Solid State Chemistry

Elaine A. Moore studied chemistry as an undergraduate at Oxford University and then stayed on to complete a DPhil in theoretical chemistry with Peter Atkins. After a two-year postdoctoral position at the University of Southampton, she joined the Open University in 1975, becoming a lecturer in chemistry in 1977, senior lecturer in 1998, and reader in 2004. She retired in 2017 and currently has an honorary position at the Open University. She has produced OU teaching texts in chemistry for courses at levels 1, 2, and 3 and written texts in astronomy at level 2 and physics at level 3. She is coauthor of Metals and Life (RSC Publishing, 2009) and of Concepts in Transition Metal Chemistry (RSC Publishing, 2010), which were part of a level 3 Open University course in inorganic chemistry and co-published with the Royal Society of Chemistry. She was team leader for the production and presentation of an Open University level 2 chemistry module delivered entirely online. She is a Fellow of the Royal Society of Chemistry and a Senior Fellow of the Higher Education Academy. She was co-chair for the successful Departmental submission of an Athena Swan bronze award. Her research interests are in theoretical chemistry applied mainly to solid-state systems and is author or coauthor of over 50 papers in refereed scientific journals. A long-standing collaboration in this area led to her being invited to help run a series of postgraduate workshops on computational materials science hosted by the University of Khartoum. Jennifer E. Readman Jennifer is a Senior Lecturer in Materials Chemistry and Course Leader for BSc (Hons) and MChem Chemistry. Jennifer's background is in solid state inorganic chemistry and she teaches various aspects of inorganic and physical chemistry on the undergraduate and postgraduate degrees programmes. Her research is based predominately into microporous materials, such as zeolites, metal substituted silicates. She is interested in all aspects of their chemistry such as their synthesis, structure and uses. Jennifer teaches many different aspects of inorganic and physical chemistry across all year of the undergraduate chemistry programmes. Topics include Structure & Bonding in inorganic chemistry. X-ray diffraction, Chemistry of the s and p block elements, Introductory d-block chemistry, Advanced structural techniques, Group theory and Advanced Materials Chemistry. She is the Course Leader for the undergraduate BSc(Hons) and MChem Chemistry programmes. Research interests lie in the area of solid state chemistry and particularly in the relationship between the structure of a material and it’s properties. Main interests lie in materials such as zeolites, metal-organic frameworks and metal silicates, and also techniques such as powder X-ray diffraction in the laboratory and at synchrotron sources such as the Diamond Light Source. These materials have applications in industry, predominately in the treatment of nuclear and pharmaceutical waste. Dr Readman is also interested in diffuse scattering, electron microscopy, X-ray fluorescence spectroscopy and solid state NMR. Dr Readman was awarded a Bachelors degree in chemistry from the University of Oxford and then went on to study for a PhD at the University of Birmingham under the supervision of Dr. Paul Anderson. The PhD work involved the use of zeolite frameworks to acts as host for metal and metal oxide nanoparticles. Postdoctoral work was carried out at the State University of New York at Stony Brook where the project involved using 17-O solid state NMR to study zeolites. Followed by SINTEF in Oslo, Norway where the research project investigated carbon dioxide absorbents for use in the clean fuel production. After returning to the UK Dr Readman returned to the University of Birmingham working on a joint chemistry/biochemistry project with Dr. Joe Hriljac and Prof. Lynne Macaskie investigating synthetic and bio-manufactured layered phosphates for the remediation of nuclear waste. Before coming to work at UCLan, Dr Readman worked at Durham University under the supervision of Prof. John Evans working on negative thermal expansion materials/ Lesley E. Smart studied chemistry at Southampton University, United Kingdom, and after completing a PhD in Raman spectroscopy, she moved to a lectureship at the (then) Royal University of Malta. After returning to the United Kingdom, she took an SRC Fellowship to Bristol University to work on X-ray crystallography. From 1977 to 2009, she worked at the Open University chemistry department as a lecturer, senior lecturer, and Molecular Science Programme director, and held an honorary senior lectureship there until her death in 2016. At the Open University, she was involved in the production of undergraduate courses in inorganic and physical chemistry and health sciences. She was the coordinating editor and an author of The Molecular World course, a series of eight books and DVDs co-published with the Royal Society of Chemistry, authoring two of these, The Third Dimension (RSC Publishing, 2002) and Separation, Purification and Identification (RSC Publishing, 2002). Her most recent books are Alcohol and Human Health (Oxford University Press, 2007) and Concepts in Transition Metal Chemistry (RSC Publishing, 2010). She has an entry in Mothers in Science: 64 Ways to Have It All (RSC Publishing, 2016; downloadable from the Royal Society website). She served on the Council of the Royal Society of Chemistry and as the chair of their Benevolent Fund. Her research interests were in the characterisation of the solid state, and she authored publications on single-crystal Raman studies, X-ray crystallography, Zintl phases, pigments, and heterogeneous catalysis and fuel cells. Neil Allan School of Chemistry University of Bristol, Bristol, United Kingdom Mary Anne White Department of Chemistry Dalhousie University Halifax, Canada

Chapter 1 – An Introduction to Crystal Structures

Jennifer E. Readman and Lesley E. Smart

1.1 Introduction

1.2 Close packing

1.3 Body-centred and Primitive Structures

1.4 Lattices and Unit Cells

1.4.1 Lattices

1.4.2 One- and Two- Dimensional Unit Cells

1.4.3 Three-Dimensional Lattices and Their Unit Cells

1.5 Crystalline solids

1.5.1 Unit cell stoichiometry and Fractional Coordinates

1.5.2 Ionic Solids with Formula MX

1.5.2.1 Caesium Chloride

1.5.2.2 Sodium Chloride

1.5.2.3 Zinc Blende & Wurtzite

1.5.2.4 Nickel Arsenide

1.5.3 Solids with General Formula MX2

1.5.3.1 Fluorite and Anti-Fluorite

1.5.3.2 Cadmium Chloride and Cadmium Iodide

1.5.3.3 Rutile

1.5.3.4 -Cristobalite

1.5.4 Other Important Crystal Structures

1.5.4.1 Rhenium trioxide

1.5.4.2 Perovskite

1.5.4.3 Spinel and Inverse Spinel

1.5.5 Miscellaneous Oxides

1.6 Ionic Radii and the Radius Ratio Rule

1.7 Extended Covalent Arrays

1.8 Molecular Structures

1.9 Lattice Energy

1.9.1 Born-Haber Cycle

1.9.2 Calculating Lattice Enthalpies

1.9.3 Calculations Using Thermodynamic Cycles and Lattice Energies

1.10 Symmetry

1.10.1 Symmetry Notation

1.10.2 Axes of Symmetry

1.10.3 Planes of Symmetry

1.10.4 Inversion

1.10.5 Inversion Axes, Improper Symmetry Axes, and the Identity Element

1.10.6 Operations

1.10.7 Symmetry in Crystals

1.10.8 Translational Symmetry Elements

1.10.9 Space groups

1.11 Miller Indices and Interplanar spacing

1.12 Quasicrystals

Summary.

Questions

Chapter 2 Scattering Techniques for Characterising Solids

Jennifer E. Readman

2.1 Introduction

2.2 X-ray Diffraction

2.2.1 The Generation of X-rays

2.2.2 Scattering of X-rays & Bragg’s Law

2.2.3 The Diffraction Experiment

2.2.4 The Powder Diffraction Pattern

2.2.5 The Intensity of Diffracted Peaks

2.2.6 The Width of Diffracted Peaks

2.2.7 Rietveld Refinement

2.2.8 Structure & Single-Crystal Diffraction solution

2.3 Synchrotron Radiation

2.3.1 Introduction

2.3.2 Generation of Synchrotron X-rays

2.3.3 Bending Magnets and Insertion Devices

2.4 Neutron Diffraction

2.4.1 Background & Production of Neutrons

2.4.2 Neutron scattering

2.4.3 Experimental Neutron Diffraction

2.4.4 Magnetic Scattering

2.5 Pair Distribution Function Analysis (PDF)

2.5.1 Introduction

2.5.2 Theoretical background

2.5.3 The Total Scattering Experiment

2.6 In-situ Experiments

2.6.1 Variable Temperature

2.6.2 Variable Pressure

2.7 Free Electron Lasers (XFELs)

2.7.1 Introduction

2.7.2 How XFEL X-rays Are Generated

2.7.3 Typical XFEL Experiments

Appendix Allowed reflections for simple cubic cells

Questions

Chapter 3 – Non-Scattering Characterisation Techniques

Jennifer E. Readman

3.1 Introduction

3.2 Electron Microscopy

3.2.1 Scanning Electron Microscopy (SEM}

3.2.2 Transmission Electron Microscopy (TEM)

3.2.3 Electron Diffraction (ED)

3.2.4 Scanning Transmission Electron Microscopy (STEM)

3.2.5 Energy Dispersive X-Ray Analysis (EDS / EDX)

3.2.6 Electron Energy Loss Spectroscopy (EELS)

3.2.7 Scanning Tunnelling Microscopy (STM) & Atomic Force Microscopy (AFM)

3.3 X-ray Spectroscopy

3.3.1 Introduction

3.3.2 X-ray Fluorescence Spectroscopy (XRF)

3.3.3 X-ray Absorption Spectroscopy

3.3.4 EXAFS

3.3.5 XANES

3.3.6 Experimental XAS

3.3.7 X-ray Photoelectron Spectroscopy (XPS)

3.4 Solid State NMR

3.4.1 Introduction

3.4.2 29-Si MAS NMR

3.4.3 Quadrupolar nuclei

3.5 Surface Area Measurements

3.5.1 Gas Adsorption Isotherms

3.5.2 Classification of Isotherms

3.6 Thermal Analysis

3.6.1 Thermogravimetric analysis (TGA)

3.6.2 Differential Thermal Analysis (DTA)

3.6.3 Differential Scanning Calorimetry (DSC)

3.6.4 Temperature Programmed Reduction (TPR) & Temperature Programmed Desorption (TPD)

Summary for chapters 2 and 3,

Questions

Chapter 4 Synthesis

Elaine A. Moore and Lesley E. Smart

4.1 Introduction

4.2 High-Temperature Ceramic Methods

4.2.1 Direct Heating of Solids

4.2.2 Precursor Methods

4.2.3 Sol–Gel Methods

4.3. High-Pressure Methods

4.3.1. Using High-Pressure Gases

4.3.2. Using Hydrostatic Pressures

4.4. Chemical Vapour Deposition

4.4.1. Preparation of Semiconductors

4.4.2. Diamond Films

4.4.3 Optical Fibres

4.5. Preparing Single Crystals

4.5.1 Epitaxy Methods

4.5.2 Chemical Vapour Transport

4.5.3. Melt Methods

4.5.4 Solution Methods

4.6. Intercalation

4.7. Green Chemistry

4.7.1. Mechanochemical Synthesis

4.7.2. Microwave Synthesis

4.7.3. Hydrothermal Methods

4.7.4. Ultrasound-assisted synthesis

4.7.5 Biological-related methods

4.7. 6. Barium Titanate

4.8. Choosing a Method

Chapter 5 Solids:Bonding and Electronic Properties

Elaine A. Moore and Neil Allan

5.2. Bonding in Solids: Free electron theory

5.2.1. Electronic conductivity

5.1 Introduction

5.3. Bonding in Solids: Molecular Orbital Theory

5.3.1. Simple Metals

5.3.2. Group 14 elements

5.4. Semiconductors

5.4.1. Photoconductivity

5.4.2. Doped Semiconductors

5.5. p-n junction and field effect transistors

5.5.1. Flash Memory

5.6. Bands in compounds: Gallium Arsenide

5.7. Bands in d-block compounds: transition metal monoxides

5.8. Superconductivity

5.8.1. BCS Theory of superconductivity

5.8.2. High temperature superconductors: cuprates

5.8.3. Iron superconductors

5.9. Summary

Questions

Chapter 6 Defects and Non-stoichiometry

Elaine A. Moore and Lesley E. Smart

6.1. Introduction

6.2 Point Defects and Their Concentration

6.2.1 Intrinsic Defects

6.2.2 Concentration of Defects

6.2.3 Extrinsic Defects

6.2.4 Defect Nomenclature

6.3 Nonstoichiometric Compounds

6.3.1 Nonstoichiometry in Wüstite (FeO) and MO-Type Oxides

6.3.2 Uranium Dioxide

6.3.3 Titanium Monoxide Structure

6.4 Extended Defects

6.4.1 Crystallographic shear

6.4.2 Planar Intergrowths

6.4.3 Block Structures

6.4.4 Pentagonal Columns

6.4.5 Infinitely Adaptive Structures

6.5 Properties of Nonstoichiometric Oxides

6.5.1. Transition metal monoxides

6.6 Summary

Questions

Chapter 7 Batteries and Fuel Cells

Elaine A. Moore and Lesley E. Smart

7.1. Introduction

7.2. Ionic conductivity in solids

7.3. Solid electrolytes

7.3.1 Silver-ion conductors

7.3.2. Lithium-ion conductors

7.3.3. Sodium-ion conductors

7.3.4. Oxide-ion conductors

7.4. Lithium-based batteries

7.5. Sodium-based batteries

7.6. Fuel cells

7.6.1. Solid oxide fuel cells

7.6.2. Proton Exchange Membrane cells

7.7. Summary

Questions

Chapter 8 Microporous and Mesoporous solids

Jennifer E. Readman (and Lesley E. Smart ?)

8.1. Introduction

8.2 Silicates

8.3. Zeolites

8.3.1. Background

8.3.2. Composition and Structure of Zeolites.

8.3.3. Zeolite Nomenclature

8.3.4. Si/Al ratios in Zeolites

8.3.5. Exchangeable Cations

8.3.6 Synthesis of Zeolites

8.3.7. Uses of Zeolites

8.4. Zeotypes

8.4.1. Aluminophosphates

8.4.2. Mixed Coordination Metallosilicates

8.5. Metal-Organic Frameworks (MOFs)

8.5.1. Composition and Structure of MOFs

8.5.2. Example MOF Structures

8.5.3. Breathing MOFs

8.5.4. Synthesis of MOFs

8.5.5. Applications of MOFs

8.6. Zeolite-like MOFs

8.7. Covalent Organic Frameworks

8.8. Mesoporous Silicas

8.9. Clays

Summary

Questions

Chapter Optical 9 and Thermal Properties of Solids

Elaine A. Moore

9.1 Introduction

9.2. Interaction of Light with atoms

9.2.1. Ruby Laser

9.2.2. Phosphors for LEDs

9.3. Colour Centres

9.4. Absorption and Emission of Radiation in Continuous Solids

9.4.1. Gallium Arsenide Laser

9.4.2. Quantum Wells: Blue laser

9.4.3. Light emitting diodes (LEDs)

9.4.4. Photovoltaic (Solar) Cells

9.5. Carbon-based conducting polymers

9.5.1. Polyacetylene

9.5.2. Bonding in Polyacetylene and related polymers

9.5.3 Organic LEDs (QLEDs)

9.6. Refraction

9.6.1. Calcite

9.6.2. Optical Fibres

9.7. Photonic crystals

9.8. Thermal properties of Materials

9.8.1 Heat Capacity

9.8.2. Thermal Energy Storage

9.8.3. Thermal Expansion

9.8.4. Thermal conductivity

9.8.5 Thermal devices

9.9 Summary

Questions

Chapter 10 Magnetic and Electrical Properties

Elaine A. Moore

10.1. Introduction

10.2. Magnetic Susceptibility

10.3. Paramagnetism in metal complexes

10.4. Ferromagnetic Metals

10.4.1. Magnetic Domains

10.4.2 Permanent magnets

10.4.3 Magnetic Shielding

10.5. Ferromagnetic compounds: chromium dioxide

10.6. Antiferromagnetism: transition metal monoxides

10.7. Ferrimagnetism: ferrites

10.7.1. Magnetic strips on swipe cards

10.8. Spiral Magnetism

10.9 Giant, Tunneling and colossal magnetoresistance

10.9.1 Giant Magnetoresistance

10.9.2. Tunneling Magnetoresistance

10.9.3 Car steering angle sensors

10.9.4 Colossal Magnetoresistance: manganites

10.10 Magnetic properties of superconductors

10.11 Electrical Polarisation

10.12. Piezoelectric crystals A-Quartz

10.13 Ferroelectric effect

10.13.1. Capacitors

10.14. Multiferroics

10.14.1. Type 1 multiferroics:bismuth ferrite

10.14.2. Type 2 multiferroics: terbium manganite

10.15. Summary

Questions

Chapter 11 Nanostructures

Elaine A. Moore and Lesley E. Smart

11.1. Introduction

11.2. Consequences of the nanoscale

11.2.1. Nanoparticle morphology

11.2.2. Mechanical Properties

11.2.3 Melting temperature

11.2.4. Electronic properties

11.2.5. Optical Properties

11.2.6 Magnetic Properties

11.3. Nanostructural Carbon

11.3.1. Carbon Black

11.3.2. Graphene

11.3.3. Graphene Oxide

11.3.4. Buckminsterfullerene

11.3.5. Carbon nanotubes

11.4. Noncarbon nanostructures

11.4.1 Fumed Silica

11.4.2. Metal nanoparticles

11.4.3. Non-carbon -ene structures

11.4.4. Other non-carbon nanostructures

11.5. Synthesis of nanostructures

11.5.1 Top-down methods

11.5.2. Bottom-up methods

11.5.3 Synthesis using templates

11.6. Nanostructures in health

11.7. Safety

11.8 Summary

Questions

Chapter 12 Sustainability

Mary Anne White

12.1. Introduction

12.1.1 Definition of Materials Sustainability

12.1.2 Sustainable Materials Chemistry Goals

12.1.3 Materials Dependence in Society

12.1.4 Elemental Abundances

12.1.5 Solid State Chemistry’s Role in Sustainability

12.1.6 Material Life Cycle

12.2 Tools for Sustainable Approaches

12.2.1 Green Chemistry

12.2.2 Herfindahl-Hirschman Index (HHI)

12.2.3 Embodied Energy

12.2.4 Exergy

12.2.5 Life Cycle Assessment

12.3 Case Study: Sustainability of a Smartphone

12.4 Theoretical Approaches

12.5 Summary

Questions