The contribution of atmospheric aerosols towards radiative forcing has a very high uncertainty due to their short atmospheric lifetime. The aerosol effects are largely controlled by the density, elemental composition, and hygroscopic properties of the aerosol particles. Therefore, we have performed designed new methodology using Scanning Transmission X-ray Microscopy (STXM), Atomic force spectroscopy (AFM), micro-FTIR spectroscopy and Scanning Electron Microscopy (SEM) to quantify these important aerosol properties. Hygroscopic properties are quantified by plotting the mass of water on a single particle basis, calculated from STXM, as a function of relative humidity. Alternatively, micro-FTIR spectra have been used to study the effect of composition of aerosol particles on the hygroscopic properties of NaCl. Moreover, a unique combination of STXM and AFM has been utilized to quantify density and elemental composition of micrometer dimensional particles. This method has also been extended towards exploring mixing state of particles, consisting of heterogeneously mixed inorganic and organic compounds. In addition to these above mentioned properties, the fate of an atmospheric particle is often altered by chemical transformation and that in turn is influenced by the atmospheric RH. Therefore, we have studied an unusual keto-enol tautomerism in malonic acid particles at high RH, which is not observed in bulk. This observation could potentially be utilized to significantly improve the models to estimate Secondary Organic Aerosols (SOA). Using STXM and micro-FTIR technique, RH dependent equilibrium constant of the tautomerism reaction has been quantified as well. Organic nanocrystals capable of undergoing solid state photochemical changes in a single-crystal-to-single-crystal (SCSC) manner have been particularly important in fabricating molecular switches, data storage devices etc. Mechanical properties of these nanomaterials may control its SCSC reactivity. In addition, investigation of mechanical stiffness is important to define allowable limit of stiffness towards device application. Therefore, we studied mechanical properties of series organic nano cocrystals primarily consisting of trans-1,2-bis(4-pyridyl)ethylene and substituted resorcinol using AFM nanoindentation technique. Dependence of mechanical properties and SCSC reactivity on the resorcinol structure is also investigated as well. Moreover, photolithography on the thin film of these organic cocrystals has been performed to demonstrate its applicability as a photoresist.

A Metal-Insulator-Metal (MIM) diode is a high frequency device used for energy harvesting purpose in the RECTENNA. The main objective of this thesis work is to design, fabricate and characterize a thin-film MIM diode. A key issue associated in this research work is the development MIM diode with nanometer thin insulator region. The reason for the development of MIM diode is to rectify a wide spectrum of AC signal to usable DC power. In this thesis work, a planar MIM diode with Aluminum/Aluminum-Oxide/Gold has been fabricated. The thickness of the insulator region obtained was about 3nm. The Metal and insulator depositions were done by sputtering and plasma oxidation, respectively. I-V Characteristics of the diode was measured by making use of in-house set-up and 70% of the devices on a single wafer yielded with better result. Most of the I-V curves obtained were highly non-linear and asymmetric. Based on the I-V measurement, the logarithmic derivative of I vs. V was plotted and the tunneling behavior was also observed.

Au cours de ces travaux de thèse, la mésostructure et le comportement électrique/photoélectrique de mélanges de polymères semi-conducteur et ferroélectrique en films minces ont été étudiés pour des applications en électronique organique. Les propriétés de semi-conduction du P3HT et de ferroélectricité du P(VDF-TrFe) ont été associées au sein d’une même couche active. Il a été observé que le développement d’une morphologie de la couche active en film mince présentant des domaines bi-continus permet de conserver les propriétés intrinsèques des deux matériaux. Des dispositifs de type stockage d’informations ont été réalisés à partir de la couche active composée de 10 % P3HT – 90 % P(VDF-TrFe) et la modulation des propriétés d’injection des dispositifs par le champ ferroélectrique a été étudiée. Des cellules photovoltaïques ont également été réalisées à partir de cette couche active qui présente des propriétés optoélectroniques qui varient selon l’état de polarisation du P(VDF-TrFe). L’influence du champ ferroélectrique sur l’efficacité de la photogénération de charges du P3HT et la modulation du photocourant par l’état de polarisation du P(VDF-TrFe) ont ainsi été déterminées. / In this thesis, the mesostructure and the electric/photoelectric behavior of ferroelectric/semi-conductor polymer blends in thin films have been studied for organic electronic applications. The semi-conductivity property of P3HT was associated with the ferroelectricity of P(VDF-TrFe) in one active layer. It has been observed that the intrinsic properties of both materials remained with the bi-continous morphology of these thin films. Memory devices were fabricated based on the 10 % P3HT – 90 % P(VDF-TrFe) active layer and the modulation of the injection properties by the ferroelectric field has been studied. We have also demonstrated that the P3HT/P(VDF-TrFe) thin films exhibit optoelectronic properties which depend on the polarization state of P(VDF-TrFe). The influence of the ferroelectric field on the photogeneration of charges of P3HT and the variation of the photocurrent with the polarization state of P(VDF-TrFe) were determined.

L’industrialisation des cellules photovoltaïques organiques implique le développement de plusieurs aspects. Une augmentation des rendements de conversion, une amélioration de la stabilité et la mise au point de procédés de dépôt en ligne. Ce dernier point va passer par le développement de dépôt par voie liquide des différentes couches composant les dispositifs. Dans ma thèse je vais m’intéresser à un type de couche, les couches de transport de charges. Ces couches sont disposées entre la couche photo-active et les électrodes afin d’améliorer l’extraction des charges générées au sein de la première vers ces dernières. Je vais focaliser mon étude sur les couches de transport de trous. Afin de remplacer le matériau couramment utilisé (PEDOT:PSS), on utilise souvent les oxydes de métaux de transition.Ces matériaux habituellement évaporés, sont déposables en voie liquide à partir de suspensions de nanoparticules, ou de précurseurs (ex: sol-gel). J’ai développé 3 approches au cours de ma thèse. Dans la première, un dépôt par voie sol-gel d’oxyde de tungstène ou de vanadium a permis d’obtenir des rendements similaires à ce qui est obtenu avec les mêmes matériaux évaporés. Dans la deuxième approche un dépôt d’oxyde de cobalt (II, III),m’a permis d’améliorer l’extraction des charges. Néanmoins le matériau présente des difficultés de mise en forme ne permettant pas d’atteindre des rendements à l’état de l’art.Finalement une approche plus originale a été développée, une diffusion induite thermiquement d’un dopant, déposé par voie liquide à l’interface organique/métal m’a permis d’obtenir des rendements similaires à ce qui est obtenu avec des structures classiques. / In order to allow the industrialisation of organic photovoltaic cells, power conversion efficiency must be increased, stability must be improved, and in-line deposition processing (solution processing of each layer) must be developed. This work presents the development of solution-processed interlayers, layers inserted between the photoactive organic layer and electrodes in order to enhance charge extraction. This study is focused on the hole transport layer and, in particular, the replacement of the commonly used material PEDOT:PSS. A frequent approach to achieve this is the use of transition metal oxide layers such as MoO3 orV2O5. These oxides are usually deposited by evaporation but can be solution-processed from precursor solutions (e.g. sol-gel) or nanoparticle suspensions. This work considers three approaches. In the first, the use of sol-gel deposited tungsten or vanadium oxide led to an enhancement of hole extraction, allowing efficiencies in the range of what is expected for state of the art materials to be reached. The second approach involved the use of solution processed cobalt oxide. Although the use of this material enhanced charge extraction, due to a deposition issue, efficiency did not reach expected value. Finally, thermally induced diffusion of a solution-processed dopant was utilised, which is a novel approach. The dopant deposited at the organic/metal interface enhances hole extraction and leads to power conversion efficiencies similar to reference cells incorporating an evaporated metal oxide interlayer.

Devices for converting solar energy to electrical energy are not considerably efficient, though there are abundant renewable solar energy sources. Therefore there is a continuous call for investigation of new devices that are efficient and eco-friendly thereby contributing to harvested energy technology. This thesis characterizes the optical constant (refractive index) of a novel material, cobalt oxide-antimony doped tin oxide (CoO-ATO). Thin film of CoO-ATO is generated using spin coating of CoO-ATO solution having 76.33% chloroform, 13.47% polystyrene, 10% antimony doped tin oxide and 0.2% cobalt oxide by weight. The thin film is analyzed through ellipsometry to acquire the refractive index of the material through the visible spectrum, which is used for modeling an antireflective coating in a solar cell. The model is designed and analyzed by simulation using computer simulated technology, and the results of the analysis of a thin film or a nanofiber membrane of the novel material implemented as an antireflective coating layer that affects the absorption efficiency of the optoelectronic device. The result of the analysis showed enhancement of absorption efficiency within the visible spectrum for both thin film and nanofiber membrane of the novel material CoO-ATO. The absorption through thin film was more than that of the nanofiber membrane.

Conjugated polymers have been used in various applications (battery, supercapacitor, electromagnetic shielding, chemical sensor, biosensor, nanocomposite, light-emitting-diode, electrochromic display etc.) due to their excellent conductivity, electrochemical and optical properties, and low cost. Polyaniline has attracted the researchers from all disciplines of science, engineering, and industry due to its redox properties, environmental stability, conductivity, and optical properties. Moreover, it is a polymer with fast electroactive switching and reversible properties displayed at low potential, which is an important feature in many applications. The thin oriented polyaniline films have been fabricated using self-assembly, Langmuir-Blodgett, in-situ self-assembly, layer-by-layer, and electrochemical technique. The focus of this thesis is to synthesize and characterize polyaniline thin films with and without dyes. Also, the purpose of this thesis is to find the fastest electroactive switching PANI electrode in different electrolytic medium by studying their electrochemical properties. These films were fabricated using two deposition techniques: in-situ self-assembly and electrochemical deposition. The characterization of these films was done using techniques such as Fourier Transform Infrared Spectroscopy (FTIR), UV-spectroscopy, Scanning Electron Microscope (SEM), and X-Ray Diffraction (XRD). FTIR and UV-spectroscopy showed similar results in the structure of the polyaniline films. However, for the dye incorporated films, since there was an addition in the synthesis of the material, peak locations shifted, and new peaks corresponding to these materials appeared. The 1 layer PANI showed compact film morphology, comparing to other PANI films, which displayed a fiber-like structure. Finally, the electrochemical properties of these thin films were studied using cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in different scenarios. These scenarios included the study in different acid based electrolytes and different gel based electrolytes. The ultra-thin self-assembled PANI films were shown to have a faster switching time, especially for the 1 layer PANI, whereas the color contrast could be observed for the film containing the dye molecule. Also, HCl based electrolyte gave the best electrochemical reversibility compared to other acids used. For the gelatin and PVA based electrolytes, having the same concentration, the results were similar. Hence, the change in the electrolyte consistencies, from liquid to semi-solid, did not change the electrochemical properties of the films. Finally, in the EIS, it was shown that these PANI thin films exhibit a pseudo-capacitance behavior, and as the film thickness grew, the capacitance increased.

Thin film silicon on low temperature glass substrates is currently seen as the best path toreduce the $/W cost of photovoltaic (PV) modules. However, producing thin film polysilicon, on glass, is an ongoing research challenge. Laser crystallisation of a-Si is one of the possible methods. Typically excimer (XMR) lasers are used for laser crystallisation. This thesis introduces the copper vapour laser (CVL) as a viable alternative for thin film photovoltaic applications. The CVL, like the XMR, is a high powered, pulsed laser. However, the CVL has higher pulse rates (4-20kHz), better beam quality and a visible wavelength output (578 & 511nm). Preliminary experiments, using 600K-heated silicon-on-quartz samples, confirmed that CVL crystallisation can produce area weighted average grain size of 0.1-0.15??m, which is comparable to results reported for XMR??? s. Importantly, the CVL results used thicker films (1??m), which is more applicable to thin photovoltaic devices that need 1-10??m of silicon to be viable. The CVL??? s longer wavelength and therefore longer penetration depth (1/alpha) are proffered as the main reason for this result. Extensive laser-thermal modelling highlighted further opportunities specific to CVL crystallisation. Through-the-glass doublesided irradiation was shown in simulations to reduce thermal gradients, which would enhance crystal growth. The simulations also produced deeper melts at lower surface temperatures, reducing the thermal stress on the sample. Subsequent experiments, using silicon-on-glass, confirmed the benefit of through-the-glass doublesided irradiation by maintaining grain sizes without the usual need for substrate heating. Furthermore, Raman analysis showed that doublesided crystallisation achieved full depth crystallisation, unlike single side irradiation which produced partial crystallisation. A new mode of crystallisation, stepwise crystallisation, was also postulated whereby a series of CVL pulses could be used to incrementally increase the crystallisation depth into the silicon. Simulations confirmed the theoretical basis of the concept, with HeNe Raman spectroscopy and analysis of surface grain sizes providing indirect experimental support. The CVL??? s ability to crystallise thicker films more directly applicable to photovoltaic devices secures its viability as an alternative laser for photovoltaic applications. The through-the-glass doublesided irradiation and the stepwise crystallisation provide additional potential for increased process flexibility over XMR???s.

One of the poly-Si thin-film cells developed at the University of New South Wales (UNSW) is the EVA cell. In this work, SiN films for EVA cells as an antireflection/barrier coating were investigated. In addition, the effect of hydrogenation pre-treatment of solid phase crystallisation (SPC) on grain size and open-circuit voltage (Voc) was investigated. The SiN films deposited by PECVD were examined for uniformity of the thickness and the refractive index of the films across the position of the samples in the PECVD deposition system. A spectrophotometric analysis was used to determine these film properties. It was found that these properties were very uniform over the deposition area. Good repeatability of the depositions was also observed. A series of SiN film depositions by reactive sputtering were also performed to optimize the deposition process. Parameters adjusted during the deposition were nitrogen flow rate, substrate bias, and substrate temperature. By investigating the deposition rate, refractive index, and surface roughness of the films, the three deposition parameters were optimised. The effects of post SiN deposition treatments (a-Si deposition, SPC, RTA, and hydrogenation) on thickness and refractive index of both SiN films deposited by PECVD and reactive sputtering were investigated by using samples which have the same structure as the EVA cells. The thickness of the PECVD SiN films decreased about 6 % after all the treatments. On the other hand, the thickness reductions of the reactively sputtered SiN films were very small. The refractive index of the PECVD SiN films increased about 0.6 % after the treatments, whereas that of the reactively sputtered SiN films decreased 1.3 % after the treatments. As a possible method to improve the performance of EVA cells, hydrogenation of a-Si was investigated as a pre-treatment of SPC process. There were no obvious differences in the grainsize and the Voc of the EVA cells with and without the hydrogenation. Therefore it is likely that the hydrogenation pre-treatment of SPC does not have a beneficial effect on the performance of EVA cells.

The cost of photovoltaic electricity needs to be significantly reduced in order to achieve a high electricity market penetration. Thin-film solar cells have good potential to achieve such cost savings though (i) large-area deposition onto low-cost foreign substrates, (ii) more streamlined processing, (iii) monolithic cell interconnection, and very efficient use of the expensive semiconductor material. Polycrystalline silicon (poly-Si) on glass is a promising technology for the cost-effective large volume production of PV modules since it (i) makes use of an abundant raw material, (ii) is non-toxic, (iii) does not suffer from light-induced degradation, and (iv) does not rely on TCO layers. Usually plasma enhanced chemical vapour deposition (PECVD) is used for the layer formation. This thesis explores the use of e-beam evaporation as deposition method since it is potentially much faster and cheaper than PECVD. The resulting solar cells are referred to as EVA (from EVAporation). Two inherent shunting mechanisms in EVA cells are demonstrated to be shunting through sub-micron sized pinholes when the back electrode is deposited and shunting between the emitter and the absorber layer at the glass-side electrode. Through the improved understanding of these shunting mechanisms it was possible to develop a suitable metallisation scheme for EVA cells using an aligned deposition of emitter and back surface field line contacts and a specially developed shunt mitigation etching technique. For the first time appreciable efficiencies of up to 5.2% were demonstrated on this material. It was also shown that only very lightly doped absorber layers can lead to the required high short-circuit currents in EVA cells. The resulting cells are currently completely limited by space charge region recombination occurring with comparatively low ideality factors of only ~ 1.4 This thesis also demonstrates the usefulness of Jsc-Suns measurements and investigates optical loss mechanisms in the current devices. Advanced modelling of distributed series resistance effects, influencing Suns-Voc, m-Voc and Jsc-Suns curves, is employed. PC1D modelling is used to extract relevant device parameters. In this work it was found that the diffusion length in the best EVA cells is longer than the absorber layer and that insufficient light trapping is currently the major hurdle to higher cell efficiencies. From the obtained results it can be concluded that EVA solar cells are promising candidates for the low-cost and high-volume production of solar modules.

In polycrystalline silicon (pc-Si) thin-film solar cells, defect passivation is critical to device performance. Isoelectronic or covalently bonded impurities, hydrogenic, extended defects and defects with localized levels in the bandgap (deep level defects) are typically introduced during the fabrication of, and/or are inherent to, pc-Si thin-film solar cells. These defects dramatically affect minority carrier lifetimes. Removing and/or passivating these defects is required to maximize minority carrier lifetimes and is typically done through thermal annealing and passivation techniques. For pc-Si thin-film solar cells on low temperature glass superstrates, rapid thermal annealing (RTA) and hydrogen plasma passivation (hydrogenation) are powerful techniques to achieve effective removal and passivation of these defects. In this thesis, three silicon thin-film solar cells structures on low-temperature glass are subjected to variations in RTA high-temperature plateaus, RTA plateau times, and hydrogen plasma passivation parameters. These solar cells are referred to as ALICIA, EVA and PLASMA. By varying the RTA plateau temperature and time at plateau, the trade-off between extensive dopant diffusion and maximum defect removal is optimized. To reduce the density of point defects and to electrically activate the majority of dopants, an RTA process is shown to be essential. For all three of the thin-film solar cell structures investigated in this thesis, a shorter, higher-temperature RTA process provides the best open-circuit voltage (Voc). Extensive RTA plateau times cause excessive dopant smearing, increasing n = 2 recombination and shunt resistance losses. Hydrogenation is shown to be an essential step to achieve maximum device performance by `healing' the defects inherent to pc-Si thin-film solar cells. If the hydrogen concentration is about 1-2 times the density of oxygen in the cells as measured by secondary ion mass spectroscopy (SIMS), the cells seem to respond best to hydrogenation, with good resultant Voc and short-circuit for all cells investigated in this thesis. The effect of hydrogen passivation on the Voc is spectacular, typically increasing it by a factor of 2 to 3.5. Hydrogen de-bonding from repeated thermal treatments at increasing temperature provides a deeper understanding of what defects exist and the nature of the defects that limit the cell voltage. The variation in RTA and hydrogenation process parameters produces significant empirical insight into the effectiveness of RTA processes for point defect removal, dopant activation, point defect and grain boundary passivation, and impurity passivation. SIMS measurements are used to determine the impurities present in the cells' bulk and the amount of hydrogen available to passivate defects. From the results presented it appears that pc-Si thin-film solar cells on low-temperature glass are a promising, and potentially lower-cost, alternative to Si wafer based cells.