The kinetic energy in river streams, tidal currents, or other artificial water channels has been used as a feasible source of renewable power through different conversion systems. Thus, hydrokinetic energy conversion systems are attracting worldwide interest as another form of distributed alternative energy. Because these systems are still in early stages of development, the basic approaches need significant research. The main challenges are not only to have efficient systems, but also to convert energy more economically so that the cost-benefit analysis drives the growth of this alternative energy form. One way to view this analysis is in terms of the energy conversion efficiency per unit cost. This study presents a detailed assessment of a prototype hydrokinetic energy system along with power output costs. This experimental study was performed using commercial low-cost blades of 20 in diameter inside a tank with water flow speed up to 1.3 m/s. The work was divided into two stages: (a) a fixed-pitch blade configuration, using a radial permanent magnet generator (PMG), and (b) the same hydrokinetic turbine, with a variable-pitch blade and an axial-flux PMG. The results indicate that even though the efficiency of a simple blade configuration is not high, the power coefficient is in the range of other, more complicated designs/prototypes. Additionally, the low manufacturing and operation costs of this system offer an option for low-cost distributed power applications.

This dissertation presents to our knowledge the first demonstration of a quantum well (QW) laser monolithically integrated with internal optical pump based on a light emitting diode (LED). The LED with high efficiency is operated in a thermoelectrophotonic (TEP) regime for which it can absorb both its own emitted light and heat. The LED optical pump can reduce internal optical loss in the QW laser, and enables monolithically integrated TEP heat pumps to the semiconductor laser. The design, growth and fabrication processes of the laser chip are discussed, and its experimental data is presented. In order to further increase the TEP laser efficiency the development of QDs as the active region for TEP edge emitting laser (EEL) is studied. The usage of QD as TEP laser's active region is significant in terms of its low threshold current density, low internal optical loss and high reliability, which are mainly due to low transparency in QD laser. The crystal growth of self-organized QDs in molecular beam epitaxial (MBE) system and characterization of QDs are mentioned. The design, growth, processing and fabrication of a QD laser structure are detailed. The characteristics of laser devices with different cavity length are reported. QD active regions with different amount of material are grown to improve the active region performance. Theoretical calculations based on material parameters and semiconductor physics indicate that with proper design, the combination of high efficiency LED in TEP regime with a QD laser can result in the integrated laser chip power conversion efficiency exceeding unity.

Because of its excellent and unique physical properties, ZnO nanowires have been widely used in numerous scientific fields such as sensors, solar cells, nanogenerators, etc. Although it is believed that single crystal ZnO has a much higher electron transfer rate than TiO₂, it was found that ZnO nanowire-based dye-sensitized solar cells (DSSCs) have lower efficiencies than TiO₂ nanoparticle-based DSSCs because the density and surface area of ZnO nanowires are usually lower than that of TiO₂ nanoparticles, limiting the cell's light absorption, and because the open-root structure of ZnO nanowires results in electron back transfer that causes charge shortage of the cell. Here, experimental studies were performed that utilize strategic manipulations of the design of the ZnO nanowire based DSSCs in efforts to address and solve its key challenges. It was shown that by incorporating various blocking layers into the design of the cell, the performance of the DSSC can be improved. Specifically, by placing a hybrid blocking layer of TiO₂-P4VP polymer between the substrate and the ZnO nanowires, the conversion efficiency of the cell was 43 times higher than that of a cell without this blocking layer due to the reduction of electron back transfer. Furthermore, in efforts to improve the surface area of the ZnO nanowire array, unique three dimensional structures of ZnO nanowires were fabricated. It was found that by significantly improving the overall density and surface area of the ZnO nanowire array through distinctive hierarchal nanowire structures, the light harvesting efficiency and electron transport were enhanced allowing the DSSC to reach 5.20%, the highest reported value for 3D ZnO NW based DSSCs. Additionally, the development of a theoretical model was explored in efforts to investigate how the geometry of ZnO nanowires affects the incident photon-to-current conversion efficiency of 1D ZnO nanowire-based N719-sensitized solar cells at the maximum absorption wavelength of 543 nm.

Philosophiae Doctor - PhD (Chemistry) / Renewable energy has become the centrepiece of research in resolving the energy crisis. One of the forms of renewable energy is solar energy. This form of energy is costly to develop. Organic molecules are promising materials for the construction of next generation photovoltaic cells considering their advantage of lower cost compared to crystalline silicon that is currently used in solar cells. This forms the basis of this research, which focused on the synthesis and characterisation of poly(3- hexylthiophene) P3HT, stannum (Sn) nanoparticles and stannum-based bimetallic stannum-titanium (SnTi), stannum-chromium (SnCr) and stannum-vanadium (SnV) nanoparticles for the application in the construction of heterojunction photovoltaic cells (PVCs).

The rapid development in perovskite solar cells (PSC) has generated a tremendous interest in the photovoltaic community. The power conversion efficiency (PCE) of these devices has increased from 3.8% in 2009 to a recent certified efficiency of over 20% which is mainly the product of the remarkable properties of the perovskite absorber material. One of the most important advances occurred with the replacement of the liquid electrolyte with a solid state hole conductor which enhanced PCE values and improved the device stability. Spiro-OMeTAD (2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)- 9,9'-spirobifluorene) is the most common hole transport material in perovskite solar cells. Nevertheless, the poor conductivity, low charge transport and expensive synthetic procedure and purification have limited its commercialisation. Triphenylamines (TPA) like Spiro-OMeTAD are commonly employed due to the easy oxidation of the nitrogen centre and good charge transport. Other triarylamines have similar properties to Spiro-OMeTAD but are easier to synthesise. The aim of this doctoral thesis is to investigate different types of hole transport materials in perovskite solar cells. Three different series of triphenylamine-based HTM were designed, synthesised, characterised and studied their function in perovskite solar cells. A series of five diacetylide-triphenylamine (DATPA) derivatives (Chapter 3) with different alkyl chain length in the para position was successfully synthesised through a five step synthesis procedure. A range of characterisation techniques was carried out on the molecules including; optical, electrochemical, thermal and computational methods. The results show that the new HTMs have desirable optical and electrochemical properties, with absorption in the UV, a reversible redox property and a suitable highest occupied molecular orbital (HOMO) energy level for hole transport. Perovskite solar cell device performances were studied and discussed in detail. This project studied the effect of varying the alkyl chain length on structurally similar triarylamine-based hole transport materials on their thermal, optical, electrochemical and charge transport properties as well as their molecular packing and solar cell parameters, thus providing insightful information on the design of hole transport materials in the future. The methoxy derivative showed the best semiconductive properties with the highest charge mobility, better interfacial charge transfer properties and highest PCE value (5.63%). The use of p-type semiconducting polymers are advantageous over small molecules because of their simple deposition, low cost and reproducibility. Styrenic triarylamines (Chapter 4) were prepared by the Hartwig-Buchwald coupling followed by their radical polymerization. All monomers and polymers were fully characterised through electrochemical, spectroscopic and computational techniques showing suitable HOMO energy levels and desirable optoelectrochemical properties. The properties and performance of these monomers and polymers as HTMs in perovskite solar cells were compared in terms of their structure. Despite the lower efficiencies, the polymers showed superior reproducibility on each of the device parameters in comparison with the monomers and spiro-OMeTAD. Finally, star-shaped structures combine the advantages of both small molecules, like well-defined structures and physical properties, and polymers such as good thermal stability. Two star-shaped triarylamine-based molecules (Chapter 5) were synthesised, fully characterised and their function as hole-transport materials in perovskite solar cells studied. These materials afford a PCE of 13.63% and high reproducibility and device stability. In total this work provided three series of triarylamine-based hole transport materials for perovskite solar cells application and enabled a comparison of the pros and cons of different design structures: small-molecule, polymeric and star-shaped.

Ce travail se focalise sur l’étude de cellules solaires organiques modèles basées sur le mélange de poly(3-hexylthiophène) (P3HT) et de l'ester méthylique de l'acide [6,6]-phényl C61 butyrique (PCBM). La corrélation entre la morphologie de la couche active, les paramètres de mises en œuvre et le rendement photovoltaïque a été soigneusement étudiée afin d’obtenir l’optimisation de l’efficacité de tels dispositifs. Une méthode originale pour contrôler la séparation de phases dans ces mélanges a été proposée et consiste à l'intégration de copolymères blocs comme additifs. Trois copolymères séquencés ont été utilisés en tant qu’agents de nanostructuration et/ou d'agents de nucléation. Il a notamment été montré que l'incorporation de P3HT-b-PI permet l'augmentation du nombre de cristallites de P3HT tout en limitant l’agglomération du PCBM. D'autre part, l'incorporation de P3HT-b-P4VP dans les mélanges de P3HT:PCBM a permis de contrôler l'orientation des cristallites de P3HT, améliorant par ce fait le transport de charge dans les dispositifs. / This work investigates organic solar cells made of a blend of polymeric materials based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as model system. The correlation between the photovoltaic active layer morphology and the performance of the organic solar cell is thoroughly investigated. The chosen method for controlling phase separation in the polymeric blends is to incorporate block copolymers as additives. Three systematically selected block copolymers were used as nanostructuring and/or nucleating agents. Indeed, the incorporation of P3HT-b-PI induces the increase in the number of P3HT crystallites as well as suppresses the growth of PCBM aggregates. On the other hand, the incorporation of P3HT-b-P4VP into P3HT:PCBM decreases the crystallization of P3HT but increases its face-on orientation, a requirement for an enhanced charge transport in organic PV devices.

Abstract The qualitative and quantitative characteristics of each component layer constituting the structure of organic bulk heterojunction solar cells (OSC-BHJ) contribute significantly towards its overall performance. One of the prevalent issues resulting in reduced device efficiency is due to the conformational inhomogeneities in the active and buffer layers. The mechanical stress, extended thermal exposure and presence of mutually reactive component layers etc., affects negatively on the device stability. Effective methods to address these issues will be extensively benefited by the industry since the current commercialisation of the technology is hindered owing to the lower efficiency and stability of these devices. This dissertation focuses on methods to coherently enhance the performance and longevity of the OSC-BHJ devices. The efficiency enhancements of the devices in this work were achieved through two main routes. The first route was through morphological improvement of the active layer. The second route was through boosting the electrical characteristics of hole transporting conducting polymer layer (HTL) by controlled annealing conditions. The introduction of a suitable additive in the active layer was found to reduce unfavourable phase segregation thus resulting in enhanced morphology. Further, the annealing conditions in different atmospheres (air, nitrogen and vacuum) were found to have a clear influence on the optimum functioning of the HTL in the device. Regarding the stability improvement study done in this work, a method of employing suitable interlayer was developed to effectively abate the internal degradation occurring in the device due to etching reaction on the indium tin oxide (ITO) anode by the HTL. Moreover, experimental investigations were carried out for drawing fundamental understanding of stability degenerating issues such as the influence of mechanical defects on transparent conducting metal oxide (ITO) anode on the performance of the device and heat induced degradations in the low band gap polymer-fullerene active layer. The highlight of this research is that the discovered methods are inexpensive, efficient, and easy to adopt. The results of the study could help the technology to overcome some of its limitations and accelerate its progress towards commercialisation. / Tiivistelmä Orgaanisten heteroliitosaurinkokennojen kerrosrakenteen ominaisuudet ja laatu vaikuttavat merkittävästi aurinkokennojen toiminnallisuuteen. Erityisesti rakenteelliset epähomogeenisuudet aktiivi- ja puskurikerroksissa heikentävät kennon hyötysuhdetta. Kennojen stabiilisuutta tarkasteltaessa myös mekaanisella rasituksella, pitkittyneellä lämpöaltistuksella ja materiaalien reagoinneilla keskenään kerrosten välillä, on selkeä negatiivinen vaikutus kennojen stabiilisuuteen. Orgaanisen aurinkokennoteknologian kaupallistamisen rajoitteina ovat kennojen heikko hyötysuhde ja stabiilisuus, joten menetelmät jotka tarjoavat ratkaisuja edellä mainittuihin ongelmiin, ovat erittäin tärkeitä teknologiaa kaupallistavalle teollisuudelle. Tämä väitöskirja keskittyy johdonmukaisesti selvittämään tapoja, joilla voidaan parantaa heteroliitosaurinkokennojen hyötysuhdetta ja elinikää. Hyötysuhteen tehostamiseksi valittiin kaksi eri lähestymistapaa, joista ensimmäisessä keskityttiin aktiivikerroksen morfologian parantamiseen ja toisessa aukkoja kuljettavan kerroksen sähköisten ominaisuuksien parantamiseen lämpökäsittelyprosessin avulla. Sopivan lisäaineen avulla aktiivikerroksen ei-toivottua kiteytymistä voidaan pienentää ja parantaa näin kerroksen morfologiaa. Lisäksi työssä todettiin, että lämpökäsittelyn aikaisella ympäristöolosuhteella (ilma, typpi, tyhjiö) on merkittävä vaikutus puskurikerroksen optimaaliseen toimintaan aurinkokennossa. Stabiilisuuden parantamiseksi kehitettiin välikerroksen hyödyntämiseen perustuva menetelmä, jolla voidaan tehokkaasti vähentää kennojen sisäisessä rakenteessa tapahtuvaa toiminnallisuuden heikkenemistä, joka aiheutuu aukkoja kuljettavan kerroksen syövyttävästä vaikutuksesta indiumtinaoksidi (ITO) pohjaiseen anodiin. Tämän lisäksi työssä tutkittiin kokeellisesti stabiilisuuteen heikentävästi vaikuttavia tekijöitä, kuten mekaanisen rasituksen aiheuttamia vaurioita metallioksidi (ITO) anodissa ja lämpöaltistuksesta aiheutuvia vikoja polymeeri-fullereeni rakenteeseen perustuvassa aktiivikerroksessa. Tutkimuksen keskeisin tulos on, että esitellyt keinot aurinkokennojen hyötysuhteen ja stabiilisuuden parantamiseen ovat edullisia, tehokkaita ja helppoja hyödyntää. Tulokset voivat merkittävästi edistää orgaanisten aurinkokennojen teknistä kehitystä ja kiihdyttää niiden tuloa kaupallisiksi tuotteiksi.

The topic of this work is the passivation of the active layer of perovskite solar cells with an inverted structure. The work is divided into theoretical and experimental part. The theoretical part describes in particular the passivation and modification of the perovskite layer as well as the characteristic properties of perovskite, including structure and stability. The experimental part deals with the preparation of photovoltaic cells with an inverted structure. For the characterization of photovoltaic cells, reference samples were prepared and their active layer was modified by plasma. The most used deposition technique for the preparation of layers was the spin coating method. From the performed experiments it can be concluded that the preparation of samples and their subsequent modification under laboratory conditions does not lead to the improvement of the final parameters of photovoltaic conversion. By transferring the sample preparation and passivation of the active layer to an inert atmosphere, it was possible to produce cells with higher efficiencies (compared to the reference sample), around 10 %. Another advantage of this plasma treatment of the active layer is that it also improves the stability of the prepared structures, which even after a few days in air show almost 80 % of the original efficiency.

Diploma thesis deals with the use of organic materials in photovoltaic applications and the study of their electric and dielectric properties. The theoretical part of thesis deals issue of the use of organic polymeric materials in photovoltaics and their advantages and disadvantages. Next are the results of various studies of organic solar cells by other authors. In the practical part of the work are shown experimental results (volt-ampere characteristics and impedance spectra) of samples of organic semiconductors and their evaluation.

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