DS0104 - Innovations scientifiques et technologiques pour anticiper ou remédier les risques environnementaux

Integrated IR sensor based on SEIRA effect for an efficient detection use of low concentration chemical and biological species – LOUISE

Infrared sensor: pollutants in water and early diagnosis in medicine.

In a context of growing demand for integrated sensors for environmental and biological applications, the objective of the LOUISE project is to design and evaluate a micro-sensor for the implementation of infrared spectroscopy amplified by surface plasmonic effects.

Detection of trace of chemical pollutants in seawater or biomarker of cardiovascular disease and liver cancer

In recent decades, the seas and oceans have been subject to special monitoring taking into account the socio-economic and ecological interests at stake. The detection and measurement of trace of chemical pollutants (such as hydrocarbons or pesticides) is the cornerstone of many oceanographic issues such as environmental monitoring or the study and prediction of the spread of chemical species in complex ecosystems. The development of portable and compact sensors and analysers is fundamental for in situ studies that are highly complementary to laboratory techniques. However, the conversion of laboratory techniques into field devices requires the development of integrated micro-components capable of accurate, sensitive and high-resolution measurements in harsh environments. The ability to quickly detect, identify and monitor (bio)chemical species through the use of small integrated optical platforms is also a major requirement in the health field where the development of early diagnostic tools for medicine has become a major issue.

We are focusing our efforts, for the integrated optical platform, on chalcogenide glasses for their technological flexibility necessary to produce micro-sensors compatible and adapted to mass production. The other essential aspect of this project is the gold nano-antennas that will enhance the infrared absorption of targeted molecules (hydrocarbons and biomarkers) by plasmonic phenomena on the surface of the waveguide where the mid-infrared evanescent wave propagates. These gold nanostructures were thus deposited on the surface of the chalcogenide waveguide to improve infrared absorption and therefore the detection of the targeted molecules. The modelling developed as part of this project made it possible to optimize the coupling between the mid-infrared evanescent waves flush with the surface of the chalcogenide waveguide and the plasmons carried by the metal nanostructures in order to increase the sensitivity and resolution of this sensor based on infrared spectroscopy enhanced by surface plasmonic effects. The nanostructures were then functionalized with a layer of polymer or specific antibodies to further increase sensitivity and make detection more specific. By using the infrared spectroscopy technique enhanced by surface plasmonic effects (SEIRA) integrated into an infrared micro-sensor as proposed by the LOUISE project, we can expect to achieve very low concentrations of a few µg/L for polluting molecules and 10-12 mol/L in body fluids. This LOUISE project thus offers to the multidisciplinary French consortium the opportunity to develop infrared micro-sensors with a sensitivity amplified by a surface plasmonic effect technology.

The manufacture of waveguiding structures in chalcogenides in the Ge-Sb-Se system of variable geometries adapted for propagation in the mid-IR whose evanescent field is optimized in the LOUISE project. An extension of the numerical calculation method, not envisaged in the initial project, has been developed in order to be able to model periodic 3D structures allowing to study real, regular and large dimensional photonic structures corresponding to plasmonic sensors. Optical chips functionalized using nanoparticles or resonant nanostructures were made on the chalcogenide waveguiding structures before transfer of the waveguide, making it possible to use photolithography techniques and in particular the laser interference lithography technique combined with the lift-off technique. Numerous measurements of hydrocarbon detection by attenuated total reflection spectroscopy have been carried out in fluxes after functionalization by polymer layer of chalcogenide prism demonstrating the ability to detect hydrocarbons in complex matrices such as seawater. We have also worked on the surface functionalization of gold nanostructures by specific aptamers of the MnSOD protein, which is the biomarker targeted by the project. These studies have allowed us to optimize the surface functionalization of nanostructures and chalcogenide waveguides for use as SEIRA sensors. Transduction tests have been performed in liquid phase for isopropanol and acetic acid and optical tests are underway to evaluate the effectiveness of functionalized micro-sensors. In parallel, a portable instrument is currently under development for the detection of hydrocarbons and disease biomarkers with the aim of transferring technology to end-users.

All the results of the LOUISE project represent promising steps towards the development of a chalcogenide glass optical platform for transduction applications in the mid-infrared and optical signal processing. One of the perspectives concerns the development of microsensors based on a combination of advanced infrared photonic and electrochemical technologies combined with a microfluidic device, which in itself constitutes an original scientific and technological challenge, aimed at controlling and reducing the environmental impact of economic sectors producing pollutants, effluents and waste flowing into ground, surface and marine waters. In addition, we also propose to develop an innovative, highly sensitive and miniaturized photonic device dedicated to the detection of food contaminants by combining integrated optics, hybrid vibrational spectroscopy and nanotechnology. By bringing together recent advances in the field of plasmonic waveguides and non-linear optics in the near and mid-infrared, we can aim - based on the micro-components and modelling developed in the LOUISE project - to create new, very compact and fully integrated low-power optical devices for optical signal processing.

Within the framework of the LOUISE project, we can highlight some of the consortium's scientific productions relating to the project, such as a book chapter of the Springer Handbook of Glass concerning amorphous film deposition (Amorphous Thin Film Deposition, V. Nazabal and P. Nemec, Springer Handbook of Glass, Editors: Musgraves, J. D., Hu, J., Calvez, L. (2019) ISBN 978-3-319-93728-1, pp 1293-1332), an article describing a theoretical study of an evanescent optical sensor for the detection of liquids in the infrared (A. Gutierrez-Arroyo, E. Baudet, L. Bodiou, V. Nazabal, E. Rinnert, K. Michel, B. Bureau, F. Colas, J. Charrier, Theoretical study of an evanescent optical integrated sensor for multipurpose detection of gases and liquids in the Mid-Infrared, Sensors and Actuators B-Chemical, 242 (2017) 842), an open source article on modelling developed in LOUISE project (Discontinuities in open photonic waveguides: Rigorous 3D modeling with the finite element method, Guillaume Demésy, Gilles Renversez (cf. pdf at arxiv.org/abs/1907.11540), another publication on the functionalization aspect (Arib C.., Liu Q., Djaker N., Fu W., Lamy de la Chapelle M., Spadavecchia J., Influence of the aptamer grafting on its conformation and its interaction with targeted protein, Plasmonics, 14, 1029, 2019) not to mention several invited conferences that marked the development of the LOUISE project.

For the last decades, the seas and the oceans have become of first ecological and socio economical interests. The detection and assay of traces of chemicals is the keystone of many oceanographic problematics such as environmental monitoring or the study and forecast of spreading of chemicals in complex ecosystems (such as PAH-Polycyclic Aromatic Hydrocarbon- or pesticides). It is now well-established that the development of compact portable sensors and analyzers can be of great help to alleviate the inherent limitations of laboratory techniques in terms of both spatial and temporal resolutions. However, the conversion of bench-top systems to on field apparatus requires integrated micro-components capable of performing accurate measurement in harsh environment. The ability to quickly detect, identify and monitor (bio)-chemical species by means of integrated optical platforms of small dimension is also a major challenge in the field of Health where the development of early diagnostic tools in medicine has become an issue of great importance.

Consequently in a context of growing demand for integrated sensors for environmental and biological applications, the aim of LOUISE project is to design, assess and implement an infrared (IR) micro-component sensor based on evanescent wave spectroscopy with surface enhanced IR absorption effect (SEIRA-EWS).

To achieve this innovative micro-sensor, the LOUISE project will be focused on chalcogenide glasses for their technological flexibility: integrated platform with propagation in middle-IR, compatibility with CMOS technology and suitability for mass production. An important feature of this project lies in the gold plasmonic nanoantennas that will enhanced the IR absorption of targeted molecules (PAHs and biomarkers) deposited on the surface of the chalcogenide waveguide which propagates the MIR evanescent wave. Gold nanostructures in the form of an array of nanowires will be deposited on the chalcogenide waveguide to improve the IR absorption and thus the detection of the targeted molecules. Modeling will enable us to optimize the coupling between the MIR evanescent waves at the chalcogenide waveguide surface and the plasmon modes of the gold nanoantennas in order to increase the sensitivity and the resolution of the sensor. Then, the gold nanoantennas will be functionalized with a layer of polymer or antibodies to further increase the sensitivity and the specificity of the detection. The micro-component will be integrated into a portable instrument system and will be assessed for hydrocarbon and disease biomarkers/proteins detection during validation campaigns. Two compounds will be dealt with: fluoranthen, a PAH, and toluene. At the end of the project, the micro-component is expected to detect them at concentration as low as 0.1µg/L and 70µg/L respectively. For the biological compounds, we will focus on proteins that are known to be disease biomarkers such as the manganese superoxide dismutase involved in cardiovascular injury or liver cancer. Using SEIRA techniques integrated to IR micro-sensor as proposed by this project, we expect to reach some very low detection -limit of the order of 10-12 mol/L- in body fluids (plasma, saliva…), to develop a highly sensitive biosensor and to speed-up implementation.

The LOUISE project offers the opportunity to a multidisciplinary French consortium to develop MIR sensors with sensitivity enhanced by advanced technology.

Project coordinator

Madame Virginie Nazabal (Institut Sciences Chimiques de Rennes)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

CSPBAT Chimie, Structure et Propriétés de Biomatériaux et D'Agents Thérapeutiques
CNRS-DR12_IF CNRS délégation Provence et Corse_Institut Fresnel_UMR7249
UTT/ICD/LNIO Université de Technologie de Troyes-ICD/LNIO
ISCR Institut Sciences Chimiques de Rennes
IFREMER Institut Français de Recherche pour l'Exploitation de la Mer

Help of the ANR 469,955 euros
Beginning and duration of the scientific project: September 2015 - 36 Months

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