Mohamed Oubaha

Ultra-Low Shrinkage Hybrid Photosensitive Material for Two-Photon Polymerization Microfabrication

Investigations into the structuring by two-photon polymerization of a nonshrinking, photosensitive, zirconium sol-gel material are presented. This hybrid material can be photostructured even when it contains up to 30 mol % of zirconium propoxide (ZPO); by varying the materials inorganic content, it is possible to modify and tune its refractive index. The introduction of ZPO significantly increases the photosensitivity of the resulting photopolymer. The fabricated three-dimensional photonic crystal structures demonstrate high resolution and a clear band-stop in the near-IR region. In contrast to common practice, no additional effort is required to precompensate for shrinkage or to improve the structural stability of the fabricated photonic crystals; this, combined with the possibility of tuning this materials optical, mechanical, and chemical properties, makes it suitable for a variety of applications by two-photon polymerization manufacturing.

Two-Photon Polymerization of Hybrid Sol-Gel Materials for Photonics Applications

Two-photon polymerization of photosensitive materials has emerged as a very promising technique for the fabrication of photonic crystals and devices. We present our investigations into the structuring by two-photon polymerization of a new class of photosensitive sol-gel composites exhibiting ultra-low shrinkage. We particularly focus on two composites, the first containing a zirconium alkoxide and the second a nonlinear optical chromophore. The three-dimensional photonic crystal structures fabricated using these materials demonstrate high resolution and clear bandstops in the near IR region.

Photo-patternable hybrid ionogels for electrochromic applications

This work describes the development of photopatternable ionogels based on a hybrid organic/inorganic sol–gel material and both phosphonium (trihexyltetradecylphosphonium dicyanamide [P6,6,6,14][dca], trihexyltetradecylphosphonium bis(trifluoromethanesulfonyl)-amide [P6,6,6,14][NTf2]) and imidazolium (1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate [emIm][FAP]) room temperature ionic liquids (RTILs). Ionogels were prepared via a two step process with the RTIL content varied between 40 and 80 w/w%, and characterised via Raman and Electrochemical Impedance Spectroscopy. 1 and 2 photon polymerisation was performed on the hybrid ionogels using photolithography, resulting in three dimensional structures that were characterised using scanning electron microscopy. Electrochromic ionogels were prepared by addition of ethyl viologen dibromide (EV) to an ionogel containing [emIm][FAP] and hybrid sol–gel material. This composition was photo-polymerised on ITO electrodes by UV irradiation and subsequentially characterised viaUV/Vis spectroelectrochemistry. It was also possible to fabricate a solid state electrochromic device based on EV and switch between the colourless (oxidised) and blue (reduced) forms using a perturbation signal of 1 V.

Graphene-doped photo-patternable ionogels: tuning of conductivity and mechanical stability of 3D microstructures

This work reports for the first time the development of enhanced-conductivity, graphene-doped photo-patternable hybrid organic-inorganic ionogels and the effect of the subsequent materials condensation on the conductivity and mechanical stability of three-dimensional microstructures fabricated by multi-photon polymerisation (MPP). Ionogels were based on photocurable silicon/zirconium hybrid sol–gel materials and phosphonium (trihexyltetradecylphosphonium dicyanamide) [P6,6,6,14][DCA] ionic liquid (IL). To optimise the dispersion of graphene within the ionogel matrices, aqueous solutions of graphene were prepared, as opposed to the conventional graphene powder approach, and employed as catalysts of hydrolysis and condensation reactions occurring in the sol–gel process. Ionogels were prepared via a two step process by varying the hydrolysis degree from 25 to 50%, IL content between 0–50 w/w%, and the inorganic modifier (zirconate complex) concentration from 30 to 60 mol.% against the photocurable ormosil and they were characterised via Raman, Electrochemical Impedance Spectroscopy and Transmission Electron Microscopy. MPP was performed on the hybrid ionogels, resulting in three-dimensional microstructures that were characterised using scanning electron microscopy. It is clearly demonstrated that the molecular formulation of the ionogels, including the concentration of graphene and the zirconate network modifier, plays a critical role in the conductivity of the ionogels and influences the resulting mechanical stability of the fabricated three-dimensional microstructures. This work aims to establish for the first time the relationship between the molecular design and condensation of materials in the physico-chemistry and dynamic of ionogels.

Characterisation of novel refractometric sensing systems

Simulations and experimental results for novel refractometric-sensing platforms are presented here. The first platform is based on a multi-mode interference coupler (MMIC) in which the top and sidewalls of the coupler are exposed to a humidity-sensing enrichment layer. Sensor operation is based on the creation of self-images of the input field into the coupler, at regular intervals along the coupler. This phenomenon is due to interference between the optical modes in MMICs. Changes in the refractive index of the sensing layer cause predictable shifts in the position of the output image, which in turn affects the amount of light coupled into the output waveguide. Sensitivity enhancement has been demonstrated by fabricating longer MMICs capturing higher-ranking self-images, which are shifted more than the first self-image. Consequently, more significant changes in the amount of light coupled to the output are observed for a given refractive index change. The second platform demonstrated is a Multi-Channel Directional Coupler sensor (MCDC). It differs from the MMIC in that the sensing region now consists of multiple single-mode waveguides, which are in close enough proximity to allow light to transfer between the waveguides. Sensitivity dependance on platform length has been investigated and compared with that of the MMIC. The devices have been fabricated by the direct laser writing process on UV curable hybrid sol-gel materials. Such materials allow implementation of planar technology enabling integration on a silicon substrate. Future applications of these platforms include chemical and bio-chemical sensing is the areas of process, environmental and bio-diagnostic monitoring.

Sensing Performance of a Refractometric Optical Sensor Platform Based on Multimode Interference Couplers

This paper focuses on characterization of the sensing performance of a refractometric sensing platform based on multimode interference couplers (MMICs). Platform fabrication exploited a low-cost process using photocurable organic-inorganic hybrid sol-gel materials which were structured to form optical waveguides by direct UV laser writing. The sensing principle is based upon the high sensitivity of the optical field distribution formed in the MMIC toward changes in the refractive index of its environment. Simulations demonstrated the importance of correctly specifying the length of the MMIC section and illustrated that longer platforms are more sensitive due to a greater shift in self-image position. To characterize sensing performance, a porous sol-gel humidity sensing enrichment layer was coated on the MMIC. Relative humidity was detected by the system with a resolution of 0.097%. Refractive index resolution of the platform was determined to be ~ 2 × 10-6 RIU , which is an analyte-independent value and illustrates the generic nature of this platform. As such, this platform has immense potential for future applications as a label-free and real-time biosensor platform.

Hybrid zirconium sol-gel thin films with high refractive index

We describe the synthesis of optical quality thin film materials with high refractive index, employing zirconium based hybrid sol-gel precursors. As the zirconium propoxide precursor is unstable in the presence of a strong nucleophilic agent such as water, two synthesis routes have been performed employing a chelating agent and an organosilane precursor to avoid the formation of any undesired ZrO2 agglomerates, leading to organo-zirconate complexes and silicato-zirconate copolymers, respectively. The prepared hybrid sol-gel materials were deposited by spin-coating to form a transparent thin film on silicon substrates, and heat treated at 100 °C for the final stabilisation of the layer. The effect of the two synthesis routes on the optical properties of zirconium based hybrid sol-gel material is discussed. It was found that the nature and concentration of the organosilane precursor can significantly affect the structural properties of the deposited films. A correlation was also demonstrated between the concentration of the organosilane precursor and the refractive index of the material. By reducing the concentration of organosilane precursor, high refractive index materials were obtained. Similar behaviour was observed for the materials synthesised via chelating agent. The synthesis employing an organosilane precursor produces films with higher refractive index. A maximum refractive index of 1.746 was measured at 635nm for the deposited thin films.

Structural and Optical Characterisation of an Erbium/Ytterbium Doped Hybrid Material Developed via a Nonhydrolytic Sol-Gel Route

This paper proposes the development and structural characterisation of an Er 3 + / Yb 3 + doped hybrid organic-inorganic material synthesised by a nonhydrolytic sol-gel process. By using a pumping laser diode at 980 nm, a typical Er 3 + luminescence has been recorded in the near infrared region (1.53–1.55  μ m). However, the detected fluorescence was particularly weak compared to that generally observed in pure mineral materials, suggesting the occurrence of strong quenching due to multiphonon relaxation processes. To understand this behaviour, structural characterisation of both of the matrix and the local environment of Er 3 + ions were conducted employing infrared spectroscopy, nuclear magnetic resonance, electron paramagnetic resonance, and neutron scattering. These studies showed that the major phenomenon competing with the Er 3 + fluorescence is intimately associated to the strong vibrational modes of the organic species that involve multiphonon relaxation processes, resulting in energy dissipation within the host matrix.

3D Microstructuring of hybrid photosensitive materials by two-photon polymerization technique for applications in photonics

Two-photon polymerization is a nonlinear optical technique, which allows the fabrication of complex 3D structures with submicron resolution. In this contribution our results on application of novel hybrid materials for 3D microstructing is reported.