Cathodic Arc Synthesis of Ti-Si-C-N Thin Films from Ternary Cathodes

Abstract: Cathodic arc deposition is a powerful technique for thin film synthesis, associated with explosive phase transformations resulting in an energetic and highly ionized plasma. This Thesis presents film growth through arc deposition from compound cathodes of Ti3SiC2, providing source material for plasma and films rich in Si and C. The interest for the resulting Ti-Si-C-N films is inspired by the two ternaries Ti-Si-N and Ti-C-N, both successfully applied as corrosion  and wear resistant films, with a potential for synergistic effects in the quarternary system.When using a rotating substrate fixture setup, which is common in high capacity commercial deposition systems, the repeated passage though the plasma zone results in growth layers in the films. This effect has been observed in several coating systems, in deposition of various materials, but has not been explained in detail. The here investigated layers are characterized by a compositional modulation in Si and Ti content, which is attributed primarily to preferential resputtering in segments of rotation when the plasma has high incidence angle towards the substrate normal. For depositions in a non-reactive environment, the films consist of primarily understoichiometric TiCx, Ti, and silicide phases, and display a modest hardness (20-30 GPa) slightly improved by a decreasing layer thickness. Hence, the side effects of artificial layering from substrate rotation in deposition systems should be recognized.Adding N2 to the deposition process results in reactive growth of nitride material, formed in a wide range of compositions, and thereby enabling investigation of films in little explored parts of the Ti-Si-C-N system. The structure and properties of such films, comprising up to 12 at% Si and 16 at% C, is highly dependent on the supply of N2 during deposition. Superhard (45-50 GPa) cubic-phase (Ti,Si)(C,N) films with a nanocrystalline feathered structure is formed at N-content of 25-30 at%. At higher N2 deposition pressure, C and Si segregate to column and grain boundaries and the cubic phase assumes a more pronounced nitride character. This transformation is accompanied by substantially reduced film hardness to 20 GPa. Ti-Si-C-N films thus display a rich variety of structures with favorable mechanical properties, but in the regime of high Si and C content, the amount of N must be carefully controlled to avoid undesirable formation of weak grain boundary phases based on Si, C and N.