Effects of Oxygen, Nitrogen and Fluorine on the Crystallinity of Tungsten by Hot-Wire Assisted ALD

A heated tungsten filament (wire) is well known to generate atomic hydrogen (at-H) by catalytically cracking molecular hydrogen (H2) upon contact. This mechanism is employed in our work on hot-wire (HW) assisted atomic layer deposition (HWALD), a novel energy-enhancement technique. HWALD has been successfully utilized to deposit tungsten (W) films using alternating pulses of WF6 and at-H. Depending on the conditions, either low-resistivity α- or higher-resistivity β-crystalline phases of W can be obtained. This work aims to clarify (i) which factors are decisive for the formed crystal phase and (ii) the role of the residual gases in the film growth mechanism. In this light, the effects of adding impurities (N2O, O2, NH3 and H2O) were investigated. Oxidizing species have a retarding effect on W growth but the process can be re-initiated after stopping their supply. In contrast, nitridizing species have a permanent inhibition effect. Further, the effects of WF6 overdose were studied. The surplus of WF6 appeared to be crucial for the process: in many cases this led to the formation of β-phase W instead of the α-phase, with a memory effect lasting for several deposition runs. Extra fluorine-containing species were thus identified as the likely cause of β-phase formation.