Crystallographic defect

 

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Crystalline solids have a very regular atomic structure: that is, the local positions of atoms with respect to each other are repeated at the atomic scale. These arrangements are called crystal structures, and their study is called crystallography. However, most crystalline materials are not perfect: the regular pattern of atomic arrangement is interrupted by crystallographic defects. . The various types of defects are enumerated here.

Point defects

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Point defects are defects which are not extended in space in any dimension. There is no strict limit for how small a "point" defect should be, but typically the term is used to describe defects which involve at most a few extra or missing atoms without an ordered structure of the defective positions. 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 the vacancy in many ionic solids is called an F-center. These dislocations allow for ionic transport through crystals leading to electrochemical reactions which are frequently specified using Kröger–Vink Notation.

• Vacancies are sites which are usually occupied by an atom but which are unoccupied. 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 can form better bonds with atoms in the other directions. A vacancy (or pair of vacancies in an ionic solid) is sometimes called a Schottky defect.

• Interstitials are atoms which 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.

Schematic illustration of some simple point defect types in a monatomic solid

• 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.

• Antisite defects occur in an ordered alloy or compound. For example, some alloys have a regular structure in which every other atom is a different species; for illustration assume that type A atoms sit on the corners of a cubic lattice, and type B atoms sit in the center of the cubes. If one cube has an A atom at its center, the atom is on a site usually occupied by an atom, but it is not the correct type. This is neither a vacancy nor an interstitial, nor an impurity.

• Topological defects are regions in a crystal where the normal chemical bonding environment is topologically different from the surroundings. For instance, in a perfect sheet of graphite (graphene) all atoms are in rings containing six atoms. If the sheet contains regions where the number of atoms in a ring is different from six, while the total number of atoms remains the same, a topological defect has formed. An example is the Stone Wales defect in nanotubes, which consists of two adjacent 5-membered and two 7-membered atom rings.

Schematic illustration of defects in a compound solid, using GaAs as an example.

• Also amorphous solids may contain defects. These are naturally somewhat hard to define, but sometimes their nature can be quite easily understood. For instance, in ideally bonded amorphous silica all Si atoms have 4 bonds to O atoms and all O atoms have 2 bonds to Si atom. Thus e.g. an O atom with only one Si bond (a dangling bond) can be considered a defect in silica.

• Complexes can form between different kinds of point defects. For example, if a vacancy encounters an impurity, the two may bind together if the impurity is too large for the lattice. Interstitials can form 'split interstitial' or 'dumbbell' structures where two atoms effectively share an atomic site, resulting in neither atom actually occupying the site.

Line defects

Line defects can be described by gauge theories.

• Dislocations are linear defects around which some of the atoms of the crystal lattice are misaligned.

There are two basic types of dislocations, the edge dislocation and the screw dislocation. "Mixed" dislocations, combining aspects of both types, are also common.

An edge dislocation is shown. The dislocation line is presented in blue, the Burgers vector b in black.

Edge dislocations are caused by the termination of a plane of atoms in the middle of a crystal. In such a case, the adjacent planes are not straight, but instead bend around the edge of the terminating plane so that the crystal structure is perfectly ordered on either side. The analogy with a stack of paper is apt: if a half a piece of paper is inserted in a stack of paper, the defect in the stack is only noticeable at the edge of the half sheet.
The screw dislocation is more difficult to visualise, but basically comprises a structure in which a helical path is traced around the linear defect (dislocation line) by the atomic planes of atoms in the crystal lattice.
The presence of dislocation results in lattice strain (distortion). The direction and magnitude of such distortion is expressed in terms of a Burgers vector (b). For an edge type, b is perpendicular to the dislocation line, whereas in the cases of the screw type it is parallel. In metallic materials, b is aligned with close-packed crytallographic directions and its magnitude is equivalent to one interatomic spacing.
Dislocations can move if the atoms from one of the surrounding planes break their bonds and rebond with the atoms at the terminating edge.
It is the presence of dislocations and their ability to readily move (and interact) under the influence of stresses induced by external loads that leads to the characteristic malleability of metallic materials.
Dislocations can be observed using transmission electron microscopy, field ion microscopy and atom probe techniques. Deep level transient spectroscopy has been used for studying the electrical activity of dislocations in semiconductors, mainly silicon.

• Disclinations are line defects corresponding to "adding" or "subtracting" an angle around a line. Basically, this means that if you track the crystal orientation around the line defect, you get a rotation. Usually they play a role only in liquid crystals.

Planar defects

• Grain boundaries occur where the crystallographic direction of the lattice abruptly changes. This usually occurs when two crystals begin growing separately and then meet.

• Anti-phase boundaries occur in ordered alloys: in this case, the crystallographic direction remains the same, but each side of the boundary has an opposite phase: For example if the ordering is usually ABABABAB, an anti phase boundary takes the form of ABABBABA.

• Stacking faults occur in a number of crystal structures, but the common example is in close-packed structures. Face-centered cubic (fcc) structures differ from hexagonal close packed (hcp) structures only in stacking order: both structures have close packed atomic planes with sixfold symmetry—the atoms form equilateral triangles. When stacking one of these layers on top of another, the atoms are not directly on top of one another—the first two layers are identical for hcp and fcc, and labelled AB. If the third layer is placed so that its atoms are directly above those of the first layer, the stacking will be ABA—this is the hcp structure, and it continues ABABABAB. However there is another location for the third layer, such that its atoms are not above the first layer. Instead, the fourth layer is placed so that its atoms are directly above the first layer. This produces the stacking ABCABCABC, and is actually a cubic arrangement of the atoms. A stacking fault is a one or two layer interruption in the stacking sequence, for example if the sequence ABCABABCAB were found in an fcc structure.

 Bulk defects

• Voids are small regions where there are no atoms, and can be thought of as clusters of vacancies.
  
• Impurities can cluster together to form small regions of a different phase. These are often called precipitates.

 Mathematical classification methods

A successful mathematical classification method for physical lattice defects, which works not only with the theory of dislocations and other defects in crystals but also, e.g., for disclinations in liquid crystals and for excitations in superfluid ³He, is the topological homotopy theory.

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