The miniaturization of optical components to control and manipulate light amplitude, phase, and polarization requires micro-to nanostructured metasurfaces that provide resonant light−matter interactions to exploit optical properties in the visible and near-infrared (NIR) range (plasmonic resonances, wavelength filtering, etc.). Such metasurfaces sometimes need to be implemented under hard-use conditions, including high temperatures and strong field confinement. Transition-metal nitrides, like titanium nitride (TiN), are ideal materials to achieve such properties, but TiN's hardness and chemical inertness make patterning difficult. Here, we present an innovative direct fabrication process to easily synthesize a micro−nanostructured TiN thin film. The technological process is based on a direct photo-patternable titanium oxide TiO 2 sol−gel layer converted into TiN with a rapid thermal nitridation process. The nanoarchitecture and chemical composition of TiO 2 and TiN films were investigated by ultraviolet (UV)− visible−infrared (IR) spectroscopy and Raman spectroscopy, grazing incidence X-ray diffraction (GIXRD), and high-resolution transmission electron microscopy (HRTEM) coupled with electron energy loss spectroscopy (EELS). We obtained micro−nanotextured crystallized TiN surfaces in a significantly shorter time than with conventional nitridation processes. Due to the sol−gel approach, this work also significantly extends the chances of obtaining TiNbased metasurfaces on various substrates (glasses, plastics, etc.) in complex shapes (non-planar-based surfaces), for demanding photonic applications in the future.
This study reports the optical, electrical and mechanical properties of TiN films prepared by direct rapid thermal nitridation process from a photo-patternable TiO 2 sol-gel layer. The sol-gel approach is compatible to non-planar and large substrates and allows the micro-nanotexturing of crystallized TiN surfaces in a significantly short time, large scale and at a lower cost compared to TiN layer deposition from existing and conventional processes (CVD, PVD, ALD…). In this paper, the optical measurements are carried out by optical spectroscopy in the UV, visible and near-IR region and by ellipsometry. The resistivity and the conductivity are estimated by four-point probe method, while hardness is characterized by nano-indentation experiments. The results indicate that the TiN thin film made by sol-gel method and rapid thermal nitridation are very promising for the manufacturing of optical metasurfaces devices or new plasmonic materials.
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A new plasmonic configuration is proposed for application in a sensor and demonstrated for the detection of variations in the bulk refractive index of solutions. The configuration consists of monitoring two diffracted orders resulting from the interaction of a TM-polarized optical beam incident on a grating coupler, operating based on an effect termed the “optical switch”. The two monitored diffracted orders enable differential measurements which cancel the drift and perturbations common to both, leading to an improved detection limit, as demonstrated experimentally. The measured switch pattern associated with the grating coupler is in good agreement with theory. Bulk sensing is demonstrated under intensity interrogation via the sequential injection of solutions comprised of glycerol in water into a fluidic cell. A limit of detection of about 10−6 RIU was achieved. The optical switch configuration is easy to implement and is cost-effective, yielding a highly promising approach for the sensing and the real-time detection of biological species.
Titanium nitride (TiN) is a very promising new plasmonic material to replace traditional plasmonic materials like gold and silver, especially thanks to its thermal and chemical stability. However, its chemical resistance and its hardness make TiN difficult to microstructure. An alternative approach is to micro-nanostructure a titanium dioxide (TiO2) coating and then to use a nitridation reaction to obtain a micro-nanostructured TiN coating. This is an easy, rapid and cost-effective structuring process. In this paper, we demonstrate that rapid thermal nitridation (RTN) can be combined with nanoimprint lithography (NIL) to rapidly micro-nanostructure a TiN layer. This innovative approach is applied to a micro-nanostructured TiN layer for plasmonic response in the near infrared range. Experimental and theoretical approaches are compared.
This paper describes a tailored and versatile technology route to achieve micro and nanopatterning of both TiO2 and TiN thin films using a direct photo patternable sol–gel approach combined with a rapid thermal annealing and nitridation process. The approach consists in multi‐scale structuring TiO2 using laser direct writing or mask/colloidal lithography on a wide range of substrates including materials and of diverse geometry. These patterned TiO2 layers can subsequently be converted into a micro‐structured metallic TiN layer using a direct rapid thermal nitridation process that results in metallic thin films (TiN). This work demonstrates the versatility of this complete chain of soft chemistry based new process for patterning TiO2 and TiN thin films thereby avoiding expensive processes such as etching and lift‐off, while preserving their diffractive properties and high thermal stability, that is, up to 1000 °C under vacuum. The process is compatible with different kinds of substrates of different shapes and sizes. These results pave the way for developing a cost‐effective and time‐saving approach to different cutting‐edge applications such as metasurfaces, sensors, and applications in the luxury and decoration sector.
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