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A wide variety of nanomaterials ranging from polymer assemblies to organic and inorganic nanostructures (particles, wires, rods etc) have been actively pursued in recent years for various applications. The synthesis route of these nanomaterials had been driven through two fundamental approaches - 'Top down' and 'Bottom up'. The key aspect of their application remained in the ability to make the nanomaterials suitable for targeted location by manipulating their structure and functionalizing with active target groups. Functional nanomaterials like polyelectrolyte based multilayered thin films, nanofibres and graphene based composite materials are highlighted in the current research. Multilayer thin films were fabricated by conventional dip coating and newly developed spray coating techniques. Spray coating technique has an advantage of being applied for large scale production as compared to the dip coating technique. Conformal hydrophobic/hydrophilic and superhydrophobic/hydrophilic thermal switchable surfaces were fabricated with multilayer films of poly(allylaminehydrochloride) (PAH) and silica nanoparticles by the dip coating technique, followed by the functionalization with thermosensitive polymer-poly(N-isopropylacrylamide)(PNIPAAM) and perfluorosilane. The thermally switchable superhydrophobic/ hydrophilic polymer patch was integrated in a microfluidic channel to act as a stop valve. At 70 degree centigrade, the valve was superhydrophobic and stopped the water flow (close status) while at room temperature, the patch became hydrophilic, and allowed the flow (open status). Spray-coated multilayered film of poly(allylaminehydrochloride) (PAH) and silica nanoparticles was fabricated on polycarbonate substrate as an anti-reflection (AR) coating. The adhesion between the substrate and the coating was enhanced by treating the polycarbonate surface with aminopropyltrimethoxylsilane (APTS) and sol-gel. The coating was finally made abrasion-resistant with a further sol-gel treatment on top of AR coating, which formed a hard thin scratch-resistant film on the coating. The resultant AR coating could reduce the reflection from 5 to 0.3% on plastic. Besides multilayered films, the fabrication of polyelectrolyte based electrospun nanofibers was also explored. Ultrathin nanofibers comprising 2-weak polyelectrolytes, poly(acrylic acid) (PAA) and poly(allylaminehydrochloride) (PAH) were fabricated using the electrospinning technique and methylene blue (MB) was used as a model drug to evaluate the potential application of the fibers for drug delivery. The release of MB was controlled in a nonbuffered medium by changing the pH of the solution. Temperature controlled release of MB was obtained by depositing temperature sensitive PAA/poly(N-isopropylacrylamide) (PNIPAAM) multilayers onto the fiber surfaces. The sustained release of MB in a phosphate buffered saline (PBS) solution was achieved by constructing perfluorosilane networks on the fiber surfaces as capping layers. The fiber was also loaded with a real life anti-depressant drug (2,3-tertbutyl-4-methoxyphenol) and fiber surface was made superhydrophobic. The drug loaded superhydrophobic nanofiber mat was immersed under water, phosphate buffer saline and surfactant solutions in three separated experiments. The rate of release of durg was monitored from the fiber surface as a result of wetting with different solutions. Time dependent wetting of the superhydrophobic surface and consequently the release of drug was studied with different concentrations of surfactant solutions. The results provided important information about the underwater superhydrophobicity and retention time of drug in the nanofibers. The nanostructured polymers like nanowires, nanoribbons and nanorods had several other applications too, based on their structure. Different self-assembled structures of semiconducting polymers showed improved properties based on their architectures. Poly(3-hexylthiophene) (P3HT) supramolecular structures were fabricated on P3HT-dispersed reduced graphene oxide (RGO) nanosheets. P3HT was used to disperse RGO in hot anisole/N, N-dimethylformamide solvents, and the polymer formed nanowires on RGO surfaces through a RGO induced crystallization process. The Raman spectroscopy confirmed the interaction between P3HT and RGO, which allowed the manipulation of the composite's electrical properties. Such a bottom-up approach provided interesting information about graphene-based composites and inspired to study the interaction between RGO and the molecular semiconductor-tetrasulphonate salt of copper phthalocyanine (TSCuPc) for nanometer-scale electronics. The reduction of graphene oxide in presence of TSCuPc produced a highly stabilized aqueous composite ink with monodispersed graphene sheets. To demonstrate the potential application of the donor (TSCuPc)'acceptor (graphene) composite, the RGO/TSCuPc suspension was successfully incorporated in a thin film device and the optoelectronic property was measured. The conductivity (dark current) of the composite film decreased compared to that of pure graphene due to the donor molecule incorporation, but the photoconductivity and photoresponsivity increased to an appreciable extent. The property of the composite film overall improved with thermal annealing and optimum loading of TSCuPc molecules.

The purpose of this thesis is to make a broadband antireflection coating configuration known as a quarter-wave stack consisting of one layer of titania and of one layer of silica nanoparticles. We utilize much that is already known about silica nanoparticle deposition. The first objective of this thesis is deposition and characterization of titania nanoparticle films deposited on glass microscope slides by a technique known as Ionic Self-Assembled Multilayers or ISAM deposition. This technique takes advantage of the electrostatic attraction between oppositely charged materials and ideally results in a uniform nanoparticle film whose thickness and optical properties can be tightly controlled. Deposition of a quarter-wave stack based on ISAM deposition of silica and titania nanoparticles is significantly simpler and less expensive than alternative deposition methods. Initial attempts to deposit titania films were unsuccessful because of excess diffuse scattering due to inhomogeneities in the film. In order to reduce diffuse scattering, two approaches were considered. The first approach was to improve the deposition process itself by experimenting with different values of deposition parameters such as solution pH and solution molarity. The other approach focused on removing the large nanoparticle aggregates from the colloidal solutions of titania nanoparticles that were suspected to be responsible for rough film surfaces resulting in diffuse scattering. This approach was successful. In addition, evidence suggested that surface roughness contributed more to diffuse scattering than the bulk of the films. After minimizing diffuse scattering from titania nanoparticle films, we used known results from research on silica nanoparticle films to deposit quarter-wave stacks consisting of one layer of titania nanoparticles with high refractive index and one layer of silica nanoparticles with low refractive index. This contrast in refractive indices is a desirable characteristic of quarter-wave stacks. The thicknesses and refractive indices of the two layers in the quarter-wave stacks were measured by ellipsometry and compared to the nominal thicknesses of these layers. Finally, the reflectance was derived from a model of the quarter-wave stack and was compared to the measured reflectance. It was found that construction of a quarter-wave stack by ISAM is possible but that it will be necessary to acquire data from more experiments. / Ph. D.

Passivation of silicon surfaces remains a critical factor in achieving high conversion efficiency in solar cells, particularly in future generations of rear contact cells -the best performing cell geometry to date. In this thesis, passivation is characterised as either intrinsic or extrinsic, depending on the origin of the chemical and field effect passivation components in dielectric layers. Extrinsic passivation, obtained after film deposition or growth, has been shown to improve significantly the passivation quality of dielectric films. Record passivation has been achieved leading to surface recombination velocities below 1.5 cm/s for 1 Ωcm n-type silicon covered with thermal oxide, and 0.15 cm/s in the same material covered with a thermal SiO2/PECVD SiNx double layer. Extrinsic field effect passivation, achieved by means of corona charge and/or ionic species, has been shown to decrease by 3 to 10 times the amount of carrier recombination at a silicon surface. A new parametrisation of interface charge, and electron and hole recombination velocities in a Shockley-Read-Hall extended formalism has been used to model accurately silicon surface recombination without the need to incorporate a term relating to space-charge or surface damage recombination. Such a term is unrealistic in the case of an oxide/silicon interface. A new method to produce extrinsic field effect passivation has been developed in which charge is introduced into dielectric films at high temperature and then permanently quenched in place by cooling to room temperature. This approach was investigated using charge due to one or more of the following species: ions produced by corona discharge, Na⁺, K⁺, Cs⁺, Mg²⁺ and Ca²⁺. It was implemented on both single SiO₂ and double SiO₂/SiN_x dielectric layers which were then measured for periods of up to two years. The decay of the passivation was very slow and time constants of the order of 10,000 days were inferred for two systems: 1) corona-charge-embedded into oxide grown on textured FZ-Si, and 2) potassium ions driven into an oxide on planar FZ-Si. The extrinsic field effect passivation methods developed in this work allow more flexibility in the combined optimisation of the optical properties and the chemical passivation properties of dielectric films on semiconductors. Increases in cell Voc, Jsc and η parameters have been observed in simulations and obtained experimentally when extrinsic field effect passivation is applied to the front surface of silicon solar cells. The extrinsic passivation reported here thus represents a major advancement in controlled and stable passivation of silicon surfaces, and shows great potential as a scalable and cost effective passivation technology for solar cells.

The work deals with a comparison of existing and perspective types of passivation and anti-reflective coating for silicon solar cells. The theoretical part describes the appropriate methodology for the characterization of these layers and focuses on the passivation layers based on Al2O3. The practical part describes design and verification operations of the equipment for measuring of the amount of fixed charge in the passivation layers using corona discharge. It also describes the implementation of equipment and the results of indicative tests for positive and negative polarity of high voltage. The final part discusses the possibility of equipment improving.

Der rapide Anstieg der Bevölkerung führt zu einer dramatischen Zunahme des Brennstoff- und Energiebedarfs. Längerfristig kann die nachhaltige Energieversorgung der Menschheit nur durch erneuerbare Energiequellen gewährleistet werden. Dies motiviert die Bemühungen um alternative, sauberere Brennstofftechnologien wie z.B. die Erzeugung von Wasserstoff. Diese Arbeit untersucht die Verbesserung der optoelektronischen Eigenschaften von Silizium Photokathoden, durch optische Nanostrukturen, die die Reflexion mittels optischer Resonanzen reduzieren. Wir konzentrieren uns dabei auf die Entwicklung von Nanostrukturen , die optische Konzepte wie Mie-Resonanzen und periodische Indexprofilierung nutzen. Um diese optischen Nanostrukturen zu realisieren, verwenden wir zwei Herstellungsverfahren. Die Verfahren werden durch einen iterativen Ansatz optimiert, um zu den Nanostrukturen mit den gewünschten optischen Eigenschaften zu gelangen. Die erste Art von Nanostrukturen gehört zur Klasse der Meta-Oberflächen (Metasurfaces) und wird durch Elektronenstrahl- Lithographie und Top-Down-Herstellung implementiert. Die optischen Spektren dieser Strukturen werden dann mit Hilfe von Simulation und Experimenten eingehend untersucht. Die zweite Art von Nanostrukturen basiert auf Änderungen des Brechzahlprofils von dielektrischen periodischen Nanostrukturen. Diese Strukturen werden durch Maskenlithographie mittels Polystyrol-Kugeln hergestellt. Auch bei diesen Strukturen werden die optischen Eigenschaften vermessen und ihre physikalischen Bedeutung mit Hilfe von numerischen Simulationen analysiert. Um den Einfluss dieser Strukturen auf die Kurzschlussstromdichten von Silizium Photokathoden zu demonstrieren, charakterisieren wir den Photostrom, der über einen Silizium-Elektrolyt-pn-Übergang mit und ohne Nanostrukturen gemessen wird. Zusammenfassend stellen wir einen Vergleich der Antireflexionseigenschaften der beiden entwickelten Strukturen sowie eine Verbesserung der photoelektrochemischen Funktionalität vor. Daraus leiten wir Ideen für zukünftige Oberflächendesigns ab, welche die noch bestehenden Nachteile beider Strukturen überwinden. / Global fuel and energy demands continue to increase due to the rapid rise in population and the dependence of this increasing population on exisiting energy resources for its sustainance. This has led to efforts in developing cleaner fuel sources such as hydrogen generation. This thesis focuses on demonstrating the optical benefit of nanostructures to improve the optoelectronic functioning of silicon photocathodes which aid in hydrogen generation via nanostructured antireflection. We lay our focus on the development of nanostructures which utilise optical concepts such as Mie type resonances based on metasurfaces and periodic index profiling. Computational design is used to obtain structure parameters for achieving desired effects. To implement these optical effects we take aid of two methods of fabrication. These fabrication methods are optimised via iterative trials to arrive at nanostructures of high quality. The first type of nanostructures belong to the metasurface class. These are implemented by e-beam lithography and top down processing. The optical spectra are then comapred with aid of simulation and experiments. The second type of nanostructures belong to the class of gradually varying periodic nanostructures. We obtain these via iterative fabrication using colloidal mask lithography. In a subsequent step we analyse experimentally their optical spectra and with aid of simulations analyse their physical implication. To demonstrate an optical benefit of these structures on enhancing the short circuit current densities of silicon photocathodes, we characterise the photocurrent measured across the silicon-electrolyte pn-junction with and without nanostructures and evaluate this increase. In conclusion, we provide a comparison of the antireflection properties offered by the two developed structures as well as in terms of improving photoelectrochemical environment. As an outlook, we propose ideas to overcome the existing drawbacks of both structures.

This thesis focuses on one important component of the energy system - the window. Windows are installed in buildings mainly to create visual contact with the surroundings and to let in daylight, and should also be heat and sound insulating. This thesis covers four important aspects of windows: antireflection and switchable coatings, energy simulations and optical measurements. Energy simulations have been used to compare different windows and also to estimate the performance of smart or switchable windows, whose transmittance can be regulated. The results from this thesis show the potential of the emerging technology of smart windows, not only from a daylight and an energy perspective, but also for comfort and well-being. The importance of a well functioning control system for such windows, is pointed out. To fulfill all requirements of modern windows, they often have two or more panes. Each glass surface leads to reflection of light and therefore less daylight is transmitted. It is therefore of interest to find ways to increase the transmittance. In this thesis antireflection coatings, similar to those found on eye-glasses and LCD screens, have been investigated. For large area applications such as windows, it is necessary to use techniques which can easily be adapted to large scale manufacturing at low cost. Such a technique is dip-coating in a sol-gel of porous silica. Antireflection coatings have been deposited on glass and plastic materials to study both visual and energy performance and it has been shown that antireflection coatings increase the transmittance of windows without negatively affecting the thermal insulation and the energy efficiency. Optical measurements are important for quantifying product properties for comparisons and evaluations. It is important that new measurement routines are simple and applicable to standard commercial instruments. Different systematic error sources for optical measurements of patterned light diffusing samples using spectrophotometers with integrating spheres have been investigated and some suggestions are made for how to avoid such errors.

Les expériences de spectroscopie ont été réalisées en collaboration avec Jean-François Allard du groupe de Denis Morris de l'Université de Sherbrooke. / Le présent projet de maîtrise a pour but d’étudier les interactions optiques des films de nanotubes de carbone (FNTCs) avec les ondes THz. Des expériences d’absorption térahertz faites par spectroscopie THz dans le domaine temporel ont été entreprises sur les films dont l’épaisseur varie. Les films d’épaisseurs allant de 14 à 145 nm, sont des couches minces de nanotubes de carbone (NTCs) empilés les uns sur les autres et sont déposés sur substrats (GaAs et silicium). Une caractérisation comparative des épaisseurs des films est entreprise dans un premier temps par AFM et par ellipsométrie spectroscopique. À cause de la rugosité de la surface et de porosité des films qui compliquent les interactions de la lumière avec les films, les épaisseurs déterminées par AFM sont gardées au détriment de celles d’ellipsométrie. La relation entre les épaisseurs mesurées par AFM en fonction des épaisseurs nominales s’est révélée linéaire. Les couleurs des FNTC sont aussi caractérisées en fonction de leurs épaisseurs. L’expérience d’absorption THz sur les films consiste à enregistrer la transmission d’une impulsion THz à large bande à travers les échantillons. Sur les spectres, on détecte aussi l’impulsion de réflexion, l’écho de réflexion de l’impulsion principale THz à l’intérieur du substrat séparé par un délai temporel. La diminution du pic de l’impulsion principale THz en fonction de l’épaisseur est non linéaire et atteint une saturation pour les films les plus épais. Ce résultat est en lien direct avec les mesures quatre pointes de conductivité dc des films où l’inverse de la résistivité de feuille sature à partir des mêmes épaisseurs de film. L’écho de réflexion de l’impulsion principale à l’intérieur du substrat perd de l’amplitude plus rapidement en fonction de l’épaisseur à cause de près de deux passages supplémentaires de l’impulsion dans le film au moment de la réflexion. Finalement, une disparition de l’impulsion de réflexion à une épaisseur particulière de film (100 nm pour le GaAs et 60 nm pour le Si) démontre les propriétés antiréfléchissantes des FNTCs. / In the present masters project, the goal is to study the optical interactions of carbon nanotube films (CNTFs) with terahertz (THz) waves. The THz absorption experiments made by time domain THz spectroscopy have been undertaken on thickness-variable films. CNTFs, which have their thicknesses range from 14 to 145 nm, are thin CNT layers that are piled one on another are deposited on a substrate (GaAs or silicon). First, a comparative characterization of film thicknesses is undertaken with AFM and with spectroscopic ellipsometry. Because of surface rugosity and film porosity which has the effect of complexifying the interaction of light with the films, AFM thicknesses are held for the rest of the analysis instead of those determined with ellipsometry. AFM measured thicknesses scale linearly with respect to nominal thicknesses that are proportional to the CNT density. CNTFs’ colors reveal to be correlated with their thicknesses. THz absorption experiments consist of taking the transmission spectrum of a broad band THz pulse through the samples. On the spectra, we also detect the reflection pulse, which is the echo of the main THz pulse inside the substrate separated by a time delay. The decrease of the main THz pulse with respect to the film thickness is non linear and reaches a saturation plateau for the thickest films. This finding is in direct relationship with four-point probe sheet conductivity measurements made on the films where a saturation is also observed from the same thicknesses. The reflection pulse loses amplitude more rapidly as the film thickness increases because of two additional wave passages in the film during reflection. Lastly, a quenching of the reflection pulse which is observed at a particular film thickness (100 nm for GaAs and 60 nm for silicon) demonstrates antireflection properties for the CNTFs.

Le présent projet de maîtrise a pour but d’étudier les interactions optiques des films de nanotubes de carbone (FNTCs) avec les ondes THz. Des expériences d’absorption térahertz faites par spectroscopie THz dans le domaine temporel ont été entreprises sur les films dont l’épaisseur varie. Les films d’épaisseurs allant de 14 à 145 nm, sont des couches minces de nanotubes de carbone (NTCs) empilés les uns sur les autres et sont déposés sur substrats (GaAs et silicium). Une caractérisation comparative des épaisseurs des films est entreprise dans un premier temps par AFM et par ellipsométrie spectroscopique. À cause de la rugosité de la surface et de porosité des films qui compliquent les interactions de la lumière avec les films, les épaisseurs déterminées par AFM sont gardées au détriment de celles d’ellipsométrie. La relation entre les épaisseurs mesurées par AFM en fonction des épaisseurs nominales s’est révélée linéaire. Les couleurs des FNTC sont aussi caractérisées en fonction de leurs épaisseurs. L’expérience d’absorption THz sur les films consiste à enregistrer la transmission d’une impulsion THz à large bande à travers les échantillons. Sur les spectres, on détecte aussi l’impulsion de réflexion, l’écho de réflexion de l’impulsion principale THz à l’intérieur du substrat séparé par un délai temporel. La diminution du pic de l’impulsion principale THz en fonction de l’épaisseur est non linéaire et atteint une saturation pour les films les plus épais. Ce résultat est en lien direct avec les mesures quatre pointes de conductivité dc des films où l’inverse de la résistivité de feuille sature à partir des mêmes épaisseurs de film. L’écho de réflexion de l’impulsion principale à l’intérieur du substrat perd de l’amplitude plus rapidement en fonction de l’épaisseur à cause de près de deux passages supplémentaires de l’impulsion dans le film au moment de la réflexion. Finalement, une disparition de l’impulsion de réflexion à une épaisseur particulière de film (100 nm pour le GaAs et 60 nm pour le Si) démontre les propriétés antiréfléchissantes des FNTCs. / In the present masters project, the goal is to study the optical interactions of carbon nanotube films (CNTFs) with terahertz (THz) waves. The THz absorption experiments made by time domain THz spectroscopy have been undertaken on thickness-variable films. CNTFs, which have their thicknesses range from 14 to 145 nm, are thin CNT layers that are piled one on another are deposited on a substrate (GaAs or silicon). First, a comparative characterization of film thicknesses is undertaken with AFM and with spectroscopic ellipsometry. Because of surface rugosity and film porosity which has the effect of complexifying the interaction of light with the films, AFM thicknesses are held for the rest of the analysis instead of those determined with ellipsometry. AFM measured thicknesses scale linearly with respect to nominal thicknesses that are proportional to the CNT density. CNTFs’ colors reveal to be correlated with their thicknesses. THz absorption experiments consist of taking the transmission spectrum of a broad band THz pulse through the samples. On the spectra, we also detect the reflection pulse, which is the echo of the main THz pulse inside the substrate separated by a time delay. The decrease of the main THz pulse with respect to the film thickness is non linear and reaches a saturation plateau for the thickest films. This finding is in direct relationship with four-point probe sheet conductivity measurements made on the films where a saturation is also observed from the same thicknesses. The reflection pulse loses amplitude more rapidly as the film thickness increases because of two additional wave passages in the film during reflection. Lastly, a quenching of the reflection pulse which is observed at a particular film thickness (100 nm for GaAs and 60 nm for silicon) demonstrates antireflection properties for the CNTFs. / Les expériences de spectroscopie ont été réalisées en collaboration avec Jean-François Allard du groupe de Denis Morris de l'Université de Sherbrooke.

This thesis deals with the analysis of nano-structured layers deposited by high-frequency magnetron sputtering on the monocrystalline silicon surface. The content of the work focuses on the magnetron sputtering application as an alternative method for passivation and antireflection layers deposition of silicon solar cells. The procedure of pre-deposite silicon surface cleaning by plasma etching in the Ar/H2 gas mixture atmosphere is suggested. In the next step the silicon nitride and aluminum nitride layers with hydrogen content in Ar/N2/H2 gas mixture by magnetron sputtering are deposited. One part of the thesis describes an experimental pseudo-carbide films deposition from a silicon target in the atmosphere of acetylene (C2H2). An emphasis is placed on the research of sputtered layers properties and on the conditions on the silicon-layer interface with the help of the standard as well as special measurement methods. Sputtered layers structure is analyzed by modern X-ray spectroscopy (XPS) and by Fourier infrared spectroscopy (FTIR). Optical ellipsometry and spectrophotometry is used for the diagnostic of the layers optical properties depending upon the wavelength of incident light. A special method of determining the surface lay-out of the charge´s carrier life in the volume and on the surface of silicon is employed to investigate the passivating effects of the sputtered layers.