Crystallographic defect

Last updated October 16, 2023

A crystallographic defect is an interruption of the regular patterns of arrangement of atoms or molecules in crystalline solids. The positions and orientations of particles, which are repeating at fixed distances determined by the unit cell parameters in crystals, exhibit a periodic crystal structure, but this is usually imperfect.^[2]^[3]^[4]^[5] Several types of defects are often characterized: point defects, line defects, planar defects, bulk defects. Topological homotopy establishes a mathematical method of characterization.

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. However, these defects typically 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 (mostly impurities) 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 Defecttypes.png — 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.

Due to fundamental limitations of material purification methods, materials are never 100% pure, which by definition induces defects in crystal structure. 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. In some cases where the radius of the substitutional atom (ion) is substantially smaller than that of the atom (ion) it is replacing, its equilibrium position can be shifted away from the lattice site. These types of substitutional defects are often referred to as off-center ions. 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 than 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^[6]^[7] occur in an ordered alloy or compound when atoms of different type exchange positions. 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 a B atom, and is thus an antisite defect. 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. Compounddefects.png — Schematic illustration of defects in a compound solid, using GaAs as an example.

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.^[8] Moreover, defects can also be defined in amorphous solids based on empty or densely packed local atomic neighbourhoods, and the properties of such 'defects' can be shown to be similar to normal vacancies and interstitials in crystals.^[9]^[10]^[11]
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.^[12]^[13]

Line defects

Line defects can be described by gauge theories.

Dislocations are linear defects, around which the atoms of the crystal lattice are misaligned.^[14] There are two basic types of dislocations, the edge dislocation and the screw dislocation. "Mixed" dislocations, combining aspects of both types, are also common.

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 crystallographic 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 were thought to play a role only in liquid crystals, but recent developments suggest that they might have a role also in solid materials, e.g. leading to the self-healing of cracks.^[15]

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.
Antiphase 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 (hexagonal close-packed crystal), an antiphase boundary takes the form of ABABBABA.
Stacking faults occur in a number of crystal structures, but the common example is in close-packed structures. They are formed by a local deviation of the stacking sequence of layers in a crystal. An example would be the ABABCABAB stacking sequence.
A twin boundary is a defect that introduces a plane of mirror symmetry in the ordering of a crystal. For example, in cubic close-packed crystals, the stacking sequence of a twin boundary would be ABCABCBACBA.
On planes of single crystals, steps between atomically flat terraces can also be regarded as planar defects. It has been shown that such defects and their geometry have significant influence on the adsorption of organic molecules^[16]

Bulk defects

Three-dimensional macroscopic or bulk defects, such as pores, cracks, or inclusions
Voids — small regions where there are no atoms, and which 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.^[17]

Computer simulation methods

Density functional theory, classical molecular dynamics and kinetic Monte Carlo ^[18] simulations are widely used to study the properties of defects in solids with computer simulations.^[9]^[10]^[11]^[19]^[20]^[21]^[22] Simulating jamming of hard spheres of different sizes and/or in containers with non-commeasurable sizes using the Lubachevsky–Stillinger algorithm can be an effective technique for demonstrating some types of crystallographic defects.^[23]

Related Research Articles

<span class="mw-page-title-main">Crystal structure</span> Ordered arrangement of atoms, ions, or molecules in a crystalline material

In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns that repeat along the principal directions of three-dimensional space in matter.

<span class="mw-page-title-main">Supersolid</span> State of matter

In condensed matter physics, a supersolid is a spatially ordered material with superfluid properties. In the case of helium-4, it has been conjectured since the 1960s that it might be possible to create a supersolid. Starting from 2017, a definitive proof for the existence of this state was provided by several experiments using atomic Bose–Einstein condensates. The general conditions required for supersolidity to emerge in a certain substance are a topic of ongoing research.

An F center or Farbe center is a type of crystallographic defect in which an anionic vacancy in a crystal lattice is occupied by one or more unpaired electrons. Electrons in such a vacancy in a crystal lattice tend to absorb light in the visible spectrum such that a material that is usually transparent becomes colored. The greater the number of F centers, the more intense the color of the compound. F centers are a type of color center.

Diamond is the allotrope of carbon in which the carbon atoms are arranged in the specific type of cubic lattice called diamond cubic. It is a crystal that is transparent to opaque and which is generally isotropic. Diamond is the hardest naturally occurring material known. Yet, due to important structural brittleness, bulk diamond's toughness is only fair to good. The precise tensile strength of bulk diamond is little known; however, compressive strength up to 60 GPa has been observed, and it could be as high as 90–100 GPa in the form of micro/nanometer-sized wires or needles, with a corresponding maximum tensile elastic strain in excess of 9%. The anisotropy of diamond hardness is carefully considered during diamond cutting. Diamond has a high refractive index (2.417) and moderate dispersion (0.044) properties that give cut diamonds their brilliance. Scientists classify diamonds into four main types according to the nature of crystallographic defects present. Trace impurities substitutionally replacing carbon atoms in a diamond's crystal structure, and in some cases structural defects, are responsible for the wide range of colors seen in diamond. Most diamonds are electrical insulators and extremely efficient thermal conductors. Unlike many other minerals, the specific gravity of diamond crystals (3.52) has rather small variation from diamond to diamond.

<span class="mw-page-title-main">Crystallographic defects in diamond</span>

Imperfections in the crystal lattice of diamond are common. Such defects may be the result of lattice irregularities or extrinsic substitutional or interstitial impurities, introduced during or after the diamond growth. The defects affect the material properties of diamond and determine to which type a diamond is assigned; the most dramatic effects are on the diamond color and electrical conductivity, as explained by the electronic band structure.

In materials science, hardness is a measure of the resistance to localized plastic deformation, such as an indentation or a scratch (linear), induced mechanically either by pressing or abrasion. In general, different materials differ in their hardness; for example hard metals such as titanium and beryllium are harder than soft metals such as sodium and metallic tin, or wood and common plastics. Macroscopic hardness is generally characterized by strong intermolecular bonds, but the behavior of solid materials under force is complex; therefore, hardness can be measured in different ways, such as scratch hardness, indentation hardness, and rebound hardness. Hardness is dependent on ductility, elastic stiffness, plasticity, strain, strength, toughness, viscoelasticity, and viscosity. Common examples of hard matter are ceramics, concrete, certain metals, and superhard materials, which can be contrasted with soft matter.

In crystallography, a Frenkel defect is a type of point defect in crystalline solids, named after its discoverer Yakov Frenkel. The defect forms when an atom or smaller ion leaves its place in the lattice, creating a vacancy and becomes an interstitial by lodging in a nearby location. In elemental systems, they are primarily generated during particle irradiation, as their formation enthalpy is typically much higher than for other point defects, such as vacancies, and thus their equilibrium concentration according to the Boltzmann distribution is below the detection limit. In ionic crystals, which usually possess low coordination number or a considerable disparity in the sizes of the ions, this defect can be generated also spontaneously, where the smaller ion is dislocated. Similar to a Schottky defect the Frenkel defect is a stoichiometric defect. In ionic compounds, the vacancy and interstitial defect involved are oppositely charged and one might expect them to be located close to each other due to electrostatic attraction. However, this is not likely the case in real material due to smaller entropy of such a coupled defect, or because the two defects might collapse into each other. Also, because such coupled complex defects are stoichiometric, their concentration will be independent of chemical conditions.

A Schottky defect is an excitation of the site occupations in a crystal lattice leading to point defects named after Walter H. Schottky. In ionic crystals, this defect forms when oppositely charged ions leave their lattice sites and become incorporated for instance at the surface, creating oppositely charged vacancies. These vacancies are formed in stoichiometric units, to maintain an overall neutral charge in the ionic solid.

<span class="mw-page-title-main">Bubble raft</span> Array of bubbles

A bubble raft is an array of bubbles. It demonstrates materials' microstructural and atomic length-scale behavior by modelling the {111} plane of a close-packed crystal. A material's observable and measurable mechanical properties strongly depend on its atomic and microstructural configuration and characteristics. This fact is intentionally ignored in continuum mechanics, which assumes a material to have no underlying microstructure and be uniform and semi-infinite throughout.

A charge density wave (CDW) is an ordered quantum fluid of electrons in a linear chain compound or layered crystal. The electrons within a CDW form a standing wave pattern and sometimes collectively carry an electric current. The electrons in such a CDW, like those in a superconductor, can flow through a linear chain compound en masse, in a highly correlated fashion. Unlike a superconductor, however, the electric CDW current often flows in a jerky fashion, much like water dripping from a faucet due to its electrostatic properties. In a CDW, the combined effects of pinning and electrostatic interactions likely play critical roles in the CDW current's jerky behavior, as discussed in sections 4 & 5 below.

In materials science, an interstitial defect is a type of point crystallographic defect where an atom of the same or of a different type, occupies an interstitial site in the crystal structure. When the atom is of the same type as those already present they are known as a self-interstitial defect. Alternatively, small atoms in some crystals may occupy interstitial sites, such as hydrogen in palladium. Interstitials can be produced by bombarding a crystal with elementary particles having energy above the displacement threshold for that crystal, but they may also exist in small concentrations in thermodynamic equilibrium. The presence of interstitial defects can modify the physical and chemical properties of a material.

The nitrogen-vacancy center is one of numerous point defects in diamond. Its most explored and useful property is its photoluminescence, which allows observers to read out its spin-state. The NV center's electron spin, localized at atomic scales, can be manipulated at room temperature by external factors such as magnetic, or electric fields, microwave radiation, or optical light, resulting in sharp resonances in the intensity of the photoluminescence. These resonances can be explained in terms of electron spin related phenomena such as quantum entanglement, spin–orbit interaction and Rabi oscillations, and analysed using advanced quantum optics theory. An individual NV center can be used as a basic unit for a quantum computer, a qubit, and used for quantum cryptography. Further potential applications in novel fields of electronics and sensing include spintronics, masers, and quantum sensors. If the charge is not specified the term "NV center" refers to the negatively charged NV⁻ center.

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In condensed-matter physics, a collision cascade is a set of nearby adjacent energetic collisions of atoms induced by an energetic particle in a solid or liquid.

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In condensed-matter physics, the binary collision approximation (BCA) is a heuristic used to more efficiently simulate the penetration depth and defect production by energetic ions in solids. In the method, the ion is approximated to travel through a material by experiencing a sequence of independent binary collisions with sample atoms (nuclei). Between the collisions, the ion is assumed to travel in a straight path, experiencing electronic stopping power, but losing no energy in collisions with nuclei.

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Off-center ions in crystals are substitutional impurity ions whose equilibrium position is shifted away from the regular lattice site. The magnitude of the shift typically ranges from 0.2 to 1.0 Å. There are two possible mechanisms that can cause impurity ion displacement. If the impurity ion is smaller than the regular ion, the displacement arises because the repulsive forces between the impurity ion and its nearest neighbors stabilizing the ion at the regular site are strongly weakened. If the impurity ion is bigger than the regular ion, the displacement arises because of different covalency of the chemical bonds with the nearest neighbors for the impurity and regular ions.

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