Investigating on the microstructure and optical properties of Au, Ag and Cu implanted TiN thin films: The effects of surface oxidation and ion-induced defects

In the present paper, the effects of metal ion implantation on the structural and optical properties of TiN thin films have been investigated. TiN films of 170 nm thickness were grown by d.c. reactive sputtering on Si (100) wafers and then irradiated at 5 x 1016 ions/cm2 with either Au, Ag, or Cu ions by using two different energies per each implanted metal. The results showed that as deposited TiN crystallizes in the form of a fcc cubic structure, with the crystallites preferentially oriented along the (111) plane. For all implanted layers, the cubic structure was preserved, but compared to as deposited TiN the crystallites were smaller and the lattice was contracted. These changes were correlated with the depth distribution of Au, Ag and Cu ions and assigned to implantation-induced damage that was larger when higher ion energies were used. High-resolution oS spectra of the surface of as deposited sample showed the coexistence of TiN, TiO2 and TiOxNy phases and this was related to the surface oxidation of the films due to the exposure to air. After implantation, the results were almost similar for all metals, showing an increase in TiO2 contribution and the formation of pure metallic Au and Ag phases, while copper is in the Cu2+ state, which is attributed to Cu(II)-oxide and Cu(OH)2. The microstructural characteristics including defect formation, changes in crystallite size and lattice contraction, and also growth of different metallic phases during implantations were correlated with the findings of the optical characterization of the implanted films. For the as deposited film we found an energy gap of 2.91 eV, which was lower than the value typical for TiN. After implantation the gap was shifted to higher energies, while at the visible part of the region, the existence of additional energy levels, at photon energies below 2.9 eV was observed. Besides, all implanted films showed degraded photocatalytic activity compared to as deposited TiN, among which Cu-implanted samples exhibited the best photocatalytic performances. The lower photocatalytic activity of Au and Ag implanted films compared to Cu implantations was ascribed to larger structural defects and the formation of less favorable electronic states.