Organic-inorganic halide perovskite/crystalline silicon four-terminal tandem solar cells

Tandem solar cells constructed from a crystalline silicon (c-Si) bottom cell and a low-cost top cell offer a promising way to ensure long-term price reductions of photovoltaic modules. We present a four-terminal tandem solar cell consisting of a methyl ammonium lead triiodide (CH3NH3PbI3) top cell and a c-Si heterojunction bottom cell. The CH3NH3PbI3 top cell exhibits broad-band transparency owing to its design free of metallic components and yields a transmittance of >55% in the near-infrared spectral region. This allows the generation of a short-circuit current density of 13.7 mA cm(-2) in the bottom cell. The four-terminal tandem solar cell yields an efficiency of 13.4% (top cell: 6.2%, bottom cell: 7.2%), which is a gain of 1.8%(abs) with respect to the reference single-junction CH3NH3PbI3 solar cell with metal back contact. We employ the four-terminal tandem solar cell for a detailed investigation of the optical losses and to derive guidelines for further efficiency improvements. Based on a power loss analysis, we estimate that tandem efficiencies of similar to 28% are attainable using an optically optimized system based on current technology, whereas a fully optimized, ultimate device with matched current could yield up to 31.6%.

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

Single and multi-junction thin film silicon solar cells for flexible photovoltaics

Thomas Söderström

This thesis investigates amorphous (a-Si:H) and microcrystalline (μc-Si:H) solar cells deposited by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) in the n-i-p or substrate configuration. It focuses on processes that allow the use of non transparent and flexible substrates such as plastic foil with Tg < 180°C like poly-ethylene-naphtalate (PEN). In the first part of the work, we concentrate on the light trapping properties of a variety of device configurations. One original test structure consists of n-i-p solar cells deposited directly on glass covered with low pressure chemical vapour deposition (LP-CVD) ZnO. For this device, silver is deposited below the LP-CVD ZnO or white paint is applied at the back of the substrate as back reflector. This avoids the parasitic plasmonic absorptions in the back reflectors, which are observed for conventional rough metallic back contacts. Furthermore, the size and morphology of the LP-CVD ZnO is varied and the relation between the substrate morphology and the short circuit current density (Jsc) is experimentally explored. As a result, the Jsc can be increased by 23% for a-Si:H and 28% for μc-Si:H solar cells compared to the case of flat substrate and the role of the size and shape can be clearly separated. We also explore the optical behavior of single and multi-junction devices prepared with different back and front contacts. The back contact consists either of a 2D periodic grid with moderate slope, or of LP-CVD ZnO with random pyramids of various sizes. The front contacts are either a 70 nm thick, nominally flat ITO or a rough 2 microns thick LP-CVD ZnO. We observe that, for a-Si:H, the cell performance is critically dependent on the combination of thin flat or thick rough front TCOs and the back contact. Indeed, for a-Si:H, a thick LP-CVD ZnO front contact provides more light trapping on the 2D periodic substrate. The Jsc relatively increases by 7 % with LP-CVD ZnO compared to ITO. Then, we study the influence of the thick and thin TCOs in conjunction with thick absorbers like triple junction or mc-Si:H solar cells. Because of the different nature of the optical systems, thick (> 1 micron) against thin (

University of Neuchâtel2009

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