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Pyroelectricity (from the two Greek words ''pyr'' meaning fire, and
electricity
Electricity is the set of physical phenomena associated with the presence and motion of matter that has a property of electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as describ ...
) is a property of certain crystals which are naturally electrically polarized and as a result contain large electric fields. Pyroelectricity can be described as the ability of certain materials to generate a temporary
voltage
Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a static electric field, it corresponds to the work needed per unit of charge to ...
when they are heated or cooled.
[ The change in temperature modifies the positions of the atoms slightly within the ]crystal structure
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 ...
, such that the polarization of the material changes. This polarization change gives rise to a voltage across the crystal. If the temperature stays constant at its new value, the pyroelectric voltage gradually disappears due to leakage current
In electronics, leakage is the gradual transfer of electrical energy across a boundary normally viewed as insulating, such as the spontaneous discharge of a charged capacitor, magnetic coupling of a transformer with other components, or flow of cu ...
. The leakage can be due to electrons moving through the crystal, ions moving through the air, or current leaking through a voltmeter
A voltmeter is an instrument used for measuring electric potential difference between two points in an electric circuit. It is connected in parallel. It usually has a high resistance so that it takes negligible current from the circuit.
A ...
attached across the crystal.
Explanation
Pyroelectric charge in mineral
In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
s develops on the opposite faces of asymmetric crystals. The direction in which the propagation of the charge tends is usually constant throughout a pyroelectric material, but, in some materials, this direction can be changed by a nearby electric field. These materials are said to exhibit ferroelectricity
Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field. All ferroelectrics are also piezoelectric and pyroelectric, with the a ...
. All known pyroelectric materials are also piezoelectric
Piezoelectricity (, ) is the electric charge that accumulates in certain solid materials—such as crystals, certain ceramics, and biological matter such as bone, DNA, and various proteins—in response to applied mechanical stress. The word '' ...
. Despite being pyroelectric, novel materials such as boron aluminum nitride (BAlN) and boron gallium nitride (BGaN) have zero piezoelectric response for strain along the c-axis at certain compositions, the two properties being closely related. However, note that some piezoelectric materials have a crystal symmetry that does not allow pyroelectricity.
Pyroelectric materials are mostly hard and crystals, however, soft pyroelectricity can be achieved by using electret
An electret (formed as a portmanteau of ''electr-'' from "electricity" and ''-et'' from "magnet") is a dielectric material that has a quasi-permanent electric charge or dipole polarization (electrostatics), polarisation. An electret generates int ...
s.
Pyroelectricity is measured as the change in net polarization (a vector) proportional to a change in temperature. The total pyroelectric coefficient measured at constant stress is the sum of the pyroelectric coefficients at constant strain (primary pyroelectric effect) and the piezoelectric contribution from thermal expansion (secondary pyroelectric effect). Under normal circumstances, even polar materials do not display a net dipole moment. As a consequence there are no electric dipole equivalents of bar magnets because the intrinsic dipole moment is neutralized by "free" electric charge that builds up on the surface by internal conduction or from the ambient atmosphere. Polar crystals only reveal their nature when perturbed in some fashion that momentarily upsets the balance with the compensating surface charge.
Spontaneous polarization is temperature dependent, so a good perturbation probe is a change in temperature which induces a flow of charge to and from the surfaces. This is the pyroelectric effect. All polar crystals are pyroelectric, so the 10 polar crystal classes are sometimes referred to as the pyroelectric classes. Pyroelectric materials can be used as infrared and millimeter wavelength radiation detectors.
An electret
An electret (formed as a portmanteau of ''electr-'' from "electricity" and ''-et'' from "magnet") is a dielectric material that has a quasi-permanent electric charge or dipole polarization (electrostatics), polarisation. An electret generates int ...
is the electrical equivalent of a permanent magnet.
Mathematical description
The pyroelectric coefficient may be described as the change in the spontaneous polarization vector with temperature:
where ''pi'' (Cm−2K−1) is the vector for the pyroelectric coefficient.
History
The first reference to the pyroelectric effect is found in writings by Theophrastus
Theophrastus (; grc-gre, Θεόφραστος ; c. 371c. 287 BC), a Greek philosopher and the successor to Aristotle in the Peripatetic school. He was a native of Eresos in Lesbos.Gavin Hardy and Laurence Totelin, ''Ancient Botany'', Routle ...
(c. 314 BC), who noted that ''lyngourion'', tourmaline
Tourmaline ( ) is a crystalline silicate mineral group in which boron is compounded with elements such as aluminium, iron, magnesium, sodium, lithium, or potassium. Tourmaline is a gemstone and can be found in a wide variety of colors.
The te ...
, could attract sawdust or bits of straw when heated. Tourmaline's properties were rediscovered in 1707 by Johann Georg Schmidt, who noted that the stone attracted only hot ashes, not cold ones. In 1717 Louis Lemery noticed, as Schmidt had, that small scraps of non-conducting material were first attracted to tourmaline, but then repelled by it once they contacted the stone. In 1747 Linnaeus
Carl Linnaeus (; 23 May 1707 – 10 January 1778), also known after his ennoblement in 1761 as Carl von Linné Blunt (2004), p. 171. (), was a Swedish botanist, zoologist, taxonomist, and physician who formalised binomial nomenclature, the ...
first related the phenomenon to electricity (he called tourmaline ''Lapidem Electricum'', "the electric stone"), although this was not proven until 1756 by Franz Ulrich Theodor Aepinus
Franz Ulrich Theodor Aepinus (13 December 172410 August 1802) was a German mathematician, scientist, and natural philosopher residing in the Russian Empire. Aepinus is best known for his researches, theoretical and experimental, in electricity an ...
.
Research into pyroelectricity became more sophisticated in the 19th century. In 1824 Sir David Brewster
Sir David Brewster KH PRSE FRS FSA Scot FSSA MICE (11 December 178110 February 1868) was a British scientist, inventor, author, and academic administrator. In science he is principally remembered for his experimental work in physical optics ...
gave the effect the name it has today. Both William Thomson in 1878 and Woldemar Voigt
Woldemar Voigt (; 2 September 1850 – 13 December 1919) was a German physicist, who taught at the Georg August University of Göttingen. Voigt eventually went on to head the Mathematical Physics Department at Göttingen and was succeeded in ...
in 1897 helped develop a theory for the processes behind pyroelectricity. Pierre Curie
Pierre Curie ( , ; 15 May 1859 – 19 April 1906) was a French physicist, a pioneer in crystallography, magnetism, piezoelectricity, and radioactivity. In 1903, he received the Nobel Prize in Physics with his wife, Marie Curie, and Henri Becq ...
and his brother, Jacques Curie
Jacques Curie (29 October 1855 – 19 February 1941) was a French physicist and professor of mineralogy at the University of Montpellier. Along with his younger brother, Pierre Curie, he studied pyroelectricity in the 1880s, leading to their d ...
, studied pyroelectricity in the 1880s, leading to their discovery of some of the mechanisms behind piezoelectricity.
Crystal classes
All crystal structures
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, macrosc ...
belong to one of thirty-two crystal classes based on the number of rotational axes and reflection planes they possess that leave the crystal structure unchanged (point groups
In geometry, a point group is a mathematical group of symmetry operations ( isometries in a Euclidean space) that have a fixed point in common. The coordinate origin of the Euclidean space is conventionally taken to be a fixed point, and every ...
). Of the thirty-two crystal classes, twenty-one are non-centrosymmetric (not having a centre of symmetry A fixed point of an isometry group is a point that is a fixed point for every isometry in the group. For any isometry group in Euclidean space the set of fixed points is either empty or an affine space.
For an object, any unique centre and, more g ...
). Of these twenty-one, twenty exhibit direct piezoelectricity
Piezoelectricity (, ) is the electric charge that accumulates in certain solid materials—such as crystals, certain ceramics, and biological matter such as bone, DNA, and various proteins—in response to applied mechanical stress. The word ''p ...
, the remaining one being the cubic class 432. Ten of these twenty piezoelectric classes are polar, i.e., they possess a spontaneous polarization, having a dipole in their unit cell, and exhibit pyroelectricity. If this dipole can be reversed by the application of an electric field, the material is said to be ferroelectric
Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field. All ferroelectrics are also piezoelectric and pyroelectric, with the ad ...
. Any dielectric material develops a dielectric polarization (electrostatics)
In classical electromagnetism, polarization density (or electric polarization, or simply polarization) is the vector field that expresses the density of permanent or induced electric dipole moments in a dielectric material. When a dielectric is ...
when an electric field is applied, but a substance which has such a natural charge separation even in the absence of a field is called a polar material. Whether or not a material is polar is determined solely by its crystal structure. Only 10 of the 32 point groups are polar. All polar crystals are pyroelectric, so the ten polar crystal classes are sometimes referred to as the pyroelectric classes.
Piezoelectric crystal classes: 1, 2, m, 222, mm2, 4, -4, 422, 4mm, -42m, 3, 32, 3m, 6, -6, 622, 6mm, -62m, 23, -43m
Pyroelectric: 1, 2, m, mm2, 3, 3m, 4, 4mm, 6, 6mm
Related effects
Two effects which are closely related to pyroelectricity are ferroelectricity
Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field. All ferroelectrics are also piezoelectric and pyroelectric, with the a ...
and piezoelectricity
Piezoelectricity (, ) is the electric charge that accumulates in certain solid materials—such as crystals, certain ceramics, and biological matter such as bone, DNA, and various proteins—in response to applied mechanical stress. The word ''p ...
. Normally materials are very nearly electrically neutral on the macroscopic level. However, the positive and negative charges which make up the material are not necessarily distributed in a symmetric manner. If the sum of charge times distance for all elements of the basic cell does not equal zero the cell will have an electric dipole moment (a vector quantity). The dipole moment per unit volume is defined as the dielectric polarization. If this dipole moment changes with the effect of applied temperature changes, applied electric field, or applied pressure, the material is pyroelectric, ferroelectric, or piezoelectric, respectively.
The ferroelectric effect is exhibited by materials which possess an electric polarization in the absence of an externally applied electric field such that the polarization can be reversed if the electric field is reversed. Since all ferroelectric materials exhibit a spontaneous polarization, all ferroelectric materials are also pyroelectric (but not all pyroelectric materials are ferroelectric).
The piezoelectric effect is exhibited by crystals (such as quartz or ceramic) for which an electric voltage across the material appears when pressure is applied. Similar to pyroelectric effect, the phenomenon is due to the asymmetric structure of the crystals that allows ions to move more easily along one axis than the others. As pressure is applied, each side of the crystal takes on an opposite charge, resulting in a voltage drop across the crystal.
Pyroelectricity should not be confused with thermoelectricity
The thermoelectric effect is the direct conversion of temperature differences to electric voltage and vice versa via a thermocouple. A thermoelectric device creates a voltage when there is a different temperature on each side. Conversely, when ...
: In a typical demonstration of pyroelectricity, the whole crystal is changed from one temperature to another, and the result is a temporary voltage across the crystal. In a typical demonstration of thermoelectricity, one part of the device is kept at one temperature and the other part at a different temperature, and the result is a ''permanent'' voltage across the device as long as there is a temperature difference. Both effects convert temperature change to electrical potential, but the pyroelectric effect converts temperature change over ''time'' into electrical potential, while the thermoelectric effect converts temperature change with ''position'' into electrical potential.
Pyroelectric materials
Although artificial pyroelectric materials have been engineered, the effect was first discovered in minerals such as tourmaline
Tourmaline ( ) is a crystalline silicate mineral group in which boron is compounded with elements such as aluminium, iron, magnesium, sodium, lithium, or potassium. Tourmaline is a gemstone and can be found in a wide variety of colors.
The te ...
. The pyroelectric effect is also present in bone
A bone is a rigid organ that constitutes part of the skeleton in most vertebrate animals. Bones protect the various other organs of the body, produce red and white blood cells, store minerals, provide structure and support for the body, ...
and tendon
A tendon or sinew is a tough, high-tensile-strength band of dense fibrous connective tissue that connects muscle to bone. It is able to transmit the mechanical forces of muscle contraction to the skeletal system without sacrificing its ability ...
.
The most important example is gallium nitride
Gallium nitride () is a binary III/ V direct bandgap semiconductor commonly used in blue light-emitting diodes since the 1990s. The compound is a very hard material that has a Wurtzite crystal structure. Its wide band gap of 3.4 eV affords ...
, a semiconductor. The large electric fields in this material are detrimental in light emitting diodes (LEDs), but useful for the production of power transistors.
Progress has been made in creating artificial pyroelectric materials, usually in the form of a thin film, using gallium nitride
Gallium nitride () is a binary III/ V direct bandgap semiconductor commonly used in blue light-emitting diodes since the 1990s. The compound is a very hard material that has a Wurtzite crystal structure. Its wide band gap of 3.4 eV affords ...
( Ga N), caesium nitrate
Caesium nitrate or cesium nitrate is a salt with the chemical formula Cs N O3. An alkali metal nitrate, it is used in pyrotechnic compositions, as a colorant and an oxidizer, e.g. in decoys and illumination flares. The caesium emissions are ch ...
( Cs N O3), polyvinyl fluoride
Polyvinyl fluoride (PVF) or –(CH2CHF)n– is a polymer material mainly used in the flammability-lowering coatings of airplane interiors and photovoltaic module backsheets. It is also used in raincoats and metal sheeting. Polyvinyl fluoride is a ...
s, derivatives of phenylpyridine, and cobalt
Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, p ...
phthalocyanine
Phthalocyanine () is a large, aromatic, macrocyclic, organic compound with the formula and is of theoretical or specialized interest in chemical dyes and photoelectricity.
It is composed of four isoindole units linked by a ring of nitrogen ato ...
. Lithium tantalate
Lithium tantalate ( Li Ta O3) is a perovskite which possesses unique optical, piezoelectric and pyroelectric properties which make it valuable for nonlinear optics, passive infrared sensors such as motion detectors, terahertz generation and de ...
( Li Ta O3) is a crystal exhibiting both piezoelectric
Piezoelectricity (, ) is the electric charge that accumulates in certain solid materials—such as crystals, certain ceramics, and biological matter such as bone, DNA, and various proteins—in response to applied mechanical stress. The word '' ...
and pyroelectric properties, which has been used to create small-scale nuclear fusion
Nuclear fusion is a reaction in which two or more atomic nuclei are combined to form one or more different atomic nuclei and subatomic particles ( neutrons or protons). The difference in mass between the reactants and products is manife ...
(" pyroelectric fusion"). Recently, pyroelectric and piezoelectric properties have been discovered in doped hafnium oxide
Hafnium(IV) oxide is the inorganic compound with the formula . Also known as hafnium dioxide or hafnia, this colourless solid is one of the most common and stable compounds of hafnium. It is an electrical insulator with a band gap of 5.3~5.7 eV. H ...
( Hf O2), which is a standard material in CMOS manufacturing.
Applications
Heat sensors
Very small changes in temperature can produce a pyroelectric potential. Passive infrared sensor
A passive infrared sensor (PIR sensor) is an electronic sensor that measures infrared (IR) light radiating from objects in its field of view. They are most often used in PIR-based motion detectors. PIR sensors are commonly used in security alarms ...
s are often designed around pyroelectric materials, as the heat of a human or animal from several feet away is enough to generate a voltage.
Power generation
A pyroelectric can be repeatedly heated and cooled (analogously to a heat engine
In thermodynamics and engineering, a heat engine is a system that converts heat to mechanical energy, which can then be used to do mechanical work. It does this by bringing a working substance from a higher state temperature to a lower state ...
) to generate usable electrical power. One group calculated that a pyroelectric in an Ericsson cycle could reach 50% of Carnot efficiency, while a different study found a material that could, in theory, reach 84-92% of Carnot efficiency (these efficiency values are for the pyroelectric itself, ignoring losses from heating and cooling the substrate, other heat-transfer losses, and all other losses elsewhere in the system). Possible advantages of pyroelectric generators for generating electricity (as compared to the conventional heat engine
In thermodynamics and engineering, a heat engine is a system that converts heat to mechanical energy, which can then be used to do mechanical work. It does this by bringing a working substance from a higher state temperature to a lower state ...
plus electrical generator
In electricity generation, a generator is a device that converts motive power (mechanical energy) or fuel-based power ( chemical energy) into electric power for use in an external circuit. Sources of mechanical energy include steam turbines, g ...
) include: potentially lower operating temperatures, less bulky equipment, and fewer moving parts. Although a few patents have been filed for such a device,[For example]
US Patent 4647836
/ref> such generators do not appear to be anywhere close to commercialization.
Nuclear fusion
Pyroelectric materials have been used to generate large electric fields necessary to steer deuterium
Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two stable isotopes of hydrogen (the other being protium, or hydrogen-1). The nucleus of a deuterium atom, called a deuteron, contains one proton and one ...
ions in a nuclear fusion
Nuclear fusion is a reaction in which two or more atomic nuclei are combined to form one or more different atomic nuclei and subatomic particles ( neutrons or protons). The difference in mass between the reactants and products is manife ...
process. This is known as pyroelectric fusion.
See also
* Electrocaloric effect, an opposite effect of pyroelectricity
*Thermoelectricity
The thermoelectric effect is the direct conversion of temperature differences to electric voltage and vice versa via a thermocouple. A thermoelectric device creates a voltage when there is a different temperature on each side. Conversely, when ...
*Kelvin probe force microscope
Kelvin probe force microscopy (KPFM), also known as surface potential microscopy, is a noncontact variant of atomic force microscopy (AFM). By raster scanning in the x,y plane the work function of the sample can be locally mapped for correlatio ...
*Lithium tantalate
Lithium tantalate ( Li Ta O3) is a perovskite which possesses unique optical, piezoelectric and pyroelectric properties which make it valuable for nonlinear optics, passive infrared sensors such as motion detectors, terahertz generation and de ...
*Zinc oxide
Zinc oxide is an inorganic compound with the formula . It is a white powder that is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement ...
References
* Gautschi, Gustav, 2002, ''Piezoelectric Sensorics'', Springer,
External links
Substantial explanations of pyroelectric detector operation
Pyroelectric Detectors for THz applications
WiredSense
Pyroelectric Infrared Detectors
DIAS Infrared
DoITPoMS Teaching and Learning Package- "Pyroelectric Materials"
laser detection with lithium tantalate
{{Webarchive, url=https://web.archive.org/web/20160303224409/http://www.kube.ch/eltec/laser_application.php , date=2016-03-03
Optical and Dielectric Properties of Sr(x)Ba(1-x)Nb(2)O(6)
Dielectric and Electrical Properties of Ce,Mn:SBN
Thermodynamics
Electrical phenomena
Energy conversion
Crystals