@phdthesis{Wolff2020,
  author    = {Wolff, Christian Michael},
  title     = {Identification and reduction of losses in perovskite solar cells},
  doi       = {10.25932/publishup-47930},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-479301},
  school      = {Universit{\"a}t Potsdam},
  pages     = {x, 158},
  year      = {2020},
  abstract  = {Perovskite solar cells have become one of the most studied systems in the quest for new, cheap and efficient solar cell materials. Within a decade device efficiencies have risen to >25\% in single-junction and >29\% in tandem devices on top of silicon. This rapid improvement was in many ways fortunate, as e. g. the energy levels of commonly used halide perovskites are compatible with already existing materials from other photovoltaic technologies such as dye-sensitized or organic solar cells. Despite this rapid success, fundamental working principles must be understood to allow concerted further improvements. This thesis focuses on a comprehensive understanding of recombination processes in functioning devices. First the impact the energy level alignment between the perovskite and the electron transport layer based on fullerenes is investigated. This controversial topic is comprehensively addressed and recombination is mitigated through reducing the energy difference between the perovskite conduction band minimum and the LUMO of the fullerene. Additionally, an insulating blocking layer is introduced, which is even more effective in reducing this recombination, without compromising carrier collection and thus efficiency. With the rapid efficiency development (certified efficiencies have broken through the 20\% ceiling) and thousands of researchers working on perovskite-based optoelectronic devices, reliable protocols on how to reach these efficiencies are lacking. Having established robust methods for >20\% devices, while keeping track of possible pitfalls, a detailed description of the fabrication of perovskite solar cells at the highest efficiency level (>20\%) is provided. The fabrication of low-temperature p-i-n structured devices is described, commenting on important factors such as practical experience, processing atmosphere \& temperature, material purity and solution age. Analogous to reliable fabrication methods, a method to identify recombination losses is needed to further improve efficiencies. Thus, absolute photoluminescence is identified as a direct way to quantify the Quasi-Fermi level splitting of the perovskite absorber (1.21eV) and interfacial recombination losses the transport layers impose, reducing the latter to ~1.1eV. Implementing very thin interlayers at both the p- and n-interface (PFN-P2 and LiF, respectively), these losses are suppressed, enabling a VOC of up to 1.17eV. Optimizing the device dimensions and the bandgap, 20\% devices with 1cm2 active area are demonstrated. Another important consideration is the solar cells' stability if subjected to field-relevant stressors during operation. In particular these are heat, light, bias or a combination thereof. Perovskite layers - especially those incorporating organic cations - have been shown to degrade if subjected to these stressors. Keeping in mind that several interlayers have been successfully used to mitigate recombination losses, a family of perfluorinated self-assembled monolayers (X-PFCn, where X denotes I/Br and n = 7-12) are introduced as interlayers at the n-interface. Indeed, they reduce interfacial recombination losses enabling device efficiencies up to 21.3\%. Even more importantly they improve the stability of the devices. The solar cells with IPFC10 are stable over 3000h stored in the ambient and withstand a harsh 250h of MPP at 85◦C without appreciable efficiency losses. To advance further and improve device efficiencies, a sound understanding of the photophysics of a device is imperative. Many experimental observations in recent years have however drawn an inconclusive picture, often suffering from technical of physical impediments, disguising e. g. capacitive discharge as recombination dynamics. To circumvent these obstacles, fully operational, highly efficient perovskites solar cells are investigated by a combination of multiple optical and optoelectronic probes, allowing to draw a conclusive picture of the recombination dynamics in operation. Supported by drift-diffusion simulations, the device recombination dynamics can be fully described by a combination of first-, second- and third-order recombination and JV curves as well as luminescence efficiencies over multiple illumination intensities are well described within the model. On this basis steady state carrier densities, effective recombination constants, densities-of-states and effective masses are calculated, putting the devices at the brink of the radiative regime. Moreover, a comprehensive review of recombination in state-of-the-art devices is given, highlighting the importance of interfaces in nonradiative recombination. Different strategies to assess these are discussed, before emphasizing successful strategies to reduce interfacial recombination and pointing towards the necessary steps to further improve device efficiency and stability. Overall, the main findings represent an advancement in understanding loss mechanisms in highly efficient solar cells. Different reliable optoelectronic techniques are used and interfacial losses are found to be of grave importance for both efficiency and stability. Addressing the interfaces, several interlayers are introduced, which mitigate recombination losses and degradation.},
  language  = {en}
}
@phdthesis{Wolff2011,
  author    = {Wolff, Christian Michael},
  title     = {East African monsoon variability since the last glacial},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-58079},
  school      = {Universit{\"a}t Potsdam},
  year      = {2011},
  abstract  = {The impact of global warming on human water resources is attracting increasing attention. No other region in this world is so strongly affected by changes in water supply than the tropics. Especially in Africa, the availability and access to water is more crucial to existence (basic livelihoods and economic growth) than anywhere else on Earth. In East Africa, rainfall is mainly influenced by the migration of the Inter-Tropical Convergence Zone (ITCZ) and by the El Ni{\~n}o Southern Oscillation (ENSO) with more rain and floods during El Ni{\~n}o and severe droughts during La Ni{\~n}a. The forecasting of East African rainfall in a warming world requires a better understanding of the response of ENSO-driven variability to mean climate. Unfortunately, existing meteorological data sets are too short or incomplete to establish a precise evaluation of future climate. From Lake Challa near Mount Kilimanjaro, we report records from a laminated lake sediment core spanning the last 25,000 years. Analyzing a monthly cleared sediment trap confirms the annual origin of the laminations and demonstrates that the varve-thicknesses are strongly linked to the duration and strength of the windy season. Given the modern control of seasonal ITCZ location on wind and rain in this region and the inverse relation between the two, thicker varves represent windier and thus drier years. El Ni{\~n}o (La Ni{\~n}a) events are associated with wetter (drier) conditions in east Africa and decreased (increased) surface wind speeds. Based on this fact, the thickness of the varves can be used as a tool to reconstruct a) annual rainfall b) wind season strength, and c) ENSO variability. Within this thesis, I found evidence for centennialscale changes in ENSO-related rainfall variability during the last three millennia, abrupt changes in variability during the Medieval Climate Anomaly and the Little Ice Age, and an overall reduction in East African rainfall and its variability during the Last Glacial period. Climate model simulations support forward extrapolation from these lake-sediment data, indicating that a future Indian Ocean warming will enhance East Africa's hydrological cycle and its interannual variability in rainfall. Furthermore, I compared geochemical analyses from the sediment trap samples with a broad range of limnological, meteorological, and geological parameters to characterize the impact of sedimentation processes from the in-situ rocks to the deposited sediments. As a result an excellent calibration for existing μXRF data from Lake Challa over the entire 25,000 year long profile was provided. The climate development during the last 25,000 years as reconstructed from the Lake Challa sediments is in good agreement with other studies and highlights the complex interactions between long-term orbital forcing, atmosphere, ocean and land surface conditions. My findings help to understand how abrupt climate changes occur and how these changes correlate with climate changes elsewhere on Earth.},
  language  = {en}
}