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The primary objective of this study is the development of transparent thin film materials in the IR enabling strong infrared absorption of organic compounds in the vicinity of metal nanoparticles by the surface plasmon effect. For developing these optical micro-sensors, hetero-structures combining gold nanoparticles and chalcogenide planar waveguides are fabricated and adequately characterized. Single As2S3 and Ge25Sb10Se65 amorphous chalcogenide thin films are prepared by radio-frequency magnetron sputtering. For the fabrication of gold nanoparticles on a chalcogenide planar waveguide, direct current sputtering is employed. Fabricated single layers or hetero-structures are characterized using various techniques to investigate the influence of deposition parameters. The nanoparticles of gold are functionalized by a self-assembled monolayer of 4-nitrothiophenol. Finally, the surface enhanced infrared absorption spectra of 4-nitrothiophenol self-assembled on fabricated Au/Ge-Sb-Se thin films hetero-structures are measured and analyzed. This optical component presents a similar to 24 enhancement factor for the detection of NO2 symmetric stretching vibration band of 4-nitrothiophenol at 1336 cm(-1).

Telluride glasses possess the widest infrared window of all amorphous materials and are key to a number of long-wavelength applications such as bio-sensing. However they are not intrinsically good glass formers and require significant materials engineering for device fabrication. Strategies for stable glass engineering are presented and the fabrication of far infrared optical fibers is described. A new type of optical sensor based on electrophoretic capture of protein is also presented. This sensor is based on a conducting telluride glass which can act as both a capture electrode and an infrared optical element for collecting vibrational signatures of target molecules such as proteins.

The development of infrared sensing platform requires adapted materials. In this work, we used sputtered gold nanoparticles on a chalcogenide glass to demonstrate that these infrared materials can be used as substrate for surface enhanced infrared absorption (SEIRA) spectroscopy. The sputtering parameters were optimized to get the highest possible enhancement. To assess it, a self-assembled monolayer of 4-nitrothiophenol was used. These preliminary results are promising and pave the way for various configurations of waveguide for integrated optical components. (C) 2012 Elsevier B.V. All rights reserved.

Chalcogenide glasses and glass-ceramics present a high interest for the production of thermal imaging lenses transparent in the 3-5 μm and 8-12 μm windows. However, chalcogenide glasses are conventionally synthesized in sealed silica ampoules which have two major drawbacks. First, the low thermal conductivity of silica limits the sample dimensions and second the silica tubes employed are single use and expensive, and represent up to 30% of the final cost of the material. The present work therefore addresses the development of innovative synthesis methods for chalcogenide glass and glass-ceramics that can present an alternative to the silica tube route. The method investigated involves melting the raw starting elements in reusable silica containers. This method is suitable for the synthesis of stable chalcogenide glasses compositions such as GeSe₄ but uncontrolled crystallization and homogenization problems are experienced for less stable compositions. The second approach involves preparation of amorphous chalcogenide powders by ball milling of raw elements. This mechanosynthesis step is followed by consolidation of the resulting powders to produce bulk glasses. Hot Uniaxial Pressing is suitable for compositions stable against crystallization. However, uncontrolled crystallization occurs for the unstable 80GeSe₂-20Ga₂Se₃ glass composition. In contrast consolidation through Spark Plasma Sintering (SPS) allows production of bulk glasses in a short duration at relatively low temperatures and is appropriate for the synthesis of unstable glasses. A sintering stage of only 2 min at 390°C is shown to be sufficient to obtain infrared transparent 80GeSe₂-20Ga₂Se₃ bulk glasses. This method enables the production of lenses with a 4-fold increase in diameter in comparison to those obtained by melt/quenching technique. Moreover, increasing the SPS treatment duration yielded infrared transparent glass-ceramics with enhanced mechanical properties. This innovative synthesis method c

GeₓSe₍₁₋ₓ₎ and AsₓSe₍₁₋ₓ₎ glasses have found use in many technological applications due to their excellent rheological properties and their wide IR transparency window. However, the low glass transition temperatures of these glasses leads to large changes in their properties, due to structural relaxation, over the weeks and months subsequent to their fabrication. Thus, obtaining a more thorough understanding of structural relaxation and its relation to the structure, composition, and processing of these glasses is important in furthering their use. Structural investigations, using NMR and Raman spectroscopies, performed on the GeₓSe₍₁₋ₓ₎ family of glasses show that the structure of these glasses is composed of two distinct microdomains. One corresponds to a rigid GeSe₂-like domain and the other corresponds to a floppy Se domain. These results are compared to other existing structural models for GeₓSe₍₁₋ₓ₎ glasses. Enthalpy measurements on both GeSe₉ and GeSe₄ optical fibers which were aged up to five years demonstrate that both compositions undergo a large amount of enthalpy relaxation in this time period. Raman spectroscopy performed concurrently with enthalpy measurements on the same GeSe₉ and GeSe₄ fibers shows that one of the structural changes taking place within the glass network is the conversion of edgesharing to corner-sharing tetrahedra in the GeSe₂-like phase. Moreover, the rate at which this conversion takes place is shown to be similar to the rate of enthalpy relaxation, suggesting that this structural change is one of the main mechanisms for structural relaxation in GeₓSe₍₁₋ₓ₎ glasses. Implementation of the Tool-Narayanaswamy-Moynihan (TNM) model as a hybrid computer model allowing the prediction of the four relaxation parameters Δh*, log(A), x, and β via optimization of simulated and experimental data was accomplished. It was found that a multi-rate version of the TNM model, which obtains an average set of model parameters via optimization of multiple

Novel telluride glasses with high electrical conductivity, wide infrared transparency and good resistance to crystallization are used to design an opto-electrophoretic sensor for detection and identification of hazardous microorganisms. The sensor is based on an attenuated total reflectance element made of Ge-As-Te glass that serves as both an optical sensing zone and an electrode for driving the migration of bio-molecules within the evanescent wave of the sensor. An electric field is applied between the optical element and a counter electrode in order to induce the migration of bio-molecules carrying surface charges. The effect of concentration and applied voltage is tested and the migration effect is shown to be reversible upon switching the electric field. The collected signal is of high quality and can be used to identify different bacterial genus through statistical spectral analysis. This technique therefore provides the ability to detect hazardous microorganisms with high specificity and high sensitivity in aqueous environments. This has great potential for online monitoring of water quality.

The present work deals with the study of infrared transparent glasses and their applications for sensor use. Their behavior under LASER irradiation, as well as the possibility to modify the surface, and the exploration of new glass compositions has been studied. Four tasks were completed with the main goal of designing infrared optical sensors. In a first task, the deposition of various thin films at the surface of a chalcogenide glass has been investigated in order to produce nano porous surfaces. Films were produced by vapor deposition and cathodic sputtering. Vapor deposition did not produce homogeneous films while cathodic sputtering lead to layers of controlled thickness which could produce a porous surface by selective etching. In a second task, the possibility of writing waveguide with femtosecond laser was investigated in Ge-Ga-S/Se-CsCl glasses. It was shown that high power leads to negative index changes unfit for light guiding, while low power lead to small positive index change. It was also shown that the filamentation method lead to homogeneous waveguide with large positive index changes. In a third task, photo-induced phenomena were investigated, especially photo-induced fluidity, on the binary system Ge-Se. The study initiated with the work on relaxation of fiber optics of composition Ge-Se₃ Ge-Se₄ and Ge-Se₉ and their response to shear stress under LASER irradiation in the Urbach region. This leads to the determination of their viscosity under irradiation as a function of the power and wavelength used. This preliminary study enabled using this technique for optical tapering of chalcogenide fibers. A tapered fiber was obtained with good control over the diameter, and length of the sensor and improved sensing sensitivity was demonstrated. Finally, exploration of new glassy systems containing no chalcogenide elements but only heavy halide compounds (PbI₂, PbBr₂, CsI…) were investigated. These amorphous ionic compounds lead to infrared window transmittin

Due to the remarkable properties of chalcogenide (Chg) glasses, Chg optical waveguides should play a significant role in the development of optical biosensors. This paper describes the fabrication and properties of chalcogenide fibres and planar waveguides. Using optical fibre transparent in the mid-infrared spectral range we have developed a biosensor that can collect information on whole metabolism alterations, rapidly and in situ. Thanks to this sensor it is possible to collect infrared spectra by remote spectroscopy, by simple contact with the sample. In this way, we tried to determine spectral modifications due, on the one hand, to cerebral metabolism alterations caused by a transient focal ischemia in the rat brain and, in the other hand, starvation in the mouse liver. We also applied a microdialysis method, a well known technique for in vivo brain metabolism studies, as reference. In the field of integrated microsensors, reactive ion etching was used to pattern rib waveguides between 2 and 300 mu m wide. This technique was used to fabricate Y optical junctions for optical interconnections on chalcogenide amorphous films, which can potentially increase the sensitivity and stability of an optical micro-sensor. The first tests were also carried out to functionalise the Chg planar waveguides with the aim of using them as (bio) sensors.

Te2As3Se5 (TAS) fibers are often used in bio-sensing applications requiring direct contact between the fiber and live cells. However, the toxicity and stability of chalcogenide glasses typically used in such bio-sensing applications are not well known. The stability and toxicity of TAS glass fibers were therefore examined. The surface of TAS fibers stored for up to three years in air were analyzed using X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), and atomic force microscopy (AFM). It is shown that an oxide layer develops on the surface of TAS fibers stored in air. This oxide layer is highly soluble in water and therefore easily removed. Additional studies using cyclic voltammetry show that the fresh TAS glass surface is insoluble in water for at least a few days, and attenuation measurements show that oxidation does not affect the transmission properties of the glass fibers. It was also determined that old, oxidized fibers pose a toxic threat to cells, while washed and new fibers show no toxic effect. Therefore, it is concluded that a soluble oxide layer forms on the surface of TAS fibers stored in air and that this layer has a toxic effect on cells in an aqueous environment. However, through etching, the oxide layer and the toxicity can be easily removed.In other applications of telluride glasses, such as the search for possible signs of life on exoplanets, a glass transmitting further into the IR is required in order to detect molecules, such as CO2. A new family of Tellurium based glasses from the Ge-Te-I ternary system has therefore been investigated for use in space and bio-sensing applications. A systematic series of compositions has been synthesized in order to explore the ternary phase diagram in an attempt to optimize the glass composition for the fiber drawing and molding process. The resulting glass transition temperature range lies between 139°C and 174°C, with deltaT values between 64°C and 124°C. The m

GeS₂-Sb₂S₃-CsCl glass-ceramics with nanoporous surfaces were synthesized and tested as optical elements. The nanoporosity is obtained through a two-step process, including controlled nucleation of CsCl nuclei in the glass matrix followed by selective etching of the nuclei with an acid solution. The porous surface is several hundred nanometers thick and results in a surface area increase of almost four orders of magnitudes. The pores size is approximately 150 nm and can be tailored by controlling the nucleation process and the etching time. It is shown that the creation of the nanoporous surface does not critically affect the optical transmission of these infrared transparent glass-ceramics. These materials can therefore be used for the design of optical elements and an ATR (Attenuated Total Reflections) plate with nanoporous surface was fabricated and tested as an optical infrared sensor. The porous element shows higher detection sensitivity in initial experiments with a coating of silane molecules. The TAS (Te₂As₃Se₅) infrared glass, used as optical sensor in many fields of applications (medicine, environment, etc), exhibits poor mechanical properties rapidly that enable it to be used. Its mechanical properties have been investigated as a function of time and environment. From a general observation, air and vacuum have dramatic effects on TAS fibers tensile strength. When ageing under static stress, they exhibit an increase of tensile strength. The structural relaxation phenomenon is hypothesized to explain these results. The coordination number, , which is a rough measure of the network rigidity, has an influence on the TAS mechanical properties. It is shown that the TAS glass exhibits photosensitive effects. This effect seems to be only a surface effect, not a volume effect in the sense that light has no influence on the kinetic of a stress relaxation experiment. Due to their low glass transition temperature, TAS fibers exhibit viscoelastic behavior at room tempe