- or 1,2-positions for the finite-sized single layer graphene sheet. Our computational study supports the experimental observation of two nitrogen atoms at the 1,3- and 1,4-positions in a single six-membered ring of graphene. Furthermore, the structures with N-N bond are the least stable among two nitrogen doped graphene structures. The effects of nitrogen doping and the positions of two nitrogen atoms on the HOMO-LUMO energy gap of pristine graphene were analyzed.     

A molecular dynamics simulation study of the effect of water–graphene interaction on the properties of confined water

The role of water in determining the structure and stability of biomacromolecules has been well studied. In this work, molecular dynamics simulations have been applied to investigate the effect of surface hydrophobicity on the structure and dynamics of water confined between graphene surfaces. In order to evaluate this effect, we apply various attractive/repulsive water–graphene interaction potentials (hydrophobicity). The properties of confined water are studied by applying a purely repulsive interaction potential between water–graphene (modelled as a repulsive r^?12 potential) and repulsive–attractive forces (modelled as an LJ(12-6) potential). Compared to the case of a purely repulsive graphene–water potential, the inclusion of repulsive–attractive forces leads to formation of sharp peaks for density and the number of hydrogen bonds. Also, it was found that repulsive–attractive graphene–water potential caused slower hydrogen bonds dynamics and restricted the diffusion coefficient of water. Consequently, it was found that hydrogen bond breakage and formation rate with the repulsive r^?12 potential model, will increase compared to the corresponding water confined with the LJ(12-6) potential.     

Si-doped graphene: an ideal sensor for NO- or NO<Subscript>2</Subscript>-detection and metal-free catalyst for N<Subscript>2</Subscript>O-reduction

Exploring and evaluating the potential applications of two-dimensional graphene is an increasingly hot topic in graphene research. In this paper, by studying the adsorption of NO, N₂O, and NO₂ on pristine and silicon (Si)-doped graphene with density functional theory methods, we evaluated the possibility of using Si-doped graphene as a candidate to detect or reduce harmful nitrogen oxides. The results indicate that, while adsorption of the three molecules on pristine graphene is very weak, Si-doping enhances the interaction of these molecules with graphene sheet in various ways: (1) two NO molecules can be adsorbed on Si-doped graphene in a paired arrangement, while up to four NO₂ molecules attach to the doped graphene with an average adsorption energy of −0.329 eV; (2) the N₂O molecule can be reduced easily to the N₂ molecule, leaving an O-atom on the Si-doped graphene. Moreover, we find that adsorption of NO and NO₂ leads to large changes in the electronic properties of Si-doped graphene. On the basis of these results, Si-doped graphene can be expected to be a good sensor for NO and NO₂ detection, as well as a metal-free catalyst for N₂O reduction.     

The effect of high concentrations and orientations of Stone–Wales defects on the thermal conductivity of graphene nanoribbons

The influence of the orientations and concentrations of the Stone–Wales (SW) defects on the thermal conductivity of zigzag and armchair graphene nanoribbons (GNRs) is explored using the reverse non-equilibrium molecular dynamics method. The results show that the thermal conductivity of GNRs with two different chirality cases reaches the minimum in the range of 0.1–0.7% defect concentration. Beyond a critical value of the SW defect concentration, the thermal conductivity increases with the increase in SW concentration for both zigzag and armchair GNRs. It is shown that at high concentrations of the SW defects, the thermal conductivity of zigzag GNRs with Type II defects is larger than the GNRs with Type I defects. Finally, the dependence of the SW defect concentration and orientation on the power spectra overlaps have also been explored.     

Ultra-compact Spatial Terahertz Switch Based on Graphene Plasmonic-Coupled Waveguide

We are proposing graphene (G)-based multilayered plasmonic spatial switch, operating at 10 THz. It is composed of hBN/Ag/hBN/G/hBN/G/hBN/SiO₂/p⁺-Si multilayers. When a 10-THz transverse magnetic (TM)-polarized signal is normally incident upon the structure top surface, the nanoaperture devised in the Ag nanolayer, acting as a grating, excites surface plasmons at the top graphene micro-ribbons/hBN interface. These surface plasmons depending on the graphenes chemical potentials can be coupled to the lower-right or left graphene micro-ribbons and continue to propagate laterally towards the corresponding output port. Numerical simulations show that a change of ∆V_G ≈ ± 2.7 V in the voltage, applied to the gated micro-ribbons, can modulate their chemical potentials sufficiently to switch the right (left) output port from ON (OFF) to OFF(ON) and vice versa. Besides its low power consumption, the switch ultra-small dimensions make it a potential spatial router suitable for THz-integrated circuit applications.

     

Controlling Optical Absorption of Graphene in Near-infrared Region by Surface Plasmons

Nowadays, graphene has many applications in optical instruments, biosensors, gas sensors, photovoltaic cells, and so on. In this study, we aimed at investigating the optical properties of graphene under the influence of plasmons created in one-dimensional photonic crystal structure by making use of the absorption spectrum. We put the gold photonic crystal in adjacent to graphene and placed an antireflection layer on top of it. Then, we studied the behavior of graphene absorption peaks in a near-infrared region. By analyzing the graphene behavior in this region, we observed that graphene absorption was increased up to 40% and graphene absorption value in absorption peak, absorption peak wavelength, absorption spectra width, and also its absorption spectra in a wide wavelength range from 1000 to 2500 nm, could be controlled by making use of different factors such as the substance of antireflection layer and photonic crystal geometric dimensions. This structure can make many applications possible for graphene such as using it to build biosensors to identify uric acid and some of the lipids that have specific significances in detecting atherosclerotic lesions as well as diagnosing the states of disease.     

Understanding the Effects of Molecular Dopant on n‐Type Organic Thermoelectric Properties

Molecular doping is a powerful method to fine‐tune the thermoelectric properties of organic semiconductors, in particular to impart the requisite electrical conductivity. The incorporation of molecular dopants can, however, perturb the microstructure of semicrystalline organic semiconductors, which complicates the development of a detailed understanding of structure–property relationships. To better understand how the doping pathway and the resulting dopant counterion influence the thermoelectric performance and transport properties, a new dimer dopant, (N‐DMBI)₂, is developed. Subsequently, FBDPPV is then n‐doped with dimer dopants (N‐DMBI)₂, (RuCp*mes)₂, and the hydride‐donor dopant N‐DMBI‐H. By comparing the UV–vis–NIR absorption spectra and morphological characteristics of the doped polymers, it is found that not only the doping mechanism, but also the shape of the counterion strongly influence the thermoelectric properties and transport characteristics. (N‐DMBI)₂, which is a direct electron‐donating dopant with a comparatively small, relatively planar counterion, gives the best power factor among the three systems studied here. Additionally, temperature‐dependent conductivity and Seebeck coefficient measurements differ between the three dopants with (N‐DMBI)₂ yielding the best thermoelectric properties. The results of this study of dopant effects on thermoelectric properties provide insight into guidelines for future organic thermoelectrics.     

Broad Tunable Nanoantenna Based on Graphene Log-Periodic Toothed Structure

A log-periodic toothed nanoantenna based on graphene is proposed, and its multi-resonance properties with respect to the variations of the chemical potential are investigated. The field enhancement and radar cross-section of the antenna for different chemical potentials are calculated, and the effect of the chemical potential on the resonance frequency is analyzed. In addition, the dependence of the resonance frequency on the substrate is also discussed. It is shown that large modulation of resonance intensity in log-periodic toothed nanoantenna can be achieved via turning the chemical potential of graphene. The tunability of the resonant frequencies of the antenna can be used to broad tuning of spectral features. The property of tunable multi-resonant field enhancement has great prospect in the field of graphene-based broadband nanoantenna, which can be applied in non-linear spectroscopy, optical sensor, and near-field optical microscopy.     

Monitoring Biophysical Properties of Lipid Membranes by Environment-Sensitive Fluorescent Probes

We review the main trends in the development of fluorescence probes to obtain information about the structure, dynamics, and interactions in biomembranes. These probes are efficient for studying the microscopic analogs of viscosity, polarity, and hydration, as well as the molecular order, environment relaxation, and electrostatic potentials at the sites of their location. Progress is being made in increasing the information content and spatial resolution of the probe responses. Multichannel environment-sensitive probes that can distinguish between different membrane physicochemical properties through multiple spectroscopic parameters show considerable promise.     

Modelling boron nitride nano-structures as catalysts in fuel cells

The dissociation of O₂ and HO₂ are important reactions that occur at the cathode of fuel cells and require catalysts to proceed. There is a need to replace the presently used platinum catalyst with less expensive materials. Modelling has been used to identify potential two-dimensional catalysts such as boron- and nitrogen-doped graphene. Here, the possibility of boron nitride nano-ribbons and nano-tubes which do not require doping are considered. Density functional calculations are used to show that O₂ and HO₂ can bond to zig–zag and armchair boron nitride nano-ribbons and nano-tubes. The bond dissociation energies (BDEs) to remove an O and an OH from O₂ and HO₂ bonded to the boron nitride ribbons and tubes are calculated and are a measure of the catalytic effectiveness of the boron nitride structures. The results show that both the zig–zag and armchair boron nitride ribbons could be a catalyst for HO₂ dissociation but not O₂ dissociation. However, zig–zag boron nitride nano-tubes are shown not to be effective catalysts for the dissociation of O₂ or HO_2. An armchair boron nitride nano-tube is shown to have a very low BDEs to remove OH from HO₂ bonded to it and could be an affective catalyst.