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    Graphene and Related Nanomaterials: Properties and Applications
    Graphene and Related Nanomaterials: Properties and Applications
    Graphene and Related Nanomaterials: Properties and Applications
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    Graphene and Related Nanomaterials: Properties and Applications

    By Paolo Bondavalli

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    Graphene and Related Nanomaterials: Properties and Applications outlines the physics and the applications of graphene-related materials, including graphene, graphene oxide and carbon nanotubes. The first chapter introduces the physics of graphene and related nanomaterials. The following sections deal with different applications spanning from gas sensors to non-volatile memories and supercapacitors. The book also covers spintronics for graphene. In each chapter, specific applications are explained in a detailed way. This book will appeal to materials scientists and engineers looking to understand more about the nature of graphene and how it is currently being used.

    • Explains how particular physical properties of graphene make it suitable for specific applications
    • Explores current applications in sensing and energy
    • Assesses the challenges of using carbon nanomaterials in engineering and evaluates future opportunities
    • Appeals to materials scientists and engineers looking to understand more about the nature of graphene and how it is currently being used
    LanguageEnglish
    PublisherElsevier Science
    Release dateOct 26, 2017
    ISBN9780323481021
    Graphene and Related Nanomaterials: Properties and Applications
    Author

    Paolo Bondavalli

    His research interests include graphene, carbon nanotubes, spintronics, and new nanomaterials for energy and energy storage. He is an R&D manager and nanomaterial/technology expert

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      Book preview

      Graphene and Related Nanomaterials - Paolo Bondavalli

      Graphene and Related Nanomaterials

      Properties and Applications

      Paolo Bondavalli

      Nanomaterial world expert

      Graphene world expert

      Table of Contents

      Cover image

      Title page

      Copyright

      Preface

      Acknowledgments

      1. Carbon and Its New Allotropes: Fullerene, Carbon Nanotubes, and Graphene

      Everything Starts From Carbon

      New Allotropes Arriving: Fullerene

      Carbon Nanotubes

      Introduction: The Lack of Lucidity of Graphene Dreamers

      Conclusion

      2. Nonvolatile Memories Based on Graphene-Based Nanomaterials

      Introduction

      Graphene-Based Nonvolatile Memories

      Graphitic-Based Nonvolatile Memory Using a Transistor Configuration

      Conclusions and Potential Applications

      3. Graphene Supercapacitors: When Material Drives Innovation

      Introduction

      Basic Physics Principles

      Interest for Graphene-Based Supercapacitors

      Graphene-Based Supercapacitors, the First Significant Publications

      Graphene and Metal Oxides Decoration to Implement Pseudocapacitance

      Conclusion

      4. The Graphenes Cousins From Dream to Reality: Critical Review

      Introduction

      Silicene: The 2D Silicons Cousin

      Germanene

      Germanane

      Stanene

      Transition Metal Dichalcogenide Monolayers

      Black Phosphorus (Phosphorene)

      2D Carbides and Nitrides (MXenes)

      Conclusions

      5. Graphene and Spintronics, the Good Match?

      But What Is Indeed Spin and Spintronics?

      Spintronics: A New Science Is Born

      Graphene and Spintronics

      The Pioneering Works

      Conclusions and Perspectives

      6. Graphene, Microelectronics/Nanoelectronics, and More Than Moore

      Microelectronics: An History of Dimensions

      More Than Moore: What Is That?

      Beyond CMOS: A New Way to See Future

      Which Is the Role of Graphene? A New Approach? A New Material?

      Potential Breakthrough: Where Graphene Can Be the Game Changer

      A Real Disruptive Concept: Some Examples of All-Spin Logic Device (Memory and Logic in the Same Block)

      Conclusions

      Index

      Copyright

      Elsevier

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      Copyright © 2018 Elsevier Inc. All rights reserved.

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      This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

      Notices

      Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

      Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

      To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

      Library of Congress Cataloging-in-Publication Data

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      A catalogue record for this book is available from the British Library

      ISBN: 978-0-323-48101-4

      For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

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      Preface

      Graphene is a very humble material. The graphite of the pencils that most of us have used since elementary schools are nothing but many graphene layers stacked on top of each other. Yet, starting with the groundbreaking experiments by Andre Geim, Konstantin Novoselov, and coworkers in 2004, research on graphene has grown in an explosive manner. This explosion is due to the many superlative, sometimes unique, properties that graphene exhibits: being only one atomic layer thick, it is the thinnest possible material, yet it is completely impermeable, it is extremely strong and flexible, it has the highest thermal and electrical conductivities, etc. It occupies a strange position between electrical conductors and insulators, which gives it unique and tunable optical properties. Many of these characteristics have interesting scientific consequences and lead to rather exotic phenomena, but perhaps more importantly, they suggest a wide range of technological advantages.

      Graphene was the first widely studied atomically thin material, but in the recent years it has been followed by an increasing cohort of other two-dimensional materials such a hexagonal boron nitride, transition metal dichalcogenides, or monoelemental structures such as silicene, stannine, or germanene. Most of these other materials are still in the domain of basic research, but as we learn more about them, how to combine them and how to control their properties, they will undoubtedly join graphene in contributing to the technological change.

      It is impossible for any author to give a comprehensive overview of the science and applications of graphene and related materials. You must make choices and focus on the topics where your expertise is most prominent or which you regard as particularly promising, on the short or long term. Paolo Bondavalli has chosen to cover some applications that are at the verge of commercialization, such as graphene-based supercapacitors, as well as more long-term topics such as spintronics. I think this mixture portrays well the flavor of graphene research today: it is not a featureless field with constant maturity, but spans the range from already commercialized products (mostly graphene composites) to very speculative ideas such as graphene space sails that exploit photon pressure from the Sun. This heterogeneity is very beneficial: the mature fields provide solutions that the more speculative or disruptive ideas can benefit from.

      An important issue to recognize when it comes to any disruptive technology is overblown expectations or hype. At early stages of technology development hype is created both by researchers and companies who apply for funding and by journalists who wish to sell magazines or advertising. Initially this is not only inevitable but it is also necessary: an overly pessimistic attitude would be detrimental to progress. However, as time passes and our understanding grows, so must our sense of realism do as well. The mere fact that we can do something using a new technology does not mean that it is the best way of doing it. It is clear that graphene technology has arrived at this phase, and we see fewer headlines of the type Graphene will replace steel (in the context of ship building) or Graphene will replace silicon (in the context of digital electronics). We do not need that, reality is impressive enough.

      Jari Kinaret,     Director, Graphene Flagship, and Professor of Physics, Chalmers University of Technology

      Acknowledgments

      This book is dedicated to my small, wonderful, gorgeous girl, Camille, and to my strong wife, Emmanuelle. They always supported me.

      I would like to thank Prof. Jary Kinaret for kindly accepting to write the preface of this book. It was an honor. I would like to thank the Graphene Flagship for supporting my research in the unlimited research field of 2D nanomaterials.

      I would like to thank also my colleagues at TRT for fruitful discussions on spintronics (Paolo Bortolotti, Pierre Seneor, Bruno Dlubak at joint unit CNRS/Thales) and 2D (Pierre Legagneux, MicroNanolaboratory in Thales). I do not want to forget my colleagues and friends Gilles Feugnet, Giuseppe Bellomonte, Marie-Blandine Martin, Daniele Pinna, Richard Lebourgeois, and all the others, for supporting me and for the good mood!

      A special thanks to Prof. Costas Charitidis and Prof. Elias Koumoulos, and all their PhD students (Kate, Stavros, Dimitris, et al.) of the National Technical University of Athens for all the scientific discussions and nanomaterials and for their friendship.

      Thank you very much and enjoy!

      1

      Carbon and Its New Allotropes

      Fullerene, Carbon Nanotubes, and Graphene

      Abstract

      Carbon is one of the most diffused elements known to man, considering that it is the basis of life on our planet and taking into account its unusual ability to form polymers at temperatures commonly encountered on Earth. It is the 4th most abundant chemical element in the universe by mass, 15th most abundant element in the Earth's crust, and it is also the 2nd abundant element by mass in human body (around 20% after oxygen). Indeed, carbon-related materials are the basic building blocks of virtually all organic chemistry and of the 20  million known molecules. Carbon has been known since prehistoric time considering that woods, composed of carbon, have been widely used for warming and cooking from prehistoric time. Specifically, carbon is a chemical element with symbol C, atomic number 6, and electron configuration [He]2s² 2p². Its name origins from the Latin word carbo, which means coal. Until the middle of the 1980s, to define the allotropes of carbon, we should have answered graphite and diamond. As allotropes, we define different manners in which some atoms of the same origin can rearrange themselves changing the way in which they are bonded. These different ways of rearranging themselves, change the properties of the final macromaterials. For example, graphite is black and quite soft, but diamond is transparent and one of the hardest materials discovered up to now. But what is the way in which carbon atoms are rearranged in these two materials?

      Keywords

      Carbon nanotubes; Chirality vector; CNTFET; Diamond; Drain voltage; Graphene

      Chapter Outline

      Everything Starts From Carbon

      New Allotropes Arriving: Fullerene

      Nanomedicine Potential Applications

      Drug Delivery

      Solar Cells

      Considerations

      Carbon Nanotubes

      Explanation of the Saito Rule

      Introduction: Main Applications for Carbon Nanotubes

      Carbon Nanotube—Based Transistors: Physics

      CNTFETs: Physics Considerations on the Schottky Model

      CNTFET-Based Sensors

      Considerations

      Introduction: The Lack of Lucidity of Graphene Dreamers

      A Short History and Context of the Graphene Discovery

      Theoretical Prediction and the Fallen Myth of Nonexistence of 2D Materials

      Conclusion

      References

      Everything Starts From Carbon

      Carbon is one of the most diffused elements known to man, considering that it is the basis of life on our planet and taking into account its unusual ability to form polymers at temperatures commonly encountered on Earth. It is the 4th most abundant chemical element in the universe by mass, 15th most abundant element in the Earth's crust, and it is also the 2nd abundant element by mass in human body (around 20% after oxygen). Indeed, carbon-related materials are the basic building blocks of virtually all organic chemistry and of the 20 million known molecules. Carbon has been known since prehistoric time considering that woods, composed of carbon, have been widely used for warming and cooking from prehistoric time. Specifically, carbon is a chemical element with symbol C, atomic number 6, and electron configuration [He]2s² 2p². Its name origins from the Latin word carbo, which means coal. Until the middle of the 1980s, to define the allotropes of carbon, the answer would have been graphite and diamond (see Fig. 1.1). As allotropes, we define different manners in which some atoms of the same origin can rearrange themselves changing the way in which they are bonded. These different ways of rearranging themselves, change the properties of the final macromaterials. For example, graphite is black and quite soft, but diamond is transparent and one of the hardest materials discovered up to now. But what is the way in which carbon atoms are rearranged in these two materials?

      In case of diamond, if we consider a carbon atom, its atomic state is composed of six electrons that are in different orbitals. Each orbital constitutes an energetic state. Specifically two electrons are in the 1S, 2S, and 2P orbitals (indeed there are three 2P orbitals). When two atoms of carbon are linked together, from an energetic point of view, it is more convenient for the electrons to move in one electron from the 2S orbital to one of the three disposable 2P orbitals (2Px, 2Py, 2Pz). Indeed, to move one electron from an orbital 2S to an orbital 2P, it is necessary to employ 4  eV. When the carbon atoms are linked, if the configuration is, as told previously, 1S² 2S¹ 2P¹x 2P¹y 2P¹z, it is possible to obtain four covalent bonds, between four carbon atoms that will lower the energy more than 4  eV. A covalent bond is obtained when two atoms share their electrons in an equal way. It happens that to lower the energy of the new systems composed by the two bonded atoms, we observe a mixing of the four orbitals 2S¹ 2P¹x 2P¹y 2P¹z of the two atoms. We are dealing with the so-called sp³ hybridization. In this specific case the carbon atoms are rearranged in 3D tetrahedral configuration as shown in the following picture [1] (Fig. 1.2).

      Figure 1.1  (Left) Diamond. (Right) Graphite sample.

      If we analyze the case of graphite [2], we observe that it is constituted by more layers of atoms arranged in a 2D structure (we will see that each of these layers is called graphene!). These sorts of foils are kept together by the Van der Walls forces. These weak intermolecular forces are the residual attractive or repulsive forces between molecules or atomic groups that do not arise from a covalent bond, or electrostatic interaction of ions or of ionic groups with one another or with neutral molecules. In graphite, each carbon atom is linked to the other three. In this case we have no more four bonds as in case of diamond. This is related to the fact that we do not have the hybridization of four orbitals. We will obtain three sp² orbitals with mutual angles of 120  degrees and the last nonhybridized will be perpendicular to the plan (Fig. 1.3).

      New Allotropes Arriving: Fullerene

      Since the middle of the 1980s, three new carbon allotropes have been discovered: the fullerenes, the carbon nanotubes (CNTs), and last but not least the graphene. But let us start with fullerene. A fullerene [3] is a molecule composed by carbon atoms arranged to achieve a spherical or a cylindrical shape. The most famous spherical ones are the C60, which are composed of 60 carbon atoms. C60 is a hollow sphere in which the surface contains 20 hexagons and 12 pentagons (see Fig. 1.4). They are also called Buckminsterfullerene, inspired by the name of the architect of the dome of Olympic stadium of Montreal (Richard Buckminster Fuller). In this case also we can observe that the atoms show sp² hybridization as in case of the graphite with each atom linked with three neighbours. The existence of the C60 was predicted in 1970 by Prof. E. Osawa of the Technical University of Toyohashi [4]. He had seen that the structure of the molecule of corannulene (see Fig. 1.4), which is a chemical compound with formula C20H10, was simply a part of a more complex structure with the shape of a ball of football. Therefore, he suggested the existence of fullerene. This idea did not reach the scientific community out of Japan, and it stayed local. Finally, fullerene was obtained for the first time in 1985 by Richard Smalley, Robert Curl, and Harold Kroto at Rice University. At that time, they were particularly interested in small clusters of carbon atoms; indeed from their first experiment, they observed peaks in their mass spectra corresponding to larger clusters with even numbers of carbon atoms. Under certain experimental conditions, the peak corresponding to 60 carbon atoms was found to be hugely dominant, and hence the most stable cluster. Another peak corresponded to 70 carbon atoms. These peaks corresponded to C60 and C70 [5]. These clusters had been already spotted by other scientists, but only the team of Rice understood the real importance of their findings. Observing the impressing stability of these 60 carbon atoms clusters, they suggested their closed-up arrangement and were able to propose a rational structure for C60. However, only when the large-scale synthesis, through the evaporation and recondensation of graphite using an arc-discharge method, and X-ray diffraction analysis of C60 were reported by Krätschmer and Huffman [6] in 1990, the existence of these new allotropes of carbon was confirmed. Nowadays, fullerenes can be prepared on the ton scale. Thanks to their discovery, scientists from Rice won the Nobel Prize in chemistry in 1996 [7] (for their discovery of fullerenes).

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