Trimethylindium

Trimethylindium
Names
Preferred IUPAC name
Trimethylindium
Systematic IUPAC name
Trimethylindigane[1]
Other names
Trimethylindane, indium trimethyl
Identifiers
3385-78-2 YesY
3D model (Jmol) Interactive image
ChemSpider 69370 YesY
ECHA InfoCard 100.020.183
EC Number 222-200-9
PubChem 76919
Properties
InC
3H
9
Molar mass 159.922 g mol−1
Appearance White, opaque crystals
Density 1.568 g cm−3 (at 20 °C)
Melting point 88 °C (190 °F; 361 K)
Boiling point 134 °C (273 °F; 407 K) (decomposes above 101 °C (214 °F; 374 K))
Reacts
Thermochemistry
150.5-169.7 kJ mol−1
Hazards
Main hazards Pyrophoric
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Trimethylindium (abbr: TMI or TMIn), In(CH3)3, (CAS #: 3385-78-2) is the preferred organometallic source of indium for metalorganic vapour phase epitaxy (MOVPE) of indium-containing compound semiconductors, such as InP, InAs, InN, InSb, GaInAs, InGaN, AlGaInP, AlInP, AlInGaNP, etc. TMI is a white, crystalline and sublimable solid, with melting point 88 °C. TMI is pyrophoric (ignites spontaneously upon contact with air), and its decomposition is often found to be uncontrollable as the temperature of its surrounding exceeds its melting point (i.e. > 88 °C) and reaches 101 °C and above. TMI is also reported to exhibit autocatalytic behavior during its thermal decomposition.[2] TMI therefore needs to be handled with the utmost care and caution, e.g. stored in preferably cool, dry place at 0-25 °C, and operating temperatures under 50 °C in order to avoid deterioration. TMI also reacts extremely violently with oxidizers and polyhalogenated compounds (such as CCl4 or CBrCl3), with which TMI is therefore incompatible. Hence, mixtures of TMI with oxidizers and/or polyhalogenated compounds must be avoided as they are potentially dangerous and explosive.

Preparation and Reactions

Trimethylindium, InMe3 can be produced by reacting InCl3 in diethyl ether solution either with the Grignard reagent, MeMgI, or methyllithium, LiMe.[3]

InCl3 + 3LiMe → Me3In.OEt2 + 3LiCl
InCl3 + 3MeMgI → Me3In.OEt2 + 3MgClI
the ether is removed at 25 °C in vacuo

InMe3 is a Lewis acid, weaker than trimethylaluminium, AlMe3 and trimethylgallium, GaMe3. It forms adducts with secondary amines and phosphines.[4] A complex with the heterocyclic triazine ligand PriN(CH2)3 forms a complex with 6 coordinate In, where the C-In-C angles are 114°-117° with three long bonds to the tridentate ligand with N-In-N angles of 48.6° and long In-N bonds of 278 pm.[5]

Structure

In the gaseous state InMe3 is monomeric, with a trigonal planar structure, and in benzene solution it is tetrameric.[4] In the solid state there are two polymorphs, a tetragonal phase which is obtained, for example, by sublimation and a lower density rhombohedral phase discovered in 2005,[6] when InMe3 re-crystallised from hexane solution.

In the tetragonal form InMe3 is tetrameric as in benzene solution and there is bridging between tetramers to give an infinite network. Each indium atom is five coordinate, in a distorted trigonal planar configuration, the three shortest bonds,(ca. 216 pm ) are those in the equatorial plane, with longer axial bonds, 308 pm for the In-C bonds joining the InMe3 units to form the tetramers and 356 pm for the In-C linking the tetramers into an infinite network.[7] The solid state structures of GaMe3 and TlMe3 are similar.[7] The association in the solid state accounts for the high melting point of 89°-89.8 °C compared to triethylindium which melts at -32 °C.[4]

The rhombohedral form of InMe3 consists of cyclic hexamers with 12 membered (InC)6 rings in an extended chair conformation. The hexamers are interlinked into an infinite network. Indium atoms are five coordinate the equatorial In-C distances average 216.7pm almost identical to the average for the tetragonal form, and the axial bonds are 302.8pm joining the InMe3 units into hexamers and 313.4 pm linking the hexamers to form the infinite network.[6]

Semiconductor grade TMI

The advancements in synthesis and purification chemistries have now made it possible to attain highest purity in TMI (99.9999% pure or greater), which is imperative for improved performance of semiconductor applications. Recent reports indicate some of the best electrical properties for InP alloys so far, by MOVPE using highest purity TMI available today, e.g. electron mobilities (Hall data) as high as 287,000 cm²/Vs at 77 K and 5400 cm²/Vs at 300 K, and background carrier concentration as low as 6×1013 cm−3,[8][9] which were not practically achievable in the past.

Accurate vapor pressure equation for TMI

The vapor pressure equations reported in the literature for TMI have been found to offer overestimated vapor pressure of TMI, often by as much as 20–40%. Not knowing the accurate vapor pressure has thus been a concern to crystal growers. In a recent study,[10] it was experimentally confirmed that the vapor pressure equation, log P (Torr)=10.98–3204/T (K), provides the most accurate vapor pressures of TMI within a wide range of MOVPE growth conditions.

References

  1. ↑ "Trimethylindium - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information. 27 March 2005. Descriptors Computed from Structure. Retrieved 21 September 2011.
  2. ↑ Chemistry of Materials (2000); doi:10.1021/cm990497f
  3. ↑ Main Group compounds in Inorganic Syntheses, vol 31, Schultz, Neumayer, Marks; Ed., Alan H. Cowley, John Wiley & Sons, Inc., 1997, ISBN 0471152889
  4. 1 2 3 CVD of compound semiconductors, Precursor Synthesis, Development and Applications, Anthony C. Jones, Paul O'Brien, John Wiley & Sons, 2008, ISBN 3527292942
  5. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
  6. 1 2 Lewiński, Janusz; Zachara, Janusz; Starowieyski, Kazimierz B.; Justyniak, Iwona; Lipkowski, Janusz; Bury, Wojciech; Kruk, Przemysław; Woźniak, Robert (2005). "A Second Polymorphic Form of Trimethylindium: Topology of Supramolecular Architectures of Group 13 Trimethyls". Organometallics. 24 (20): 4832–4837. doi:10.1021/om050386s. ISSN 0276-7333.
  7. 1 2 Inorganic Chemistry, (2d edition), Catherine E. Housecroft, Alan G. Sharpe, Pearson Education, 2005, ISBN 0130399132 , ISBN 978-0130399137
  8. ↑ Shenai, Deo V.; Timmons, Michael L.; Dicarlo, Ronald L.; Lemnah, Gregory K.; Stennick, Robert S. (2003). "Correlation of vapor pressure equation and film properties with trimethylindium purity for the MOVPE grown III–V compounds". Journal of Crystal Growth. 248: 91. doi:10.1016/S0022-0248(02)01854-7.
  9. ↑ Shenai, Deodatta V.; Timmons, Michael L.; Dicarlo, Ronald L.; Marsman, Charles J. (2004). "Correlation of film properties and reduced impurity concentrations in sources for III/V-MOVPE using high-purity trimethylindium and tertiarybutylphosphine". Journal of Crystal Growth. 272: 603. doi:10.1016/j.jcrysgro.2004.09.006.
  10. ↑ Shenai-Khatkhate, Deodatta V.; Dicarlo, Ronald L.; Ware, Robert A. (2008). "Accurate vapor pressure equation for trimethylindium in OMVPE". Journal of Crystal Growth. 310 (7–9): 2395. doi:10.1016/j.jcrysgro.2007.11.196.
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