Perovskite/Silicon Tandem Solar Cells: Toward Affordable Ultra-High Efficiency Photovoltaics ?

Nowadays the photovoltaics market is dominated by crystalline silicon solar cells, which are approaching their theoretical efficiency limit. Novel solutions have to be found for photovoltaics to further enhance its competitiveness with other energy sources. One of the most promising approaches lies in combining market-proven silicon solar cell technology, having a low optical band gap, with an efficient near-infrared transparent wide-band gap top cell to form a tandem cell. Organic-inorganic halide perovskite solar cells are promising candidates for top cells, showing high efficiencies with simple and cost-effective device fabrication. We first develop perovskite solar cells specifically for tandem applications. We develop and optimize a hybrid sequential deposition method combining thermal evaporation and solution processing to fabricate perovskite absorber materials with specifically tailored optoelectronic properties. These materials are systematically investigated for their optical, structural and electronic properties, and then applied in perovskite solar cells both in n-i-p and p-i-n configurations, for which we show several charge transport materials combinations. As a replacement for the standard metal opaque rear electrode of perovskite cells, we develop a TCO-based transparent electrode, for which sputtered IZO is presented as a good candidate thanks to its high carrier mobility and broadband transparency. Sputtering-induced damages are reduced by the introduction of a buffer layer: MoOx for n-i-p cells and SnO2 for p-i-n cells. The parasitic absorption losses in the MoOx are described in details. We then discuss the parasitic absorption losses in charge transport layers and TCOs, with experimental comparison of various materials. The optimisation of the perovskite absorber deposition method and the improvement of the charge transport layers and transparent electrode allows the fabrication 1cm2 area semitransparent perovskite solar cells with >16% efficiency. We then integrate the semitransparent perovskite cells in mechanically stacked 4-terminal tandem solar cells. The challenges in reducing the strong parasitic absorption and reflection losses are first discussed. We then demonstrate 4-terminal tandem measurements with >25% total efficiency with a small area top cell. With larger 1cm2 area top cells, we fabricate integrated 4-terminal tandem devices with both subcells having similar size and total efficiency >23%. The integration of perovskite solar cells in 2-terminal monolithically connected tandem solar cells with silicon heterojunction bottom cells is finally presented. First, we show the development of a TCO-based recombination layer and the important reflection losses and interference effects observed in all-flat devices. The origins of parasitic absorption losses in monolithic tandems are then explained and new architectures and materials are investigated supported by optical simulations. We then replace the polished wafers by fully textured silicon bottom cells for better light management. The development of a tandem device with the top cell conformally coated onto the textured bottom cell is explained, leading to >25% certified power conversion efficiency. The end of the thesis presents preliminary results on the up-scalability and light soaking stability of the developed textured tandems, as well as a proof-of-concept of a first perovskite/perovskite/silicon triple junction solar cell on textured wafers.

Advanced Architectures and Processing for High-Efficiency Silicon Heterojunction Solar Cells

Jonas Geissbühler

Crystalline silicon solar cells currently represent the largest part of the photovoltaic market. In response to the demand for higher efficiency devices, silicon heterojunction technology, which merges a crystalline silicon wafer with thin amorphous silicon (a-Si:H) films enabling the achievement of passivating contacts, may be considered as one of the most promising approaches for the next generation of industrial solar cells. These cells demonstrate record energy conversion efficiency enabled by excellent surface passivation leading to open-circuit voltages close to the theoretical limit. Despite the remarkable electronic properties of a-Si:H, its narrow bandgap induces significant parasitic light absorption. The aim of this thesis is to mitigate this loss through novel cell architectures and new fabrication processes. The outcome of this work is four-fold: First, a new silicon heterojunction solar cell structure is investigated that decouples the optical and electrical properties of the window layers through localized front contacts. By using shadow masking for the film patterning, we demonstrate the feasibility of the new cell structure under the condition that a sufficiently high contact coverage be maintained. Second, for the patterning of a-Si:H layers, we develop a hydrogen plasma etching technique carried out in a PECVD reactor. In particular, we show that a critical thickness of the intrinsic a-Si:H layer is needed to provide sufficient shielding of the amorphous/ crystalline interface to ensure good passivation. This technique enables the patterning of a-Si:H layers with nanometric accuracy while preserving the surface passivation. A third important outcome of this thesis is the replacement of the front metallization¿usually made by screen-printing of a silver paste¿with a copper front grid formed by electrodeposition. To ensure sufficient adhesion of the metallic fingers, a first process based on a double electrodeposition of a nickel/copper stack is presented. Important improvements in light management are realized with this metallization scheme, reducing the finger width from 70 um to 15 um which leads to a short-circuit gain of 1.1 mA cm2. In a second step, a simplified process based on a copper seed layer is proposed, further improving the metallization adhesion and making this technique compatible with chemically sensitive transparent conductive oxides such as zinc-oxide-based materials. The fourth outcome of this work is the replacement of the p-doped a-Si:H hole collector with a highly transparent molybdenum oxide (MoOx) film. We show that this material is an efficient hole collector if the post-deposition processes are carried out below 130 °C. From an optical point of view, this layer enables an improvement equivalent to 0.8 mA cm2 of the cell¿s response in the blue part of the spectrum. Nevertheless, this gain is reduced by the modification of the MoOx film induced during the TCO sputtering process, which leads to broadband parasitic light absorption. Finally, by merging this MoOx hole collector with the electrodeposited copper front metallization, remarkable fill factors of 80.3% are obtained leading to a certified efficiency of 22.5% for a 4 cm2 solar cell.

EPFL2015

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

L'oxyde de zinc par dépôt chimique en phase vapeur comme contact électrique transparent et diffuseur de lumière pour les cellules solaires

Sylvie Faÿ

Zinc oxide (ZnO) is a material that belongs to the family of Transparent Conductives Oxides (TCO). Its non-toxicity and the abundant availability in the Earth's crust of its components make it an ideal candidate as electrical transparent contact for thin-film amorphous and/or microcrystalline silicon solar cells. The Low-Pressure Chemical Vapour Deposition (LP-CVD) method allows one to obtain rough ZnO layers, which can effectively scatter the light that passes through them. This high scattering capacity increases the path of the light within the solar cell and therefore enhances its probability to be absorbed by the solar cell, and consequently the photogenerated current. This thesis work studies in detail the LP-CVD technology used for deposition of ZnO layers, which are employed as TCO layers for amorphous, microcrystalline and "micromorph" (microcrystalline/amorphous tandem) solar cells developped at the Institute of Microtechnology of the University of Neuchâtel. The chapter 3 is a detailed study of the growth of ZnO layers on a glass substrate. This study reveals a columnar microstructure of the ZnO layers, which are composed of large conical monocrystals. The tops of these monocrystals emerge at the surface of the ZnO layers as pyramids, which give to such layers their rough aspect and therefore their capacity of scattering the light. The two following chapters represent a study of the effect of variations in deposition parameters on the optical properties (transparency and scattering power), electrical properties (conductivity), and structural properties of ZnO layers. The deposition parameters varied thereby are the various gas flows, the substrate temperature, and the process pressure. In particular, a strong influence of the substrate temperature on the microstructure of the ZnO layers is observed. A variation of ten degrees of this deposition temperature leads to abrupt variations of the optical and electrical properties of the layers. From these various studies, a strong correlation is established, between the scattering power, the electrical properties, and the microstructure of the ZnO layers deposited by LP-CVD: The higher the pyramidal grains at the surface of the layers, the higher the scattering capacity of these layers. The larger the monocrystals within the bulk of the layers, the higher the mobility of the free electrons. This enhanced mobility leads to an increase of the conductivity of the layers. Finally, the chapter 6 of this thesis work describes the various situations where LP-CVD ZnO layers are used as transparent electrical contacts and light scattering layers in thin-film silicon solar cells. It is schown that, by incorporating ZnO layers developped in this work in the photovoltaic devices, an increase of 8% in the photogenerated current is obtained, compared to the performances of solar cells using standard commercially available TCO.

EPFL2003