Effect of sulfurization conditions on structural and electrical properties of copper sulfide films

We examined the structural and electrical properties of copper sulfide films as a function of the sulfurization time of 70-nm-thick Cu films. Copper sulfide films with various phases such as mixed metallic Cu-chalcocite, chalcocite, roxbyite, and mixed roxbyite-covellite phases were formed with increasing sulfurization time. The Cu∕S atomic percentage ratio of the films decreased with increasing sulfurization time, and films with various compositions such as Cu-rich and stoichiometric copper sulfide with underlying unreacted Cu as well as pure stoichiometric and S-rich copper sulfide were obtained. The surface morphology and the electrical resistivity of the films depended on the chemical phase and composition of the films. The resistivity decreased with increasing Cu deficiency in the films. Distinct switching of the resistance from high to low-state, and vice versa, with the reversal of the bias polarity of the film was observed only for the mixed metallic Cu-chalcocite phased film with underlying Cu. However, the chalcocite film with underlying Cu exhibited a semiconducting behavior. This indicated that excess Cu within the chalcocite film is required for the observation of the switching behavior of the resistance.