Refractometry Studies of the Optical Properties of Polymer Films and the Development of Polymer Coated Refractive Index Sensors

Sensors for real-time monitoring of environmental contaminants are essential for protecting ecosystems and human health. Refractive index sensing is a non-selective technique that can be used to measure almost any analyte. Miniaturized refractive index sensors, such as silicon-on-insulator (SOI) microring resonators are one possible platform, but require coatings selective to the analytes of interest. A homemade prism refractometer is reported and used to characterize the interactions between polymer films and liquid or vapour-phase analytes. A camera was used to capture both Fresnel reflection and total internal reflection within the prism. For thin-films (d = 10 μm - 100 μm), interference fringes were also observed. Fourier analysis of the interferogram allowed for simultaneous extraction of the average refractive index and film thickness with accuracies of ∆n = 1-7 ×10-4 and ∆d < 3-5%. The refractive indices of 29 common organic solvents as well as aqueous solutions of sodium chloride, sucrose, ethylene glycol, glycerol, and dimethylsulfoxide were measured at λ = 1550 nm. These measurements will be useful for future calibrations of near-infrared refractive index sensors. A mathematical model is presented, where the concentration of analyte adsorbed in a film can be calculated from the refractive index and thickness changes during uptake. This model can be used with Fickian diffusion models to measure the diffusion coefficients through the bulk film and at the film-substrate interface. The diffusion of water and other organic solvents into SU-8 epoxy was explored using refractometry and the diffusion coefficient of water into SU-8 is presented. Exposure of soft baked SU-8 films to acetone, acetonitrile and methanol resulted in rapid delamination. The diffusion of volatile organic compound (VOC) vapours into polydimethylsiloxane and polydimethyl-co-polydiphenylsiloxane polymers was also studied using refractometry. Diffusion and partition coefficients are reported for several analytes. As a model system, polydimethyl-co-diphenylsiloxane films were coated onto SOI microring resonators. After the development of data acquisition software, coated devices were exposed to VOCs and the refractive index response was assessed. More studies with other polymers are required to test the viability of this platform for environmental sensing applications.

High-sensitivity refractive index sensor based on large-angle tilted fiber grating with carbon nanotube deposition

This paper presents a highly sensitive ambient refractive index (RI) sensor based on 81° tilted fiber grating (81°-TFG) structure UV-inscribed in standard telecom fiber (62.5μm cladding radius) with carbon nanotube (CNT) overlay deposition. The sensing mechanism is based on the ability of CNT to induce change in transmitted optical power and the high sensitivity of 81°-TFG to ambient refractive index. The thin CNT film with high refractive index enhances the cladding modes of the TFG, resulting in the significant interaction between the propagating light and the surrounding medium. Consequently, the surrounding RI change will induce not only the resonant wavelength shift but also the power intensity change of the attenuation band in the transmission spectrum. Result shows that the change in transmitted optical power produces a corresponding linear reduction in intensity with increment in RI values. The sample shows high sensitivities of ∼207.38nm/RIU, ∼241.79nm/RIU at RI range 1.344-1.374 and ∼113.09nm/RIU, ∼144.40nm/RIU at RI range 1.374-1.392 (for X-pol and Y-pol respectively). It also shows power intensity sensitivity of ∼ 65.728dBm/RIU and ∼ 45.898 (for X-pol and Y-pol respectively). The low thermal sensitivity property of the 81°-TFG offers reduction in thermal cross-sensitivity and enhances specificity of the sensor.

Modal analysis of anisotropic diffused-channel waveguide by a scalar finite element method

A procedure to model optical diffused-channel waveguides is presented in this work. The dielectric waveguides present anisotropic refractive indexes which are calculated from the proton concentration. The proton concentration inside the channel is calculated by the anisotropic 2D-linear diffusion equation and converted to the refractive indexes using mathematical relations obtained from experimental data, the arbitrary refractive index profile is modeled by a. nodal expansion in the base functions. The TE and TM-like propagation properties (effective index) and the electromagnetic fields for well-annealed proton-exchanged (APE) LiNbO3 waveguides are computed by the finite element method.

Optical Microring Resonators based on ion-implanted LiNbO3 ridge waveguides

The growing interest for Integrated Optics for sensing, telecommunications and even electronics is driving research to find solutions to the new challenges issued by a more and more fast, connected and smart world. This thesis deals with the design, the fabrication and the characterisation of the first prototypes of Microring Resonators realised using ion implanted Lithium Niobate (LiNbO3) ridge waveguides. Optical Resonator is one among the most important devices for all tasks described above. LiNbO3 is the substrate commonly used to fabricate optical modulators thanks to its electro-optic characteristics. Since it is produced in high quantity, good quality and large wafers its price is low compared to other electro-optic substrate. We propose to use ion implantation as fabrication technology because in the other way standard optical waveguides realised in LiNbO3 by Proton Exchange (PE) or metal diffusion do not allow small bending radii, which are necessary to keep the circuit footprint small. We will show in fact that this approach allows to fabricate waveguides on Lithium Niobate that are better than PE or metal diffused waveguides as it allows smaller size devices and tailoring of the refractive index profile controlling the implantation parameters. Moreover, we will show that the ridge technology based on enhanced etching rate via ion implantation produces a waveguide with roughness lower than a dry etched one. Finally it has been assessed a complete technological process for fabrication of Microring Resonator devices in Lithium Niobate by ion implantation and the first prototypes have been produced.

Synthese und Charakterisierung einer Hydrogelmatrix für die Multianalyt-Sensorik

Gegenstand und Ziel der vorliegenden Arbeit war die Synthese und Charakterisierung einer Hydrogelmatrix, welche für die Herstellung eines vielseitig verwendbaren Sensors, der mehrere Analyten (Proteine, DNA etc.) in hoher Verdünnung (c0 < 50 fM) aus kleinsten Probenmengen (Volumina <20 nl) schnell (t < 1 min) und parallel nachweisen kann, Verwendung finden soll. Der Fokus der Arbeit lag dabei in der Synthese und Charakterisierung von Copolymeren als Hydrogelmatrix, welche geeignetes temperaturabhängiges Verhalten zeigen. Die Copolymere wurden in eine dreidimensionale Netzwerkstruktur überführt und auf einer Goldoberfläche kovalent angebunden, um Delamination zu vermeiden und die Untersuchung mittels Oberflächenplasmonenresonanz-Spektroskopie (SPR) und Optischer Wellenleiter-Spektroskopie (OWS) zu erlauben. Weiterhin wurde das temperaturabhängige Verhalten der Polymernetzwerke in Wasser mittels optischen Messungen (SPR/OWS) untersucht, um Erkenntnisse über die Quell- und Kollabiereigenschaften des Hydrogels zu gewinnen. Um temperaturschaltbare Hydrogele herzustellen, wurden auf N-Isopropylacrylamid (NIPAAm) basierende Polymere synthetisiert. Es wurde sowohl die für Hydrogele übliche Methode der freien radikalischen Vernetzungspolymerisation in Wasser, wie eine neue, auf Benzophenoneinheiten basierende Syntheseroute, welche die freie radikalische Polymerisation in organischem Medium nutzt, verwendet. Die synthetisierten Polymere sind Copolymere aus N‑Isopropylacrylamid (NIPAAm) und 4-Methacryloyloxybenzophenon (MABP). NIPAAm ist dabei für das temperaturschaltbare Verhalten der Gele verantwortlich und MABP dient als Photovernetzer. Weitere Copolymere, die neben den genannten Monomeren noch andere Funktionen, wie z.B. ionische Gruppen oder Aktivesterfunktionen enthalten, wurden ebenfalls synthetisiert. Das temperaturabhängige Quellverhalten in Bezug auf die chemische Zusammensetzung wurde mit der Oberflächenplasmonenresonanz-Spektroskopie (SPR) und Optischen Wellenleiter-Spektroskopie (OWS) untersucht. Es zeigte sich, dass die Anwesenheit von Salz im Hydrogel (Natriumacrylat als Monomer, P4S) Inhomogenität, in Form eines Brechungsindexgradienten senkrecht zur Substratoberfläche, hervorruft. Dies ist nicht der Fall, wenn statt des Salzes die Säure (Methacrylsäure als Monomer, P4A) verwendet wird. Durch die Inhomogenität lassen sich die Filme mit dem Natriummethacrylat nicht mehr mit dem, üblicherweise zur Auswertung genutzten, Kastenmodell beschreiben. Die Anwendung der Wentzel-Kramers-Brillouin-Näherung (WKB) auf die Messdaten führt hingegen zu dem gewünschten Ergebnis. Man findet ein kastenähnliches Brechungsindexprofil für das Hydrogel mit der Säure (P4A) und ein Gradientenprofil für das Gel mit dem Salz (P4S). Letzteres ist nicht nur hydrophiler und insgesamt stärker gequollen, sondern ragt auch weiter in die überstehende Wasserphase hinein. Anhand eines säurehaltigen Hydrogels (P8A) konnte der quellungshemmende Einfluss von hohen Salzkonzentrationen gezeigt werden. Weiterhin wurde während des Quellvorgangs eine gewisse Anisotropie gefunden, die aber im vollständig gequollenen und vollständig kollabierten Zustand nicht mehr vorliegt. Anhand eines Hydrogels ohne ionisierbare Gruppen (P9) wurde die Reversibilität des Quell- und Kollabiervorgangs gezeigt. Bei einem Vergleich zwischen einem säurehaltigen Hydrogel (P8A, Quellgrad von 7,3) und einem ohne ionisierbare Gruppen (P9, Quellgrad von 6,1), hat die Anwesenheit der 8 mol% Säuregruppen eine leichte Verstärkung der Quellung um den Faktor 1,2 bewirkt. Rasterkraftmikroskopische Untersuchungen (AFM) an diesen beiden Hydrogelen im getrockneten Zustand, haben gezeigt, dass nach dem Quellen, Kollabieren und Trocknen bei beiden Gelen Porenstrukturen sehr unterschiedlicher Ausmaße vorliegen.

Functional dextran-based hydrogels

Dextran-based polymers are versatile hydrophilic materials, which can provide functionalized surfaces in various areas including biological and medical applications. Functional, responsive, dextran based hydrogels are crosslinked, dextran based polymers allowing the modulation of response towards external stimuli. The controlled modulation of hydrogel properties towards specific applications and the detailed characterization of the optical, mechanical, and chemical properties are of strong interest in science and further applications. Especially, the structural characteristics of swollen hydrogel matrices and the characterization of their variations upon environmental changes are challenging. Depending on their properties hydrogels are applied as actuators, biosensors, in drug delivery, tissue engineering, or for medical coatings. However, the field of possible applications still shows potential to be expanded. rnSurface attached hydrogel films with a thickness of several micrometers can serve as waveguiding matrix for leaky optical waveguide modes. On the basis of highly swelling and waveguiding dextran based hydrogel films an optical biosensor concept was developed. The synthesis of a dextran based hydrogel matrix, its functionalization to modulate its response towards external stimuli, and the characterization of the swollen hydrogel films were main interests within this biosensor project. A second focus was the optimization of the hydrogel characteristics for cell growth with the aim of creating scaffolds for bone regeneration. Matrix modification towards successful cell growth experiments with endothelial cells and osteoblasts was achieved.rnA photo crosslinkable, carboxymethylated dextran based hydrogel (PCMD) was synthesized and characterized in terms of swelling behaviour and structural properties. Further functionalization was carried out before and after crosslinking. This functionalization aimed towards external manipulation of the swelling degree and the charge of the hydrogel matrix important for biosensor experiments as well as for cell adhesion. The modulation of functionalized PCMD hydrogel responses to pH, ion concentration, electrochemical switching, or a magnetic force was investigated. rnThe PCMD hydrogel films were optically characterized by combining surface plasmon resonance (SPR) and optical waveguide mode spectroscopy (OWS). This technique allows a detailed analysis of the refractive index profile perpendicular to the substrate surface by applying the Wentzel Kramers Brillouin (WKB) approximation. rnIn order to perform biosensor experiments, analyte capturing units such as proteins or antibodies were covalently coupled to the crosslinked hydrogel backbone by applying active ester chemistry. Consequently, target analytes could be located inside the waveguiding matrix. By using labeled analytes, fluorescence enhancement was achieved by fluorescence excitation with the electromagnetic field in the center of the optical waveguide modes. The fluorescence excited by the evanescent electromagnetic field of the surface plasmon was 2 3 orders of magnitude lower. Furthermore, the signal to noise ratio was improved by the fluorescence excitation with leaky optical waveguide modes.rnThe applicability of the PCMD hydrogel sensor matrix for clinically relevant samples was proofed in a cooperation project for the detection of PSA in serum with long range surface plasmon spectroscopy (LRSP) and fluorescence excitation by LRSP (LR SPFS). rn

Photoinduced modifications in fiber gratings inscribed directly by infrared femtosecond irradiation

The structure of fiber Bragg gratings inscribed pointby-point by an infrared femtosecond laser is studied by quantitative phase microscopy. Results show that these gratings present a central region with a depressed refractive index surrounded by an outer corona with increased refractive index. The refractive index profile suggests the presence of microvoids embedded in a region of the core. © 2006 IEEE.

The spectral sensitivity of long period gratings fabricated in elliptical core D-shaped optical fibre

Long period gratings (LPGs) were written into a D-shaped optical fibre that has an elliptical core with a W-shaped refractive index profile and the first detailed investigation of such LPGs is presented. The LPGs’ attenuation bands were found to be sensitive to the polarisation of the interrogating light with a spectral separation of about 15 nm between the two orthogonal polarisation states. A finite element method was successfully used to model many of the behavioural features of the LPGs. In addition, two spectrally overlapping attenuation bands corresponding to orthogonal polarisation states were observed; modelling successfully reproduced this spectral feature. The spectral sensitivity of both orthogonal states was experimentally measured with respect to temperature and bending. These LPG devices produced blue and red wavelength shifts depending upon the orientation of the bend with measured maximum sensitivities of -3.56 and +6.51 nm m, suggesting that this type of fibre LPG may be useful as a shape/bend orientation sensor with reduced errors associated with polarisation dependence. The use of neighbouring bands to discriminate between temperature and bending was also demonstrated, leading to an overall curvature error of ±0.14 m-1 and an overall temperature error of ±0.3 °C with a maximum polarisation dependence error of ±8 × 10-2 m-1 for curvature and ±5 × 10-2 °C for temperature.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

The spectral sensitivity of long period gratings fabricated in elliptical core D-shaped optical fibre

Long period gratings (LPGs) were written into a D-shaped optical fibre that has an elliptical core with a W-shaped refractive index profile and the first detailed investigation of such LPGs is presented. The LPGs’ attenuation bands were found to be sensitive to the polarisation of the interrogating light with a spectral separation of about 15 nm between the two orthogonal polarisation states. A finite element method was successfully used to model many of the behavioural features of the LPGs. In addition, two spectrally overlapping attenuation bands corresponding to orthogonal polarisation states were observed; modelling successfully reproduced this spectral feature. The spectral sensitivity of both orthogonal states was experimentally measured with respect to temperature and bending. These LPG devices produced blue and red wavelength shifts depending upon the orientation of the bend with measured maximum sensitivities of -3.56 and +6.51 nm m, suggesting that this type of fibre LPG may be useful as a shape/bend orientation sensor with reduced errors associated with polarisation dependence. The use of neighbouring bands to discriminate between temperature and bending was also demonstrated, leading to an overall curvature error of ±0.14 m-1 and an overall temperature error of ±0.3 °C with a maximum polarisation dependence error of ±8 × 10-2 m-1 for curvature and ±5 × 10-2 °C for temperature.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Generation and performance of localised surface plasmons utilising nano-scale structured multi-layered thin films deposited upon D-shaped optical fiber

A new generation of surface plasmonic optical fibre sensors is fabricated using multiple coatings deposited on a lapped section of a single mode fibre. Post-deposition UV laser irradiation using a phase mask produces a nano-scaled surface relief grating structure, resembling nano-wires. The overall length of the individual corrugations is approximately 14 μm with an average full width half maximum of 100 nm. Evidence is presented to show that these surface structures result from material compaction created by the silicon dioxide and germanium layers in the multi-layered coating and the surface topology is capable of supporting localised surface plasmons. The coating compaction induces a strain gradient into the D-shaped optical fibre that generates an asymmetric periodic refractive index profile which enhances the coupling of the light from the core of the fibre to plasmons on the surface of the coating. Experimental data are presented that show changes in spectral characteristics after UV processing and that the performance of the sensors increases from that of their pre-UV irradiation state. The enhanced performance is illustrated with regards to change in external refractive index and demonstrates high spectral sensitivities in gaseous and aqueous index regimes ranging up to 4000 nm/RIU for wavelength and 800 dB/RIU for intensity. The devices generate surface plasmons over a very large wavelength range, (visible to 2 μm) depending on the polarization state of the illuminating light. © 2013 SPIE.

The spectral sensitivity of long period gratings fabricated in elliptical core D-shaped optical fiber

Long period gratings (LPGs) were written into a D-shaped optical fibre, which has an elliptical core with a W-shaped refractive index profile. The LPG's attenuation bands were found to be sensitive to the polarisation of the interrogating light with a spectral separation of about 15nm between the two orthogonal polarisation states. In addition, two spectrally overlapping attenuation bands corresponding to orthogonal polarisation states were observed; modelling successfully reproduced this spectral feature. The spectral sensitivity of both orthogonal states was experimentally measured with respect to temperature, surrounding refractive index, and directional bending. These LPG devices produced blue and red wavelength shifts of the stop-bands due to bending in different directions. The measured spectral sensitivities to curvatures, d?/dR , ranged from -3.56nm m to +6.51nm m. The results obtained with these LPGs suggest that this type of fibre may be useful as a shape/bend sensor. It was also demonstrated that the neighbouring bands could be used to discriminate between temperature and bending and that overlapping orthogonal polarisation attenuation bands can be used to minimise error associated with polarisation.

The sensing characteristics of long period gratings in three different types of fibre

In this paper, sensing characteristics of long period gratings in three different types of single mode optical fibre: a step-index fibre, a progressive three layered fibre and a suppressed-cladding fibre were investigated. It was found that variation in the refractive index profile and material constants of the fibre can produce a dramatic change in the spectral sensitivity for a particular measurand for a given long period grating attenuation band. © 2003 IEEE.

Design of few-mode fibers with up to 12 modes and low differential mode delay

In this paper, we investigate the design of few-mode fibers (FMFs) guiding 4 to 12 non-degenerate linearly polarized (LP) modes with low differential mode delay (DMD) over the C-band, suitable for long-haul transmission. The refractive index profile considered is composed by a graded-core with a cladding trench (GCCT). The optimization of the profile parameters aims the lowest possible DMD and macro-bend losses (MBL) lower than the ITU-T standard recommendation. The optimization results show that the optimum DMD and the MBL scale with the number of modes. Additionally, it is shown that the refractive-index relative difference at the core center is one of the most preponderant parameters, allowing to reduce the DMD at the expense of increasing MBL. Finally, the optimum DMD obtained for 12 LP modes is lower than 3 ps/km. © 2014 IEEE.