Edge stability of boron nitride nanoribbons and its application in designing hybrid BNC structures

First-principles investigations of the edge energies and edge stresses of single-layer hexagonal boron nitride (BN) are presented. The armchair edges of BN nanoribbons (BNNRs) are more stable in energy than zigzag ones. Armchair BNNRs are under compressive edge stress while zigzag BNNRs are under tensile edge stress, due to the edge reconstruction effect and edge coulomb repulsion effect. The intrinsic spin-polarization and edge saturation play important roles in modulating the edge stability of BNNRs. The edge energy difference between BN and graphene can be used to guide the design of specific hybrid BNC structures as the hybrid BNC systems prefer the low-energy edge configurations: In an armchair BNC nanoribbon (BNCNR), BN domains are expected to grow outside of C domains, while the opposite occurs in a zigzag BNCNR. More importantly, armchair BNCNRs can reproduce unique electronic properties of armchair graphene nanoribbons (GNRs), which are expected to be robust against edge functionalization or disorder. Within a certain range of C/BN ratios, zigzag BNCNRs may exhibit intrinsic half-metallicity without any external constraints. These diverse electronic properties of BNCNRs may offer unique opportunities to develop nanoscale electronics and spintronics beyond individual graphene and BN. More generally, these principles for designing BNC can also be extended to other hybrid nanostructures.      

Strain effects in graphene and graphene nanoribbons: The underlying mechanism

A tight-binding analytic framework is combined with first-principles calculations to reveal the mechanism underlying the strain effects on electronic structures of graphene and graphene nanoribbons (GNRs). It provides a unified and precise formulation of the strain effects under various circumstances-including the shift of the Fermi (Dirac) points, the change in band gap of armchair GNRs with uniaxial strain in a zigzag pattern and its insensitivity to shear strain, and the variation of the k-range of edge states in zigzag GNRs under uniaxial and shear strains which determine the gap behavior via the spin polarization interaction.      

Band gap of strained graphene nanoribbons

The band structures of strained graphene nanoribbons (GNRs) are examined using a tight-binding Hamiltonian that is directly related to the type and magnitude of strain. Compared to a two-dimensional graphene whose band gap remains close to zero even if a large strain is applied, the band gap of a graphene nanoribbon (GNR) is sensitive to both uniaxial and shear strains. The effect of strain on the electronic structure of a GNR depends strongly on its edge shape and structural indices. For an armchair GNR, a weak uniaxial strain changes the band gap in a linear fashion, whereas a large strain results in periodic oscillation of the band gap. On the other hand, shear strain always tends to reduce the band gap. For a zigzag GNR, the effect of strain is to change the spin polarization at the edges of GNR, and thereby modulate the band gap. A simple analytical model, which agrees with the numerical results, is proposed to interpret the response of the band gap to strain in armchair GNRs.      

Spin-resolved self-doping tunes the intrinsic half-metallicity of AlN nanoribbons

We present a first-principles theoretical study of electric field- and straincontrolled intrinsic half-metallic properties of zigzagged aluminium nitride （A1N） nanoribbons. We show that the half-metallic property of AIN ribbons can undergo a transition into fully-metallic or semiconducting behavior with application of an electric field or uniaxial strain. An external transverse electric field induces a full charge screening that renders the material semiconducting. In contrast, as uniaxial strain varies from compressive to tensile, a spin-resolved selective self-doping increases the half-metallic character of the ribbons. The relevant strain-induced changes in electronic properties arise from band structure modifications at the Fermi level as a consequence of a spin-polarized charge transfer between p-orbitals of the N and A1 edge atoms in a spin-resolved self-doping process. This band structure tunability indicates the possibility of designing magnetic nanoribbons with tunable electronic structure by deriving edge states from elements with sufficiently different localization properties. Finite temperature molecular dynamics reveal a thermally stable half-metallic nanoribbon up to room temperature.     

Charge transport in disordered graphene-based low dimensional materials

Two-dimensional graphene, carbon nanotubes, and graphene nanoribbons represent a novel class of low dimensional materials that could serve as building blocks for future carbon-based nanoelectronics. Although these systems share a similar underlying electronic structure, whose exact details depend on confinement effects, crucial differences emerge when disorder comes into play. In this review, we consider the transport properties of these materials, with particular emphasis on the case of graphene nanoribbons. After summarizing the electronic and transport properties of defect-free systems, we focus on the effects of a model disorder potential (Anderson-type), and illustrate how transport properties are sensitive to the underlying symmetry. We provide analytical expressions for the elastic mean free path of carbon nanotubes and graphene nanoribbons, and discuss the onset of weak and strong localization regimes, which are genuinely dependent on the transport dimensionality. We also consider the effects of edge disorder and roughness for graphene nanoribbons in relation to their armchair or zigzag orientation. This article is published with open access at Springerlink.com     

Computational model of edge effects in graphene nanoribbon transistors

We present a semi-analytical model incorporating the effects of edge bond relaxation, the third nearest neighbor interactions, and edge scattering in graphene nanoribbon field-effect transistors (GNRFETs) with armchair-edge GNR (AGNR) channels. Unlike carbon nanotubes (CNTs) which do not have edges, the existence of edges in the AGNRs has a significant effect on the quantum capacitance and ballistic I-V characteristics of GNRFETs. For an AGNR with an index of m=3p, the band gap decreases and the ON current increases whereas for an AGNR with an index of m=3p+1, the quantum capacitance increases and the ON current decreases. The effect of edge scattering, which reduces the ON current, is also included in the model. This article is published with open access at Springerlink.com     

Enhanced ferromagnetism in ZnO nanoribbons and clusters passivated with sulfur

Inspired by recent experimental results, the electronic and magnetic properties of sulfur-passivated ZnO clusters and zigzag nanoribbons have been studied using first principles calculations in the framework of the local spin density approximation. In the case of the ZnO nanoribbons, the sulfur atoms or thiol groups were attached in different ways to the zinc or oxygen atoms located at the edges, whereas in clusters, the sulfur atoms were set on the surface, mainly interacting with atoms with low-coordinate number. After an exhaustive atomic relaxation, we found that a magnetic moment emerges in zigzag nanoribbons both with and without sulfur-passivation on the edges. However, the magnitude of the magnetic moment is very sensitive to sulfur passivation. In particular, we found that when sulfur is attached to the zinc atoms in an alternating fashion along the ribbon edges, the magnetic moment is a maximum (1.4 μ_B/unit cell). In the case of clusters, we found that the Zn₁₅O₁₅ cluster exhibits a high spin moment of 5.5 μ_B when capped with sulfur atoms. Our calculations indicate that sulfur-passivating of ZnO nanosystems could be responsible for recently observed ferromagnetic responses. This article is published with open access at Springerlink.com     

A unified geometric rule for designing nanomagnetism in graphene

Based on the underlying graphene lattice symmetry and an itinerant magnetism model on a bipartite lattice, we propose a unified geometric rule for designing graphene-based magnetic nanostructures: spins are parallel (ferromagnetic (FM)) on all zigzag edges which are at angles of 0° and 120° to each other, and antiparallel (antiferromagnetic (AF)) at angles of 60° and 180°. The rule is found to be consistent with all the systems that have been studied so far. Applying the rule, we predict several novel graphene-based magnetic nanostructures: 0-D FM nanodots with the highest possible magnetic moments, 1-D FM nanoribbons, and 2-D magnetic superlattices.      

Immunity of electronic and transport properties of phosphorene nanoribbons to edge defects

We present an extensive study of the electronic properties and carrier transport in phosphorene nanoribbons (PNRs) with edge defects by using rigorous atomistic quantum transport simulations. This study reports on the size- and defect-dependent scaling laws governing the transport gap, and the mean free path and carrier mobility in the PNRs of interest for future nanoelectronics applications. Our results indicate that PNRs with armchair edges (aPNRs) are more immune to defects than zig-zag PNRs (zPNRs), while both PNR types exhibit superior immunity to defects relative to graphene nanoribbons (GNRs). An investigation of the mean free path demonstrated that even in the case of a low defect density the transport in PNRs is diffusive, and the carrier mobility remains a meaningful transport parameter even in ultra-small PNRs. We found that the electron–hole mobility asymmetry (present in large-area phosphorene) is retained only in zPNRs for W > 4 nm, while in other cases the asymmetry is smoothed out by edge defect scattering. Furthermore, we showed that aPNRs outperform both zPNRs and GNRs in terms of carrier mobility, and that PNRs generally offer a superior mobility-bandgap trade-off, relative to GNRs and monolayer MoS₂. This work identifies PNRs as a promising material for the extremely scaled transistor channels in future post-silicon electronic technology, and presents a persuasive argument for experimental work on nanostructured phosphorene.

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Synthesis and Ex situ doping of ZnTe and ZnSe nanostructures with extreme aspect ratios

We report synthesis windows for growth of millimeter-long ZnTe nanoribbons and ZnSe nanowires using vapor transport. By tuning the local conditions at the growth substrate, high aspect ratio nanostructures can be synthesized. A Cu-ion immersion doping method was applied, producing strongly p-type conduction in ZnTe and ionic conduction in ZnSe. These extreme aspect ratio wide-bandgap semiconductors have great potential for high density nanostructured optoelectronic circuits.      

Topological to trivial insulating phase transition in stanene

Electronic properties of stanene, the Sn counterpart of graphene are theoretically studied using first-principles simulations. The topological to trivial insulating phase transition induced by an out-of-plane electric field or by quantum confinement effects is predicted. The results highlight the potential to use stanene nanoribbons in gate-voltage controlled dissipationless spin-based devices and are used to set the minimal nanoribbon width for such devices, which is typically approximately 5 nm.

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Recovery of edge states of graphene nanoislands on an iridium substrate by silicon intercalation

Finite-sized graphene sheets, such as graphene nanoislands (GNIs), are promising candidates for practical applications in graphene-based nanoelectronics. GNIs with well-defined zigzag edges are predicted to have spin-polarized edge-states similar to those of zigzag-edged graphene nanoribbons, which can achieve graphene spintronics. However, it has been reported that GNIs on metal substrates have no edge states because of interactions with the substrate.We used a combination of scanning tunneling microscopy, spectroscopy, and density functional theory calculations to demonstrate that the edge states of GNIs on an Ir substrate can be recovered by intercalating a layer of Si atoms between the GNIs and the substrate. We also found that the edge states gradually shift to the Fermi level with increasing island size. This work provides a method to investigate spin-polarized edge states in high-quality graphene nanostructures on a metal substrate.

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Chemical versus thermal folding of graphene edges

Using molecular dynamics (MD) simulations, we have investigated the kinetics of the graphene edge folding process. The lower limit of the energy barrier is found to be ∼380 meV/? (or about 800 meV per edge atom) and ∼50 meV/? (or about 120 meV per edge atom) for folding the edges of intrinsic clean single-layer graphene (SLG) and double-layer graphene (DLG), respectively. However, the edge folding barriers can be substantially reduced by imbalanced chemical adsorption, such as of H atoms, on the two sides of graphene along the edges. Our studies indicate that thermal folding is not feasible at room temperature (RT) for clean SLG and DLG edges and is feasible at high temperature only for DLG edges, whereas chemical folding (with adsorbates) of both SLG and DLG edges can be spontaneous at RT. These findings suggest that the folded edge structures of suspended graphene observed in some experiments are possibly due to the presence of adsorbates at the edges.      

Lateral composition-graded semiconductor nanoribbons for multi-color nanolasers

Low-dimensional semiconductor nanostructures have attracted much interest for applications in integrated photonic and optoelectronic devices. Band gap engineering within single semiconductor nanoribbons helps to manipulate photon behavior in two different cavities (in the width and length directions) and realize new photonic phenomena and applications. In this work, lateral composition-graded semiconductor nanoribbons were grown for the first time through an improved source-moving vapor phase route. Along the width of the nanoribbon, the material can be gradually tuned from pure CdS to a highly Se-doped CdSSe alloy with a corresponding band gap modulation from 2.42 to 1.94 eV. The achieved alloy ribbons are overall high-quality crystals, and the position-dependent band-edge photoluminescence (PL) emission had a peak wavelength continuously tuned from ~515 to ~640 nm. These ribbons can realize multi-color lasing with three groups of lasing modes centered at 519, 557, and 623 nm. It was confirmed that the red lasing was from optical resonance along the length direction, while the green and yellow lasing was from optical resonance along the width direction. These novel nanoribbon structures may be applied to many integrated photonic and optoelectronic devices.

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Sandwich structured graphene-wrapped FeS-graphene nanoribbons with improved cycling stability for lithium ion batteries

Sandwich structured graphene-wrapped FeS-graphene nanoribbons (G@FeS-GNRs) were developed. In this composite, FeS nanoparticles were sandwiched between graphene and graphene nanoribbons. When used as anodes in lithium ion batteries (LIBs), the G@FeS-GNR composite demonstrated an outstanding electrochemical performance. This composite showed high reversible capacity, good rate performance, and enhanced cycling stability owing to the synergy between the electrically conductive graphene, graphene nanoribbons, and FeS. The design concept developed here opens up a new avenue for constructing anodes with improved electrochemical stability for LIBs.

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Strain-induced semiconductor to metal transition in the two-dimensional honeycomb structure of MoS2

The electronic properties of two-dimensional honeycomb structures of molybdenum disulfide (MoS₂) subjected to biaxial strain have been investigated using first-principles calculations based on density functional theory. On applying compressive or tensile bi-axial strain on bi-layer and mono-layer MoS₂, the electronic properties are predicted to change from semiconducting to metallic. These changes present very interesting possibilities for engineering the electronic properties of two-dimensional structures of MoS₂.      

Exploration of channel width scaling and edge states in transition metal dichalcogenides

We explore the impact of edge states in three types of transition metal dichalcogenides (TMDs), namely metallic Td-phase WTe₂ and semiconducting 2H-phase MoTe₂ and MoS₂, by patterning thin flakes into ribbons with varying channel widths. No obvious charge depletion at the edges is observed for any of these three materials, in contrast to observations made for graphene nanoribbon devices. The semiconducting ribbons are characterized in a three-terminal field-effect transistor (FET) geometry. In addition, two ribbon array designs have been carefully investigated and found to exhibit current levels higher than those observed for conventional one-channel devices. Our results suggest that device structures incorporating a high number of edges can improve the performance of TMD FETs. This improvement is attributed to a higher local electric field, resulting from the edges, increasing the effective number of charge carriers, and the absence of any detrimental edge-related scattering.

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<Emphasis Type="Italic">In-situ</Emphasis> fabrication of Mo<Subscript>6</Subscript>S<Subscript>6</Subscript>-nanowire-terminated edges in monolayer molybdenum disulfide

Edge structures are highly relevant to the electronic, magnetic, and catalytic properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) and their one-dimensional (1D) counterparts, i.e., nanoribbons, and should be precisely tailored for the desired application. In this work, we report the formation of novel Mo₆S₆ nanowire (NW)-terminated edges in monolayer molybdenum disulfide (MoS₂) via an e–beam irradiation process combined with high temperature heating. The atomic structures of the NW-terminated edges and the dynamic formation process were observed experimentally using scanning transmission electron microscopy. Further analysis showed that the NW-terminated edge could be formed on both the Mo-zigzag (ZZ) edge and S-ZZ edge and could exhibit a stability superior to that of the pristine ZZ and armchair (AC) edges. In addition, analogous edge structures could also be formed in MoS₂ nanoribbons and other TMD materials such as Mo_xW_1?xSe₂. We believe that these novel edge structures may impart novel properties to the 2D and 1D TMD materials and provide new opportunities for their applications in catalytic, spintronic, and electronic devices.

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Microscopic insight into the single step growth of in-plane heterostructures between graphene and hexagonal boron nitride

Graphene-h-BN hybrid nanostructures are grown in one step on the Pt(111) surface by ultra-high vacuum chemical vapor deposition using a single precursor, the dimethylamino borane complex. By varying the deposition conditions, different nanostructures ranging from a fully continuous hybrid monolayer to well-separated Janus nanodots can be obtained. The growth starts with heterogeneous nucleation on morphological defects such as Pt step edges and proceeds by the addition of small clusters formed by the decomposition of the dimethylamino borane complex. Scanning tunneling microscopy measurements indicate that a sharp zigzag in-plane boundary is formed when graphene grows aligned with the Pt substrate and consequently with the h-BN layer as well. When graphene is rotated by 30°, the graphene armchair edges are seamlessly connected to h-BN zigzag edges. This is confirmed by a thorough density functional theory (DFT) study. Angle resolved photoemission spectroscopy (ARPES) data suggests that both h-BN and graphene present the typical electronic structure of self-standing non-interacting materials.

     

Nanoseparation-inspired manipulation of the synthesis of CdS nanorods

CdS nanorods have been sorted by length using a density gradient ultracentrifuge rate separation method. The fractions containing longer rods showed relatively stronger oxygen-related surface trap emission, while the shorter ones had dominant band-edge emission. These results suggest that the final length distribution of CdS nanorods is not a result of random nucleation and growth, but is related to the local synthesis conditions. Inspired by these findings, different synthesis environments (N₂, air, and O₂) have been employed in order to tailor the length distribution. In addition to the rod length, the photoluminescence properties of CdS nanorods can also be manipulated. Increasing the oxygen partial pressure significantly changed the growth behavior of CdS nanorods by improving the anisotropic growth.