Perovskite (structure), Perovskite Structure
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Perovskite (pronunciation: ) is a calcium titanium
oxide mineral The oxide mineral class includes those minerals in which the oxide anion (O2−) is bonded to one or more metal alloys. The hydroxide-bearing minerals are typically included in the oxide class. Minerals with complex anion groups such as the sil ...
composed of
calcium titanate Calcium titanate is an inorganic compound with the chemical formula Ca Ti O3. As a mineral, it is called perovskite, named after Russian mineralogist, Lev Perovski (1792–1856). It is a colourless, diamagnetic solid, although the mineral is of ...
(chemical formula ). Its name is also applied to the class of compounds which have the same type of
crystal structure In crystallography, crystal structure is a description of ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from intrinsic nature of constituent particles to form symmetric patterns that repeat ...
as , known as the perovskite structure, which has a general
chemical formula A chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as pare ...
. Many different
cations An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
can be embedded in this structure, allowing the development of diverse engineered materials.


History

The mineral was discovered in the
Ural Mountains The Ural Mountains ( ),; , ; , or simply the Urals, are a mountain range in Eurasia that runs north–south mostly through Russia, from the coast of the Arctic Ocean to the river Ural (river), Ural and northwestern Kazakhstan.
of
Russia Russia, or the Russian Federation, is a country spanning Eastern Europe and North Asia. It is the list of countries and dependencies by area, largest country in the world, and extends across Time in Russia, eleven time zones, sharing Borders ...
by
Gustav Rose Prof Gustavus ("Gustav") Rose Royal Society of London, FRSFor HFRSE (18 March 1798 – 15 July 1873) was a German mineralogist who was a native of Berlin. He was President of the German Geological Society from 1863 to 1873. Life He was born in Be ...
in 1839 and is named after Russian mineralogist Lev Perovski (1792–1856). Perovskite's notable crystal structure was first described by
Victor Goldschmidt Victor Moritz Goldschmidt (27 January 1888 – 20 March 1947) was a Norwegian mineralogist considered (together with Vladimir Vernadsky) to be the founder of modern geochemistry and crystal chemistry, developer of the Goldschmidt Classificatio ...
in 1926 in his work on tolerance factors. The crystal structure was later published in 1945 from
X-ray diffraction X-ray diffraction is a generic term for phenomena associated with changes in the direction of X-ray beams due to interactions with the electrons around atoms. It occurs due to elastic scattering, when there is no change in the energy of the waves. ...
data on
barium titanate Barium titanate (BTO) is an inorganic compound with chemical formula BaTiO3. It is the barium salt of metatitanic acid. Barium titanate appears white as a powder and is transparent when prepared as large crystals. It is a Ferroelectricity, ferroe ...
by
Helen Dick Megaw Helen Dick Megaw (1 June 1907 – 26 February 2002) was an Irish crystallographer who was a pioneer in X-ray crystallography. She made measurements of the cell dimensions of ice and established the Perovskite crystal structure. Education and c ...
.


Occurrence

Found in the Earth's mantle, perovskite's occurrence at Khibina Massif is restricted to the silica under-saturated
ultramafic Ultramafic rocks (also referred to as ultrabasic rocks, although the terms are not wholly equivalent) are igneous and meta-igneous rocks with a very low silica content (less than 45%), generally >18% MgO, high FeO, low potassium, and are usua ...
rocks and
foidolite Foidolite () is a rare phaneritic (coarse-grained) intrusive igneous rock in which more than 60% (by volume) of light-coloured minerals are feldspathoids. Crystals of alkali feldspar, plagioclase, biotite, amphibole, pyroxene, and/or olivine ma ...
s, due to the instability in a
paragenesis Paragenesis is a petrologic concept meaning an ''equilibrium sequence of mineral phases''. It is used in studies of igneous and metamorphic rock genesis and importantly in studies of the hydrothermal deposition of ore minerals and the rock alteratio ...
with
feldspar Feldspar ( ; sometimes spelled felspar) is a group of rock-forming aluminium tectosilicate minerals, also containing other cations such as sodium, calcium, potassium, or barium. The most common members of the feldspar group are the ''plagiocl ...
. Perovskite occurs as small anhedral to subhedral crystals filling interstices between the rock-forming silicates. Perovskite is found in
contact Contact may refer to: Interaction Physical interaction * Contact (geology), a common geological feature * Contact lens or contact, a lens placed on the eye * Contact sport, a sport in which players make contact with other players or objects * C ...
carbonate A carbonate is a salt of carbonic acid, (), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word "carbonate" may also refer to a carbonate ester, an organic compound containing the carbonate group ...
skarn Skarns or tactites are coarse-grained metamorphic rocks that form by replacement of carbonate-bearing rocks during regional or contact metamorphism and metasomatism. Skarns may form by metamorphic recrystallization of impure carbonate protoliths, ...
s at Magnet Cove,
Arkansas Arkansas ( ) is a landlocked state in the West South Central region of the Southern United States. It borders Missouri to the north, Tennessee and Mississippi to the east, Louisiana to the south, Texas to the southwest, and Oklahoma ...
, US, in altered blocks of
limestone Limestone is a type of carbonate rock, carbonate sedimentary rock which is the main source of the material Lime (material), lime. It is composed mostly of the minerals calcite and aragonite, which are different Polymorphism (materials science) ...
ejected from
Mount Vesuvius Mount Vesuvius ( ) is a Somma volcano, somma–stratovolcano located on the Gulf of Naples in Campania, Italy, about east of Naples and a short distance from the shore. It is one of several volcanoes forming the Campanian volcanic arc. Vesuv ...
, in
chlorite The chlorite ion, or chlorine dioxide anion, is the halite (oxyanion), halite with the chemical formula of . A chlorite (compound) is a compound that contains this group, with chlorine in the oxidation state of +3. Chlorites are also known as s ...
and
talc Talc, or talcum, is a clay mineral composed of hydrated magnesium silicate, with the chemical formula . Talc in powdered form, often combined with corn starch, is used as baby powder. This mineral is used as a thickening agent and lubricant ...
schist Schist ( ) is a medium-grained metamorphic rock generally derived from fine-grained sedimentary rock, like shale. It shows pronounced ''schistosity'' (named for the rock). This means that the rock is composed of mineral grains easily seen with a l ...
in the
Urals The Ural Mountains ( ),; , ; , or simply the Urals, are a mountain range in Eurasia that runs north–south mostly through Russia, from the coast of the Arctic Ocean to the river Ural (river), Ural and northwestern Kazakhstan.
and
Switzerland Switzerland, officially the Swiss Confederation, is a landlocked country located in west-central Europe. It is bordered by Italy to the south, France to the west, Germany to the north, and Austria and Liechtenstein to the east. Switzerland ...
,Palache, Charles, Harry Berman and Clifford Frondel, 1944, ''Dana's System of Mineralogy'' Vol. 1, Wiley, 7th ed. p. 733 and as an accessory mineral in alkaline and
mafic A mafic mineral or rock is a silicate mineral or igneous rock rich in magnesium and iron. Most mafic minerals are dark in color, and common rock-forming mafic minerals include olivine, pyroxene, amphibole, and biotite. Common mafic rocks include ...
igneous rock Igneous rock ( ), or magmatic rock, is one of the three main rock types, the others being sedimentary and metamorphic. Igneous rocks are formed through the cooling and solidification of magma or lava. The magma can be derived from partial ...
s,
nepheline syenite Nepheline syenite is a holocrystalline Intrusion, plutonic rock that consists largely of nepheline and alkali feldspar. The rocks are mostly pale colored, grey or pink, and in general appearance they are not unlike granites, but dark green varie ...
, melilitite,
kimberlite Kimberlite is an igneous rock and a rare variant of peridotite. It is most commonly known as the main host matrix for diamonds. It is named after the town of Kimberley, Northern Cape, Kimberley in South Africa, where the discovery of an 83.5-Car ...
s and rare
carbonatite Carbonatite () is a type of intrusive rock, intrusive or extrusive rock, extrusive igneous rock defined by mineralogic composition consisting of greater than 50% carbonate minerals. Carbonatites may be confused with marble and may require geoche ...
s. Perovskite is a common mineral in the Ca-Al-rich inclusions found in some chondritic meteorites. The stability of perovskite in
igneous rocks Igneous rock ( ), or magmatic rock, is one of the three main Rock (geology)#Classification, rock types, the others being sedimentary rock, sedimentary and metamorphic rock, metamorphic. Igneous rocks are formed through the cooling and solidifi ...
is limited by its reaction relation with
sphene Titanite, or sphene (), is a calcium titanium nesosilicate mineral, Ca Ti Si O5. Trace impurities of iron and aluminium are typically present. Also commonly present are rare earth metals including cerium and yttrium; calcium may be partly rep ...
. In
volcanic rocks Volcanic rocks (often shortened to volcanics in scientific contexts) are rocks formed from lava erupted from a volcano. Like all rock types, the concept of volcanic rock is artificial, and in nature volcanic rocks grade into hypabyssal and met ...
perovskite and sphene are not found together, the only exception being an etindite from
Cameroon Cameroon, officially the Republic of Cameroon, is a country in Central Africa. It shares boundaries with Nigeria to the west and north, Chad to the northeast, the Central African Republic to the east, and Equatorial Guinea, Gabon, and the R ...
. A
rare-earth The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set of ...
-bearing variety ''knopite'' with the chemical formula is found in alkali intrusive rocks in the
Kola Peninsula The Kola Peninsula (; ) is a peninsula in the extreme northwest of Russia, and one of the largest peninsulas of Europe. Constituting the bulk of the territory of Murmansk Oblast, it lies almost completely inside the Arctic Circle and is border ...
and near Alnö,
Sweden Sweden, formally the Kingdom of Sweden, is a Nordic countries, Nordic country located on the Scandinavian Peninsula in Northern Europe. It borders Norway to the west and north, and Finland to the east. At , Sweden is the largest Nordic count ...
. A
niobium Niobium is a chemical element; it has chemical symbol, symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and Ductility, ductile transition metal. Pure niobium has a Mohs scale of mineral hardness, Mohs h ...
-bearing variety ''dysanalyte'' occurs in carbonatite near Schelingen, Kaiserstuhl,
Germany Germany, officially the Federal Republic of Germany, is a country in Central Europe. It lies between the Baltic Sea and the North Sea to the north and the Alps to the south. Its sixteen States of Germany, constituent states have a total popu ...
.


In stars and brown dwarfs

In
star A star is a luminous spheroid of plasma (physics), plasma held together by Self-gravitation, self-gravity. The List of nearest stars and brown dwarfs, nearest star to Earth is the Sun. Many other stars are visible to the naked eye at night sk ...
s and
brown dwarf Brown dwarfs are substellar objects that have more mass than the biggest gas giant planets, but less than the least massive main sequence, main-sequence stars. Their mass is approximately 13 to 80 Jupiter mass, times that of Jupiter ()not big en ...
s the formation of perovskite grains is responsible for the depletion of
titanium oxide Titanium oxide may refer to: * Titanium dioxide (titanium(IV) oxide), TiO2 * Titanium(II) oxide (titanium monoxide), TiO, a non-stoichiometric oxide * Titanium(III) oxide (dititanium trioxide), Ti2O3 * Ti3O * Ti2O * δ-TiOx (x= 0.68–0.75) * Ti ...
in the
photosphere The photosphere is a star's outer shell from which light is radiated. It extends into a star's surface until the plasma becomes opaque, equivalent to an optical depth of approximately , or equivalently, a depth from which 50% of light will esc ...
. Stars with a low temperature have dominant bands of TiO in their
spectrum A spectrum (: spectra or spectrums) is a set of related ideas, objects, or properties whose features overlap such that they blend to form a continuum. The word ''spectrum'' was first used scientifically in optics to describe the rainbow of co ...
; as the temperature gets lower for stars and brown dwarfs with an even lower mass, forms and at temperatures below 2000 K TiO is undetectable. The presence of TiO is used to define the transition between cool M-dwarf stars and the colder L-dwarfs.


Physical properties

The eponymous Perovskite crystallizes in the ''Pbnm''
space group In mathematics, physics and chemistry, a space group is the symmetry group of a repeating pattern in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of the pattern that ...
(No. 62) with
lattice constant A lattice constant or lattice parameter is one of the physical dimensions and angles that determine the geometry of the unit cells in a crystal lattice, and is proportional to the distance between atoms in the crystal. A simple cubic crystal has ...
s ''a'' = 5.39  Å, b = 5.45 Å and c = 7.65 Å. Perovskites have a nearly cubic structure with the general formula . In this structure the A-site ion, in the center of the lattice, is usually an alkaline earth or
rare-earth element The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set o ...
. B-site ions, on the corners of the lattice, are 3d, 4d, and 5d
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. The lanthanide and actinid ...
elements. The A-site cations are in 12-fold coordination with the anions, while the B-site cations are in 6-fold coordination. A large number of metallic elements are stable in the perovskite structure if the Goldschmidt tolerance factor ''t'' is in the range of 0.75 to 1.0. : t = \frac, where ''R''A, ''R''B and ''R''O are the
ionic radii Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation ...
of A and B site elements and oxygen, respectively. The stability of perovskites can be characterized with the tolerance and octahedral factors. When conditions are not fulfilled, a layered geometry for edge-sharing or face-sharing octahedra or lower B-site coordination is preferred. These are good structural bounds, but not an empirical prediction. Perovskites have sub-metallic to
metal A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, electricity and thermal conductivity, heat relatively well. These properties are all associated wit ...
lic luster, colorless streak, and cube-like structure along with imperfect
cleavage Cleavage may refer to: Science * Cleavage (crystal), the way in which a crystal or mineral tends to split * Cleavage (embryo), the division of cells in an early embryo * Cleavage (geology), foliation of rock perpendicular to stress, a result of ...
and brittle tenacity. Depending on the exact compositions, colors include black, brown, gray, orange to yellow. Perovskite crystals may appear to have the
cubic crystal In crystallography, the cubic (or isometric) crystal system is a crystal system where the Crystal structure#Unit cell, unit cell is in the shape of a cube. This is one of the most common and simplest shapes found in crystals and minerals. There ...
form, but are often ''pseudocubic'' and actually crystallize in the
orthorhombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic Lattice (group), lattices result from stretching a cubic crystal system, cubic lattice along two of its orthogonal pairs by two different factors, res ...
system, as is the case for (
strontium titanate Strontium titanate is an oxide of strontium and titanium with the chemical formula strontium, Srtitanium, Tioxygen, O3. At room temperature, it is a centrosymmetric paraelectricity, paraelectric material with a Perovskite (structure), perovskite st ...
, with the larger
strontium Strontium is a chemical element; it has symbol Sr and atomic number 38. An alkaline earth metal, it is a soft silver-white yellowish metallic element that is highly chemically reactive. The metal forms a dark oxide layer when it is exposed to ...
cation in the A-site, is cubic). Perovskite crystals have been mistaken for
galena Galena, also called lead glance, is the natural mineral form of lead(II) sulfide (PbS). It is the most important ore of lead and an important source of silver. Galena is one of the most abundant and widely distributed sulfide minerals. It crysta ...
; however, galena has a better metallic luster, greater density, perfect cleavage and true cubic symmetry.


Perovskite derivatives


Double perovskites

A double perovskite has a formula of and replaces half the B sites with B, where A are alkaline or rare earth metals and B are transition metals. The cation arrangement will differ based on charge, coordination geometry, and the ratio between A cation and B cation radii. The B and B cations lead to different ordering schemes. These ordering schemes are rock salt, columnar, and layered structures. Rock salt is an alternating, three-dimensional checkerboard of B and B' polyhedra. This structure is the most common from an electrostatic point of view, as the B sites will have different valence states. Columnar arrangement can be viewed as sheets of B-cation polyhedral viewed from the 11direction. Layered structures are seen as sheets of B and B polyhedra.


Lower dimensional perovskites

3D perovskites form when there is a smaller cation in the A site so octahedra can be corner shared. 2D perovskites form when the A-site cation is larger so octahedra sheets are formed. In 1D perovskites, a chain of octahedra is formed while in 0D perovskites, individual octahedra are separated from each other. Both 1D and 0D perovskites lead to quantum confinement and are investigated for lead-free
perovskite solar cell A perovskite solar cell (PSC) is a type of solar cell that includes a perovskite-structured compound, most commonly a hybrid organic–inorganic lead or tin halide-based material as the light-harvesting active layer. Perovskite materials, such a ...
materials.


See also

* Perovskite nanocrystal *
Perovskite light-emitting diode Perovskite light-emitting diodes (PeLEDs) are candidates for display and lighting technologies. Researchers have shown interest in perovskite light-emitting diodes (PeLEDs) owing to their capacity for emitting light with narrow bandwidth, adjusta ...
*
Perovskite solar cell A perovskite solar cell (PSC) is a type of solar cell that includes a perovskite-structured compound, most commonly a hybrid organic–inorganic lead or tin halide-based material as the light-harvesting active layer. Perovskite materials, such a ...
*
Post-perovskite Post-perovskite (pPv) is a high-pressure phase of magnesium silicate (MgSiO3). It is composed of the prime oxide constituents of the Earth's rocky mantle (MgO and SiO2), and its pressure and temperature for stability imply that it is likely to occu ...
*
Silicate perovskite Silicate perovskite is either (the magnesium end-member is called bridgmanite) or (calcium silicate known as davemaoite) when arranged in a perovskite structure. Silicate perovskites are not stable at Earth's surface, and mainly exist in the l ...


References


External links

* * {{Authority control Calcium minerals Titanium minerals Oxide minerals Orthorhombic minerals Minerals in space group 62 Perovskites Minerals described in 1839