CARBON-BASED HYBRID PLATFORMS FOR NOVEL PHOTOVOLTAIC DEVICES: BURIED INTERFACE CHEMISTRY AND CHARGE CARRIERS DYNAMICS

Current photovoltaic (PV) market is strongly dominated by an intense use of silicon. Although it is the second most abundant element on the Earth crust, after oxygen, Si is never present in its pure form but always bounded with other elements, and relatively complex and expensive purification procedures are needed in order to have clean, crystalline and optimally doped pure silicon. This issue, joined with the ever-increasing demand of clean Si by almost all the technological modern applications, led scientists all over the world to look for suitable alternatives. One of the most promising options, is to try to substitute silicon with carbon, essentially for two reasons: (i) pure C not only exists in nature but can also be obtained and purified through easy and low-cost processes, (ii) carbon can behave as a metal or a semiconductor without being doped, depending only on the particular allotrope. Moreover, carbon allotropes capability of arranging in various geometry allows C-based materials to assume different dimensionality, starting from the quasi zero-dimensional fullerene to three-dimensional diamonds. This makes carbon nanomaterials excellent candidate for a wide range of electrical and technological devices, offering the possibility to chose the suitable allotropes depending on the particular task that is needed to be fulfilled. For photovoltaic application, a semiconducting material which can provide dissociation sites for excitons is necessary. To accomplish this role, the mono-dimensional form of C, carbon nanotubes (CNTs), revealed to be a perfect substitute of p-type silicon, on one side of the junction because CNTs are naturally p-doped in air. Moreover, thanks to their peculiar geometry and extraordinary electrical conductivity, they are able to provide excellent transport path for the dissociated carriers with a very good transparency (which allows a relevant amount of incident light to reach the depletion region). In the first chapter of this thesis, carbon nanotubes will be introduced, emphasizing the properties which make this nanostructured materials optimal for PV applications. Then, the different types of carbon/silicon heterojunctions will be analyzed, starting from the classical semiconductor theory, to a more complex and realistic model. At the end of the chapter CNTs solar cells state of the art will be presented, highlighting the open questions at which this thesis is aimed to answer. The experimental techniques, such as angle-resolved X-rays photoelectron spectroscopy (AR-XPS) and transient reflectivity (TR) measurements, used to reach this goal will be presented in Chapter 2, together with the description of the manufacturing processes that yielded to the creation of three different series of PV devices, with an improvement of the efficiency from 0.1% to 12.2% in three years. In the third chapter, we will show how the complex buried interface between CNTs and Si can be investigated and modelled by means of photoelectron spectroscopy techniques. A complex oxide interface, composed by silicon dioxide and non-stoichiometric silicon oxide, has been unveiled and possible effects on the power conversion efficiency of PV devices are outlined. A systematic study on the chemical and physical properties of the buried interface will be presented in Chapter 4. Oxides have been alternatively removed and regrown using suitable acids and the effects on the PV performances will be discussed in detail in this chapter. The doping effects of acids on the carbon nanotubes will also be investigated through Raman spectroscopy. Acid effects on the heterojunctions will be unambiguously shown by the XPS measurements, and the matching of these data with the electrical PV measurements allows us to discuss the nature of the heterojunction in more detail. In order to properly address the operation mechanism of these devices, which can be either a conventional p-n or a metal-insulator-semiconductor (MIS) junction, the dynamics of charge transfer processes at the interface will be investigated in Chapter 5 with time-resolved pump-probe reflectivity measurement. The aim is to find a correlation between the thickness of the buried SiOxlayer and the carriers photogeneration and transport, comparing the device electrical parameter with the ultrafast behavior, analyzed by time-resolved reflectivity. These last findings, along with several improvements in the CNTs dispersion and deposition, have led to the creation of optimized third-series solar cells with a record efficiency of 12.2%, which will be fully characterized at the end of this last chapter through a combination of suitable experimental techniques, in order to highlight the factors which contributed to this huge jump in the power conversion efficiency. The stability in time of this optimized PV devices will finally be discussed

Predicting reverse electrodialysis performance in the presence of divalent ions for renewable energy generation

Reverse electrodialysis (RED) is an electro-membrane process to harvest renewable energy from salinity gradients. RED process models have been developed in the past, but they mostly assume that only NaCl is present in the feedwaters, which results in unrealistically high predictions. In the present work, an existing simple model is extended to accommodate the presence of magnesium ions and sulfate in the feedwaters, and potentially even more complex mixtures. All power loss mechanisms deriving from the presence of multivalent ions are included in the new model: increased membrane electrical resistance, uphill transport of multivalent ions from the river to the seawater compartment, and membrane permselectivity loss. This new model is validated with experimental and literature data of membrane electrical resistance (at 10 mol. % MgCl2 for the CEMs and 25 mol. % Na2SO4 for the AEMs), RED stack performance (up to 50 mol. % MgCl2 or Na2SO4 in the feedwaters), and ion transport (at 10 mol. % MgCl2 or Na2SO4 in the feedwaters) showing very good agreement between model predictions and experimental data. Finally, we showed that the developed model not only describes experimental data but can also predict RED performances under a variety of conditions and cross-flow configurations (single-stage with and without electrode segmentation, multi-stage in co-current and counter-current mode) and feedwater compositions (only NaCl, with Na2SO4, with MgCl2, and with MgSO4). It thus provides a very valuable tool to design and evaluate RED process systems

Combining stereolithography and replica molding : on the way to superhydrophobic polymeric devices for photovoltaics

A strategy combining stereolithography (SL) and soft-lithography for the straightforward fabrication of superhydrophobic bulk devices is reported. Microtextured masters are rapidly prototyped by SL and passivated with a perfluorosilane. Such surface treatment enables the faultless fabrication of negative microstructured polydimethylsiloxane molds ultimately utilized to obtain bulk polymeric micropatterned structures by replica molding. As illustrative proof of concept, this approach is employed in the field of photovoltaics to realize the first example of superhydrophobic luminescent solar concentrators (LSCs) showing superior self-cleaning properties. Following our strategy, a new dye-doped acrylate mixture is developed and optimized to ensure complete wetting of the hollow microstructures present on the mold. By judiciously tailoring the photoinitiator concentration and by implementing a tailored double-step UV-irradiation process, complete UV-photopolymerization is achieved despite the significant thickness of the target samples. The high fidelity replication of the original SL-printed features on the daughter replicas as well as their super water-repellency are successfully demonstrated. The performance of the resulting superhydrophobic LSCs is investigated at varying device dimensions and found to be comparable with state-of-the-art systems. This study demonstrates the potential of high-resolution SL-printing in combination with replication techniques as a versatile tool to reproducibly fabricate microstructured superhydrophobic polymeric bulk devices in a straightforward fashion

Influence of sulfate on anion exchange membranes in reverse electrodialysis

Reverse electrodialysis (RED) is a technology producing renewable energy from the mixing of river and seawater. In natural salinity gradients, multivalent ions are present, which lead to a reduced RED power output. Transport of multivalent ions against the concentration gradient and their trapping inside the membranes leads to a lower driving force and increased membrane resistance. The present work focuses on the effect of sulfate ions on anion exchange membranes in RED. A monovalent ion selective membrane ability to retain a higher open circuit voltage is offset by the higher resistance in the presence of sulfate, leading to losses in normalized power outputs (−25%) comparable to a standard grade membrane. Longer term experiments revealed that membrane resistance increases over time. This study highlights the need to address uphill transport, resistance increase, and decreased permselectivity of anion exchange membranes in presence of multivalent ions

Electrode segmentation in reverse electrodialysis: Improved power and energy efficiency

Reverse electrodialysis harvests energy from salinity gradients establishing a renewable energy source. High energy efficiencies are fundamental to up-scale the process and to minimize feedwater pre-treatment and pumping costs. The present work investigates electrode segmentation to strategically optimize the output power density and energy efficiency. Electrode segmentation allows the current density to be tuned per electrode segment. Segmentation experiments were performed with a dedicated electrode configuration in a cross-flow stack using a wide range of residence times. Moreover, an experimentally validated model was extended and used to further compare single and segmented electrode configurations. While operating the electrode segments, the highest efficiencies were obtained when considering the overall power, i.e. not maximized by segment. Results show that at a given net power density (0.92 W·m−2), electrode segmentation increases the net energy efficiency from 17% to 25%, which is a relative increase of 43%. Plus, at 40% net energy efficiency the net power output for a segmented electrode configuration (0.67 W·m−2) is 39% higher than in a single electrode configuration. Higher power density reduces capital investment and higher energy efficiency reduces operating costs. Electrode segmentation increases these parameters compared to a single electrode and can be potentially applied for up-scaling

Gas sensing at the nanoscale: Engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules

The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption

Hybridized C-O-Si Interface States at the Origin of Efficiency Improvement in CNT/Si Solar Cells

Despite the astonishing values of the power conversion efficiency reached, in just less than a decade, by the carbon nanotube/silicon (CNT/Si) solar cells, many doubts remain on the underlying transport mechanisms across the CNT/Si heterojunction. Here, by combining transient optical spectroscopy in the femtosecond timescale, X-ray photoemission, and a systematic tracking of I-V curves across all phases of the interlayer SiOx growth at the interface, we grasp the mechanism that adequately preserves charge separation at the junction, hindering the photoexcited carrier recombination. Moreover, supported by ab initio calculations aimed to model the complex CNT-Si heterointerface, we show that oxygen-related states at the interface act as entrapping centers for the photoexcited electrons, thus preventing recombination with holes that can flow from Si to CNT across the SiOx layer

Rivestimenti sol-gel ibridi fotoreticolabili a temperatura ambiente per luminescent downshifting su celle solari polimeriche flessibili

Un nuovo rivestimento ibrido multifunzionale ad alta durabilità è stato applicato come matrice per luminescent downshifting (LDS) su dispositivi fotovoltaici organici polimerici (OPV) flessibili. Il coating è ottenuto incorporando un fluoroforo organico in una resina fluoropolimerica debitamente funzionalizzata, reticolabile tramite un meccanismo dual-cure a temperatura ambiente, che lo rende idoneo per l’impiego su substrati sensibili al calore. Modulando il contenuto di fluoroforo, si è ottenuto un incremento di efficienza massimo del 4% e un notevole aumento di stabilità per dispositivi rivestiti con il coating LDS rispetto a sistemi di controllo. Questo valore rappresenta il massimo incremento di efficienza su dispositivi OPV flessibili con rivestimenti polimerici. In conclusione, l’approccio presentato in questo lavoro rappresenta una via immediata per l’ottenimento di dispositivi OPV con efficienza e stabilità migliorate