The growth of ultrathin films of Si3N4 directly on Si surfaces is studied with valence band photoemission. The information from these studies about the growth mechanism and the changes of the electronic structure is enhanced by the use of various photon energies with synchrotron radiation. The silicon nitride films are grown isothermally on the Si(1 0 0) and Si(1 1 1) surfaces by reactions with atomic N. The atomic nitrogen is produced by using a remote, microwave excited nitrogen plasma. The growth under these conditions was earlier shown to be self limiting. The details in the valence band spectra are identified and resolved with numerical methods, and followed systematically during the growth. Thus the identification of Si surface states, Si-nitride interface states and bulk nitride states becomes possible. The previously obtained separation between amorphous and crystalline growth occurring around 500 °C is further supported in the present studies.
