Composition and Interface Engineering of High Performing Perovskite Solar Cells

Perovskite solar cells have been established as a disruptive technology in the domain of photo-voltaics. Their facile, low-temperature processing and high-power conversion efficiency make them stand-out among other mature solar technologies. The performance of perovskite solar cells is pro-foundly tied to an interplay of material properties of singular thin films that are assembled to form the photovoltaic device stack. An understanding of optoelectronic, morphological, and other key charac-teristics of each layer and its interfaces is instrumental in advancing the science of perovskite solar cells. Since their inception after just over a decade, much work on perovskite solar cell has been stag-nant to bring the technology to the market. The long-term stability remains foremostly the main hin-drance to facilitating technology transfer. Therefore, the work presented in this thesis explores multi-ple interface and compositional approaches to promote stability and other photovoltaic parameters of perovskite solar cells.In the second chapter of the thesis, a light-soaking exploration was done on perovskite sam-ples that utilize single (TiO2 and SnO2) and bilayered (TiO2/SnO2) electron transporting materials. The work aims to expand consensus on the optoelectronic and morphological features of light-soaked samples and link them with long-term stability. Upon preliminary testing, maximum power point tracking on each sample reveals efficiency preservation of SnO2 and TiO2/SnO2 samples over the course of 1000 hours while prominent degradation was revealed for the TiO2 sample. On a secondary investigation, light-soaking characterizations were performed where fresh and light-soaked samples were characterized to obtain photoluminescence, microscopic, and crystallographic features. The work reveals the added benefit of employing TiO2/SnO2 transporting bilayers to improve both the stability and power conversion efficiency of a perovskite solar cell. Building on an effort to understand TiO2/SnO2 bilayer behaviors, the third chapter investigates the role of halide passivating elements in SnO2 on the performance of perovskite solar cells. The study utilizes three metalorganic precursors based on acetylacetone complexes with chloride and bromide groups to fabricate SnO2 layers at different annealing temperatures. Upon thermal and elemental in-vestigations, the study clearly links the presence of amorphous halide elements in SnO2 to the power conversion efficiency of perovskite solar cells. More-in-depth, the optimal SnO2 annealing tempera-ture for bromide containing samples 250 ï°C compared with 220 ï°C for chloride containing samples. The higher temperature tolerance tendency was correlated to bromideâs lower sublimation sensitivity. Overall, the study highlights the importance of amorphous passivating elements in SnO2 for high per-forming planar perovskite solar cells. Finally, the fourth chapter involves a novel cation mixing approach for 2D perovskites at the interface of the 3D perovskite and the hole transporting layer. Alkyl ammonium halides have been widely used to form light-stable 2D perovskite films upon interaction with excess PbI2. In this study, different alkyl chain cations (propylammonium iodide and octylammonium iodide) were mixed in one solution to form a novel 2D perovskite crystal lattice. Photoluminescence and x-ray diffraction spec-troscopy investigations reveal a unique crystal lattice and a uniform quasi-2

Computational Modeling of Thin-Film Silicon Solar Cells and Modules

Thomas Andreas Lanz

Solar photovoltaic energy production relies on the direct conversion of sunlight into electricity. Silicon thin-film solar cells represent a reliable and environmentally friendly technology to make photovoltaics economically viable. As these solar cells do not contain any rare or toxic materials they are an ideal candidate for the large scale deployment of solar energy. At the same time photovoltaic energy production is ideal for off-grid, stand-alone installations. This thesis presents new methods and results on computational engineering of thin-film silicon solar cells and modules. Computational engineering employs numerical methods and simulation techniques to address engineering challenges. Predictive numerical simulations allow for device optimizations that otherwise require substantial experimental effort and they may lead to new insights into the device physics which is the basis for further improvements in terms of cell efficiency and lifetime. We discuss the development of two new simulation methods and present several case studies that illustrate their use in solar cell characterization and optimization. The first presented method addresses optical simulations, i.e. the interaction of the solar cell with sunlight. Our optical model is based on the net-radiation method that considers incoherent, ray-like propagation of light. We extend the net-radiation method with thin-film optics to allow for arbitrary sequences of thick and thin layers. Experimentally, advanced techniques such as optimized surface textures have been developed to increase the absorption in the solar cell and thereby to increase the produced current. We illustrate how our optical model takes into account these textures by means of azimuth integrated light scattering properties to formulate a computationally efficient model of light propagation within the solar cell. Our optical model thus integrates coherent and incoherent propagation of light as well as a non-iterative treatment of ligth scattering. It bridges the gap between wave and ray optics that alternative approaches are most often facing. We first apply the method to study a recently proposed rear electrode architecture based on lithium fluoride and aluminum in amorphous silicon solar cells. Our model-based optical analysis identifies the increased reflectivity of this back electrode as its main advantage. Secondly, we then explore the potential performance gains in microcrystalline silicon solar cells that can be reached by eliminating absorption in layers that do not contribute to the photogeneration of solar cell current. Finally, our optical model is also suited for other solar cell technologies and we illustrate its extension and application to light extraction calculations in light emitting diodes (LEDs). Our optical model has been incorporated into the software package setfos, commercialized by Fluxim Inc. It is thus available to the research community. We then turn to address large area solar modules. A new method based on the finite element method (FEM) is presented to calculate the electrical charge and heat transport in these devices and how it is influenced by defects as well as partial shading. We identify such defects with surface temperature measurements by means of lock-in thermography and demonstrate how our model accounts for the thermal signature of localized defects. Taking into account the large aspect ratio of thin-film solar modules we show how geometrical projections can be used to reduce the model complexity, leading to a numerically efficient approach based on the finite element method. We demonstrate this by presenting full current-voltage curves of solar modules under partial shading.

EPFL2013

Investigation of Lead-free perovskites for Optoelectronic Application

Alexander Fedorovskiy

The search for new energy sources and materials is at the foundations of scientific and technological progress. These two, often interconnected, fundamental elements open a way to create novel designs and improve existing ones for all types of machines and devices.Perovskite solar cells (PSCs) are a great example of this kind of system. Achievements in halide perovskite materials research made a remarkably rapid growth of energy conversion efficiency in PSC technology possible. In turn, a manufacturing process for the technology is potentially cheaper and more straightforward (relative to Si-based). As a result, the PSCs can be a solid background for producing the next generation of solar cells.However, unfortunately, PSCs are still not ready for a market, primarily because of three problems: large-scale production, stability, and toxicity. The first problem is mainly a result of the rawness of the technology, requires mostly resolving engineering tasks, and is not a fundamental barrier. The second problem â stability has a deeper connection to the properties of the material itself. The nature of degradation processes in PSCs is not completely clear. Still, different studies have found some promising ways to stabilize PSCs for a range of thousands of hours. Thus, a combination of engineering and material research can solve this problem, despite its deeper basis.The third problem, toxicity, is a fundamental property of the high efficient PSCs because of its lead-based compound. Lead is one of the critical components of halide perovskites used in the technology, and at the same time, this metal has confirmed toxicity. The water solubility of lead in halide perovskites (primarily as PbI2 and PbBr2) complicates the situation for the whole lifecycle of the devices - from production to recycling. The toxicity of the materials used in PSCs can affect one of the main goals of solar energy: to be produced safe, clean, and sustainable.Taking into account these facts, I focused this thesis on searching for lead-free alternatives for PSCs.Initially, I focused on searching for a model to predict promising vacancy-ordered double perovskites' formability as part of initial screening. I demonstrated the applicability of the geometrical approach based on Goldschmidt's Tolerance Factor for a simple, easy-to-use formability prediction technique for this class of materials. During this part of the study, I also demonstrated a difference between using the method for classic and vacancy-ordered perovskites.In the next part, I used a novel approach based on deep learning to design a new model of perovskite formability. As a result, I successfully forecast perovskite formability with an accuracy of over 98% for the best case. Moreover, I found that the resulting models were able to find some inaccuracies in the original data.Following, I synthesized and researched the structure and properties of tellurium-based vacancy-ordered perovskites. During the research, I found an unexpected complex situation of the optical gap determination for the materials. To solve this challenge, I demonstrated different approaches of absorption spectra fitting and cross-referenced it with other experimental data.

EPFL2021

Material Development for Perovskite/Silicon Tandem Photovoltaics

Peter Joseph Fiala

The developed world is built on the fact that energy is readily available and functionally infinite. The electricity from the wall, the gas at the station, and the heat in our homes are reliable and low-cost. But this comfort is so far only possible through the combustion of fossilized carbon sources. This is not a sustainable system. Not only are these sources finite, but the long-term effects of this much combustion are catastrophic for our planet and species. Transitioning from current energy production to sustainable sources will require the development and deployment of a diverse group of technologies. Chief among these is the generation of electricity from sunlight, or photovoltaics (PV).Most modern PV is based on crystalline silicon. Silicon PV alone could be scaled to provide the necessary energy production, but this could be realized more quickly and efficiently if more advanced technologies are used. The defining metric is the cost per generated electricity. In the case of silicon, the current cost breakdown of materials, manufacturing, installation, and system costs leaves little room for further price reduction; and light-to-electricity efficiencies are near their practical limit. Of the proposed alternatives, the pairing of silicon with a thin film of lead-halide perovskite in a multijunction or "tandem" architecture is one of the most promising. This splits the solar spectrum in two, and raises the theoretical maximum efficiency from 33.3% to 45.1% based on each material better using its segment than any one material could use the full spectrum. The central goal of this thesis was therefore to advance the capability of this type of solar cell while remaining within the constraints of industrially-plausible production methods.Towards this goal, we first isolated perovskite layers to study what limits their performance. This led to improvements in the bulk material quality, the interfaces with adjacent materials, and the layer morphology. We reduced bulk disorder via balancing the annealing temperature, time, and environment. The interfaces were improved by selecting passivating materials which were compatible with our deposition methods. We further observed a complex interplay between the materials used and the environment of the annealing, which illuminated critical dependencies of device performance and gave us a more complete understanding of our material. Finally the morphology was improved via high-temperature annealing. This was enabled by a surface-binding additive which reduced the detrimental effects of such an anneal while preserving the benefits, resulting in a perovskite with less internal resistance. From there, we moved outside of the perovskite layer and developed a light scattering ZnO layer which increased the optical performance and absorption of our cells. Returning to the main goal of the thesis, the lessons learned from work on isolated perovskites were applied in tandems on textured silicon. We additionally increased the perovskite layer thickness and made the bottom-cell more robust to processing damages. Together, the result was a stabilized efficiency of 27.3%. This is better than any silicon cell to date, but work remains to achieve 30% and beyond, extend material stability, scale up the deposition area, and transfer these capabilities to industry. Together, the work done as a part of this thesis represents a step forward in the journey towards carbon-neutral energy production.

EPFL2022