Emeline Baudet

Structure, nonlinear properties, and photosensitivity of (GeSe_2)_100-x(Sb_2Se_3)_x glasses

Chalcogenide glasses from (GeSe2)​100-​x(Sb2Se3)​x system were synthesized, with x varying from 5 to 70, in order to evaluate the influence of antimony selenide addn. on nonlinear optical properties and photosensitivity. Nonlinear refractive index and two photon absorption coeffs. were measured both at 1064 nm in picosecond regime using the Z-​scan technique and at 1.55 μm in femtosecond regime using an original method based on direct anal. of beam profile change while propagating in the chalcogenide glasses. The study of their photosensitivity at 1.55 μm revealed highly glass compn. dependent behavior and quasi-​photostable compns. have been identified in femtosecond regime. To better understand these characteristics, the evolution of the glass transition temp., d. and structure with the chem. compn. were detd.

RF sputtered amorphous chalcogenide thin films for surface enhanced infrared absorption spectroscopy

The primary objective of this study is the development of transparent thin film materials in the IR enabling strong infrared absorption of organic compounds in the vicinity of metal nanoparticles by the surface plasmon effect. For developing these optical micro-sensors, hetero-structures combining gold nanoparticles and chalcogenide planar waveguides are fabricated and adequately characterized. Single As2S3 and Ge25Sb10Se65 amorphous chalcogenide thin films are prepared by radio-frequency magnetron sputtering. For the fabrication of gold nanoparticles on a chalcogenide planar waveguide, direct current sputtering is employed. Fabricated single layers or hetero-structures are characterized using various techniques to investigate the influence of deposition parameters. The nanoparticles of gold are functionalized by a self-assembled monolayer of 4-nitrothiophenol. Finally, the surface enhanced infrared absorption spectra of 4-nitrothiophenol self-assembled on fabricated Au/Ge-Sb-Se thin films hetero-structures are measured and analyzed. This optical component presents a ~24 enhancement factor for the detection of NO2 symmetric stretching vibration band of 4-nitrothiophenol at 1336 cm−1.

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.

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.

Selenide sputtered films development for MIR environmental sensor

A micro-sensor based on selenide glasses for evanescent wave detection in mid-infrared spectral range was designed and fabricated. Ge-Sb-Se thin films were successfully deposited by radio-frequency magnetron sputtering. In order to characterize them spectroscopic ellipsometry, atomic force microscopy and contact angle measurements were employed to study near and middle infrared refractive index, surface roughness and the wettability, respectively. Selenide sputtered films were micro-patterned by means of reactive ion etching with inductively coupled plasma process enabling single-mode propagation at a wavelength of 7.7 µm for a waveguide width between 8 and 12 µm. Finally, optical waveguide surface was functionalized by deposition of a hydrophobic polymer, which will permit detection of organic molecules in water. Thus, the optical transducer is a ridge waveguide composed by cladding and guiding Ge-Sb-Se sputtered layers exhibiting a tailored refractive index contrast and a polymer layer onto its surface ready for environmental detections in middle infrared.

Experimental design approach for deposition optimization of RF sputtered chalcogenide thin films devoted to environmental optical sensors

The development of the optical bio-chemical sensing technology is an extremely important scientific and technological issue for diagnosis and monitoring of diseases, control of industrial processes, environmental detection of air and water pollutants. Owing to their distinctive features, chalcogenide amorphous thin films represent a keystone in the manufacture of middle infrared integrated optical devices for a sensitive detection of biological or environmental variations. Since the chalcogenide thin films characteristics, i.e. stoichiometric conformity, structure, roughness or optical properties can be affected by the growth process, the choice and control of the deposition method is crucial. An approach based on the experimental design is undoubtedly a way to be explored allowing fast optimization of chalcogenide film deposition by means of radio frequency sputtering process. Argon (Ar) pressure, working power and deposition time were selected as potentially the most influential factors among all possible. The experimental design analysis confirms the great influence of the Ar pressure on studied responses: chemical composition, refractive index in near-IR (1.55 µm) and middle infrared (6.3 and 7.7 µm), band-gap energy, deposition rate and surface roughness. Depending on the intended application and therefore desired thin film characteristics, mappings of the experimental design meaningfully help to select suitable deposition parameters.

Pulsed laser deposited GeTe-rich GeTe-Sb2Te3 thin films.

Pulsed laser deposition technique was used for the fabrication of Ge-Te rich GeTe-Sb2Te3 (Ge6Sb2Te9, Ge8Sb2Te11, Ge10Sb2Te13, and Ge12Sb2Te15) amorphous thin films. To evaluate the influence of GeTe content in the deposited films on physico-chemical properties of the GST materials, scanning electron microscopy with energy-dispersive X-ray analysis, X-ray diffraction and reflectometry, atomic force microscopy, Raman scattering spectroscopy, optical reflectivity, and sheet resistance temperature dependences as well as variable angle spectroscopic ellipsometry measurements were used to characterize as-deposited (amorphous) and annealed (crystalline) layers. Upon crystallization, optical functions and electrical resistance of the films change drastically, leading to large optical and electrical contrast between amorphous and crystalline phases. Large changes of optical/electrical properties are accompanied by the variations of thickness, density, and roughness of the films due to crystallization. Reflectivity contrast as high as ~0.21 at 405 nm was calculated for Ge8Sb2Te11, Ge10Sb2Te13, and Ge12Sb2Te15 layers.

Laser Desorption Ionization of As2Ch3 (Ch = S, Se, and Te) Chalcogenides Using Quadrupole Ion Trap Time-of-Flight Mass Spectrometry: A Comparative Study

AbstractLaser desorption ionization using time-of-flight mass spectrometer afforded with quadrupole ion trap was used to study As2Ch3 (Ch = S, Se, and Te) bulk chalcogenide materials. The main goal of the study is the identification of species present in the plasma originating from the interaction of laser pulses with solid state material. The generated clusters in both positive and negative ion mode are identified as 10 unary (Sp+/– and Asm+/–) and 34 binary (AsmSp+/–) species for As2S3 glass, 2 unary (Seq+/–) and 26 binary (AsmSeq+/–) species for As2Se3 glass, 7 unary (Ter+/–) and 23 binary (AsmTer+/–) species for As2Te3 material. The fragmentation of chalcogenide materials was diminished using some polymers and in this way 45 new, higher mass clusters have been detected. This novel approach opens a new possibility for laser desorption ionization mass spectrometry analysis of chalcogenides as well as other materials. Graphical abstractᅟ

Development of an evanescent optical integrated sensor in the mid-infrared for detection of pollution in groundwater or seawater

Abstract The detection of molecules dissolved in liquid medium can be envisaged by means of an optical integrated sensor operating in middle infrared range. The intended sensor is composed of a cladding and a guiding selenide sputtered layers transparent in middle infrared. Hence, Ge-Sb-Se thin films were selected in view of tailored refractive index contrast, successfully deposited by radio frequency magnetron sputtering and characterized. To maximize the evanescent field at a wavelength of 7.7 µm, a suitable selenide waveguide allowing measuring the optical transmitted power was designed by performing computer simulations based on the effective index method enabling single-mode propagation for a waveguide width between 8 and 12 µm. Selenide sputtered films were micro-patterned using reactive ion etching with inductively coupled plasma process. Finally, optical waveguide surface was functionalized by the deposition of a hydrophobic polymer, which will permit detection of organic molecules in water.

Tb3+ doped Ga5Ge20Sb10Se65-xTex (x = 0-375) chalcogenide glasses and fibers for MWIR and LWIR emissions

Chalcogenide glasses with a nominal composition of Ga5Ge20Sb10Se65-xTex (x = 0, 10, 20, 25, 30, 32.5, 35, 37.5) were synthesized. Their physico-chemical properties, glass network structure and optical properties are clearly modified via the substitution of selenium by tellurium. Based on a detailed study of the Ga5Ge20Sb10Se65-xTexTex bulk glasses properties, the Ga5Ge20Sb10Se45Te20 seleno-telluride glass optimal composition has been selected for fiber drawing. The luminescence properties of Tb3+ (500 ppm) doped Ga5Ge20Sb10Se65 and Ga5Ge20Sb10Se45Te20 bulk glasses and fibers were studied. Radiative transitions parameters calculated from the Judd-Ofelt theory are compared to the experimental values. Mid-wavelength infrared emission in the range of 4.3-6.0 μm is attributed to the 7F5→7F6 transition of Tb3+ ions with a corresponding experimental lifetime of 8.9 and 7.8 ms for the selenide and seleno-telluride matrix, respectively. The 7F4→7F6 emission was recorded at 3.1 μm with a good signal-to-noise ratio, evidencing a rather strong emission from the 7F4 manifold. Finally, although it was expected that the phonon energy will be lower for telluride glasses, selenide glasses are still more suitable for mid-wavelength infrared and long wavelength infrared emissions with well-defined emissions from 3.1 to 8 μm.