By Dixon R.N., Thomson C.
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Extra info for A Review of the Recent Literature
The near-perfect linearity of this plot is typical of substitutions for a number of ligand pairs in all of the maingroup compounds we have examined to date, including those of C, Si, B, Al, and In. We are thus conﬁdent that the values given here are sufﬁciently accurate to be used for the qualitative analysis below and that the low uncertainties reported are a reﬂection of the high degree of convergence in the calculations. In contrast, methyl-for-chlorine substitution is decidedly nonlinear, a feature also displayed by the lighter Group 14 compounds.
However, at the relatively low temperatures typical of tin oxide CVD (∼ 873–973 K), we do not expect these oxides to form, based on the equilibrium calculations described above. , based on minimization of the Gibbs free energy), but there are also exothermic reaction pathways that we expect to be kinetically favorable. The primary tin carrier in the CVD process could therefore be a tin hydroxide. Complete conversion to SnO2 would most likely occur via reactions on the surface. 1 Equilibrium Predictions Figure 18 indicates that the most stable tin compounds for an input reaction mixture containing MTBC with excess H2 O and O2 (2% MBTC/5% H2 O/20% O2 ) are again tin hydroxides, with Cl3 SnOH being the most stable tin-containing species.
At lower temperatures, which premixed reactants would encounter as they enter a CVD reactor, complexes of the tin subchlorides SnCl3 and SnCl2 with water, as well as SnCl4 and the hydroxide Cl3 SnOH, are predicted to form. Since little or no MBTC decomposition is expected at these temperatures , formation of such species seems kinetically unlikely. More plausible would be direct formation of a water-MBTC complex, as discussed above (Sect. 6). Although we do not have thermodynamic data for these complexes, the absence of SnCl4 (H2 O)2 , which was included in the calculations, suggests that analogous complexes involving MBTC would not be stable at these temperatures.
A Review of the Recent Literature by Dixon R.N., Thomson C.