Volume detection based on porous silicon waveguide for CO2 mid-infrared spectroscopy.

A mid-infrared (mid-IR) porous silicon (PSi) waveguide gas sensor was fabricated. PSi guiding and confinement layers were prepared by electrochemical anodization. Ridge waveguides were patterned using standard i-line photolithography and reactive ion etching. Due to the open pores, light and gas molecules interact in the inside volume, unlike bulk material in which the interaction takes place with the evanescent part of the light. Propagation losses are measured for a wavelength range spanning from λ = 3.9 to 4.55 µm with a value of 11.4 dB/cm at λ = 4.28 µm. The influence of native oxidation and ageing on the propagation losses was investigated. Limit of detection (LoD) of 1000 ppm is obtained with the waveguide sensor at the carbon dioxide (CO2) absorption peak at λ = 4.28 µm.

Carbon dioxide mid-infrared sensing based on Dy3+-doped chalcogenide waveguide photoluminescence.

Climate-active gases, notably carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O), display fundamental absorption bands in the mid-infrared (mid-IR). The detection and monitoring of those gases could be enabled by the development of mid-IR optical sources. Broadband mid-IR on-chip light emission from rare-earth-doped chalcogenide photonic integrated circuits could provide a compact, efficient, and cost-effective gas sensing solution. Mid-IR photoluminescence of dysprosium-doped selenide ridge waveguides obtained under optical pumping at a telecommunication wavelength (∼1.3 µm) is investigated for Dy3+ ion concentrations in the 2500-10,000 ppmw range. CO2 detection at around 4.3 µm is then demonstrated based on absorption of this broadband mid-IR emission.

Ionic Conductivity and Structure of Glasses Synthesized by Mechanical-Milling Methods in the x[Na2S]-(100 - x) [0.5GeS2-0.5Ga2S3] System.

Chalcogenide glasses in the Na2S-GeS2-Ga2S3 pseudoternary system were synthesized using a combination route of melt-quenching and mechanical-milling methods. First, a glass rich in germanium (90GeS2-10Ga2S3) is synthesized by melt-quenching synthesis in a silica tube sealed under vacuum. This glass is used as a precursor for the second step of mechanochemistry to explore the Na2S-GeS2-Ga2S3 pseudoternary system. By using this synthesis route, the glass-forming ability is improved as the vitreous domain is enlarged, especially for Na- and Ga-rich compositions. The as-obtained amorphous powders are characterized by Raman spectroscopy, differential scanning calorimetry, X-ray total scattering, and pair distribution function (PDF) analysis. The evolution of the Raman features observed is reproduced using density functional theory calculations. Impedance spectroscopy was performed to determine the conductivity of the new glasses. The addition of germanium sulfide to the Na2S-Ga2S3 pseudobinary system enables one to increase the conductivity by 1 order of magnitude. The highest room-temperature ionic conductivity, as measured by impedance spectroscopy, is 1.8 × 10-5 S·cm-1.

Genetic architecture and genomic selection of fatty acid composition predicted by Raman spectroscopy in rainbow trout.

BACKGROUND: In response to major challenges regarding the supply and sustainability of marine ingredients in aquafeeds, the aquaculture industry has made a large-scale shift toward plant-based substitutions for fish oil and fish meal. But, this also led to lower levels of healthful n-3 long-chain polyunsaturated fatty acids (PUFAs)-especially eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids-in flesh. One potential solution is to select fish with better abilities to retain or synthesise PUFAs, to increase the efficiency of aquaculture and promote the production of healthier fish products. To this end, we aimed i) to estimate the genetic variability in fatty acid (FA) composition in visceral fat quantified by Raman spectroscopy, with respect to both individual FAs and groups under a feeding regime with limited n-3 PUFAs; ii) to study the genetic and phenotypic correlations between FAs and processing yields- and fat-related traits; iii) to detect QTLs associated with FA composition and identify candidate genes; and iv) to assess the efficiency of genomic selection compared to pedigree-based BLUP selection. RESULTS: Proportions of the various FAs in fish were indirectly estimated using Raman scattering spectroscopy. Fish were genotyped using the 57 K SNP Axiom™ Trout Genotyping Array. Following quality control, the final analysis contained 29,652 SNPs from 1382 fish. Heritability estimates for traits ranged from 0.03 ± 0.03 (n-3 PUFAs) to 0.24 ± 0.05 (n-6 PUFAs), confirming the potential for genomic selection. n-3 PUFAs are positively correlated to a decrease in fat deposition in the fillet and in the viscera but negatively correlated to body weight. This highlights the potential interest to combine selection on FA and against fat deposition to improve nutritional merit of aquaculture products. Several QTLs were identified for FA composition, containing multiple candidate genes with indirect links to FA metabolism. In particular, one region on Omy1 was associated with n-6 PUFAs, monounsaturated FAs, linoleic acid, and EPA, while a region on Omy7 had effects on n-6 PUFAs, EPA, and linoleic acid. When we compared the effectiveness of breeding programmes based on genomic selection (using a reference population of 1000 individuals related to selection candidates) or on pedigree-based selection, we found that the former yielded increases in selection accuracy of 12 to 120% depending on the FA trait. CONCLUSION: This study reveals the polygenic genetic architecture for FA composition in rainbow trout and confirms that genomic selection has potential to improve EPA and DHA proportions in aquaculture species.

Toward Chalcogenide Platform Infrared Sensor Dedicated to the In Situ Detection of Aromatic Hydrocarbons in Natural Waters via an Attenuated Total Reflection Spectroscopy Study.

The objective of this study is to demonstrate the successful functionalization of the surface of a chalcogenide infrared waveguide with the ultimate goal of developing an infrared micro-sensor device. First, a polyisobutylene coating was selected by testing its physico-chemical compatibility with a Ge-Sb-Se selenide surface. To simulate the chalcogenide platform infrared sensor, the detection of benzene, toluene, and ortho-, meta- and para-xylenes was efficaciously performed using a polyisobutylene layer spin-coated on 1 and 2.5 µm co-sputtered selenide films of Ge28Sb12Se60 composition deposited on a zinc selenide prism used for attenuated total reflection spectroscopy. The thickness of the polymer coating was optimized by attenuated total reflection spectroscopy to achieve the highest possible attenuation of water absorption while maintaining the diffusion rate of the pollutant through the polymer film compatible with the targeted in situ analysis. Then, natural water, i.e., groundwater, wastewater, and seawater, was sampled for detection measurement by means of attenuated total reflection spectroscopy. This study is a valuable contribution concerning the functionalization by a hydrophobic polymer compatible with a chalcogenide optical sensor designed to operate in the mid-infrared spectral range to detect in situ organic molecules in natural water.

Co-sputtered Pr3+-doped Ga-Ge-Sb-Se active waveguides for mid-infrared operation.

This work reports on the properties of luminescent waveguides based on quaternary Ga-Ge-Sb-Se amorphous thin films doped with praseodymium. The waveguides were fabricated via magnetron co-sputtering, followed by inductively coupled plasma reactive ion etching. The initial thin film thickness and optical properties were assessed and the spectroscopic properties of the waveguides were measured. The measurements show promising results-it is possible to obtain mid-infrared fluorescence at 2.5 and 4.5 µm by injecting near-infrared light at 1.5 µm as the pump beam. By comparing waveguides with various praseodymium concentrations, the optimal doping content for maximum fluorescence intensity was identified to be close to 4100 ppmw. Finally, correlation between the intensity of mid-infrared emission and the width/length of the waveguide is shown.

GaTe-Sb2Te3 thin-films phase change characteristics.

A radio frequency magnetron co-sputtering technique exploiting GaTe and ${\rm Sb}_2 {\rm Te}_3$Sb2Te3 targets was used for the fabrication of Ga-Sb-Te thin films. Prepared layers cover broad region of chemical composition (${\sim}{10.0 {-} 26.3}\,\, {\rm at.}$∼10.0-26.3at. % of Ga, ${\sim}{19.9 {-} 34.4}\,\, {\rm at.}$∼19.9-34.4at. % of Sb) while keeping Te content fairly constant (53.8-55.6 at. % of Te). Upon crystallization induced by annealing, large variations in electrical contrast were found, reaching a sheet resistance ratio of ${{R}_{\rm annealed}}/{{R}_{\rm as - deposited}}\;\sim{2.2} \times {{10}^{ - 8}}$Rannealed/Ras-deposited∼2.2×10-8 for the ${{\rm Ga}_{26.3}}{{\rm Sb}_{19.9}}{{\rm Te}_{53.8}}$Ga26.3Sb19.9Te53.8 layer. Phase transition from the amorphous to crystalline state further leads to huge changes of optical functions demonstrated by optical contrast values up to $|\Delta n| + |\Delta k| = {4.20}$|Δn|+|Δk|=4.20 for ${{\rm Ga}_{26.3}}{{\rm Sb}_{19.9}}{{\rm Te}_{53.8}}$Ga26.3Sb19.9Te53.8 composition.

Linear and nonlinear optical properties of co-sputtered Ge-Sb-Se amorphous thin films.

Amorphous Ge-Sb-Se thin films were co-sputtered from ${{\rm GeSe}_4}$GeSe4 and ${{\rm Sb}_2}{{\rm Se}_3}$Sb2Se3 targets. Depending on the film composition, linear optical properties were studied by ellipsometry. The Kerr coefficient and two-photon absorption coefficient were estimated using Sheik-Bahae's formalism for co-sputtered films of ${{\rm GeSe}_4} {\text -} {\rm Sb}_2{{\rm Se}_3}$GeSe4-Sb2Se3 compared to ${{\rm GeSe}_2}{\text -}{\rm Sb}_2{{\rm Se}_3}$GeSe2-Sb2Se3 pseudo-binary system and ${{\rm As}_2}{{\rm Se}_3}$As2Se3 as reference. The Kerr coefficient was found within the range of $4.9 {\unicode {x2013}}- 21 \times {10^{ - 18}}$4.9--21×10-18. Quantitatively by means of a figure of merit at 1.55 µm, thin films with compositions of ${{\rm Ge}_7}{\rm Sb}_{25}{\rm Se}_{68}$Ge7Sb25Se68 and ${{\rm Ge}_9}{\rm Sb}_{20}{\rm Se}_{71}$Ge9Sb20Se71 having an estimated Kerr coefficient of about ${10.1} \times {10^{ - 18}}\;{{\rm m}^2}{{\rm W}^{ - 1}}$10.1×10-18m2W-1 and ${13.4} \times {10^{ - 18}}\;{{\rm m}^2}{{\rm W}^{ - 1}}$13.4×10-18m2W-1 should be considered for the future nonlinear optical integrated platforms. Such compositions being close to ${({{\rm GeSe}_4})_{50}}{({{\rm Sb}_2}{{\rm Se}_3})_{50}}$(GeSe4)50(Sb2Se3)50 pseudo-binary (i.e., ${\rm Ge}_{7.5}{\rm Sb}_{25.0}{\rm Se}_{67.5}$Ge7.5Sb25.0Se67.5) provides just the trade-off between a high Kerr coefficient and low optical losses related to two-photon absorption.

Anodic bonding of mid-infrared transparent germanate glasses for high pressure - high temperature microfluidic applications.

High pressure/high-temperature microreactors based on silicon-Pyrex® microfabrication technologies have attracted increasing interest in various applications providing optical access in high-pressure flow processes. However, they cannot be coupled to infrared spectroscopy due to the limited optical transparency (up to ~2.7 µm in the infrared region) of the Pyrex® glass substrate employed in the microreactor fabrication. To address this limitation, the alternative approach proposed in this work consists in replacing the Pyrex® glass in the microreactor by a mid-infrared transparent glass with thermal and mechanical properties as close as possible or even better to those of the Pyrex®, including its ability for silicon-wafers coupling by the anodic bonding process. Glasses based on germanate GeO2, known for their excellent transmission in the mid-infrared range and thermal/thermo-mechanical properties, have been thus evaluated and developed for this purpose. The optical, mechanical, thermal and electrical conductivity properties of adapted glass compositions belonging to five vitreous systems have been systemically investigated. The glass composition 70GeO2-15Al2O3-10La2O3-5Na2O (mol.%) was defined as the best candidate and produced in large plates of 50 mm diameter and 1 mm thickness. Anodic bonding tests with Si-wafers have been then successfully conducted, paving the way for the development of fully mid-infrared transparent silicon-glass microreactors.

7 to 8 µm emission from Sm3+ doped selenide fibers.

We report on the observation of the long wave-infrared (LWIR) emission centered at 7.3 µm of Sm3+ doped chalcogenide fibers. The chemical composition of the selenide glass host matrix (Ga5Ge20Sb10Se65) enables the drawing of 500 ppm and 1000 ppm Sm3+ doped fibers. By means of conventional glass elaboration methods, these Sm3+ doped fibered materials exhibit a significant emission band from 6.5 to 8.5 µm with a maximum emission around 7.3 µm whether they are excited at 1.45 µm or at 2.05 µm. Absorption spectra, Judd-Ofelt analysis, NIR, MWIR and LWIR luminescence spectra are presented and discussed.

8 µm luminescence from a Tb3+ GaGeSbSe fiber.

In this Letter, we report for the first time, to the best of our knowledge, on an emission at 8 µm from Tb3+-doped Ga5Ge20Sb10Se65 chalcogenide fibers with doping levels at 1000 ppm and 500 ppm. These fibers were drawn following conventional melt-quenching methods and pumped at 2.05 µm using a Tm3+: YAG laser. The spectroscopic properties of the emitting F47 manifold are investigated to rule out any parasitic signal mimicking the real Tb3+ 8 µm emission. Time-resolved spectroscopic experiments are presented to build a comprehensive study of this 8 µm fluorescence recorded with a clear signal-to-noise ratio.

Design of praseodymium-doped chalcogenide micro-disk emitting at 4.7 µm.

A compact amplifier based on chalcogenide Pr3+-doped micro-disk coupled to two ridge waveguides is designed and refined by means of a home-made computer code. The gain G ≈ 7.9 dB is simulated for a Pr3+ concentration of 10 000 ppm, input signal power of -30 dBm at the wavelength 4.7 µm and input pump power of 50 mW at the wavelength 1.55 µm. In the laser behavior, i.e. without input signal, the maximum slope efficiency S = 8.1 × 10-4 is obtained for an input pump power of 2 mW. This value is about six times higher than that simulated for an optimized erbium-doped micro-disk.

Photostability of pulsed-laser-deposited AsxTe100-x (x=40, 50, 60) amorphous thin films.

AsxTe100-x amorphous thin films were fabricated by a pulsed laser deposition technique with the aim of finding photostable layers in as-deposited but preferably in relaxed (annealed) state. Photostability was studied in terms of the films' stability of refractive index and bandgap under near-bandgap light irradiation. As40Te60 and As50Te50 layers were found to be photostable in both as-deposited as well as relaxed states. Moreover, As50Te50 layers present the lowest surface roughness. These characteristics make pulsed-laser-deposited As50Te50 thin films promising for applications in nonlinear optics.

Optical characterization at 7.7 µm of an integrated platform based on chalcogenide waveguides for sensing applications in the mid-infrared.

A selenide integrated platform working in the mid-infrared was designed, fabricated and optically characterized at 7.7 µm. Ge-Sb-Se multilayered structures were deposited by RF magnetron sputtering. Using i-line photolithography and fluorine-based reactive ion etching, ridge waveguides were processed as Y-junction, spiral and S-shape waveguides. Single-mode optical propagation at 7.7 µm was observed by optical near-field imaging and optical propagation losses of 2.5dB/cm are measured. Limits of detection of 14.2 ppm and 1.6 ppm for methane and nitrous oxide, respectively, could be potentially measured by using this platform as an evanescent field sensor. Hence, these technological, experimental and theoretical results represent a first step towards the development of an integrated optical sensor operating in the mid-infrared wavelength range.

Laser desorption ionization time-of-flight mass spectrometry of erbium-doped Ga-Ge-Sb-S glasses.

RATIONALE: Rare earth-doped sulphide glasses in the Ga-Ge-Sb-S system present radiative emissions from the visible to the middle infrared range (mid-IR) range, which are of interest for a variety of applications including (bio)-chemical optical sensing, light detection, and military counter-measures. The aim of this work was to reveal structural motifs present during the fabrication of thin films by plasma deposition techniques as such knowledge is important for the optimization of thin film growth. METHODS: The formation of clusters in plasma plume from different concentrations of erbium-doped Ga5Ge20Sb10S65 glasses (0.05, 0.1, and 0.5 wt. % of erbium) using laser (337 nm) desorption ionization (LDI) was studied by time-of-flight mass spectrometry (TOF MS) in both positive and negative ion mode. The stoichiometry of the Ga(m)Ge(n)Sb(o)S(p)(+/-) clusters was determined via isotopic envelope analysis and computer modelling. RESULTS: Several Ga(m)Ge(n)Sb(o)S(p)(+/-) singly charged clusters were found but, surprisingly, only four species (Sb3S4(+/-), GaSb2S(p)(+/-) (p = 4, 5), Ga3Sb2S7(+/-) ) were common to both ion modes. For the first time, species containing rare earths (GaSb2SEr(+) and GaS6 Er2(+)) were identified in the plasma formed from rare earth-doped chalcogenide glasses, directly confirming the importance of gallium presence for rare earth bonding within the glassy matrix. CONCLUSIONS: The local structure of Ga-Ge-Sb-S glasses is at least partly different from the structure of species identified in plasma by mass spectrometry, as deduced from Raman scattering spectroscopy analysis; these glasses are mainly formed by [GeS4/2]/[GaS4/2] tetrahedra and [SbS3/2] pyramids. Extended X-ray absorption fine structure measurements show that Er(3+) ions in Ga-Ge-Sb-S glasses are surrounded by 7 sulphur atoms.

Praseodymium-Doped Ge20In5Sb10Se65 Films Based on Argon Plasma Cosputtering for Infrared-Luminescent Integrated Photonic Circuits.

In this paper, we report on the infrared luminescence of amorphous praseodymium-doped Ge20In5Sb10Se65 waveguides, which can be used as infrared sources in photonic integrated circuits on silicon substrates. Amorphous chalcogenide thin films were deposited by radiofrequency magnetron cosputtering using an argon plasma whose deposition parameters were optimized for chalcogenide materials. The micropatterning as ridge waveguides of the chalcogenide cosputtered films was performed using photolithography and plasma-coupled reactive ion etching techniques. The influence of the rare earth concentration within those thin films on their optical properties and rare earth spectroscopic properties was investigated. Using an excitation wavelength of 1.55 µm, the mid-infrared luminescence of Pr3+ ions from 2.5 to 5.5 µm was clearly demonstrated for studied chalcogenide materials. A wide range of waveguide widths and doping ratios were tested, assessing the ability of the cosputtering technique to preserve the luminescence properties of the rare earth ions initially observed in the bulk glass through the thin-film deposition and patterning process.

Red and orange Pr3+:LiYF4 planar waveguide laser.

In this Letter we report on room temperature continuous wave laser operation in the red (639 nm, (3)P(0)→(3)F(2)) and orange (604 nm, (3)P(0)→(3)H(6)) spectral regions of Pr(3+)-doped LiYF(4) planar waveguides fabricated by liquid phase epitaxy. Output powers of 25 and 12 mW and slope efficiencies of 5% and 6% were achieved at 639 and 604 nm, respectively, by pumping with an optically pumped semiconductor laser operating at 479.2 nm.

From selenium- to tellurium-based glass optical fibers for infrared spectroscopies.

Chalcogenide glasses are based on sulfur, selenium and tellurium elements, and have been studied for several decades regarding different applications. Among them, selenide glasses exhibit excellent infrared transmission in the 1 to 15 µm region. Due to their good thermo-mechanical properties, these glasses could be easily shaped into optical devices such as lenses and optical fibers. During the past decade of research, selenide glass fibers have been proved to be suitable for infrared sensing in an original spectroscopic method named Fiber Evanescent Wave Spectroscopy (FEWS). FEWS has provided very nice and promising results, for example for medical diagnosis. Then, some sophisticated fibers, also based on selenide glasses, were developed: rare-earth doped fibers and microstructured fibers. In parallel, the study of telluride glasses, which can have transmission up to 28 µm due to its atom heaviness, has been intensified thanks to the DARWIN mission led by the European Space Agency (ESA). The development of telluride glass fiber enables a successful observation of CO2 absorption band located around 15 µm. In this paper we review recent results obtained in the Glass and Ceramics Laboratory at Rennes on the development of selenide to telluride glass optical fibers, and their use for spectroscopy from the mid to the far infrared ranges.

Low-power plasmon-soliton in realistic nonlinear planar structures.

We study the propagation of nonlinear waves in layered nonlinear dielectric/linear dielectric/metal planar structures. We develop vector models that describe the light propagation in such configurations and allow us to obtain both one- and two-dimensional solutions. We compute the nonlinear dispersion relation and the field profiles, and estimate losses. We use our models to design realistic structures, in terms of linear and nonlinear properties, which support soliton waves with a plasmon tail at low peak power around or below 1 GW/cm(2). These results open the way for potential observation of such states in chalcogenide waveguides associated with silica and metal films. In the proposed structures, the nonlinearity confines the field in both transverse directions. A recordable plasmonic part of the field extends in air.

Tailoring of Multisource Deposition Conditions towards Required Chemical Composition of Thin Films.

The model to tailor the required chemical composition of thin films fabricated via multisource deposition, exploiting basic physicochemical constants of source materials, is developed. The model is experimentally verified for the two-source depositions of chalcogenide thin films from Ga-Sb-Te system (tie-lines GaSb-GaTe and GaSb-Te). The thin films are deposited by radiofrequency magnetron sputtering using GaSb, GaTe, and Te targets. Prepared thin films are characterized by means of energy dispersive X-ray analysis coupled with a scanning electron microscope to determine the chemical composition and by variable angle spectroscopic ellipsometry to establish film thickness. Good agreement between results of calculations and experimentally determined compositions of the co-deposited thin films is achieved for both the above-mentioned tie-lines. Moreover, in spite of all the applied simplifications, the proposed model is robust to be generally used for studies where the influence of thin film composition on their properties is investigated.