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In
crystallography Crystallography is the branch of science devoted to the study of molecular and crystalline structure and properties. The word ''crystallography'' is derived from the Ancient Greek word (; "clear ice, rock-crystal"), and (; "to write"). In J ...
, a vacancy is a type of point defect in a
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
where an
atom Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
is missing from one of the lattice sites.Ehrhart, P. (1991) "Properties and interactions of atomic defects in metals and alloys", chapter 2, p. 88 in ''Landolt-Börnstein, New Series III'', Vol. 25, Springer, Berlin Crystals inherently possess imperfections, sometimes referred to as
crystallographic defect A crystallographic defect is an interruption of the regular patterns of arrangement of atoms or molecules in Crystal, crystalline solids. The positions and orientations of particles, which are repeating at fixed distances determined by the Crysta ...
s. Vacancies occur naturally in all crystalline materials. At any given temperature, up to the
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state of matter, state from solid to liquid. At the melting point the solid and liquid phase (matter), phase exist in Thermodynamic equilib ...
of the material, there is an equilibrium
concentration In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', '' molar concentration'', '' number concentration'', ...
(ratio of vacant lattice sites to those containing atoms). At the melting point of some metals the ratio can be approximately 1:1000. This temperature dependence can be modelled by :N_ = N \exp\left(\frac\right) where is the vacancy concentration, is the energy required for vacancy formation, is the
Boltzmann constant The Boltzmann constant ( or ) is the proportionality factor that relates the average relative thermal energy of particles in a ideal gas, gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin (K) and the ...
, is the
absolute temperature Thermodynamic temperature, also known as absolute temperature, is a physical quantity which measures temperature starting from absolute zero, the point at which particles have minimal thermal motion. Thermodynamic temperature is typically expres ...
, and is the concentration of atomic sites i.e. : N = \frac where is density, the
Avogadro constant The Avogadro constant, commonly denoted or , is an SI defining constant with an exact value of when expressed in reciprocal moles. It defines the ratio of the number of constituent particles to the amount of substance in a sample, where th ...
, and the
molar mass In chemistry, the molar mass () (sometimes called molecular weight or formula weight, but see related quantities for usage) of a chemical substance ( element or compound) is defined as the ratio between the mass () and the amount of substance ...
. It is the simplest point defect. In this system, an atom is missing from its regular atomic site. Vacancies are formed during
solidification Freezing is a phase transition in which a liquid turns into a solid when its temperature is lowered below its freezing point. For most substances, the melting and freezing points are the same temperature; however, certain substances possess dif ...
due to vibration of atoms, local rearrangement of atoms, plastic deformation and ionic bombardments. The creation of a vacancy can be simply modeled by considering the energy required to break the bonds between an atom inside the crystal and its nearest neighbor atoms. Once that atom is removed from the lattice site, it is put back on the surface of the crystal and some energy is retrieved because new bonds are established with other atoms on the surface. However, there is a net input of energy because there are fewer bonds between surface atoms than between atoms in the interior of the crystal.


Material physics

In most applications vacancy defects are irrelevant to the intended purpose of a material, as they are either too few or spaced throughout a multi-dimensional space in such a way that force or charge can move around the vacancy . In the case of more constrained structures like
carbon nanotube A carbon nanotube (CNT) is a tube made of carbon with a diameter in the nanometre range ( nanoscale). They are one of the allotropes of carbon. Two broad classes of carbon nanotubes are recognized: * ''Single-walled carbon nanotubes'' (''S ...
s however, vacancies and other crystalline defects can significantly weaken the material.


Vacancy Diffusion

Vacancies are essential to atomic diffusion in crystalline solids. Atoms move by hopping into adjacent vacant lattice sites, a process known as vacancy diffusion. This mechanism becomes increasingly important at elevated temperatures, where the equilibrium concentration of vacancies rises exponentially. Vacancy-mediated diffusion governs many processes in materials science, including sintering, creep, and phase transformations. For example, in pure copper at 1000 K, the vacancy concentration is approximately one in 10,000 atoms.Callister, W.D., & Rethwisch, D.G. (2014). *Materials Science and Engineering: An Introduction* (9th ed.). Wiley.


See also

*
Crystallographic defect A crystallographic defect is an interruption of the regular patterns of arrangement of atoms or molecules in Crystal, crystalline solids. The positions and orientations of particles, which are repeating at fixed distances determined by the Crysta ...
* Schottky defect *
Frenkel defect 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 (usually cation) leaves its place in the structure, creating a vacan ...


References


External links


Crystalline Defects in Silicon
{{Crystallography Crystallographic defects