Lessons learned from device modeling of organic & perovskite solar cells

Our rising need for energy combined with the realization that we need to drastically reduce our consumption of fossil energy to mitigate climate change, forces us to find better and cleaner ways to produce energy. While the price of solar energy has significantly decreased over the past two decades there is still a long way to go for solar to be a truly important part of our energy production.To increase the relative proportion of our energy produced with solar we not only need to make more efficient solar panels but also diversify the applications. Organic and perovskite solar cells present advantages for both objectives, they can be used in combination with classical technology in tandem or multi-junction structures to improve their efficiency. They can also be used in a broader range of applications as both technology can be solution-processed, made flexible, semi-transparent and perform well under low light intensity conditions. These characteristics open many doors for the future, where solar energy production will not only be confined to roof-top and solar farms applications but also in a more building-integrated fashion such as semi-transparent solar windows or even used to power internet of things products.In the work presented in this thesis, we used simulation to gain more insight into the limitations of organic and perovskite solar cells, whether those are due to a poor extraction or significant recombination. We provide guidelines on how to optimize the solar cells and also refined the analysis of known characterization methods to make them adequate for this class of materials studied

Influence du climat, de la disponibilité des ressources et de la taille des populations sur la phénologie et les patrons de migration du caribou migrateur, "Rangifer tarandus"

De nombreuses populations migratrices sont actuellement en déclin. Les changements climatiques entrainent des modifications dans les habitats des espèces migratrices et la phénologie des processus naturels, lesquels se répercutent sur la migration, une période critique pour ces espèces. Comprendre comment les variables environnementales et climatiques affectent la phénologie et les patrons de migration est donc crucial. Ma thèse s'intéresse à l'impact du climat, des ressources alimentaires et de la compétition sur les migrations printanières et automnales des caribous migrateurs, Rangifer tarandus, des troupeaux Rivière-George (TRG) et Rivière-aux-Feuilles (TRF) du Nord-du-Québec et du Labrador. Le premier volet de ma thèse propose une approche objective, basée sur la détection des changements dans la structure des déplacements saisonniers, pour identifier les dates de départ et arrivée en migration. Validée à l'aide de trajets simulés, elle a été appliquée aux migrations printanières et automnales de femelles caribous. Le second volet porte sur l'impact des conditions environnementales sur la phénologie des migrations de printemps et d'automne. Il montre que la phénologie de la migration est principalement affectée par les conditions climatiques rencontrées lors de la migration, les conditions d'enneigement affectant notamment les coûts des déplacements. Au printemps, les caribous subissent des conditions défavorables lorsque la fonte des neiges est précoce. À l'automne, ils semblent ajuster leurs déplacements et migrent plus vite quand la neige débute tôt pour limiter les coûts de déplacement dans une neige profonde. Le troisième volet porte sur les patrons de migration à l'automne et montre que ceux-ci sont affectés essentiellement par une compétition intra- et inter-troupeaux pour les aires d'hivernages. Les caribous du TRG répondent à une augmentation de la compétition sur les aires les plus proches de l'aire de mise bas, liée à une taille de population élevée, en migrant préférentiellement vers les aires les plus éloignées. L'utilisation des aires hivernales par les caribous du TRF est, quant à elle, contrainte par la présence et l’abondance du TRG, cette contrainte diminuant à mesure que le TRG décline et abandonne les migrations vers les aires d'hivernages communes aux deux troupeaux. Cette thèse améliore notre compréhension de l'influence des facteurs environnementaux sur la phénologie et les patrons de migration du caribou migrateur. Ces connaissances sont très utiles pour comprendre l'impact des changements climatiques et établir les plans de conservation pour les espèces migratrices.Several populations of migratory species are actually declining. Climate changes affect the habitat of migratory species and the phenology of natural processes, and impact the migration, a critical period for migratory species. Thus, it is crucial to understand how environmental and climatic variables affect the timing and the patterns of migration. This thesis assesses the impact of climate, food resources and competition on the spring and fall migrations of migratory caribou, Rangifer tarandus, from the Rivière-George (RGH) and Rivière-aux-Feuilles (RFH) herds, in Northern Québec and Labrador. The first part of my thesis presents an objective approach, based on the detection of changes in the structure of seasonal movements, to assess the departure and the arrival dates of the migrations. The approach was validated on simulated paths, and was then applied on the spring and fall migrations of female caribou. The second part focuses on the impact of environmental conditions on the phenology of the spring and fall migrations. It revealed that migration is mainly affected by the climatic conditions encountered during migration, snow conditions partly determining the cost of movements. In the spring, caribou suffer from adverse conditions when the snowmelt is early. In the fall, caribou adjust their movements and migrate faster when snowfall occurs early to limit the cost of moving through deep snow. The third part of my thesis focuses on fall migration patterns and revealed that migration patterns are mainly affected by intra- and inter-herds competition for the winter ranges. Caribou from RGH migrate preferentially toward the furthest winter ranges in response to increased competition, linked with a high population size, limiting the competition on the closest winter ranges. The use of the winter ranges by caribou from RFH is constrained by the abundance of RGH. This constraint decreased as RGH declined and abandoned the migrations toward the winter ranges commonly used by both herds. My thesis increases our knowledge of the environmental factors that affect the phenology and patterns of caribou migrations. This knowledge is useful to understand the impact of climate changes and establish conservation plans for migratory species

Detecting changes in the annual movements of terrestrial migratory species : using the first-passage time to document the spring migration of caribou

Background : Migratory species face numerous threats related to human encroachment and climate change. Several migratory populations are declining and individuals are losing their migratory behaviour. To understand how habitat loss or changes in the phenology of natural processes affect migrations, it is crucial to clearly identify the timing and the patterns of migration. We propose an objective method, based on the detection of changes in movement patterns, to identify departure and arrival dates of the migration. We tested the efficiency of our approach using simulated paths before applying it to spring migration of migratory caribou from the Rivière-George and Rivière-aux-Feuilles herds in northern Québec and Labrador. We applied the First-Passage Time analysis (FPT) to locations of 402 females collected between 1986 and 2012 to characterize their movements throughout the year. We then applied a signal segmentation process in order to segment the path of FPT values into homogeneous bouts to discriminate migration from seasonal range use. This segmentation process was used to detect the winter break and the calving ground use because spring migration is defined by the departure from the winter range and the arrival on the calving ground. Results : Segmentation of the simulated paths was successful in 96% of the cases, and had a high precision (96.4% of the locations assigned to the appropriate segment). Among the 813 winter breaks and 669 calving ground use expected to be detected on the FPT profiles, and assuming that individuals always reduced movements for each of the two periods, we detected 100% of the expected winter breaks and 89% of the expected calving ground use, and identified 648 complete spring migrations. Failures to segment winter breaks or calving ground use were related to individuals only slowing down or performing less pronounced pauses resulting in low mean FPT. Conclusion : We show that our approach, which relies only on the analysis of movement patterns, provides a suitable and easy-to-use tool to study species exhibiting variations in their migration patterns and seasonal range use

Impact of Electrodes on Recombination in Bulk Heterojunction Organic Solar Cells

In recent years, the efficiency of organic solar cells (OSCs) has increased to more than 13%, although different barriers are on the way for reaching higher efficiencies. One crucial barrier is the recombination of charge carriers, which can either occur as the bulk recombination of photogenerated charges or the recombination of photogenerated charges and electrodic induced charges (EICs). This work studies the impact of EICs on the recombination lifetime in OSCs. To this end, the net recombination lifetime of photogenerated charge carriers in the presence of EICs is measured by means of conventional and newly developed transient photovoltage techniques. Moreover, a new approach has been introduced to exclusively measure the bulk recombination lifetime, i.e., in the absence of EICs; this approach was conducted by depositing transparent insulating layers on both sides of the OSC active layer. An examination of these approaches on OSCs with different active layer materials, thicknesses, and varying light intensities determined that the EICs can only reduce the recombination lifetime of the photogenerated charges in OSCs with very weak recombination strength. This work supports that for OSCs with highly reduced recombination strength, eliminating the recombination of photogenerated charges and EICs is critical for achieving better performance. Therefore, the use of a proper blocking layer suppresses EIC recombination in systems with very weak recombination.</p

Identification of the dominant recombination process for perovskite solar cells based on machine learning

Over the past decade, perovskite solar cells have become one of the major research interests of the photovoltaic community, and they are now on the brink of catching up with the classical inorganic solar cells, with efficiency now reaching up to 25%. However, significant improvements are still achievable by reducing recombination losses. The aim of this work is to develop a fast and easy-to-use tool to pinpoint the main losses in perovskite solar cells. We use large-scale drift-diffusion simulations to get a better understanding of the light intensity dependence of the open-circuit voltage and how it correlates to the dominant recombination process. We introduce an automated identification tool using machine learning methods to pinpoint the dominant loss using the light intensity-dependent performances as an input. The machine learning was trained using >2 million simulations and gives an accuracy of the prediction up to 82%. Le Corre et al. demonstrate the application of machine learning methods to identify the dominant recombination process in perovskite solar cells with 82% accuracy. The machine learning algorithms are trained and tested using large-scale drift-diffusion simulations, and their applicability on real solar cells is also demonstrated on devices previously reported

Charge Carrier Extraction in Organic Solar Cells Governed by Steady-State Mobilities

Charge transport in organic photovoltaic (OPV) devices is often characterized by steady-state mobilities. However, the suitability of steady-state mobilities to describe charge transport has recently been called into question, and it has been argued that dispersion plays a significant role. In this paper, the importance of the dispersion of charge carrier motion on the performance of organic photovoltaic devices is investigated. An experiment to measure the charge extraction time under realistic operating conditions is set up. This experiment is applied to different blends and shows that extraction time is directly related to the geometrical average of the steady-state mobilities. This demonstrates that under realistic operating conditions the steady-state mobilities govern the charge extraction of OPV and gives a valuable insight in device performance

Key Parameters Requirements for Non‐Fullerene‐Based Organic Solar Cells with Power Conversion Efficiency &gt;20%

The reported power conversion efficiencies (PCEs) of nonfullerene acceptor (NFA) based organic photovoltaics (OPVs) now exceed 14% and 17% for single‐junction and two‐terminal tandem cells, respectively. However, increasing the PCE further requires an improved understanding of the factors limiting the device efficiency. Here, the efficiency limits of single‐junction and two‐terminal tandem NFA‐based OPV cells are examined with the aid of a numerical device simulator that takes into account the optical properties of the active material(s), charge recombination effects, and the hole and electron mobilities in the active layer of the device. The simulations reveal that single‐junction NFA OPVs can potentially reach PCE values in excess of 18% with mobility values readily achievable in existing material systems. Furthermore, it is found that balanced electron and hole mobilities of &gt;10−3 cm2 V−1 s−1 in combination with low nongeminate recombination rate constants of 10−12 cm3 s−1 could lead to PCE values in excess of 20% and 25% for single‐junction and two‐terminal tandem OPV cells, respectively. This analysis provides the first tangible description of the practical performance targets and useful design rules for single‐junction and tandem OPVs based on NFA materials, emphasizing the need for developing new material systems that combine these desired characteristics

Understanding Dark Current-Voltage Characteristics in Metal-Halide Perovskite Single Crystals

Hybrid halide perovskites have great potential for application in optoelectronic devices. However, an understanding of some basic properties, such as charge-carrier transport, remains inconclusive, mainly due to the mixed ionic and electronic nature of these materials. Here, we perform temperature-dependent pulsed-voltage space-charge-limited current measurements to provide a detailed look into the electronic properties of methylammonium lead tribromide (MAPbBr(3)) and methylammonium lead triiodide (MAPbI(3)) single crystals. We show that the background carrier density in these crystals is orders of magnitude higher than that expected from thermally excited carriers from the valence band. We highlight the complexity of the system via a combination of experiments and drift-diffusion simulations and show that different factors, such as thermal injection from the electrodes, temperature-dependent mobility, and trap and ion density, influence the free-carrier concentration. We experimentally determine effective activation energies for conductivity of (349 +/- 10) meV for MAPbBr3 and (193 +/- 12) meV for MAPbI(3), which includes the sum of all of these factors. We point out that fitting the dark current density-voltage curve with a drift-diffusion model allows for the extraction of intrinsic parameters, such as mobility and trap and ion density. From simulations, we determine a charge-carrier mobility of 12.9 cm(2)/Vs, a trap density of 1.52 x 10(13) cm(-3), and an ion density of 3.19 x 10(12) cm(-3) for MAPbBr(3) single crystals. Insights into charge-carrier transport in metal-halide perovskite single crystals will be beneficial for device optimization in various optoelectronic applications

Caribou herd dynamics : impacts of climate change on traditional and sport harvesting

Caribou (Rangifer tarandus) are a key species in Arctic ecosystems including northern Québec and Labrador. They play a central role in the ecology of predators and the structure of Arctic plant communities. In addition, caribou provide socioeconomic and cultural benefits from subsistence and sport hunting activities. Changes in the distribution and abundance of caribou due to global climate change would have serious biological, societal, and economic implications. Direct and indirect consequences of climate change on migratory caribou herds may include alteration in habitat use, migration patterns, foraging behaviour and demography. For example, caribou may experience a further northerly shift in distribution due to several factors including longer ice-free periods, increases in snowfall and extreme weather events, alterations in the fire regime, and changes in the distribution of insects and predators. Future research by Caribou Ungava, a research group interested in the ecology of migratory caribou in the context of climate change, will address the factors outlining variations in the population dynamics of caribou, implications for survival and reproduction, as well as the response of caribou habitat to different climate change scenarios. Management efforts focusing on mitigating greenhouse gases to reduce the potential effects of climate change, preserving high quality habitat, limiting anthropogenic landscape disturbances, and managing hunting in a sustainable manner, could alleviate stressors on migratory caribou of the QuébecLabrador peninsula

The contamination of the surface of Vesta by impacts and the delivery of the dark material

The Dawn spacecraft observed the presence of dark material, which in turn proved to be associated with OH and H-rich material, on the surface of Vesta. The source of this dark material has been identified with the low albedo asteroids, but it is still a matter of debate whether the delivery of the dark material is associated with a few large impact events, to micrometeorites or to the continuous, secular flux of impactors on Vesta. The continuous flux scenario predicts that a significant fraction of the exogenous material accreted by Vesta should be due to non-dark impactors likely analogous to ordinary chondrites, which instead represent only a minor contaminant in the HED meteorites. We explored the continuous flux scenario and its implications for the composition of the vestan regolith, taking advantage of the data from the Dawn mission and the HED meteorites. We used our model to show that the stochastic events scenario and the micrometeoritic flux scenario are natural consequences of the continuous flux scenario. We then used the model to estimate the amounts of dark and hydroxylate materials delivered on Vesta since the LHB and we showed how our results match well with the values estimated by the Dawn mission. We used our model to assess the amount of Fe and siderophile elements that the continuous flux of impactors would mix in the vestan regolith: concerning the siderophile elements, we focused our attention on the role of Ni. The results are in agreement with the data available on the Fe and Ni content of the HED meteorites and can be used as a reference frame in future studies of the data from the Dawn mission and of the HED meteorites. Our model cannot yet provide an answer to the fate of the missing non-carbonaceous contaminants, but we discuss possible reasons for this discrepancy.Comment: 31 pages, 7 figures, 4 tables. Accepted for publication on the journal ICARUS, "Dark and Bright Materials on Vesta" special issu