New Frontiers in Electron Beam–Driven Chemistry in and around Graphene

Modern aberration corrected transmission electron microscopes offer the potential for electron beam sensitive materials, such as graphene, to be examined with low energy electrons to minimize, and even avoid, damage while still affording atomic resolution, and thus providing excellent characterization. Here in this review, the exploits in which the electron beam interactions, which are often considered negative, are explored to usefully drive a wealth of chemistry in and around graphene, importantly, with no other external stimuli. After introducing the technique, this review covers carbon phase reactions between amorphous carbon, graphene, fullerenes, carbon chains, and carbon nanotubes. It then explores different studies with clusters and nanoparticles, followed by coverage of single atom and molecule interactions with graphene, and finally concludes and highlights the anticipated exciting future for electron beam driving chemistry in and around graphene.     

Irradiation of carbon nanotubes with a focused electron beam in the electron microscope

The paper reviews in-situ electron irradiation studies of carbon nanotubes in electron microscopes. It is shown that electron irradiation at high specimen temperature can lead to a variety of structural modifications and new morphologies of nanotubes. Radiation defects such as vacancies and interstitials are created under irradiation, but the cylindrically closed graphene layers reconstruct locally and remain coherent. The generation of curvature in graphene layers with non-hexagonal rings allows us to alter the topology of nanotubes. Several examples of irradiation-induced modifications of single- and multi-wall nanotubes are shown. Conclusions about the mobility of interstitials and vacancies are drawn which are important to explain the behaviour and the properties of nanotubes with an atomic arrangement deviating from the hexagonal network of graphene.     

Enhanced electron field emission from carbon nanotubes irradiated by energetic C ions

The field emission performance and structure of the vertically aligned multi-walled carbon nanotube arrays irradiated by energetic C ion with average energy of 40 keV have been investigated. During energetic C ion irradiation, the curves of emission current density versus the applied field of samples shift firstly to low applied fields when the irradiation doses are less than 9.6 x 10(16) cm(-2), and further increase of dose makes the curves reversing to a high applied field, which shows that high dose irradiation in carbon nanotube arrays makes their field emission performance worse. After energetic ion irradiation with a dose of 9.6 x 1016 cm(-2), the turn-on electric field and the threshold electric field of samples decreased from 0.80 and 1.13 V/microm to 0.67 and 0.98 V/microm respectively. Structural analysis of scanning electron microscopy, transmission electron microscopy and Raman spectroscopy indicates that the amorphous carbon nanowire/carbon nanotube hetero nano-structures have been fabricated in the C ion irradiated carbon nanotubes. The enhancement of electron field emission is due to the formation of amorphous carbon nanowires at the tip of carbon nanotube arrays, which is an electron emitting material with low work function.     

Bundling up carbon nanotubes through Wigner defects

We show, using ab initio total energy density functional theory, that the so-called Wigner defects, an interstitial carbon atom right beside a vacancy, which are present in irradiated graphite, can also exist in bundles of carbon nanotubes. Due to the geometrical structure of a nanotube, however, this defect has a rather low formation energy, lower than the vacancy itself, suggesting that it may be one of the most important defects that are created after electron or ion irradiation. Moreover, they form a strong link between the nanotubes in bundles, increasing their shear modulus by a sizable amount, clearly indicating its importance for the mechanical properties of nanotube bundles.     

Controlled growth-reversal of catalytic carbon nanotubes under electron-beam irradiation

The growth of carbon nanotubes from Ni catalysts is reversed and observed in real time in a transmission electron microscope, at room temperature. The Ni catalyst is found to be Ni3C and remains attached to the nanotube throughout the irradiation sequence, indicating that C most likely diffuses on the surface of the catalyst to form nanotubes. We calculate the energy barrier for saturating the Ni3C (2-13) surface with C to be 0.14 eV, thus providing a low-energy surface for the formation of graphene planes.     

Defect studies on as-synthesized and purified carbon nanostructures produced by arc-discharge in solution process

Carbon nanostructures are synthesized using a novel arc-discharge in solution process. A multitude of defects on nanotubes and nanostructures is found. Evidence of these defects in as-synthesized carbon nanostructures is explored using high-resolution transmission electron microscopy (HRTEM). Tri-, tetra-, penta-, hexa-, heptagonal, toroidal, oval, and spherical nanoshells are found in HRTEM investigation along with carbon nanotubes, carbon nanohorns, carbon rods, nanoporous carbon, dislodged graphene sheets, and amorphous carbon. Purifications are carried out through two oxidation methods to eliminate the amorphous carbon. Several different defects caused by oxidations are also found in purified samples.     

Atomic-scale electron-beam sculpting of near-defect-free graphene nanostructures

In order to harvest the many promising properties of graphene in (electronic) applications, a technique is required to cut, shape, or sculpt the material on the nanoscale without inducing damage to its atomic structure, as this drastically influences the electronic properties of the nanostructure. Here, we reveal a temperature-dependent self-repair mechanism that allows near-damage-free atomic-scale sculpting of graphene using a focused electron beam. We demonstrate that by sculpting at temperatures above 600 °C, an intrinsic self-repair mechanism keeps the graphene in a single-crystalline state during cutting, even though the electron beam induces considerable damage. Self-repair is mediated by mobile carbon ad-atoms that constantly repair the defects caused by the electron beam. Our technique allows reproducible fabrication and simultaneous imaging of single-crystalline free-standing nanoribbons, nanotubes, nanopores, and single carbon chains.     

Toughening Mechanisms in Carbon Nanotube-Reinforced Amorphous Carbon Matrix Composites

Crack deflection and penetration at the interface of multi-wall carbon nanotube/amorphous carbon composites were studied via molecular dynamics simulations. In-situ strength of double-wall nanotubes bridging a matrix crack was calculated under various interfacial conditions. The structure of the nanotube reinforcement -ideal multi-wall vs. multi-wall with interwall sp³ bonding - influences the interfacial sliding and crack penetration. When the nanotube/matrix interface is strong, matrix crack penetrates the outermost layer of nanotubes but it deflects within the nanotubes with certain sp³ interwall bond density, resulting in inner wall pullout. With increasing the sp³ interwall bond density, the fracture mode becomes brittle; the fracture energy decrease while the bridging strength increases and then decreases. Our results suggest that the outermost nanotube wall can serve as a sacrificial layer such that the interface may be designed by effectively putting it inside the nanotubes. Controlling the density of sp³ interwall bond within the multiwall carbon nanotube makes the transition from brittle to tough failure modes in the composites even when the matrix/nanotube interface is strong.     

Boron nitride and carbon double-wall hetero-nanotubes: first-principles calculation of electronic properties

First-principles calculations based on density functional theory with the generalized gradient approximation were carried out to investigate the electronic properties of boron nitride and carbon double-wall hetero-nanotubes of different chirality and size. The results show that the electronic structures of the double-wall hetero-nanotubes near the Fermi level are dominated by the p?electrons of carbon atoms, regardless of whether the carbon nanotube is inside or outside the boron nitride nanotube. Double-wall hetero-nanotubes consisting of semiconducting carbon and boron nitride nanotubes are semiconductors. An opening of a band gap is observed for armchair carbon and boron nitride double-wall hetero-nanotubes with small intertube spacing due to the intertube interaction and the changes of symmetry.     

Field emission from a selected multiwall carbon nanotube

The electron field emission characteristics of individual multiwalled carbon nanotubes were investigated by a piezoelectric nanomanipulation system operating inside a scanning electron microscopy chamber. The experimental set-up ensures a precise evaluation of the geometric parameters (multiwalled carbon nanotube length and diameter and anode-cathode separation) of the field emission system. For several multiwalled carbon nanotubes, reproducible and quite stable emission current behaviour was obtained, with a dependence on the applied voltage well described by a series resistance modified Fowler-Nordheim model. A turn-on field of ～30?V?μm(-1) and a field enhancement factor of around 100 at a cathode-anode distance of the order of 1?μm were evaluated. Finally, the effect of selective electron beam irradiation on the nanotube field emission capabilities was extensively investigated.     

Symmetry analysis of relative motions in a double-wall carbon nanotube

The binding energy of a double-wall carbon nanotube (DWNT) is theoretically studied as a function of the relative longitudinal shift and relative rotation of the component single-wall carbon nanotubes (SWNTs). It is shown that the binding energy is an oscillating function of the relative shift and rotation, with the oscillation period depending on the relations between symmetry elements of the SWNTs. The results of numerical calculations of the binding energy of DWNTs, performed in the approximation of weak van der Waals interlayer interaction, are presented.     

Si(111)衬底上多层石墨烯薄膜的外延生长

利用固源分子束外延(SSMBE)技术, 在Si(111)衬底上沉积碳原子外延生长石墨烯薄膜, 通过反射式高能电子衍射(RHEED)、红外吸收谱(FTIR)、拉曼光谱(RAMAN)和X射线吸收精细结构谱(NEXAFS)等手段对不同衬底温度(400、600、700、800℃)生长的薄膜进行结构表征. RAMAN和NEXAFS结果表明: 在800℃下制备的薄膜具有石墨烯的特征, 而 400、600和700℃生长的样品为非晶或多晶碳薄膜. RHEED和FTIR结果表明, 沉积温度在600℃以下时C原子和衬底Si原子没有成键, 而衬底温度提升到700℃以上, 沉积的C原子会先和衬底Si原子反应形成SiC缓冲层, 且在800℃沉积时缓冲层质量较好. 因此在Si衬底上制备石墨烯薄膜需要较高的衬底温度和高质量的SiC缓冲层.     

Optically transparent carbon nanowire thin film

Thin films of amorphous carbon nanowire (a-CNW) have been fabricated from crossed multi-walled carbon nanotube (MWCNT) thin film. The fabrication was done by means of ion beam irradiation on various substrates. It is found that the a-CNW thin films show electrical conduction behaviour, and electrical conductivity varies after annealing. In addition, the transmission spectra in the visible range reveal that the film has above 90% optical transmission. It can be ascribed to the fact that the decreased crystallinity of MWCNTs by ion beam irradiation has caused the incremental increase of optical transmission. We also report on a method for cutting or destroying a-CNWs using low-energy focused electron beam from a scanning electron microscope.     

Microwave-assisted synthesis and characterization of zinc oxide/carbon nanotube composites

A composite material of zinc oxide and carbon nanotubes were successfully synthesized via a sol process using zinc acetate dihydrate and treated multi-wall carbon nanotubes under microwave irradiation. The morphology, microstructure and chemical bonding of as-obtained composites were well characterized using X-ray diffraction, scanning electron microscope, transmission electron microscope, and Fourier transform infrared spectroscopy. Zinc oxide nanoparticles were dispersively coated on the surface of carbon nanotube when the precursor was dried under microwave irradiation without post-annealing. X-ray diffraction results obviously showed the mixture of two phases of carbon nanotube and wurzite zinc oxide whose size is approximately 15 nm. The formation of zinc oxide nanoparticles on carbon nanotube surface in the composite prepared by microwave heating is much better than the composite heated by conventional annealing. Fourier transform infrared spectroscopic results suggest that carboxylic groups and uniform heating by microwave heating could play key roles on the nucleation of zinc oxide on carbon nanotube surface.     

Catalytic action of gold and copper crystals in the growth of carbon nanotubes

Multi-wall carbon nanotubes are grown in a chemical vapor deposition process by using bulk gold and copper substrates as catalysts. Nanotube growth starts from a nanometer-sized roughness on the metal surfaces and occurs in a mechanism where the catalyst particle is either at the tip (Au) or root (Cu) of the growing nanotube. Whereas Au leads to nanotubes with good structural perfection, nanotubes grown from Cu show a higher density of defects. High-resolution transmission electron microscopy shows the bonding between Au and carbon at the metal-nanotube interface whereas no bonds between Cu and carbon occur. Highly mobile Au or Cu atoms adsorb at the growing edge of a carbon nanotube from where diffusion along the nanotube wall can lead to the formation of Au or Cu nanowires inside the central hollow of carbon nanotubes.     

电子束辐照对碳纳米管结构及性能的影响

对近年来电子束辐照碳纳米管(CNTs)的研究进展进行了评述,重点阐述了电子束辐照对CNTs的结构缺陷、管径、力学性能、电性能和场发射性能的影响,探讨了电子束辐照技术在CNTs切割和焊接方面的独特优势,并对辐照温度和入射电子能等条件对CNTs辐照效果的影响进行了分析。可以预期,采用电子束辐照处理CNTs仍将是未来一段时间研究的热点之一。     

Solvent-free derivatization of pristine multi-walled carbon nanotubes with dithiols

We report on direct solvent-free derivatization of pristine multi-walled carbon nanotubes (MWNTs) with aliphatic dithiols (1,4-butanedithiol, 1,6-hexanedithiol and 1,8-octanedithiol), by means of heating at 130–150 °C under reduced pressure. This method requires no additional chemical activation and about 2 h only for completion. Studies by high-resolution transmission electron microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy showed that dithiol-derivatized MWNTs have a high affinity to ZnCl₂ in solution, which covers the nanotubes with a dense amorphous layer. According to PM3 semi-empirical calculations, employing a closed-cap zigzag (10,0) single-walled carbon nanotube (SWNT) model incorporating a Stone-Wales defect, site-specificity of the addition depends on the mutual position of pentagons. If the nanotube contains pyracylene units or Stone-Wales defect, the addition takes place on their 6,6 or 7,7 bonds, respectively, whereas for isolated pentagons, preferential reaction sites are their C–C bonds. Ideal graphene sheet sidewalls with cylindrical curvature are relatively inert (although one cannot discard the possibility to activate the reaction by heating). Dithiol groups introduced in the way proposed can be used as chemical linkers for anchoring metal complexes and nanoparticles to carbon nanotubes, attaching SWNTs to gold tips for atomic force and scanning tunneling microscopy, and potentially for adsorption and concentration of trace metal ions.     

A graphene oxide-carbon nanotube grid for high-resolution transmission electron microscopy of nanomaterials

A novel grid for use in transmission electron microscopy is developed. The supporting film of the grid is composed of thin graphene oxide films overlying a super-aligned carbon nanotube network. The composite film combines the advantages of graphene oxide and carbon nanotube networks and has the following properties: it is ultra-thin, it has a large flat and smooth effective supporting area with a homogeneous amorphous appearance, high stability, and good conductivity. The graphene oxide-carbon nanotube grid has a distinct advantage when characterizing the fine structure of a mass of nanomaterials over conventional amorphous carbon grids. Clear high-resolution transmission electron microscopy images of various nanomaterials are obtained easily using the new grids.     

Femtosecond laser induced micropatterning of graphene film

Micropatterning of CVD synthesized large area graphene film is demonstrated with femtosecond laser cutting process. Homogenous microribbon or other patterned structure can be fabricated without using any resist or other material containing the graphene surface within a very short duration. Once the suitable laser beam doses are determined, sharp edge profile and clean etching are obtained. Scanning electron microscopic study shows that the patterned microribbon is having 5 μm width and mm in length. The width of the patterned microribbon can be controlled with control of laser energy and preprogramming of laser ablation process. Raman study at the edge of the microribbon shows increase in D peak and appearance of D + G mode, signifying edge defects. The defect can be explained from the breaking of sp² carbon hybridization with oxidation due to laser etching. The Raman study shows no amorphous carbon formation with laser cutting of the graphene film. The presented process shows a simple way to make patterned microribbon on large area graphene sheet which can be extremely necessary for microelectronics fabrication.     

In situ mechanical property measurements of amorphous carbon-boron nitride nanotube nanostructures

To understand the mechanical properties of amorphous carbon (a-C)/boron nitride nanotube (BNNT) nanostructures, in?situ mechanical tests are conducted inside a transmission electron microscope equipped with an integrated atomic force microscope system. The nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation. We demonstrate multiple in situ tensile, compressive, and lap shear tests with a-C/BNNT hybrid nanostructures. The tensile strength of the a-C/BNNT hybrid nanostructure is 5.29?GPa with about 90?vol% of a-C. The tensile strength and strain of the end-to-end joint structure with a-C welding is 0.8?GPa and 5.2% whereas the lap shear strength of the side-by-side joint structure with a-C is 0.25?GPa.