Photonic crystal (PC) technology potentially offers lossless control of light propagation at a size scale near the order of the wavelength of light. The advantages and benefits of using such a technology in commercial devices are staggering. Yet, the commercial development of PC structures has been slow. Challenges associated with the repeatable fabrication and testing of structures has been identified as one cause of the slow development pace. To address these challenges, a development methodology that utilizes PC structures operating in the long-wavelength infrared is presented. One-dimensional PC structures, consisting of alternating regions of silicon and air are fabricated and characterized by measuring the transmittance or reflectance of the structure over the wavelength range from 5 쭠to 15 쭮 For the measurements, a model of the focused infrared beam is developed, tested and employed to characterize the structures. A novel measurement method, enabling the calculation of the single-angle plane-wave transmittances and reflectances from composite, multiple-angle transmittance and reflectance measurements, is formulated, tested and applied to PC structures. A new spectral characterization tool using a discretely tunable carbon-dioxide laser is presented and demonstrated. A measurement apparatus employing an FTIR microspectroscopy system is developed and measurements are recorded for the single-angle plane-wave characterization method. Single-angle plane-wave transmittances and reflectances calculated from composite multiple-angle measurements are shown to be in excellent agreement with theory. The results of this research are analyzed to identify the advantages and limitations of the long-wavelength infrared method.

The microstructure and residual stress of Ni thin film coating on Si influence the properties significantly, which play an important role in advanced applications of the electric and magnetic properties. The properties of Ni thin film deposited on Si at various temperatures and for different thickness have been studied in this work. Samples were characterized by nanoindentation, Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), electrical measurement, grazing angle X-ray diffraction (XRD) and photo reflection spectroscopy of white light. The nanoindentation measurements reveal similar loading curves and young¡¦s modulus for Ni thin films on Si at different deposition temperatures. However, the higher the deposition temperature, the lower is the hardness of the Ni thin film on Si. A maximum stress occurs at deposition temperature of 88-122 ¢XC. From FTIR spectra an unusual IR oscillating absorption of the Ni/Si film was observed from the samples which was deposited at 230 ¢XC for 15 min (23 nm) and for 30 min (52 nm) compared to other deposition duration and deposition temperatures at room temperature, 88 ¢XC, and 122 ¢XC. Furthermore, annealing experiments of the samples were performed after deposited at room temperature, and then annealed at respective temperatures of 88, 122, 230 ¢XC for the durations of 15 min and 30 min for comparison. However, the unmoral IR oscillation doesn¡¦t occur else where. The phase change of Ni/Si was analyzed by grazing angle XRD. A single phase of NiSi (103) structure was observed only in the samples deposited at 230 ¢XC. Further study of the oscillation in the FTIR spectra shows its origin should be related to surface plasmon resonance (SPR) mode. The SPR absorption peaks at 471 nm and 616 nm are analyzed by a photo reflection experiment. The SPR absorption is due to the nano structure of nickel silicide on Ni/Si surface formed during deposition at 230 ¢XC.

This thesis research focuses on the characterization of thinfilms made of poly(vinylidene fluoride) (PVDF) using an atomic force microscope. Thinfilms of PVDF were fabricated by a spin coating method with different conditions and characterized using the Atomic Force Microscopy (AFM) for morphological changes. Phase and conformational changes of PVDF were investigated using both wide angle X-ray diffraction (WAXD) and Fourier Transform Infrared Spectroscopy (FTIR). From this analysis, in-situ corona poling with annealing of spin-cast PVDF enabled a phase change from α to the mixture of β and γ phases. This process can decrease the complexity of the conventional method which requires mechanical stretching before poling PVDF in addition to thermal annealing for β phase transformation. This thesis describes some materials and surface properties of solution-cast PVDF thinfilms with various conditions such as topography and phase image, adhesion force, friction force, and roughness. Through the AFM topography and phase images, polymeric behavior and spherulites are discussed in the later part of the thesis.

In this thesis, using Micro-Photoluminescence (£g-PL), continuous-wave time-resolved photoluminescence (CWPL/TRPL) and Fourier transform infrared (FTIR) analysis, silicon rich nc-Si (nano-crystal Silicon) samples with various emission wavelength (760 30 nm and 390 10 nm) are investigated to understand the proper explanation of the emission mechanism. The model of increasing Si¡ÐO ¡ÐSi bondings during thermal process by enhancing the annealing or deposition time, induced blue shifts in PL spectrums and increased the rate of Schockley-Read-Hall recombination which resulted in the enhancement of its fluorescence is provided.

In order to measure the thickness of a protein layer on a structured surface of silicon rubber, we have used ellipsometry and Fourier transform infrared (FTIR)-spectroscopy. The aim was to determine whether this type of measurement method can be used on protein layers or not. By hot-embossing a specific pattern of micrometre-sized pillars was created on the surface of the silicon rubber, which then was exposed to a phosphate buffer solution (PBS) containing human serum albumin (HSA) protein. FTIR measurements confirmed that proteins had attached to the surface. Ellipsometric studies were made and even though the protein layer was too thin to be measured, a simulation was made that revealed that a protein layer needs to be at least 1,5 nm to be measured properly with this method. We can also see that the protein molecules can get out of the solution, to find their way into the small pits of the samples.

Fourier Transform Infrared (FTIR) has been use to discriminate different pathogens by signals from cells infected with these versus normal cells as references. To do the statistical analysis, Partial Least Square Regression (PLSR) was utilized to distinguish any two kinds of virus‐infected cells and normal cells. Validation using Bootstrap method and Cross‐validations were employed to calculate the shrinkages of Area Under the ROC Curve (AUC) and specificities corresponding to 80%, 90%, and 95% sensitivities. The result shows that our procedure can significantly discriminate these pathogens when we compare infected cells with the normal cells. On the height of this success, PLSR was applied again to simultaneously compare two kinds of virus‐infected cells and the normal cells. The shrinkage of Volume Under the Surface (VUS) was calculated to do the evaluation of model diagnostic performance. The high value of VUS demonstrates that our method can effectively differentiate virus‐infected cells and normal cells.

A sampling-window based approach was developed to collect and analyze the gases evolved during fire performance testing using the cone calorimeter. For this purpose, a Fourier Transform Intra-red (FTIR) Spectroscopy system and a Novatec analyzer were coupled to the cone calorimeter. An experimental gas sampling apparatus was designed and constructed and a sampling-window based method was developed. The sampling-window based method was initially tested using blue Styrofoam samples, then a small number of intumescent materials were also examined. Using the new integrated system, spectral scans were taken with an FTIR using 30s, 45s and 60s sampling windows, during off-gasing, fire growth, steady heat release rate, and fire decay stages of cone calorimeter testing. By focusing the sampling window on a specific stage of fire development the tests indicated that high concentrations of toxic gases were evolved during sample off-gasing, before ignition. In contrast to other methods that are designed to obtain total toxic gas yield over the full course of a cone calorimeter fire performance test, the sampling-window method here allows for a greater understanding of fire gas evolution at the various stages of fire growth and development. With the cone calorimeter coupled with a preconfigured “out of the box” lightweight portable ambient air analyzer and the sampling-window based approach developed, the fire gases associated with the polystyrene (blue Styrofoam) could be identified along with a number of the fire gases typically associated with the intumescent foam. For further analysis of fire gases produced, a calibrated, lab quality FTIR, with a higher resolution than the preconfigured “out of the box” lightweight portable ambient air analyzer may be required. However the system configuration and methodology would remain the same as developed here. The sampling-window based approach developed is useful for use in the development of other gas sampling techniques and can be used with other complimentary techniques such as Gas Chromatography (GC) and Mass Spectroscopy (MS). In such a combined Cone Calorimeter-GC-MS system, the GC is used to separate the various fire gases while the MS is used to identify all the components at a molecular level, and provide a more concise analysis of evolved fire gases. It is therefore recommended that the GC-MS technique also be developed for the cone calorimeter and used to compliment the FTIR technique developed in this study.

About a hundred samples of y-manganese dioxide covering three materials coded SBP- A, Faradiser M and R2 have been reduced chemically by insertion of H through controlled additions of hydrazine hydrate solutions at about 1 °C. The H-inserted samples and the starting materials were subjected to chemical analysis for oxidation state, X-ray diffraction (XRD) for structure study and Fourier Transform Infrared (FTIR) spectroscopy to gain information on OH bonding. Additional techniques including FTIR spectroscopy at low temperature (~ -180 °C), electrode potential measurement and scanning electron microscopy (SEM) have also been applied. The intergrowth structure of the starting materials consisted of ramsdellite intercepted with pyrolusite layers, known as de Wolff faults, and quantified by the fraction of pyrolusite layers Pr. An additional structural parameter for these materials was the amount of micro twinning (Tw) across the 021/061 ramsdellite planes. This parameter, introduced by Pannetier, is given in percent. Values of (Pr , Tw) have been given as (0.41 , 17) for SBP-A, (0.70,10) for Faradiser M and (0.41, ~100) for R2. Upon H-insertion, the structure of the starting materials expanded homogeneously in a direction and to an extent which depended on the Pr and Tw parameters. Faradiser M, with high Pr and very low Tw, expanded homogeneously in the direction of the b lattice dimension up to an insertion level of 0.69 of s in MnOn/Hs. Above this level, the initial structure changed suddenly into the structure of the final product: the insertion then proceeded homogeneously in the new phase. The main changes were an expansion of the octahedra and a rotation leading to hinged tunnels. This is the first time that the existence of two solid solutions in the MnO2/H system has been noted. With SBP-A, the amount of microtwinning restricted the homogeneous expansion of SBP-A to s = 0.28, which occurred predominantly in the a direction. Further insertion broke the twinning boundary and formed a demicrotwinned phase of composition MnOn Ho.68 in which the tunnels were also hinged. Thereafter H-insertion proceeded heterogeneously from 0.28 to 0.68 in s. Above s = 0.68, the structure developed homogeneously towards that of the fully H-inserted product. The extensive microtwinning in R2 allowed for a homogeneous expansion, thought to be isotropic to maintain the microtwinned structure, up to s = 0.39. Higher insertion levels led to the expansion to proceed heterogeneously to a composition of MnOn Ho.63. Above s = 0.63, a new phase, the final product, was formed with fully demicrotwinned structure and fully hinged tunnels. R-insertion into y-manganese dioxide has never been reported to occur in three stages previously. The FTIR study at room temperature has shown absence of OH bond vibrations at insertion levels prior to the hinging of the tunnels, in contrast to their presence after the structure has rotated and the tunnels had hinged. This is seen as a strong indication of H mobility in the initial structure. The hinging is necessary for OH bonding as it brings the 02 and 01 oxygens closer allowing the proton to bond both covalently and by H-bonding. At low temperature, initially mobile hydrogen could be trapped and OR bonds formed only in H-inserted R2. This was linked to 061-microtwinning. The absence of OH bonds at low temperature in SBP-A and Faradiser M led to the conclusion that these materials have no 061 micro twinning faults. The absence of OH bonds at low temperature in the starting materials, particularly in R2, strongly questions the postulated OH groups in the structure of y-MnO2, according to the cation vacancy model. Electrode potential data supported the above conclusions in terms of the stages of the H-insertion. The battery activity of the materials seemed to be related to the extent at which the materials kept the initial structure with non-hinged tunnels. Comparison with previous works on the same materials suggested that the differences could be accounted for by the kinetics of the H-insertion. While protons in this work were released spontaneously on the surface of the MnO x , their diffusion into the bulk was slow due to the low temperature. In the compared literature, the reverse applies.

The aim of this work was to assess the potential of FTIR spectroscopy in the analysis of the cis and trans fatty acid contents of fats and oils. Preliminary studies on the liquid and solution phase spectra of individual FAME'S (fatty acid methyl esters), and on mixtures of FAME'S, were conducted to establish whether spectral features enhanced by FTIR could be used to provide improved methods of determining cis and trans contents. A number of previously unreported bands and spectral features associated with the cis and trans isolated double bond(s) were discovered. None of the trans bands were considered suitable for quantitation, however, methods of determining the cis content were developed, based on the the two bands listed below. These methods were compared with current IR methods, and with a capillary GC method. (a) The CIS C=C stretching band (1654 cm-1). (b) An unassigned band at 913 cm-1, observed only in the spectra of non-conjugated di- and tri-unsaturated FAME'S. All the established methods as well as those developed in this work, for the quantitative analysis of FAME'S have inherent disadvantages. For example, with the capillary GC method, difficulties are encountered in resolving and identifying samples containing complex mixtures of isomers. With the IR techniques, the difficulties involve the elimination of interfering bands, and the absorbance of similar fatty acids at the same frequencies. The application of GC-FTIR was seen as a logical extension of this project, because it offered a great potential for the separation and charactisation of components of complex mixtures. Studies conducted on vapour phase spectra showed that the identification of many FAME'S could be ascertained from various band ratios. Furthermore, band ratios could be used to quantify the cis/trans content of co-eluting isomers. Different types of capillary columns were tried, and optimum conditions established where possible.

Despite the scientific progress in the last decades in terms of therapeutic agents to fight cancer there is still the need of developing safer and more effective drugs. Developing an innovative drug is not only very expensive, but also highly time consuming; furthermore, the number of anticancer agents that fail in clinical trials with high attrition rates mainly caused by unexpected toxicity and lack of efficacy far outweighs those considered effective, which indicates that drug screening processes require further improvements. In this project the application of Fourier transform infrared microspectroscopy is evaluated in order to develop a spectral based model that could be used to describe the drug-cell interaction and also to discriminate between the metabolic modifications due to a particular drug and the inherent cell cycle of a cell. A computational method was built using the FTIR spectra from a highly resistant renal cell carcinoma cell line, Caki-2, in order to discriminate between the phases of the continuous cell cycle that cells undergo while proliferating in vitro. Such model enabled the discrimination of early events of the cell cycle (G0/G1 phase cells) from G2/M phase cells with a prediction accuracy of 90% and 92.9% respectively. On the other hand, when the RMieS-corrected FTIR spectra corresponding to G0/G1, S and G2/M phases were modelled, the algorithm was able to retrieve each stage of proliferation with 82.3%, 71.8% and 84.4% accuracy respectively. Although the average accuracy yielded by the method was relatively low compared with what has previously been reported in the literature, these results emphasize the need to correct the data from physical distortions due to size and prove the principle that it is possible to create a method for identifying different events of the cell cycle based on the data that the FTIR spectroscopy provides, as well as using the scattering profile characteristic of each phase of development. Once the underlying biochemistry of proliferating Caki-2 cells were characterised by FTIR, the cells were treated with 5-Fluorouracil and paclitaxel, two widely used cytotoxic agents known to induce cellular damage at S or G2/M phase of the cell cycle respectively. The FTIR spectra collected were analysed via multivariate and bivariate techniques. Results demonstrated that, after 24 hours of treatment at the IC50 concentration of each drug, Caki-2 cells displayed spectral features consistent with early stages of apoptosis. These spectral characteristics did not appear to be linked either to the drug’s mode of action or the cell’s cycle phase. The cell’s proliferation stage was not the main classification trend among the drug-treated spectra; nevertheless, the cell cycle phase of each drug-treated population was successfully retrieved by an optimized model capable to classify such phases with an average accuracy of 77.98%. Altogether, this study offers a new perspective when analysing FTIR data from single cells as a function of the cell cycle and also when investigating the biochemical response of a cell line to a given anticancer agent.