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Tungsten hexafluoride
From Wikipedia, the free encyclopedia
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Tungsten(VI) fluoride, also known as Tungsten hexafluoride

tungsten hexafluoride, is the inorganic
compound of tungsten and fluorine with the
formula WF6. This corrosive, colorless
compound is a gas under standard conditions.
With a density of about 13 g/L (roughly 11
times heavier than air.[1][2][3]), WF6 is one of
the heaviest known gases under standard
IUPAC name
conditions[4]. WF6 gas is most commonly
Tungsten hexafluoride
used in the production of semiconductor Tungsten(VI) fluoride
circuits and circuit boards through the process Identifiers
of chemical vapor deposition – upon CAS number 7783-82-6
decomposition, molecules of WF6 leave a
PubChem 522684
residue of metallic tungsten. This layer serves
Properties
as low-resistive metallic "interconnects."[5]
Molecular formula WF6
Molar mass 297.83 g/mol
Appearance Colorless gas
Contents Density 13.0 g/L, gas
Melting point
2.3 °C (275.45 K)
■ 1 Properties
■ 2 Synthesis Boiling point
■ 3 Reactions 17.1 °C (290.25 K)
■ 4 Applications in semiconductor
industry Solubility in water Hydrolyzes
■ 4.1 Silicon Structure
■ 4.2 Hydrogen Molecular shape Octahedral
■ 4.3 Silane and germane Dipole moment zero
Hazards
■ 5 Other applications
■ 6 Safety EU Index Not listed
■ 7 Related compounds Flash point Non-flammable
■ 8 Trivia Related compounds
■ 9 References Other anions Tungsten hexachloride
Tungsten hexabromide
Other cations Chromium(V) fluoride
Molybdenum(VI) fluoride
Properties Related compounds Tungsten(IV) fluoride
Tungsten(V) fluoride
At ambient pressure and temperatures above (what is this?) (verify)
17 °C, tungsten hexafluoride is a colorless[4] (http://en.wikipedia.org/w/index.php?
title=Tungsten_hexafluoride&diff=cur&oldid=263462885)
diamagnetic gas. The WF6 molecule is Except where noted otherwise, data are given for materials
octahedral with the symmetry point group of in their standard state (at 25 °C, 100 kPa)
Oh. The W–F bond distances are 183.2 pm.[6] Infobox references
Between 2.3 and 17 °C, tungsten hexafluoride
condenses into a pale yellow liquid having the density of 3.44 g/cm3 at 15 °C. At 2.3 °C it freezes
into a white solid having a cubic crystalline structure, the lattice constant of 628 pm and calculated

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density 3.99 g/cm3. At −9 °C this structure transforms into an orthorhombic solid with the lattice
constants of a = 960.3 pm, b = 871.3 pm, and c = 504.4 pm, and the density of 4.56 g/cm3. In this
phase, the W–F distance is 181 pm, and the mean closest intermolecular contacts are 312 pm.
Whereas WF6 gas is one of the heaviest gases, with the density exceeding that of the heaviest
elemental gas radon (9.73 g/L), the density of WF6 in the liquid and solid state is rather moderate.[7]

Synthesis
Tungsten hexafluoride is commonly produced by the exothermic reaction of fluorine gas with
tungsten powder at a temperature between 350 and 400 °C:[8]

W + 3 F2 → WF6

The gaseous product is condensed and separated by distillation from WOF4, a common impurity. In
a variation on the direct fluorination, the metal is placed in a heated reactor, slightly pressurized to
1.2 to 2.0 psi (8.3 to 14 kPa), with a constant flow of WF6 infused with a small amount of fluorine
gas.[9]

The fluorine gas in the above method can be substituted by ClF, ClF3 or BrF3. An alternative
procedure for producing tungsten fluoride is to react tungsten trioxide (WO3) with HF, BrF3 or SF4.
Tungsten fluoride can also be obtained by conversion of tungsten hexachloride:[4]

WCl6 + 6 HF → WF6 + 6 HCl or

WCl6 + 2 AsF3 → WF6 + 2 AsCl3 or
WCl6 + 3 SbF5 → WF6 + 3 SbF3Cl2

Reactions
On contact with water, tungsten fluoride gives hydrogen fluoride (HF) and tungsten oxyfluorides,
eventually forming tungsten trioxide:[4]

WF6 + 3 H2O → WO3 + 6 HF

Unlike some other metal fluorides, WF6 is not a useful fluorinating agent nor is it a powerful
oxidant. It can be reduced to the yellow tetramer WF4.[10]

Applications in semiconductor industry

The dominant application of tungsten fluoride is in semiconductor industry, where it is widely used
for depositing tungsten metal in a chemical vapor deposition process. The expansion of the industry
in the 1980s and 1990s resulted in the increase of WF6 consumption, which remains at around 200
tonnes per year worldwide. Tungsten metal is attractive because of its relatively high thermal and
chemical stability, as well as low resistivity (5.6 µΩ·cm) and electromigration. Whereas WF6 is
favored over relative compounds, such as WCl6 or WBr6, because of its higher vapor pressure
resulting in higher deposition rates. Since 1967, two WF6 deposition routes have been developed
employed, thermal decomposition and hydrogen reduction.[11] The required WF6 gas purity is rather
high and varies between 99.98% and 99.9995% depending on the application.[4]

WF6 molecules have to be split up in the CVD process. The decomposition is usually facilitated by
mixing WF6 with hydrogen, silane, germane, diborane, phosphine, and related hydrogen-containing
gases.

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Silicon

WF6 reacts upon contact with silicon substrate.[4] The WF6 decomposition on silicon is temperature-
dependent:

2 WF6 + 3 Si → 2 W + 3 SiF4 below 400 °C and

WF6 + 3 Si2 → W + 3 SiF2 above 400 °C.

This dependence is crucial as twice more silicon is being consumed at higher temperatures. The
deposition occurs selectively on pure Si only, but not on silicon oxide or nitride, thus the reaction is
highly sensitive to the contamination or substrate pre-treatment. The decomposition reaction is fast,
but saturates when the tungsten layer thickness reaches 10–15 micrometers. The saturation occurs
because the tungsten layer stops diffusion of WF6 molecules to the Si substrate which is the only
catalyst of molecular decomposition in this process.[4]

If the deposition occurs not in inert but in oxygen containing atmosphere (air) then instead of
tungsten, a tungsten oxide layer is produced.[12]

Hydrogen
The deposition process occurs at temperatures between 300 and 800 °C and results in formation of
hydrofluoric acid vapors:

WF6 + 3 H2 → W + 6 HF

The crystallinity of the produced tungsten layers can be controlled by altering the WF6/H2 ratio and
the substrate temperature: low ratios and temperatures result in (100) oriented tungsten crystallites
whereas higher values favor the (111) orientation. Formation of HF is a drawback as the HF vapor is
very aggressive and etches away most materials. Also, the deposited tungsten shows poor adhesion
to the silicon dioxide which the main passivation material in semiconductor electronics. Therefore,
SiO2 has to be covered with an extra buffer layer prior to the tungsten deposition. On the other hand,
etching by HF may be beneficial to remove unwanted impurity layers.[4]

Silane and germane

The characteristic features of tungsten deposition from the WF6/SiH4 are high speed, good adhesion
and layer smoothness. The drawbacks are explosion hazard and high sensitivity of the deposition rate
and morphology to the process parameters, such as mixing ratio, substrate temperature, etc.
Therefore, silane is commonly used to create a thin tungsten nucleation layer. It is then switched to
hydrogen, that slows down the deposition and cleans up the layer.[4]

Deposition from WF6/GeH4 mixture is similar to that of WF6/SiH4, but the tungsten layer becomes
contaminated with relatively (compared to Si) heavy germanium up to concentrations of 10–15 %.
This increases tungsten resistance from about 5 to 200 µΩ·cm.[4]

Other applications
WF6 can be used for the production of tungsten carbide.

As a heavy gas, WF6 can be used as a buffer to control gas reactions. For example, it slows down the
chemistry of the Ar/O2/H2 flame and reduces the flame temperature.[13]

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Safety
Tungsten hexafluoride is an extremely corrosive compound that attacks any tissue. Exposure of
humans to the gas first affects the eyes and respiratory tracts causing irritation, loss of vision, cough
and excessive formation of saliva and sputum. Upon mixing with the body fluids, the gas transforms
into hydrofluoric acid which burns the skin and mucous tissues of the respiratory tract. Upon
prolonged exposure, this results in pneumonitis and pulmonary edema and could be fatal. Because of
the formation of hydrofluoric acid upon reaction of WF6 with humidity, WF6 storage vessels have
Teflon gaskets.[14]

Related compounds
See also: hexafluoride

The high symmetry of the WF6 molecule is seen in most related compounds. However, it is
interesting to note that tungsten hexahydride (WH6) and hexamethyltungsten (W(CH3)6) adopt a
trigonal prismatic structure.[15][16] Numerous hexafluorides are known with other metals and
metalloids. Such MF6 compounds characteristically form dense gases, however, when element M is
heavier than tungsten, the compound is either liquid or solid at room temperature.

Trivia
In his book Uncle Tungsten, Oliver Sacks describes how his uncle—an avid fan of tungsten and
tungsten chemistry—wanted WF6-filled balloons for his 65th birthday.[17] However, WF6 would
react with most organic materials, including rubber.

References
1. ^ Jean-Pierre Roucan, Marie-Christine Noel-Dutriax. Proprietes Physiques des Composes Mineraux
(http://books.google.com/?id=BpPmFsA4yn4C&pg=PT138) . Ed. Techniques Ingénieur. p. 138.
http://books.google.com/?id=BpPmFsA4yn4C&pg=PT138.
2. ^ Gas chart (http://www.qualiflow.com/pdf/faq_gas_chart.pdf)
3. ^ Matheson gas MSDS (http://www.vngas.com/pdf/MTG_MSDS/MAT24560000220003-Tungsten-
Hexafluoride.pdf)
4. ^ a b c d e f g h i j Erik Lassner, Wolf-Dieter Schubert (1999). Tungsten: properties, chemistry, technology
of the element, alloys, and chemical compounds (http://books.google.com/?
id=foLRISkt9gcC&pg=PA168#v=onepage&q=) . Springer. pp. 111, 168. ISBN 0-30645053-4.
http://books.google.com/?id=foLRISkt9gcC&pg=PA168#v=onepage&q=.
5. ^ Tungsten and Tungsten Silicide Chemical Vapor Deposition
(http://www.timedomaincvd.com/CVD_Fundamentals/films/W_WSi.html) .
6. ^ Lide, D. R., ed. (2005), CRC Handbook of Chemistry and Physics (86th ed.), Boca Raton (FL): CRC
Press, ISBN 0-8493-0486-5 p. 4-93.
7. ^ Levy, J (1975). "The structures of fluorides XIII: The orthorhombic form of tungsten hexafluoride at
193 K by neutron diffraction". Journal of Solid State Chemistry 15: 360. doi:10.1016/0022-4596(75)
90292-3 (http://dx.doi.org/10.1016%2F0022-4596%2875%2990292-3) .
8. ^ Homer F. Priest; Swinehert, Carl F. (1950). "Anhydrous Metal Fluorides". Inorg. Synth. (Wiley-
Interscience) 3: 171–183. doi:10.1002/9780470132340.ch47 (http://dx.doi.org/10.1002%
2F9780470132340.ch47) . ISBN 978-0-47013162-6.
9. ^ U.S. Patent 6,544,889 (http://www.google.com/patents?vid=6544889) "Method for tungsten chemical
vapor deposition on a semiconductor substrate" Issued on April 8, 2003
10. ^ Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth
-Heinemann. ISBN 0-7506-3365-4.

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11. ^ Aigueperse, Jean; Paul Mollard, Didier Devilliers, Marius Chemla, Robert Faron, Renée Romano, Jean
Pierre Cuer (2005). "Fluorine Compounds, Inorganic". in Ullmann. Encyclopedia of Industrial
Chemistry. Weinheim: Wiley-VCH.
12. ^ Rein U. Kirss and Lamartine Meda (1998). "Chemical vapor deposition of tungsten oxide". Applied
Organometallic Chemistry 12 (3): 155. doi:10.1002/(SICI)1099-0739(199803)12:3<155::AID-
AOC688>3.0.CO;2-Z (http://dx.doi.org/10.1002%2F%28SICI%291099-0739%28199803%2912%3A3%
3C155%3A%3AAID-AOC688%3E3.0.CO%3B2-Z) .
13. ^ Semi-conducting metal oxide nanoparticles from a low-pressure premixed H2/O2/Ar flame: Synthesis
and Characterization (http://books.google.com/?id=0B5HI9TNmakC&pg=PT64) . Cuvillier Verlag.
p. 64. ISBN 3-86727816-4. http://books.google.com/?id=0B5HI9TNmakC&pg=PT64.
14. ^ Tungsten fluoride MSDS (http://www.orcbs.msu.edu/msds/LINDE_MSDS/pdf/154.pdf) , Linde Gas
15. ^ Haaland, Arne; Hammel, Andreas; Rypdal, Kristin; Volden, Hans V. (1990). "The coordination
geometry of gaseous hexamethyltungsten is not octahedral". Journal of the American Chemical Society
112: 4547. doi:10.1021/ja00167a065 (http://dx.doi.org/10.1021%2Fja00167a065) .
16. ^ Frank Weinhold, Clark R. Landis (2005). Valency and bonding: a natural bond orbital donor-acceptor
perspective (http://books.google.com/?id=6153Kt2ikggC&pg=PA427) . Cambridge University Press.
p. 427. ISBN 0-52183128-8. http://books.google.com/?id=6153Kt2ikggC&pg=PA427.
17. ^ Oliver Sacks (2001). Uncle Tungsten: Memories of a Chemical Boyhood. Knopf. ISBN 0-37540448-1.
Retrieved from "http://en.wikipedia.org/wiki/Tungsten_hexafluoride"
Categories: Tungsten compounds | Fluorides | Metal halides | Lachrymatory agents | Octahedral
compounds

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