2000
DOI: 10.1021/cm000107l
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Molecular Orbital Studies of Titanium Nitride Chemical Vapor Deposition:  Gas Phase Complex Formation, Ligand Exchange, and Elimination Reactions

Abstract: The chemical vapor deposition (CVD) of titanium nitride can be carried out with TiCl4 or Ti(NR2)4 and NH3. The present study uses molecular orbital methods to examine complexes of NH3 with TiCl4 and Ti(NH2)4 and the subsequent reaction paths for ligand exchange and elimination reactions which may occur in the gas phase. Geometry optimizations were carried out at the B3LYP/6-311G(d) level of density functional theory, and energies were calculated using a variety of levels of theory, up to G2 for systems with fi… Show more

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Cited by 25 publications
(32 citation statements)
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“…The calculated energetics for the analogous pathway to generate Ta Supplementary Information (Fig. 3S) for comparison and their activation barriers were similarly as high as $45 kcal/ mol [22][23][24]. The use of NH 3 as a co-reactant, however, decreased the carbon content in the CVD films from 30 to 1 at% [4], consistent with a facile pathway for elimination of carboncontaining ligands.…”
Section: Resultsmentioning
confidence: 82%
See 1 more Smart Citation
“…The calculated energetics for the analogous pathway to generate Ta Supplementary Information (Fig. 3S) for comparison and their activation barriers were similarly as high as $45 kcal/ mol [22][23][24]. The use of NH 3 as a co-reactant, however, decreased the carbon content in the CVD films from 30 to 1 at% [4], consistent with a facile pathway for elimination of carboncontaining ligands.…”
Section: Resultsmentioning
confidence: 82%
“…Fig. 3a illustrates the calculated energetics of the transamination of a dimethylamido ligand of TBDTMT with NH 3 [24][25][26]. The NH 3 addition to the unsaturated Ta center has a reaction enthalpy (DH1 298 ) of À2.1 kcal/mol.…”
Section: Resultsmentioning
confidence: 99%
“…14 However, according to the theoretical ab initio studies conducted on the ammonolysis of TiCl 4 (g)-NH 3 (g) gas phase reaction and the gas-liquid reaction of TiCl 4 (g)-NH 3 (l), substitution of up to three Cl atoms (x 5 3) by NH 2 groups appears to follow an exothermic reaction with excess NH 3 , while the complete ammonolysis of TiCl 4 to form Ti(NH 2 ) 4 is largely endothermic. [18][19][20] The formation of Ti(NH) 2 , however, requires more energy. The room-temperature reaction study by Fowles and Pollard 14 shows that the fully reacted powder contains three chlorine species (x 5 3) replaced by the amide (NH 2 ) groups.…”
Section: Resultsmentioning
confidence: 99%
“…When the temperature is raised to 10001C in the case of N 2 and Ar, the ends of the tube are at a high enough temperature to sublime NH 4 Cl and the atmosphere is probably similar to that of a TiCl 4 -N 2 -H 2 system where TiN is formed around 9001-10001C with the possibility of dissociation of NH 3 into N 2 and H 2 . 20 Table II show the crystallite size of the TiN determined from XRD line broadening of (200) peak at 42.71 using the Scherrer equation. The crystallite size calculations were performed five times for TiN obtained at each temperature and the mean and standard deviation have been included in Table II.…”
Section: August 2005mentioning
confidence: 99%
“…5,6 Despite that a great deal of attention has been paid to this system, the mechanism of this CVD reaction is not yet understood. There are several recent calculations 7,8 to explore the CVD reaction in gas phase, using gradient-corrected density functional theory with the Becke three-parameter exchange functional and the Lee-Yang-Parr correction functional (B3LYP). All these calculations have been examined the subsequent reactions paths for ligand exchange and elimination reactions, but were limited to the single molecule reactant.…”
Section: Introductionmentioning
confidence: 99%