Characterization of a perfect sinusoidal grating profile using an artificial neural network for plasmonic-based sensors.

In this paper, we present a system intended to detect a targeted perfect sinusoidal profile of a diffraction grating during its manufactured process. Indeed, the sinusoidal nature of the periodic structure is essential to ensure optimal efficiency of specific applications as plasmonic sensors (surface plasmon resonance -based sensors). A neural network is implemented to characterize the geometrical shape of the structure under testing at the end of the laser interference lithography process. This decision tool operates in classifier mode prior to further processing. Then, the geometrical parameters of the structure can be reliably determined if necessary. Two solutions can be considered: the detection of a fixed geometrical shape operating on a binary mode and the identification of a geometrical shape from a limited number of profiles. These methods are validated in the context of plasmonic sensors on experimental sinusoidal grating structures with a grating period of 627 nm.

Performance of Grating Couplers Used in the Optical Switch Configuration.

Surface plasmon resonance is an effect widely used for biosensing. Biosensors based on this effect operate in different configurations, including the use of diffraction gratings as couplers. Gratings are highly tunable and are easy to integrate into a fluidic system due to their planar configuration. We discuss the optimization of plasmonic grating couplers for use in a specific sensor configuration based on the optical switch. These gratings present a sinusoidal profile with a high depth/period ratio. Their interaction with a p-polarized light beam results in two significant diffracted orders (the 0th and the -1st), which enable differential measurements cancelling noise due to common fluctuations. The gratings are fabricated by combining laser interference lithography with nanoimprinting in a process that is aligned with the challenges of low-cost mass production. The effects of different grating parameters such as the period, depth and profile are theoretically and experimentally investigated.

Common-mode plasmon sensing scheme as a high-sensitivity compact SPR sensor.

A deep metal grating enables quasi-phase-matched simultaneous excitation of two counterpropagating surface plasmon modes by means of its +1st and -2nd diffraction orders. The resulting angular reflection spectra of the scattered -1st and zeroth orders exhibit three interleaved zeros and maxima in a range centered around the Littrow angle. The spectra differ thoroughly from the usual reflection dip resulting from single-order plasmon coupling that produces strong absorption. The zeroth and -1st orders exhibit two crossing angles enabling high-sensitivity common-mode detection schemes designed to reject variations in source power and environmental noise. The proof of concept and experimental assessment of this new surface plasmon resonance (SPR) sensing scheme are demonstrated by monitoring gases in a pressure-controlled chamber. A limit of detection (LOD) of 2 × 10-7 refractive index unit (RIU) was achieved.

Differential Sensing with Replicated Plasmonic Gratings Interrogated in the Optical Switch Configuration.

A new plasmonic configuration is proposed for application in a sensor and demonstrated for the detection of variations in the bulk refractive index of solutions. The configuration consists of monitoring two diffracted orders resulting from the interaction of a TM-polarized optical beam incident on a grating coupler, operating based on an effect termed the "optical switch". The two monitored diffracted orders enable differential measurements which cancel the drift and perturbations common to both, leading to an improved detection limit, as demonstrated experimentally. The measured switch pattern associated with the grating coupler is in good agreement with theory. Bulk sensing is demonstrated under intensity interrogation via the sequential injection of solutions comprised of glycerol in water into a fluidic cell. A limit of detection of about 10-6 RIU was achieved. The optical switch configuration is easy to implement and is cost-effective, yielding a highly promising approach for the sensing and the real-time detection of biological species.

Metal-coated concave cone in a fused-silica rod as a multi-function plasmonic element.

A collimated light beam parallel to the axis of a fused-quartz cylinder impinging on a 90° apex angle concave cone cut in a quartz rod is transformed into a cylindrical wave by total internal reflection. A thin metal film at the quartz-air interface enables excitation of the plasmon mode at the air side that can polarize the cylindrical wave and/or has the potential to monitor physical, chemical, or biological quantities or events at the inner wall of the cone. The present Letter first analyzes the plasmon coupling mechanism and conditions. It then describes the diamond-grinding technique achieving a smooth cone wall and the finest possible tip. The experimental evidence of the polarization conversion is brought on a diamond-grinded section of fused-silica rod and gold coating of the concave wall.

Quantitative investigation on a period variation reduction method for the fabrication of large-area gratings using two-spherical-beam laser interference lithography.

Gratings produced by two-spherical-beam Laser Interference Lithography (LIL) will have a nonuniform period, and the associated period variation is larger with the increase of the substrate size. This work quantitatively investigates a noninvasive method for improving the period variation on 4-inch silicon wafers. By temporarily deforming the flexible silicon wafer using a customized concave vacuum chuck [J. Vac. Sci. Technol. B19(6), 2347 (2001)10.1116/1.1421558], we show that the fabricated gratings will have improved period uniformity, with the period variation reduced by 86% at the 1000 nm central grating period setting. This process is a simple and efficient way to achieve linear gratings without altering the LIL configuration with two spherical beams. We present experimental results on the impact of a concave vacuum chuck on the chirp reduction at different grating period settings. Then, we compare two different LIL configurations with different wavelength sources concerning their influence on the efficiency of period variation reduction. Finally, the flatness of the 4-inch silicon wafers due to the temporary bending process is verified using optical profilometry measurements.

Versatile Zirconium Oxide (ZrO2) Sol-Gel Development for the Micro-Structuring of Various Substrates (Nature and Shape) by Optical and Nano-Imprint Lithography.

Zirconium oxide (ZrO2) is a well-studied and promising material due to its remarkable chemical and physical properties. It is used, for example, in coatings for corrosion protection layer, wear and oxidation, in optical applications (mirror, filters), for decorative components, for anti-counterfeiting solutions and for medical applications. ZrO2 can be obtained as a thin film using different deposition methods such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). These techniques are mastered but they do not allow easy micro-nanostructuring of these coatings due to the intrinsic properties (high melting point, mechanical and chemical resistance). An alternative approach described in this paper is the sol-gel method, which allows direct micro-nanostructuring of the ZrO2 layers without physical or chemical etching processes, using optical or nano-imprint lithography. In this paper, the authors present a complete and suitable ZrO2 sol-gel method allowing to achieve complex micro-nanostructures by optical or nano-imprint lithography on substrates of different nature and shape (especially non-planar and foil-based substrates). The synthesis of the ZrO2 sol-gel is presented as well as the micro-nanostructuring process by masking, colloidal lithography and nano-imprint lithography on glass and plastic substrates as well as on plane and curved substrates.

Influence of the Micro-Nanostructuring of Titanium Dioxide Films on the Photocatalytic Degradation of Formic Acid under UV Illumination.

Surface micro-nanostructuring can provide new functionalities and properties to coatings. For example, it can improve the absorption efficiency, hydrophobicity and/or tribology properties. In this context, we studied the influence of micro-nanostructuring on the photocatalytic efficiency of sol-gel TiO2 coatings during formic acid degradation under UV illumination. The micro-nanostructuring was performed using the UV illumination of microspheres deposited on a photopatternable sol-gel layer, leading to a hexagonal arrangement of micropillars after development. The structures and coatings were characterized using Raman spectroscopy, ellipsometry, atomic force microscopy and scanning electron microscopy. When the sol-gel TiO2 films were unstructured and untreated at 500 °C, their effect on formic acid's degradation under UV light was negligible. However, when the films were annealed at 500 °C, they crystallized in the anatase phase and affected the degradation of formic acid under UV light, also depending on the thickness of the layer. Finally, we demonstrated that surface micro-nanostructuring in the form of nanopillars can significantly increase the photocatalytic efficiency of a coating during the degradation of formic acid under UV light.

A versatile technology for colloidal crystal transfer using parylene coatings and hydrosoluble polymers.

We propose a novel versatile colloidal crystal transfer technique compatible with a wide range of water-insoluble substrates regardless of their size, material, and wettability. There are no inherent limitations on colloidal particles material and size. The method possibilities are demonstrated via the colloidal transfer on quartz, glass substrates with a flat and curved surface, and via the fabrication of 3D colloidal structure with 5 overlaid colloidal monolayers. The process occurs at a room temperature in water and is independent from the illumination conditions, which makes it ideal for experimental manipulations with sensitive functional substrates. We performed the nanosphere photolithography process on a photosensitive substrate with a transferred colloidal monolayer. The metallized hexagonal arrays of nanopores demonstrated a clear resonant plasmonic behavior. We believe that due to its high integration possibilities the proposed transfer technique will find applications in a large-area surface nanotexturing, plasmonics, and will speed up a device fabrication process.

Effect of roughness on surface plasmons propagation along deep and shallow metallic diffraction gratings.

The roughness of shallow or deep metallic diffraction gratings modifies the propagation of surface plasmon mode along the metallic-air interface. The scattering losses lead to a spectral or angular broadening of the surface plasmon resonance (SPR) and to a shift of the resonance wavelength and coupling angle. This mechanism is deeply analyzed both experimentally and theoretically to overcome these effects when such structures, in particular deep ones, are used as SPR-based sensors.

Impact of γ-rays Irradiation on Hybrid TiO2-SiO2 Sol-Gel Films Doped with RHODAMINE 6G.

In the present paper, we investigate how the optical and structural properties, in particular the observed photoluminescence (PL) of photocurable and organic-inorganic TiO2-SiO2 sol-gel films doped with Rhodamine 6G (R6G) are affected by γ-rays. For this, four luminescent films, firstly polymerized with UV photons (365 nm), were submitted to different accumulated doses of 50 kGy, 200 kGy, 500 kGy and 1 MGy while one sample was kept as a reference and unirradiated. The PL, recorded under excitations at 365 nm, 442 nm and 488 nm clearly evidences that a strong signal peaking at 564 nm is still largely present in the γ-irradiated samples. In addition, M-lines and Fourier-transform infrared (FTIR) spectroscopies are used to quantify the radiation induced refractive index variation and the chemical changes, respectively. Results show that a refractive index decrease of 7 × 10-3 at 633 nm is achieved at a 1 MGy accumulated dose while a photo-induced polymerization occurs, related to the consumption of CH=C, Si-OH and Si-O-CH3 groups to form Ti-O and Si-O bonds. All these results confirm that the host matrix (TiO2-SiO2) and R6G fluorophores successfully withstand the hard γ-ray exposure, opening the way to the use of this material for sensing applications in radiation-rich environments.

Compensation of disorder for extraordinary optical transmission effect in nanopore arrays fabricated by nanosphere photolithography.

The work considers the effect of extraordinary optical transmission (EOT) in polycrystalline arrays of nanopores fabricated via nanosphere photolithography (NPL). The use of samples with different qualities of polycrystalline structure allows us to reveal the role of disorder for EOT. We propose a phenomenological model which takes the disorder into account in numerical simulations and validate it using experimental data. Due to the NPL flexibility for the structure geometry control, we demonstrate the possiblity to partially compensate the disorder influence on EOT by the nanopore depth adjustments. The proposed experimental and theoretical results are promising to reveal the NPL limits for EOT-based devices and stimulate systematic studies of disorder compensation designs.

Comparison between the UV and X-ray Photosensitivities of Hybrid TiO2-SiO2 Thin Layers.

The photo-induced effects on sol-gel-based organo TiO2-SiO2 thin layers deposited by the dip-coating technique have been investigated using two very different light sources: A light-emitting diode (LED) emitting in the UV (at 365 nm, 3.4 eV) and an X-ray tube producing 40 keV mean-energy photons. The impact of adding a photo-initiator (2,2-dimethoxy-2-phenylacetophenone-DMPA) on the sol-gel photosensitivity is characterized namely in terms of the photo-induced refractive index measured through M-line spectroscopy. Results show that both silica-titania sol-gel films with or without the photo-initiator are photosensitive to both photon sources. The induced refractive index values reveal several features where slightly higher refractive indexes are obtained for the sol-gel containing the photo-initiator. UV and X-ray-induced polymerization degrees are discussed using Fourier-transform infrared (FTIR) spectroscopy where the densification of hybrid TiO2-SiO2 layers is related to the consumption of the CH=C groups and to the decomposition of Si-OH and Si-O-CH3 bonds. X-rays are more efficient at densifying the TiO2-SiO2 inorganic and organic network with respect to the UV photons. Hard X-ray photolithography, where no cracks or damages are observed after intense exposition, can be a promising technique to design submicronic-structure patterns on TiO2-SiO2 thin layers for the building of optical sensors.

Enhancement of Both Faraday and Kerr Effects with an All-Dielectric Grating Based on a Magneto-Optical Nanocomposite Material.

We report on the design, fabrication, and characterization of an all-dielectric one-dimensional (1D) resonant device formed by a silicon nitride grating impregnated by a low-index magneto-optical silica-type matrix. This impregnation is realized through the dipping of the 966 nm periodic template in a sol-gel solution previously doped with CoFe2O4 nanoparticles, and able to fill the grating slits. By a proper adjustment of the geometrical parameters of such a photonic crystal membrane, simultaneous excitation of transverse electric (TE) and transverse magnetic (TM) polarization resonances is nearly achieved at 1570 nm. This TE/TM phase-matching situation leads to a fivefold enhancement of the Faraday effect in the resonance area with an increased merit factor of 0.32°. Moreover, the device demonstrates its ability to enhance longitudinal and transverse Kerr effects for the other directions of the applied magnetic field. Taking benefits from the ability of the nanocomposite material to be processed on photonic platforms, and despite its quite low magneto-optical activity compared to classical magnetic materials, this work proves that an all-dielectric 1D device can produce a high magneto-optical sensitivity to every magnetic field directions.

Systematic study of resonant transmission effects in visible band using variable depth gratings.

The article focuses on depth-dependent visible band transmission effects in a symmetrical "insulator-metal-insulator" diffraction system based on a variable depth grating. These effects were studied both experimentally and theoretically in TM and TE polarizations. In particular, the existence of an optimized grating depth for plasmon-mediated resonant transmission was confirmed experimentally, and differences in TE and TM transmission behavior are discussed. We utilize a simple and flexible fabrication approach for rapid synthesis of apodized structures with adiabatically varying depth based on a beat pattern of two interferential lithography exposures. The present study can be useful in the fields of transmission-based optical security elements and biosensors.

Surface Plasmon Resonance Based Temperature Sensors in Liquid Environment.

The aim of this work is to measure the temperature variations by analyzing the plasmon signature on a metallic surface that is periodically structured and immersed in a liquid. A change in the temperature of the sample surface induces a modification of the local refractive index leading to a shift of the surface plasmon resonance (SPR) frequency due to the strong interaction between the evanescent electric field and the metallic surface. The experimental set-up used in this study to detect the refractive index changes is based on a metallic grating permitting a direct excitation of a plasmon wave, leading to a high sensibility, high-temperature range and contactless sensor within a very compact and simple device. The experimental set-up demonstrated that SPR could be used as a non-invasive, high-resolution temperature measurement method for metallic surfaces.

Direct S-matrix calculation for diffractive structures and metasurfaces.

The paper presents a derivation of analytical components of S matrices for arbitrary planar diffractive structures and metasurfaces in the Fourier domain. The attained general formulas for S-matrix components can be applied within both formulations in the Cartesian and curvilinear metric. A numerical method based on these results can benefit from all previous improvements of the Fourier domain methods. In addition, we provide expressions for S-matrix calculation in the case of periodically corrugated layers of two-dimensional materials, which are valid for arbitrary corrugation depth-to-period ratios. As an example, the derived equations are used to simulate resonant grating excitation of graphene plasmons and the impact of a silica interlayer on corresponding reflection curves.

Periodic TiO2 Nanostructures with Improved Aspect and Line/Space Ratio Realized by Colloidal Photolithography Technique.

This paper presents substantial improvements of the colloidal photolithography technique (also called microsphere lithography) with the goal of better controlling the geometry of the fabricated nano-scale structures-in this case, hexagonally arranged nanopillars-printed in a layer of directly photopatternable sol-gel TiO2. Firstly, to increase the achievable structure height the photosensitive layer underneath the microspheres is deposited on a reflective layer instead of the usual transparent substrate. Secondly, an increased width of the pillars is achieved by tilting the incident wave and using multiple exposures or substrate rotation, additionally allowing to better control the shape of the pillar's cross section. The theoretical analysis is carried out by rigorous modelling of the photonics nanojet underneath the microspheres and by optimizing the experimental conditions. Aspect ratios (structure height/lateral structure size) greater than 2 are predicted and demonstrated experimentally for structure dimensions in the sub micrometer range, as well as line/space ratios (lateral pillar size/distance between pillars) greater than 1. These nanostructures could lead for example to materials exhibiting efficient light trapping in the visible and near-infrared range, as well as improved hydrophobic or photocatalytic properties for numerous applications in environmental and photovoltaic systems.

Microstructuring of Mesoporous Titania Films Loaded with Silver Salts to Enhance the Photocatalytic Degradation of Methyl Blue under Visible Light.

The microstructuring of the distribution of silver nanoparticles (NPs) in mesoporous titania films loaded with silver salts, using two-beam interference lithography leading to 1 Dimension (1D) grating, induces variations in the photocatalytic efficiency. The influence of the structuration was tested on the degradation of methyl blue (MB) under ultraviolet (UV) and visible illumination, giving rise to a significant improvement of the photocatalytic efficiency. The periodic distribution of the NPs was characterized by transmission electron microscopy (TEM), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and scanning electron microscopy (SEM).

Condensation phenomenon detection through surface plasmon resonance.

The aim of this work is to optically detect the condensation of acetone vapor on an aluminum plate cooled down in a two-phase environment (liquid/vapor). Sub-micron period aluminum based diffraction gratings with appropriate properties, exhibiting a highly sensitive plasmonic response, were successfully used for condensation experiments. A shift in the plasmonic wavelength resonance has been measured when acetone condensation on the aluminum surface takes place due to a change of the surrounding medium close to the surface, demonstrating that the surface modification occurs at the very beginning of the condensation phenomenon. This paper presents important steps in comprehending the incipience of condensate droplet and frost nucleation (since both mechanisms are similar) and thus to control the phenomenon by using an optimized engineered surface.