Inorganic nanoribbons with unpassivated zigzag edges: Half metallicity and edge reconstruction

We have investigated the electronic and structural properties of inorganic nanoribbons (BN, AlN, GaN, SiC, and ZnO) with unpassivated zigzag edges using density functional theory calculations. We find that, in general, the unpassivated zigzag edges can lead to spin-splitting of energy bands. More interestingly, the inorganic nanoribbons AlN and SiC with either one or two edges unpassivated are predicted to be half metallic. Possible structural reconstruction at the unpassivated edges and its effect on the electronic properties are investigated. The unpassivated N edge in the BN nanoribbon and P edge in the AlP nanoribbon are energetically less stable than the corresponding reconstructed edge. Hence, edge reconstruction at the two edges may occur at high temperatures. Other unpassivated edges of the inorganic nanoribbons considered in this study are all robust against edge reconstruction.      

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.      

CO dissociation and CO+O reactions on a nanosized iron cluster

Catalysis over metal nanoparticles is essential for the growth of carbon nanotubes and all the properties of the resulting nanotube, such as diameter and chirality, are affected by the metal particle. Thus, it is very important to understand the carbon chemistry taking place on nanometer size metal particles. Here we present the first ab initio computational study of chemical reactions on a nanosized iron cluster. The clusters have reaction sites, such as edges and vertexes between the facets, Which have not been studied before. First principles electronic structure calculations, fully incorporating the effects of spin polarization and non-collinear magnetic moments, have been used to investigate CO disproportionation on an isolated Fe₅₅ cluster. After CO dissociation, O atoms remain on the surface while C atoms move into the cluster, presumably as the initial step toward carbide formation. Here we show that the lowest CO dissociation barrier found on the cluster (0.77 eV) is lower than on most previously studied Fe surfaces. This dissociation occurs on a vertex between the facets. Several possible paths for CO₂ formation were identified. The calculated lowest reaction barrier is 1.08 eV, which is comparable to the barrier of 0.65 eV obtained by experiment.      

Tuning the morphology of chevron-type graphene nanoribbons by choice of annealing temperature

Bottom-up synthesis of graphene nanoribbons (GNRs) by surface-assisted polymerization and cyclodehydrogenation of specifically designed precursor monomers has been shown to yield precise edges and doping. Here we use a precursor monomer containing sulfur atoms to fabricate nanostructures on a Au(111) surface at different annealing temperatures. The nanostructures have distinct configurations, varying from sulfur-doped polymers to sulfur-doped chevron-type GNRs (CGNRs) and, finally, pristine graphene nanoribbons with specific edges of periodic five-member carbon rings. Non-contact atomic force microscopy provides clear evidence for the cleavage of C–S bonds and formation of pristine CGNRs at elevated annealing temperatures. First-principles calculations show that the CGNRs exhibit negative differential resistance.

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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.      

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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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     

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.      

Synthesis of WS2 and MoS2 fullerene-like nanoparticles from solid precursors

Inorganic fullerene-like WS₂ and MoS₂ nanoparticles have been synthesized using exclusively solid precursors, by reaction of the corresponding metal oxide nanopowder, sulfur and a hydrogen-releasing agent (NaBH₄ or LiAlH₄), achieved either by conventional furnace heating up to ∼900 °C or by photothermal ablation at far higher temperatures driven by highly concentrated white light. In contrast to the established syntheses that require toxic and hazardous gases, working solely with solid precursors permits relatively safer reactor conditions conducive to industrial scale-up.      

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.

     

Direct evidence for lip-lip interactions in multi-walled carbon nanotubes

The stability of open edged multi-walled carbon nanotubes has been investigated by using in situ high resolution transmission electron microscopy at elevated temperatures. Formation of inter-shell structures was experimentally observed for the first time and attributed to a robust interaction between adjacent concentric shells (so-called lip-lip interaction). The fl uctuating behavior of the inter-shell structures suggests a mechanism by which the carbon atoms can pass in or out through the inter-shell edges during carbon nanotube growth or shrinkage processes. This article is published with open access at Springerlink.com     

Density functional theory and tight binding-based dynamical studies of carbon metal systems of relevance to carbon nanotube growth

Density functional theory (DFT) and tight binding (TB) models have been used to study systems containing single-walled carbon nanotubes (SWNTs) and metal clusters that are of relevance to SWNT growth and regrowth. In particular, TB-based Monte Carlo (TBMC) simulations at 1000 or 1500 K show that Ni atoms that are initially on the surface of the SWNT or that are clustered near the SWNT end diffuse to the nanotube end so that virtually none of the Ni atoms are located inside the nanotube. This occurs, in part, due to the lowering of the Ni atom energies when they retract from the SWNT to the interior of the cluster. Aggregation of the atoms at the SWNT end does not change the chirality within the simulation time, which supports the application of SWNT regrowth (seeded growth) as a potential route for chirality-controlled SWNT production. DFT-based geometry optimisation and direct dynamics at 2000 K show that Cr and Mo atoms in Cr₅Co₅₀ and Mo₅Co₅₀ clusters prefer to be distributed in the interior of the clusters. Extension of these calculations should deepen our understanding of the role of the various alloy components in SWNT growth.      

Equilibrium piezoelectric potential distribution in a deformed ZnO nanowire

The equilibrium piezoelectric potential distribution in a deformed ZnO semiconductive nanowire has been systematically investigated in order to reveal its dependence on the donor concentration, applied force, and geometric parameters. In particular, the donor concentration markedly affects the magnitude and distribution of the electric potential. At a donor concentration of N _D>10¹⁸ cm⁻³, the piezopotential is almost entirely screened. Among the other parameters, a variation in the length of the nanowire does not significantly affect the potential distribution.      

<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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Design of a carbon nanotube/magnetic nanoparticle-based peroxidase-like nanocomplex and its application for highly efficient catalytic oxidation of phenols

We report a novel nanotechnology-based approach for the highly efficient catalytic oxidation of phenols and their removal from wastewater. We use a nanocomplex made of multi-walled carbon nanotubes (MWNTs) and magnetic nanoparticles (MNPs). This nanocomplex retains the magnetic properties of individual MNPs and can be effectively separated under an external magnetic field. More importantly, the formation of the nanocomplex enhances the intrinsic peroxidase-like activity of the MNPs that can catalyze the reduction of hydrogen peroxide (H₂O₂). Significantly, in the presence of H₂O₂, this nanocomplex catalyzes the oxidation of phenols with high efficiency, generating insoluble polyaromatic products that can be readily separated from water.      

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.      

Two distinct fluorescent quantum clusters of gold starting from metallic nanoparticles by pH-dependent ligand etching

Two fluorescent quantum clusters of gold, namely Au₂₅ and Au₈, have been synthesized from mercaptosuccinic acid-protected gold nanoparticles of 4–5 nm core diameter by etching with excess glutathione. While etching at pH ∼3 yielded Au₂₅, that at pH 7–8 yielded Au₈. This is the first report of the synthesis of two quantum clusters starting from a single precursor. This simple method makes it possible to synthesize well-defined clusters in gram quantities. Since these clusters are highly fluorescent and are highly biocompatible due to their low metallic content, they can be used for diagnostic applications. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Zigzag zinc blende ZnS nanowires: Large scale synthesis and their structure evolution induced by electron irradiation

Large scale zigzag zinc blende single crystal ZnS nanowires have been successfully synthesized during a vapor phase growth process together with a small yield of straight wurtzite single crystal ZnS nanowires. AuPd alloy nanoparticles were utilized to catalyze a vapor-solid-solid growth process of both types of ZnS nanowires, instead of the more common vapor-liquid-solid growth process. Surprisingly, the vapor-phase grown zigzag zinc blende ZnS nanowires are metastable under high-energy electron irradiation in a transmission electron microscope, with straight wurtzite nanowires being much more stable. Upon exposure to electron irradiation, a wurtzite ZnO nanoparticle layer formed on the zigzag zinc blende ZnS nanowire surface with concomitant displacement damage. Both electron inelastic scattering and surface oxidation as a result of electron-beam heating occur during this structure evolution process. When prolonged higher-voltage electron irradiation was applied, local zinc blende ZnS nanowire bodies evolved into ZnS-ZnO nanocables, and dispersed ZnS-ZnO nanoparticle networks. Random AuPd nanoparticles were observed distributed on zigzag ZnS nanowire surfaces, which might be responsible for a catalytic oxidation effect and speed up the surface oxidation-induced structure evolution.      

Synthesis and optical properties of cubic gold nanoframes

This paper describes a facile method of preparing cubic Au nanoframes with open structures via the galvanic replacement reaction between Ag nanocubes and AuCl₂ ⁻. A mechanistic study of the reaction revealed that the formation of Au nanoframes relies on the diffusion of both Au and Ag atoms. The effect of the edge length and ridge thickness of the nanoframes on the localized surface plasmon resonance peak was explored by a combination of discrete dipole approximation calculations and single nanoparticle spectroscopy. With their hollow and open structures, the Au nanoframes represent a novel class of substrates for applications including surface plasmonics and surface-enhanced Raman scattering.