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Author(s):   Creighton, J.R.; Wang, G.T.;
Title:   Kinetics of metal organic-ammonia adduct decomposition: implications for Group-III Nitride MOCVD
Journal:   J. Phys. Chem. A
Volume:   109
Page(s):   10554 - 10562
Year:   2005
Reference type:   Journal article
Squib:   2005CRE/WAN10554-10562

Reaction:   GaMe3:NH3 → GaMe2NH2 + CH4
Reaction order:   1
Temperature:   298 - 573 K
Pressure:  6.67E-2 - 0.27 bar
Rate expression:   1.0x1012 [s-1] e-129704 [J/mole]/RT
Category:  Experiment
Data type:   Derived from fitting to a complex mechanism
Pressure dependence:   None reported
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Thermal
Time resolution:   By end product analysis
Analytical technique:   Fourier transform (FTIR)
Comments:   FTIR spectroscopic study of reations involving adducts of Trimethylaluminum and Trimethylgallium with ammonia (NH3). Temperature range 298-573K, 50-200 torr H2 bath gas. Detected CH4 and -NH2 group in product stream. Measured conversion as a function of residence time to get rate expressions.

Directly measured decomposition of AlMe3:NH3 adduct to AlMe2NH2 + CH4. Indirectly measured decomposition of GaMe3:NH3 to GaMe2NH2 + CH4 assuming a preexponential and some complex chemistry. Also studied the association reactions AlMe3 + NH3 -> AlMe3:NH2 and AlMe2NH2 + AlMe2NH2 -> [AlMe2NH2]2, but no rate expressions were determined.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [s-1]
298 1.84E-11
300 2.61E-11
325 1.43E-9
350 4.40E-8
375 8.58E-7
400 1.16E-5
425 1.15E-4
450 8.80E-4
475 5.46E-3
500 2.82E-2
525 1.25E-1
550 4.81E-1
573 1.50E0