Nano Today
Volume 5, Issue 4, August 2010, Pages 351-372
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Review
Graphene and graphite nanoribbons: Morphology, properties, synthesis, defects and applications

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Summary

Carbon is a unique and very versatile element which is capable of forming different architectures at the nanoscale. Over the last 20 years, new members of the carbon nanostructure family arose, and more are coming. This review provides a brief overview on carbon nanostructures ranging from C60 to graphene, passing through carbon nanotubes. It provides the reader with important definitions in carbon nanoscience and concentrates on novel one- and two-dimensional layered carbon (sp2 hybridized), including graphene and nanoribbons. This account presents the latest advances in their synthesis and characterization, and discusses new perspectives of tailoring their electronic, chemical, mechanical and magnetic properties based on defect control engineering. It is foreseen that some of the structures discussed in the review will have important applications in areas related to electronics, spintronics, composites, medicine and many others.

Introduction

The discovery of C60 Buckminsterfullerene, a beautiful cage-like carbon molecule of 7 Å in diameter (Fig. 1a) [1], stimulated the creativity and imagination of scientists and paved the way to a whole new chemistry and physics of nanocarbons (Fig. 1) [2], [3], [4]. Soon after, carbon nanostructures related papers started to increase in number almost exponentially. However, it is important to note that 5 years earlier (1980), Sumio Iijima first reported electron microscope images of nested carbon nanocages (also known as graphitic onions) when studying amorphous carbon films prepared by thermal vacuum deposition. In 1988, Kroto and McKay proposed that such graphitic onions observed by Iijima consisted of nested icosahedral Fullerenes (C60@C240@C540@C960.) containing only pentagonal and hexagonal carbon rings (Fig. 1b) [5]. In 1992, Daniel Ugarte observed the reconstruction of polyhedral graphitic particles (nested giant fullerenes) into almost spherical carbon onions [6], due to high-energy electron irradiation inside a high-resolution transmission electron microscope (HRTEM). Similarly, Chuvilin et al. have recently observed the creation of defects on graphene and the eventual formation of C60 upon electron irradiation in a HRTEM [7].

Regarding tubular graphene (rolled graphene sheets known as nanotubes), Endo, and coworkers appear to be the first to report the existence of thin single and multi-walled graphitic nanotubes (SWCNTs and MWCNTs) (Fig. 1c) using HRTEM. These nanotubes were produced using a modified chemical vapor deposition (CVD) method used to produce carbon fibers [8], but this 1976 paper did not have a broad impact at that time. The study of carbon nanotubes (CNTs) started in earnest when Sumio Iijima confirmed in 1991 [9], using electron diffraction, that the structure of MWCNTs consisted of nested graphene tubules exhibiting fullerene-like caps [10]. He termed these structures “graphite microtubules”. They were produced via an arc-discharge between graphite electrodes in an inert atmosphere (no metal catalyst was used); the same method for producing fullerenes [9]. The synthesis of SWCNTs was reported a couple of years later, in 1993, by Iijima's group [11] and Bethune's group [12] using a carbon arc in conjunction with metal catalysts. Soon after, other graphitic nanostructures were successfully produced, including: nanocones (Fig. 1d) [13], peapods [14], nanohorns (Fig. 1d) [15], carbon rings or toroids (Fig. 1e) [16]. More recently, the two-dimensional crystalline allotrope of carbon, called graphene (Fig. 1f), was isolated using the so-called “scotch-tape method”, where an ingenious method for its observation under an optical microscope was described [17]. As in the case of CNTs, previous works reporting graphene from the reduction of graphene oxide [18] and torn from graphite with an STM tip [19] appeared ahead of its time and did not receive much attention. The relatively easy production of graphene using Novoselov's method, and the peculiar properties of this 2D atomic crystal have heavily stimulated an extensive study of graphene for the first time. New carbon structures with sp2 hybridization, such as bilayer and few-layer graphene, graphene and graphitic nanoribbons have subsequently emerged, each with novel and unusual properties (Fig. 2).

The series of events described above clearly demonstrate that carbon is a fascinating element and is able to form various morphologies at the nanoscale, possessing different physicochemical properties, some of them yet unknown. There are several reviews and dedicated journal issues on the synthesis and properties of graphene (see, for instance [20], [21]). However, the other sp2 hybridized carbon structures that have emerged from the study of graphene deserve as much of attention as graphene. This review intends to summarize the latest theoretical and experimental advances related to novel one- and two-dimensional layered carbon (sp2 hybridized).

Section snippets

The different types of graphene-like nanostructures

By looking at the different morphologies of graphene-based nanostructures discovered so far, and all other possibilities still to be found, it is important to provide some important definitions related to different sp2-like hybridized nanocarbons. In this manuscript the following definitions regarding graphene-like structures will be used:

Properties of graphene and few-layered graphene

The crystal structure of graphene can be thought of as two equivalent carbon triangular sub-lattices. Due to symmetry considerations, the hopping of electrons between the sub-lattices leads to the formation of two energy bands, which intersect at the K point (Fig. 2a) [39]. Near these crossing points, the electron energy is linearly dependent on the wave vector. This linear dispersion results in massless excitons, which are described by the Dirac equation. Dirac fermions (electrons or holes)

Synthesis of graphitic and graphene nanoribbons

There is a wide spectrum of methods available to produce carbon nanoribbons, from CVD, through chemical treatments of graphite to the unzipping of carbon nanotubes.

Defects in graphene and graphitic nanoribbons

Defects play a crucial role in the properties of crystals and nanostructures, including graphitic systems. Graphene-like systems are so versatile that they can accommodate different kinds of defects that change completely their structure and also their physicochemical properties. In particular, defects which change the structure could also change the topology or the curvature. However, it is difficult to identify accurately and quantitatively the type of defects contained in graphene-like

Doped graphitic nanoribbons

Doping of graphene and graphene nanoribbons is relevant because, depending on the location of the dopants and their concentration, their physicochemical properties could be tuned and controlled. In this context, Cervantes-Sodi, et al. [142] reported theoretical studies related to the doping of graphene nanoribbons with N, B and O atoms. They noted that when doping nanoribbons, edge-type and substitutional doping induce different electronic properties to the systems and, in some cases,

Characterization of graphene materials by Raman spectroscopy and other techniques

In the early days of the study of graphene, with the use of the optical microscope, the identification of graphene flakes was a simple but tedious task. Quantifying the number of layers implied the use of time consuming techniques (AFM, TEM) and required prior sample preparation. However, in 2006, Ferrari et al. reported the Raman spectra of single-, double- and few-layer graphene produced with Novoselov's “scotch-tape” technique [147]. Clear signals specific for each single-, double and few

Applications

Graphene is a unique material because its displays an outstanding electron transport at room temperature, in which electrons behave as massless particles without experiencing scattering. Therefore, the imminent applications of this layered material are in electronics such as in the fabrication of ultrafast transistors [154] able to operate in the terahertz frequency range. Its low capacitance is also important in the fabrication of biosensors or chemical sensors due to the resulting low values

Conclusions

The production of GNRs is a rapidly advancing field, and novel synthetic methods and advances towards their applications will be developed. A challenge however will remain for facile integration of graphene into electronic devices: control over the deposition of GNRs, control on the atomic edge arrangements and creating efficient electrical contacts. This is only the tip of the iceberg since other layered materials such as BN, MoS2, WS2, ZnO, TiO2, etc., could also generate nanoribbons. In this

Mauricio Terrones obtained his B.Sc. degree in Engineering Physics with first class honours at Universidad Iberoamericana, and was distinguished as the Best Student of Mexico in Engineering Physics in 1992. In 1994 he started his doctorate degree with Sir Prof. Harold W. Kroto (Nobel Laureate, FRS) and received his D.Phil. degree from University of Sussex in 1997. He has co-authored more than 270 publications in international journals, and counts with more than 9000 citations to his work (His H

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    Mauricio Terrones obtained his B.Sc. degree in Engineering Physics with first class honours at Universidad Iberoamericana, and was distinguished as the Best Student of Mexico in Engineering Physics in 1992. In 1994 he started his doctorate degree with Sir Prof. Harold W. Kroto (Nobel Laureate, FRS) and received his D.Phil. degree from University of Sussex in 1997. He has co-authored more than 270 publications in international journals, and counts with more than 9000 citations to his work (His H index is 52). He has numerous awards including: the Alexander von Humboldt Fellowship, the Mexican National Prize for Chemistry, the Javed Husain Prize and the Albert Einstein medal from UNESCO, the TWAS Prize in Engineering Physics, the Carbon Prize given by the Japanese Carbon Society, the Somiya Award by the International Union of Materials Research Societies, among others. Aged 41, he currently holds a chair of excellence at Universidad Carlos III of Madrid, and he was the pioneer of the National Laboratory for Nanoscience and Nanotechnology Research (LINAN) at IPICYT in Mexico. His research now concentrates on the theory, synthesis and characterization of novel layered nanomaterials, including graphene, and he will join Shinshu University (Japan), as outstanding professor, from August 2010.

    Andrés R. Botello-Méndez received his BS in Physics Engineering in 2004 from ITESM (Mexico), and his PhD in Applied Sciences (Nanoscience and Nanotechnology) in 2009 from IPICYT (Mexico). He has worked in the study of the electronic properties of ZnO and carbon nanostructures. He is mainly involved in theoretical and experimental studies of the properties of one-dimensional nanostructures from layered compounds. Presently, he is doing a postdoctoral stay at the Institute of Condensed Matter and Nanosciences (ICMN) of the Catholic University of Louvain in Belgium were he obtained the Marcel de Merre Prize of Louvain.

    Jessica Campos-Delgado received her B.S. in Physics Engineering from the State University of San Luis Potosi, Mexico in 2005. She enrolled the graduated program of Applied Sciences at the Institute of Science and Technology of San Luis Potosi in Mexico and obtained her PhD degree in 2009. She is currently working as a Post-Doc at the National Institute of Metrology, Standardization and Industrial Quality of Brazil. Her research interests are towards the synthesis of carbon nanostructures and their characterization through Raman spectroscopy and electron microscopy.

    Florentino López-Urías carried out his BSc degree in Physical Sciences at the Autonomous University of Sinaloa (México). He pursued his MSc. in Physical Sciences at the Autonomous University of San Luis Potosí (México), and received the PhD degree in Physics from the University Paul Sabatier in Toulouse (France). His research interests include theoretical and experimental aspects of graphene materials as well as diverse magnetic nanostructures.

    Yadira I. Vega-Cantú received her Ph.D. from Rice University (USA) in 2002, where she worked in Professor W. Edward Billups research group. Her thesis work, received the Harry B. Weiser Award, and her postdoctoral stay dealt with industrial projects. Currently, she is a Professor in the Nanoscience and Nanotechnology program at the Advanced Materials Department at IPICYT. She currently advises eight graduate students. Her research interests include chemistry of carbon nanotubes, carbon nanoribbons and graphene, characterization and processing of polymer nanocomposites and development of applications such as actuators and sensors.

    Fernando J. Rodríguez-Macías has a B.S. (Chemistry, with honours) from ITESM (México). He worked on carbon nanotubes with Professor Richard E. Smalley at Rice University (USA) during his M.A. (1999). He participated in interdisciplinary research in Materials Science at Rice for his Ph.D. (Chemistry, 2004) and a postdoctoral stay with Professor Enrique V. Barrera, producing a patent and papers related to nanotube composites. He joined IPICYT in 2005 and he is currently a Professor in the Nanoscience and Nanotechnology program, advising five graduate students. His research interests include composites of nanocarbons and their chemical modification to control the interface, doped-carbon nanotubes, graphene, biocompatibility of nanomaterials and bionanotechnology.

    Ana Laura Elías received her Ph.D. degree in Nanoscience and Nanotechnology from IPICyT (México) in 2006. She has a Physics background, form her undergraduate degree (UASLP-Mexico, 2002). Ana Laura has visited several institutions for research stays, such as LANL (in New Mexico, USA), MIT (Cambridge, MA), ASU (Tempe, AZ), UNAM (Mexico City), Rice University (Houston, TX) and RPI (Troy, NY). She was a postdoctoral research fellow at Shinshu University (Japan), in the group of Prof. Morinobu Endo and at IPICyT (Mexico). Currently, she is a postdoctoral research fellow at Rice University, in Prof. Ajayan's group (since June 2009).

    Emilio Muñoz-Sandoval obtained his PhD in Physics from the Universidad Autónoma de San Luis Potosí (México), and carried out postdoctoral stays at UNAM (México) and the Netherlands. His current research deals with production and characterization of different carbon nanomaterials and ferromagnetic nanoparticles encapsulated in carbon nanostructures. During the 9 years, working with Professors Terrones and collaborators Emilio has acquired invaluable experimental expertise by evolving a multidisciplinary approach combining the production of nanomaterials with electron microscopy and magnetometry techniques for analysis. In order to control the size and morphology, he has developed several routes to deposit catalytic nanoparticles. Magnetron sputtering deposition has been the most successful method to achieve these goals.

    Abraham G. Cano-Márquez got a Bachelor's diploma in Chemistry at the Universidad Autonoma de San Luis Potosí (México), whence he also received a master's degree in Physical Chemistry after studying the electromicrogravimetric behaviour of a sulfonated polyaniline. He will soon finish his PhD studies at IPICYT (México). His research interests are the development of carbon-based nanostructures, focusing in the study of graphene-like materials and devices. He is also interested in the study of polyanilines and their composites with carbon materials for the development of new actuators for use in robotics and prosthetics. He is part of the team that introduced the exfoliation technique for the unzipping of multi-walled carbon nanotubes.

    Jean-Christophe Charlier is Professor at the Institute of Condensed Matter and Nanosciences of the University of Louvain (UCL) and Senior Research Associate of the Fund for Scientific Research (FNRS) in Belgium. His research interests are in theoretical condensed matter physics and nanosciences covering the areas of: electronic and structural properties of crystals and reduced-dimensional solids; nanotubes, graphene and related carbon-based nanostructures; quantum transport through single molecules and other nanosystems. The objective is to explain and predict the properties of materials using first-principles theories and computational physics. He is author of about hundred scientific publications in international peer-reviewed journals.

    Humberto Terrones obtained his PhD degree from Birkbeck College in 1992 (University of London) under the supervision of Prof. Alan L. Mackay (FRS). Following a postdoctoral stay at Cambridge University (UK), Humberto joined the Institute of Physics at (UNAM) in Mexico City. He then moved to IPICYT as Head of the Advanced Materials Department, to work mainly in nanosciences and nanotechnology introducing a multidisciplinary character to research. He is presently visiting Professor at the Institute of Condensed Matter and Nanosciences of the Université Catholique de Louvain in Belgium. Alan L. Mackay and HumbertoTerrones were the first to introduce the concept of curvature in layered materials to understand and propose new nanostructures.

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