Tantalum nitride

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Tantalum nitride
TaNstructure.jpg
TaNstructure2.jpg
Names
Other names
Tantalum mononitride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.031.613 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-788-4
PubChem CID
  • InChI=1S/N.Ta
  • N#[Ta]
Properties
TaN
Molar mass 194.955 g/mol
Appearanceblack crystals
Density 14.3 g/cm3
Melting point 3,090 °C (5,590 °F; 3,360 K)
insoluble
Structure
Hexagonal, hP6
P-62m, No. 189
Hazards
Flash point Non-flammable
Related compounds
Other cations
Vanadium nitride
Niobium 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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Tantalum nitride (TaN) is a chemical compound, a nitride of tantalum. There are multiple phases of compounds, stoichimetrically from Ta2N to Ta3N5, including TaN.

Contents

As a thin film TaN find use as a diffusion barrier and insulating layer between copper interconnects in the back end of line of computer chips. Tantalum nitrides are also used in thin film resistors.

Phase diagram

The tantalum - nitrogen system includes several states including a nitrogen solid solution in Tantalum, as well as several nitride phases, which can vary from expected stoichiometry due to lattice vacancies. [1] Annealing of nitrogen rich "TaN" can result in conversion to a two phase mixture of TaN and Ta5N6. [1]

Ta5N6 is thought to be the more thermally stable compound - though it decomposes in vacuum at 2500 °C to Ta2N. [1] It was reported the decomposition in vacuum from Ta3N5 via Ta4N5, Ta5N6, ε-TaN, to Ta2N. [2]

Preparation

TaN is often prepared as thin films. Methods of depositing the films include RF-magnetron-reactive sputtering, [3] [4] Direct current (DC) sputtering, [5] Self-propagating high-temperature synthesis (SHS) via 'combustion' of tantalum powder in nitrogen, [1] low‐pressure metalorganic chemical vapor deposition (LP‐MOCVD), [6] ion beam assisted deposition (IBAD), [7] and by electron beam evaporation of tantalum in concert with high energy nitrogen ions. [8]

Depending on the relative amount of N2, the deposited film can vary from (fcc) TaN to (hexagonal) Ta2N as nitrogen decreases. [4] A variety of other phases have also been reported from deposition including bcc and hexagonal TaN; hexagonal Ta5N6; tetragonal Ta4N5; orthorhombic Ta6N2.5, Ta4N, or Ta3N5. [4] The electrical properties of TaN films vary from metallic conductor to insulator depending on the relative nitrogen ratio, with N rich films being more resistive. [9]

Uses

It is sometimes used in integrated circuit manufacture to create a diffusion barrier or "glue" layers between copper, or other conductive metals. In the case of BEOL processing (at c. 20 nm), copper is first coated with tantalum, then with TaN using physical vapour deposition (PVD); this barrier coated copper is then coated with more copper by PVD, and infilled with electrolytically coated copper, before being mechanically processed (grind/polishing). [10]

It also has application in thin film resistors. [3] It has the advantage over nichrome resistors of forming a passivating oxide film which is resistant to moisture. [11]

Related Research Articles

<span class="mw-page-title-main">Boron nitride</span> Refractory compound of boron and nitrogen with formula BN

Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form.

<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.

A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films is a fundamental step in many applications. A familiar example is the household mirror, which typically has a thin metal coating on the back of a sheet of glass to form a reflective interface. The process of silvering was once commonly used to produce mirrors, while more recently the metal layer is deposited using techniques such as sputtering. Advances in thin film deposition techniques during the 20th century have enabled a wide range of technological breakthroughs in areas such as magnetic recording media, electronic semiconductor devices, integrated passive devices, LEDs, optical coatings, hard coatings on cutting tools, and for both energy generation and storage. It is also being applied to pharmaceuticals, via thin-film drug delivery. A stack of thin films is called a multilayer.

In chemistry, a nitride is an inorganic compound of nitrogen. The "nitride" anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications, such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics. Metal nitrido complexes are also common.

Ion beam assisted deposition is a materials engineering technique which combines ion implantation with simultaneous sputtering or another physical vapor deposition technique. Besides providing independent control of parameters such as ion energy, temperature and arrival rate of atomic species during deposition, this technique is especially useful to create a gradual transition between the substrate material and the deposited film, and for depositing films with less built-in strain than is possible by other techniques. These two properties can result in films with a much more durable bond to the substrate. Experience has shown that some meta-stable compounds like cubic boron nitride (c-BN), can only be formed in thin films when bombarded with energetic ions during the deposition process.

<span class="mw-page-title-main">Titanium nitride</span> Ceramic material

Titanium nitride is an extremely hard ceramic material, often used as a physical vapor deposition (PVD) coating on titanium alloys, steel, carbide, and aluminium components to improve the substrate's surface properties.

<span class="mw-page-title-main">Metalorganic vapour-phase epitaxy</span> Method of producing thin films (polycrystalline and single crystal)

Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. It is a process for growing crystalline layers to create complex semiconductor multilayer structures. In contrast to molecular-beam epitaxy (MBE), the growth of crystals is by chemical reaction and not physical deposition. This takes place not in vacuum, but from the gas phase at moderate pressures. As such, this technique is preferred for the formation of devices incorporating thermodynamically metastable alloys, and it has become a major process in the manufacture of optoelectronics, such as Light-emitting diodes, its most widespread application. It was first demonstrated in 1967 at North American Aviation Autonetics Division in Anaheim CA by Harold M. Manasevit.

<span class="mw-page-title-main">Ion plating</span> Method of coating solid surfaces with ions

Ion plating (IP) is a physical vapor deposition (PVD) process that is sometimes called ion assisted deposition (IAD) or ion vapor deposition (IVD) and is a modified version of vacuum deposition. Ion plating uses concurrent or periodic bombardment of the substrate, and deposits film by atomic-sized energetic particles called ions. Bombardment prior to deposition is used to sputter clean the substrate surface. During deposition the bombardment is used to modify and control the properties of the depositing film. It is important that the bombardment be continuous between the cleaning and the deposition portions of the process to maintain an atomically clean interface. If this interface is not properly cleaned, then it can result into a weaker coating or poor adhesion.

<span class="mw-page-title-main">Zinc nitride</span> Chemical compound

Zinc nitride (Zn3N2) is an inorganic compound of zinc and nitrogen, usually obtained as (blue)grey crystals. It is a semiconductor. In pure form, it has the anti-bixbyite structure.

Electron-beam physical vapor deposition, or EBPVD, is a form of physical vapor deposition in which a target anode is bombarded with an electron beam given off by a charged tungsten filament under high vacuum. The electron beam causes atoms from the target to transform into the gaseous phase. These atoms then precipitate into solid form, coating everything in the vacuum chamber with a thin layer of the anode material.

<span class="mw-page-title-main">Vanadium nitride</span> Chemical compound

Vanadium nitride, VN, is a chemical compound of vanadium and nitrogen.

<span class="mw-page-title-main">Vacuum deposition</span> Method of coating solid surfaces

Vacuum deposition is a group of processes used to deposit layers of material atom-by-atom or molecule-by-molecule on a solid surface. These processes operate at pressures well below atmospheric pressure. The deposited layers can range from a thickness of one atom up to millimeters, forming freestanding structures. Multiple layers of different materials can be used, for example to form optical coatings. The process can be qualified based on the vapor source; physical vapor deposition uses a liquid or solid source and chemical vapor deposition uses a chemical vapor.

<span class="mw-page-title-main">Physical vapor deposition</span> Method of coating solid surfaces with thin films

Physical vapor deposition (PVD), sometimes called physical vapor transport (PVT), describes a variety of vacuum deposition methods which can be used to produce thin films and coatings on substrates including metals, ceramics, glass, and polymers. PVD is characterized by a process in which the material transitions from a condensed phase to a vapor phase and then back to a thin film condensed phase. The most common PVD processes are sputtering and evaporation. PVD is used in the manufacturing of items which require thin films for optical, mechanical, electrical, acoustic or chemical functions. Examples include semiconductor devices such as thin-film solar cells, microelectromechanical devices such as thin film bulk acoustic resonator, aluminized PET film for food packaging and balloons, and titanium nitride coated cutting tools for metalworking. Besides PVD tools for fabrication, special smaller tools used mainly for scientific purposes have been developed.

<span class="mw-page-title-main">Sputter deposition</span> Method of thin film application

Sputter deposition is a physical vapor deposition (PVD) method of thin film deposition by the phenomenon of sputtering. This involves ejecting material from a "target" that is a source onto a "substrate" such as a silicon wafer. Resputtering is re-emission of the deposited material during the deposition process by ion or atom bombardment. Sputtered atoms ejected from the target have a wide energy distribution, typically up to tens of eV. The sputtered ions can ballistically fly from the target in straight lines and impact energetically on the substrates or vacuum chamber. Alternatively, at higher gas pressures, the ions collide with the gas atoms that act as a moderator and move diffusively, reaching the substrates or vacuum chamber wall and condensing after undergoing a random walk. The entire range from high-energy ballistic impact to low-energy thermalized motion is accessible by changing the background gas pressure. The sputtering gas is often an inert gas such as argon. For efficient momentum transfer, the atomic weight of the sputtering gas should be close to the atomic weight of the target, so for sputtering light elements neon is preferable, while for heavy elements krypton or xenon are used. Reactive gases can also be used to sputter compounds. The compound can be formed on the target surface, in-flight or on the substrate depending on the process parameters. The availability of many parameters that control sputter deposition make it a complex process, but also allow experts a large degree of control over the growth and microstructure of the film.

High-power impulse magnetron sputtering is a method for physical vapor deposition of thin films which is based on magnetron sputter deposition. HIPIMS utilises extremely high power densities of the order of kW⋅cm−2 in short pulses (impulses) of tens of microseconds at low duty cycle of < 10%. Distinguishing features of HIPIMS are a high degree of ionisation of the sputtered metal and a high rate of molecular gas dissociation which result in high density of deposited films. The ionization and dissociation degree increase according to the peak cathode power. The limit is determined by the transition of the discharge from glow to arc phase. The peak power and the duty cycle are selected so as to maintain an average cathode power similar to conventional sputtering (1–10 W⋅cm−2).

<span class="mw-page-title-main">Titanium aluminium nitride</span> Group of metastable hard coatings

Titanium aluminium nitride (TiAlN) or aluminium titanium nitride is a group of metastable hard coatings consisting of nitrogen and the metallic elements aluminium and titanium. This compound as well as similar compounds(such as TiN and TiCN) are most notably used for coating machine tools such and endmills and drills to change their properties, such as increased thermal stability and/or wear resistance. Four important compositions are deposited in industrial scale by physical vapor deposition methods:

<span class="mw-page-title-main">Tantalum(V) ethoxide</span> Chemical compound

Tantalum(V) ethoxide is a metalorganic compound with formula Ta2(OC2H5)10, often abbreviated as Ta2(OEt)10. It is a colorless solid that dissolves in some organic solvents but hydrolyzes readily. It is used to prepare films of tantalum(V) oxide.

<span class="mw-page-title-main">High-entropy alloy</span> Alloys with high proportions of several metals

High-entropy alloys (HEAs) are alloys that are formed by mixing equal or relatively large proportions of (usually) five or more elements. Prior to the synthesis of these substances, typical metal alloys comprised one or two major components with smaller amounts of other elements. For example, additional elements can be added to iron to improve its properties, thereby creating an iron-based alloy, but typically in fairly low proportions, such as the proportions of carbon, manganese, and others in various steels. Hence, high-entropy alloys are a novel class of materials. The term "high-entropy alloys" was coined by Taiwanese scientist Jien-Wei Yeh because the entropy increase of mixing is substantially higher when there is a larger number of elements in the mix, and their proportions are more nearly equal. Some alternative names, such as multi-component alloys, compositionally complex alloys and multi-principal-element alloys are also suggested by other researchers.

Two dimensional hexagonal boron nitride is a material of comparable structure to graphene with potential applications in e.g. photonics., fuel cells and as a substrate for two-dimensional heterostructures. 2D h-BN is isostructural to graphene, but where graphene is conductive, 2D h-BN is a wide-gap insulator.

<span class="mw-page-title-main">Beta-tungsten</span> Metastable phase of tungsten

Beta-tungsten (β-W) is a metastable phase of tungsten widely observed in tungsten thin films. While the commonly existing stable alpha-tungsten (α-W) has a body-centered cubic (A2) structure, β-W adopts the topologically close-packed A15 structure containing eight atoms per unit cell, and it irreversibly transforms to the stable α phase through thermal annealing of up to 650 °C. It has been found that β-W possesses the giant spin Hall effect, wherein the applied charge current generates a transverse spin current, and this leads to potential applications in magnetoresistive random access memory devices.

References

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  2. Terao, Nobuzo (1971), "Structure of Tantalum Nitrides", Japanese Journal of Applied Physics, 10 (2): 248–259, Bibcode:1971JaJAP..10..248T, doi:10.1143/JJAP.10.248, S2CID   122356023
  3. 1 2 Akashi, Teruhisa (2005), "Fabrication of a Tantalum-Nitride Thin-Film Resistor with a Low-Variability Resistance", IEEJ Transactions on Sensors and Micromachines, 125 (4): 182–187, Bibcode:2005IJTSM.125..182A, doi: 10.1541/ieejsmas.125.182
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  5. Lima, Lucas; Moreiraa, Milena D.; Cioldin, Fred; Diniza, José Alexandre; Doi, Ioshiaki (2010), "Tantalum Nitride as Promising Gate Electrode for MOS Technology", ECS Trans., 31 (1): 319–325, Bibcode:2010ECSTr..31a.319L, doi:10.1149/1.3474175, S2CID   97901262
  6. Tsai, M. H.; Sun, S. C. (1995), "Metalorganic chemical vapor deposition of tantalum nitride by tertbutylimidotris(diethylamido)tantalum for advanced metallization", Appl. Phys. Lett., 67 (8): 1128, Bibcode:1995ApPhL..67.1128T, doi:10.1063/1.114983
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  9. Kim, Deok-kee; Lee, Heon; Kim, Donghwan; Kim, Young Keun (October 2005), "Electrical and mechanical properties of tantalum nitride thin films deposited by reactive sputtering", Journal of Crystal Growth, 283 (3–4): 404–408, Bibcode:2005JCrGr.283..404K, doi:10.1016/j.jcrysgro.2005.06.017
  10. LaPedus, Mark (26 June 2012), "Challenges Mount For Interconnect", semiengineering.com
  11. Licari, James J.; Enlow, Leonard R. (1998), Hybrid Microcircuit technology Handbook (2nd ed.), Noyes Publications, § 2.5 Characteristics of Tantalum Nitride Resistors, pp.83-4