Solid-state chemistry

Solid-state chemistry, also sometimes referred as materials chemistry, is the study of the synthesis, structure, and properties of solid phase materials. It therefore has a strong overlap with solid-state physics, mineralogy, crystallography, ceramics, metallurgy, thermodynamics, materials science and electronics with a focus on the synthesis of novel materials and their characterization. A diverse range of synthetic techniques, such as the ceramic method and chemical vapour depostion, make solid-state materials. Solids can be classified as crystalline or amorphous on basis of the nature of order present in the arrangement of their constituent particles. Their elemental compositions, microstructures, and physical properties can be characterized through a variety of analytical methods.

Because of its direct relevance to products of commerce, solid state inorganic chemistry has been strongly driven by technology. Progress in the field has often been fueled by the demands of industry, sometimes in collaboration with academia. Applications discovered in the 20th century include zeolite and platinum-based catalysts for petroleum processing in the 1950s, high-purity silicon as a core component of microelectronic devices in the 1960s, and “high temperature” superconductivity in the 1980s. The invention of X-ray crystallography in the early 1900s by William Lawrence Bragg was an enabling innovation. Our understanding of how reactions proceed at the atomic level in the solid state was advanced considerably by Carl Wagner's work on oxidation rate theory, counter diffusion of ions, and defect chemistry. Because of his contributions, he has sometimes been referred to as the father of solid state chemistry.

Given the diversity of solid-state compounds, an equally diverse array of methods are used for their preparation. Synthesis can range from high-temperature methods, like the ceramic method, to gas methods, like chemical vapour deposition. Often, the methods prevent defect formation or produce high-purity products.

The ceramic method is one of the most common synthesis techniques. The synthesis occurs entirely in the solid state.  The reactants are ground together, formed into a pellet using a pellet press and hydraulic press, and heated at high temperatures. When the temperature of the reactants are sufficient, the ions at the grain boundaries react to form desired phases. Generally ceramic methods give polycrystalline powders, but not single crystals.

Using a mortar and pestle, ResonantAcoustic mixer, or ball mill, the reactants are ground together, which decreases size and increases surface area of the reactants. If the mixing is not sufficient, we can use techniques such as co-precipitation and sol-gel. A chemist forms pellets from the ground reactants and places the pellets into containers for heating. The choice of container depends on the precursors, the reaction temperature and the expected product. For example, metal oxides are typically synthesized in silica or alumina containers. A tube furnace heats the pellet. Tube furnaces are available up to maximum temperatures of 2800 °C.

Molten flux synthesis can be an efficient method for obtaining single crystals. In this method, the starting reagents are combined with flux, an inert material with a melting point lower than that of the starting materials. The flux serves as a solvent. After the reaction, the excess flux can be washed away using an appropriate solvent or it can be heat again to remove the flux by sublimation if it is a volatile compound.

Crucible materials have a great role to play in molten flux synthesis. The crucible should not react with the flux or the starting reagent. If any of the material is volatile, it is recommended to conduct the reaction in a sealed ampule. If the target phase is sensitive to oxygen, a carbon- coated fused silica tube or a carbon crucible inside a fused silica tube is often used which prevents the direct contact between the tube wall and reagents.

Chemical vapour transport results in very pure materials. The reaction typically occurs in a sealed ampoule. A transporting agent, added to the sealed ampoule, produces a volatile intermediate species from the solid reactant. For metal oxides, the transporting agent is usually Cl₂ or HCl. The ampoule has a temperature gradient, and, as the gaseous reactant travels along the gradient, it eventually deposits as a crystal. An example of an industrially-used chemical vapor transport reaction is the Mond process. The Mond process involves heating impure nickel in a stream of carbon monoxide to produce pure nickel.