Narrow Graphene Nanoribbons Research Articles

Unzipping of carbon nanotubes is geometry-dependent

Carbon nanotube (CNT) unzipping is a facile and efficient technique to produce narrow graphene nanoribbons. The diameter and chirality of CNTs control the geometry of the unzipped nanoribbons. In this work, we analyze the energetics of oxidation- and hydrogenation-induced unzipping processes. Empirical reactive potential-based energy calculations show that there is a geometry-dependent energy barrier for oxidation-induced unzipping, which is absent in the exothermal hydrogenation process. These results are discussed by considering the unzipping process as crack nucleation and propagation processes in a pre-stressed cylindrical shell. Fitting our simulation data through the theoretical model provides a quantitative way to estimate the key parameters in CNT unzipping that can be used to optimize the experimental procedure.

Nitrogen-Doping Induced Self-Assembly of Graphene Nanoribbon-Based Two-Dimensional and Three-Dimensional Metamaterials.

Narrow graphene nanoribbons (GNRs) constructed by atomically precise bottom-up synthesis from molecular precursors have attracted significant interest as promising materials for nanoelectronics. But there has been little awareness of the potential of GNRs to serve as nanoscale building blocks of novel materials. Here we show that the substitutional doping with nitrogen atoms can trigger the hierarchical self-assembly of GNRs into ordered metamaterials. We use GNRs doped with eight N atoms per unit cell and their undoped analogues, synthesized using both surface-assisted and solution approaches, to study this self-assembly on a support and in an unrestricted three-dimensional (3D) solution environment. On a surface, N-doping mediates the formation of hydrogen-bonded GNR sheets. In solution, sheets of side-by-side coordinated GNRs can in turn assemble via van der Waals and π-stacking interactions into 3D stacks, a process that ultimately produces macroscopic crystalline structures. The optoelectronic properties of these semiconducting GNR crystals are determined entirely by those of the individual nanoscale constituents, which are tunable by varying their width, edge orientation, termination, and so forth. The atomically precise bottom-up synthesis of bulk quantities of basic nanoribbon units and their subsequent self-assembly into crystalline structures suggests that the rapidly developing toolset of organic and polymer chemistry can be harnessed to realize families of novel carbon-based materials with engineered properties.

Synthesis, charge transport and device applications of graphene nanoribbons

Graphene is a promising material for high-performance electronics owing to its exotic electronic structure and high mobility. However, the lack of a band gap poses an obstacle to the realization of device applications. The challenge of creating a band gap in graphene has stimulated extensive research on graphene nanoribbons. Over the past few years, atomic precision synthesis, ballistic charge transport, and high on/off ratio logic transistors have been successfully demonstrated in graphene nanoribbons. In this article, we review this subject with a special focus on material synthesis, charge transport and device applications. We will see that the transport properties and device performances depend highly on the quality of the materials and their synthesis methods. We also stress the importance of making high-quality narrow graphene nanoribbon materials for both fundamental research and electronic applications. Scalable synthesis and processing remain a long-term goal in graphene nanoribbon research for any real applications.

Bending and buckling of narrow armchair graphene nanoribbons via STM manipulation

Semiconducting graphene nanoribbons (GNRs) are envisioned to play an important role in future electronics. This requires the GNRs to be placed on a surface where they may become strained. Theory predicts that axial strain, i.e. in-plane bending of the GNR, will cause a change in the band gap of the GNR. This may negatively affect device performance. Using the tip of a scanning tunneling microscope we controllably bent and buckled atomically well-defined narrow armchair GNR and subsequently probed the changes in the local density of states. These experiments show that the band gap of 7-ac-GNR is very robust to in-plane bending and out-of-plane buckling.

Electronic property and charge carrier mobility of extended nanowires built from narrow graphene nanoribbon and atomic carbon chain

This work presented theoretical studies on the extended nanowires constructed from narrow graphene nanoribbons and atomic carbon chains by using self-consistent field crystal orbital method based on density functional theory. The size and connection effects on geometrical structure, relative stability and electronic property of these one-dimensional (1D) nanowires have been addressed systemically and in details. It is found that the ratio of narrow graphene nanoribbons and CC units may be the key factor to the relative thermodynamic stability of these 1D wires based on the obtained Gibbs free energy. All the extended nanowires studied have a direct band gap according to the calculated electronic band structures. The obtained band gaps of the nanowires are in the range of 0.918–2.015eV. These flexible band gaps imply the possibility to modulate the electronic properties of these extended wires by turning the sizes and connections. Furthermore, a quantitative relation between the band gap and the ratio of phenylene and CC units is obtained. Moreover, we calculate the charge carrier mobility of the extended nanowires based on the deformation potential theory and effective mass approach. The frontier crystal orbital analyses are performed to get a better understanding of the charge carrier mobility for the 1D nanowires with various sizes and connections.

Spin-dependent Seebeck effects in a graphene nanoribbon coupled to two square lattice ferromagnetic leads

We theoretically investigate spin-dependent Seebeck effects for a system consisting of a narrow graphene nanoribbon (GNR) contacted to square lattice ferromagnetic (FM) electrodes with noncollinear magnetic moments. Both zigzag-edge graphene nanoribbons (ZGNRs) and armchair-edge graphene nanoribbons (AGNRs) were considered. Compared with our previous work with two-dimensional honeycomb-lattice FM leads, a more realistic model of two-dimensional square-lattice FM electrodes is adopted here. Using the nonequilibrium Green's function method combining with the tight-binding Hamiltonian, it is demonstrated that both the charge Seebeck coefficient SC and the spin-dependent Seebeck coefficient SS strongly depend on the geometrical contact between the GNR and the leads. In our previous work, SC for a semiconducting 15-AGNR system near the Dirac point is two orders of magnitude larger than that of a metallic 17-AGNR system. However, SC is the same order of magnitude for both metallic 17-AGNR and semiconducting 15-AGNR systems in the present paper because of the lack of a transmission energy gap for the 15-AGNR system. Furthermore, the spin-dependent Seebeck coefficient SS for the systems with 20-ZGNR, 17-AGNR, and 15-AGNR is of the same order of magnitude and its maximum absolute value can reach 8 μV/K. The spin-dependent Seebeck effects are not very pronounced because the transmission coefficient weakly depends on spin orientation. Moreover, the spin-dependent Seebeck coefficient is further suppressed with increasing angle between the relative alignments of magnetization directions of the two leads. Additionally, the spin-dependent Seebeck coefficient can be strongly suppressed for larger disorder strength. The results obtained here may provide valuable theoretical guidance in the experimental design of heat spintronic devices.

Graphene nanoribbon field-effect transistors on wafer-scale epitaxial graphene on SiC substrates

We report the realization of top-gated graphene nanoribbon field effect transistors (GNRFETs) of ∼10 nm width on large-area epitaxial graphene exhibiting the opening of a band gap of ∼0.14 eV. Contrary to prior observations of disordered transport and severe edge-roughness effects of graphene nanoribbons (GNRs), the experimental results presented here clearly show that the transport mechanism in carefully fabricated GNRFETs is conventional band-transport at room temperature and inter-band tunneling at low temperature. The entire space of temperature, size, and geometry dependent transport properties and electrostatics of the GNRFETs are explained by a conventional thermionic emission and tunneling current model. Our combined experimental and modeling work proves that carefully fabricated narrow GNRs behave as conventional semiconductors and remain potential candidates for electronic switching devices.

Formation of Helices in Graphene Nanoribbons under Torsion.

We use objective boundary conditions and self-consistent charge density-functional-based tight-binding to simulate at the atomistic scale the formation of helices in narrow graphene nanoribbons with armchair edges terminated with fluorine and hydrogen. We interpret the microscopic data using an inextensible, unshearable elastic rod model, which considers both bending and torsional strains. When fitted to the atomistic data, the simple rod model uses closed-form solutions for a cubic equation to predict the strain energy and morphology at a given twist angle and the crossover point between pure torsion and a helix. Our modeling and simulation bring key insights into the origin of the helical graphene morphologies stored inside of carbon nanotubes. They can be useful for designing chiral nanoribbons with tailored properties.

Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons.

The possibility that non-magnetic materials such as carbon could exhibit a novel type of s-p electron magnetism has attracted much attention over the years, not least because such magnetic order is predicted to be stable at high temperatures. It has been demonstrated that atomic-scale structural defects of graphene can host unpaired spins, but it remains unclear under what conditions long-range magnetic order can emerge from such defect-bound magnetic moments. Here we propose that, in contrast to random defect distributions, atomic-scale engineering of graphene edges with specific crystallographic orientation--comprising edge atoms from only one sub-lattice of the bipartite graphene lattice--can give rise to a robust magnetic order. We use a nanofabrication technique based on scanning tunnelling microscopy to define graphene nanoribbons with nanometre precision and well-defined crystallographic edge orientations. Although so-called 'armchair' ribbons display quantum confinement gaps, ribbons with the 'zigzag' edge structure that are narrower than 7 nanometres exhibit an electronic bandgap of about 0.2-0.3 electronvolts, which can be identified as a signature of interaction-induced spin ordering along their edges. Moreover, upon increasing the ribbon width, a semiconductor-to-metal transition is revealed, indicating the switching of the magnetic coupling between opposite ribbon edges from the antiferromagnetic to the ferromagnetic configuration. We found that the magnetic order on graphene edges of controlled zigzag orientation can be stable even at room temperature, raising hopes of graphene-based spintronic devices operating under ambient conditions.

Impurity electrons in narrow electric-field-biased armchair graphene nanoribbons

We present an analytical investigation of the quasi-Coulomb impurity states in a narrow gapped armchair graphene nanoribbon (GNR) in the presence of a uniform external electric field directed parallel to the ribbon axis. The effect of the ribbon confinement is taken to be much greater than that of the impurity electric field, which in turn considerably exceeds the external electric field. Under these conditions we employ the adiabatic approximation assuming that the motion parallel (``slow'') and perpendicular (``fast'') to the ribbon axis are separated adiabatically. In the approximation of the isolated size-quantized subbands induced by the ``fast'' motion, the complex energies of the impurity electron are calculated in explicit form. The real and imaginary parts of these energies determine the binding energy and width of the quasidiscrete state, respectively. The energy width increases with increasing the electric field and ribbon width. The latter forms the background of the mechanism of dimensional ionization. The $S$ matrix---the basic tool of study of the transport problems---can be trivially derived from the phases of the wave functions of the continuous spectrum presented in explicit form. In the double-subband approximation, we calculate the complete widths of the impurity states caused by the combined effect of the electric field and the Fano resonant coupling between the impurity states of the discrete and continuous spectra associated with the ground and first excited size-quantized subbands. Our analytical results are shown to be in agreement with those obtained by other theoretical approaches. Estimates of the expected experimental values for the typically employed GNRs show that for weak electric field the impurity quasidiscrete states remain sufficiently stable to be observed in the corresponding experiment, while a relatively strong field unlocks the captured electrons to further restore their contribution to the transport.

Effects of Stone-Wales Defect Symmetry on the Electronic Structure and Transport Properties of Narrow Armchair Graphene Nanoribbon

We report a first principles calculation to investigate the electron transport properties of defected armchair graphene nanoribbon (AGNR) influenced by Stone-Wales (SW) defect. The SW defect is found to be able to effectively influence the electronic structure of the defected AGNRs, and their electron transport behaviors can exhibit prominent differences depending on the symmetry of the nanostructured morphology. Moreover, our simulations have revealed that the introducing of the SW defect could be favorable for the electron transport of the defective AGNR. Our investigation has confirmed the possibility of tuning the electron transport of graphene nanoribbon by introducing a topological defect, which could be helpful to extending the field of applications for graphene nanoribbon-based nanodevices.

Band gap opening in zigzag graphene nanoribbon modulated with magnetic atoms

The effects of magnetic atom on the band structure of zigzag-edged graphene nanoribbons are investigated by the density functional theory. The results show that for narrow zigzag-edged graphene nanoribbons, the band gap can be opened duo to the spin-up/spin-down charges being re-enriched on the edge sites. However, for the wide zigzag-edged graphene nanoribbons, a spin-up/spin-down half-metallic property can be observed. Moreover, it is found that the Seebeck coefficients in the narrow zigzag-edged graphene nanoribbons are reversed and enlarged, which provides a way to design novel thermoelectric device.

Electronic Properties of Au-Doped Narrow Armchair Graphene Nanoribbons: A First Principle Calculations

The centre Au-doped armchair graphene nanoribbons (AGNRs) are investigated using the local density approximation based on density function theory. The charge density, electronic energy band and project density of states of centre Au-doped AGNRs are calculated. Our results indicate the charge density is transferred between C and Au atoms and mainly located on the Au atoms. The centre Au-doped AGNRs are an indirect band gap semiconductor with an energy gap of 1.046 eV. The Fermi level is located on valence band so that the AGNRs of doping Au become into degenerate semiconductor. The project density of states is calculated to reveal localization and hybridization between C-2pand Au-6s, 5delectronic states. The localization and hybridization are much stronger in the valence band. The hybridization between C-2pand Au-6pelectronic states are strongly in the conduction band.

Exciton-dominated optical response of ultra-narrow graphene nanoribbons.

Narrow graphene nanoribbons exhibit substantial electronic bandgaps and optical properties fundamentally different from those of graphene. Unlike graphene--which shows a wavelength-independent absorbance for visible light--the electronic bandgap, and therefore the optical response, of graphene nanoribbons changes with ribbon width. Here we report on the optical properties of armchair graphene nanoribbons of width N=7 grown on metal surfaces. Reflectance difference spectroscopy in combination with ab initio calculations show that ultranarrow graphene nanoribbons have fully anisotropic optical properties dominated by excitonic effects that sensitively depend on the exact atomic structure. For N=7 armchair graphene nanoribbons, the optical response is dominated by absorption features at 2.1, 2.3 and 4.2 eV, in excellent agreement with ab initio calculations, which also reveal an absorbance of more than twice the one of graphene for linearly polarized light in the visible range of wavelengths.

Bulk properties of solution-synthesized chevron-like graphene nanoribbons.

Graphene nanoribbons (GNRs) have received a great deal of attention due to their promise for electronic and optoelectronic applications. Several recent studies have focused on the synthesis of GNRs by the bottom-up approaches that could yield very narrow GNRs with atomically precise edges. One type of GNRs that has received a considerable attention is the chevron-like GNR with a very distinct periodic structure. Surface-assisted and solution-based synthetic approaches for the chevron-like GNRs have been developed, but their electronic properties have not been reported yet. In this work, we synthesized chevron-like GNRs in bulk by a solution-based method, characterized them by a number of spectroscopic techniques and measured their bulk conductivity. We demonstrate that solution-synthesized chevron-like GNRs are electrically conductive in bulk, which makes them a potentially promising material for applications in organic electronics and photovoltaics.

Seebeck effects in a graphene nanoribbon coupled to two ferromagnetic leads

We theoretically investigate the Seebeck effects for the system of a narrow graphene nanoribbon between two ferromagnetic (FM) electrodes with noncollinear magnetic moments. Both zigzag-edge graphene nanoribbons (ZGNRs) and armchair-edge graphene nanoribbons (AGNRs) have been considered. By using the nonequilibrium Green's function method combining with the tight-binding Hamiltonian, it is demonstrated that, the Seebeck coefficients are sensitive to the chirality and width of the nanoribbon in the absence of magnetic field. Compared with 22-ZGNR and metallic 17-AGNR systems, semiconducting 15-AGNR system is found to posses superior thermoelectric performance, its Seebeck coefficients can be improved by two orders of magnitude. Meanwhile, the Seebeck coefficients for both 22-ZGNR and metallic 17-AGNR systems are the same order as that of graphene system. Furthermore, the Seebeck coefficients are strongly dependent on the magnetization M as well as magnetic configuration of the two FM leads. Particularly, the Seebeck coefficient drastically enhances when the magnetization of the two FM leads is in antiparallel configuration. Interestingly, the Seebeck coefficient for both 22-ZGNR and metallic 17-AGNR systems increases with increasing temperature T, while it decreases with increasing T for semiconducting 15-AGNR system. Moreover, the dependence Seebeck coefficients on magnetic flux ϕ show an oscillation behavior. The results obtained here may provide a valuable theoretical guidance to experimentally design heat spintronic devices.

In-situ electro-polymerization of graphene nanoribbon/polyaniline composite film: Application to sensitive electrochemical detection of dobutamine

The present paper demonstrates the capability of narrow graphene nanoribbons (GNRs) in constructing new sensing platforms. Graphene nanoribbons have been synthesized via a simple solvothermal route through unzipping of carbon nanotubes, which was confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy analysis. These narrow carbon sheets were used to form a composite film by in-situ electro-polymerization with aniline. The produced graphene nanoribbon/polyaniline (GNR/PANI) composite film showed impressive performance in electrochemical determination of dobutamine (DBT). Under optimal conditions, in comparison to bare glassy carbon electrode a significant increase in peak current was observed on the surface of GNR/PANI modified glassy carbon electrode (up to 10 times), which is ascribed to the higher specific surface area induced by GNRs in combination with the electrocatalytic effect of polyaniline layer. We believe that such a composite film has a great potential in different applications including sensors, supercapacitors and etc.

Large-scale solution synthesis of narrow graphene nanoribbons

According to theoretical studies, narrow graphene nanoribbons with atomically precise armchair edges and widths of <2 nm have a bandgap comparable to that in silicon (1.1 eV), which makes them potentially promising for logic applications. Different top-down fabrication approaches typically yield ribbons with width >10 nm and have limited control over their edge structure. Here we demonstrate a novel bottom-up approach that yields gram quantities of high-aspect-ratio graphene nanoribbons, which are only ~1 nm wide and have atomically smooth armchair edges. These ribbons are shown to have a large electronic bandgap of ~1.3 eV, which is significantly higher than any value reported so far in experimental studies of graphene nanoribbons prepared by top-down approaches. These synthetic ribbons could have lengths of >100 nm and self-assemble in highly ordered few-micrometer-long 'nanobelts' that can be visualized by conventional microscopy techniques, and potentially used for the fabrication of electronic devices.

Edge-Sensitive Semiconducting Behaviour in Low-Defect Narrow Graphene Nanoribbons

Low-defect graphene nanoribbons (GNRs) derived from the unzipping of carbon nanotubes have exhibited large energy band gaps (transport gaps), despite having widths in the order of ~100 nm. Here, we report on the unique semiconducting behaviour of very narrow, low-defect GNRs, with widths of less than 20 nm. Narrow GNRs are highly resistive, and additional annealing is required to reduce their resistivity. The GNRs display ambipolar rather than evident semiconducting behaviour (p- and n-types), exhibiting normalized Ion/ Ioff as great as ~106 (close to those in a few nm-order-width GNRs) and which are very sensitive to the atmosphere and the termination of the GNRs' edges by foreign atoms (hydrogen for n-type and oxygen for p-type). It is also revealed that the activation energy (Ea ~35 meV) estimated from the temperature dependence of the minimum conductance is smaller than those in ~100 nm width GNRs. The observed sharp conductance peak on back-gate voltage (Vbg) dependence and its strong correlation with the Ea value suggest the presence of possible resonant tunnelling through shallow impurity levels with the small Ea introduced by the edge terminations by foreign atoms, which provides the observed unique behaviour, including the high Ion/ Ioff. An energy band gap as large as ~215 meV is also confirmed from the Ioff voltage region on Vbg. These narrow GNRs must open the door to large-scale graphene integration circuits based on CMOS-like behaviour.

Molecular mobility on graphene nanoribbons

Graphene nanoribbons (GNRs) have been proposed to be used as nanoscale mass-conveyor highways. However, how factors such as edge confinement, edge rippling, ribbon twisting, and thermal fluctuations affect the mobility of admolecules on GNRs for such application remains unknown. Using molecular dynamics (MD) simulations, we address these issues by investigating the surface mobility of a physisorbed C60 admolecule on pristine GNRs. We show that the absorption energy and edge energy barrier of a GNR are able to keep and confine the admolecule motion only on one side of the GNR. The twisting of narrow GNRs in combination with thermal fluctuations causes the admolecule to move in a helical trajectory, and thus markedly affects its mobility. As the GNR width increases, its twisting is gradually inhibited, and the motion of the admolecule becomes planar. A comparison between the results from our MD simulations and those from the confined Langevin model indicates that the distinct behavior of molecular mobility on narrow GNRs is due to their twisting rather than geometrical confinement. These findings shed light on the important factors that control the characteristics of the GNR-based mass transport highways.