Solid-state chemistry

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Solid-state chemistry, also sometimes referred as materials chemistry, is the study of the
synthesis, structure, and properties of solid phase materials, particularly, but not necessarily
exclusively of, non-molecular solids. 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 characterisation.
Solids can be classified as crystalline or amorphous on basis of the nature of order present in the
arrangement of their constituent particles.

History[edit]
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, well ahead of academic curiosity. 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 crystallographyin the early 1900s by William
Lawrence Bragg enabled further 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 this, he has sometimes been
referred to as the father of solid state chemistry.[1]

Synthetic methods[edit]
Given the diversity of solid state compounds, an equally diverse array of methods[2] are used for their
preparation. For organic materials, such as charge transfer salts, the methods operates near room
temperature and are often similar to the techniques of organic synthesis. Redox reactions are
sometimes conducted by electrocrystallisation, as illustrated by the preparation of the Bechgaard
salts from tetrathiafulvalene.
Oven techniques[edit]
For thermally robust materials, high temperature methods are often employed. For example, bulk
solids are prepared using tube furnaces, which allow reactions to be conducted up to ca. 1100 °C.
Special equipment e.g. ovens consisting of a tantalum tube through which an electric current is
passed can be used for even higher temperatures up to 2000 °C. Such high temperatures are at
times required to induce diffusion of the reactants, but this depends strongly on the system studied.
Some solid state reactions already proceed at temperatures as low as 100 °C.
Melt methods[edit]
One method often employed is to melt the reactants together and then later anneal the solidified
melt. If volatile reactants are involved the reactants are often put in an ampoule that is evacuated -
ofnt mixture cold e.g. by keeping the bottom of the ampoule in liquid nitrogen- and then sealed. The
sealed ampoule is then put in an oven and given a certain heat treatment....
Solution methods[edit]
It is possible to use solvents to prepare solids by precipitation or by evaporation. At times the solvent
is used hydrothermal that is under pressure at temperatures higher than the normal boiling point. A
variation on this theme is the use of flux methods, where a salt of relatively low melting point is
added to the mixture to act as a high temperature solvent in which the desired reaction can take
place. this can be very useful
Gas reactions[edit]
Many solids react vigorously with reactive gas species like chlorine, iodine, oxygen etc. Others
form adducts with other gases, e.g. CO or ethylene. Such reactions are often carried out in a tube
that is open ended on both sides and through which the gas is passed. A variation of this is to let the
reaction take place inside a measuring device such as a TGA. In that case stoichiometric information
can be obtained during the reaction, which helps identify the products.
A special case of a gas reaction is a chemical transport reaction. These are often carried out in a
sealed ampoule to which a small amount of a transport agent, e.g. iodine is added. The ampoule is
then placed in a zone oven. This is essentially two tube ovens attached to each other which allows a
temperature gradient to be imposed. Such a method can be used to obtain the product in the form of
single crystals suitable for structure determination by X-ray diffraction.
Chemical vapour deposition is a high temperature method that is widely employed for the
preparation of coatings and semiconductors from molecular precursors
Air and moisture sensitive materials[edit]
Many solids are hygroscopic and/or oxygen sensitive. Many halides e.g. are very 'thirsty' and can
only be studied in their anhydrous form if they are handled in a glove box filled with dry (and/or
oxygen-free) gas, usually nitrogen.

Characterization[edit]
New phases, phase diagrams, structures[edit]
The synthetic methodology and the characterization of the product often go hand in hand in the
sense that not one but a series of reaction mixtures are prepared and subjected to heat treatment.
The stoichiometry is typically varied in a systematic way to find which stoichiometries will lead to new
solid compounds or to solid solutions between known ones. A prime method to characterize the
reaction products is powder diffraction, because many solid state reactions will produce
polycristalline ingots or powders. Powder diffraction will facilitate the identification of known phases
in the mixture. If a pattern is found that is not known in the diffraction data libraries an attempt can be
made to index the pattern, i.e. to identify the symmetry and the size of the unit cell. (If the product is
not crystalline the characterization is typically much more difficult.)
Once the unit cell of a new phase is known, the next step is to establish the stoichiometry of the
phase. This can be done in a number of ways. Sometimes the composition of the original mixture will
give a clue, if one finds only one product -a single powder pattern- or if one was trying to make a
phase of a certain composition by analogy to known materials but this is rare. Often considerable
effort in refining the synthetic methodology is required to obtain a pure sample of the new material. If
it is possible to separate the product from the rest of the reaction mixture elemental analysis can be
used. Another way involves SEM and the generation of characteristic X-rays in the electron beam.
The easiest way to solve the structure is by using single crystal X-ray diffraction.
The latter often requires revisiting and refining the preparative procedures and that is linked to the
question which phases are stable at what composition and what stoichiometry. In other words, what
does the phase diagram looks like.[3] An important tool in establishing this is thermal
analysis techniques like DSC or DTA and increasingly also, thanks to the advent
of synchrotrons temperature-dependent powder diffraction. Increased knowledge of the phase
relations often leads to further refinement in synthetic procedures in an iterative way. New phases
are thus characterized by their melting points and their stoichiometric domains. The latter is
important for the many solids that are non-stoichiometric compounds. The cell parameters obtained
from XRD are particularly helpful to characterize the homogeneity ranges of the latter.
Further characterization[edit]
In many -but certainly not all- cases new solid compounds are further characterized[4] by a variety of
techniques that straddle the fine line that (hardly) separates solid-state chemistry from solid-state
physics.
Optical properties[edit]
For non-metallic materials, it is often possible to obtain UV/VIS spectra. In the case of
semiconductors that will give an idea of the band gap.