Bradley D. Fahlman Materials Chemistry Fourth Edition Materials Chemistry Bradley D. Fahlman Materials Chemistry Fourth Edition Bradley D. Fahlman Department of Chemistry and Biochemistry Central Michigan University Mount Pleasant, MI, USA ISBN 978-3-031-18783-4 ISBN 978-3-031-18784-1 (eBook) https://doi.org/10.1007/978-3-031-18784-1 1st &2nd editions: © Springer Science+Business Media B.V. 2007, 2011 3rd edition: © Springer Nature B.V. 2018 4th edition: © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland Preface As we surge ahead with global electrification of the transportation industry, advanced materials will continue to play a critical role—not only for the battery packs—but also to expand the electrical grid needed to enable the impending surge in power use. However, beyond the transportation sector, breakthroughs in materials design will also be essential to help us address the effects of climate change and energy shortages, homeland security threats, and to fight next-generation diseases. An increasing focus on sustainability within the framework of a circular economy will also be needed to ensure that nonrenewable resources remain available for future generations. It is truly exciting to think about the potential breakthroughs coming in the next few years as artificial intelligence (AI) and machine learning (ML) have greatly expanded our capacity in the design of novel materials. The next steps in our technological journey are governed only by our creativity and steadfast ability to apply fundamental scien- tific knowledge. This latter quality represents the overarching goal of this textbook— to provide a suitable breadth and depth coverage of various classes of materials to help enable the development of next-generation devices and applications. As with previous editions, Materials Chemistry focuses on the ‘structure vs. prop- erty’ assessment of both inorganic and organic materials, from their bulk to nanos- tructure regime. The content presented herein is most appropriate for junior or senior undergraduate students, as well as first-year graduate students in chemistry, physics, and engineering disciplines. In addition, this textbook has also been widely used by researchers in industry as a primer to learn about various materials classes or charac- terization techniques. Each chapter includes a comprehensive reference list, which is essential for more detailed research. For such a broad and rapidly evolving field as materials chemistry, it is a daunting task to remain contemporary. However, we have attempted to do so through extensive updates and expansions to provide an innovative and practical perspective throughout. After providing a historical perspective in the first chapter, this edition provides an expanded discussion of sustainability—a topic that is often overlooked in our zeal to fabricate faster and better devices—but absolutely essential to ensure the survival of future generations. In addition to reorganization and rewriting for clarity throughout, this edition includes the following new sections: v vi Preface ● Materials design via combinatorial and machine learning approaches (Chap. 1) ● Kroger-Vink notation for defects (Chap. 2) ● Additive manufacturing (AM) for metallurgy (Chap. 3) ● Negative capacitance field effect transistors (NCFETs; Chap. 4) ● 3-D printing of polymers (Chap. 5) ● New toxicity studies of nanomaterials (Chap. 6) ● Core-shell quantum dots (Chap. 6) ● Heat-assisted magnetic recording (Chap. 6) ● Dynamic light scattering (DLS) techniques (Chap. 7). In addition, the section related to nanotoxicity was extensively updated to reflect the latest discoveries. This book also continues to be the first to provide detailed processing information for the latest technology node of integrated circuit design, based on FinFETs. Over 100 additional references were added throughout this edition, and the end-of-chapter questions and bibliographies were extensively revised to reflect the current state of the art. As with previous editions, Appendices are also provided that contain an updated and expanded timeline of major materials development and the complete transcript of Nobel Laureate Feynman’s speech “There’s Plenty of Room at the Bottom”. A collection of materials-related laboratory experiments is also included, which are suitable for both undergraduate or graduate curricula. I wish to thank my wife, Diyonn, for her love and continued support and encour- agement. Our frequent travels across an expansive globe continually remind me how fortunate I am to have found my true soulmate. Our two kitties, Cash and Sissy, also played a role in the 4th edition by reminding me when to take cuddle breaks! I also am extremely appreciative for the input provided by students and instructors who have either adopted, or have considered the adoption, of Materials Chemistry.I continue to offer thanks to every reader of this book and solicit your comments to my email ([email protected]). Please let me know what you think of this edition; I promise to incorporate your suggestions to strengthen future editions. Mount Pleasant, MI, USA Bradley D. Fahlman, Ph.D. January 2023 Contents 1 What is “Materials Chemistry”? ................................. 1 1.1 Historical Perspectives ...................................... 2 1.2 “Bottom-Up” Materials Synthesis ............................. 5 1.3 Materials Discovery ........................................ 6 1.4 Materials Sustainability ..................................... 12 Further Reading ................................................. 29 2 Solid-State Chemistry .......................................... 31 2.1 Structural Order ............................................ 31 2.2 Bonding in Solids I: Intermolecular Forces ..................... 32 2.2.1 Ionic Solids ......................................... 33 2.2.2 Metallic Solids ...................................... 35 2.2.3 Covalent Network Solids .............................. 36 2.2.4 Molecular Solids ..................................... 36 2.3 Bonding in Solids II: Band Theory ............................ 40 2.4 The Crystalline State ........................................ 45 2.4.1 Crystal Growth Techniques ............................ 49 2.4.2 Crystal Structures .................................... 52 2.4.3 Crystal Symmetry and Space Groups ................... 59 2.4.4 Archetypical Interstitial Crystal Lattices ................. 71 2.4.5 Superconductivity of Perovskites: Toward a Room-Temperature Superconductor ................... 87 2.4.6 Crystal Imperfections ................................. 94 2.4.7 Physical Properties of Crystals ......................... 112 2.5 Ceramics .................................................. 128 2.5.1 Sol–Gel Processing ................................... 134 2.5.2 Cementitious Materials ............................... 139 2.5.3 Biomaterials Applications ............................. 144 2.6 Glasses ................................................... 147 2.7 Solid-State Case Study I: Solid Electrolytes for Energy Storage Applications ........................................ 159 vii viii Contents 2.8 Solid-State Case Study II: Porous Materials: Zeolites And Metal–Organic Frameworks (MOFs) ...................... 166 Further Reading ................................................. 188 3 Metals ......................................................... 191 3.1 Mining and Processing of Metals ............................. 191 3.1.1 Powder Metallurgy ................................... 206 3.1.2 Additive Manufacturing (AM) ......................... 212 3.2 Metallic Structures and Properties ............................ 213 3.2.1 Phase Behavior of Iron-Carbon Alloys .................. 215 3.2.2 Hardening Mechanisms of Steels ....................... 222 3.2.3 Stainless Steels ...................................... 237 3.2.4 Nonferrous Metals and Alloys ......................... 242 3.3 Metal Surface Treatments for Corrosion Resistance .............. 263 3.4 Magnetism ................................................ 266 3.5 Metals Case Study: Hydrogen Storage ......................... 276 Further Reading ................................................. 288 4 Semiconductors ................................................ 291 4.1 Properties and Types of Semiconductors ....................... 291 4.2 Silicon-Based Applications .................................. 299 4.2.1 Silicon Wafer Production .............................. 300 4.2.2 Integrated Circuits ................................... 303 4.2.3 Field-Effect Transistors (FETs) ........................ 305 4.2.4 Transistor Scaling: Advantages and Limitations .......... 312 4.2.5 Integrated Circuit Fabrication .......................... 324 4.2.6 Thin-Film Deposition Methodologies ................... 350 4.3 Light-Emitting Diodes: There is Life Outside of Silicon! ......... 367 4.4 Thermoelectric (TE) Materials ............................... 377 4.5 Semiconductors Case Study: Photovoltaic (Solar) Cells .......... 383 Further Reading ................................................. 404 5 Polymeric Materials ............................................ 407 5.1 Polymer Classifications and Nomenclature ..................... 408 5.2 Polymerization Mechanisms ................................. 416 5.3 “Soft Materials” Applications: Structure Versus Properties ........ 448 5.3.1 3-D Printing ......................................... 452 5.3.2 Biomaterials Applications ............................. 464 5.3.3 Conductive Polymers ................................. 485 5.3.4 “Soft” Lithography ................................... 495 5.4 Polymer Additives .......................................... 503 Further Readings ................................................ 531 Contents ix 6 Nanomaterials ................................................. 533 6.1 The Toxicity of Nanomaterials ............................... 534 6.2 What is “Nanotechnology”? .................................. 556 6.3 Nanoscale Building Blocks and Applications ................... 558 6.3.1 Zero-Dimensional Nanomaterials ...................... 562 6.3.2 One-Dimensional Nanostructures ...................... 625 6.3.3 Two-Dimensional Nanostructures ...................... 660 6.4 Important Nanomaterials Applications I: Lithium-Ion Batteries .................................................. 670 6.5 Important Nanomaterials Applications II: Nanoelectromechanical Systems (NEMS) ...................... 678 Further Reading ................................................. 718 7 Materials Characterization ...................................... 721 7.1 Light Scattering ............................................ 722 7.2 X-ray Scattering ............................................ 727 7.2.1 X-ray Diffraction (XRD) .............................. 731 7.2.2 Small-Angle X-ray Scattering (SAXS) .................. 743 7.3 Optical Microscopy ......................................... 744 7.4 Electron Microscopy ........................................ 747 7.4.1 Transmission Electron Microscopy (TEM) ............... 756 7.4.2 Scanning Electron Microscopy (SEM) .................. 776 7.5 Surface Characterization Techniques Based on Particle Bombardment .............................................. 788 7.5.1 Photoelectron Spectroscopy (PES) ...................... 788 7.5.2 X-ray Absorption Fine Structure (XAFS) ................ 790 7.5.3 Ion-Bombardment Techniques ......................... 792 7.5.4 Atom-Probe Tomography (APT) ....................... 803 7.6 Scanning Probe Microscopy (SPM) ........................... 804 7.7 Bulk Characterization Techniques ............................. 811 Further Reading ................................................. 829 Appendix A: Timeline of Materials and Technological Discoveries ...... 831 Appendix B: “There’s Plenty of Room at the Bottom” ................ 845 Appendix C: Materials-Related Laboratory Experiments ............. 857 Index ............................................................. 885 Chapter 1 What is “Materials Chemistry”? Life in the twenty-first century is ever-dependent on an unlimited variety of advanced materials. In our consumptive world, it is easy to take for granted the macro-, micro-, and nanoscale building blocks that comprise any item ever produced. We are spoiled by the technology that adds convenience to our lives such as microwave ovens, laptop computers, cell phones and tablets, and improved modes of transportation. However, we rarely take time to think about and appreciate the materials that constitute these modern engineering feats. The term material may be broadly defined as any solid-state substance or device that may be used to address a current or future societal need.1 For instance, simple building materials such as glass, wood, aluminum, etc. address our need of shelter. Other more intangible materials such as nanoscale components are also considered as materials, even if a particular nanomaterial may not yet be widely proven for applications.2 A general classification of various types of materials is illustrated in Fig. 1.1. Although this indicates sharp distinctions between various classes, there is often ambiguity regarding the proper taxonomy for a specific material. For example, a thin film is defined as having a thickness of less than 1 µm; however, if the thickness drops to below 100 nm, the film may be more accurately classified as a 2-D nanomaterial.3 Likewise, liquid crystals are best described as having properties intermediate between amorphous and crystalline phases, and composites typically involve both inorganic and organic components. The broadly defined discipline of materials chemistry is focused on understanding the relationships between the arrangement of atoms, ions, or molecules comprising a material, and its physical and chemical properties. By this designation, common disciplines such as polymer, solid-state, and surface chemistry would all be placed within the scope of materials chemistry. This broad field consists of studying the structure and properties of existing materials, synthesizing and characterizing new materials, and using advanced computational techniques to understand the properties of existing materials or those that have not yet been fabricated. © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 1 B. D. Fahlman, Materials Chemistry, https://doi.org/10.1007/978-3-031-18784-1_1