Crystallographic defect

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Crystalline solids exhibit a periodic crystal structure. The positions of atoms or molecules occur on repeating fixed distances, determined by the unit cell parameters. However, the arrangement of atom or molecules in most crystalline materials is not perfect. The regular patterns are interrupted by crystallographic defects.[1][2][3][4]


Point defects

Point defects are defects that occur only at or around a single lattice point. They are not extended in space in any dimension. Strict limits for how small a point defect is, are generally not defined explicitly, but typically these defects involve at most a few extra or missing atoms. Larger defects in an ordered structure are usually considered dislocation loops. For historical reasons, many point defects, especially in ionic crystals, are called centers: for example a vacancy in many ionic solids is called a luminescence center, a color center, or F-center. These dislocations permit ionic transport through crystals leading to electrochemical reactions. These are frequently specified using Kröger–Vink Notation.

  • Vacancy defects are lattice sites which would be occupied in a perfect crystal, but are vacant. If a neighboring atom moves to occupy the vacant site, the vacancy moves in the opposite direction to the site which used to be occupied by the moving atom. The stability of the surrounding crystal structure guarantees that the neighboring atoms will not simply collapse around the vacancy. In some materials, neighboring atoms actually move away from a vacancy, because they experience attraction from atoms in the surroundings. A vacancy (or pair of vacancies in an ionic solid) is sometimes called a Schottky defect.
  • Interstitial defects are atoms that occupy a site in the crystal structure at which there is usually not an atom. They are generally high energy configurations. Small atoms in some crystals can occupy interstices without high energy, such as hydrogen in palladium.
  • A nearby pair of a vacancy and an interstitial is often called a Frenkel defect or Frenkel pair. This is caused when an ion moves into an interstitial site and creates a vacancy.
  • Impurities occur because materials are never 100% pure. In the case of an impurity, the atom is often incorporated at a regular atomic site in the crystal structure. This is neither a vacant site nor is the atom on an interstitial site and it is called a substitutional defect. The atom is not supposed to be anywhere in the crystal, and is thus an impurity. There are two different types of substitutional defects. Isovalent substitution and aliovalent substitution. Isovalent substitution is where the ion that is substituting the original ion is of the same oxidation state as the ion it is replacing. Aliovalent substitution is where the ion that is substituting the original ion is of a different oxidation state as the ion it is replacing. Aliovalent substitutions change the overall charge within the ionic compound, but the ionic compound must be neutral. Therefore a charge compensation mechanism is required. Hence either one of the metals is partially or fully oxidised or reduced, or ion vacancies are created.

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