Hafnium(IV) oxide is the

inorganic compound An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorgan ...

with the

formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...

. Also known as hafnium dioxide or hafnia, this colourless solid is one of the most common and stable compounds of

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 ...

. It is an electrical insulator with a

band gap In solid-state physics and solid-state chemistry, a band gap, also called a bandgap or energy gap, is an energy range in a solid where no electronic states exist. In graphs of the electronic band structure of solids, the band gap refers to t ...

of 5.3~5.7 eV. Hafnium dioxide is an intermediate in some processes that give hafnium metal. Hafnium(IV) oxide is quite inert. It reacts with strong

acid An acid is a molecule or ion capable of either donating a proton (i.e. Hydron, hydrogen cation, H+), known as a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis ...

s such as concentrated

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...

and with strong bases. It dissolves slowly in

hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...

to give fluorohafnate anions. At elevated temperatures, it reacts with

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 ...

in the presence of

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 ...

carbon tetrachloride Carbon tetrachloride, also known by many other names (such as carbon tet for short and tetrachloromethane, also IUPAC nomenclature of inorganic chemistry, recognised by the IUPAC), is a chemical compound with the chemical formula CCl4. It is a n ...

to give hafnium tetrachloride.

Structure

Hafnia typically adopts the same structure as

zirconia Zirconium dioxide (), sometimes known as zirconia (not to be confused with zirconium silicate or zircon), is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral ba ...

(ZrO₂). Unlike TiO₂, which features six-coordinate Ti in all phases, zirconia and hafnia consist of seven-coordinate metal centres. A variety of other crystalline phases have been experimentally observed, including cubic

fluorite Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon. The Mohs scal ...

(Fmm), tetragonal (P4₂/nmc), monoclinic (P2₁/c) and orthorhombic (Pbca and Pnma). It is also known that hafnia may adopt two other orthorhombic metastable phases (space group Pca2₁ and Pmn2₁) over a wide range of pressures and temperatures, presumably being the sources of the ferroelectricity observed in thin films of hafnia. Thin films of hafnium oxides deposited by

atomic layer deposition Atomic layer deposition (ALD) is a thin-film deposition technique based on the sequential use of a gas-phase chemical process; it is a subclass of chemical vapour deposition. The majority of ALD reactions use two chemicals called wiktionary:precu ...

are usually crystalline. Because

semiconductor A semiconductor is a material with electrical conductivity between that of a conductor and an insulator. Its conductivity can be modified by adding impurities (" doping") to its crystal structure. When two regions with different doping level ...

devices benefit from having amorphous films present, researchers have alloyed hafnium oxide with aluminum or silicon (forming hafnium silicates), which have a higher crystallization temperature than hafnium oxide.

Applications

Hafnia is used in

optical coating An optical coating is one or more thin-film optics, thin layers of material deposited on an optical component such as a lens (optics), lens, prism (optics), prism or mirror, which alters the way in which the optic reflection (physics), reflects a ...

s, and as a

high-κ dielectric In the semiconductor industry, the term high-κ dielectric refers to a material with a high dielectric constant (κ, kappa), as compared to silicon dioxide. High-κ dielectrics are used in semiconductor manufacturing processes where they are usual ...

DRAM Dram, DRAM, or drams may refer to: Technology and engineering * Dram (unit), a unit of mass and volume, and an informal name for a small amount of liquor, especially whisky or whiskey * Dynamic random-access memory, a type of electronic semicondu ...

capacitors and in advanced

metal–oxide–semiconductor upright=1.3, Two power MOSFETs in amperes">A in the ''on'' state, dissipating up to about 100 watt">W and controlling a load of over 2000 W. A matchstick is pictured for scale. In electronics, the metal–oxide–semiconductor field- ...

devices. Hafnium-based oxides were introduced by

Intel Intel Corporation is an American multinational corporation and technology company headquartered in Santa Clara, California, and Delaware General Corporation Law, incorporated in Delaware. Intel designs, manufactures, and sells computer compo ...

in 2007 as a replacement for silicon oxide as a gate insulator in

field-effect transistors The field-effect transistor (FET) is a type of transistor that uses an electric field to control the Electric current, current through a semiconductor. It comes in two types: JFET, junction FET (JFET) and MOSFET, metal-oxide-semiconductor FET (M ...

. The advantage for transistors is its high

dielectric constant The relative permittivity (in older texts, dielectric constant) is the permittivity of a material expressed as a ratio with the electric permittivity of a vacuum. A dielectric is an insulating material, and the dielectric constant of an insul ...

: the dielectric constant of HfO₂ is 4–6 times higher than that of SiO₂. The dielectric constant and other properties depend on the deposition method, composition and microstructure of the material. Hafnium oxide (as well as doped and oxygen-deficient hafnium oxide) attracts additional interest as a possible candidate for resistive-switching memories and CMOS-compatible ferroelectric field effect transistors ( FeFET memory) and memory chips. Because of its very high melting point, hafnia is also used as a refractory material in the insulation of such devices as

thermocouple A thermocouple, also known as a "thermoelectrical thermometer", is an electrical device consisting of two dissimilar electrical conductors forming an electrical junction. A thermocouple produces a temperature-dependent voltage as a result of the ...

s, where it can operate at temperatures up to 2500 °C. Multilayered films of hafnium dioxide, silica, and other materials have been developed for use in

passive cooling Passive cooling is a building design approach that focuses on heat gain control and heat dissipation in a building in order to improve the indoor thermal comfort with low or no energy consumption. This approach works either by preventing heat fro ...

of buildings. The films reflect sunlight and radiate heat at wavelengths that pass through Earth's atmosphere, and can have temperatures several degrees cooler than surrounding materials under the same conditions.

References

{{oxygen compounds Hafnium compounds High-κ dielectrics Transition metal oxides Ferroelectric materials