Initial phase formation in thin film and bulk Fe/Si couples has been investigated using transmission and scanning electron microscopy (TEM and SEM). For the thin film couples, ≈165 nm of Fe was deposited by electron beam evaporation onto <111> oriented Si substrates. SiO2 capping layers (≈100nm thick) were used to protect the Fe from oxidation during subsequent annealing. Bulk diffusion couples were fabricated by clamping together polycrystalline Fe pieces and <111> oriented single crystal Si pieces and sealed in evacuated (≈10-4 torr) quartz capsules. Annealing of thin film couples was done at temperatures ranging from 300°C to 500°C for up to several hours. Bulk couples were annealed at 700°C for up to ≈1000hrs.
Interfacial reactions were detected in as deposited thin film couples. A layer =5nm thick was identified, through electron diffraction, as poorly crystalline off-stoichiometric Fe3Si. Iron was the major diffuser during the formation of Fe3Si. During annnealing off-stoichiometric Fe3Si transformed to stoichiometric Fe3Si. FeSi was the next phase to form - initially detected after annealing at 300°C for 3 hrs. Similar results were obtained for bulk couples. The first phase to form was ordered stoichiometric Fe3Si (initially detected after 7 hrs), followed by FeSi (≈23 hrs) and then FeSi2 (>200 hrs). The formation behavior of these phase is discussed.