This module aims to
•Enhance students' understanding of the fundamental nature of ordered crystalline solids
•Develop the concept that the structure of materials impact on their properties and applications
•Provide an introduction to the use of diffraction methods to characterise crystal structures
•Describe characterisation techniques, for both crystalline and disordered materials.
•Outline electronic structure in the solid state.
•Describe a range of materials manufacturing techniques.
•Explain the origin of magnetism in the solid state.
•Outline the practical implications of magnetic materials
•Describe how we make and study magnetic inorganic solids
•Highlight current research trends in inorganic magneto chemistry

(LO1) Understand and describe the characteristics of the crystalline solid state

(LO2) Be able to perform simple analyses of powder X-ray diffraction data

(LO3) Describe the factors affecting the crystal structures formed by ionic compounds

(LO4) Understand that solid structures directly influences the physical and functional properties of materials, and describe examples

(LO5) Understand the solid-state electronic structure of inorganic materials

(LO6) Appreciate the real-world relevance of materials design.

(LO7) Understand the microscopic origins of magnetism, and describe the mechanisms which lead to collective magnetic behaviour

(LO8) Interpret magnetic data and classify types of inorganic magnetic materials.

(LO9) Recognise the uses of magnetic materials.

(S1) Problem solving skills

Lectures. 34 x 1 hr in-person lectures.

Coursework. Material delivered in lectures is supported by 3 x 1 hr small group tutorials (example problem sets will be provided for formative assessment) and 4 x 1 hr whole group workshops.
Two workshops will be used for CA support and additional formative assessment; two will be used for feedback on the CA work.

Lectures: 34 hr
Workshops: 4 hr
Tutorials: 3 hr

Introduction to Solid State Chemistry (Dr. Sam Chong)
•Basic concepts in crystalline solids (builds on CHEM111)
o What is a crystal? – lattices, unit cells, symmetry
o Describing crystal structures – fractional coordinates, Miller indices
o Close packing of spheres in metallic solids
o Simple ionic solids derived from close-packed structures
o Rationalising structure types using radius ratio rule, and its limitations

•Diffraction characterisation of crystalline solids
o Interference of waves, Braggs' law
o Concept of the reciprocal lattice, relation to the direct lattice and diffraction
o Diffraction intensities and systematic absences
o Experimental aspects of X-ray diffraction and uses of powder X-ray diffraction (PXRD)
o Application of concepts to indexing PXRD patterns and deducing lattice centring
o Limitations and compl ementary experimental methods (scattering, spectroscopy, imaging and microscopy techniques)

•Solid state structures of functional inorganic materials
o Structure-function relationships and applications of functional solids
o Polymorphism - concept and examples in ionic solids, contrasts in physical properties
o Spinels - normal vs. inverse structures and contributing factors
o Perovskites - use of tolerance factor to predict perovskite distortion
o Covalent solids - properties and structures of carbon allotropes
o Framework solids - structures and properties of zeolites, metal-organic frameworks

•Introducing complexity
o Hybrid structures (MOFs, hybrid perovskites, fullerides)
o Structure of the YBCO high temperature superconductor as a perovskite superstructure
o Structure of point and extended defects
o Doping, non-stoichiometry and disorder
o Infl uence of defect structure on functional properties and applications (examples from ionic conduction, MOFs)
o Methods for the characterisation of defective and disordered solids; pair distribution function, transmission electron microscopy

Electronic and Magnetic materials (Dr. John Claridge)
•Synthesis of inorganic solids
o Compare polycrystalline and single crystal samples and the advantages and disadvantages of their syntheses
o Outline methods for synthesis of polycrystalline samples
o Consider the difference in experimental conditions required for direct synthesis in the solid-state vs. in solution
o Develop overview of single crystal growth methods

•Electrons in Solids
o Qualitative description of distinction between metals, semi-conductors, and insulators (atomic vs. molecular electronic structure)
o Density of states and Fermi energy, and experimental evidence for these conce pts
o Conductivity (Carrier density and temperature dependence)
o Electronic structure of simple metals and transition metals
o Band gap manipulation (Semi-conductor doping / Silicon vs. III/V systems)
o Mott-Hubbard insulators and the breakdown of the band model

•Introduction to magnetochemistry
o Introduce the concept that solids contain magnetic moments that interact with one another in a variety of different ways, giving rise to a diverse range of exciting and useful bulk materials properties
o Describe several key manifestations and applications of magnetism as well as compare orders of magnitude of magnetic field strengths
o Familiarise with units of magnetism

•The origin of magnetism in materials
o Revisit spin and orbital angular momenta and their relevant quantum numbers and magnetic moments
o Introduce the Bohr magneton as a convenient unit for atomic magnetism< /p>

•Magnetic moments of isolated atoms or ions
o Describe the coupling of spin and orbital angular momenta and revise Hund’s rules to arrive at ground state magnetic moments and term symbols of rare-earth ions
o Describe the effects of crystal fields and orbital quenching of magnetic moments of 3d transition metals to arrive at a spin-only formula
o Compare calculated and observed magnetic moments of rare-earth and transition metal ions

•Magnetisation and magnetic susceptibility
o Classify diamagnets and paramagnets by the sign and temperature-dependence of their magnetic susceptibilities and compare some common materials
o For paramagnetism, demonstrate Curie’s Law and how – through the measurement of bulk magnetic susceptibility – we can determine the atomic magnetic moment of a materia
l
•Magnetic interactions in the solid state
o Compare ferromagnetic, antif erromagnetic and ferrimagnetic states, with examples, that can be produced via magnetic interactions
o Consider the energy scale of the dipolar interaction to show that this is too low in energy to account for the high-temperature magnetic order observed in many magnetic materials
o Describe the concept of exchange to derive the Heisenberg Hamiltonian. Outline how exchange can occur directly, but more frequently indirectly through the indirect superexchange mechanism
o Make use of orbital overlap diagrams to show how 90º and 180º bonding interactions lead to ferro- and antiferromagnetic orders, respectively

•Measuring magnetic order in solids
o Give an overview of magnetometry techniques and the capabilities for measuring magnetisation at the University of Liverpool
o Describe how neutrons are very useful for studying magnetic materials

•Introduction to multiferroic materials
o Introduce the concept that coupling the order of spin, charge and lattice degrees of freedom in materials presents a major grand challenge in modern solid-state chemistry research
o Define the concepts of ferroelectricity and ferroelasticity in analogy with ferromagnetism and detail the technological importance of coupling ferroic orders of solids