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    Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials
    Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials
    Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials
    Ebook1,067 pages16 hours

    Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials

    By Serhii Shafraniuk

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    Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials describes thermoelectric phenomena and thermal transport in graphene and other 2-dimentional nanomaterials and devices. Graphene, which is an example of an atomic monolayered material, has become the most important growth area in materials science research, stimulating an interest in other atomic monolayeric materials.

    The book analyses flow management, measurement of the local temperature at the nanoscale level and thermoelectric transducers, with reference to both graphene and other 2D nanomaterials. The book covers in detail the mechanisms of thermoelectricity, thermal transport, interface phenomena, quantum dots, non-equilibrium states, scattering and dissipation, as well as coherent transport in low-dimensional junctions in graphene and its allotropes, transition metal dichalcogenides and boron nitride.

    This book aims to show readers how to improve thermoelectric transducer efficiency in graphene and other nanomaterials. The book describes basic ingredients of such activity, allowing readers to gain a greater understanding of fundamental issues related to the heat transport and the thermoelectric phenomena of nanomaterials. It contains a thorough analysis and comparison between theory and experiments, complemented with a variety of practical examples.

    • Shows readers how to improve the efficiency of heat transfer in graphene and other nanomaterials with analysis of different methodologies
    • Includes fundamental information on the thermoelectric properties of graphene and other atomic monolayers, providing a valuable reference source for materials scientists and engineers
    • Covers the important models of thermoelectric phenomena and thermal transport in the 2D nanomaterials and nanodevices, allowing readers to gain a greater understanding of the factors behind the efficiency of heat transport in a variety of nanomaterials
    LanguageEnglish
    PublisherElsevier Science
    Release dateJul 15, 2017
    ISBN9780323444903
    Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials
    Author

    Serhii Shafraniuk

    Serhii E. Shafraniuk is Research Associate Professor at the Department of Physics and Astronomy, Northwestern University. At Northwestern (2002-present) he serves as a Principle Investigator (PI) in research projects related to electromagnetic properties of carbon nanotube and graphene, field effect transistors, thermoelectric transport in carbon nanotube and graphene multi-barrier devices, and qubits. He has received the B.A. degree (cum laude) and the Ph.D. degree in physics from Kiev State University, Ukraine, in 1980 and 1985, respectively. Besides, Serhii had been honored the Doctor of Sciences degree from the Institute of Metal Physics, Academy of Sciences of Ukraine in 2001. His thesis work has focused on non-equilibrium phenomena in inhomogeneous superconductors. Before coming to the USA, Serhii had been working in various leading research centers in Europe and Japan (1990-2002). In particular from 1995 to 1999, he was a Foreign Research Staff Member at the Research Institute of Electrical Communication, Tohoku University, Japan. Prof. Shafraniuk has served as organizing committee member of several International Symposiums and Conferences related to the superconductivity nanoscience, and condensed matter.

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      Thermoelectricity and Heat Transport in Graphene and Other 2D Nanomaterials - Serhii Shafraniuk

      Thermoelectricity and Heat Transport in Graphene and other 2D Nanomaterials

      Serhii E. Shafraniuk

      Table of Contents

      Cover

      Title page

      Copyright

      Preface

      Introduction

      Chapter 1: Thermal transport in graphene and its allotropes

      Abstract

      1.1. Thermoelectric transducer

      1.2. Components of the heat transport

      1.3. The phonon and electron fractions of the heat flow in graphene

      1.4. Low-energy electron excitations in graphene

      1.5. Relativistic dirac equation describing chiral fermions

      1.6. Berry phase and topological singularity in graphene

      1.7. Klein paradox and chiral tunneling

      1.8. Electron and hole excitations in graphene

      1.9. Topologically protected heavy chiral fermion state in graphene stripe

      Problems

      Chapter 2: Lattice dynamics and thermal flux

      Abstract

      2.1. Lattice oscillations in graphene

      2.2. Phonon Boltzmann equation

      2.3. Lattice thermal conductivity

      2.4. Phonon relaxation rates

      2.5. Phonon group velocity

      2.6. A model of lattice oscillations in 2D materials

      2.7. Long-wavelength phonons in carbon nanotubes

      2.8. Microscopic description of phonons in graphene

      2.9. Effective mass equations

      2.10. Electron–phonon interaction

      2.11. Electron–phonon scattering and resistivity

      2.12. Propagation of phonons in two-dimensional crystals

      2.13. Phonon thermal conductivity of graphene nanoribbons

      2.14. Phonon transport momentum diagram in graphene

      Problems

      Chapter 3: Graphene thermoelectric transducers

      Abstract

      3.1. Thermoelectricity on the nanoscale

      3.2. Efficiency of the thermoelectric device

      3.3. Quantum model of electronic thermal transport

      3.4. Elastic collisions and electron transport

      3.5. Peltier cooling in carbon nanotube junctions

      3.6. Fourier law

      3.7. Phonon part of the thermal conductivity

      3.8. Microscopic model of the thermoelectric phenomena

      3.9. The graphene thermoelectric transducer based on nanoribbon with nanopores

      3.10. Transduction by a graphene ribbon with heavy chiral fermions

      3.11. Blocking of the phonon flow with multilayered electrodes

      3.12. Molecular dynamics simulations

      3.13. Nonequilibrium thermal injection

      3.14. Prospects thermoelectricity of graphene

      Problems

      Chapter 4: Experimental study of thermoelectricity in carbon nanotubes and graphene

      Abstract

      4.1. Measuring the thermal conductivity of graphene

      4.2. Thermometry and thermal management of carbon nanotube circuits

      4.3. Transduction between electrical energy and the heat in a carbon nanotube using a voltage-controlled doping

      4.4. Conclusions

      4.5. Modeling parameters of the CNT transducer

      4.6. Raman scattering

      4.7. The degrees of freedom

      4.8. Infrared radiation and molecular vibrations

      4.9. Light scattering processes

      4.10. Stokes and anti-Stokes scattering

      4.11. Fluorescence

      4.12. Selection rules

      4.13. Stimulated Raman scattering and Raman amplification

      4.14. Requirement of the coherence

      4.15. Practical implementations

      4.16. Raman spectra of higher-orders

      4.17. Raman spectroscopy of graphene

      4.18. Kohn anomalies, double resonance, and D and G peaks

      4.19. Deducing of electron–phonon coupling from the Raman line width

      4.20. G and D peaks in graphene

      4.21. Failure of adiabatic Born–Oppenheimer approximation in graphene

      4.22. The role of atomic and structural disorder

      4.23. Edges of the graphene ribbons

      Problems

      Chapter 5: Role of structural defects and imperfections

      Abstract

      5.1. Phonon scattering in a few-layer graphene

      5.2. Scattering of chiral fermions on impurities

      5.3. Time of scattering of a heavy fermion on the impurities in graphene

      5.4. Scattering in two dimensions

      5.5. Phonon drag effect

      5.6. Screening by the interacting electrons

      5.7. Plasma oscillations

      5.8. Plasma excitations in graphene

      5.9. Effect of electron scattering on heavy adatoms and nanopores

      5.10. Bimodal phonon scattering in graphene grain boundaries

      Problems

      Chapter 6: Contribution of many-body effects into thermoelectricity and heat transport in graphene

      Abstract

      6.1. Electron–electron interaction

      6.2. Electron self-energy

      6.3. Quasiparticle excitation energy

      6.4. Computational results

      6.5. Phonon–phonon scattering rates in carbon nanotubes and graphene

      6.6. Excitons

      6.7. Wannier–Mott excitons

      6.8. Excitonic states

      6.9. Experimental study of excitons in graphene

      6.10. Scattering of electrons on indirect excitons

      6.11. Polariton excitations in layered 2D materials

      6.12. Tomonaga–Luttinger liquid

      6.13. Basic equations

      6.14. Probing of the one-dimensional quantum wells by using the photon-assisted tunneling

      6.15. Photon-assisted tunneling into the TLL state

      6.16. The Tunneling Density of States of a long quantum well

      6.17. Identifying the charge and the spin boson energy levels

      Problems

      Chapter 7: Principles of thermoelectric transport on nanoscale

      Abstract

      7.1. Thermal and electric transport on nanoscale

      7.2. Phonon–electron scattering in 2D atomic monolayers

      7.3. Quantized magnetothermoelectric transport in low-dimensional junctions

      Problems

      Chapter 8: THz-induced thermoelectric and thermal transport in atomic monolayers

      Abstract

      8.1. Local cooling in carbon nanotube quantum dots induced by the THz field

      8.2. Measurement of dielectric function of the monolayer transition-metal dichalcogenides

      8.3. Photo-thermoelectric response in graphene-metal contacts induced by terahertz field

      Problems

      Index

      Copyright

      Elsevier

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      The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom

      50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

      Copyright © 2018 Elsevier Inc. All rights reserved.

      No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

      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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      British Library Cataloguing-in-Publication Data

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

      ISBN: 978-0-323-44397-5

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

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      Preface

      The book was motivated during my work, which I started back in 2005. An interest to graphene and other two-dimensional (2D) nanomaterials is fueled by their intriguing properties, showing a potential to creating the thermoelectric transducer with a tremendously high efficiency. In particular, chirality and Klein tunneling of electric charge carriers in graphene allow creating the topologically protected quantized states, which are robust to the lattice imperfections. Efficient doping with the gate electrodes allows changing the local carrier concentration in wide limits, leading to a high thermopower. The nanostructuring and alloying diminish the phonon part of the thermal flux by orders of magnitude. By combining the above methods, one can considerably improve the thermopower and electric current, while reduce the thermal flux, resulting in a high efficiency of the transducer. Thus, those unique properties provide much wider opportunities, which are not available in conventional bulk materials. A balanced use of the aforementioned properties forms a basis for a variety of unique technological solutions in many areas of human life. To accomplish a commercially viable green-energy solution, the dimensionless figure of merit must exceed four. If thermoelectric devices with large figure of merit ≥ 4 were constructed, they would resolve a huge variety of heating and cooling problems at both the macro- and nanoscales, with no mechanical parts involved, no operational carbon footprint, and without toxic chemical residue output.

      Although my first experience with Peltier cooling in carbon nanotubes was theoretical, the following experiments conducted in our group revealed interesting phenomena, which required better understanding. Furthermore, questions, which emerged from the experiments led to further development of theory. Besides graphene, the study of the thermoelectricity and heat transport was extended to other 2D materials and heterostructures formed on their basis. The book is focused mostly on the thermal and electric transport properties of the gated graphene, its allotropes, and other relevant atomic monolayers, such as transition metal dichalcogenides (TMD) and black phosphorene. Graphene is the first example of 2D materials and forms the basis for new thermoelectric and nanoelectronic applications. Unconventional thermoelectric properties of graphene, its allotropes, and other 2D materials constitute the key factor creating of a strong potential of the new material in a variety of applications. Many ideas proposed in the graphene research are frontier and futuristic, although some have immediate technological output. Thus, a deep understanding of the thermal and electric transport in the 2D nanomaterials is critical for the development of the next generation technologies.

      The core scientific principles of the thermoelectric graphene applications, however, are grounded in physics and chemistry. There are currently numerous specialized graphene and graphene-related texts or monographs at the graduate and senior undergraduate levels. This book is targeted to a wide audience ranging between graduate students and postdoctoral fellows to mature researchers and industrial engineers. It has evolved from the author’s own research experience and from interaction with other scientists at other institutions.

      The book includes the following topics: an introduction and a historical perspective of thermoelectricity in graphene; basic physical principles and the simplest mathematical models; lattice dynamics and thermal flux, principles of graphene thermoelectric transducers, experimental research of the thermal transport, nanostructuring and alloying, the role of many body effects, principles of thermoelectric transport on the nanoscale, and THz-induced thermoelectric and thermal transport in atomic monolayers. This book is appropriate for graduate students, postdoctoral fellows, researchers, and engineers at academic and industrial institutions. The book is practical and user friendly and can be adopted for teaching of graduate students in nanoscience and nanotechnology, materials science and engineering, and physics and chemistry. The book can be an instructor-friendly textbook for research fellows and industrial engineers. The book offers numerous interesting, well-illustrated, and recent examples from the author’s research work. The book also has a combined and unique multidisciplinary flavor needed when working in the field of nanoscale science.

      I am grateful to Dr. H. Weinstock for valuable discussions over the course of 10 years. I would like to thank Prof. M.G. Kanatzidis for valuable remarks and comments during the preparation of this book. Dr. I.P. Nevirkovets and Prof. V. Chandrasekhar have also contributed with significant discussions and valuable advice. Several chapters of this book (i.e., Chapters 2, 3, 5, 6, 7, 8) were initialized during my research work supported by AFOSR grant FA9550-11-1-0311.

      Serhii E. Shafraniuk

      Introduction

      Search for novel solutions to increase efficiency of transducers that directly convert heat to electricity or vice-versa has focused on low-dimensional materials. Such materials are sought in order to maximize the efficiency and performance of thermoelectric (TE) devices in the course of the energy conversion process. Typical TE devices (2006) are formed from two different conducting materials, one containing positive charge carriers (holes) and the other negative charge carriers (electrons). An electric current passing through the device forces the both types of charge carriers move away from the junction, thereby conveying the heat away causing the cooling of the junction. In a similar fashion, a heat source causes the electric charge carriers to escape from the junction, forming an electrical generator. A strong advantage of the TE transducers is that they contain no moving parts, but low efficiencies have limited their use to specialty applications, such as cooling laser diodes.

      Graphene and other two-dimensional (2D) nanomaterials, due to their unique properties represent new era in the field of energy transduction. The potential of those novel materials to creating of a TE transducer with a tremendously high efficiency stems from the nanotechnological capabilities to considerably improve the thermopower and electric current, while reduce the thermal flux. This is achieved by accurate combination novel properties, which are not available in conventional bulk materials. For instance, one uses the topologically protected quantized states, which result from chirality and Klein tunneling of electric charge carriers in graphene and are robust to the lattice imperfections. A high thermopower is obtained using doping by the gate electrodes allowing to change the local carrier concentration in wide limits. In addition, the phonon component of the thermal flux is reduced by orders of magnitude when using of the nanostructuring and alloying.

      Experimental data obtained during the study of temperature distribution and thermopower in graphene ribbons and carbon nanotubes indicate that efficient TE devices can be fabricated by using the nanoscale technology. As the elementary excitations in graphene and carbon nanotube are chiral fermions, their scattering on the phonons is minimized. Furthermore, this facilitates engineering of topologically protected quantized states, which are insensitive to scattering on defects and lattice imperfections. For such reasons, the contribution of scattering processes in the TE transport is minimized. Therefore, the electric charge transport and the thermopower both benefit from the reduced scattering. An additional increase of electronic transport coefficients takes place at expense of interference effects and of electrode doping by applying of appropriate gate voltages. Another problem is that the heat conductance due to the propagation of phonons is also significant which tends to decrease the figure of merit. The last hurdle is avoided by using multilayered metallic electrodes and multiple terminal configurations to decouple the electron and phonon components of the thermal flux by redirecting them along different paths. New opportunities arise from the ability to controlling and manipulating by the electronic and phonon transport on the nanoscale, which suggests a bright future for a successful development of graphene and carbon nanotube electronics. A direct measurement of energy transport in nonequilibrium nanoscale junctions can be accomplished by taking benefits of recent advances of thermal microscopy techniques. In this way, one can directly probe a variety of basic thermodynamic properties. Remarkable application of the mentioned novel research method is, e.g., an immediate mapping of the nonequilibrium temperature distribution in a quantum system subject to a thermal gradient or voltage bias. A relevant problem in this scope is how to define the local temperature on the nanoscale. Although that theoretical problem is not new, the recent experiments have sparked an impressive wave of interest to the topic and motivated intensive efforts to solve the number of fundamental issues. There are many remaining questions related to the meaning of temperature on the atomic (or subatomic) scale, the relationship between the Fourier’s law of heat conduction and the quantum heat transport, and the fundamental limits of the tip-environment coupling. Other topics of interest are related to quantum interference effects on the local temperature distribution. When a nanostructure is exposed to external fields and biases, the fermionic (electronic) and bosonic (phonon or photon) degrees of freedom distributions are characterized by different effective temperatures because in general they do not correspond to one another away from equilibrium. That difference is quite essential in small grapheme and carbon nanotube junctions, where the electron–phonon coupling is weak, or in scanning tunneling devices operating in the tunneling regime, where there is no phonon heat transport. Finding the correspondence among the temperatures of these distinct degrees of freedom will definitely represent new insights into the nature of the nonequilibrium transport problem.

      This book reviews principles of TE devices and strategies for increasing their efficiency by implementing of novel atomic monolayer materials. New advanced materials (Baheti et al., 2008; Kim et al., 2001; Reddy et al., 2007) would not only help to cool nanoelectronics, but could also provide energy benefits in refrigeration and when using waste heat to generate electrical power. A special case is graphene (Geim and Novoselov, 2007; Katsnelson et al., 2006; Novoselov et al., 2012), depicted in Fig. I.1, which is a 2D allotrope of carbon forming an atomic monolayer sheet (Shafraniuk, 2015). A single-atomic graphene layer looks like a composition of benzene rings stripped of their hydrogen atoms (Pauling, 1972). Its honeycomb structure is composed of hexagons. To explore the properties of graphene is to help to understand the electronic properties of all the other allotropes (Geim, 2009a). There is a whole family of other recently discovered 2D materials, including transition metal dichalcogenides and black phosphine, also having the atomic monolayer structure. The atomic monolayers have indicated remarkable TE properties, constituting a potential basis for creating of highly efficient TE transducers (Ouyang and Guo, 2009; Shafranjuk, 2014). Therefore in this book we focus our attention how to select an appropriate material to achieve the energy conversion highest efficiency.

      Figure I.1   A Graphene Monolayer

      The TE generators directly converting heat into electricity, or refrigerators using electricity to pump heat from cold to hot (Hicks and Dresselhaus, 1993; Hicks et al., 1993), both without any moving parts or bulk fluids are lightweight, small, and inexpensive, and they are able to completely eliminate the need for CFCs or HCFCs, and also in heavy compressors in small-scale refrigeration. Most of disruptions in refrigerator occur due to gas leaks or due to the failure of moving parts in the compressor. Furthermore, the former pose environmental problems. Therefore, TE transducers are potentially more reliable and they are much less prone to failure because no moving parts are involved. Major implementations for the TE devices include cooling laser diodes and electronic coolers for picnic baskets. In addition, a TE device can also be used to generate electricity, when a source of heat is present. Although the TE devices are very useful, their implementation area remains still too narrow.

      Major obstacle, which prevents the wide scale use of TE devices is their low efficiency. One characterizes efficiency of a refrigerator in terms of the coefficient of performance (COP), which represents the amount of cooling divided by the electrical energy input needed to obtain the cooling. According to the laws of thermodynamics, the maximum efficiency, which is called the Carnot efficiency, cannot be exceeded. One finds the COP at Carnot efficiency as COP = Tcold/(Thot–Tcold), where Thot and Tcold are the temperatures of the ambient environment and of the coldest part of the refrigerator, respectively. A percentage of the Carnot efficiency determines the real efficiency of a device. The TE transducers operate at ∼10% of Carnot efficiency, whereas the efficiency of a compressor-based refrigerator grows with size. For instance, a kitchen refrigerator works at ∼30% of Carnot efficiency, while the largest air conditioners for big buildings operate at ∼90%. The TE transducers are typically used when rapid on-off cycling is required at low temperature differences. In addition, the TE transducers are useful, when the small size, low weight, or high reliability are more important than the efficiency. Nevertheless, up to now, except for the Carnot limit, there is no established limit to the potential efficiency of a TE device.

      The basic factors determining the efficiency of a TE transducer are the materials used to fabricate the device. This directs the current focus of research to finding better materials. Overcoming the low efficiencies by implementing new materials at reasonable cost would revolutionize the cooling industry. A variety of other areas, such as microelectronics, will also benefited from the development of active cooling technologies. For instance, higher operating frequencies, higher capacitance, and larger microelectronic chip size have caused an increase of requirements to the heat dissipation from 1997 to 2005 by twice. Furthermore, operating of devices below room temperature holds allows improving reliability and speed of CMOS-based microprocessors. Other potential applications of the TE devices are the electrical generators, utilizing the waste heat, generated in engine combustion to make automobiles more efficient. This illustrates large economic benefits of development of the higher efficiency TE materials. According to conservative estimates based on the current TE materials prices, the world market for efficient TE materials alone will achieve billions of dollars per year. The net economic impact will become even larger, if one includes the value added to systems, including the TE devices, such as home refrigerators or computers, and many new applications. This book discusses research to improve the materials used to fabricate TE transducers.

      A schematic of a TE cooler is shown in Fig. I.2. Typical TE devices are fabricated by joining two doped semiconducting materials together, one n-type and the other p-type. According to a French scientist Jean Peltier, who discovered this effect in 1834, when electric current flows from the n-type material toward the p-type, the charge carriers in both materials are moved away from the junction, carrying the heat away. Then the junction is cooled, because the electrical current removes heat from the junction out. Magnitude of the heat flow away from the junction, dQ/dt, meaning the energy per second, is dQ/dt = ΠI. If the heat is not supplied to the junction, temperature of the junction decreases. By carefully selecting the materials, Π can be made to be large enough to produce significant cooling, ensuring the temperature drop by 50°C. A similar device can also be used to generate electricity when the junction is heated. In the latter case, the heat is transferred owing to flow of the electrical carriers from the junction to the base, which generates a finite voltage between the two ends of the device (Fig. I.2). In addition, there are side heat generation effects occurring in addition to the heat flow away from the junction in a TE cooler. The flowing electrical current through the device leads to Joule heating, which is proportional to the device resistance (R) times the square of the current (I²): RI². In addition, if there is a finite temperature difference across the junction, the heat will stream back toward the junction driven by the temperature difference, i.e., dQ/dt = K∆T, where K is the thermal conductance of the material. Such the heat loads restrict the temperature drop at the junction. Since the dependence of the Peltier cooling and the Joule heating versus electric current I for the latter), one finds the maximum decrease in the junction temperature by optimizing the current. When the electric current is optimal, the maximal cooling temperature of the junction is proportional to Π²/(RK). This means that the cooling is increased for large Π and small R and K, thereby minimizing the heat load terms.

      Figure I.2   Thermoelectric Transducer, Which Converts Electric Current into the Heat Flux

      (A) The schematics of the single Peltier cooler element composed of two N and P conductors with the charge carriers of opposite sign. (B) The battery of thermoelectric transducers where the electric current flows in series while the heat flux occurs in parallel.

      Another closely related phenomenon was discovered in 1822 by Thomas Seebeck. He has detected a finite electrical voltage, arising between the hot and cold ends of a material, which is placed in a temperature gradient. This effect is characterized by the thermopower S = V/∆T, which is defined as the voltage divided by the temperature difference, representing the basis of the TE power generator discussed above. Experiments performed by Lord Kelvin in 1854 indicated that Π = (Sp–Sn)T, where S is the thermopower of each material (n or p-type) and T is the temperature of the junction. This result has been proven in 1931 by Lars Onsager. Despite that an immediate measurement of Π is not straightforward, S is very easy to measure. Taking into account the geometric factors determining the resistance and thermal conductance, one defines the figure of merit of the materials as Z = S²/ρk, where ρ is the electrical resistivity and k is the thermal conductivity. Typically, a more convenient a dimensionless ZT, Z times T, is used. The best materials for the TE devices operating near room temperature today have ZT ∼ 1. This value has not been improved significantly since the late 1950s, and has increased by only a few tens of a percent. The corresponding materials are alloys of antimony and bismuth tellurides with adding of other elements to dope the semiconductors. The TE coolers with ZT ∼ 1 have only 10% of Carnot efficiency. When ZT is infinite, one can even achieve 100% of Carnot efficiency, but such the devices technologically are not demanded. The Carnot efficiency ∼30%, which is the case for home refrigeration, is accomplished by a TE device with a ZT ∼ 4. However, improving ZT by a factor of 4 remains a serious challenge. The question is why achieving of ZT > 4 remains so indefinable? Using conventional conductors as materials for fabricating the TE coolers requires adequate understanding of electrical carriers. Although the electronic band structure represents a great achievement of modern quantum mechanics, this works well for simplest materials only. On the contrary, many of new ternary and quaternary compounds adopt new structure types which cannot be predicted beforehand, and without the crystal structure, electronic band structure cannot be reliably computed. This circumstance is most often serves as a limiting factor in obtaining improvements in most other materials applications.

      This motivates interest in the TE devices made of the novel 2D materials, such as graphene (Castro et al., 2007; Fal’ko and Geim, 2007; Geim and Novoselov, 2007; Novoselov et al., 2007), the transition metal dichalcogenides, and black phosphorene (Shafraniuk, 2015). Those materials have relatively simple electronic structure, which also can be readily dynamically manipulated by applying external biasing fields. In particular, instead of changing the chemical compositions of the ternary and quaternary compounds by fabricating thousands of samples to adjusting of their electric and thermal properties, it is much easier to alter such the properties merely by changing the bias voltage or a magnetic field, which is accomplished in junctions based on the 2D atomic monolayer materials.

      As compared to the traditional ternary and quaternary compounds (DiSalvo, 1999; Marchand et al., 1999; Proctor et al., 1999a,b; Wang and DiSalvo, 1999), used to fabricate TE devices nowadays, where the theory is used only as a guide to suggesting of the general material characteristics, the theoretical prediction of the atomic monolayers is much easier to accomplish. The existing theoretical methods are well developed to describe adequately and with a high precision the properties of the 2D atomic monolayers that might be better suited for TE devices. Given the slow advance in TE efficiencies since the late 1950s, why this is a good time to look for better TE materials? Progress in fabricating of variety of the 2D materials and especially in their characterizations has been rapid and allows much more complicated structures to be studied than those used in present TE devices. Frequently, atom-by-atom control of the growth of artificially structured or compositionally graded materials can be achieved. Using the contemporary computers one can rapidly model realistic electronic description of the TE devices based on the 2D atomic monolayer materials. The current state of the research in this area opens new opportunities in developing TE transducers with outstanding performance characteristics. This book focuses on reviewing of current TE approaches and research.

      A basic problem is that the three parameters in ZT (S, ρ, and k) are dependent on each other. In particular, as S increases, then ρ follows it. An optimal solution seems to be to use heavily doped sheets of the 2D materials to produce a carrier density of about 10¹²–10¹³ cm-2, which roughly corresponds to the volume charge density 10¹⁹–10²⁰ cm−3. For graphene and carbon nanotubes, these are practically accomplished by using so-called electrode doping. Furthermore, in graphene and in the other 2D atomic monolayers, k has two contributions (Balandin et al., 2008; Ghosh et al., 2008; Parvizi et al., 2008), one from the electrical carriers, ke, and one from the lattice vibrations, phonons, kph. Although ke is proportional to 1/ρ, in graphene kph is much greater than ke, so that one challenge is to minimize kph. One solution has been known for a while: use heavy atomic impurities (DiSalvo, 1999). At room temperature and above, heavier atomic masses reduce the atomic vibration frequencies and the thermal flux. Nevertheless, the low vibration frequencies contribute to an increase of the electrical resistivity. Another solution implies adding other atoms in the 2D sheets to prepare structurally complex materials. This tends to lower the fraction of vibrational modes, i.e., phonons that carry heat efficiently related to the acoustic modes by the factor 1/N where N is the number of the excessive atoms. Furthermore, a disorder of random atomic substitution in an alloy scatters the phonons, which reduces the thermal conductivity at the expense of increasing the electrical conductivity (DiSalvo, 1999). The latter solution implies the preparing of materials having a particular kind of structural complexity, so that other component elements act like a rattle in a cage, which is constructed from the other elements framework. Rattling oscillations lower the lattice thermal conductivity, almost without increasing the resistivity, since the carriers travel only in the limited framework. It can be regarded as a phonon glass or an electron crystal (DiSalvo, 1999), since such the glasses have the lowest of all lattice thermal conductivities. Hopefully, one can synthesize such materials and to rapidly determine their structure. After the lattice thermal conductivity has been reduced, the electronic factors must be improved. For the electron transport in semiconductors, one finds that ZT monotonically increases versus the two basic parameters: one of them is the band gap EG while the other parameter B in turn depends on a number of materials parameters as discussed below. Here we assume that the carrier density (n- or p-type) in the conducting shoulders is appropriately adjusted by doping to an optimal level. In order to maximize ZT for a given B, the band gap EG must exceed the thermal energy kT by a factor of ∼10. An approximate formula for B where kph must be minimized as discussed above, μ is the electronic mobility, m is the band mass determined by the density of states, and Nv is the degeneracy of the band extrema near the Fermi level, which is limited by the crystalline symmetry and typically achieves Nv = 6–8. In cubic space groups, Nv might be as high as 48, followed by values of 24 in hexagonal groups, 16 in tetragonal, 8 in orthorhombic, and 4 or less in the remaining groups. When the number of atoms in the unit cell of the compound is large, this increases the maximum value of Nv. Basically, there is no recipe how to design materials with high Nv. Although the electronic mobility μ must be high, it in turn depends on the band mass m. In particular, μ is inversely proportional to m in the direction of the current flow, provided that μ = eτ/mi, where τ is the carrier scattering time. Therefore, B . Summarizing, a long scattering time τ takes place, if the electronegativity differences between the elements in the material are negligible and optical vibrations have weak coupling to the carriers. Although the latter condition is difficult to fulfil, a small coupling is preferred when each atom is surrounded by a large number of near neighbors, amounting like six or greater.

      Remarkable electrical, mechanical, and thermal properties of graphene, a 2D allotrope of carbon, have attracted a strong attention (Balandin et al., 2008; Castro Neto et al., 2009; Das Sarma et al., 2007; Dresselhaus and Araujo, 2010; Fal’ko and Geim, 2007; Ferrari et al., 2006; Geim 2009b; Geim, 2011; Shao et al., 2008; Shafraniuk, 2015). Additional prospects to further enhancing the physical properties are opened using the techniques like the electrode doping by applying a gate potential, introduction of controlled defects and disorders, and different types of electrical confinement (Han et al., 2007a,b; Ozyilmaz et al., 2007). The performance of a TE device described by its TE figure of merit (ZT), depends on electrical conductance (σ), Seebeck coefficient (S) and thermal conductance (k) according to the relation, ZT = S²σT/k. A high magnitude of thermal conductivity in graphene was recognized as an obstacle to an immediate using it as a TE material. However, this obstacle was overcome, e.g., in nanostructured materials due to phonon boundary scattering and lateral quantum confinement of electrons (Balandin et al., 2008; Ghosh et al., 2008; Hicks and Dresselhaus, 1993; Hicks et al., 1993; Parvizi et al., 2008). The nanostructuring approach for graphene permits a permissible tradeoff among the basic TE parameters, which can be used to greatly reduce its high thermal conductivity while maintaining of a very high electrical conductivity, thereby greatly enhancing the performance. The effectiveness of the nanostructuring has been confirmed in several experimental works. In particular, the nanostructuring has allowed a two order of magnitude improvement of ZT in the silicon nanowires (Boukai et al., 2008; Hochbaum et al., 2008). Furthermore, a strong increase of the TE efficiency has been accomplished in bulk nanostructured materials and in the nanoscale complex materials (Majumdar, 2004; Snyder and Toberer, 2008). Therefore, the reduction of the thermal conductivity using the nanostructuring represents a natural solution for the quasi-one–dimensional graphene nanoribbon (GNR). Exploiting this method along with other remarkable properties such as band-gap opening (Ozyilmaz et al., 2007), makes such the systems to become a good candidate for fabricating the nanoscale TE devices. As it was theoretically explained in reference (Haskins et al., 2011), the thermal and electrical properties of graphene can be controlled independently through defect engineering. Several theoretical work has been carried out to investigate the performance of graphene and GNRs as TE materials. The reduction of thermal conductivity of GNRs without degrading their electrical performance was considered by many researchers, who theoretically investigated the antidot lattices (Gunst et al., 2011), edge disorders (Savin et al., 2010), edge passivation (Hu et al., 2010), random hydrogen vacancies (Ni et al., 2009), doping carbon isotopes (Zhang et al., 2010), mechanical strain (Wei et al., 2011), superlattices 20, GNR junctions, and nanopore GNRs (Chang and Nikolic, 2012; Haskins et al., 2011). In particular, Chang et al. (2014) proposed the use of heavy adatoms and nanopores to enhance the TE property of GNRs, predicting a ZT value of 3 at low temperature (T = 40 K). Other proposals involved by using of armchair edged GNRs with antidots, predicting ZT ∼ 0.25. The resonant tunneling effect of mixed edged GNRs, according to work Mazzamuto et al. (2011) could give a ZT value above unity. In addition, Liang et al. (2012) have proposed so-called nanowiggles, where the resonant tunneling effect also enhances the TE performance characterized by ZT of 0.79 at room temperature. A 1.5–3 times increase for semiconducting GNRs was predicted for a hybrid graphene/boron nitride structure proposed in reference (Yang et al., 2012) to improve the TE properties. The role of edge disorders in armchair GNRs was studied theoretically in reference (Mazzamuto et al., 2011). However, the authors of reference (Mazzamuto et al., 2011) concluded that the cumulative effect of the edge roughness is rather negative, because along with reducing of the thermal conductance, the electrical performance degrades as well, giving an overall negative impact on ZT. Furthermore, the authors of reference (Sevincli and Cuniberti, 2010) have predicted that by introducing edge roughness a ZT of 4 can be accomplished for zigzag GNRs. Analogously, Chang and Nikolic (2012) have proposed the use of GNRs with periodic arrays of nanopores for long structures. They predicted that ZT ∼ 2 is achieved at room temperature using a TE transducer of length 1.2 μm. The reduced thermal conductivity was anticipated at expense of using a long wire with a length of the order of micrometers. The aforementioned work was purely theoretical with no experimental validation of other groups who investigated the thermopower of graphene experimentally (Checkelsky and Ong, 2009; Wei et al., 2009; Wang and Shi, 2011).

      Desirable features of a new semiconductor material with high ZT are as follows: (1) a high magnitude of Nv, corresponding to the symmetry crystal structure with a large number of heavy elements per unit cell, resulting in low kph, (2) small differences of electronegativity between the elements in the compound presuming either the high mobility or long scattering time, (3) an additional reduction of the lattice thermal conductivity by alloying or rattling, (4) high effective mass, and (5) doping the material to a high surface carrier density of about 10¹²–10¹³ cm−2, giving the optimal S²/ρk ratios.

      Theoretical predictions of the TE structures based on carbon nanotubes, graphene, transition metal dichalcogenides, and black phosphorene forecast that such materials will have more favorable TE properties than the conventional systems, due to further increases in the density of states and availability of the dynamical electrode doping. Nevertheless, a number of methods that have been developed for reduction of phonon part of the thermal conductivity still require detailed experimental verification. It is too early now to claim, whether such the approaches hold promise.

      The efforts toward fabricating of better TE devices have been accelerated due to recent advances in materials synthesis techniques, in X-ray diffraction technology, and in computational capabilities. Existing theoretical models bring an optimism that TE devices with ZT > 4 will be manufactured soon. However, an inability to predict new structures and compositions of new solid-state compounds makes the search strategy of more efficient materials and solutions to remain indefinite. Nonetheless, the recent growth of research activities resulted in discoveries of novel, complex, and structurally beautiful compositions and devices, and some of these classes of TE devices may indeed be the answer to justify the efforts. The research groups participating in those efforts are implementing advanced methods to speed up the search, thereby creating a hope that the advances will come soon.

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      Further reading

      Anon. Thermoelectric Handbook. Boca Raton, London, New York, NY: CRC Press, Taylor & Francis; 2006.

      Chapter 1

      Thermal transport in graphene and its allotropes

      Abstract

      In this chapter, using a simplest model, we introduce the figure of merit, characterizing the overall efficiency of thermoelectric transducers. Then we describe different components of the thermal flux. Among the components of the heat transport we briefly discuss the mechanisms of the heat transfer due do conduction, the convective heat transfer, transient heat transfer, the real bodies versus the Kirchhoff’s law, radiation heat transfer between planar surfaces and the Matthiessen’s rule. Furthermore, we briefly discuss the emission and absorption of phonons, electron–electron scattering, mechanisms of the electric and thermal conductivity of semiconductors, determining the phonon and electron fractions of the heat flow in graphene. Basic scenario of the thermal transport in graphene depends on the spectrum of the crystal lattice oscillations, phonons and on the spectrum of electron excitations. Therefore, we consider details of electronic spectrum of graphene at the end of this chapter.

      Keywords

      figure of merit

      thermoelectric transducer

      thermal flux

      convective heat transfer

      transient heat transfer

      Matthiessen’s rule

      phonon spectrum

      1.1. Thermoelectric transducer

      This chapter considers basic insights of the thermoelectric and heat transfer phenomena, focusing on general discussion of main mechanisms using simplest models. An immediate transforming of heat flux into electric current and vice-versa is regarded as the thermoelectric effect (DiSalvo, 1999). This conversion occurs by the thermoelectric devices creating a voltage drop due to temperature difference between the opposite sides. On the contrary, when a voltage is applied across the device, it induces a temperature difference. On the microscopic scale, a finite temperature gradient pushes the charge carriers in the material from the hot-side to the cold-side. This effect is exploited in a variety of applications, e.g., to cool objects, to generate electricity or to measure temperature. Since one can easily inverse the polarity of the applied voltage to switch between the cooling and heating, the thermoelectric devices can be used as temperature controllers. Historically, the thermoelectric phenomena had been discovered and studied as three independent effects, the Seebeck effect, Peltier effect, and Thomson effect. All the three effects are thermodynamically reversible. There is also a closely related effect of Joule heating due to electric current, flowing through a resistive material, which however, is irreversible. A thermoelectric transducer (TET) is a solid-state device, which transforms the heat and electric energy from one form to another. Widely known types of TET are the thermoelectric refrigerator exploiting the Peltier effect and the electric energy generator based on the Seebeck effect. Very attractive features of TET are the absence of moving parts, compact size, an ability for a precise temperature control, and reliability, which makes the TET by a unique device. TET finds many applications in a variety of fields ranging from mere food and beverage coolers to portable energy transducers and highly sophisticated temperature control systems in space vehicles (DiSalvo, 1999). Growing usage of TET to solve severe electricity generation and cooling problems, especially in the electronics industry. The examples are the cooling of laser diodes or sensors of THz and infrared fields. The high demand and significant economic values urge the manufacturers to marketing of a wide variety of TET (DiSalvo, 1999). The capabilities of TET are characterized by using of their performance curves and of several limit values, including the maximum temperature difference ∆Tmax the TET can achieve, the corresponding input current Imax and voltage Vmax, and the maximum amount of heat Qmax that can be absorbed at ∆T = 0 on the cold-side. Here ∆T = Th−Tc, Th, and Tc are the temperatures of the hot (h) and cold (c) sides. Such the characteristics are necessary to optimize TET for a highest performance, to finding the operating parameters in the course of simple calculations, and simulate the overall thermoelectric transducers by implementing commercially available CFD software (Fig. 1.1).

      Figure 1.1   (A) A schematic of a TE couple. It is composed of two electrically conducting materials: one n-type and the other p-type. They are joined at the top by a metal (black bar) to make a junction. When the current flows as shown, the negatively charged electrons in the n-type material flow from the junction toward the base, while the positively charged holes in the p-type material also flow from the junction to the base. Both carriers conduct heat away from the junction and the junction becomes cold. Commercially available devices contain from 18 to 128 couples. (B) When the junction is instead heated, both types of carriers conduct heat to the cold base and a voltage difference is generated at the two base electrodes. This type of thermoelectric generator is used in some space missions for system power, with a radioactive plutonium mass as the heat source. In terrestrial uses, any source of heat above ambient temperature could be used.

      A serious disadvantage of existing TET, which restricts their wider implementation for cooling of objects and energy generation, is a relatively low-efficiency of the thermoelectric process. A critical breakthrough in this area requires better knowledge of thermoelectric mechanisms on the nanoscale, whose physics is still not well-understood. Therefore, the available now TET devices in terms of performance cannot yet compete, e.g., with more efficient and powerful internal combustion engines, or the cryogenic coolers. Despite an impressive progress in creating of novel thermoelectric materials and devices, present day technology still must be improved before being able to meet existing criteria to the clean energy transducers.

      In this respect, a promising direction of research is implementing of the novel low-dimensional materials (Baheti et al., 2008; Kim et al., 2001; Reddy et al., 2007), whose properties can be tuned on nanoscale dynamically and in wide limits. Using the recently developed methods of the nanotechnology, this allows achieving a desired optimal combination of the electric and thermal transport properties, providing a high efficiency of the thermoelectric transducer. A necessary condition is obtaining of an accurate knowledge of basic physical properties of the TET materials. Unfortunately, this information in most cases is missing. This section describes a simple approach to calculate the physical characteristics of a TET device, including Seebeck voltage SM, electrical resistance RM, and thermal conductance KM, using common parameters listed in the vendor datasheet. They typically include ∆Tmax, occurring at I = Imax, assuming that no heat Qc is absorbed at the cold surface, i.e., Qc = 0. The input current Imax resulting in greatest ∆T, voltage Vmax at ∆T = ∆Tmax and the maximum amount of heat Qmax that can be absorbed at cold-side. The fundamental physical parameters, like Seebeck coefficient s, electric resistivity ρ, and the thermal conductivity k are then deduced provided that the number of couples N of the cross-sectional area A to the length L of each thermoelectric element are known.

      , arising due to the Seebeck effect represents an electromotive force (emf), which alters the Ohm’s law by generating currents, despite that the voltage difference is absent (or vice-versa). This gives the electric current as

      (1.1)

      In the steady state, where I = 0, the voltage V . One can see that emf does not depend on the electric resistivity ρ, which allows determining the temperature T by mere measuring the voltage V . This approach is used to identify the unknown metal alloys.

      A simple model of the Peltier cooler (PC) is based on the following. We assume that the heat Qc absorbed at the cold surface is determined by the thermal balance condition formulated as

      (1.2)

      where the first term in the square brackets constitutes the thermoelectric power, the second term is the Joule heat, and the third term is the thermal flux between the hot and cold surfaces. The electric bias voltage V across the PC is

      (1.3)

      while the second term corresponds to the Seebeck voltage. The Joule power then is

      (1.4)

      is defined as

      (1.5)

      The Seebeck coefficient SM of the whole PC, its resistance RM and the thermal conductance KM are defined as

      (1.6)

      (1.7)

      (1.8)

      In these terms, Eqs. (1.2), (1.3), and (1.4) are rewritten as

      (1.9)

      (1.10)

      (1.11)

      The basic parameters, like the Seebeck coefficient s, electric resistivity ρ and thermal conductivity k are fundamental physical properties of the PC materials and SM, RM, and KM are the physical characteristics of the TET as a whole device. The figure of merit Z characterizes the ability of a PC to transduce the heat into electricity or vice-versa, thereby representing a key characteristic of the PC performance. Although these parameters basically are required to modeling of the transducing processes, they are not always well-known. That is why practically important to establish the connection between the set of parameters, which are typically known, like, e.g., ∆Tmax, Imax, Vmax, and Qmax on the one hand, and the required parameters SM, RM, and KM (or such as s, ρ, and k) on the other hand. The required connection between the two sets of parameters is established as follows. A careful look at Eq. (1.2) suggests that ∆T is proportional to I² when Qc vanishes, i.e.,

      (1.12)

      The condition of maximum of ∆T is obtained by differentiating Eq. (1.12) with respect to I, which gives

      (1.13)

      Solving Eq. (1.13), respectively to I gives the value allowing to achieve the maximal temperature difference ∆T

      (1.14)

      The last expression (1.14) suggests how to achieve the maximum temperature difference ∆Tmax, by selecting I, which plays here the role of the maximum current Imax. This corresponds to a maximum voltage Vmax. Substituting the value of Imax from Eq. (1.14) into Eq. (1.12), we obtain ∆Tmax as

      (1.15)

      After replacing in Eq. , we obtain an expression for Vmax as

      (1.16)

      Typically, the known listed TET specifications parameters are ∆Tmax, Imax, Vmax at a certain temperature Tin Eqs. (1.14) and (1.15), we arrive to the following formulas

      (1.17)

      (1.18)

      We emphasize that the maximum amount of

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