Electrografting of poly (carbazole-co-acrylamide) onto highly oriented pyroltic graphite. A cyclovoltammetric, atomic force microscopic and ellipsometric study

The electrocopolymerization of carbazole and acrylamide on highly oriented pyrolytic graphite (HOPG) from ACN solutions via cyclovoltammetry (CV) was studied in order to evaluate the possibility to deposit uniform and thin but pinhole-free and still reactive coatings onto graphite-like substrates. The morphology of the coatings was investigated using atomic force microscopy and the coating thicknesses and optical parameters were measured using ellipsometry. It was found that under the chosen conditions thin (coating thickness hf>180 nm) and relatively smooth (root mean square surface roughness RMS<150 nm) P(Cz-co-AAm)-coatings exhibiting a uniform globuoidal morphology can be deposited onto graphite. From a certain coating thickness (hf>50 nm) no pinholes could be detected. It was found that the thickness of the deposited coatings increases almost linearly with increasing number of CV-cycles while keeping all other experimental parameters (scan rate and comonomer concentration ratio) constant. No influence of the comonomer concentration ratio on the film thickness and coating appearance could be observed, however, at quite low initial concentrations. However, the CV-scanning rate has quite a significant influence on the thickness of the deposited coatings. Higher scan rates (100 mV/s) result in thin (hf≈22 nm) coatings whereas at lower scan rates (<50 mV/s) coatings with thicknesses of approximately 50 nm were obtained. The optical coating parameters (the refractive index n and extinction coefficient k) seem to be independent of the deposition parameters and therefore averaged values of n̄=1.54±0.03 and k̄=0.08±0.03 were obtained.

Optical fibre sensors with applications in gas and biological sensing

This thesis describes the study of various grating based optical fibre sensors for applications in refractive index sensing. The sensitivity of these sensors has been studied and in some cases enhanced using novel techniques. The major areas of development are as follows. The sensitivity of long period gratings (LPGs) to surrounding medium refractive index (SRI) for various periods was investigated. The most sensitive period of LPG was found to be around 160 µm and this was due to the core mode coupling to a single cladding mode but phase matching at two wavelength locations, creating two attenuation peaks, close to the waveguide dispersion turning point. Large angle tilted fibre gratings (TFGs) have similar behaviour to LPGs, in that they couple to the co-propagating cladding modes. The tilted structure of the index modulation within the core of the fibre gives rise to a polarisation dependency, differing the large angle TFG from a LPG. Since the large angle TFG couple to the cladding mode they are SRI sensitive, the sensitivity to SRI can be further increased through cladding etching using HF acid. The thinning of the cladding layer caused a reordering of the cladding modes and shifted to more SRI sensitive cladding modes as the investigation discovered. In a SRI range of 1.36 to 1.40 a sensitivity of 506.9 nm/URI was achieved for the etched large angle TFG, which is greater than the dual resonance LPG. UV inscribed LPGs were coated with sol-gel materials with high RIs. The high RI of the coating caused an increase in cladding mode effective index which in turn caused an increase in the LPG sensitivity to SRI. LPGs of various periods of LPG were coated with sol-gel TiO2 and the optimal thickness was found to vary for each period. By coating of the already highly SRI sensitive 160µm period LPG (which is a dual resonance) with a sol-gel TiO2, the SRI sensitivity was further increased with a peak value of 1458 nm/URI, which was an almost 3 fold increase compared to the uncoated LPG. LPGs were also inscribed using a femtosecond laser which produced a highly focused index change which was no uniform throughout the core of the optical fibre. The inscription technique gave rise to a large polarisation sensitivity and the ability to couple to multiple azimuthal cladding mode sets, not seen with uniform UV inscribed gratings. Through coupling of the core mode to multiple sets of cladding modes, attenuation peaks with opposite wavelength shifts for increasing SRI was observed. Through combining this opposite wavelength shifts, a SRI sensitivity was achieved greater than any single observed attenuations peak. The maximum SRI achieved was 1680 nm/URI for a femtosecond inscribed LPG of period 400 µm. Three different types of surface plasmon resonance (SPR) sensors with a multilayer metal top coating were investigated in D shape optical fibre. The sensors could be separated into two types, utilized a pre UV inscribed tilted Bragg grating and the other employed a post UV exposure to generate surface relief grating structure. This surface perturbation aided the out coupling of light from the core but also changed the sensing mechanism from SPR to localised surface plasmon resonance (LSPR). This greatly increased the SRI sensitivity, compared to the SPR sensors; with the gold coated top layer surface relief sensor producing the largest SRI sensitivity of 2111.5nm/URI was achieved. While, the platinum and silver coated top layer surface relief sensors also gave high SRI sensitivities but also the ability to produce resonances in air (not previously seen with the SPR sensors). These properties were employed in two applications. The silver and platinum surface relief devices were used as gas sensors and were shown to be capable of detecting the minute RI change of different gases. The calculated maximum sensitivities produced were 1882.1dB/URI and 1493.5nm/URI for silver and platinum, respectively. Using a DFB laser and power meter a cheap alternative approach was investigated which showed the ability of the sensors to distinguish between different gases and flow rates of those gases. The gold surface relief sensor was coated in a with a bio compound called an aptamer and it was able to detect various concentrations of a biological compound called Thrombin, ranging from 1mM to as low as 10fM. A solution of 2M NaCl was found to give the best stripping results for Thrombin from the aptamer and showed the reusability of the sensor. The association and disassociation constants were calculated to be 1.0638×106Ms-1 and 0.2482s-1, respectively, showing the high affinity of the Aptamer to thrombin. This supports existing working stating that aptamers could be alternative to enzymes for chemical detection and also helps to explain the low detection limit of the gold surface relief sensor.

Fibre gratings in novel optical fibres for applications in sensing

This thesis presents the fabrication of fibre gratings in novel optical fibres for sensing applications. Long period gratings have been inscribed into photonic crystal fibre using the electric-arc technique. The resulting sensing characteristics were found to depend on the air-hole geometry of the particular fibre. This provides the potential of designing a fibre to have enhanced sensitivity to a particular measure and whilst removing unwanted cross sensitivities. Fibre Bragg gratings have been fabricated in a variety of polymer optical fibres, including microstructured polymer optical fibre, using a continuous wave helium cadmium laser. The thermal response of the gratings have been characterised and found to have enhanced sensitivity compared to fibre Bragg gratings in silica optical fibre. The increased sensitivity has been harnessed to achieve a grating based device in single mode step index polymer optical fibre by fabricating an electrically tunable fibre Bragg grating. This was accomplished by coating the grating region in a thin layer of copper, which upon application of a direct current, causes a temperature induced Bragg wavelength shift.

Characterization of infrared surface plasmon resonances generated from a fiber-optical sensor utilizing tilted Bragg gratings

We demonstrate the use of tilted fiber gratings to assist with the generation of infrared surface plasmons on a metal film coating the flat of a D-shaped fiber. The wavelength of the strong (>25 dB) resonance is tunable over similar to 1000 nm by adjusting the polarization state of the light and is highly sensitive to the refractive index of any aqueous medium surrounding the fiber (sensitivity= 3365 nm).

Characterisation and performance of a Terfenol-D coated femtosecond laser inscribed optical fibre Bragg sensor with a laser ablated microslot for the detection of static magnetic fields

We present a novel device for the characterisation of static magnetic fields through monitoring wavelength shifts of femtosecond inscribed fibre Bragg grating and micromachined slot, coated with Terfenol-D. The device was sensitive to static magnetic fields and can be used as a vectoral sensor for the detection of magnetic fields as low as 0.046 mT with a resolution of ± 0.3mT in transmission and ± 0.7mT in reflection. The use of a femtosecond laser to both inscribe the FBGs and micromachine the slot in a single stage prior to coating the device significantly simplifies the fabrication.

Formation and characterization of ultra-sensitive surface plasmon resonance sensor based upon a nano-scale corrugated multi-layered coated D-shaped optical fiber

We present experimental results on the performance of a series of coated, D-shaped optical fiber sensors that display high spectral sensitivities to external refractive index. Sensitivity to the chosen index regime and coupling of the fiber core mode to the surface plasmon resonance (SPR) is enhanced by using specific materials as part of a multi-layered coating. We present strong evidence that this effect is enhanced by post ultraviolet radiation of the lamellar coating that results in the formation of a nano-scale surface relief corrugation structure, which generates an index perturbation within the fiber core that in turn enhances the coupling. We have found reasonable agreement when we modeling the fiber device. It was found that the SPR devices operate in air with high coupling efficiency in excess of 40 dB with spectral sensitivities that outperform a typical long period grating, with one device yielding a wavelength spectral sensitivity of 12000 nm/RIU in the important aqueous index regime. The devices generate SPRs over a very large wavelength range, (visible to 2 mu m) by alternating the polarization state of the illuminating light.

Femtosecond laser inscribed Bragg sensor in Terfenol-D coated optical fibre with ablated microslot for the detection of static magnetic fields

A novel device for the detection and characterisation of static magnetic fields is presented. It consists of a femtosecond laser inscribed fibre Bragg grating (FBG) that is incorporated into an optical fibre with a femtosecond laser micromachined slot. The symmetry of the fibre is broken by the micro-slot, producing non-uniform strain across the fibre cross section. The sensing region is coated with Terfenol-D making the device sensitive to static magnetic fields, whereas the symmetry breaking results in a vectorial sensor for the detection of magnetic fields as low as 0.046 mT with a resolution of ±0.3mT in transmission and ±0.7mT in reflection. The sensor output is directly wavelength encoded from the FBG filtering, leading to simple demodulation through the monitoring of wavelength shifts that result as the fibre structure changes shape in response to the external magnetic field. The use of a femtosecond laser to both inscribe the FBG and micro-machine the slot in a single stage, prior to coating the device, significantly simplifies the sensor fabrication.

Femtosecond laser inscribed Bragg sensor in Terfenol-D coated optical fibre with ablated microslot for the detection of static magnetic fields

A novel device for the detection and characterisation of static magnetic fields is presented. It consists of a femtosecond laser inscribed fibre Bragg grating (FBG) that is incorporated into an optical fibre with a femtosecond laser micromachined slot. The symmetry of the fibre is broken by the micro-slot, producing non-uniform strain across the fibre cross section. The sensing region is coated with Terfenol-D making the device sensitive to static magnetic fields, whereas the symmetry breaking results in a vectorial sensor for the detection of magnetic fields as low as 0.046 mT with a resolution of ±0.3mT in transmission and ±0.7mT in reflection. The sensor output is directly wavelength encoded from the FBG filtering, leading to simple demodulation through the monitoring of wavelength shifts that result as the fibre structure changes shape in response to the external magnetic field. The use of a femtosecond laser to both inscribe the FBG and micro-machine the slot in a single stage, prior to coating the device, significantly simplifies the sensor fabrication.

Grating based devices in polymer optical fibre

We describe recent research into devices based on fibre Bragg gratings in polymer optical fibre. Firstly, we report on the inscription of gratings in a variety of microstructured polymer optical fibre: single mode, few moded and multimoded, as well as fibre doped with trans-4-stilbenmethanol. Secondly, we describe research into an electrically tuneable filter using a metallic coating on a polymer fibre Bragg grating. Finally we present initial results from attempts to produce more complex grating structures in polymer fibre: a Fabry-Perot cavity and a phase-shifted grating.

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.

An ultra-sensitive localised surface plasmon resonance fibre device for environmental sensing based upon a structured bi-metal coating

We demonstrate a bi-metal coating (platinum and gold or silver) localised surface plasmon resonance fibre device that produces an index spectral sensitivity of over 11,000 nm/RIU, yielding an index resolution of 5×10-6in the aqueous index regime, consisting of a structured multi-layered thin film on D-shaped fibre. © 2014 SPIE.