The Structure of W/C (0.15 < γ < 0.8) Multilayers Annealed in Argon or Air

We report the effect that thermal annealing in inert and oxidizing atmospheres, and with and without encapsulating layers, has on the structure of tungsten/carbon [W/C] multilayer thin films. This study focuses on the tungsten component and deals mainly with multilayers where the ratio of thickness of tungsten layers is equal to or greater than for the carbon layers (that is, γ ≤ 0.5). This is in contrast to prior studies where the tungsten layer thickness was generally held constant and the carbon layer was varied. Thermal annealing in inert atmospheres produces reactions and other structural changes in the tungsten and carbide layers which depend on the as-deposited multilayer structure which depends, in turn, on the thickness of the tungsten layer. In samples where both the tungsten and carbide fractions of the multilayer are completely amorphous as deposited, which is the case for thin tungsten layers (thickness of tungsten (t_w) < 4 nm/period), the reactions in the tungsten layer forming crystalline tungsten and tungsten carbide occur at annealing temperatures above 900°C. The layer pair spacing, or period, (d), in this group shows an expansion of up to 10–15% of the original value as has been reported in the past. Changes in both the tungsten and carbide layers, and their interfaces, contribute to changes in d spacing and relative thickness of the high and low Z components. When the tungsten layer thickness exceeds 4 nm per period the tungsten is partially crystallized in as-prepared samples. In such multilayers interfacial reactions, producing an oriented partially crystalline W₂C/C superlattice, occur at temperatures of 600°C and below. The fact that W₂C crystallites in one period can form a structure which is correlated to W₂C crystallites in neighboring layers is somewhat surprising, since layers are presumably still separated by amorphous carbon which is still visible via Raman. The expansion of the layer pair spacing is relatively small (<5%) in this group and, more importantly, mostly involves increases in the thickness of the high Z components. Samples annealed in air at temperatures below 300°C are progressively destroyed by the oxidation of both tungsten and carbide layers. Encapsulation of similar multilayers with a thin (30 nm) dielectric layer of any of several types can retard oxidation to 600°C. The silicon-containing encapsulants generally perform better. Failure at this temperature is seen to occur from pinhole formation.