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Traditionally, critical infrastructures demand for high dependability, being the services they provide essential to human beings and the society at large. However, more recent attention to cautious usage of energy resources is changing this vision and calls for solutions accounting for appropriate multi-requirements combinations when developing a critical infrastructure. In such a context, analysis supports able to assist the designer in envisioning a satisfactory trade-off among the multi-requirements for the system at hand are highly helpful. In this paper, the focus is on the railway sector and the contribution is a stochastic model-based analysis framework to quantitatively assess trade-offs between dependability indicators and electrical energy consumption incurred by the rail switch heating system.Moving from a preliminary study that concentrated on energy consumption only, the analysis framework has been extended to become a solid support to devise appropriate tuning of the heating policy that guarantees satisfactory trade-offs between dependability and energy consumption. An evaluation campaign in a variety of climate scenarios demonstrates the feasibility and utility of the developed framework.

Power system controls are vulnerable to cyber-attacks that can seriously affect and even inhibit their operation. Such attacks may affect large portions of the power system, make repair difficult and cause huge societal impact, so pressure to ensure cyber-security of control and communication systems is now strong worldwide. Several cyber-security frameworks were developed, but it is rather difficult to anticipate adoption costs and benefits, and this hampers their generalised adoption. T his paper focuses on the outcome of two case studies (concerning the Italian power generation and the Polish transmission systems. The socio-economic impact of failures and the costs of standard adoption are estimated on an objective basis. It is up to public authorities to decide whether to require the adoption of security standards to operators in the electric system. The nature of public good of security underlines the necessity of public support for this operation, but we discuss the extent and the management of this support.

Silicon carbide/silicon rich carbide multilayers, aimed at the formation of silicon nanodots for photovoltaic applications, have been studied. The electrical properties have been investigated at the nano-scale by conductive Atomic Force Microscopy (c-AFM) and at macro-scale by temperature dependent conductivity measurements. The mixture is composed of highly conductive Si nanoclusters and moderately conductive SiC nanoclusters in a disordered matrix. The conduction mechanism takes place via band states induced by the disorder at the interface between nanodot clusters. Structural properties have been extracted by optical spectroscopy analyses. The results contribute to the understanding of the microscopical electronic mechanisms of the composite material, which is a candidate for third generation photovoltaics.

Halide perovskites are the leading candidates for next-generation, low-cost optoelectronics with power conversion efficiencies well above 25%. However, operational stability remains a key challenge. Although there is an understanding that the microscale and nanoscale play a consequential role in determining the macroscopic performance and stability, significant gaps remain in the mechanistic understanding of degradation processes at the nanoscale and the mechanisms for stability in cation-alloyed systems. Nanoscale hexagonal phase impurities have been identified as problematic for operational stability, leading to both performance losses and morphological degradation. However, it is still unclear at what stage these phase impurities originate. Understanding this better is critical in order to mitigate the harmful effects of these phase impurities on performance and operational stability. Cation alloying is a commonly used technique in the field to mitigate these hexagonal phase impurities, although not without its challenges. In this thesis study, the nanoscale structural landscape of key halide perovskite compositions is studied. By taking snapshots of the perovskite at different states of the annealing process, the impact of phase impurities on device performance is characterised. Thereon, the mechanism by which composition dictates photostability in FA-rich perovskite absorber layers is studied. It is demonstrated that the composition impacts the degree of octahedral tilt, which is essential to restricting the transition to hexagonal phase impurities. Additionally, it is demonstrated that while a judicious mix of A-site cations can be used to stabilise the photoactive black phase of halide perovskites, it is challenging to achieve this homogeneously over large areas, necessitating a search for alternative or complementary approaches to stabilise perovskite via octahedral tilt. Using scanning electron diffraction (SED) studies, the spacegroup of additive-stabilised-CsPbI3 is demonstrated to be a low symmetry tilted γ-phase. Furthermore, using SED, the nanoscale structural landscape of mixed-phase CsPbI3 absorber layers is studied and it is demonstrated that both narrow-bandgap γ-phase and wide-bandgap δ-phase co-exist at the nanoscale, enabling stable and bright white-light emission. Overall, this thesis provides insights into the role of nanoscale structure in dictating the properties and behaviour of halide perovskites and offers rational guidelines for their optimisation and use in optoelectronic devices. Additionally, it is demonstrated that SED is a powerful tool for studying these materials at the atomic scale, allowing for the detailed characterisation of their structures and properties.

Self-organizing nanopatterns can enable economically competitive, industrially applicable light-harvesting platforms for thin-film solar cells. In this work, we present transparent solar cell substrates having quasiperiodic uniaxial nanowrinkle patterns with high optical haze values. The self-organized nanowrinkle template is created by controlled heat-shrinking of metal-deposited pre-stretched polystyrene sheets. A scalable UV nanoimprinting method is used to transfer the nanopatterns to glass substrates on which single-junction hydrogenated amorphous silicon p-i-n solar cells are subsequently fabricated. The structural and optical analyses of the solar cell show that the nanowrinkle pattern is replicated throughout the solar cell structure leading to enhanced absorption of light. The efficient broadband light-trapping in the nanowrinkle solar cells results in very high 18.2 mA/cm2 short-circuit current density and 9.5% energy-conversion efficiency, which respectively are 35.8% and 39.7% higher than the values obtained in flat-substrate solar cells. The cost- and time-efficient technique introduces a promising new approach to customizable light-management strategies in thin-film solar cells.

This study provides the first comprehensive overview of the sustainability performance of the hotel sector in the Himalayan region: Sagarmatha National Park and Buffer Zone, using both environmental, economic, and technical criteria. In particular, the performance of 45 buildings in this region were measured and quantified in terms of life cycle based carbon footprint, life cycle costs, heat loss rate, number of guests, energy consumption, and area. Buildings were classified into three types: traditional, semi-modern and modern. The statistical analysis included testing for significant differences between such categories by means of ANOVA, and determination of the correlation between the same parameters. Results show a significant difference between the buildings’ total carbon footprint and operation stage carbon footprint while, there is no significant difference between the buildings’ life cycle costs. Traditional buildings have on average the largest carbon footprint and life-cycle cost over the typical building lifespan of 50 years of building lifespan. The ANOVA tests highlight how heat loss rate, size of the building and number of tourists in the hotels are significantly different across the building types. A strong positive correlation is observed between environmental impact, economic impact and energy consumption for the household activities, and a negative correlation with the number of guests and building size. By considering several buildings, this study allows to draw new and more general conclusions about effective sustainability strategies in the whole hotel sector in the Himalayan region. In particular, it shows that reducing impacts in the operation stage should be highly prioritized, focusing on reducing energy consumption and heat loss and shifting to the use of renewable energy sources.

Formate production via both CO2 reduction and cellulose oxidation in a solar-driven process is achieved by a semiartificial biohybrid photocatalyst consisting of immobilized formate dehydrogenase on titanium dioxide (TiO2|FDH) producing up to 1.16±0.04 mmolformate gTiO2-1 in 24 hours. Isotopic labelling experiments with 13C-labelled substrates support the mechanism of stoichiometric formate formation through both redox half-reactions. TiO2|FDH was further immobilized on hollow glass microspheres to perform more practical floating photoreforming allowing vertical solar light illumination with optimal light exposure of the photocatalyst to real sunlight. Enzymatic cellulose depolymerization coupled to the floating photoreforming catalyst generates 0.36±0.04 mmolformate mirr-2 after 24 h. This work thus presents simultaneous solar-driven valorization of waste streams, demonstrates the advantages of biohybrid photocatalysts in photoreforming for the first time and will provide inspiration for the development of future semi-artificial waste-to-chemical conversion strategies.

Over the past decade, lead-halide perovskites (LHPs) have demonstrated significant potential in terms of their performance across a wide range of optoelectronic devices, including solar cells, photodetectors and light-emitting diodes. However, the toxicity of lead and instability issue of LHPs are still concerns for their widespread implementation. These successes, but also the challenges of LHPs have motivated great efforts across multiple disciplines to search for lead-free and stable alternatives that can have similar optoelectronic properties to LHPs, namely ‘perovskite-inspired materials (PIMs)’. With the deeper understanding of defect tolerance displayed in LHPs, a large number of PIMs have been identified until now. Among all the identified PIMs, ternary chalcogenides or ABZ2 materials, are believed to be one of the most promising alternatives so far, owing to their simple fabrication protocols, strong absorption and high stability in air. Particularly, AgBiS2 solar cells have demonstrated the highest efficiency (9.17%) among all bismuth-based solar cells. Nevertheless, studies into ternary chalcogenides are mostly limited to AgBiS2 photovoltaics, and the investigations into other potential ABZ2 materials or broader applications are rare so far. Therefore, this thesis will aim to investigate the optoelectronic properties of another promising while rarely investigated ABZ2 material – NaBiS2, and also the potential of AgBiS2 as near-infrared (NIR) photodetectors. In the first project of this thesis, NaBiS2 nanocrystals (NCs) have been shown to exhibit extremely strong absorption, along with a comparatively sharp absorption onset. However, optical-pump-terahertz-probe (OPTP) measurements indicated that most free charge-carriers in NaBiS2 NCs will be localised within a few picoseconds. These localised charge-carriers only exhibited low mobility of around 0.03 cm2 V-1 s-1 and could not transport effectively even though they might be rather long-lived in NaBiS2 and unaffected by intentionally-introduced defects. With help from density functional theory (DFT) calculations, all of these unusual characteristics in NaBiS2 have been shown to closely associate with intrinsic cation disorder, which was also observed in AgBiS2. Although post-annealing is effective for improving cation inhomogeneity and enhancing absorption in AgBiS2, its effect on NaBiS2 was found to be rather minor, which also indicated that the charge-carrier localisation process in NaBiS2 could not be significantly mitigated after annealing. Based on the fundamental insights acquired in the first project, the possibility of further improving charge-carrier transport in NaBiS2 NCs through ligand exchange treatment was investigated in my second project. Using a variety of correlated spectroscopic characterisation techniques, I found that NaBiS2 NCs treated by inorganic iodide ligands had enhanced sum mobility and surface photovoltage (SPV) signals, which implies an improvement in the macroscopic charge-carrier transport. However, the ultrafast localisation process was still observed in these iodide-treated NaBiS2 NCs, suggesting that their cation disorder was not greatly changed. At the same time, the defect capture rates were also found to be lower in the iodide-treated NaBiS2 NCs based on my two proposed models for describing charge-carrier dynamics. As a result, solar cells based on these iodide-treated NaBiS2 NCs could exhibit a peak external quantum efficiency (EQE) value over 50%, along with a power conversion efficiency exceeding 0.7%. Although this is an order of magnitude larger than previous reports, I found ion migration to be a limiting factor for NaBiS2 devices from temperature-dependent transient current measurements, where a low activation energy of only 88 meV was extracted. In my third project, AgBiS2 photodetectors were fabricated and characterised in depth. Aside from the broadband photo-response across from ultra-violet (UV) to near-infrared (NIR) region, AgBiS2 photodetectors have demonstrated an extremely high cut-off frequency (f-3dB) on MHz order, indicating their great potential in applications requiring fast device response such as optical communications. The mechanism behind this fast response was studied, and a relatively long drift length compared to the AgBiS2 film thickness is believed to be the key reason. Similar to NaBiS2 devices, ion migration was also found easy in AgBiS2 devices with an activation energy of 124 meV, which could lead to their increasing noise currents with time. Importantly, these noise currents could be also effectively suppressed when optimising the AgBiS2 film thickness, in which a balance between large shunt resistant and cumulative quantity of defects should be reached. Finally, owing to the small bandgap of AgBiS2 NCs (~1.2 eV), AgBiS2 photodetectors could effectively monitor the heartbeat rates by probing the transmission change of blood vessels illuminated by NIR light, which has been widely used in the medical field owing to its deeper penetration in tissues. These three projects not only uncovered several remarkable optoelectronic characteristics of ABZ2 materials, but also investigated possible methods to further alter these characteristics. Although ABZ2 materials have shown great potential as light harvesters, it can be seen that both cation disorder (or charge-carrier localisation) and ion migration are still limiting the performance. More studies on the root causes of both phenomena, and how to effectively suppress their effects on the materials, would be hence crucial in the future work. With more understandings on this material class, we could expect more efficient, stable, and cleaner optoelectronic devices to be realised in the future.

The optical and photovoltaic properties of Si NCs / SiC multilayers (MLs) are investigated using a membrane-based solar cell structure. By removing the Si substrate in the active cell area, the MLs are studied without any bulk Si substrate contribution. The occurrence is confirmed by scanning electron microscopy and light-beam induced current mapping . Optical characterization combined with simulations allows us to determine the absorption within the ML absorber layer, isolated from the other cell stack layers. The results indicate that the absorption at wavelengths longer than 800 nm is only due to the SiC matrix. The measured short-circuit current is significantly lower than that theoretically obtained from absorption within the ML absorber, which is ascribed to losses that limit carrier extraction. The origin of these losses is discussed in terms of the material regions where recombination takes place. Our results indicate that carrier extraction is most efficient from the Si NCs themselves, whereas recombination is strongest in SiC and residual a-Si domains . Together with the observed onset of the external quantum efficiency (EQE) at 700-800 nm, this fact is an evidence of quantum confinement in Si NCs embedded in SiC on device level.