[57]Fe Mossbauer studies of surface interactions in a PVD process.

A critical stage of the combined steered arc and unbalanced magnetron process is the metal ion pre-treatment which improves the adhesion of the TiN coating. In this study, Conversion Electron Mossbauer Spectroscopy (CEMS) has been used to investigate surface interactions in a commercial Arc Bond Sputtering (ABS) coating system. A novel application of the Liljequist theory of CEMS has been used to determine ion etch rates for deposited natural iron on stainless steel substrates, for various Ti ion pre¬treatment processes. The approach has estimated an etch rate of 60 nm min.'1 for samples positioned without substrate rotation at a cathode-sample distance of 250 mm. This has been calculated to correspond to a bias current density of 6.68 Amps m-2. Similar experiments involving modes of rotation yield an average etch rate of approximately 40 nm min.-1 To detect small quantities of iron containing phases formed during a pre-treatment process it has been necessary to enrich substrates with the Mossbauer isotope, 57Fe to achieve greater surface sensitivity. The enrichment used the technique of the deposition of an estimated 25 nm of 57Fe on polished mild steel substrates followed by annealing to generate an 57Fe diffusion profile into the near surface region. A diffusion model has been used to predict the 57Fe depth profile due to the adopted annealing process parameters. Verification of the estimated thickness of the deposited 57Fe overlayer and the diffusion profile has been provided by SIMS and SNMS. Using the 57Fe enriched mild steel samples, CEMS has investigated the formation of iron- titanium phases after a typical industrial ten minute pre-treatment process using substrate rotation, at a substrate bias voltage of -1200 V. Significant phase formation of both crystalline Fe[x]Ti[1-x] and amorphous Fe[x]Ti[1-x] have been identified. The formation of the crystalline phase has been confirmed by XRD. Using a model of the 57Fe isomer shift dependence of x, in amorphous alloys yielded x=0.31 +/-0.08 for Fe[x]Ti[1-x] Further experiments using an estimated 25 nm of 57Fe deposited on mild steel without annealing, showed the presence of magnetite and a small quantity of crystalline FeTi for a 25 s pre¬treatment process. After a 300 s pre-treatment time the oxide layer is removed and significant quantities of both crystalline and amorphous FeTi are formed. CEMS has also showed increased 57Fe removal at a 6 x 10-5 mbar Ar operating pressure within the coating chamber compared with a pre-treatment performed at a higher Ar pressure of 3 x 10-3 mbar, showing the greater effect of the Ti ion etching under these conditions. During the experiments performed at different Ar pressures, CEMS also identified iron carbonitride phases. Similar phases have also been identified in the early growth stages of a compound layer in a process performed using a modified Balzers coating system. CEMS has proved to be a powerful technique, enabling the investigation of surface interaction phenomena occurring in the near surface region of 57Fe enriched substrates treated by Physical Vapour Deposition (PVD) processes. The information provided by the technique makes it strategically important in the future research of interface regions generated by PVD processes.