Structure-dependent optical properties of Au/Ag irradiated TiN thin films

Titanium nitride (TiN) is an attractive alternative for modern and future photonic applications, as its optical properties can be engineered over a wide spectral range. In this study, we have used sequential implantation of gold and silver ions with varying ion fluence, as well as subsequent annealing, in order to modify the optical and plasmonic properties of TiN thin films and correlated this to their structural properties. Our investigations show that the columnar structure of the TiN films is partially destroyed upon implantation, but metallic Au and Ag nanoparticles are formed. The irradiation further induces a reduction of the lattice constant as well as changes the TiN stoichiometry and grain size. From the optical point of view, the implanted films possess less metallicity with increasing Ag fluence and losses several times lower than the as-deposited film, which can be correlated with the deficiency of nitrogen and additional defects. Subsequent annealing partially recovered the destroyed columnar structure, and the films become more metallic where the optical losses are much smaller in comparison to the as-implanted situation, being comparable to those of pure Au and Ag. In this way, by varying the implantation fluence of silver ions properly while keeping the gold fluence constant, we were able to optimize experimental parameters in such a way to ensure the formation of TiN with desirable optical performances

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 × 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 XPS 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