DS0710 - Sciences et technologies des composants nanoélectroniques et nanophotoniques

Localized SUrface Plasmon REsonance in highly doped seMiconductors for infrarEd Biosensing – SUPREME-B

Localised SUrface Plasmon REsonance in highly doped seMiconductors for infrarEd Biosensing

Develop plasmonic resonators based on highly doped semiconductor (HDSC).<br />Fabricate HDSC plasmonic resonators with photo-, interferential-, e-beam lithography and wet or dry etching.<br />Near field and far field optical characterization of the HDSC plasmonic resonators.<br />Surface functionalisation of the HDSC plasmonic resonators. Integration into a label-free biosensor.

General objectives and main issues

The project objective is to demonstrate the feasibility of a new type of biosensor for the detection of biomolecules in the infrared range (near 10 µm). The novelty lies in the use of plasmonic resonators based on highly doped semiconductors to increase further the field enhancement compared to gold based nanostructures. Working in the infrared range presents a real interest for two main reasons: the plasmonic resonances are much stronger and sensitive to refractive index changes than in the visible range for SPR measurements and it is possible to directly identify by SEIRA measurements the biomolecule spectral signature thanks to the associated vibrations active in the infrared.

To develop plasmonic resonators based on highly doped semiconductors (HDSC) in the infrared (around 10 µm) using the consortium's skills in near- and far-field optical characterization techniques and modeling (UM and UTT). An electromagnetic field enhancement by one order of magnitude is expected in comparison with the state of the art in this wavelength range according to the selected geometry.
- Grow the HDSC layers by molecular beam epitaxy (MU).
- Fabricate HDSC plasmon resonators using optical, interferential and electronic lithography, and wet and/or dry etching (UM/UTT) techniques.
- Characterize with near-field and far-field the HDSC (UM/UTT) plasmonic resonators.
- Functionalize the surface of the HDSC plasmonic resonators (SiKÉMIA), in order to integrate them to a label-free biosensor. The biological receptors will be selected so as to allow, on the one hand, the functionalization and passivation of the semiconductor surface and, on the other hand, to limit the fouling phenomena which are very present in the case of Au (UM/Sikémia/UTT).

The simulations of 1D-arrays of Si-doped InAsSb on GaSb are completed. The optimal structures for probing the index variation and the detection of molecules are known. The 3D parametric electromagnetic simulations have allowed to identify 2-D geometries which are particularly interesting in terms of field exaltation and spatial density in the gap-plasmon regime.
Far-field measurements confirm the simulation results.
Near-field measurements have yielded results that allow us to better understand the physics of these structures, especially when approaching the plasma frequency.
Wet etching is perfectly under control. We are able to monitor the plasmon resonances in any spectral range beyond 9µm. We can adapt the doping level and the geometry of 1-D or 2-D plasmonic resonators. The techniques of laser interferential lithography are best suited for our materials.
The surface functionalization of the nanostructures has been demonstrated. We continue to stabilize the experimental protocol to ensure the reproducibility of the semiconductor surface functionalization process (InAsSb, GaSb).
Several micro-fluidic circuits have been realized: wells and a complete circuit. They are operational even if they remain rudimentary.
We have highlighted the first results of SEIRA and SPR sensing. Enhancement factor greater than 10^4 and sensitivities of SPR-sensing of the order of 1000 nm/RIU were measured.

Stabilize the technological processes for the fabrication of two-dimensional structures. Optimize the dry etching to densify structures and reduce their size.
Use efficiently the lightning rod effect to improve the enhancement factor of SEIRA.
To obtain a more accurate mapping of the near-field profile of the nanostructures.
Functionalize the plasmonic resonators with the biotin-streptavidin couple in a microfluidic circuit.

“Direct measurement of the effective infrared dielectric response of highly doped semiconductor metamaterial” A. Al Mohtar, A. Bruyant, S. Blaize, T. Taliercio, L. Cerutti, M. Kazan, Nanotechnology 28, 125701 (2017)
«Fano-like resonances sustained by Si doped InAsSb plasmonic resonators integrated in GaSb matrix«, Thierry Taliercio, Vilianne NTsame Guilengui, Laurent Cerutti, Jean-Baptiste Rodriguez, Franziska Barho, Maria-José Milla Rodrigo, Fernando Gonzalez-Posada, Eric Tournié, Michael Niehle, and Achim Trampert, Optics Express 23 (23), 246763 (2015).
«All-semiconductor plasmonic gratings for biosensing applications in the mid-infrared spectral range«, Franziska B. Barho, Fernando Gonzalez-Posada, Maria-Jose Milla-Rodrigo, Mario Bomers, Laurent Cerutti, and Thierry Taliercio, Optics Express 24 (14), 16176 (2016).
«Localized Surface-Plasmon Resonance Frequency Tuning in Highly Doped InAsSb/GaSb 1- Dimensional Nanostructures.«, Maria-Jose Milla-Rodrigo, Franziska B. Barho, Fernando Gonzalez-Posada, Laurent Cerutti, Mario Bomers, Jean-Baptiste Rodriguez, Eric Tournié and Thierry Taliercio, Nanotechnology 27, 425501 (2016).
”Wavelength-scale light concentrator made by direct 3D laser writing of polymer metamaterials« , J. Moughames, S. Jradi, T.M. Chang, S. Akil, Y. Battie, A. En Naciri, Z. Herro, S. Guenneau, S. Enoch, L. Joly, J. Cousin and A. Bruyant, soumise à Scientific Report

The SUPREME-B objective is to develop a new kind of biosensors based on all-semiconductor plasmonics

Making the right diagnosis in the case of illness is a crucial but not easy task, and generally, relies on invasive medical testing. Several alternative techniques have recently emerged, notably analysis based on the use of surface plasmon resonances (SPR). The basis: an analyte is deposited on a metallic surface shined with light. The analyte concentration is measured through the modification of the medium refractive index that affects the surface plasmon polariton, thus the reflected light properties (wavelength, angle, phase and intensity). The weak sensitivity to small size molecules is the major limitation of SPR biosensors. Therefore, localized surface plasmon resonance (LSPR) systems have been recently proposed, mainly based on gold nanoparticles and used in the visible or near infrared wavelength range, to increase the sensitivity. However, to extend the detection range into the infrared is essential to achieve a higher LSPR intensity, i.e. a higher sensitivity and easier molecule identification due to their specific infrared spectral signatures. Technically, the best performances are obtained by Surface Enhanced Raman Scattering (SERS), which is difficult to integrate and quite expensive, or by Surface Enhanced Infrared Absorption (SEIRA) which is a more direct and innovative technique.
Highly doped semiconductors (HDSC) are the best candidate for SEIRA, or infrared SPR. Indeed, we have theoretically predicted a sensitivity critical point one order of magnitude higher compared to gold systems, explained by a higher plasmonic field exaltation due to the distinct HDSC permittivity, e.g. a real part with low negative values combined with a low imaginary part. Furthermore, nanostructured HDSC are easy to integrate with light sources and/or detectors or integrated spectrometers to form lab on chips at a reduced cost. HDSC appear as an ideal choice for infrared plasmonics. However, their use is at an infancy stage. Recently we have demonstrated the potential of using HDSC for LSPR applications in the infrared range, theoretically and experimentally. We have generated LSPR in the infrared using highly doped InAsSb layers grown lattice-matched on GaSb substrates.

At the end of the project we will have achieved:

The Design and fabrication of an optimized HDSC-based LSPR device, to reach resonances in the 6-15 µm IR range for SEIRA or SPR measurements, with at least one-order-of-magnitude enhancement of the near electromagnetic field of the LSPR compared to the state-of-art.
The integration of the HDSC-based LSPR structure to a label-free biosensor (without label molecule which amplifies the target signal) by functionalizing the surface of the InAsSb resonators.

The starting point of the project is the complementary knowhow of the consortium with the capability of IES to realize LSPR structures based on InAsSb/GaSb heterostructures, the expertise of UTT in plasmonics, infrared near-field characterizations and nanofabrication, and of SiKÉMIA (SME) for the surface activation and bio-functionalization.

First, IES and UTT will design, realise, characterise and optimise the LSPR structures. Secondly, SiKÉMIA will propose the most adapted chemical ligand between organophosphorous and organosilyl compounds to attach the selected biomolecules (biotin streptavidin, antibody, etc.) to study on InAsSb and/or GaSb. In the same time, IES will propose a microfluidic circuit to drive molecules to the LSPR sensor and accurately control the analyte volume and decrease the limit of detection of the sensor. Finally, IES and SiKÉMIA will realise the biosensing proof-of-concept by coupling a broad-band light source directly to the LSPR biosensor or via a waveguide supporting the LSPR biosensor. The reflected or transmitted signal will be analyzed by a FTIR spectrometer to obtain the SEIRA or SPR signal.

Project coordination

Thierry Taliercio (Institut d'Electronique du Sud)

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

Sikémia Sikémia
UTT Université de Technologie de Troyes - Institut Charles Delaunay - LNIO
IES Institut d'Electronique du Sud

Help of the ANR 526,172 euros
Beginning and duration of the scientific project: September 2014 - 42 Months

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