The emergence of concentrator photovoltaics for perovskite solar cells

The emergence of high-efficiency photovoltaic research is undergoing intense study and is technologically desirable to meet sustainable energy and environmental demand. However, every single solar cell has a theoretical power conversion efficiency limit, and, thus, without compromising the cost, the power conversion efficiency enhancement of a solar cell is highly challenging. As a convenient solution, concentrating photovoltaics can focus sunlight onto an extremely high-efficiency solar cell integrating various optics. Concentrating photovoltaics use optical devices that collect and redirect the light toward the smaller photovoltaic cell and reduce the demand for the mined elements required for the solar cell fabrication. The research interest from the photovoltaic community has concentrated on organic-inorganic hybrid halide perovskite absorbers, and nowadays, perovskite solar cells manifest their outstanding contribution among the low-cost photovoltaic technologies. Inevitably, large-area perovskite solar cells suffer a lot with their poor stability, hindering their commercialization pace. Thus, the implementation of concentrating photovoltaic technology in perovskite solar cells demonstrates an inherent advantage using a smaller size solar cell. This review provides an overview of concentrating photovoltaic technology implementation, including their recent research and development portfolio, their economic benefits in combination with inexpensive optical elements and tracking systems, limitations, challenges, and relative scope of the future study, focusing on the emerging perovskite solar cell technology.

Strategies to Optimizing Dye-Sensitized Solar Cells

Sophie Wenger

Dye-sensitized solar cells (DSCs) constitute a novel class of hybrid organic-inorganic solar cells. At the heart of the device is a mesoporous film of titanium dioxide (TiO2) nanoparticles, which are coated with a monolayer of dye sensitive to the visible region of the solar spectrum. The role of the dye is similar to the role of chlorophyll in plants; it harvests solar light and transfers the energy via electron transfer to a suitable material (here TiO2) to produce electricity — as opposed to chemical energy in plants. DSCs are fabricated of abundant and cheap materials using inexpensive processes (e.g. screen-printing) and are likely to be a significant contributor to the future commercial photovoltaic technology portfolio. The work conducted during this thesis aimed at optimizing the DSC using three different strategies: The use of versatile organic sensitizers for stable and efficient DSCs, the study of tandem device architectures in combination with other solar cells to harvest a larger fraction of the solar spectrum, and the development of a validated optoelectric model of the DSC. Organic donor-π-acceptor dyes are an interesting alternative to the standard metal-organic complexes used in DSCs. Efficient photovoltaic conversion and stable performance could be demonstrated with three classes of donor systems, namely diphenylamine, difluorenylaminophenyl, and π-extended tetrathiafulvalene. The highest conversion efficiencies were obtained with a difluorenylaminophenyl donor system (η = 8.3 % with a volatile electrolyte and η = 7.6 % with a solvent-free ionic liquid, which was a new record for organic dyes at the time of publication). Surprisingly, efficient regeneration of the oxidized dye by the I-/I3- redox mediator was found with the π-extended tetrathiafulvalene system, even though the thermodynamic driving force was as low as 150 mV. So far driving forces of 300-500 mV had been regarded as necessary for efficient regeneration of the dye cation. Also, important structure-property relationships pertaining to the recombination of electrons with the electrolyte and to the stability of the device could be identified (i.e. effect of linear vs. branched structure, linker length, and moieties used). The power conversion efficiency of solar cells can be extended beyond the limit for a single cell (∼ 30 %) by using multiple cells with different optical gaps in a tandem device. DSCs and chalcopyrite Cu(In,Ga)Se2 (CIGS) solar cells have complementary optical gaps and are thus suitable systems for integration in a tandem device. It was shown that a monolithic DSC/CIGS tandem device has the potential for increased efficiency over a mechanically stacked device due to increased light transmission to the bottom cell, and a monolithic DSC/CIGS device with an initial efficiency of η = 12.2 % was demonstrated. The degradation of the devices — induced by the corrosion of the CIGS cell in contact with the I-/I3- redox mediator — could be retarded with a protective thin conformal ZnO/TiO2 oxide layer coated on the CIGS cell by atomic layer deposition. Finally, an experimentally validated optical and electrical model of the DSC has been developed to assist the optimization process, which is predominantly conducted by empirical means in the DSC research community. The optical model allows to accurately calculate the internal quantum efficiency of devices, i.e. the ratio of extracted electrons to absorbed photons by the dye, a crucial and so far difficult to determine characteristic. Intrinsic parameters — like injection efficiency, electron diffusion length, or distribution of trap states in the TiO2 — can be extracted from experimental steady-state and time-dependent data with the electric model. The model allows to make a comprehensive and quantitative loss analysis of the different optical and electric loss channels in the DSC. The model has been implemented with a graphical user interface for straightforward usage. All three optimization strategies — organic dyes, tandem architecture, and device modeling — developed during this thesis make a valuable contribution to the development and commercialization of inexpensive and high efficiency DSCs. They enable a comprehensive view of the system and pave the way for a systematic analysis and reduction of losses, which has been the ultimate route to success for several established photovoltaic technologies.

EPFL2010

Interface engineering in solid-state dye-sensitized solar cells

Jessica Krüger

Dye-sensitised nanocrystalline solar cells are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic device. In particular dye-sensitised cells based on spiro-MeOTAD have gained attention as promising approach towards an organic solid-state solar cell. However, the efficiency in such dye-sensitised solid-state solar devices (SSD) was so far only ca. 10 % of the values reported at AM1.5 for the classical dye-sensitised solar cell with an electrolyte hole transporting medium (DSSC). The objective of the present work is to study the limitations that emerge from the exchange of the electrolyte by the solid-state system and that oppose photovoltaic photon-to-electron conversion as high as for the DSSC. Interfacial charge recombination is an important loss mechanism in dye-sensitised solar cells. This is particularly true for SSD, as the solid hole-transporting medium is less efficient in screening of internal fields which assist recombination. A variety of strategies were tested in the SSD to minimise interfacial charge recombination. The most promising approach was the blending of the hole-transporting medium with tert.-butylpyridine (tBP) and lithium ions. Optical and electrochemical techniques, such as nanosecond laser spectroscopy, impedance spectroscopy and photovoltaic characterisation measurements, were used to study the impact of the additives on the SSD. Both lithium ions as well as tBP were found to increase the open circuit potential of the SSD. At the same time tBP was found to considerably lower the current output. The interaction of the additives was studied and their concentration in the spiro-MeOTAD medium optimised. The doping of the spiro-MeOTAD film, which was intended to support the hole transport, was found to enhance interfacial recombination significantly. The morphological properties of the TiO2, in particular layer thickness, particle size and film porosity, play a more important role in the SSD than in the DSSC. Penetration of the hole conductor into the TiO2 pores and electron diffusion length are coupled to these properties. As a result the light harvesting cannot be controlled at will via the TiO2 film thickness and the active surface area for dye adsorption. An enhanced light harvesting for thin TiO2 layers offers advantages for the charge transport and the formation of the interpenetrating network. The dye uptake in presence of silver ions was found to increase the dye loading and to significantly improve the device performance of thin TiO2 layer devices. The mechanism of this simple dye modification technique was studied by a variety of spectroscopic techniques. From spectroscopic evidence it is inferred that the silver is binding to the sensitiser via the ambidentate thiocyanate, allowing the formation of ligand-bridged dye complexes. The beneficial influence of the silver ions on the photovoltaic performance was not limited to the application of the standard N3 dye nor to the spiro-MeOTAD. SSDs were furthermore studied by frequency resolved techniques. Intensity modulated photocurrent spectroscopy (IMPS) and intensity modulated photovoltage spectroscopy (IMVS) were performed over a wide range of illumination intensities. The IMPS and IMVS responses provide information about charge transport and electron-hole recombination processes respectively. For the range of light intensities investigated, the dynamic photocurrent response appears to be limited by the transport of electrons in the nanocrystalline TiO2 film rather than by the transport of holes in the spiro-MeOTAD. The diffusion length of electrons in the TiO2 was found to be 4.4 μm. This value was almost independent of the light intensity as a consequence of the fact that the electron diffusion coefficient and the rate constant for electron-hole recombination both increase in the same way with light intensity but with opposite sign. The results of this work provide for a substantial improvement of the overall photovoltaic performance compared to earlier results for this type of SSD. However, this study reveals also that high conversion efficiencies as are measured for DSSC are not likely to be reachable with the spiro-MeOTAD system due to the significantly slower charge transport in the spiro-MeOTAD compared to the electrolyte redox mediator.

EPFL2003

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