Core-shell titanium dioxide-titanium nitride nanotube arrays with near-infrared plasmon resonances

Titanium nitride (TiN) is a ceramic with high electrical conductivity which in nanoparticle form, exhibits localized surface plasmon resonances (LSPRs) in the visible region of the solar spectrum. The ceramic nature of TiN coupled with its dielectric loss factor being comparable to that of gold, render it attractive for CMOS polarizers, refractory plasmonics, surface-enhanced Raman scattering and a whole host of sensing applications. We report core-shell TiO₂-TiN nanotube arrays exhibiting LSPR peaks in the range 775-830 nm achieved by a simple, solution-based, low cost, large area-compatible fabrication route that does not involve laser-writing or lithography. Self-organized, highly ordered TiO₂ nanotube arrays were grown by electrochemical anodization of Ti thin films on fluorine-doped tin oxide-coated glass substrates and then conformally coated with a thin layer of TiN using atomic layer deposition. The effects of varying the TiN layer thickness and thermal annealing on the LSPR profiles were also investigated. Modeling the TiO₂-TiN core-shell nanotube structure using two different approaches, one employing effective medium approximations coupled with Fresnel coefficients, resulted in calculated optical spectra that closely matched the experimentally measured spectra. Modeling provided the insight that the observed near-infrared resonance was not collective in nature, and was mainly attributable to the longitudinal resonance of annular nanotube-like TiN particles redshifted due to the presence of the higher permittivity TiO₂ matrix. The resulting TiO₂-TiN core-shell nanotube structures also function as visible light responsive photocatalysts, as evidenced by their photoelectrochemical water-splitting performance under light emitting diode illumination using 400, 430 and 500 nm photons.