Domain epitaxial growth of TiN/Si(001), TiN/GaAs(001), and Si/TiN/Si(001) heterostructures by laser physical vapor deposition: Theory and experiment

We have successfully deposited epitaxial titanium nitride films on (001) silicon and (001) gallium arsenide substrates and multilayer Si/TiN/Si(001) epitaxial heterostructures using pulsed laser (KrF: λ = 248 nm, τ = 25 ns) physical vapor deposition. The deposition of TiN was carried out at a substrate temperature of 600°C on Si(001) and 400°C on GaAs(00l). The interfaces were sharp without any indication of interfacial reaction. The epitaxial relationships were found to be <001> TiN ‖<001> Si on the silicon substrate, <001> Si ‖<001> TiN |<001> Si on the heterostructure, and [1-10] TiN‖[110] GaAs and [001] TiN ‖[110] GaAs on the GaAs substrate. The growth in these large-mismatch systems is modeled and the various energy terms contributing to the growth of these films are determined. The domain matching epitaxy provides a mechanism of epitaxial growth in systems with large lattice mismatch.The epitaxial growth is characterized by domain epitaxial orientation relationships with m lattice constants of epilayer matching with n of the substrate and with a small residual domain mismatch present in the epilayer. This residual mismatch is responsible for a coherent strain energy. The magnitude of compression of Ti-N bond in the first atomic layer, contributing to the chemical free energy of the interface during the initial stages of growth, is found to be a very important factor in determining the orientation relationship. This result was used to explain the differences in the orientaion relationships between TiN/Si and TiN/GaAs systems. The various energy terms associated with the domain epitaxial growth are evaluated to illustrate that the domain epitaxial growth is energetically favorable compared to the lattice mismatched epitaxial growth. The results of this analysis illustrate that the observed variations in the epitaxial growth are consistent with the minimum energy configurations associated with the domain epitaxial growth.