Intermediate Phase Enhances Inorganic Perovskite and Metal Oxide Interface for Efficient Photovoltaics

Interfacial modification is crucial to fully develop the potential of semiconductor devices, including the revolutionary halide perovskite-based optoelectronics, such as photovoltaics, light-emitting diodes, and photodetectors. The all-inorganic halide perovskites, which are potential long-term stable photovoltaic materials, are suffering from poor interfacial contact with metal oxide charge-selective layer, severely limiting the power conversion efficiency and stability of inorganic perovskite solar cells. Here, we propose an intermediate-phase engineering strategy to improve the inorganic perovskite/metal oxide interface by utilizing volatile salts. The introduction of organic cations (such as methylammonium and formamidinium), which can be doped into the perovskite lattice, leads to the formation of an organic-inorganic hybrid perovskite intermediate phase, promoting a robust interfacial contact through hydrogen bonding. A champion CsPb(I0.75Br0.25)(3)-based device with a power conversion efficiency of 17.0% and an open-circuit voltage of 1.34 V was realized, implying that a record of over 65% of the Shockley-Queisser efficiency limit is achieved.

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

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

Spectral splitting photovoltaics using perovskite and wideband dye-sensitized solar cells

Antonio Abate, Fabrizio Giordano, Michael Graetzel, Ulf Anders Hagfeldt, Mohammad Khaja Nazeeruddin, Kazuteru Nonomura

The extension of the light absorption of photovoltaics into the near-infrared region is important to increase the energy conversion efficiency. Although the progress of the lead halide perovskite solar cells is remarkable, and high conversion efficiency of >20% has been reached, their absorption limit on the long-wavelength side is similar to 800 nm. To further enhance the conversion efficiency of perovskite-based photovoltaics, a hybridized system with near-infrared photovoltaics is a useful approach. Here we report a panchromatic sensitizer, coded DX3, that exhibits a broad response into the near-infrared, up to similar to 1100 nm, and a photocurrent density exceeding 30 mA cm(-2) in simulated air mass 1.5 standard solar radiation. Using the DX3-based dye-sensitized solar cell in conjunction with a perovskite cell that harvests visible light, the hybridized mesoscopic photovoltaics achieved a conversion efficiency of 21.5% using a system of spectral splitting.