The diploma thesis deals with the study of perovskite solar cells with a regular n-i-p architecture. The theoretical part of this work is mainly focused on the stability of perovskite solar cells, i.e. thermal stability and the influence of UV radiation on final perovskite solar cell stability. Furthermore, the deposition methods, the architecture of solar cells and the materials used for the preparation of electron and hole transport layers were described in more detail. The experimental part deals with the optimization of the preparation of perovskite solar cells (especially in terms of resulting photovoltaic conversion efficiency), with a description of the structure preparation process of the final photovoltaic cell and the interpretation of the measured results.

The work deals with the theory of preparing perovskite solar cells. How about basic structures and the specific types of training opportunities and reproducibility of results. In the third part describes the complete preparation of the article, which reached the highest efficiency and the procedure for subsequent repetition of the experiment

Important aspects of adhesion occur at interfaces, including structures that may be different from those in the bulk materials. However, probing the orientation of molecules in functional adhesives poses a significant challenge because adhesive molecules are always located at a buried interface. The limited penetration depth of surface-specific analysis prohibits the study of buried interfaces using those techniques. The large quantity of bulk molecules relative to the adhesive molecules interacting at the interface results in the bulk signal swamping out adhesive signal in bulk analysis techniques. An interface-specific technique is required to study functional adhesives. One such technique that has shown promise in recent years is Vibrational sum frequency generation (VSFG) spectroscopy. This technique is useful for studying interactions that occur at surfaces and interfaces because it selectively probes regions of broken inversion symmetry. Despite the ability of VSFG to isolate signal from a buried interface, a non-resonant signal that is produced simultaneously with the resonant signal corrupts the vibrational data of interest and greatly impedes reliable analysis of VSFG spectra. Over the last several years, researchers have experimentally removed non-resonant signal by delaying the upconverting pulse with respect to the initial excitation. Obtaining reliable results from VSFG data depends upon complete removal of non-resonant signal. However, complete removal of non-resonant signal presents a challenge because it can be present in spectra even when the indicators of non-resonant signal are absent. By taking advantage of polarization selection rules for VSFG and the differing symmetry of an azimuthally isotropic film and an azimuthally non-isotropic substrate, spectra containing non-resonant signal can be easily identified. These and other advances in VSFG methodology have enabled the study of surface and interfacial systems of interest. In a study of the effects of plasma treatment on polystyrene thin films, plasma exposure was found to affect not only the free surface but also portions of the sub-surface polymer, challenging previous assumptions that plasma effects are constrained to the free surfaces of materials. The next step is to use VSFG to study functional adhesives under known amounts of applied stress. An apparatus is in place to simultaneously collect VSFG spectra during mechanical testing of a functional adhesive, and in preliminary studies, an increase in VSFG non-resonant signal has been observed when a pulling force is applied to the adhesive bond.

In nature, microscopic surface textures impact useful function, such as the drag reduction of shark skin (Dean & Bhushan, 2010) and superhydrophobicity of the lotus leaf(Pan, Kota, Mabry, & Tuteja, 2013). In this study, we explore these phenomena by re-creating microscopic surface textures via the method of interfacial flow instability in drying polyvinylidene fluoride (PVDF) acetone solutions. In general, PVDF films can be made using either spin coating or electrospray deposition with various weight concentrations in acetone. In order to study the morphology of the porous structure of PVDF films, wet deposition samples were fabricated by spin coating or near-field electrospray. Possible theories are discussed and examined to explain the formation of these porous structures resulting in development of a well-controlled method to create porous PVDF films with various pore sizes and pore densities. All samples are characterized and found to exhibit superhydrophobicity and drag reduction. To connect porous PVDF film morphology to the established field of dry particle fabrication, PVDF particle synthesis by far-field electrospray is also reviewed and discussed. An established method to generate polymer particles of different morphologies in other polymers (Almeria-Diez, 2012) by electrospray drying is confirmed using PVDF as well. Due to the ability of scalable and re-configurable electrospray, the microscopic surface textures can be applied to areas of any size to reduce drag or impart water-repelling properties.

Solar energy as the most abundant source of energy is clean, non-pollutant, and completely renewable, which provides energy security, independence, and reliability. Organic-inorganic hybrid perovskite solar cells (PSCs) revolutionized the photovoltaics field not only by showing high efficiency of above 22% in just a few years but also by providing cheap and facile fabrication methods. In this dissertation, fabrication of PSCs in both ambient air conditions and environmentally controlled N2-filled glove-box are studied. Several characterization methods such as SEM, XRD, EDS, Profilometry, four-point probe measurement, EQE, and current-voltage measurements were employed to examine the quality of thin films and the performance of the PSCs. A few issues with the use of equipment for the fabrication of thin films are addressed, and the solutions are provided. It is suggested to fabricate PSCs in ambient air conditions entirely, to reduce the production cost. So, in this part, the preparation of the solutions, the fabrication of thin films, and the storage of materials were performed in ambient air conditions regardless of their humidity sensitivity. Thus, for the first part, the fabrication of PSCs in ambient air conditions with relative humidity above ~36% with and without moisture sensitive material, i.e., Li-TFSI are provided. Perovskite materials including MAPbI3 and mixed cation MAyFA(1-y)PbIxBr(1-x) compositions are investigated. Many solution-process parameters such as the spin-coating speed for deposition of the hole transporting layer (HTL), preparation of the HTL solution, impact of air and light on the HTL conductivity, and the effect of repetitive measurement of PSCs are investigated. The results show that the higher spin speed of PbI2 is critical for high-quality PbI2 film formation. The author also found that exposure of samples to air and light are both crucial for fabrication of solar cells with larger current density and better fill factor. The aging characteristics of the PSCs in air and vacuum environments are also investigated. Each performance parameter of air-stored samples shows a drastic change compared with that of the vacuum-stored samples, and both moisture and oxygen in air are found to influence the PSCs performances. These results are essential towards the fabrication of low-cost, high-efficiency PSCs in ambient air conditions. In the second part, the research is focused on the fabrication of high-efficiency PSCs using the glove-box. Both single-step and two-step spin-coating methods with perovskite precursors such as MAyFA(1-y)PbIxBr(1-x) and Cesium-doped mixed cation perovskite with a final formula of Cs0.07MA0.1581FA0.7719Pb1I2.49Br0.51 were considered. The effect of several materials and process parameters on the performance of PSCs are investigated. A new solution which consists of titanium dioxide (TiO2), hydrochloric acid (HCl), and anhydrous ethanol is introduced and optimized for fabrication of quick, pinhole-free, and efficient hole-blocking layer using the spin-coating method. Highly reproducible PSCs with an average power conversion efficiency (PCE) of 15.4% are fabricated using this solution by spin-coating method compared to the conventional solution utilizing both spin-coating with an average PCE of 10.6% and spray pyrolysis with an average PCE of 13.78%. Moreover, a thin layer of silver is introduced as an interlayer between the HTL and the back contact. Interestingly, it improved the current density and, finally the PCEs of devices by improving the adhesion of the back electrode onto the organic HTL and increasing the light reflection in the PSC. Finally, a highly reproducible fabrication procedure for cesium-doped PSCs using the anti-solvent method with an average PCE of 16.5%, and a maximum PCE of ~17.5% is provided.

Currently organic-inorganic hybrid perovskite solar cells (PSCs) is one kind of promising photovoltaic technology due to low production cost, easy fabrication method and high power conversion efficiency. Charge transport layers are found to be critical for device performance and stability. A traditional electron transport layer (ETL), such as TiO2 (Titanium dioxide), is not very efficient for charge extraction at the interface. Compared with TiO2, SnO2 (Tin (IV) Oxide) possesses several advantages such as higher mobility and better energy level alignment. In addition, PSCs with planar structure can be processed at lower temperature compared to PSCs with other structures. In this thesis, planar-structure perovskite solar cells with SnO2 as the electron transport layer are fabricated. The one-step spin-coating method is employed for the fabrication. Several issues are studied such as annealing the samples in ambient air or glovebox, different concentration of solution used for the samples, the impact of using filter for solutions on samples. Finally, a reproducible fabrication procedure for planer-structure perovskite solar cells with an average power conversion efficiency of 16.8%, and a maximum power conversion efficiency of 18.1% is provided.

Thin polymer films and their properties have been investigated. The characteristics of crystalline polymers according to film thickness have been improved using polycaprolactone (PCL). The melting enthalpy of PCL has increased when the film thickness decreased and the peak melting temperature showed no significant changes with film thickness. Film thickness variation influenced surface roughness and crystal size. Optical microscope images showed the rougher surface of thicker films. The spinning time has shown no influence on film thickness and no significant changes to surface roughness. Thin films of block copolymers were used in the surface modification study; films studied included poly(styrene-b-butadiene-b-styrene) (SBS) and poly(styrene-b-isoprene-b-styrene) (SIS) and their surface modifications have been controlled using different methods of treatment. Films of SIS heated at different temperatures have shown different surface texture and roughness. Films treated at low temperature (45 °C) had smooth surfaces when compared with films heated at high temperature (120 °C and 160 °C). Phase separation of SIS heated at (120 °C and 160 °C) caused bulges of different sizes to cover the surface. The height and width of the bulges showed variation with film thickness and heating. Substrate interaction with SBS and SIS block copolymer films showed different surface texture when using the same type of substrate and different texture were obtained when SBS solutions were spun onto different substrates. It has been demonstrated that using different solvents in copolymer preparation caused different texture. Thermal and surface property variations with film thickness have been improved using amorphous polymers. Surface roughness of poly(methyl methacrylate) PMMA and disperse red 1-poly(methyl methacrylate) DR1-PMMA, PMMA has improved using thickness variation. Glass transition temperature measurement has increased when film thickness was increased. The glass transition temperature (Tg) and surface roughness of UV15 UV - curable coating polymer has been modified using UV curing and heating methods. Tg variation was observed when curing time and curing intensity were changed causing the optical properties of the polymer to be more variable. A plasma etcher caused wrinkles to occur on the surface of unheated UV15. Tg of UV15 increased when curing time increased. The Fourier Transform Infrared Spectroscopy (FTIR) spectra of cured UV15 film have shown peak variations of the ester and carbon double bond regions over the range of 1850-1700 cm-1. Urethane-Urea (UU) Polymer thin films were used to investigate optical properties and develop an optical waveguide. Absorption and transmission properties of light using non-linear optical (NLO) polymer was investigated and used in optical waveguide fabrication. Refractive indices were measured to examine UU films at two different wavelengths. A UU film of 1 µm thickness caused a maximum absorption at max = 471 nm also obtained at 810 nm wavelength. Many methods of fabrication were used; photolithography, plasma etching in a barrel reactor and thin film deposition using sputtering and evaporation. Etched depths from 1 μm to 100 μm were obtained. An optical waveguide has been prepared using plasma etching of a cured UV15 as a cladding layer on a silicon substrate.

Ultrathin film nanocomposites are becoming increasingly important for specialized performance of commercial coatings. Critical challenges for ultrathin film nanocomposites include their synthesis and characterization as well as their performance properties, including surface roughness, optical properties (haze, refractive index as examples), and mechanical properties. The objective of this work is to control the surface roughness of ultrathin film nanocomposites by changing the average particle size and the particle volume fraction (loading) of monomodal particle size distributions. This work evaluated one-layer and two-layer films for their surface properties. Monodispersed colloidal silica nanoparticles were incorporated into an acrylate-based monomer system as the model system. Ultrathin nanocomposites were prepared with three different size colloidal silica (13, 45, and 120 nm nominal diameters) at three different particle loadings (20, 40, and 50 vol. % inorganic solids). Silica particles were characterized using DLS and TEM. AFM was used to measure the root mean square roughness (Rq), ΔZ, and location-to-location uniformity of one-layer and two-layer nanocomposite coatings. Developing an understanding about the properties affected by the type and amount of particles used in a nanocomposite can be used as a tool with nanocharacterization techniques to quickly modify and synthesize desired ultrathin film coatings.

A new technique for sample preparation and trace analysis of organic pollutants in water using mixed-phase thin film (MPTF) devices, combined with direct thermal desorption, cold trapping, gas chromatography-mass spectrometry (GC-MS) is presented for the first time. Two novel analytical devices, Carboxen/polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) TF samplers were fabricated using spin coating technique and glass wool fabric mesh as substrate. The samplers were easily tailored in size and shape by cutting tools. Good durability and flat-shape stability were observed during extractions and stirring in water. The latter characteristic obviates the need for an extra framed holder for rapid thin film microextraction (TFME) and makes the samplers more robust and user-friendly. The analytical performance of the MPTF devices was satisfactorily illustrated and compared with those of solid phase microextraction (SPME) fibers and PDMS thin film membrane using water samples spiked with seven N–nitrosamines (NAs), known as disinfection by-products (DBPs) in drinking water. Marked enhancement of extraction efficiencies (typically more than one order of magnitude) for the N-nitrosamines, including the hydrophilic ones, was obtained with the MPTF devices under generally pre-equilibrium conditions, compared to the SPME fibers and PDMS thin film membrane. The analytical results obtained in this study, including linearity, repeatability and detection levels at low ng/L for the tested compounds, indicate that the new thin film devices are promising for rapid sampling and sample preparation of trace levels of polar organic pollutants in water with sensitivities higher than SPME fibers and with a wide application range typical of mixed-phase coatings. The user-friendly format and robustness of the novel devices are also advantageous for on-site applications, which is the ultimate use of thin film samplers. Moreover, the thin film fabrication approach developed in this study offers the possibility of making other novel samplers with PDMS or different absorptive polymers such as polyacrylate (PA) and polyethylene glycol (PEG) as particle-free, or as particle-loaded thin films with a variety of adsorptive solid particles. In another development in the course of this research, the performance and accuracy of the SPME fiber approach for sample preparation of selected DBPs were demonstrated and compared with the conventional liquid-liquid extraction (LLE) method by real drinking water samples analysis in collaboration with Health Canada. Four regulated trihalomethanes (THMs) and seven other DBPs known as priority by-products, including four haloacetonitriles, two haloketones and chloropicrin, were analyzed in real samples during two separate comparative studies. In each study, duplicate samples from several water treatment and distribution systems in Canada, collected and stabilized under the same protocol, were analyzed in parallel by two independent labs; in the University of Waterloo by an optimized headspace SPME-GC-MS and in Health Canada by a LLE-GC-ECD (electron capture detection) method equivalent to EPA 551.1. The values for the concentration of the analytes in the samples obtained by the two methods were in good agreement with each other in majority of the cases indicating that SPME affords the promise of a dependable sample preparation technique for rapid DBPs analysis. In particular, it was shown that the SPME fiber approach combined with GC-MS is a fast reliable alternative to the LLE-GC-ECD (EPA 551.1) method for analysis of the regulated THMs in the concentration ranges that are typical and relevant for drinking water samples.

Este trabalho apresenta a síntese dos plumbatos de estrutura tipo perovskita (ABO3) PbTiO3, PbZrO3 e Pb(Ti,Zr)O3 por rota sol-gel não aquosa, bem como da produção de filmes finos dos precursores desses compostos sobre substratos de polimetilmetacrilato. Os compostos PbTiO3, PbZrO3 e Pb(Ti,Zr)O3 foram preparados e em seguida caracterizados pela técnica de difração de raios X (DRX) e por análise termogravimétrica (ATG). A molhabilidade entre a solução precursora e o substrato foi avaliada pela medida do ângulo de contato. A deposição dos filmes sobre substratos de PMMA foi feita pelo método de spin-coating, e os filmes produzidos foram caracterizados por espectrofotometria UV-Visível, elipsometria espectral e microscopia eletrônica de varredura (MEV). Os compostos preparados apresentaram a fase perovskita quando tratados a 750°C, no entanto, com tratamentos térmicos a temperaturas abaixo do ponto de fusão do PMMA (120ºC) ainda há alta quantidade de matéria orgânica, o que impossibilita a verificação clara das fases cristalinas. A solução não aquosa do sol-gel apresentou-se molhante ao substrato, o que valida a utilização do método de spin-coating para deposição dos filmes. Os filmes obtidos apresentam transparência na faixa de luz visível, elevada uniformidade na espessura e presença de trincas cuja quantidade aumentou com o número de camadas de deposição. Os valores de índice de refração variaram de 1,7 e 2,0, sendo crescente na ordem PbZrO3, Pb(Ti,Zr)O3 e PbTiO3. Os valores de energia de band gap óptico determinados com base nos valores de transmitância e espessura dos filmes foram entre 3,3 e 3,4 eV para todos os plumbatos investigados. / This work describes the synthesis of plumbates of perovskite-type structure (ABO3) PbTiO3, PbZrO3 and Pb(Ti,Zr)O3 by non-aqueous sol-gel route as well as the production of thin films of these compounds precursors on polymethyl methacrylate substrates. The compounds PbTiO3, PbZrO3 and Pb(Ti,Zr)O3 were prepared and then characterized by of X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The wettability between the precursor solution and the substrate was evaluated by measuring the contact angle. The deposition of the films on PMMA substrates were made by spin-coating method, and the produced films were characterized by UV-Visible, spectral ellipsometry and scanning electron microscopy (SEM). The compounds had the perovskite phase when treated at 750 °C, however, with thermal treatments at temperatures below the melting point of PMMA (120 ° C) there is still high amount of organic matter, making it impossible to clear verification of crystalline phases. The non-aqueous sol-gel showed up wetting to the substrate, which validates the use of the spin-coating method for films deposition. The obtained films exhibit transparency in the visible light range, high uniformity in thickness and presence of cracks whose amount increased with the number of deposited layers. The refractive index values ranged from 1.7 to 2.0, and increasing in the order PbZrO3, Pb(Ti,Zr)O3 and PbTiO3. The optical band gap energy values based on the transmittance values and thickness of the films were between 3.3 and 3.4 eV for all investigated plumbates.