Silicides
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A silicide is a type of
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
that combines
silicon Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...
and a usually more
electropositive Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...
element. Silicon is more
electropositive Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...
than
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
. In terms of their physical properties, silicides are structurally closer to
boride A boride is a compound between boron and a less electronegative element, for example silicon boride (SiB3 and SiB6). The borides are a very large group of compounds that are generally high melting and are covalent more than ionic in nature. Some b ...
s than to
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of th ...
s. Because of size differences however silicides are not isostructural with borides and carbides. Bonds in silicides range from
conductive In physics and electrical engineering, a conductor is an object or type of material that allows the flow of Electric charge, charge (electric current) in one or more directions. Materials made of metal are common electrical conductors. The flow ...
metal-like structures to
covalent A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atom ...
or ionic. Silicides of all non-
transition metals 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 ...
have been described except
beryllium Beryllium is a chemical element; it has Symbol (chemistry), symbol Be and atomic number 4. It is a steel-gray, hard, strong, lightweight and brittle alkaline earth metal. It is a divalent element that occurs naturally only in combination with ...
. Silicides are used in
interconnect In telecommunications, interconnection is the physical linking of a carrier's network with equipment or facilities not belonging to that network. The term may refer to a connection between a carrier's facilities and the equipment belonging to its ...
s.


Structure

Silicon atoms in silicides can have many possible organizations: *Isolated silicon atoms: electrically conductive (or semiconductive) CrSi,
MnSi Manganese monosilicide (MnSi) is an intermetallic compound, a silicide of manganese. It occurs in cosmic dust as the mineral brownleeite. MnSi has a cubic crystal lattice with no inversion center; therefore its crystal structure is helical, wit ...
,
FeSi Iron monosilicide (FeSi) is an intermetallic compound, a silicide of iron that occurs in nature as the rare mineral naquite. It is a narrow-bandgap semiconductor with a room-temperature electrical resistivity of around 10 kΩ·cm and unusual ...
,
CoSi COSI (), officially the Center of Science and Industry, is a science museum and research center in Columbus, Ohio. COSI was opened to the public on 29 March 1964 and remained there for 35 years. In 1999, COSI was moved to a facility, designed ...
, , , , , , *Si2 pairs: ,
hafnium Hafnium is a chemical element; it has symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dm ...
and
thorium Thorium is a chemical element; it has symbol Th and atomic number 90. Thorium is a weakly radioactive light silver metal which tarnishes olive grey when it is exposed to air, forming thorium dioxide; it is moderately soft, malleable, and ha ...
silicides *Si4
tetrahedra In geometry, a tetrahedron (: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular Face (geometry), faces, six straight Edge (geometry), edges, and four vertex (geometry), vertices. The tet ...
: KSi, RbSi, CsSi *Si''n'' chains: USi, , CaSi, SrSi, YSi *Planar hexagonal
graphite Graphite () is a Crystallinity, crystalline allotrope (form) of the element carbon. It consists of many stacked Layered materials, layers of graphene, typically in excess of hundreds of layers. Graphite occurs naturally and is the most stable ...
-like Si layers: β-USi2, silicides of other
lanthanoid The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 Metal, metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium ...
s and
actinoid The actinide () or actinoid () series encompasses at least the 14 metallic chemical elements in the 5f series, with atomic numbers from 89 to 102, actinium through nobelium. Number 103, lawrencium, is also generally included despite being part ...
s *Corrugated hexagonal Si layers: CaSi2 *Open three-dimensional Si skeletons: SrSi2, ThSi2, α-USi2


Preparation and reactivity

Most silicides are produced by direct combination of the elements. However, the process is extremely
exothermic In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity (e ...
and control of the reaction poor. In rare cases, a metal oxide can undergo silicobaric reduction, in which pure silicon deoxygenates the metal to a silicon oxide, which is then removed by a vacuum. Alternatively, molten aluminum or copper are adequate solvents for the alloying. A silicide prepared by a self-aligned process is called a
salicide The term salicide refers to a technology used in the microelectronics industry used to form electrical contacts between the semiconductor device and the supporting interconnect structure. The salicide process involves the reaction of a metal thi ...
. This is a process in which silicide contacts are formed only in those areas in which deposited metal (which after annealing becomes a metal component of the silicide) is in direct contact with silicon, hence, the process is self-aligned. It is commonly implemented in MOS/
CMOS Complementary metal–oxide–semiconductor (CMOS, pronounced "sea-moss ", , ) is a type of MOSFET, metal–oxide–semiconductor field-effect transistor (MOSFET) semiconductor device fabrication, fabrication process that uses complementary an ...
processes for ohmic contacts of the source, drain, and poly-Si gate.


Alkali and alkaline earth metals

Group 1 and 2 silicides e.g. Na2Si and Ca2Si react with water, yielding hydrogen and/or silanes.
Magnesium silicide Magnesium silicide, Mg2Si, is an inorganic compound consisting of magnesium and silicon. As-grown Mg2Si usually forms black crystals; they are semiconductors with n-type conductivity and have potential applications in thermoelectric generators. Cr ...
reacts with
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
to give
silane Silane (Silicane) is an inorganic compound with chemical formula . It is a colorless, pyrophoric gas with a sharp, repulsive, pungent smell, somewhat similar to that of acetic acid. Silane is of practical interest as a precursor to elemental ...
: :Mg2Si + 4 HCl → SiH4 + 2 MgCl2
Group 1 Group 1 may refer to: * Alkali metal, a chemical element classification for Alkali metal * Group 1 (motorsport), a regulation set of the FIA for series-production touring cars used in motorsport. * Group One Thoroughbred horse races, the leading e ...
silicides are even more reactive. For example, sodium silicide, Na2Si, reacts rapidly with water to yield
sodium silicate Sodium silicate is a generic name for chemical compounds with the formula or ·, such as sodium metasilicate (), sodium orthosilicate (), and sodium pyrosilicate (). The anions are often polymeric. These compounds are generally colorless tra ...
, Na2SiO3, and
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
gas. Rubidium silicide is
pyrophoric A substance is pyrophoric (from , , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolithium compounds and triethylb ...
, igniting in contact with air.


Transition metals and other elements

The
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 ...
silicides are usually inert to aqueous solutions. At red heat, they react with
potassium hydroxide Potassium hydroxide is an inorganic compound with the formula K OH, and is commonly called caustic potash. Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which utili ...
,
fluorine Fluorine is a chemical element; it has Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard temperature and pressure, standard conditions as pale yellow Diatomic molecule, diatomic gas. Fluorine is extre ...
, and
chlorine Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
. Mercury,
thallium Thallium is a chemical element; it has Symbol (chemistry), symbol Tl and atomic number 81. It is a silvery-white post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Che ...
,
bismuth Bismuth is a chemical element; it has symbol Bi and atomic number 83. It is a post-transition metal and one of the pnictogens, with chemical properties resembling its lighter group 15 siblings arsenic and antimony. Elemental bismuth occurs nat ...
, and
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
are
immiscible Miscibility () is the property of two chemical substance, substances to mix in all mixing ratio, proportions (that is, to fully dissolution (chemistry), dissolve in each other at any concentration), forming a homogeneity and heterogeneity, homoge ...
with liquid silicon.


Applications

Silicide
thin films A thin film is a layer of materials ranging from fractions of a nanometer ( monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many ...
have applications in microelectronics due to their high electrical conductivity, thermal stability, corrosion resistance, and compatibility with
photolithographic Photolithography (also known as optical lithography) is a process used in the manufacturing of integrated circuits. It involves using light to transfer a pattern onto a substrate, typically a silicon wafer. The process begins with a photosensit ...
wafer A wafer is a crisp, often sweet, very thin, flat, light biscuit, often used to decorate ice cream, and also used as a garnish on some sweet dishes. They frequently have a waffle surface pattern but may also be patterned with insignia of the foo ...
processes. For example silicides formed over layers of
polysilicon Polycrystalline silicon, or multicrystalline silicon, also called polysilicon, poly-Si, or mc-Si, is a high purity, polycrystalline form of silicon, used as a raw material by the solar photovoltaic and electronics industry. Polysilicon is produ ...
, called polycides, are commonly used as an interconnect material in integrated circuits for their high conductivity. Silicides formed through the salicide process also see use as a low
work function In solid-state physics, the work function (sometimes spelled workfunction) is the minimum thermodynamic work (i.e., energy) needed to remove an electron from a solid to a point in the vacuum immediately outside the solid surface. Here "immediately" ...
metal in ohmic and Schottky contacts. High work function metals are often not ideal for use in metal–semiconductor junctions directly due to fermi–level pinning where the Schottky barrier potential of the junction becomes locked around 0.7–0.8V. For this reason low forward-voltage Schottky diodes and ohmic interconnects between a semiconductor and a metal often utilize a thin layer of silicide at the metal–semiconductor interface.


List (incomplete)

*
Nickel silicide Nickel silicides include several intermetallic compounds of nickel and silicon. Nickel silicides are important in microelectronics as they form at junctions of nickel and silicon. Additionally thin layers of nickel silicides may have application ...
, NiSi * Sodium silicide, NaSi *
Magnesium silicide Magnesium silicide, Mg2Si, is an inorganic compound consisting of magnesium and silicon. As-grown Mg2Si usually forms black crystals; they are semiconductors with n-type conductivity and have potential applications in thermoelectric generators. Cr ...
, Mg2Si *
Platinum silicide Platinum silicide, also known as platinum monosilicide, is the inorganic compound with the formula PtSi. It is a semiconductor that turns into a superconductor when cooled to 0.8 K. Structure and bonding The crystal structure of PtSi is orthorho ...
, PtSi (platinum is actually more electronegative than silicon) * Titanium silicide, TiSi2 *
Tungsten silicide Tungsten disilicide (WSi2) is an inorganic compound, a silicide of tungsten. It is an electrically conductive ceramic material. Chemistry Tungsten disilicide can react violently with substances such as strong acids, fluorine, oxidizers, and inter ...
, WSi2 *
Molybdenum disilicide Molybdenum disilicide (MoSi2, or molybdenum silicide), an intermetallic compound, a silicide of molybdenum, is a refractory ceramic with primary use in heating elements. It has moderate density, melting point 2030 °C, and is electrically ...
, MoSi2 * Neptunium silicide, NpSi2


See also

* Binary compounds of silicon


References

{{Monatomic anion compounds Anions