Solid state lattices, defects

Chapter 6 Defects in solid state lattices an introduction 177... 

There are many type of emitters gas phase atoms and ions molecules in the gas, solution, or solid phase metal ions as an integral part of a solid state lattice energy traps or activator sites, which may be a specific ion or site defect, in a semiconductor or other sohd conjugated polymers semiconductors as either a solid, or as a colloidal dispersion in some other medium or solution and hot metals. In aU but the latter three cases emission is from a locahsed emitter, with both states involved in the transition localised in a small region of space, on an atom, ion, or molecule. However, for semiconductors, some emissive polymers, and hot metals, the states involved in the transition extend across a relatively large region of space and a large number of atoms. 

Dislocation theory as a portion of the subject of solid-state physics is somewhat beyond the scope of this book, but it is desirable to examine the subject briefly in terms of its implications in surface chemistry. Perhaps the most elementary type of defect is that of an extra or interstitial atom—Frenkel defect [110]—or a missing atom or vacancy—Schottky defect [111]. Such point defects play an important role in the treatment of diffusion and electrical conductivities in solids and the solubility of a salt in the host lattice of another or different valence type [112]. Point defects have a thermodynamic basis for their existence in terms of the energy and entropy of their formation, the situation is similar to the formation of isolated holes and erratic atoms on a surface. Dislocations, on the other hand, may be viewed as an organized concentration of point defects they are lattice defects and play an important role in the mechanism of the plastic deformation of solids. Lattice defects or dislocations are not thermodynamic in the sense of the point defects their formation is intimately connected with the mechanism of nucleation and crystal growth (see Section IX-4), and they constitute an important source of surface imperfection. 

An additional problem is encountered when the isolated solid is non-stoichiometric. For example, precipitating Mn + as Mn(OH)2, followed by heating to produce the oxide, frequently produces a solid with a stoichiometry of MnO ) where x varies between 1 and 2. In this case the nonstoichiometric product results from the formation of a mixture of several oxides that differ in the oxidation state of manganese. Other nonstoichiometric compounds form as a result of lattice defects in the crystal structure. ... 

The fluid mechanics origins of shock-compression science are reflected in the early literature, which builds upon fluid mechanics concepts and is more concerned with basic issues of wave propagation than solid state materials properties. Indeed, mechanical wave measurements, upon which much of shock-compression science is built, give no direct information on defects. This fluids bias has led to a situation in which there appears to be no published terse description of shock-compressed solids comparable to Kormer s for the perfect lattice. Davison and Graham described the situation as an elastic fluid approximation. A description of shock-compressed solids in terms of the benign shock paradigm might perhaps be stated as ... 

Conventional physical descriptions of materials in the solid state are concerned with solids in which properties are controlled or substantially influenced by the crystal lattice. When defects are treated in typical solid state studies, they are considered to modify and cause local perturbations to bonding controlled by lattice properties. In these cases, defect concentrations are typically low and usually characterized as either point, linear, or higher-order defects, which are seldom encountered together. 

In the first chapter, we defined the nature of a solid in terms of its building blocks plus its structure and symmetry. In the second chapter, we defined how structures of solids are determined. In this chapter, we will examine how the solid actually occurs in Nature. Consider that a solid is made up of atoms or ions that are held together by covalent/ionic forces. It is axiomatic that atoms cannot be piled together and forced to form a periodic structure without mistakes being made. The 2nd Law of Thermodynamics demands this. Such mistakes seriously affect the overall properties of the solid. Thus, defeets in the lattice are probably the most important aspect of the solid state since it is impossible to avoid defects at the atomistic level. Two factors are involved ... 

Crystalline solids are built up of regular arrangements of atoms in three dimensions these arrangements can be represented by a repeat unit or motif called a unit cell. A unit cell is defined as the smallest repeating unit that shows the fuU symmetry of the crystal structure. A perfect crystal may be defined as one in which all the atoms are at rest on their correct lattice positions in the crystal structure. Such a perfect crystal can be obtained, hypothetically, only at absolute zero. At all real temperatures, crystalline solids generally depart from perfect order and contain several types of defects, which are responsible for many important solid-state phenomena, such as diffusion, electrical conduction, electrochemical reactions, and so on. Various schemes have been proposed for the classification of defects. Here the size and shape of the defect are used as a basis for classification. 

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