Fano-like resonances sustained by Si doped InAsSb plasmonic resonators integrated in GaSb matrix

By using metal-free plasmonics, we report on the excitation of Fano-like resonances in the mid-infrared where the Fano asymmetric parameter, q, varies when the dielectric environment of the plasmonic resonator changes. We use silicon doped InAsSb alloy deposited by molecular beam epitaxy on GaSb substrate to realize the plasmonic resonators exclusively based on semiconductors. We first demonstrate the possibility to realize high quality samples of embedded InAsSb plasmonic resonators into GaSb host using regrowth technique. The high crystalline quality of the deposited structure is confirmed by scanning transmission electron microscopy (STEM) observation. Second, we report Fano-like resonances associated to localized surface plasmons in both cases: uncovered and covered plasmonic resonators, demonstrating a strong line shape modification. The optical properties of the embedded structures correspond to those modeled by finite-difference time-domain (FDTD) method and by a model based on Fano-like line shape. Our results show that all-semiconductor plasmonics gives the opportunity to build new plasmonic structures with embedded resonators of highly doped semiconductor in a matrix of un-doped semiconductor for mid-IR applications

Ingénierie de résonateurs plasmoniques à base de semi-conducteurs fortement dopés pour l’exaltation de l’absorption de molécules dans le moyen infrarouge

The detection and identification of biological and chemical substances can be performed with biosensors. Biosensors are required to be simple and rapid to use, small, and sensitive in order to detect minute amounts of analyte molecules. Plasmonic devices have proven their utility as biosensing transducers. Surface plasmon-polaritons (SPP), collective oscillations of the electron cloud in metallic media coupled to an electromagnetic wave, are sensitive to the refractive index of their environment, providing thus an efficient way to probe the presence of molecules by the refractive index modification. This technique is called surface plasmon resonance (SPR) sensing. Moreover, SPP confine the incident electric field to sub-wavelength dimensions and enhance the field strength. Molecules located in these so-called field hotspots interact more efficiently with incident light due to a coupling mechanism mediated by the SPP, so that their infrared (IR) absorption cross section is increased. While IR spectroscopy is a standard tool for molecular identification, it does not provide sufficient sensitivity for the detection of smallest quantities. Exploiting the surface enhanced IR absorption (SEIRA) due to the plasmonic enhancement enables the detection of small amounts of analyte.While surface plasmons were mainly discovered using noble metals such as gold and silver, nowadays other material systems are also considered which display complementary or improved properties compared to the standard materials in plasmonics, especially to enlarge the spectral range where plasmonic effects can be observed and exploited. Material science enables to tailor the dielectric function of a material and consequently to control the plasmonic properties. Highly doped III-V semiconductors constitute an alternative to gold and silver for mid-IR plasmonics, due to their dielectric function which resembles the one of the noble metals, but shifted to the mid-IR spectral range. Indeed, InAsSb in the IR is even less lossy than gold in the visible. SEIRA using plasmonic resonances spectrally tuned to molecular absorption lines, or resonant SEIRA, requires nanoantenna substrates displaying their resonances in the IR. Highly doped InAsSb grown lattice matched on GaSb substrates is an interesting material system for this task. InAsSb is plasmonic for wavelengths above approximately 5 µm.In this work, we propose InAsSb:Si/GaSb nanostructures as SEIRA and SPR substrates for an application in biosensing devices. InAsSb nanoantennas on GaSb substrates have been prepared using photolithography and wet chemical etching by a citric acid: hydrogen peroxyde solution or alternatively, by interferential lithography and reactive ion etching, especially to reduce the lattice parameter. An optical characterization of the structures was performed by FTIR spectroscopy, supported by numerical finite-difference time-domain (FDTD) calculations which were also applied to study the impact of geometrical parameters on the optical response. Notably, two types of structure designs were proposed: one-dimensional periodic gratings and two-dimensional arrays of rectangular shaped nanoantennas which provide localized surface plasmon resonances (LSPR) in both polarization directions contrary to the gratings and enable hence a dual band optical response. SPR sensing and SEIRA have successfully been demonstrated using both types of structures, with proof-of-concept analytes such as different polymers and the aromatic compound vanillin with absorption features at high IR wavelengths. A bulk sensitivity in the range of 10² to 10^3 nm/RIU was reached. The vibrational signals increased of factors ranging between approximately 1.2-5.7, and the SEIRA enhancement was estimated to be in the range of 10^3 to 10^4 for the rectangular nanoantenna arrays.La détection et l'identification des substances biologiques ou chimiques peuvent être accomplies par des biocapteurs. On exige des biocapteurs d'être simple et rapide à utiliser, d'avoir une taille réduite, et d'être suffisamment sensible afin de pouvoir détecter des molécules en petite quantité. Des dispositifs plasmoniques se sont révélés adaptés pour l'usage en tant qu'élément transducteur des biocapteurs. Les plasmon-polaritons de surface (SPP) sont des oscillations collectives du nuage électronique des métaux, couplées à des ondes électromagnétiques. Leur fréquence de résonance dépend de l'indice de réfraction de leur environnement diélectrique. Ceci permet de sonder de manière efficace la présence des molécules par la modification de l'indice de réfraction engendrée par celles-ci. La technique reposant sur ce principe s'appelle la détection par résonance des plasmons de surface (SPR sensing en anglais). De plus, les SPP confinent le champ électrique incident à des volumes sub-longueurs d'onde et l'exaltent ainsi. Les molécules qui se situent dans ces zones de forte exaltation du champ électrique interagissent plus efficacement avec la lumière incidente par l'intermédiaire du SPP, tel que leur section efficace de l'absorption infrarouge (IR) augmente. La spectroscopie IR est une technique standard d'identification de molécules en quantités suffisantes. Pour améliorer la sensibilité, la spectroscopie vibrationnelle d'absorption exaltée par la surface (SEIRA pour surface enhanced infrared absorption en anglais) est particulièrement bien adaptée.Alors que la plasmonique s'est principalement développée dans le visible via les métaux nobles, les semi-conducteurs III-V fortement dopés présentent une alternative intéressante pour la plasmonique dans le moyen IR. Leur fonction diélectrique ressemble à celle des métaux nobles dans le visible, mais décalée dans le moyen IR. Leur densité de charges moindre que celle de l'or permet de réduire considérablement leurs pertes. La spectroscopie SEIRA utilise des nanoantennes plasmoniques dont les résonances se situent dans l'IR pour couvrir la gamme spectrale des modes vibrationnels moléculaires. L'InAsSb fortement dopé accordé en maille sur un substrat en GaSb présente des propriétés plasmoniques au-delà de 5 µm de longueurs d'onde.Dans ce manuscrit, nous proposons des nanostructures en InAsSb:Si/GaSb pour développer un biocapteur utilisant les techniques de SEIRA et de SPR "sensing". Les nanostructures ont été réalisées soit par photolithographie et gravure chimique humide soit par lithographie interférentielle et gravure par plasma réactif. Les caractérisations optiques ont été effectuées par spectroscopie IR à transformée de Fourier. Des calculs numériques par la méthode des différences finies dans le domaine temporel (FDTD) ont permis d'étudier l'effet des paramètres géométriques sur la réponse optique des structures. Deux types de structure ont été proposés : des réseaux unidimensionnels ainsi que des réseaux bidimensionnels de nanoantennes rectangulaires supportant des résonances de plasmon de surface localisé (LSPR) dans les deux directions de polarisation de la lumière par rapport aux axes de la structure. Ce type de structures permet ainsi une réponse optique ayant des résonances dans deux bandes spectrales différentes. Les techniques de SPR "sensing" et de SEIRA ont été démontrées pour l'ensemble des structures uni- et bidimensionnelles. Différents types d'analytes comme les polymères et le benzaldéhyde vanilline ont servi de systèmes de tests pour les structures plasmoniques. Les sensibilités se situent entre 10² et 10^3 nm/RIU. Les facteurs d'augmentation des signaux vibrationnels obtenus sont compris dans une gamme de 1,2 à 5,7 et les facteurs d'exaltation ont été évalués autour de 10^3 à 10^4 pour les réseaux bidimensionnels de nanoantennes plasmoniques

Absorbeurs parfaits à base de semi-conducteurs fortement dopés pour la spectroscopie vibrationnelle exaltée

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All-semiconductor plasmonic metamaterials for mid-infrared perfect absorption and selective thermal emission

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Etude spectroscopique de structures résonantes à plasmons de surface localisés par nanoscopie infrarouge au voisinage de la fréquence plasma

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Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

Tailored plasmonic nanoantennas are neededfor diverse applications, among those sensing. Surfaceenhancedinfrared absorption (SEIRA) spectroscopy usingadapted nanoantenna substrates is an efficient techniquefor the selective detection of molecules by their vibrationalspectra, even in small quantity. Highly doped semiconductorshave been proposed as innovative materials forplasmonics, especially for more flexibility concerning thetargeted spectral range. Here, we report on rectangularshaped,highly Si-doped InAsSb nanoantennas sustainingpolarization switchable longitudinal and transverseplasmonic resonances in the mid-infrared. For small arrayperiodicities, the highest reflectance intensity is obtained.Large periodicities can be used to combine localized surfaceplasmon resonances (SPR) with array resonances,as shown in electromagnetic calculations. The nanoantennaarrays can be efficiently used for broadband SEIRAspectroscopy, exploiting the spectral overlap between thelarge longitudinal or transverse plasmonic resonancesand narrow infrared active absorption features of an analytemolecule. We demonstrate an increase of the vibrationalline intensity up to a factor of 5.7 of infrared-activeabsorption features of vanillin in the fingerprint spectralregion, yielding enhancement factors of three to fourorders of magnitude. Moreover, an optimized readout forSPR sensing is proposed based on slightly overlappinglongitudinal and transverse localized SPR

Infrared near-field nanoscopy study of all-semiconductor plasmonic gratings near plasma frequency

International audienc

Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

Tailored plasmonic nanoantennas are needed for diverse applications, among those sensing. Surface-enhanced infrared absorption (SEIRA) spectroscopy using adapted nanoantenna substrates is an efficient technique for the selective detection of molecules by their vibrational spectra, even in small quantity. Highly doped semiconductors have been proposed as innovative materials for plasmonics, especially for more flexibility concerning the targeted spectral range. Here, we report on rectangular-shaped, highly Si-doped InAsSb nanoantennas sustaining polarization switchable longitudinal and transverse plasmonic resonances in the mid-infrared. For small array periodicities, the highest reflectance intensity is obtained. Large periodicities can be used to combine localized surface plasmon resonances (SPR) with array resonances, as shown in electromagnetic calculations. The nanoantenna arrays can be efficiently used for broadband SEIRA spectroscopy, exploiting the spectral overlap between the large longitudinal or transverse plasmonic resonances and narrow infrared active absorption features of an analyte molecule. We demonstrate an increase of the vibrational line intensity up to a factor of 5.7 of infrared-active absorption features of vanillin in the fingerprint spectral region, yielding enhancement factors of three to four orders of magnitude. Moreover, an optimized readout for SPR sensing is proposed based on slightly overlapping longitudinal and transverse localized SPR

Pedestal formation of all-semiconductor gratings through GaSb oxidation for mid-IR plasmonics

Mid-IR localized surface plasmon resonances (LSPR) have been demonstrated in nanoribbons of highly Si-doped InAsSb alloys on GaSb substrates. We show that the slow, steady and selective oxidation of GaSb in water leads to an all-semiconductor mid-IR pedestal configuration consisting of highly doped InAsSb plasmonic resonators on top of GaSb pedestals embedded in an amorphous oxide layer. The homogeneity of the pedestal structure is imaged with an attenuated-total reflection Fourier transform infrared (ATR-FTIR) microscope by measuring around the plasmonic excitation at the plasma wavelength of 5.5 mu m. As the plasmonic properties are influenced by modifications of the surrounding medium, we show for all-semiconductor gratings with defined doping level and defined grating geometry, that the GaSb oxidation process allows post-fabrication targeting of mid-IR plasmonic resonances to cover the mid-IR range from 5 to 20 mu m. Additionally, the pedestal formation reduces the refractive index mismatch between the two interfaces of the plasmonic resonators which allows the exploitation of a second plasmonic peak and which favors plasmonic field enhancement at the top (air-) side of the structure relevant for enhanced molecular vibration spectroscopy

Microfluidic surface-enhanced infrared spectroscopy with semiconductor plasmonics for the fingerprint region

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