Studio delle proprieta ottiche di film di silicon oxynitrides (sion) per applicazioni fotovoltaiche

Nelle celle solari HIT (Heterojunction Intrinsic Thin layer) attualmente in circolazione il materiale maggiormente utilizzato è sicuramente il silicio, per la sua buona caratteristica di assorbimento e disponibilità in natura. Tuttavia, la struttura amorfa del silicio impiegato come emettitore, limita fortemente la conducibilità e aumenta gli effetti di degradazione legati all'esposizione alla luce. In quest'ottica, nel presente lavoro di tesi, vengono analizzati sottili layers di Silicon Oxynitride ossigenato, depositati in forma nanocristallina presso l'Università di Costanza su substrati in vetro, tramite PECVD (Plasma-Enhanced Chemical Vapor Deposition). Il materiale, che non presenta i difetti intrinseci della forma amorfa, è dal punto di vista delle proprietà fisiche fondamentali ancora poco conosciuto e rappresenta una possibile alternativa agli analoghi campioni in forma amorfa. Le misure e le analisi presentate in questa tesi, svolte presso il Dipartimento di Fisica e Astronomia di Bologna, sono finalizzate ad indagare le principali proprietà ottiche, quali l'energy gap e l'indice di rifrazione dei layers. I risultati ottenuti, espressi in funzione dei parametri di deposizione, mostrano che un aumento della concentrazione di ossigeno in fase di deposito implica un aumento lineare dell'ampiezza dell'energy gap e un calo dell'indice di rifrazione. Anche altri parametri come la potenza di deposito e il tempo di annealing sembrano giocare un ruolo importante sul valore dell'energy gap. I risultati appaiono inoltre essere in buon accordo con quanto ottenuto da studi precedenti su layers simili ma con una maggiore fase amorfa. In conclusione, la possibilità di regolare il valore dell'energy gap e l'indice di rifrazione in base ai parametri di deposizione, unita alle buone prerogative tipiche dei materiali cristallini, conferisce al materiale buone prospettive per applicazioni fotovoltaiche come emettitori in celle ad eterogiunzione o rivestimenti con proprietà antiriflettenti

Proprietà ottiche di film sottili a base di silicio per applicazioni fotovoltaiche

Questa tesi ha come obiettivo quello di misurare la dipendenza spettrale di alcune proprietà ottiche, come trasmittanza e riflettanza, al fine di ricavare l’energy gap di film sottili costituiti da nanocrystalline silicon oxynitride (nc-SiOxNy) per applicazioni in celle solari HIT (Heterojunction Intrinsic Thin layer). Questi campioni sono stati depositati presso l’Università di Konstanz (Germania) tramite tecnica PECVD (Plasma-Enhanced Chemical Vapor Deposition). Questo materiale risulta ancora poco conosciuto per quanto riguarda le proprietà optoelettroniche e potrebbe presentare una valida alternativa a silicio amorfo (a-Si) e ossido di silicio idrogenato amorfo (a-SiOx:H) che sono attualmente utilizzati in questo campo. Le misure sono state effettuate presso i laboratori del Dipartimento di Fisica e Astronomia, settore di Fisica della Materia, dell’Università di Bologna. I risultati ottenuti mostrano che i campioni che non hanno subito alcun trattamento termico (annealing) presentano un energy gap che cresce linearmente rispetto alla diluizione di protossido di azoto in percentuale. Nei campioni analizzati sottoposto ad annealing a 800°C si è osservato un aumento dell’Eg dopo il trattamento. Un risultato ottimale consiste in un gap energetico maggiore di quello del silicio amorfo (a-Si) e del silicio amorfo idrogenato (a-Si:H), attualmente utilizzati in questa tipologia di celle, per evitare che questo layer assorba la luce solare che deve invece essere trasmessa al silicio sottostante. Per questo motivo i valori ottenuti risultano molto promettenti per future applicazioni fotovoltaiche.

Deposizione elettrochimica di film polimerici foto-attivi per la realizzazione di celle solari

Plastic solar cells bear the potential for large-scale power generation based on flexible, lightweight, inexpensive materials. Since the discovery of the photo-induced electron transfer from a conjugated polymer (electron-donor) to fullerene or its derivatives molecules (electron-acceptors), followed by the introduction of the bulk heterojunction concept which means donors and acceptors blended together to realize the fotoactive layer, materials and deposition techniques have been extensively studied. In this work, electrochemical-deposition methods of polymeric conductive films were studied in order to realize bulk heterojunction solar cells. Indium Tin Oxide (ITO) glass electrodes modified with a thin layer of poly(3,4-ethylenedioxythiophene) (PEDOT) were electrochemically prepared under potentiodynamic and potentiostatic conditions; then those techniques were applied for the electrochemical co-deposition of donor and acceptor on modified ITO electrode to produce the active layer (blend). For the deposition of the electron-donor polymer the electropolymerization of many functionalized thiophene monomers was investigated while, as regards acceptors, fullerene was used first, then the study was focused on its derivative PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). The polymeric films obtained (PEDOT and blend) were electrochemically and spectrophotometrically characterized and the film thicknesses were evaluated by atomic force microscopy (AFM). Finally, to check the performances and the efficiency of the realized solar cells, tests were carried out under standard conditions. Nowadays bulk heterojunction solar cells are still poorly efficient to be competitively commercialized. A challenge will be to find new materials and better deposition techniques in order to obtain better performances. The research has led to several breakthroughs in efficiency, with a power conversion efficiency approaching 5 %. The efficiency of the solar cells produced in this work is even lower (lower than 1 %). Despite all, solar cells of this type are interesting and may represent a cheaper and easier alternative to traditional silicon-based solar panels.

Simulazione numerica di celle solari in silicio ad eterogiunzione ad un sole e in concentrazione

Il lavoro di tesi ha come obiettivo lo studio e lo sviluppo tramite simulazioni numeriche di due celle in silicio ad eterogiunzione, una con parametri forniti dal CNR (Comitato Nazionale delle Ricerche) ed un’altra di tipo HIT (Heterojunction with Intrinsic Thin-layer). Lo studio e lo sviluppo delle due celle sono stati effettuati mediante un flusso TCAD il quale permette una maggiore flessibilità e completezza nella descrizione dei modelli fisici ed elettrici.

Nanocrystalline Silicon Based Films for Renewable Energy Applications

The present thesis is focused on the study of innovative Si-based materials for third generation photovoltaics. In particular, silicon oxi-nitride (SiOxNy) thin films and multilayer of Silicon Rich Carbide (SRC)/Si have been characterized in view of their application in photovoltaics. SiOxNy is a promising material for applications in thin-film solar cells as well as for wafer based silicon solar cells, like silicon heterojunction solar cells. However, many issues relevant to the material properties have not been studied yet, such as the role of the deposition condition and precursor gas concentrations on the optical and electronic properties of the films, the composition and structure of the nanocrystals. The results presented in the thesis aim to clarify the effects of annealing and oxygen incorporation within nc-SiOxNy films on its properties in view of the photovoltaic applications. Silicon nano-crystals (Si NCs) embedded in a dielectric matrix were proposed as absorbers in all-Si multi-junction solar cells due to the quantum confinement capability of Si NCs, that allows a better match to the solar spectrum thanks to the size induced tunability of the band gap. Despite the efficient solar radiation absorption capability of this structure, its charge collection and transport properties has still to be fully demonstrated. The results presented in the thesis aim to the understanding of the transport mechanisms at macroscopic and microscopic scale. Experimental results on SiOxNy thin films and SRC/Si multilayers have been obtained at macroscopical and microscopical level using different characterizations techniques, such as Atomic Force Microscopy, Reflection and Transmission measurements, High Resolution Transmission Electron Microscopy, Energy-Dispersive X-ray spectroscopy and Fourier Transform Infrared Spectroscopy. The deep knowledge and improved understanding of the basic physical properties of these quite complex, multi-phase and multi-component systems, made by nanocrystals and amorphous phases, will contribute to improve the efficiency of Si based solar cells.

Energy gap in the aetiology of body weight gain and obesity: A challenging concept with a complex evaluation and pitfalls

The concept of energy gap(s) is useful for understanding the consequence of a small daily, weekly, or monthly positive energy balance and the inconspicuous shift in weight gain ultimately leading to overweight and obesity. Energy gap is a dynamic concept: an initial positive energy gap incurred via an increase in energy intake (or a decrease in physical activity) is not constant, may fade out with time if the initial conditions are maintained, and depends on the 'efficiency' with which the readjustment of the energy imbalance gap occurs with time. The metabolic response to an energy imbalance gap and the magnitude of the energy gap(s) can be estimated by at least two methods, i.e. i) assessment by longitudinal overfeeding studies, imposing (by design) an initial positive energy imbalance gap; ii) retrospective assessment based on epidemiological surveys, whereby the accumulated endogenous energy storage per unit of time is calculated from the change in body weight and body composition. In order to illustrate the difficulty of accurately assessing an energy gap we have used, as an illustrative example, a recent epidemiological study which tracked changes in total energy intake (estimated by gross food availability) and body weight over 3 decades in the US, combined with total energy expenditure prediction from body weight using doubly labelled water data. At the population level, the study attempted to assess the cause of the energy gap purported to be entirely due to increased food intake. Based on an estimate of change in energy intake judged to be more reliable (i.e. in the same study population) and together with calculations of simple energetic indices, our analysis suggests that conclusions about the fundamental causes of obesity development in a population (excess intake vs. low physical activity or both) is clouded by a high level of uncertainty.

Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

Zero-bias conductance and energy gap measurements in LaNiO3-YBa2Cu3O7-x junctions

Conductance measurements of junctions between a high- superconductor and a metallic oxide have been carried out along the a-b plane to examine the tunnel-junction spectra. For these measurements, in situ films have been grown on c-axis oriented thin films using the pulsed laser deposition technique. Two distinctive energy gaps have been observed along with conductance peaks around zero bias. The analysis of zero-bias conductance and energy gap data suggests the presence of midgap states located at the centre of a finite energy gap. The results obtained are also in accordance with the d-wave nature of high- superconductors.

On the paradoxical relation between the melting temperature and forbidden energy gap of nanoparticles

We comment on the paradox that seems to exist about a correlation between the size-dependent melting temperature and the forbidden energy gap of nanoparticles. By analyzing the reported expressions for the melting temperature and the band gap of nanoparticles, we conclude that there exists a relation between these two physical quantities. However, the variations of these two quantities with size for semiconductors are different from that of metals. (C) 2010 American Institute of Physics.[doi:10.1063/1.3466920].

Non-Marcus energy gap dependence of electron transfer rate in contact ion pairs. Novel interplay between relaxation and reaction in solution

Electron transfer reactions between donor-acceptor pairs in solution and in organized media exhibit diverse behaviour. Recent experiments have indicated an interesting breakdown of the Marcus parabolic energy gap dependence in the normal regime for back electron transfer from contact ion pairs. A novel explanation of this breakdown has recently been proposed (M. Tachiya and S. Murata, J. Am. Chem. Sec., 116(1994) 2434) which attributes the breakdown to the interplay between the relaxation in the reactant well and the reaction. A particularly interesting aspect of the model is that it envisages the electron transfer in the normal regime to take place from a completely non-equilibrium condition. In this article a time dependent solution of the model is presented for the first time, after generalizing it to include a realistic initial population distribution. The decay of the contact ion pair population is completely non-exponential. This can be used to check the validity of the Tachiya-Murata model. The dynamics of electron transfer from the solvent separated ion pair, which seem to obey the Marcus relation, is exponential.

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.

Current dependence of the energy gap in superconductors : a direct measurement

From the tunneling characteristics of a tin-tin oxide-lead junction, a direct measurement has been made of the energy-gap variation for a superconductor carrying a current in a compensated geometry. Throughout the region investigated – several temperatures near T_c and down to a reduced temperature t = 0.8 –the observed current dependence agrees quite well with predictions based on the Ginzburg-Landau-Gor’kov theory. Near T_c the predicted temperature dependence is also well verified, though deviations are observed at lower temperatures; even for the latter, the data are internally consistent with the temperature dependence of the experimental critical current. At the lowest temperature investigated, t = 0.8, a small “Josephson” tunneling current allowed further a direct measurement of the electron drift velocity at low current densities. From this, a preliminary experimental value of the critical velocity, believed to be the first reported, can be inferred in the basis of Ginzburg-Landau theory. For tin at t = 0.8, we find v_c = 87 m/sec. This value does not appear fully consistent with those predicted by recent theories for superconductors with short electronic mean-free-paths.

Effect of dry oxidation on the energy gap and chemical composition of CVD graphene on nickel

The findings presented herein show that the electronic properties of CVD graphene on nickel can be altered from metallic to semiconducting by introducing oxygen adsorbates via UV/ozone or oxygen plasma treatment. These properties can be partially recovered by removing the oxygen adsorbates via vacuum annealing treatment. The effect of oxidation is studied by scanning tunneling microscopy/spectroscopy (STM/STS) and X-ray photoelectron spectroscopy (XPS). As probed by STM/STS, an energy gap opening of 0.11-0.15 eV is obtainable as the oxygen/carbon atomic ratio reaches 13-16%. The corresponding XPS spectra show a significant monotonic increase in the concentration of oxygenated functional groups due to the oxidation treatments. This study demonstrates that the opening of energy gap in CVD graphene can be reasonably controlled by a combination of UV/ozone or oxygen plasma treatment and vacuum annealing treatment. © 2013 Elsevier B.V.