Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Diversity in a simple co-crystal: racemic and kryptoracemic behaviour.

The crystal structure containing (+/-)-3-methyl-2-phenylbutyramide with salicylic acid is the first example of a kryptoracemate co-crystal. It exhibits the first temperature mediated reversible single-crystal to single-crystal transition between two kryptoracemate forms, in addition to crystallising in another, racemic, form. Theoretical calculations and structural analysis reveal that there are only small differences in both energy and packing arrangements between the three forms. These results suggest that co-crystals can be an opportunity to investigate kryptoracemate behaviour.

Self-assembly of gold nanocrystals into discrete coupled plasmonic structures

Development of methodologies for the controlled chemical assembly of nanoparticles into plasmonic molecules of predictable spatial geometry is vital in order to harness novel properties arising from the combination of the individual components constituting the resulting superstructures. This paper presents a route for fabrication of gold plasmonic structures of controlled stoichiometry obtained by the use of a di-rhenium thio-isocyanide complex as linker molecule for gold nanocrystals. Correlated scanning electron microscopy (SEM)—dark-field spectroscopy was used to characterize obtained discrete monomer, dimer and trimer plasmonic molecules. Polarization-dependent scattering spectra of dimer structures showed highly polarized scattering response, due to their highly asymmetric D∞h geometry. In contrast, some trimer structures displayed symmetric geometry (D3h), which showed small polarization dependent response. Theoretical calculations were used to further understand and attribute the origin of plasmonic bands arising during linker-induced formation of plasmonic molecules. Theoretical data matched well with experimentally calculated data. These results confirm that obtained gold superstructures possess properties which are a combination of the properties arising from single components and can, therefore, be classified as plasmonic molecules