By Mark D. Allendorf, A. M. B. van Mol (auth.), Roland A. Fischer (eds.)
Material synthesis by way of the transformation of organometallic compounds (precursors) by way of vapor deposition concepts equivalent to chemical vapor deposition (CVD) and atomic layer deposition (ALD) has been within the leading edge of recent day examine and improvement of latest fabrics. There exists a necessity for brand spanking new routes for designing and synthesizing new precursors in addition to the appliance of validated molecular precursors to derive tuneable fabrics for technological calls for. in regards to the precursor chemistry, a such a lot specific knowing of the mechanistic complexity of fabrics formation from molecular precursors is essential for additional improvement of recent procedures and complex fabrics. to stress and stimulate examine in those parts, this quantity contains a variety of case reviews masking quite a few key-aspects of the interaction of precursor chemistry with the method stipulations of fabrics formation, fairly the similarities and changes of CVD, ALD and nanoparticle synthesis, e.g. colloid chemistry, concerning adapted molecular precursors.
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In these cases, higher levels of theory are required. For tin compounds, we ﬁnd that compounds containing unsaturated oxygen atoms are particularly problematic, and for these cases we developed approaches using coupled cluster (CC) theory to predict the electronic energy. Although CC theory is not a true multireference approach, it is found that using high levels of this theory including at least a perturbative correction for connected triples (the CCSD(T) method) can successfully correct for the effects of a multireference wave function in weak to moderately multireference systems .
The total pressure was 1 atm. These conditions are similar to those used in commercial tin oxide CVD processes. Note that in the following discussion of reaction mechanisms, all heats of reaction (∆HR◦ ) are given at 298 K. 1 SnCl4 Global equilibrium calculations for SnCl4 in N2 and with excess O2 reveal that SnCl4 is the most stable tin species over a wide temperature range. Experimentally it is found that no deposition of tin oxide occurs from 1–3% SnCl4 + 20% O2 mixtures at temperatures up to at least 923 K .
Additional theory directed toward determining transition states for possible HCl elimination reactions and experiments to measure rate constants of reactions with water are needed, however, to provide a quantitative assessment of the importance of this chemistry. 5 Gas-Phase Reaction Pathways: Equilibrium Calculations and Mechanism Analysis Although the temperatures typically encountered in tin oxide CVD processes are too low and the residence times to short to expect that the system will come to thermodynamic equilibrium, calculation of the equilibrium composition using Gibbs free energy minimization techniques is a useful starting point for the development of chemical mechanisms.