Hafnium(IV) oxide

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Hafnium(IV) oxide
Kristallstruktur Zirconium(IV)-oxid.png
Hafnium(IV) oxide.jpg
Names
IUPAC name
Hafnium(IV) oxide
Other names
Hafnium dioxide
Hafnia
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.818 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-013-2
PubChem CID
UNII
  • InChI=1S/Hf.2O Yes check.svgY
    Key: CJNBYAVZURUTKZ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Hf.2O/rHfO2/c2-1-3
    Key: CJNBYAVZURUTKZ-MSHMTBKAAI
  • O=[Hf]=O
Properties
HfO2
Molar mass 210.49 g/mol
Appearanceoff-white powder
Density 9.68 g/cm3, solid
Melting point 2,758 °C (4,996 °F; 3,031 K)
Boiling point 5,400 °C (9,750 °F; 5,670 K)
insoluble
23.0·10−6 cm3/mol
Hazards
Flash point Non-flammable
Related compounds
Other cations
Titanium(IV) oxide
Zirconium(IV) oxide
Related compounds
Hafnium nitride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Hafnium(IV) oxide is the inorganic compound with the formula HfO
2
. 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. [1] Hafnium dioxide is an intermediate in some processes that give hafnium metal.

Contents

Hafnium(IV) oxide is quite inert. It reacts with strong acids such as concentrated sulfuric acid and with strong bases. It dissolves slowly in hydrofluoric acid to give fluorohafnate anions. At elevated temperatures, it reacts with chlorine in the presence of graphite or carbon tetrachloride to give hafnium tetrachloride.

Structure

Hafnia typically adopts the same structure as zirconia (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 (Fm3m), tetragonal (P42/nmc), monoclinic (P21/c) and orthorhombic (Pbca and Pnma). [2] 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, [3] presumably being the sources of the ferroelectricity observed in thin films of hafnia. [4]

Thin films of hafnium oxides deposited by atomic layer deposition are usually crystalline. Because semiconductor 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. [5]

Applications

Hafnia is used in optical coatings, and as a high-κ dielectric in DRAM capacitors and in advanced metal–oxide–semiconductor devices. [6] Hafnium-based oxides were introduced by Intel in 2007 as a replacement for silicon oxide as a gate insulator in field-effect transistors. [7] The advantage for transistors is its high dielectric constant: the dielectric constant of HfO2 is 4–6 times higher than that of SiO2. [8] 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 [9] and CMOS-compatible ferroelectric field effect transistors (FeFET memory) and memory chips. [10] [11] [12] [13]

Because of its very high melting point, hafnia is also used as a refractory material in the insulation of such devices as thermocouples, where it can operate at temperatures up to 2500 °C. [14]

Multilayered films of hafnium dioxide, silica, and other materials have been developed for use in passive cooling 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. [15]

Related Research Articles

<span class="mw-page-title-main">Chemical vapor deposition</span> Method used to apply surface coatings

Chemical vapor deposition (CVD) is a vacuum deposition method used to produce high-quality, and high-performance, solid materials. The process is often used in the semiconductor industry to produce thin films.

<span class="mw-page-title-main">Hafnium</span> Chemical element, symbol Hf and atomic number 72

Hafnium is a chemical element with the 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 Dmitri Mendeleev in 1869, though it was not identified until 1923, by Dirk Coster and George de Hevesy, making it the penultimate stable element to be discovered. Hafnium is named after Hafnia, the Latin name for Copenhagen, where it was discovered.

<span class="mw-page-title-main">Silicon dioxide</span> Oxide of silicon

Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula SiO2, commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is abundant as it comprises several minerals and as a synthetic products. All forms are white or colorless, although impure samples can be colored.

<span class="mw-page-title-main">Zirconium dioxide</span> Chemical compound

Zirconium dioxide is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabilized cubic structured zirconia, cubic zirconia, is synthesized in various colours for use as a gemstone and a diamond simulant.

<span class="mw-page-title-main">Pyroelectricity</span> Voltage created when a crystal is heated

Pyroelectricity 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 when they are heated or cooled. The change in temperature modifies the positions of the atoms slightly within the crystal structure, so 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. The leakage can be due to electrons moving through the crystal, ions moving through the air, or current leaking through a voltmeter attached across the crystal.

A thin-film transistor (TFT) is a special type of field-effect transistor (FET) where the transistor is made by thin film deposition. TFTs are grown on a supporting substrate. A common substrate is glass, because the traditional application of TFTs is in liquid-crystal displays (LCDs). This differs from the conventional bulk metal oxide field effect transistor (MOSFET), where the semiconductor material typically is the substrate, such as a silicon wafer.

In semiconductor manufacturing, a low-κ is a material with a small relative dielectric constant relative to silicon dioxide. Low-κ dielectric material implementation is one of several strategies used to allow continued scaling of microelectronic devices, colloquially referred to as extending Moore's law. In digital circuits, insulating dielectrics separate the conducting parts from one another. As components have scaled and transistors have gotten closer together, the insulating dielectrics have thinned to the point where charge build up and crosstalk adversely affect the performance of the device. Replacing the silicon dioxide with a low-κ dielectric of the same thickness reduces parasitic capacitance, enabling faster switching speeds and lower heat dissipation. In conversation such materials may be referred to as "low-k" rather than "low-κ" (low-kappa).

<span class="mw-page-title-main">Yttrium(III) oxide</span> Chemical compound

Yttrium oxide, also known as yttria, is Y2O3. It is an air-stable, white solid substance.

In the semiconductor industry, the term high-κ dielectric refers to a material with a high dielectric constant, as compared to silicon dioxide. High-κ dielectrics are used in semiconductor manufacturing processes where they are usually used to replace a silicon dioxide gate dielectric or another dielectric layer of a device. The implementation of high-κ gate dielectrics is one of several strategies developed to allow further miniaturization of microelectronic components, colloquially referred to as extending Moore's Law. Sometimes these materials are called "high-k", instead of "high-κ".

<span class="mw-page-title-main">Hafnium tetrachloride</span> Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

<span class="mw-page-title-main">Tantalum pentoxide</span> Chemical compound

Tantalum pentoxide, also known as tantalum(V) oxide, is the inorganic compound with the formula Ta
2
O
5
. It is a white solid that is insoluble in all solvents but is attacked by strong bases and hydrofluoric acid. Ta
2
O
5
is an inert material with a high refractive index and low absorption, which makes it useful for coatings. It is also extensively used in the production of capacitors, due to its high dielectric constant.

<span class="mw-page-title-main">Vanadium(IV) oxide</span> Chemical compound

Vanadium(IV) oxide or vanadium dioxide is an inorganic compound with the formula VO2. It is a dark blue solid. Vanadium(IV) dioxide is amphoteric, dissolving in non-oxidising acids to give the blue vanadyl ion, [VO]2+ and in alkali to give the brown [V4O9]2− ion, or at high pH [VO4]4−. VO2 has a phase transition very close to room temperature (~68 °C (341 K)). Electrical resistivity, opacity, etc, can change up several orders. Owing to these properties, it has been used in surface coating, sensors, and imaging. Potential applications include use in memory devices, phase-change switches, passive radiative cooling applications, such as smart windows and roofs, that cool or warm depending on temperature, aerospace communication systems and neuromorphic computing.

Resistive random-access memory is a type of non-volatile (NV) random-access (RAM) computer memory that works by changing the resistance across a dielectric solid-state material, often referred to as a memristor.

Hafnium silicate is the hafnium(IV) salt of silicic acid with the chemical formula of HfSiO4.

<span class="mw-page-title-main">Conductive atomic force microscopy</span> Method of measuring the microscopic topography of a material

In microscopy, conductive atomic force microscopy (C-AFM) or current sensing atomic force microscopy (CS-AFM) is a mode in atomic force microscopy (AFM) that simultaneously measures the topography of a material and the electric current flow at the contact point of the tip with the surface of the sample. The topography is measured by detecting the deflection of the cantilever using an optical system, while the current is detected using a current-to-voltage preamplifier. The fact that the CAFM uses two different detection systems is a strong advantage compared to scanning tunneling microscopy (STM). Basically, in STM the topography picture is constructed based on the current flowing between the tip and the sample. Therefore, when a portion of a sample is scanned with an STM, it is not possible to discern if the current fluctuations are related to a change in the topography or to a change in the sample conductivity.

Polysilicon depletion effect is the phenomenon in which unwanted variation of threshold voltage of the MOSFET devices using polysilicon as gate material is observed, leading to unpredicted behavior of the electronic circuit. Because of this variation High-k Dielectric Metal Gates (HKMG) were introduced to solve the issue.

Flexible silicon refers to a flexible piece of mono-crystalline silicon. Several processes have been demonstrated in the literature for obtaining flexible silicon from single crystal silicon wafers.

A ferroelectric field-effect transistor is a type of field-effect transistor that includes a ferroelectric material sandwiched between the gate electrode and source-drain conduction region of the device. Permanent electrical field polarisation in the ferroelectric causes this type of device to retain the transistor's state in the absence of any electrical bias.

<span class="mw-page-title-main">Hafnium nitrate</span> Chemical compound

Hafnium(IV) nitrate is an inorganic compound, a salt of hafnium and nitric acid with the chemical formula Hf(NO3)4.

Hafnium compounds are compounds containing the element hafnium (Hf). Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79 angstroms). Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties. Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. Some compounds of hafnium in lower oxidation states are known.

References

  1. Bersch, Eric; et al. (2008). "Band offsets of ultrathin high-k oxide films with Si". Phys. Rev. B. 78 (8): 085114. Bibcode:2008PhRvB..78h5114B. doi:10.1103/PhysRevB.78.085114.
  2. Table III, V. Miikkulainen; et al. (2013). "Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends". Journal of Applied Physics . 113 (2): 021301–021301–101. Bibcode:2013JAP...113b1301M. doi:10.1063/1.4757907.
  3. T. D. Huan; V. Sharma; G. A. Rossetti, Jr.; R. Ramprasad (2014). "Pathways towards ferroelectricity in hafnia". Physical Review B . 90 (6): 064111. arXiv: 1407.1008 . Bibcode:2014PhRvB..90f4111H. doi:10.1103/PhysRevB.90.064111. S2CID   53347579.
  4. T. S. Boscke (2011). "Ferroelectricity in hafnium oxide thin films". Applied Physics Letters . 99 (10): 102903. Bibcode:2011ApPhL..99j2903B. doi:10.1063/1.3634052.
  5. J.H. Choi; et al. (2011). "Development of hafnium based high-k materials—A review". Materials Science and Engineering: R. 72 (6): 97–136. doi:10.1016/j.mser.2010.12.001.
  6. H. Zhu; C. Tang; L. R. C. Fonseca; R. Ramprasad (2012). "Recent progress in ab initio simulations of hafnia-based gate stacks". Journal of Materials Science . 47 (21): 7399–7416. Bibcode:2012JMatS..47.7399Z. doi:10.1007/s10853-012-6568-y. S2CID   7806254.
  7. Intel (11 November 2007). "Intel's Fundamental Advance in Transistor Design Extends Moore's Law, Computing Performance".
  8. Wilk G. D., Wallace R. M., Anthony J. M. (2001). "High-κ gate dielectrics: Current status and materials properties considerations". Journal of Applied Physics. 89 (10): 5243–5275. Bibcode:2001JAP....89.5243W. doi:10.1063/1.1361065.{{cite journal}}: CS1 maint: multiple names: authors list (link), Table 1
  9. K.-L. Lin; et al. (2011). "Electrode dependence of filament formation in HfO2 resistive-switching memory". Journal of Applied Physics . 109 (8): 084104–084104–7. Bibcode:2011JAP...109h4104L. doi:10.1063/1.3567915.
  10. Imec (7 June 2017). "Imec demonstrates breakthrough in CMOS-compatible Ferroelectric Memory".
  11. The Ferroelectric Memory Company (8 June 2017). "World's first FeFET-based 3D NAND demonstration".
  12. T. S. Böscke; J. Müller; D. Bräuhaus (7 Dec 2011). "Ferroelectricity in hafnium oxide: CMOS compatible ferroelectric field effect transistors". 2011 International Electron Devices Meeting. IEEE. pp. 24.5.1–24.5.4. doi:10.1109/IEDM.2011.6131606. ISBN   978-1-4577-0505-2.
  13. Nivole Ahner (August 2018). Mit HFO2 voll CMOS-kompatibel (in German). Elektronik Industrie.
  14. Very High Temperature Exotic Thermocouple Probes product data, Omega Engineering, Inc., retrieved 2008-12-03
  15. "Aaswath Raman | Innovators Under 35 | MIT Technology Review". August 2015. Retrieved 2015-09-02.